CN109331814B - Composite carbon-noble metal catalyst, preparation method thereof and application thereof in synthesis of 2-tetrahydrofurfuryl acid - Google Patents
Composite carbon-noble metal catalyst, preparation method thereof and application thereof in synthesis of 2-tetrahydrofurfuryl acid Download PDFInfo
- Publication number
- CN109331814B CN109331814B CN201810976582.5A CN201810976582A CN109331814B CN 109331814 B CN109331814 B CN 109331814B CN 201810976582 A CN201810976582 A CN 201810976582A CN 109331814 B CN109331814 B CN 109331814B
- Authority
- CN
- China
- Prior art keywords
- noble metal
- graphene quantum
- reaction
- quantum dot
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 93
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 239000002253 acid Substances 0.000 title claims abstract description 46
- 230000015572 biosynthetic process Effects 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000003786 synthesis reaction Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 141
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000007864 aqueous solution Substances 0.000 claims abstract description 73
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 66
- 239000002096 quantum dot Substances 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002923 metal particle Substances 0.000 claims abstract description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 6
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 239000010948 rhodium Substances 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000004931 aggregating effect Effects 0.000 claims abstract description 3
- 238000013329 compounding Methods 0.000 claims abstract description 3
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 114
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 87
- 238000003760 magnetic stirring Methods 0.000 claims description 62
- 229910052757 nitrogen Inorganic materials 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 47
- 238000000502 dialysis Methods 0.000 claims description 44
- 229910052724 xenon Inorganic materials 0.000 claims description 34
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 34
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000012528 membrane Substances 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 25
- 239000000706 filtrate Substances 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 23
- 238000004458 analytical method Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 16
- 238000001728 nano-filtration Methods 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 13
- 238000000197 pyrolysis Methods 0.000 claims description 13
- 238000005286 illumination Methods 0.000 claims description 12
- 239000011268 mixed slurry Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 239000010970 precious metal Substances 0.000 claims description 10
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 4
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 4
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 4
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 4
- BBVIQHLJRNEBBW-UHFFFAOYSA-L Cl[Ir]Cl Chemical compound Cl[Ir]Cl BBVIQHLJRNEBBW-UHFFFAOYSA-L 0.000 claims description 2
- 229910021640 Iridium dichloride Inorganic materials 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 23
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 238000002791 soaking Methods 0.000 description 20
- 230000035484 reaction time Effects 0.000 description 12
- 208000012839 conversion disease Diseases 0.000 description 10
- 230000001678 irradiating effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 238000011978 dissolution method Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- 229930186147 Cephalosporin Natural products 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 206010060862 Prostate cancer Diseases 0.000 description 1
- 208000000236 Prostatic Neoplasms Diseases 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003560 cancer drug Substances 0.000 description 1
- 229940124587 cephalosporin Drugs 0.000 description 1
- 150000001780 cephalosporins Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- UOPIRNHVGHLLDZ-UHFFFAOYSA-L dichlororhodium Chemical compound Cl[Rh]Cl UOPIRNHVGHLLDZ-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- HDCRDACZYDHUQX-UHFFFAOYSA-M sodium;furan-2-carboxylate Chemical compound [Na+].[O-]C(=O)C1=CC=CO1 HDCRDACZYDHUQX-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Images
Classifications
-
- B01J35/393—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Abstract
The invention discloses a composite carbon-noble metal catalyst, a preparation method thereof and application thereof in synthesizing 2-tetrahydrofurfuryl acid. The catalyst consists of graphene quantum dots, a graphene quantum dot compound and noble metal particles, wherein the noble metal particles are deposited on the surface of the graphene quantum dot compound, and the graphene quantum dot compound and the graphene quantum dots deposited with the noble metal particles are uniformly dispersed in a pure water solvent; the graphene quantum dot composite is an amorphous nano carbon-based material formed by aggregating and compounding a plurality of graphene quantum dots with the average size of 1-10nm, and the size of the amorphous nano carbon-based material is 20-100 nm; the noble metal is one of platinum, palladium, iridium, ruthenium and rhodium, and the average particle size is 1-10 nm. The invention provides the application of the catalyst aqueous solution in the synthesis of 2-tetrahydrofurfuryl acid, hydrogen does not need to be added in the synthesis process, and the characteristics of high conversion rate, high catalytic activity, high reaction rate and high stability are shown by combining the reaction conditions of photo-thermal reaction and photo-thermal reaction.
Description
(I) technical field
The invention relates to a composite carbon-noble metal catalyst, a preparation method thereof and application thereof in synthesizing 2-tetrahydrofurfuryl acid.
(II) technical background
2-tetrahydrofurfuryl acid is an important medical intermediate, can be used for preparing cephalosporin antibiotic drugs, oxazine drugs for treating hypertension, prostate cancer drugs and the like, and occupies a very important position in the production of fine chemicals at home and abroad. Generally, the method for preparing 2-tetrahydrofurfuryl acid is divided into two methods, one method is that sodium furoate is catalyzed by Raney nickel at high temperature and high pressure to carry out hydrogenation reaction, and then the 2-tetrahydrofurfuryl acid is obtained by acidification, extraction and pressure distillation. The method has harsh reaction conditions, consumes a large amount of strong acid and strong base in the preparation process, has higher requirements on equipment and has larger environmental pollution. The second method is to use noble metal to catalyze 2-furoic acid for hydrogenation reaction in one step, although the reaction activity is higher, the selectivity is low, and the catalyst is unstable. Therefore, the research on the efficient and stable catalyst is a key step in the catalytic hydrogenation reaction of the furoic acid.
Disclosure of the invention
The first object of the present invention is to provide an aqueous solution of a composite carbon-noble metal catalyst, which has good water solubility, can be uniformly and stably dispersed and stored in an aqueous solvent, and reduces the reduction in activity due to oxidation of the active sites of the noble metal.
The second purpose of the invention is to provide a preparation method of the composite carbon-precious metal catalyst aqueous solution, which is simple and novel, economical and energy-saving, and beneficial to industrial application.
The third purpose of the invention is to provide the application of the composite carbon-noble metal catalyst aqueous solution in the synthesis of 2-tetrahydrofurfuryl acid, hydrogen does not need to be added in the synthesis process, and the composite carbon-noble metal catalyst aqueous solution combines the reaction conditions of photo-thermal reaction and has the characteristics of high conversion rate, high catalytic activity, high reaction rate and high stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a composite carbon-precious metal catalyst aqueous solution, wherein the composite carbon-precious metal catalyst consists of graphene quantum dots, a graphene quantum dot composite and precious metal particles, wherein the precious metal particles are deposited on the surface of the graphene quantum dot composite, and the graphene quantum dot composite and the graphene quantum dots deposited with the precious metal particles are uniformly dispersed in a pure water solvent; the graphene quantum dot composite is an amorphous nano carbon-based material formed by aggregating and compounding a plurality of graphene quantum dots with the average size of 1-10nm, and the size of the amorphous nano carbon-based material is 20-100 nm; the noble metal is one of platinum, palladium, iridium, ruthenium and rhodium, and the average particle size is 1-10 nm; the mass ratio of the noble metal to the carbon in the composite carbon-noble metal catalyst is 0.1-3: 1.2-9, wherein the total mass of the graphene quantum dot and the graphene quantum dot composite is 100%, and the mass fraction of the graphene quantum dot composite is 60-98%.
The invention provides a preparation method of a composite carbon-noble metal catalyst aqueous solution, which comprises the following steps:
1) preparing a noble metal salt aqueous solution with the noble metal content of 0.01-0.3 g/mL;
2) placing citric acid solid powder in a reaction container, heating to melt, then heating to 200-250 ℃ at the speed of 1-5 ℃/min, keeping at the temperature of 200-250 ℃ for 0.5-2h, finishing the pyrolysis process, and after cooling to room temperature, slowly dropwise adding deionized water to ensure that the feed ratio of the citric acid to the deionized water is 10-30 g: 200-500 mL, starting magnetic stirring until the solid is completely dissolved, dialyzing the obtained mixed solution to obtain a graphene quantum dot aqueous solution, wherein the yield of the graphene quantum dots is 20-30% of the mass of the added citric acid;
3) placing the graphene quantum dot aqueous solution obtained in the step 2) into a reaction container, replacing air with nitrogen or inert gas, setting the magnetic stirring speed to be 800-1500 rpm, starting stirring, setting the water bath temperature to be 30-90 ℃, then placing the reactor under a xenon lamp light source, setting the light source working power to be 150-300W, setting the irradiation time to be 0.5-3 h, and dialyzing the mixed solution obtained after the illumination is finished to obtain a graphene quantum dot composite aqueous solution, wherein the graphene quantum dot composite is 60-98% of the mass of the added graphene quantum dots;
4) slowly dropwise adding the noble metal salt aqueous solution obtained in the step 1) into the reaction container in the step 3), so that the feeding ratio of the citric acid to the noble metal salt aqueous solution is 10-30 g: 10-30 mL, replacing air with nitrogen or inert gas, setting the magnetic stirring speed to be 1200-1800 rpm, starting stirring, setting the water bath temperature to be 30-50 ℃, the ultrasonic frequency to be 50000-80000 Hz, the light source working power to be 100-150W, the light wavelength to be 300-380 nm, and the irradiation time to be 0.01-4 h, and obtaining the aqueous solution of the composite carbon-noble metal catalyst after stirring. The catalyst was stored in the shade at 0 ℃.
Further, the noble metal salt is one of palladium chloride, palladium nitrate, chloropalladic acid, palladium acetate, platinum dichloride, platinum tetrachloride, chloroplatinic acid, platinum nitrate, sodium chloroplatinate, rhodium chloride, rhodium nitrate, rhodium acetate, iridium dichloride, iridium trichloride, ruthenium trichloride and ruthenium nitrate.
Further, in step 2), the dialysis conditions are preferably: the obtained mixed solution is soaked in deionized water for dialysis for 12h at room temperature in a dialysis bag with molecular weight cutoff of 500 Da.
Further, in step 3), the dialysis conditions are preferably: the obtained mixed solution is soaked in deionized water at room temperature in a dialysis bag with molecular weight cutoff of 3000Da for dialysis for 12 h.
Further, in the step 4), before adding the noble metal salt into the reaction container, the pH value of the noble metal salt aqueous solution is adjusted to 0.5-2.0. Can be adjusted by using acid corresponding to the anion corresponding to the noble metal salt.
Further, the inert gas may be one of argon and helium.
The invention further provides application of the composite carbon-noble metal catalyst aqueous solution in the reaction of synthesizing 2-tetrahydrofurfuryl acid shown in the formula (II) by catalyzing and hydrogenating 2-furoic acid shown in the formula (I),
the application specifically comprises the following steps: according to the feeding ratio of 100-400 mL: 100-400 mL: 5-10 g of composite carbon-precious metal catalyst aqueous solution, methanol and 2-furoic acid shown in formula (I) are added into an intermittent photo-thermal stirring reaction kettle, the reaction kettle is sealed, nitrogen is introduced, whether the high-pressure reaction kettle leaks air or not is checked, if the high-pressure reaction kettle does not leak air, the nitrogen is introduced to replace air, the reaction temperature is set to be 90-250 ℃, the magnetic stirring speed is 1000-2000 rpm, the light source working power is 50-100W, the light wavelength is 250-300 nm, a heating program and the magnetic stirring are started to start the reaction, a light source working switch is started to carry out the reaction, the reaction is stopped until the conversion rate is 100%, the stirring is stopped, the temperature is reduced to room temperature, slurry is taken out and filtered, the filtrate can be subjected to reduced pressure distillation to obtain a product, and filter residues left on a filter membrane can be returned to the reaction kettle for catalyst application.
Further, the end point of the reaction was determined by: after reacting for a period of time, introducing nitrogen into the reactor, taking out the mixed slurry, filtering by a nanofiltration membrane to obtain a 2-tetrahydrofurfuryl acid aqueous solution shown in the formula (II), and then taking the filtrate for product analysis.
Furthermore, the nanofiltration membrane is made of polyamide with a pore diameter of about 1-2 nm.
Further, the light source used is a xenon lamp, and the specific light wavelength is filtered by a filter with the corresponding wavelength.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the composite carbon-noble metal catalyst, nano-sized graphene quantum dots directly interact with a metal precursor, the composite carbon-noble metal catalyst is formed by in-situ reduction in water by a photo-deposition method, and is stored in a form of aqueous solution, so that the dispersion is uniform and stable, and the reduction of activity caused by oxidation of noble metal active sites can be reduced.
2) The invention uses the water solution of the composite carbon-noble metal catalyst to catalyze the 2-furoic acid to carry out the in-situ hydrogenation reaction for synthesizing the 2-tetrahydrofurfuryl acid, and uses the methanol as the hydrogen source, thereby avoiding the potential safety hazard caused by using the hydrogen. The product separation is easy after the reaction, the reaction rate of the in-situ hydrogen hydrogenation in the adsorption state in the synthesis process is still high, and the selectivity of the 2-tetrahydrofurfuryl acid can reach more than 99.0 percent.
3) The catalyst synthesis method is simple, convenient, environment-friendly and harmless, and is beneficial to industrial application.
(IV) description of the drawings
Fig. 1 is a TEM image of the composite carbon-noble metal catalyst prepared in example 1.
(V) detailed description of the preferred embodiments
The technical solutions of the present invention are further described below with specific examples, but the scope of the present invention is not limited thereto.
Example 1
A conventional method for dissolving noble metal salt is adopted to prepare 0.3g/mL chloroplatinic acid solution and 0.3g/mL chloroplatinic acid solution. Placing 30g of citric acid solid powder in a reaction container, heating to be molten, heating to 250 ℃ at a speed of 5 ℃/min, keeping the temperature at 250 ℃ for 2h, finishing the pyrolysis process, slowly dropwise adding 500mL of deionized water after cooling to room temperature, starting magnetic stirring until the solid is completely dissolved, soaking the obtained mixed solution in a dialysis bag with the molecular weight cutoff of 500Da for dialysis for 12h at room temperature, and finally obtaining a graphene quantum dot aqueous solution, wherein the yield of the graphene quantum dots is 30% of the mass of the added citric acid. Placing the reactor under a xenon lamp light source, replacing air in the reactor with nitrogen, setting a magnetic stirring speed of 1500rpm, starting stirring, keeping the water bath temperature at 60 ℃, placing the reactor under the xenon lamp light source, setting the light source working power at 300W, irradiating for 3 hours, soaking the obtained mixed solution after the illumination in a dialysis bag with the molecular weight cutoff of 3000Da at room temperature, dialyzing for 12 hours in deionized water, and finally obtaining a graphene quantum dot compound aqueous solution, wherein the graphene quantum dot compound accounts for 98% of the mass of the added graphene quantum dots; slowly dropwise adding 5mL of chloropalladate solution and 5mL of chloroplatinic acid solution into the solution, replacing air with argon, setting a magnetic stirring speed of 1800rpm, starting stirring, setting a water bath temperature of 30 ℃, an ultrasonic frequency of 80000Hz, a xenon lamp light source working power of 150W, a light wavelength of 380nm, and irradiating for 4 hours to finally obtain an aqueous solution of the composite carbon-noble metal catalyst. The catalyst was stored in the shade at 0 ℃. The particle size of the graphene quantum dots is 1-5 nm, the particle size of the graphene quantum dot composite is 40-50 nm, and the particle size of the metal particles is 6-8 nm. The mass ratio of noble metals (Pd and Pt) to carbon, characterized by ICP, was 3: 9.
example 2
A0.01 g/mL chloropalladate solution and a 0.01g/mL palladium nitrate solution are prepared by adopting a conventional dissolving method of noble metal salt. Placing 10g of citric acid solid powder into a reaction container, heating to be molten, heating to 200 ℃ at a speed of 1 ℃/min, keeping the temperature at 200 ℃ for 0.5h, finishing the pyrolysis process, slowly dropwise adding 200mL of deionized water after cooling to room temperature, starting magnetic stirring until the solid is completely dissolved, soaking the obtained mixed solution in a dialysis bag with the molecular weight cutoff of 500Da at room temperature for dialysis for 12h, and finally obtaining a graphene quantum dot aqueous solution, wherein the yield of the graphene quantum dots is 20% of the mass of the added citric acid. Placing the reactor under a xenon lamp light source, replacing air in the reactor with helium, setting a magnetic stirring speed of 800rpm, starting stirring, setting a water bath temperature of 90 ℃, placing the reactor under the xenon lamp light source, setting a light source working power of 150W, irradiating for 0.5h, soaking a mixed solution obtained after the illumination is finished in a dialysis bag with a molecular weight cutoff of 3000Da at room temperature, dialyzing for 12h in deionized water, and finally obtaining a graphene quantum dot compound aqueous solution, wherein the graphene quantum dot compound accounts for 60% of the mass of the added graphene quantum dots; slowly dropwise adding 5mL of chloropalladate solution and 5mL of palladium nitrate solution into the solution, replacing air with nitrogen, setting the magnetic stirring speed at 1200rpm, starting stirring, setting the water bath temperature at 50 ℃, setting the ultrasonic frequency at 50000Hz, setting the working power of a xenon lamp light source at 100W, setting the light wavelength at 300nm, and setting the irradiation time at 0.01h to finally obtain the aqueous solution of the composite carbon-noble metal catalyst. The catalyst was stored in the shade at 0 ℃. The particle size of the graphene quantum dots is 2-5 nm, the particle size of the graphene quantum dot composite is 40-100 nm, and the particle size of the metal particles is 6-7 nm. The mass ratio of noble metal (Pd) to carbon, characterized by ICP, was 0.1: 1.2.
example 3
A palladium nitrate solution of 0.01g/mL and a rhodium dichloride solution of 0.01g/mL are prepared by adopting a conventional dissolving method of noble metal salt. Placing 10g of citric acid solid powder into a reaction container, heating to be molten, heating to 200 ℃ at a speed of 1 ℃/min, keeping the temperature at 200 ℃ for 0.5h, finishing the pyrolysis process, slowly dropwise adding 200mL of deionized water after cooling to room temperature, starting magnetic stirring until the solid is completely dissolved, soaking the obtained mixed solution in a dialysis bag with the molecular weight cutoff of 500Da at room temperature for dialysis for 12h, and finally obtaining a graphene quantum dot aqueous solution, wherein the yield of the graphene quantum dots is 20% of the mass of the added citric acid. Placing the reactor under a xenon lamp light source, replacing air in the reactor with nitrogen, setting a magnetic stirring speed of 800rpm, starting stirring, keeping a water bath temperature at 60 ℃, placing the reactor under the xenon lamp light source, setting a light source working power of 200W, irradiating for 1h, soaking the obtained mixed solution after the illumination in a dialysis bag with a molecular weight cutoff of 3000Da at room temperature for dialysis for 12h, and finally obtaining a graphene quantum dot compound aqueous solution, wherein the graphene quantum dot compound accounts for 80% of the mass of the added graphene quantum dots; slowly dropwise adding 15mL of chloropalladate solution and 15mL of chloroplatinic acid solution into the solution, replacing air with helium, setting a magnetic stirring speed of 1500rpm, starting stirring, setting a water bath temperature of 40 ℃, setting an ultrasonic frequency of 60000Hz, setting a xenon lamp light source working power of 120W, setting a light wavelength of 300nm, and irradiating for 2 hours to finally obtain an aqueous solution of the composite carbon-noble metal catalyst. The catalyst was stored in the shade at 0 ℃. The particle size of the graphene quantum dots is 3-7 nm, the particle size of the graphene quantum dot composite is 25-60 nm, and the particle size of the metal particles is 7-9 nm. The mass ratio of the noble metals (Pd and Rh) to carbon, characterized by ICP, was 0.3: 1.6.
example 4
A platinum dichloride solution of 0.1g/mL is prepared by adopting a conventional dissolution method of noble metal salt. Placing 20g of citric acid solid powder into a reaction container, heating to be molten, heating to 220 ℃ at a speed of 2 ℃/min, keeping the temperature at 220 ℃ for 2h, finishing the pyrolysis process, slowly dropwise adding 400mL of deionized water after cooling to room temperature, starting magnetic stirring until the solid is completely dissolved, soaking the obtained mixed solution in a dialysis bag with the molecular weight cutoff of 500Da for dialysis for 12h at room temperature, and finally obtaining a graphene quantum dot aqueous solution, wherein the yield of the graphene quantum dots is 25% of the mass of the added citric acid. Placing the reactor under a xenon lamp light source, replacing air in the reactor with nitrogen, setting a magnetic stirring speed of 1300rpm, starting stirring, keeping the water bath temperature at 40 ℃, placing the reactor under the xenon lamp light source, setting the light source working power of 250W, irradiating for 1.5h, soaking the obtained mixed solution after the illumination in a dialysis bag with the molecular weight cutoff of 3000Da at room temperature, dialyzing for 12h in deionized water, and finally obtaining a graphene quantum dot compound aqueous solution, wherein the graphene quantum dot compound accounts for 80% of the mass of the added graphene quantum dots; slowly dropwise adding 20mL of platinum dichloride solution into the solution, replacing air with nitrogen, setting the magnetic stirring speed to be 1500rpm, starting stirring, setting the water bath temperature to be 40 ℃, setting the ultrasonic frequency to be 60000Hz, setting the working power of a xenon lamp light source to be 130W, setting the light wavelength to be 310nm, and setting the irradiation time to be 2.5h, thereby finally obtaining the aqueous solution of the composite carbon-noble metal catalyst. The catalyst was stored in the shade at 0 ℃. The particle size of the graphene quantum dots is 4-7 nm, the particle size of the graphene quantum dot composite is 30-65 nm, and the particle size of the metal particles is 7-9 nm. The mass ratio of noble metal (Pt) to carbon, characterized by ICP, was 2: 4.
example 5
A solution of 0.02g/mL chloroplatinic acid is prepared by adopting a conventional dissolution method of noble metal salt. Placing 15g of citric acid solid powder into a reaction container, heating to be molten, heating to 230 ℃ at a speed of 3 ℃/min, keeping the temperature at 230 ℃ for 1h, finishing the pyrolysis process, slowly dropwise adding 500mL of deionized water after cooling to room temperature, starting magnetic stirring until the solid is completely dissolved, soaking the obtained mixed solution in a dialysis bag with the molecular weight cutoff of 500Da for dialysis for 12h at room temperature, and finally obtaining a graphene quantum dot aqueous solution, wherein the yield of the graphene quantum dots is 25% of the mass of the added citric acid. Placing the reactor under a xenon lamp light source, replacing air in the reactor with nitrogen, setting a magnetic stirring speed of 1400rpm, starting stirring, carrying out water bath at the temperature of 50 ℃, placing the reactor under the xenon lamp light source, setting the working power of the light source to be 150W, irradiating for 3 hours, soaking the obtained mixed solution after the illumination in a dialysis bag with the molecular weight cutoff of 3000Da at room temperature, dialyzing for 12 hours in deionized water, and finally obtaining a graphene quantum dot compound aqueous solution, wherein the graphene quantum dot compound accounts for 70% of the mass of the added graphene quantum dots; slowly dropwise adding 10mL of chloroplatinic acid solution into the solution, replacing air with nitrogen, setting the magnetic stirring speed to be 1800rpm, starting stirring, setting the water bath temperature to be 30 ℃, the ultrasonic frequency to be 60000Hz, the working power of a xenon lamp light source to be 150W, the light wavelength to be 320nm, and the irradiation time to be 3.5h, thereby finally obtaining the aqueous solution of the composite carbon-noble metal catalyst. The catalyst was stored in the shade at 0 ℃. The particle size of the graphene quantum dots is 6-8 nm, the particle size of the graphene quantum dot composite is 20-55 nm, and the particle size of the metal particles is 7-10 nm. The mass ratio of noble metal (Pt) to carbon, characterized by ICP, was 0.2: 2.625.
example 6
A solution of 0.05g/mL chloroplatinic acid is prepared by adopting a conventional dissolution method of noble metal salt. Placing 25g of citric acid solid powder into a reaction container, heating to be molten, heating to 250 ℃ at a speed of 3 ℃/min, keeping the temperature at 250 ℃ for 1h, finishing the pyrolysis process, slowly dropwise adding 500mL of deionized water after cooling to room temperature, starting magnetic stirring until the solid is completely dissolved, soaking the obtained mixed solution in a dialysis bag with the molecular weight cutoff of 500Da for dialysis for 12h at room temperature, and finally obtaining a graphene quantum dot aqueous solution, wherein the yield of the graphene quantum dots is 25% of the mass of the added citric acid. Placing the reactor under a xenon lamp light source, replacing air in the reactor with nitrogen, setting a magnetic stirring speed of 1400rpm, starting stirring, keeping the water bath temperature at 40 ℃, placing the reactor under the xenon lamp light source, setting the light source working power of 150W, irradiating for 2 hours, soaking the obtained mixed solution after the illumination in a dialysis bag with the molecular weight cutoff of 3000Da at room temperature, dialyzing for 12 hours in deionized water, and finally obtaining a graphene quantum dot compound aqueous solution, wherein the graphene quantum dot compound accounts for 70% of the mass of the added graphene quantum dots; slowly dropwise adding 15mL of chloroplatinic acid solution into the solution, replacing air with nitrogen, setting the magnetic stirring speed to be 1500rpm, starting stirring, setting the water bath temperature to be 60 ℃, setting the ultrasonic frequency to be 65000Hz, setting the working power of a xenon lamp light source to be 150W, setting the light wavelength to be 330nm, and setting the irradiation time to be 3.5h, thereby finally obtaining the aqueous solution of the composite carbon-noble metal catalyst. The catalyst was stored in the shade at 0 ℃. The particle size of the graphene quantum dots is 6-10 nm, the particle size of the graphene quantum dot composite is 30-65 nm, and the particle size of the metal particles is 8-10 nm. The mass ratio of noble metal (Pt) to carbon, characterized by ICP, was 0.75: 4.5.
example 7
A rhodium chloride solution with the concentration of 0.03g/mL is prepared by adopting a conventional noble metal salt dissolving method. Placing 10g of citric acid solid powder into a reaction container, heating to be molten, heating to 250 ℃ at a speed of 3 ℃/min, keeping the temperature at 250 ℃ for 1.5h, finishing the pyrolysis process, slowly dripping 300mL of deionized water after cooling to room temperature, starting magnetic stirring until the solid is completely dissolved, soaking the obtained mixed solution in a dialysis bag with the molecular weight cutoff of 500Da at room temperature for dialysis for 12h, and finally obtaining a graphene quantum dot aqueous solution, wherein the yield of the graphene quantum dots is 20% of the mass of the added citric acid. Placing the reactor under a xenon lamp light source, replacing air in the reactor with nitrogen, setting a magnetic stirring speed of 1400rpm, starting stirring, keeping the water bath temperature at 40 ℃, placing the reactor under the xenon lamp light source, setting the light source working power of 150W, irradiating for 3 hours, soaking the obtained mixed solution after the illumination in a dialysis bag with the molecular weight cutoff of 3000Da at room temperature for dialysis for 12 hours in deionized water, and finally obtaining a graphene quantum dot compound aqueous solution, wherein the graphene quantum dot compound accounts for 85% of the mass of the added graphene quantum dots; slowly dropwise adding 15mL of rhodium chloride solution into the solution, replacing air with nitrogen, setting the magnetic stirring speed to be 1500rpm, starting stirring, setting the water bath temperature to be 50 ℃, setting the ultrasonic frequency to be 75000Hz, setting the working power of a xenon lamp light source to be 150W, setting the light wavelength to be 340nm, and setting the irradiation time to be 4h, thereby finally obtaining the aqueous solution of the composite carbon-noble metal catalyst. The catalyst was stored in the shade at 0 ℃. The particle size of the graphene quantum dots is 8-10 nm, the particle size of the graphene quantum dot composite is 20-80 nm, and the particle size of the metal particles is 8-9 nm. ICP characterization, precious metal (Rh) to carbon mass ratio of 0.45: 1.7.
example 8
Preparing 0.2g/mL iridium trichloride solution by adopting a conventional noble metal salt dissolving method. Placing 10g of citric acid solid powder into a reaction container, heating to be molten, heating to 250 ℃ at a speed of 3 ℃/min, keeping the temperature at 250 ℃ for 1.5h, finishing the pyrolysis process, slowly dripping 300mL of deionized water after cooling to room temperature, starting magnetic stirring until the solid is completely dissolved, soaking the obtained mixed solution in a dialysis bag with the molecular weight cutoff of 500Da at room temperature for dialysis for 12h, and finally obtaining a graphene quantum dot aqueous solution, wherein the yield of the graphene quantum dots is 25% of the mass of the added citric acid. Placing the reactor under a xenon lamp light source, replacing air in the reactor with nitrogen, setting a magnetic stirring speed of 1500rpm, starting stirring, keeping the water bath temperature at 70 ℃, placing the reactor under the xenon lamp light source, setting the light source working power of 250W, irradiating for 2.5 hours, soaking the obtained mixed solution after the illumination in a dialysis bag with the molecular weight cutoff of 3000Da at room temperature, dialyzing for 12 hours in deionized water, and finally obtaining a graphene quantum dot compound aqueous solution, wherein the graphene quantum dot compound accounts for 90% of the mass of the added graphene quantum dots; slowly dropwise adding 20mL of iridium trichloride solution into the solution, replacing air with nitrogen, setting the magnetic stirring speed at 1600rpm, starting stirring, keeping the water bath temperature at 50 ℃, keeping the ultrasonic frequency at 75000Hz, keeping the working power of a xenon lamp light source at 130W, keeping the irradiation time at 2.5h, keeping the light wavelength at 360nm, and finally obtaining the aqueous solution of the composite carbon-noble metal catalyst. The catalyst was stored in the shade at 0 ℃. The particle size of the graphene quantum dots is 8-10 nm, the particle size of the graphene quantum dot composite is 25-40 nm, and the particle size of the metal particles is 6-9 nm. The mass ratio of the noble metal (Ir) to the carbon is 0.4: 2.25.
example 9
A conventional dissolution method of noble metal salt is adopted to prepare 0.04g/mL ruthenium nitrate solution. Placing 25g of citric acid solid powder into a reaction container, heating to be molten, heating to 250 ℃ at a speed of 3 ℃/min, keeping the temperature at 250 ℃ for 1.5h, finishing the pyrolysis process, slowly dropping 400mL of deionized water after cooling to room temperature, starting magnetic stirring until the solid is completely dissolved, soaking the obtained mixed solution in a dialysis bag with the molecular weight cutoff of 500Da for dialysis for 12h at room temperature, and finally obtaining a graphene quantum dot aqueous solution, wherein the yield of the graphene quantum dots is 30% of the mass of the added citric acid. Placing the reactor under a xenon lamp light source, replacing air in the reactor with nitrogen, setting a magnetic stirring speed of 1500rpm, starting stirring, carrying out water bath at the temperature of 30 ℃, placing the reactor under the xenon lamp light source, setting the working power of the light source to be 250W, carrying out irradiation for 2.5h, soaking the obtained mixed solution after the illumination in a dialysis bag with the molecular weight cutoff of 3000Da at room temperature, dialyzing for 12h in deionized water, and finally obtaining a graphene quantum dot compound aqueous solution, wherein the graphene quantum dot compound accounts for 95% of the mass of the added graphene quantum dots; slowly dropwise adding 10mL of ruthenium nitrate solution into the solution, replacing air with nitrogen, setting the magnetic stirring speed at 1600rpm, starting stirring, setting the water bath temperature at 50 ℃, the ultrasonic frequency at 75000Hz, the working power of a xenon lamp light source at 120W, the irradiation time at 2.5h and the light wavelength at 370nm, and finally obtaining the aqueous solution of the composite carbon-noble metal catalyst. The catalyst was stored in the shade at 0 ℃. The particle size of the graphene quantum dots is 8-10 nm, the particle size of the graphene quantum dot composite is 25-45 nm, and the particle size of the metal particles is 7-9 nm. The mass ratio of noble metal (Ru) to carbon, characterized by ICP, was 0.4: 7.125.
example 10
A solution of 0.25g/mL chloroplatinic acid is prepared by adopting a conventional dissolution method of noble metal salt. Placing 25g of citric acid solid powder into a reaction container, heating to be molten, heating to 250 ℃ at a speed of 3 ℃/min, keeping the temperature at 250 ℃ for 1.5h, finishing the pyrolysis process, slowly dropping 400mL of deionized water after cooling to room temperature, starting magnetic stirring until the solid is completely dissolved, soaking the obtained mixed solution in a dialysis bag with the molecular weight cutoff of 500Da for dialysis for 12h at room temperature, and finally obtaining a graphene quantum dot aqueous solution, wherein the yield of the graphene quantum dots is 30% of the mass of the added citric acid. Placing the reactor under a xenon lamp light source, replacing air in the reactor with nitrogen, setting a magnetic stirring speed of 1500rpm, starting stirring, carrying out water bath at the temperature of 30 ℃, placing the reactor under the xenon lamp light source, setting the working power of the light source to be 250W, carrying out irradiation for 2.5h, soaking the obtained mixed solution after the illumination in a dialysis bag with the molecular weight cutoff of 3000Da at room temperature, dialyzing for 12h in deionized water, and finally obtaining a graphene quantum dot compound aqueous solution, wherein the graphene quantum dot compound accounts for 65% of the mass of the added graphene quantum dots; slowly dropwise adding 10mL of chloroplatinic acid solution into the solution, replacing air with nitrogen, setting the magnetic stirring speed to be 1800rpm, starting stirring, setting the water bath temperature to be 40 ℃, setting the ultrasonic frequency to be 75000Hz, setting the working power of a xenon lamp light source to be 150W, setting the irradiation time to be 2.5h, and setting the light wavelength to be 370nm, and finally obtaining the aqueous solution of the composite carbon-noble metal catalyst. The catalyst was stored in the shade at 0 ℃. The particle size of the graphene quantum dots is 8-10 nm, the particle size of the graphene quantum dot composite is 25-45 nm, and the particle size of the metal particles is 8-10 nm. The mass ratio of noble metal (Pt) to carbon, characterized by ICP, was 2.5: 4.9.
comparative example 1
Physical parameters of the carrier activated carbon are as follows: ash 2.5 wt% and specific surface area 1200m2The specific surface area of the micropores accounts for not less than 85 percent, the particle size of the activated carbon particles is D10:2.5 mu m, D50:12 mu m and D90:30 mu m; the material of the active carbon is coconut shell.
Preparing a conventional carbon-supported palladium hydrogenation catalyst: drying and dehydrating 12g of coconut shell activated carbon at 100 ℃ for 4h in vacuum; then treating the mixture for 6 hours at 50 ℃ in 200mL of hydrochloric acid solution with the concentration of 2mol/mL, washing the mixture to be neutral, and mixing and stirring the mixture with 50mL of water; and dropwise adding hydrochloric acid to adjust the pH value to 1, heating to 50 ℃, dropwise adding 20ml of 0.03g/ml chloropalladite solution, stirring for 5h, then adjusting the pH value to 8, continuously stirring for 1h, then washing to neutrality, then drying at 120 ℃ under vacuum for 6h, then reducing at 150 ℃ under a mixed gas of hydrogen and argon, and reducing for 3h to obtain the 5 wt% Pd/C catalyst.
Comparative example 2
A conventional method for dissolving noble metal salt is adopted to prepare 0.001g/mL chloropalladic acid solution and 0.001g/mL chloroplatinic acid solution. Mixing 1g of citric acid solid powder, 5ml of chloropalladite solution and 5ml of chloroplatinic acid solution, setting the water bath temperature to be 30 ℃, starting magnetic stirring for 3 hours, and after stirring is finished, carrying out low-temperature vacuum drying on the mixed solution (the low-temperature vacuum drying condition is that the relative vacuum degree is minus 0.099MPa, the temperature is minus 10 ℃, and the drying time is 10 hours) to obtain the citric acid and precious metal complex solid powder; then placing the complex solid powder into a round-bottom flask, heating to melt, heating to 200 ℃ at a speed of 1 ℃/min, keeping the temperature at 200 ℃ for 0.5h, after the pyrolysis process is finished and the temperature is reduced to room temperature, slowly dropwise adding 50ml of deionized water, starting magnetic stirring until the solid is completely dissolved, and finally performing low-temperature vacuum drying on the solution (the low-temperature vacuum drying condition is that the relative vacuum degree is-0.099 MPa, the temperature is-10 ℃, and the drying time is 10h) to obtain the composite carbon-noble metal catalyst solid powder. Reducing the obtained sample by adopting a liquid-phase reducing agent, wherein the liquid-phase reducing agent is a glucose aqueous solution, the temperature is 10 ℃, the time is 10 hours, and the molar ratio of metal to the reducing agent is 1: 2, the volume ratio of the catalyst to the aqueous solution of the reducing agent is 1: 2. after reduction is finished, centrifugal separation and water washing are adopted until no reducing agent exists, and the reducing agent is retained in a state that the volume ratio of ethanol to water is 1: 1 in the mixed solution. The catalyst has the particle size of 17nm, the average particle size of carbon dots is 8nm, and the average particle size of metal particles is 9nm by TEM representation. The mass ratio of the noble metals (Pd and Pt) to the carbon dots was 0.01: 0.5.
example 11
Adding 400mL of the composite carbon-noble metal catalyst aqueous solution of the embodiment 1, 400mL of methanol and 5g of 2-furoic acid into a batch photothermal stirring reaction kettle, sealing the reaction kettle, introducing nitrogen, checking whether the high-pressure reaction kettle leaks air or not, introducing nitrogen at 1.0MPa to replace air if the high-pressure reaction kettle does not leak air, and repeating the operation for 3 times. Then, setting the reaction temperature at 90 ℃, the magnetic stirring speed at 1000rpm, the light source working power at 50W and the light wavelength at 250nm, starting a temperature raising program, starting the reaction by magnetic stirring, and starting a light source working switch. After reacting for a period of time, introducing nitrogen into the reactor, taking out the mixed slurry, carrying out product analysis on the filtrate obtained by filtering with a nanofiltration membrane, determining that the conversion rate is 100%, stopping stirring, cooling to room temperature, opening the kettle, taking out the slurry, filtering, carrying out reduced pressure distillation on the filtrate to obtain a product, and returning the filter residue left on the filter membrane to the reaction kettle for catalyst application. The analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 2-tetrahydrofurfuryl acid is 99.0 percent, and the reaction time is 20 hours.
Example 12
Adding 100mL of the composite carbon-noble metal catalyst aqueous solution of the embodiment 2, 100mL of methanol and 10g of 2-furoic acid into an intermittent photo-thermal stirring reaction kettle, sealing the reaction kettle, introducing nitrogen, checking whether the high-pressure reaction kettle leaks air or not, introducing nitrogen at 1.0MPa to replace air if the high-pressure reaction kettle does not leak air, and repeating the operation for 3 times. Then, setting the reaction temperature to be 250 ℃, the magnetic stirring speed to be 2000rpm, the light source working power to be 100W and the light wavelength to be 300nm, starting a temperature raising program, starting the reaction by magnetic stirring, and starting a light source working switch. After reacting for a period of time, introducing nitrogen into the reactor, taking out the mixed slurry, carrying out product analysis on the filtrate obtained by filtering with a nanofiltration membrane, determining that the conversion rate is 100%, stopping stirring, cooling to room temperature, opening the kettle, taking out the slurry, filtering, carrying out reduced pressure distillation on the filtrate to obtain a product, and returning the filter residue left on the filter membrane to the reaction kettle for catalyst application. The analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 2-tetrahydrofurfuryl acid is 99.1 percent, and the reaction time is 15 hours.
Example 13
Adding 150mL of the composite carbon-noble metal catalyst aqueous solution of the embodiment 3, 150mL of methanol and 6g of 2-furoic acid into an intermittent photo-thermal stirring reaction kettle, sealing the reaction kettle, introducing nitrogen, checking whether the high-pressure reaction kettle leaks air or not, introducing nitrogen at 1.0MPa to replace air if the high-pressure reaction kettle does not leak air, and repeating the operation for 3 times. Then, setting the reaction temperature at 150 ℃, the magnetic stirring speed at 1500rpm, the light source working power at 90W and the light wavelength at 260nm, starting a temperature raising program, starting the reaction by magnetic stirring, and starting a light source working switch. After reacting for a period of time, introducing nitrogen into the reactor, taking out the mixed slurry, carrying out product analysis on the filtrate obtained by filtering with a nanofiltration membrane, determining that the conversion rate is 100%, stopping stirring, cooling to room temperature, opening the kettle, taking out the slurry, filtering, carrying out reduced pressure distillation on the filtrate to obtain a product, and returning the filter residue left on the filter membrane to the reaction kettle for catalyst application. The analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 2-tetrahydrofurfuryl acid is 99.0 percent, and the reaction time is 13 hours.
Example 14
200mL of the composite carbon-noble metal catalyst aqueous solution of example 4, 200mL of methanol and 7g of 2-furoic acid are added into an intermittent photo-thermal stirring reaction kettle, the reaction kettle is sealed, nitrogen is introduced, whether the high-pressure reaction kettle leaks air or not is checked, if the high-pressure reaction kettle does not leak air, the nitrogen is introduced to replace the air under 1.0MPa, and the operation is repeated for 3 times. Then, setting the reaction temperature to be 200 ℃, the magnetic stirring speed to be 1600rpm, the light source working power to be 80W, the light wavelength to be 270nm, starting a temperature raising program, starting the reaction by magnetic stirring, and starting a light source working switch. After reacting for a period of time, introducing nitrogen into the reactor, taking out the mixed slurry, carrying out product analysis on the filtrate obtained by filtering with a nanofiltration membrane, determining that the conversion rate is 100%, stopping stirring, cooling to room temperature, opening the kettle, taking out the slurry, filtering, carrying out reduced pressure distillation on the filtrate to obtain a product, and returning the filter residue left on the filter membrane to the reaction kettle for catalyst application. The analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 2-tetrahydrofurfuryl acid is 99.4 percent, and the reaction time is 16 hours.
Example 15
Adding 250mL of the composite carbon-noble metal catalyst aqueous solution of the embodiment 5, 250mL of methanol and 8g of 2-furoic acid into a batch photothermal stirring reaction kettle, sealing the reaction kettle, introducing nitrogen, checking whether the high-pressure reaction kettle leaks air or not, introducing nitrogen at 1.0MPa to replace air if the high-pressure reaction kettle does not leak air, and repeating the operation for 3 times. Then, setting the reaction temperature at 200 ℃, the magnetic stirring speed at 1600rpm, the light source working power at 100W and the light wavelength at 280nm, starting a temperature-raising program, starting the reaction by magnetic stirring, and starting a photo-thermal working switch. After reacting for a period of time, introducing nitrogen into the reactor, taking out the mixed slurry, carrying out product analysis on the filtrate obtained by filtering with a nanofiltration membrane, determining that the conversion rate is 100%, stopping stirring, cooling to room temperature, opening the kettle, taking out the slurry, filtering, carrying out reduced pressure distillation on the filtrate to obtain a product, and returning the filter residue left on the filter membrane to the reaction kettle for catalyst application. The analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 2-tetrahydrofurfuryl acid is 99.0 percent, and the reaction time is 10 hours.
Example 16
Adding 300mL of the composite carbon-noble metal catalyst aqueous solution of the embodiment 6, 300mL of methanol and 9g of 2-furoic acid into an intermittent photo-thermal stirring reaction kettle, sealing the reaction kettle, introducing nitrogen, checking whether the high-pressure reaction kettle leaks air or not, introducing nitrogen at 1.0MPa to replace air if the high-pressure reaction kettle does not leak air, and repeating the operation for 3 times. Then, setting the reaction temperature at 100 ℃, the magnetic stirring speed at 1800rpm, the light source working power at 60W and the light wavelength at 290nm, starting a temperature raising program, starting the reaction by magnetic stirring, and starting a photo-thermal working switch. After reacting for a period of time, introducing nitrogen into the reactor, taking out the mixed slurry, carrying out product analysis on the filtrate obtained by filtering with a nanofiltration membrane, determining that the conversion rate is 100%, stopping stirring, cooling to room temperature, opening the kettle, taking out the slurry, filtering, carrying out reduced pressure distillation on the filtrate to obtain a product, and returning the filter residue left on the filter membrane to the reaction kettle for catalyst application. The analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 2-tetrahydrofurfuryl acid is 99.5 percent, and the reaction time is 18 hours.
Example 17
Adding 300mL of the composite carbon-noble metal catalyst aqueous solution of the embodiment 7, 300mL of methanol and 9g of 2-furoic acid into an intermittent photo-thermal stirring reaction kettle, sealing the reaction kettle, introducing nitrogen, checking whether the high-pressure reaction kettle leaks air or not, introducing nitrogen at 1.0MPa to replace air if the high-pressure reaction kettle does not leak air, and repeating the operation for 3 times. Then, setting the reaction temperature at 150 ℃, the magnetic stirring speed at 1800rpm, the light source working power at 70W and the light wavelength at 300nm, starting a temperature raising program, starting the reaction by magnetic stirring, and starting a light source working switch. After reacting for a period of time, introducing nitrogen into the reactor, taking out the mixed slurry, carrying out product analysis on the filtrate obtained by filtering with a nanofiltration membrane, determining that the conversion rate is 100%, stopping stirring, cooling to room temperature, opening the kettle, taking out the slurry, filtering, carrying out reduced pressure distillation on the filtrate to obtain a product, and returning the filter residue left on the filter membrane to the reaction kettle for catalyst application. The analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 2-tetrahydrofurfuryl acid is 99.5 percent, and the reaction time is 10 hours.
Example 18
Adding 300mL of the composite carbon-noble metal catalyst aqueous solution of the embodiment 8, 300mL of methanol and 10g of 2-furoic acid into an intermittent photo-thermal stirring reaction kettle, sealing the reaction kettle, introducing nitrogen, checking whether the high-pressure reaction kettle leaks air or not, introducing nitrogen at 1.0MPa to replace air if the high-pressure reaction kettle does not leak air, and repeating the operation for 3 times. Then, setting the reaction temperature at 180 ℃, the magnetic stirring speed at 1900rpm, the light source working power at 80W and the light wavelength at 250nm, starting the temperature raising program, starting the magnetic stirring reaction, and starting the light source working switch. After reacting for a period of time, introducing nitrogen into the reactor, taking out the mixed slurry, carrying out product analysis on the filtrate obtained by filtering with a nanofiltration membrane, determining that the conversion rate is 100%, stopping stirring, cooling to room temperature, opening the kettle, taking out the slurry, filtering, carrying out reduced pressure distillation on the filtrate to obtain a product, and returning the filter residue left on the filter membrane to the reaction kettle for catalyst application. The analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 2-tetrahydrofurfuryl acid is 99.6 percent, and the reaction time is 12 hours.
Example 19
350mL of the composite carbon-noble metal catalyst aqueous solution of the embodiment 9, 350mL of methanol and 10g of 2-furoic acid are added into an intermittent photo-thermal stirring reaction kettle, the reaction kettle is sealed, nitrogen is introduced, whether the high-pressure reaction kettle leaks air or not is checked, if the high-pressure reaction kettle does not leak air, the nitrogen is introduced to replace the air under 1.0MPa, and the operation is repeated for 3 times. Then, setting the reaction temperature at 90 ℃, the magnetic stirring speed at 1500rpm, the light source working power at 100W and the light wavelength at 300nm, starting a temperature raising program, starting the reaction by magnetic stirring, and starting a photo-thermal working switch. After reacting for a period of time, introducing nitrogen into the reactor, taking out the mixed slurry, carrying out product analysis on the filtrate obtained by filtering with a nanofiltration membrane, determining that the conversion rate is 100%, stopping stirring, cooling to room temperature, opening the kettle, taking out the slurry, filtering, carrying out reduced pressure distillation on the filtrate to obtain a product, and returning the filter residue left on the filter membrane to the reaction kettle for catalyst application. The analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 2-tetrahydrofurfuryl acid is 99.3 percent, and the reaction time is 22 hours.
Example 20
Adding 400mL of the 10 composite carbon-noble metal catalyst aqueous solution, 400mL of methanol and 8g of 2-furoic acid into an intermittent photo-thermal stirring reaction kettle, sealing the reaction kettle, introducing nitrogen, checking whether the high-pressure reaction kettle leaks air or not, introducing nitrogen at 1.0MPa to replace air if the high-pressure reaction kettle does not leak air, and repeating the operation for 3 times. Then, setting the reaction temperature at 100 ℃, the magnetic stirring speed at 1800rpm, the light source working power at 60W and the light wavelength at 300nm, starting a temperature raising program, starting the reaction by magnetic stirring, and starting a photo-thermal working switch. After reacting for a period of time, introducing nitrogen into the reactor, taking out the mixed slurry, carrying out product analysis on the filtrate obtained by filtering with a nanofiltration membrane, determining that the conversion rate is 100%, stopping stirring, cooling to room temperature, opening the kettle, taking out the slurry, filtering, carrying out reduced pressure distillation on the filtrate to obtain a product, and returning the filter residue left on the filter membrane to the reaction kettle for catalyst application. The analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 2-tetrahydrofurfuryl acid is 99.8 percent, and the reaction time is 14 hours.
Examples 21 to 30
The results of the catalytic hydrogenation reaction using the catalyst of comparative example 1 under the reaction conditions corresponding to examples 11 to 20 are shown in table 1.
TABLE 1 results of using the catalyst of comparative example 1 under the reaction conditions corresponding to examples 11 to 20
| Examples | Reaction conditions | Conversion rate% | Selectivity% | Reaction time h |
| Example 21 | Example 11 | 95.00 | 93.29 | 24 |
| Example 22 | Example 12 | 94.98 | 95.98 | 16 |
| Example 23 | Example 13 | 96.43 | 96.36 | 15 |
| Example 24 | Example 14 | 91.36 | 95.26 | 14 |
| Example 25 | Example 15 | 93.25 | 94.25 | 12 |
| Example 26 | Example 16 | 90.25 | 93.14 | 16 |
| Example 27 | Example 17 | 91.69 | 96.58 | 10 |
| Example 28 | Example 18 | 91.89 | 93.85 | 22 |
| Example 29 | Example 19 | 92.21 | 94.47 | 16 |
| Example 29 | Example 20 | 94.21 | 94.74 | 26 |
Examples 31 to 40
Comparative examples 31 to 40 are the results of applying the catalysts of examples 1 to 10 to the catalytic hydrogenation reaction under the conditions of the thermal catalytic reaction (excluding the light irradiation conditions) corresponding to examples 11 to 20, and are shown in Table 2.
Table 2 application results of the catalysts of examples 1 to 10 under the thermal catalytic reaction conditions corresponding to examples 11 to 20
Examples 41 to 50
Comparative examples 41 to 50 are the results of the catalytic hydrogenation reaction of the catalysts of examples 1 to 10 under the photo-thermal catalytic reaction conditions corresponding to examples 11 to 20, wherein 1.0MPa of hydrogen was added without adding cyclohexene, and are shown in Table 3.
TABLE 3 application results of the catalysts of examples 1-10 with hydrogen as hydrogen source under the photo-thermal catalytic reaction conditions corresponding to examples 11-20
Examples 51 to 60
The results of the catalytic hydrogenation reaction using the catalyst of comparative example 2 under the reaction conditions corresponding to examples 11 to 20 are shown in Table 4.
TABLE 4 results of using the catalyst of comparative example 2 under the reaction conditions corresponding to examples 11 to 20
Example 61
The results of the experiment for applying the catalyst of example 20. As shown in table 5.
TABLE 5 results of the experiment for applying catalyst of example 61
| Number of times of application | Conversion rate% | Selectivity% | Reaction time h |
| 1 | 100 | 99.8 | 14 |
| 2 | 100 | 99.6 | 13.5 |
| 3 | 100 | 99.4 | 14 |
| 4 | 100 | 99.5 | 15.5 |
| 5 | 100 | 99.5 | 15.5 |
| 6 | 100 | 99.3 | 16 |
| 7 | 100 | 99.5 | 14.5 |
| 8 | 100 | 99.3 | 14 |
| 9 | 100 | 99.2 | 15.5 |
| 10 | 100 | 99.2 | 16 |
| 11 | 100 | 99.3 | 15 |
| 12 | 100 | 99.5 | 16.5 |
| 13 | 100 | 99.3 | 17 |
| 14 | 100 | 99.0 | 17.5 |
| 15 | 100 | 99.1 | 18 |
Claims (10)
1. A composite carbon-noble metal catalyst aqueous solution is disclosed, wherein the composite carbon-noble metal catalyst is composed of graphene quantum dots, a graphene quantum dot composite and noble metal particles, wherein the noble metal particles are deposited on the surface of the graphene quantum dot composite, and the graphene quantum dot composite and the graphene quantum dots deposited with the noble metal particles are uniformly dispersed in a pure water solvent; the graphene quantum dot composite is an amorphous nano carbon-based material formed by aggregating and compounding a plurality of graphene quantum dots with the average size of 1-10nm, and the size of the amorphous nano carbon-based material is 20-100 nm; the noble metal is one of platinum, palladium, iridium, ruthenium and rhodium, and the average particle size is 1-10 nm; the mass ratio of the noble metal to the carbon in the composite carbon-noble metal catalyst is 0.1-3: 1.2-9, wherein the total mass of the graphene quantum dot and the graphene quantum dot composite is 100%, and the mass fraction of the graphene quantum dot composite is 60-98%.
2. A method for preparing the aqueous composite carbon-noble metal catalyst solution of claim 1, comprising:
1) preparing a noble metal salt aqueous solution with the noble metal content of 0.01-0.3 g/mL;
2) placing citric acid solid powder in a reaction container, heating to melt, then heating to 200-250 ℃ at the speed of 1-5 ℃/min, keeping at the temperature of 200-250 ℃ for 0.5-2h, finishing the pyrolysis process, and after cooling to room temperature, slowly dropwise adding deionized water to ensure that the feed ratio of the citric acid to the deionized water is 10-30 g: starting magnetic stirring until the solid is completely dissolved after 200-500 mL of the solution is obtained, and dialyzing the obtained mixed solution to obtain a graphene quantum dot aqueous solution;
3) placing the graphene quantum dot aqueous solution obtained in the step 2) into a reaction container, replacing air with nitrogen or inert gas, setting the magnetic stirring speed to be 800-1500 rpm, starting stirring, setting the water bath temperature to be 30-90 ℃, then placing the reactor under a xenon lamp light source, setting the light source working power to be 150-300W, setting the irradiation time to be 0.5-3 h, and dialyzing the mixed solution obtained after the illumination is finished to obtain a graphene quantum dot composite aqueous solution, wherein the graphene quantum dot composite is 60-98% of the mass of the added graphene quantum dots;
4) slowly dropwise adding the noble metal salt aqueous solution obtained in the step 1) into the reaction container in the step 3), so that the feeding ratio of the citric acid to the noble metal salt aqueous solution is 10-30 g: 10-30 mL, replacing air with nitrogen or inert gas, setting the magnetic stirring speed to be 1200-1800 rpm, starting stirring, setting the water bath temperature to be 30-50 ℃, the ultrasonic frequency to be 50000-80000 Hz, the light source working power to be 100-150W, the light wavelength to be 300-380 nm, and the irradiation time to be 0.01-4 h, and obtaining the composite carbon-noble metal catalyst aqueous solution after stirring.
3. The method of claim 2, wherein: the noble metal salt is one of palladium chloride, palladium nitrate, chloropalladic acid, palladium acetate, platinum dichloride, platinum tetrachloride, chloroplatinic acid, platinum nitrate, sodium chloroplatinate, rhodium chloride, rhodium nitrate, rhodium acetate, iridium dichloride, iridium trichloride, ruthenium trichloride and ruthenium nitrate.
4. The production method according to claim 2 or 3, characterized in that: further, in the step 4), before adding the noble metal salt into the reaction vessel, the pH of the noble metal salt aqueous solution is adjusted to 0.5-2.0, and an acid corresponding to an anion of the noble metal salt is used for adjustment.
5. The method of claim 4, wherein: in step 2), the dialysis conditions were: the obtained mixed solution is soaked in deionized water for dialysis for 12h at room temperature in a dialysis bag with molecular weight cutoff of 500 Da.
6. The method of claim 4, wherein: in step 3), the dialysis conditions were: the obtained mixed solution is soaked in deionized water at room temperature in a dialysis bag with molecular weight cutoff of 3000Da for dialysis for 12 h.
7. The use of the aqueous solution of the composite carbon-noble metal catalyst according to claim 1 in the catalytic hydrogenation of 2-furoic acid represented by formula (I) to synthesize 2-tetrahydrofurfuryl acid represented by formula (II),
the application specifically comprises the following steps: according to the feeding ratio of 100-400 mL: 100-400 mL: 5-10 g of composite carbon-precious metal catalyst aqueous solution, formic acid and 2-furoic acid shown in formula (I) are added into an intermittent photo-thermal stirring reaction kettle, the reaction kettle is sealed, nitrogen is introduced, whether the high-pressure reaction kettle leaks air or not is checked, if the high-pressure reaction kettle does not leak air, the nitrogen is introduced to replace air, the reaction temperature is set to be 90-250 ℃, the magnetic stirring speed is 1000-2000 rpm, the light source working power is 50-100W, the light wavelength is 250-300 nm, a heating program and the magnetic stirring are started to start the reaction, a light source working switch is started to carry out the reaction, the reaction is stopped until the conversion rate is 100%, the stirring is stopped, the temperature is reduced to room temperature, slurry is taken out and filtered, the filtrate can be subjected to reduced pressure distillation to obtain a product, and filter residues left on a filter membrane can be returned to the reaction kettle for catalyst application.
8. The use of claim 7, wherein: the end point of the reaction was determined by: after reacting for a period of time, introducing nitrogen into the reactor, taking out the mixed slurry, filtering by a nanofiltration membrane to obtain a 2-tetrahydrofurfuryl acid aqueous solution shown in the formula (II), and taking the filtrate for product analysis.
9. The use of claim 8, wherein: the nanofiltration membrane is made of polyamide and has a pore diameter of 1-2 nm.
10. Use according to any one of claims 7 to 9, wherein: the light source used is a xenon lamp, and the specific light wavelength is obtained by filtering through a filter with the corresponding wavelength.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810976582.5A CN109331814B (en) | 2018-08-25 | 2018-08-25 | Composite carbon-noble metal catalyst, preparation method thereof and application thereof in synthesis of 2-tetrahydrofurfuryl acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810976582.5A CN109331814B (en) | 2018-08-25 | 2018-08-25 | Composite carbon-noble metal catalyst, preparation method thereof and application thereof in synthesis of 2-tetrahydrofurfuryl acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109331814A CN109331814A (en) | 2019-02-15 |
| CN109331814B true CN109331814B (en) | 2021-11-19 |
Family
ID=65296600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810976582.5A Active CN109331814B (en) | 2018-08-25 | 2018-08-25 | Composite carbon-noble metal catalyst, preparation method thereof and application thereof in synthesis of 2-tetrahydrofurfuryl acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109331814B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110498780B (en) * | 2019-09-18 | 2021-08-17 | 浙江清和新材料科技有限公司 | Method for preparing tetrahydrofurfuryl acid by gas-phase hydrogenation of furoic acid |
| CN110841632B (en) * | 2019-11-18 | 2023-01-13 | 湖北大学 | Controllable synthesis method and application of palladium-carbon nano composite catalyst |
| WO2021261393A1 (en) * | 2020-06-22 | 2021-12-30 | 東レ・ファインケミカル株式会社 | Method for producing tetrahydrofuran-2-carboxylic acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103325579A (en) * | 2013-06-20 | 2013-09-25 | 中南大学 | Reduction carbon quantum dot/RuO2 composite material and preparing and application method thereof |
| KR101691815B1 (en) * | 2015-07-10 | 2017-01-02 | 성균관대학교산학협력단 | Gas sensor for sensing nerve agent using 2-dimensional nanosheet |
| CN107413330A (en) * | 2017-03-31 | 2017-12-01 | 浙江工业大学 | A kind of catalyst and preparation method and application |
| CN107413335A (en) * | 2017-03-31 | 2017-12-01 | 浙江工业大学 | A kind of mesoporous carbon microspheres carry composite catalyst and preparation method and application |
-
2018
- 2018-08-25 CN CN201810976582.5A patent/CN109331814B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103325579A (en) * | 2013-06-20 | 2013-09-25 | 中南大学 | Reduction carbon quantum dot/RuO2 composite material and preparing and application method thereof |
| KR101691815B1 (en) * | 2015-07-10 | 2017-01-02 | 성균관대학교산학협력단 | Gas sensor for sensing nerve agent using 2-dimensional nanosheet |
| CN107413330A (en) * | 2017-03-31 | 2017-12-01 | 浙江工业大学 | A kind of catalyst and preparation method and application |
| CN107413335A (en) * | 2017-03-31 | 2017-12-01 | 浙江工业大学 | A kind of mesoporous carbon microspheres carry composite catalyst and preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109331814A (en) | 2019-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109331814B (en) | Composite carbon-noble metal catalyst, preparation method thereof and application thereof in synthesis of 2-tetrahydrofurfuryl acid | |
| CN102553579B (en) | Preparation method of high-dispersity supported nano metal catalyst | |
| CN109433242B (en) | Nitrogen-doped porous carbon-loaded molybdenum carbide catalyst and preparation method and application thereof | |
| CN108712931B (en) | Catalyst for producing 2, 5-furandicarboxylic acid and method for producing 2, 5-furandicarboxylic acid using the same | |
| JP6994458B2 (en) | Process for catalytic hydrogenation of halonitroaromatics | |
| CN110743544A (en) | Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof | |
| Guan et al. | Pickering HIPEs derived hierarchical porous nitrogen-doped carbon supported bimetallic AuPd catalyst for base-free aerobic oxidation of HMF to FDCA in water | |
| CN106732564A (en) | The preparation method and application of aromatic hydrogenation rhodium/activated-carbon catalyst | |
| CN101569859A (en) | Method for preparing halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst | |
| CN108380208B (en) | Pd-Mg/C catalyst for preparing 2, 3-dichloropyridine by catalytic hydrogenation of 2,3, 6-trichloropyridine and preparation method thereof | |
| CN111574483A (en) | Preparation method of 2, 5-furandimethanol | |
| CN109876832B (en) | Catalyst for synthesizing furan methylamine and preparation method thereof | |
| CN106693961A (en) | Palladium-carbon catalyst and preparation method and application thereof | |
| CN113422080B (en) | Preparation method and application of carbon-supported non-platinum palladium-ruthenium-tungsten alloy nanoparticle electrocatalyst for alkaline hydrogen oxidation | |
| CN109331851B (en) | Composite carbon nitrogen-noble metal catalyst and preparation method and application thereof | |
| CN107684921B (en) | Catalyst for converting TMBQ into TMHQ and preparation method thereof | |
| CN113501761A (en) | Method for continuously producing N, N-diethyl-1, 3-propane diamine by one-step method | |
| CN102861573A (en) | Carrier type platinum-ruthenium catalyst and application to hydrogenation of halide-containing nitro compound | |
| JP5823756B2 (en) | Method for producing sugar alcohol | |
| CN109529902B (en) | Method for synthesizing vitamin E intermediate under catalysis of high-stability palladium-nickel-carbon catalyst | |
| CN111167439A (en) | Chrysanthemum-shaped Pd nano particle | |
| Xu et al. | Photoinduced enhanced catalytic activity for Suzuki-Miyaura coupling reaction using porous poly (lactic acid) fiber with palladium/graphitic carbon nitride | |
| CN111545196A (en) | Preparation method of ruthenium-carbon catalyst for selective hydrogenation | |
| WO2019131270A1 (en) | Activated carbon, metal-carrying activated carbon using same and hydrogenation reaction catalyst | |
| JP5894387B2 (en) | Method for producing sugar alcohol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |