CN106925262A - A kind of photocatalysis prepares the catalyst and preparation method and application of 2,5 furandicarboxylic acids - Google Patents
A kind of photocatalysis prepares the catalyst and preparation method and application of 2,5 furandicarboxylic acids Download PDFInfo
- Publication number
- CN106925262A CN106925262A CN201710221820.7A CN201710221820A CN106925262A CN 106925262 A CN106925262 A CN 106925262A CN 201710221820 A CN201710221820 A CN 201710221820A CN 106925262 A CN106925262 A CN 106925262A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- photocatalysis
- prepares
- hydroxymethyl furfural
- oxygen
- 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.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical class OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010931 gold Substances 0.000 claims abstract description 16
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 14
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010948 rhodium Substances 0.000 claims abstract description 10
- 229910052737 gold Inorganic materials 0.000 claims abstract description 8
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004332 silver Substances 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 71
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 68
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 61
- 229910052760 oxygen Inorganic materials 0.000 claims description 61
- 239000001301 oxygen Substances 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 229910001868 water Inorganic materials 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 230000009467 reduction Effects 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000000470 constituent Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 239000010453 quartz Substances 0.000 claims description 20
- 238000007789 sealing Methods 0.000 claims description 20
- 238000013019 agitation Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 9
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 7
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910002676 Pd(NO3)2·2H2O Inorganic materials 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 3
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 52
- 230000007613 environmental effect Effects 0.000 abstract description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 54
- 239000003643 water by type Substances 0.000 description 35
- 239000000243 solution Substances 0.000 description 19
- 238000004128 high performance liquid chromatography Methods 0.000 description 18
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 229910052724 xenon Inorganic materials 0.000 description 18
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 18
- 238000001027 hydrothermal synthesis Methods 0.000 description 16
- 239000002105 nanoparticle Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 12
- 229910000629 Rh alloy Inorganic materials 0.000 description 6
- 229910000929 Ru alloy Inorganic materials 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- -1 saccharide compound Chemical class 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical class OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- 229910019032 PtCl2 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- JMGVPAUIBBRNCO-UHFFFAOYSA-N [Ru].[Ag] Chemical compound [Ru].[Ag] JMGVPAUIBBRNCO-UHFFFAOYSA-N 0.000 description 2
- CQKBIUZEUFGQMZ-UHFFFAOYSA-N [Ru].[Au] Chemical compound [Ru].[Au] CQKBIUZEUFGQMZ-UHFFFAOYSA-N 0.000 description 2
- YPPQDPIIWDQYRY-UHFFFAOYSA-N [Ru].[Rh] Chemical compound [Ru].[Rh] YPPQDPIIWDQYRY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000003353 gold alloy Substances 0.000 description 2
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 2
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- OYJSZRRJQJAOFK-UHFFFAOYSA-N palladium ruthenium Chemical compound [Ru].[Pd] OYJSZRRJQJAOFK-UHFFFAOYSA-N 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910002710 Au-Pd Inorganic materials 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- 229910018885 Pt—Au Inorganic materials 0.000 description 1
- 229910018967 Pt—Rh Inorganic materials 0.000 description 1
- YDZWPBPSQHXITB-UHFFFAOYSA-N [Rh].[Au] Chemical compound [Rh].[Au] YDZWPBPSQHXITB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- ZZCNKSMCIZCVDR-UHFFFAOYSA-N barium(2+);dioxido(dioxo)manganese Chemical compound [Ba+2].[O-][Mn]([O-])(=O)=O ZZCNKSMCIZCVDR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- 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
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/23—
-
- B01J35/39—
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- B01J35/393—
-
- B01J35/50—
-
- 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
- B01J37/04—Mixing
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- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- 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
- B01J37/18—Reducing with gases containing free hydrogen
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- 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
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three 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
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Abstract
A kind of photocatalysis prepares the catalyst of 2,5 furandicarboxylic acids, including carrier and active metal component, and by final catalyst weight, the mass fraction of active metal component is 1% 20%, and remaining is carrier.Described carrier is the one kind in Graphene, carborundum, aluminum oxide, silica, activated carbon or carbonitride.Described active metal component is one or two in gold, palladium, platinum, silver, ruthenium, rhodium.The present invention has environmental protection, safety simple to operate, high conversion rate, the good advantage of selectivity.
Description
Technical field
The present invention relates to catalyst and preparation method and application that a kind of photocatalysis prepares 2,5- furandicarboxylic acids.
Background technology
As the increasingly depleted and current social of the fossil energy such as coal, oil, day hot gas on the earth are to energy demand
Continuous rising, people in the urgent need to find a kind of environmental protection and reproducible new energy.Biomass be it is unique it is carbon containing can
Regenerated resources, and rich reserves on earth, easily obtain, and are the ideal materials for substituting fossil energy.
It is the significant process during biomass are converted to prepare chemicals by saccharide compound conversion.5 hydroxymethyl furfural is sugar
Important Platform compound in class conversion, is generated by hexoses such as glucose and fructose by dehydration.By different degrees of oxygen
Change, 5 hydroxymethyl furfural can be converted into DFF (DFF), 5- methylol -2- furancarboxylic acids (HMFCA), 5- first
The compound such as acyl group -2- furancarboxylic acids (FFCA) and 2,5- furandicarboxylic acids (FDCA) (Scheme 1).Wherein, 2,5- furans two
Formic acid just listed 12 kinds of bio-based platform chemicals in 2004 by USDOE, as the substitute of terephthalic acid (TPA),
Can be used to manufacture biodegradable polyesters plastics, anticorrosive and fire proofing material, energy chemistry product, pharmaceutical intermediate etc..
The main method of synthesis 2,5- furandicarboxylic acids is metering oxidizing process, homogeneous catalytic oxidation method and heterogeneous catalysis at present
Oxidizing process.Metering oxidizing process uses NaOCl, BaMnO4, KMnO4, N2O4And HNO3Deng strong oxidizer, not only can corrosion reaction set
It is standby, and very big harm can be caused to environment.Using homogeneous catalyst, then it is relatively low to there is product yield, catalyst and product
The problems such as separating difficult.By contrast, heterogeneous catalytic oxidation method has catalysis activity high, and catalyst is easily reclaimed, and the product for obtaining
The advantages of product are selectively high, is the main method for synthesizing FDCA at present.Chinese patent (CN103626726) is open
One kind prepares 2,5- furans in aqueous phase solution using acid carrier carried noble metal catalysis 5 hydroxymethyl furfural selective oxidation
Mutter the method for dioctyl phthalate.The method reaction condition is gentle, and reaction efficiency is high, and selectivity is good, however it is necessary that adding in the reaction big
Amount aqueous slkali.But, the addition of alkali not only increases the risk of reactor corrosion, and the product for obtaining needs acidification,
Result in the increase of production cost.Chinese patent (CN104529957) discloses a kind of by 5 hydroxymethyl furfural preparation 2,5- furans
Mutter the method for dioctyl phthalate, have the advantages that reaction condition is relatively gentle, cheap and product yield high, but production process need it is a large amount of
Organic solvent and tert-Butanol peroxide, environment can be polluted, and tert-Butanol peroxide is inflammable in atmosphere, greatly increase
The risk of production operation.It is that raw material produces 2,5- furans two with glucose that Chinese patent (CN105859663) is disclosed a kind of
The method of formic acid, the raw material sources of the method are extensive, but complex operation, and used sodium pyrophosphate, dimethylacetamide
Amine, alkali and concentrated hydrochloric acid etc. have the raw material of pollution to environment.
The content of the invention
The catalyst and preparation method of 2,5- furandicarboxylic acids are prepared it is an object of the invention to provide a kind of photocatalysis and answer
With the method environmental protection, safety simple to operate, high conversion rate, selectivity is good.
The present invention provides a kind of method that photocatalysis prepares FDCA, it is well known that light-catalyzed reaction is one
Green environmental protection technique, using storage is abundant and reproducible solar energy promotes the synthesis of FDCA, can drop
Low reaction temperatures and reaction time, improve reactivity and selectivity, eliminate dependence of the reaction to aqueous slkali, with it is low into
The advantages of sheet, pollution-free, high conversion and selectivity.Reaction equation of the invention is as follows
Catalyst of the invention is a kind of supported, heterogeneous catalyst, and wherein catalyst includes carrier and active metal group
Point, by final catalyst weight, the mass fraction of active metal component is 1%-20%, and remaining is carrier.
Carrier as described above is in Graphene, carborundum, aluminum oxide, silica, activated carbon or carbonitride
Kind；Active metal component is one or two in gold, palladium, platinum, silver, ruthenium, rhodium.
The particle diameter of active metal particles as described above is less than 50 nanometers.
The preparation method of catalyst of the present invention comprises the following steps：
Soluble metallic salt containing active component is configured to the aqueous solution, by catalyst proportion of composing, catalyst is carried
After body mixes with soluble metal salt solution, it is transferred in reactor, plus deionized water is to the mass ratio of water and catalyst carrier
It is 30-90：1,5-15h is reacted at 150-220 DEG C, after use water and absolute ethyl alcohol are respectively washed three times respectively after natural cooling,
10-24h is dried at 60-100 DEG C, is finally placed in tube furnace, in H24-8h, wherein H are reduced in/Ar atmosphere2Volume integral
Number is 5-10%, and gas flow rate is 5-15mL/min, and reduction temperature is 300-500 DEG C.
The soluble metallic salt containing active component is as described above：HAuCl4、Pd(NO3)2·2H2O、H2PtCl6·
6H2O、AgNO3、RuCl3Or RhCl3, the concentration of soluble metal saline solution is 0.01-0.1mol/L.
The method that the photocatalysis that the present invention is provided prepares FDCA, its detailed process is as follows：
(1) 3-12 is compared according to 5 hydroxymethyl furfural and solvent quality：1, added after 5 hydroxymethyl furfural is mixed with solvent
Catalyst, wherein 5 hydroxymethyl furfural are 5-200 with the mol ratio of metal active constituent in catalyst：1, suspension is formed, so
It is transferred to afterwards in the closed reactor with quartz window；
(2) after being purged by reactor sealing and with oxygen, oxygen, the wherein mol ratio of 5 hydroxymethyl furfural and oxygen are filled with
It is 0.01-0.1：1；
(3) under agitation, heating response system, to 60-200 DEG C, is 0.01-5W/cm in intensity2Illumination under enter
Row reaction 0.5-12h.
Solvent as described above is the water without alkaline matter such as distilled water or deionized water.
Illumination as described above is the artificial light source irradiation of direct irradiation of sunlight or simulated solar irradiation.
The features of the present invention is process route environmental protection, and reaction temperature is low, and transformation efficiency is high, and (5 hydroxymethyl furfural turns
Rate is more than 90%), good product selectivity (selectivity of FDCA is more than 90%), catalyst stability
It is good, with larger application value and prospect.Most notable of which feature be effectively can promote to react using solar energy into
OK, and target product can be directly obtained, without carrying out acidification.
Brief description of the drawings
Fig. 1 is that the catalyst of the embodiment of the present invention 18 is recycled 10 times, FDCA yield variation diagram.
Specific embodiment
Specific examples below helps to understand the present invention, but present invention is not limited thereto.
Embodiment 1
Weigh 0.98g Graphenes and 1.1mL HAuCl4After the aqueous solution (0.01mol/L) mixing, hydrothermal reaction kettle is transferred to
In, plus 88mL deionized waters, 5h is reacted at 150 DEG C, after respectively washing is obtained for three times with water and absolute ethyl alcohol respectively after natural cooling
To black powder, 24h is dried at 80 DEG C, be finally placed in tube furnace, in H25h, wherein H are reduced in/Ar atmosphere2Body
Fraction is 5%, and gas flow rate is 15mL/min, and reduction temperature is 400 DEG C.Can obtain the graphene-supported metallic gold (Au of 1g
The particle diameter of 2wt%) catalyst, wherein gold nano grain is 11 nanometers.
By the above-mentioned catalyst of 1g, 0.25mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added with quartz window
Closed reactor, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 2.5mmol oxygen, in stirring condition
Under be warmed up to 60 DEG C, intensity be 0.5W/cm2The lower reaction 12h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural and solvent quality ratio
It is 3.15：1,5 hydroxymethyl furfural is 24.0 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.1：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 2
Weigh 0.99g Graphenes and 1.0mL RuCl3After the aqueous solution (0.01mol/L) mixing, hydrothermal reaction kettle is transferred to
In, plus 29mL deionized waters, 15h is reacted at 220 DEG C, after respectively washing is obtained for three times with water and absolute ethyl alcohol respectively after natural cooling
To black powder, 10h is dried at 100 DEG C, be finally placed in tube furnace, in H28h, wherein H are reduced in/Ar atmosphere2's
Volume fraction is 10%, and gas flow rate is 15mL/min, and reduction temperature is 500 DEG C.Can obtain the graphene-supported metal Ru (Ru of 1g
The particle diameter of 1wt%) catalyst, wherein ruthenium nano-particle is 8 nanometers.
By the above-mentioned catalyst of 1g, 0.5mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the close of quartz window
Reactor is closed, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 50mmol oxygen, under agitation
120 DEG C are warmed up to, are 0.5W/cm in intensity2The lower reaction 5h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural and solvent quality ratio
6.3：1,5 hydroxymethyl furfural is 50.5 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.01：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 3
Weigh 0.90g carborundum and 0.51mL H2PtCl3·6H2After the O aqueous solution (0.1mol/L) mixing, hydro-thermal is transferred to
In reactor, plus 80mL deionized waters, 10h is reacted at 180 DEG C, after respectively being washed with water and absolute ethyl alcohol respectively after natural cooling
Obtain dark green powder three times, 10h is dried at 100 DEG C, be finally placed in tube furnace, in H25h is reduced in/Ar atmosphere,
Wherein H2Volume fraction be 5%, gas flow rate is 5mL/min, and reduction temperature is 400 DEG C.The load of 1g carborundum can be obtained
Metal platinum (Pt10wt%) catalyst, the wherein particle diameter of Pt nanoparticle are 32 nanometers.
By the above-mentioned catalyst of 1g, 1mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the closed of quartz window
Reactor, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 80mmol oxygen, rises under agitation
Temperature, to 200 DEG C, is 0.5W/cm in intensity2The lower reaction 0.5h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural is with solvent quality ratio
12.6：1,5 hydroxymethyl furfural is 19.5 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.013：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 4
Weigh 0.95g carborundum and 0.46mL AgNO3After the aqueous solution (0.1mol/L) mixing, hydrothermal reaction kettle is transferred to
In, plus 85mL deionized waters, 12h is reacted at 220 DEG C, after respectively washing is obtained for three times with water and absolute ethyl alcohol respectively after natural cooling
To dark green powder, 10h is dried at 90 DEG C, be finally placed in tube furnace, in H24h, wherein H are reduced in/Ar atmosphere2's
Volume fraction is 6%, and gas flow rate is 15mL/min, and reduction temperature is 500 DEG C.Can obtain 1g carborundum carried metal silver (Ag
The particle diameter of 5wt%) catalyst, wherein silver nano-grain is 19 nanometers.
By the above-mentioned catalyst of 1g, 0.5mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the close of quartz window
Reactor is closed, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 40mmol oxygen, under agitation
60 DEG C are warmed up to, are 0.01W/cm in intensity2The lower reaction 12h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural and solvent quality ratio
It is 6.3：1,5 hydroxymethyl furfural is 10.8 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.013：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 5
Weigh 0.98g aluminum oxide and 0.19mL Pd (NO3)2·2H2After the O aqueous solution (0.1mol/L) mixing, water is transferred to
In thermal response kettle, plus 78mL deionized waters, 24h is reacted at 150 DEG C, after respectively being washed with water and absolute ethyl alcohol respectively after natural cooling
Wash three times and obtain grey powder, 20h is dried at 60 DEG C, be finally placed in tube furnace, in H25h is reduced in/Ar atmosphere,
Wherein H2Volume fraction be 10%, gas flow rate is 10mL/min, and reduction temperature is 500 DEG C.Can obtain 1g alumina loads
Metal Palladium (Pd2wt%) catalyst, the wherein particle diameter of palladium nano-particles are 9 nanometers.
By the above-mentioned catalyst of 1g, 1mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the closed of quartz window
Reactor, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 50mmol oxygen, rises under agitation
Temperature, to 150 DEG C, is 5W/cm in intensity2The lower reaction 10h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural is with solvent quality ratio
12.6：1,5 hydroxymethyl furfural is 53.2 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.02：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 6
Weigh 0.85g silica and 1.46mL RhCl3After the aqueous solution (0.1mol/L) mixing, hydro-thermal reaction is transferred to
In kettle, plus 24mL deionized waters, 10h is reacted at 200 DEG C, respectively washed three times after water and absolute ethyl alcohol is used after natural cooling respectively
Black powder is obtained, 10h is dried at 100 DEG C, be finally placed in tube furnace, in H25h, wherein H are reduced in/Ar atmosphere2
Volume fraction be 10%, gas flow rate is 15mL/min, and reduction temperature is 400 DEG C.Can obtain 1g silica supported metals
Rhodium (Rh15wt%) catalyst, the wherein particle diameter of rhodium nanoparticles are 33 nanometers.
By the above-mentioned catalyst of 1g, 1mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the closed of quartz window
Reactor, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 60mmol oxygen, rises under agitation
Temperature, to 120 DEG C, is 1W/cm in intensity2The lower reaction 7h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural is with solvent quality ratio
12.6：1,5 hydroxymethyl furfural is 6.9 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.017：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 7
Weigh 0.99g activated carbon and 0.5mL HAuCl4After the aqueous solution (0.01mol/L) mixing, hydrothermal reaction kettle is transferred to
In, plus 49mL deionized waters, 10h is reacted at 200 DEG C, after respectively washing is obtained for three times with water and absolute ethyl alcohol respectively after natural cooling
To black powder, 10h is dried at 90 DEG C, be finally placed in tube furnace, in H25h, wherein H are reduced in/Ar atmosphere2Body
Fraction is 5%, and gas flow rate is 10mL/min, and reduction temperature is 400 DEG C.Can obtain the activated carbon loaded metallic gold (Au of 1g
The particle diameter of 1wt%) catalyst, wherein gold nano grain is 5 nanometers.
By the above-mentioned catalyst of 1g, 1mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the closed of quartz window
Reactor, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 90mmol oxygen, rises under agitation
Temperature, to 150 DEG C, is 0.8W/cm in intensity2The lower reaction 5h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural is with solvent quality ratio
12.6：1,5 hydroxymethyl furfural is 197.0 with metal active constituent mol ratio：1(mol:Mol), 5 hydroxymethyl furfural and oxygen
Mol ratio is 0.011：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 8
Weigh 0.97g carbonitrides and 3.0mL RuCl3After the aqueous solution (0.01mol/L) mixing, hydrothermal reaction kettle is transferred to
In, plus 75mL deionized waters, 12h is reacted at 220 DEG C, after respectively washing is obtained for three times with water and absolute ethyl alcohol respectively after natural cooling
To buff powder, 12h is dried at 100 DEG C, be finally placed in tube furnace, in H28h, wherein H are reduced in/Ar atmosphere2
Volume fraction be 10%, gas flow rate is 10mL/min, and reduction temperature is 500 DEG C.Can obtain 1g carbonitride supported metal rutheniums
(Ru3wt%) particle diameter of catalyst, wherein ruthenium nano-particle is 17 nanometers.
By the above-mentioned catalyst of 1g, 1mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the closed of quartz window
Reactor, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 100mmol oxygen, rises under agitation
Temperature, to 180 DEG C, is 0.5W/cm in intensity2The lower reaction 10h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural is with solvent quality ratio
12.6：1,5 hydroxymethyl furfural is 33.7 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.01：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 9
Weigh 0.94g carborundum and 0.1mL HAuCl4And 0.4mLRuCl3After the aqueous solution (0.1mol/L) mixing, plus 65mL
Deionized water, is transferred in hydrothermal reaction kettle, and 10h is reacted at 220 DEG C, after each with water and absolute ethyl alcohol respectively after natural cooling
Washing obtains black powder three times, and 10h is dried at 100 DEG C, is finally placed in tube furnace, in H2Reduced in/Ar atmosphere
8h, wherein H2Volume fraction be 5%, gas flow rate is 15mL/min, and reduction temperature is 500 DEG C.1g carborundum is can obtain to bear
Gold-ruthenium alloy (Au 2wt%, Ru 4wt%) catalyst is carried, the wherein particle diameter of gold-ruthenium alloy nano particle is 23 nanometers.
By the above-mentioned catalyst of 1g, 0.5mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the close of quartz window
Reactor is closed, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 40mmol oxygen, under agitation
90 DEG C are warmed up to, are 1W/cm in intensity2The lower reaction 12h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural is with solvent quality ratio
12.6：1,5 hydroxymethyl furfural is 10.1 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.013：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 10
Weigh 0.96g Graphenes and 0.5mL H2PtCl2·H2O and 1.5mL HAuCl4The aqueous solution (0.01mol/L) mixes
Afterwards, plus 65mL deionized waters, be transferred in hydrothermal reaction kettle, 10h reacted at 200 DEG C, after after natural cooling respectively with water and
Respectively washing obtains black powder three times to absolute ethyl alcohol, and 10h is dried at 80 DEG C, is finally placed in tube furnace, in H2/ Ar gas
5h, wherein H are reduced in atmosphere2Volume fraction be 5%, gas flow rate is 15mL/min, and reduction temperature is 400 DEG C.Can obtain 1g
Graphene-supported platinum-gold alloy (Pt 1wt%, Au 3wt%) catalyst, the wherein particle diameter of platinum-gold alloy nanoparticle are received for 9
Rice.
By the above-mentioned catalyst of 1g, 1mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the closed of quartz window
Reactor, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 70mmol oxygen, rises under agitation
Temperature, to 100 DEG C, is 0.5W/cm in intensity2The lower reaction 10h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural is with solvent quality ratio
12.6：1,5 hydroxymethyl furfural is 49.1 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.014：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 11
Weigh 0.85g carbonitrides and 0.4mL AgNO3With 0.9mL Pd (NO3)2·2H2The O aqueous solution (0.1mol/L) mixes
Afterwards, plus 50mL deionized waters, be transferred in hydrothermal reaction kettle, 10h reacted at 200 DEG C, after after natural cooling respectively with water and
Respectively washing obtains black powder three times to absolute ethyl alcohol, and 10h is dried at 60 DEG C, is finally placed in tube furnace, in H2/ Ar gas
5h, wherein H are reduced in atmosphere2Volume fraction be 5%, gas flow rate is 15mL/min, and reduction temperature is 400 DEG C.Can obtain 1g
Carbonitride loads silver-palladium alloy (Ag 5wt%, Pd 10wt%) catalyst, and the wherein particle diameter of silver-palladium alloy nano particle is 41
Nanometer.
By the above-mentioned catalyst of 1g, 1mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the closed of quartz window
Reactor, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 60mmol oxygen, rises under agitation
Temperature, to 120 DEG C, is 0.2W/cm in intensity2The lower reaction 6h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural is with solvent quality ratio
12.6：1,5 hydroxymethyl furfural is 7.1 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.017：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 12
Weigh 0.94g activated carbon and 0.55mL HAuCl4With 1.95mL RhCl3After the aqueous solution (0.05mol/L) mixing, plus
82mL deionized waters, are transferred in hydrothermal reaction kettle, and 10h is reacted at 200 DEG C, after after natural cooling respectively use water and anhydrous second
Respectively washing obtains black powder three times to alcohol, and 10h is dried at 100 DEG C, is finally placed in tube furnace, in H2In/Ar atmosphere
Reduction 5h, wherein H2Volume fraction be 5%, gas flow rate is 15mL/min, and reduction temperature is 300 DEG C.Can obtain 1g activity
Carbon gold-supported-rhodium alloy (Au 2wt%, Rh 4wt%) catalyst, the wherein particle diameter of gold-rhodium alloy nano particle are 18 nanometers.
By the above-mentioned catalyst of 1g, 1mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the closed of quartz window
Reactor, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 40 mmol oxygen, rises under agitation
Temperature, to 200 DEG C, is 0.5W/cm in intensity2The lower reaction 10h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural is with solvent quality ratio
12.6：1,5 hydroxymethyl furfural is 20.4 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.025：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 13
Weigh 0.90g aluminum oxide and 1.1mL HAuCl4With 2.8mL Pd (NO3)2·2H2The O aqueous solution (0.02mol/L) is mixed
After conjunction, be transferred in closed hydrothermal reaction kettle, plus 68mL deionized waters, 10h reacted at 150 DEG C, after after natural cooling respectively
With water and absolute ethyl alcohol, respectively washing obtains black powder three times, and 10h is dried at 90 DEG C, is finally placed in tube furnace,
H25h, wherein H are reduced in/Ar atmosphere2Volume fraction be 5%, gas flow rate is 14mL/min, and reduction temperature is 400 DEG C.Can
Obtain 1g alumina loads gold-palldium alloy (Au 4wt%, Pd 6wt%) catalyst, the wherein grain of gold-palldium alloy nano particle
Footpath is 29 nanometers.
By the above-mentioned catalyst of 1g, 1mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the closed of quartz window
Reactor, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 10mmol oxygen, rises under agitation
Temperature, to 100 DEG C, is 1W/cm in intensity2The lower reaction 8h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural is with solvent quality ratio
12.6：1,5 hydroxymethyl furfural is 13.0 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.1：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 14
Weigh 0.97g silica and 0.6mL HAuCl4With 1.9mL AgNO3After the aqueous solution (0.01mol/L) mixing, turn
In moving to hydrothermal reaction kettle, plus 46mL deionized waters, 10h is reacted at 200 DEG C, after using water and anhydrous second after natural cooling respectively
Respectively washing obtains black powder three times to alcohol, and 24h is dried at 60 DEG C, is finally placed in tube furnace, in H2In/Ar atmosphere also
Former 5h, wherein H2Volume fraction be 5%, gas flow rate is 12mL/min, and reduction temperature is 400 DEG C.Can obtain 1g titanium dioxides
Silicon loads gold-silver alloy (Au 1wt%, Ag 2wt%) catalyst, and the wherein particle diameter of gold-silver alloy nano particle is 8 nanometers.
By the above-mentioned catalyst of 1g, 1mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the closed of quartz window
Reactor, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 80mmol oxygen, rises under agitation
Temperature, to 110 DEG C, is 0.5W/cm in intensity2The lower reaction 8h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural is with solvent quality ratio
12.6：1,5 hydroxymethyl furfural is 42.3 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.013：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 15
Weigh 0.94g Graphenes and 2.8mL Pd (NO3)2·2H2O and 3.0mL RuCl3The aqueous solution (0.01mol/L) is mixed
After conjunction, plus 42mL deionized waters, it is transferred in hydrothermal reaction kettle, 10h is reacted at 200 DEG C, after uses water after natural cooling respectively
Respectively washed with absolute ethyl alcohol three times and obtain black powder, 10h is dried at 90 DEG C, be finally placed in tube furnace, in H2/Ar
5h, wherein H are reduced in atmosphere2Volume fraction be 10%, gas flow rate is 15mL/min, and reduction temperature is 400 DEG C.It is available
Graphene-supported palladium-the ruthenium alloys of 1g (Pd 3wt%, Ru 3wt%) catalyst, the particle diameter of wherein palladium-ruthenium alloy nano particle is
22 nanometers.
By the above-mentioned catalyst of 1g, 1mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the closed of quartz window
Reactor, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 100mmol oxygen, rises under agitation
Temperature, to 100 DEG C, is 0.5W/cm in intensity2The lower reaction 12h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural is with solvent quality ratio
12.6：1,5 hydroxymethyl furfural is 17.3 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.01：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 16
Weigh 0.90g carborundum and 0.49mL RuCl3With 0.49mL RhCl3After the aqueous solution (0.1mol/L) mixing, transfer
Into hydrothermal reaction kettle, plus 80mL deionized waters, 10h is reacted at 200 DEG C, after using water and absolute ethyl alcohol after natural cooling respectively
Each washing obtains dark green powder three times, and 10h is dried at 100 DEG C, is finally placed in tube furnace, H2In/Ar atmosphere also
Former 5h, wherein H2Volume fraction be 5%, gas flow rate is 15mL/min, reduction temperature be 500 DEG C.Can obtain 1g carbonizations
Silicon loads ruthenium-rhodium alloy (Ru 5wt%, Rh 5wt%) catalyst, and the wherein particle diameter of ruthenium-rhodium alloy nano particle is 31 nanometers.
By the above-mentioned catalyst of 1g, 1mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the closed of quartz window
Reactor, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 60mmol oxygen, rises under agitation
Temperature, to 90 DEG C, is 0.01W/cm in intensity2The lower reaction 6h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural is with solvent quality ratio
12.6：1,5 hydroxymethyl furfural is 10.2 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.017：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 17
Weigh 0.90g carbonitrides and 0.5mL H2PtCl2·6H2O (0.01mol/L) and 0.87mL RhCl3(0.1mol/
L) after aqueous solution mixing, it is transferred in hydrothermal reaction kettle, plus 70mL deionized waters, 10h is reacted at 200 DEG C, treat natural cooling
With water and absolute ethyl alcohol, respectively washing obtains buff powder three times respectively afterwards, and 10h is dried at 100 DEG C, is finally placed on pipe
In formula stove, in H25h, wherein H are reduced in/Ar atmosphere2Volume fraction be 5%, gas flow rate is 15mL/min, and reduction temperature is
300℃.Can obtain 1g carbonitrides Supported Pt Nanoparticles-rhodium alloy (Pt 1wt%, Rh 9wt%) catalyst, wherein platinum-rhodium alloy nano
The particle diameter of particle is 33 nanometers.
By the above-mentioned catalyst of 1g, 1mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the closed of quartz window
Reactor, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 20mmol oxygen, rises under agitation
Temperature, to 90 DEG C, is 0.8W/cm in intensity2The lower reaction 12h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural is with solvent quality ratio
12.6：1,5 hydroxymethyl furfural is 10.8 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.05：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one.
Embodiment 18
Weigh 0.80g activated carbon and 1.39mL AgNO3With 0.49mL RuCl3After the aqueous solution (0.1mol/L) mixing, plus go
70mL ionized waters, are transferred in closed hydrothermal reaction kettle, and 10h is reacted at 200 DEG C, after after natural cooling respectively with water and anhydrous
Respectively washing obtains black powder three times to ethanol, and 10h is dried at 100 DEG C, is finally placed in tube furnace, in H2/ Ar atmosphere
Middle reduction 5h, wherein H2Volume fraction be 5%, gas flow rate is 15mL/min, and reduction temperature is 400 DEG C.Can obtain 1g work
Property carbon load silver-ruthenium alloy (Ag 15wt%, Ru 5wt%) catalyst, the wherein particle diameter of silver-ruthenium alloy nano particle receives for 49
Rice.
By the above-mentioned catalyst of 1g, 1mmol 5 hydroxymethyl furfurals and 10mL deionized waters are added and carry the closed of quartz window
Reactor, included polytetrafluoroethyllining lining after sealing with oxygen clean for several times, is passed through 30mmol oxygen, rises under agitation
Temperature, to 120 DEG C, is 1.2W/cm in intensity2The lower reaction 12h of xenon lamp irradiation.Wherein 5 hydroxymethyl furfural is with solvent quality ratio
12.6：1,5 hydroxymethyl furfural is 5.3 with metal active constituent mol ratio：1,5 hydroxymethyl furfural is with oxygen molar ratio
0.033：1.Reaction solution is analyzed after being extracted with DMSO with high performance liquid chromatography, the results are shown in Table one, and catalyst is recycled
10 times, FDCA yield is not substantially reduced, and as a result sees Fig. 1.
The different catalysts photochemical catalytic oxidation HMF of table 1. generates FDCA results
| Case study on implementation | Catalyst | HMF conversion ratios (%) | FDCA selectivity (%) |
| 1 | Au/graphene | 95 | 93 |
| 2 | Ru/graphene | 94 | 99 |
| 3 | Pt/SiC | 90 | 96 |
| 4 | Ag/SiC | 96 | 99 |
| 5 | Pd/Al2O3 | 100 | 98 |
| 6 | Rh/SiO2 | 99 | 98 |
| 7 | Au/C | 100 | 97 |
| 8 | Ru/C3N4 | 100 | 95 |
| 9 | Au‐Ru/SiC | 100 | 99 |
| 10 | Pt‐Au/graphene | 100 | 99 |
| 11 | Ag‐Pd/C3N4 | 100 | 98 |
| 12 | Au‐Rh/C | 100 | 95 |
| 13 | Au‐Pd/Al2O3 | 100 | 99 |
| 14 | Au‐Ag/SiO2 | 100 | 99 |
| 15 | Pd‐Ru/graphene | 100 | 99 |
| 16 | Ru‐Rh/SiC | 91 | 99 |
| 17 | Pt‐Rh/C3N4 | 93 | 98 |
| 18 | Ag‐Ru/C | 100 | 99 |
Note：Graphene is Graphene in table, and C is activated carbon, and HMF is 5 hydroxymethyl furfural, and FDCA is 2,5- furans two
Formic acid.
Claims (10)
1. a kind of photocatalysis prepares the catalyst of 2,5- furandicarboxylic acids, it is characterised in that catalyst includes carrier and active metal
Component, by final catalyst weight, the mass fraction of active metal component is 1%-20%, and remaining is carrier.
2. a kind of photocatalysis as claimed in claim 1 prepares the catalyst of 2,5- furandicarboxylic acids, it is characterised in that described
Carrier is the one kind in Graphene, carborundum, aluminum oxide, silica, activated carbon or carbonitride.
3. a kind of photocatalysis as claimed in claim 1 prepares the catalyst of 2,5- furandicarboxylic acids, it is characterised in that described
Active metal component is one or two in gold, palladium, platinum, silver, ruthenium, rhodium.
4. a kind of photocatalysis as claimed in claim 1 prepares the catalyst of 2,5- furandicarboxylic acids, it is characterised in that described
The particle diameter of active metal is less than 50 nanometers.
5. a kind of photocatalysis as described in claim any one of 1-4 prepares the preparation side of the catalyst of 2,5- furandicarboxylic acids
Method, it is characterised in that comprise the following steps：
Soluble metallic salt containing active component is configured to the aqueous solution, by catalyst proportion of composing, by catalyst carrier with
After soluble metal salt solution mixing, it is transferred in reactor, plus deionized water to the mass ratio of water and catalyst carrier is 30-
90：1, in 150-220o5-15 h are reacted under C, after respectively being washed three times with water and absolute ethyl alcohol respectively after natural cooling, in 60-
100o10-24 h are dried under C, is finally placed in tube furnace, in H24-8h, wherein H are reduced in/Ar atmosphere2Volume fraction
It is 5-10%, gas flow rate is 5-15mL/min, and reduction temperature is 300-500oC。
6. a kind of photocatalysis as claimed in claim 5 prepares the preparation method of the catalyst of 2,5- furandicarboxylic acids, its feature
It is that the soluble metallic salt containing active component is：HAuCl4、Pd(NO3)2·2H2O、 H2PtCl6·6H2O、AgNO3、
RuCl3Or RhCl3。
7. a kind of photocatalysis as claimed in claim 5 prepares the preparation method of the catalyst of 2,5- furandicarboxylic acids, its feature
The concentration for being soluble metal saline solution is 0.01-0.1 mol/L.
8. a kind of photocatalysis as described in claim any one of 1-4 prepares the application of the catalyst of 2,5- furandicarboxylic acids, its
It is characterised by comprising the following steps：
（1）Compare 3-12 according to 5 hydroxymethyl furfural and solvent quality：1, catalysis is added after 5 hydroxymethyl furfural is mixed with solvent
Agent, wherein 5 hydroxymethyl furfural are 5-200 with the mol ratio of metal active constituent in catalyst：1, form suspension, Ran Houzhuan
In moving to the closed reactor with quartz window；
（2）After being purged by reactor sealing and with oxygen, oxygen is filled with, wherein 5 hydroxymethyl furfural is with the mol ratio of oxygen
0.01-0.1：1；
（3）Under agitation, heating response system is to 60-200oC, is 0.01-5 W/cm in intensity2Illumination under carry out it is anti-
Answer 0.5-12h.
9. a kind of photocatalysis as claimed in claim 8 prepares the application of the catalyst of 2,5- furandicarboxylic acids, it is characterised in that
Described solvent is distilled water or deionized water.
10. a kind of photocatalysis as claimed in claim 8 prepares the application of the catalyst of 2,5- furandicarboxylic acids, it is characterised in that
Described illumination is the artificial light source irradiation of direct irradiation of sunlight or simulated solar irradiation.
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