CN110479379A - A kind of covalent organic frame material catalyst and its preparation method and application based on load Ru nano particle - Google Patents
A kind of covalent organic frame material catalyst and its preparation method and application based on load Ru nano particle Download PDFInfo
- Publication number
- CN110479379A CN110479379A CN201910804180.1A CN201910804180A CN110479379A CN 110479379 A CN110479379 A CN 110479379A CN 201910804180 A CN201910804180 A CN 201910804180A CN 110479379 A CN110479379 A CN 110479379A
- Authority
- CN
- China
- Prior art keywords
- organic frame
- covalent organic
- load
- nano particle
- frame material
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 239000000463 material Substances 0.000 title claims abstract description 49
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 25
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 239000010953 base metal Substances 0.000 claims abstract description 8
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 24
- 238000006555 catalytic reaction Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims description 11
- 150000001555 benzenes Chemical class 0.000 claims description 10
- 239000004570 mortar (masonry) Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical class CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical group N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- LQWHPYPUHPQSRX-UHFFFAOYSA-N 1,1'-biphenyl;pyridine Chemical class C1=CC=NC=C1.C1=CC=CC=C1C1=CC=CC=C1 LQWHPYPUHPQSRX-UHFFFAOYSA-N 0.000 claims description 2
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 claims description 2
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical class [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 70
- 229910021529 ammonia Inorganic materials 0.000 abstract description 35
- 238000003786 synthesis reaction Methods 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 8
- 239000012901 Milli-Q water Substances 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 2
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 229910021607 Silver chloride Inorganic materials 0.000 description 15
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 10
- 229920000557 Nafion® Polymers 0.000 description 10
- 238000005070 sampling Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000005518 electrochemistry Effects 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- XEYBHCRIKKKOSS-UHFFFAOYSA-N disodium;azanylidyneoxidanium;iron(2+);pentacyanide Chemical compound [Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].[O+]#N XEYBHCRIKKKOSS-UHFFFAOYSA-N 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 229940083618 sodium nitroprusside Drugs 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- NDDSQNNCTJFKBX-UHFFFAOYSA-K OC1=C(C(=O)[O-])C=CC=C1.C(CC(O)(C(=O)O)CC(=O)[O-])(=O)[O-].[Na+].[Na+].[Na+] Chemical compound OC1=C(C(=O)[O-])C=CC=C1.C(CC(O)(C(=O)O)CC(=O)[O-])(=O)[O-].[Na+].[Na+].[Na+] NDDSQNNCTJFKBX-UHFFFAOYSA-K 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000002153 concerted effect Effects 0.000 description 2
- 230000009514 concussion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- -1 ruthenium Chemical class 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
-
- B01J35/33—
-
- B01J35/615—
-
- B01J35/647—
-
- 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
- B01J37/06—Washing
-
- 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
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
Abstract
The invention discloses a kind of covalent organic frame material catalyst and its preparation method and application based on load Ru nano particle, catalyst the preparation method comprises the following steps: benzene derivative, pyridine derivate and conductive carbon material are sufficiently mixed to obtain mixture A, mixture A and base metal salt are placed in tube furnace, high-temperature calcination in a nitrogen atmosphere, calcined product is successively cleaned with hydrochloric acid solution and deionized water, it is dry, obtain covalent organic frame support powder；The covalent organic frame support powder of gained and ruthenium metal salt are fully ground to being uniformly mixed and are placed in tube furnace and high-temperature calcination in a nitrogen atmosphere, after calcined product milli-Q water, drying is to get the covalent organic frame material catalyst based on load Ru nano particle.Catalyst of the invention has high-specific surface area, biggish aperture, and the particle for being supported on the ruthenium metal on covalent organic frame support powder is small, dispersion degree is high, and being applied to electrochemical reduction nitrogen synthesis ammonia has good catalytic activity.
Description
Technical field
The invention belongs to electro-catalysis technical fields, and in particular to a kind of covalent organic frame based on load Ru nano particle
Material catalyst and its preparation method and application.
Background technique
Ammonia is a kind of alkaline, colourless, lighter-than-air gas with penetrating odor.It is upper life in world wide
Most chemicals is produced, is the main raw material(s) for manufacturing nitrogenous fertilizer and compound fertilizer.It is closed to improve nitrogen conversion ratio and improve
At the economy of ammonia process, the selection of catalyst and using most important, at present people to oneself through having done numerous studies, to find
Electrochemistry formated ammonia catalyst with more stable chemical property and thermodynamic property and good economic benefits.Oneself is through having perhaps
Multi-catalyst is constantly found under study for action.Rod et al. earliest using density functional theory to low temperature electrochemical synthesize ammonia into
Research is gone, it is believed that carrying out low temperature electrochemical synthesis ammonia on the surface of iron or ruthenium catalyst is feasible (Journal Of
Chemical Physics, 2000,112 (12): 5343-5347).Catalyst master used in current electrochemistry formated ammonia
To include two class of noble metal catalyst and non-precious metal catalyst, the transition metal such as ruthenium, brill, lead member is commonly used in noble metal catalyst
Plain to combine with skilful iron ore carrier or conductive metal, cathode catalysis material is made in common infusion process, such catalyst catalytic performance
The defects of superior, but its electric conductivity is poor, electron rich group easily makes catalyst poisoning, expensive limit they application and
Development.In order to find the synthesis ammonia method of high business efficiency, it is contemplated that the increase of hydrazine yield is by the huge prospect of bring, Ren Menzheng
The a large amount of synthesis ammonia of research and development new method (International Journal of Hydrogen Energy, 2013,38
(34)；Applied Catalysis B:Environmental, 2014:152-153).And there is machine frame currently based on covalent
The research that the catalyst of the load of frame is applied in terms of electro-catalysis is less, and the catalytic activity of this kind of catalyst all needs to be mentioned
It is high.
Summary of the invention
For above-mentioned technical problem of the existing technology, the purpose of the present invention is to provide one kind based on Ru nanometers of load
Covalent organic frame material catalyst of particle and its preparation method and application, catalyst of the invention are a kind of supported catalysts
Agent, catalyst is at low cost, and can realize efficient electro-catalysis reduction nitrogen reaction (NRR).
A kind of preparation method of covalent organic frame material catalyst based on load Ru nano particle, feature
It is to include the following steps:
1) it takes benzene derivative, pyridine derivate and conductive carbon material to be sufficiently mixed, obtains mixture A；From lower from upper in crucible
Three layers of powder are sequentially placed, first layer powder and third layer powder are base metal salt, and second layer powder is above-mentioned preparation
Mixture A；
2) crucible is placed in tube furnace, high-temperature calcination is carried out under nitrogen protection atmosphere, calcined product successively uses salt
Acid solution and deionized water stirring and washing, the solid after cleaning are dried in vacuo covalently have machine frame at a temperature of 40-100 DEG C
Frame support powder；
3) covalently organic frame support powder and ruthenium metal salt are put into mortar jointly obtained by step 2, be fully ground until
It is uniformly mixed, is subsequently placed in tube furnace and carries out again under nitrogen protection atmosphere high-temperature calcination, calcined product is used super
It is dry to get the covalent organic frame material catalyst based on load Ru nano particle after pure water.
A kind of preparation method of covalent organic frame material catalyst based on load Ru nano particle, feature
It is in step 1), benzene derivative is terephthalonitrile, benzonitrile or isophthalodinitrile；Pyridine derivate is 2,6- pyridine diformazan
Nitrile, biphenyl pyridine or 3- picoline, base metal salt are anhydrous zinc chloride, anhydrous sodium chloride, anhydrous potassium chloride or anhydrous chlorine
Change aluminium.
A kind of preparation method of covalent organic frame material catalyst based on load Ru nano particle, feature
It is in step 1), taking the mass ratio of benzene derivative, pyridine derivate and conductive carbon material is 1: 0.5 ~ 1.5: 3 ~ 7, excellent
It is selected as 1: 1: 5；The gross mass of two layers of base metal salt in crucible and the mass ratio of mixture A are 2 ~ 3.5: 1, excellent
It is selected as 2.8: 1.
A kind of preparation method of covalent organic frame material catalyst based on load Ru nano particle, feature
It is in step 2, the temperature of high-temperature calcination is 300-500 DEG C, and the time of high-temperature calcination is 30 ~ 50h；The hydrochloric acid solution
Concentration is 0.8 ~ 1.2mol/L.
A kind of preparation method of covalent organic frame material catalyst based on load Ru nano particle, feature
It is in step 3), ruthenium metal salt is acetylacetone,2,4-pentanedione ruthenium, three ruthenium of three ruthenium trichlorides, nitrosyl nitrate ruthenium or ten dicarbapentaborane.
A kind of preparation method of covalent organic frame material catalyst based on load Ru nano particle, feature
It is in step 3), the mass ratio of covalent organic frame support powder and ruthenium metal salt is 5: 0.8 ~ 2.5.
A kind of preparation method of covalent organic frame material catalyst based on load Ru nano particle, feature
It is in step 3), the temperature of high-temperature calcination is 250 ~ 350 DEG C, and the time of high-temperature calcination is 2 ~ 4h.
The covalent organic frame material catalyst based on load Ru nano particle prepared according to above-mentioned method.
The covalent organic frame material catalyst based on load Ru nano particle restores nitrogen in catalytic electrochemical
Application in ammonia processed.
The covalent organic frame material catalyst based on load Ru nano particle restores nitrogen in catalytic electrochemical
Application in ammonia processed, it is characterised in that use two electrode system test devices, be that load Ru described will be based on to electrode with platinum filament
The covalent organic frame material catalyst of nano particle, which is coated on carbon paper, is used as working electrode, is electrolysis with inorganic base aqueous solution
Liquid carries out the reaction of electro-catalysis reduction nitrogen ammonia.
By using above-mentioned technology, compared with prior art, beneficial effects of the present invention are as follows:
(1) during catalyst preparation of the present invention, the mixture of benzene derivative, pyridine derivate and conductive carbon material is placed in two
Sandwich sandwich is formed between layer base metal salt powder, non-metal salt becomes molten condition in high-temperature burning process,
Sandwich sandwich allows the non-metal salt of melting to come into full contact with benzene derivative, pyridine derivate and conductive carbon material
Mixture, the non-metal salt of melting open three key of nitrogen nitrogen in benzene derivative and pyridine derivate using ion heat effect and form triazine
Ring, so that the covalent organic frame material that benzene derivative and pyridine derivate change formation under high-temperature calcination contains triazine
Ring structure, the covalent organic frame material containing triazine ring structure are mixed with ruthenium metal salt again, using one kettle way high-temperature calcination, warp
It crosses and washs, is dried to obtain catalyst of the invention；Thus the triazine ring in catalyst of the invention has a large amount of unpaired electrons,
So as to the growth position and granular size of confinement Ru nano particle, regulation Ru and covalent organic frame material carrier are also acted as
Between electronic structure, active component Ru and covalent organic frame carrier have concerted catalysis effect, and triazine ring is anchored ruthenium and effectively adjusts
The electronic structure for saving and optimizing the two has positive interaction hence for attack three key of nitrogen nitrogen, and catalyst recycles stability
It is good and cheap.
(2) catalyst of the invention has high-specific surface area, biggish aperture, is supported on covalent organic frame support powder
On ruthenium metal particle is small, catalyst that dispersion degree is high and of the invention mechanical strength is good.Catalyst of the invention can answer
Nitrogen performance is restored for electrochemical reduction nitrogen, and with excellent electro-catalysis.And the preparation method of catalyst of the present invention
Simply, complicated, high price ancillary equipment is not needed, noble metal dosage is few, and it is at low cost, it is not easy to poison, is easy to regulate and control, be suitble to big rule
Mould preparation, has broad application prospects.
(3) during catalyst preparation of the present invention, the purpose for mixing conductive carbon material is: improve be prepared it is covalent
The electric conductivity of organic framework materials and the multi-pore channel of structure.Covalent organic frame carrier prepared by the present invention has class graphene
Structure and preferable hole configurations have biggish specific surface area, and the Ru content of covalent organic frame supported on carriers is low and divides
Cloth uniformly provides more active site for reaction, at the same it is at low cost, stability is good.
Detailed description of the invention
Fig. 1 is that the projection electron microscope for the covalent organic frame material that embodiment 1 obtains observes figure；
Fig. 2 a is throwing of the covalent organic frame material catalyst based on load Ru nano particle of the acquisition of embodiment 1 at 50nm
Penetrate electron microscope observation figure；
Fig. 2 b is throwing of the covalent organic frame material catalyst based on load Ru nano particle of the acquisition of embodiment 1 at 20nm
Penetrate electron microscope observation figure；
Fig. 3 is the electrochemistry formated ammonia yield comparison diagram of the catalyst of embodiment 1 ~ 5；
Fig. 4 is the faradic efficiency comparison diagram of the electrochemistry formated ammonia reaction of the catalyst of embodiment 1 ~ 5.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment 1:
1) the conductive black powder of the terephthalonitrile of 0.64g, the 2,6- pyridine dimethoxy nitrile of 0.64g and 3.2g is abundant in mortar
Ground and mixed obtains mixture A.From lower from the mixture A for being above sequentially placed 6.4g anhydrous zinc chloride, above-mentioned preparation in crucible
And 6.4g anhydrous zinc chloride (i.e. mixture A is placed between two layers of anhydrous zinc chloride powder)；
2) crucible of step 1) being placed in tube furnace, carries out high-temperature calcination under nitrogen protection, calcination temperature is 400 DEG C,
Calcination time is 40 hours, and the nitrogen flow being passed through in tube furnace is 50 mL/min.Calcined product successively uses 1 mol/L
Hydrochloric acid solution and deionized water distinguish stirring and washing 12 hours, the solid after cleaning be dried in vacuo at 60 DEG C 12h to get be total to
Valence organic frame support powder (covalent organic frame support powder made from 1 step 2 of embodiment is tested through BET, for
The material of mesopore orbit structure, specific surface area are 110.4 m2/ g, average pore size 10.9323nm)；
3) it takes 2) resulting covalent organic frame support powder 50mg and acetylacetone,2,4-pentanedione ruthenium 20.8mg to be put into mortar jointly, carries out
Be fully ground until be uniformly mixed, then carry out high-temperature calcination again in tube furnace under nitrogen protection, from room temperature with 3 DEG C/
Min is warming up to 300 DEG C, and calcines 3 hours at 300 DEG C, calcined product milli-Q water, and drying is urged to get target
Agent, i.e. the covalent organic frame material catalyst based on load Ru nano particle.
Projection electron microscope is carried out to the deficiency covalent triazine frame carrier material powder that 1 step 2 of embodiment obtains
Observation, the result is shown in Figure 1, it will be seen from figure 1 that the covalent organic frame material presentation that the present embodiment obtains is two-dimensional fiber
Shape.
To 1 step 3) of embodiment finally obtain based on load Ru nano particle covalent organic frame material catalyst into
Row projection electron microscope observation, as a result as shown in Fig. 2 a and Fig. 2 b.It is uniform on catalyst from can be seen that in Fig. 2 a and Fig. 2 b
Disperse some metal Ru nanometers of little particles, and Ru nanometers of short grained partial sizes of metal are about within the scope of 1-3nm.
It is as follows that ammonia performance test is synthesized to the electro-catalysis for the catalyst that embodiment 1 obtains:
Weigh 4.0 mg based on load Ru nano particle covalent organic frame material catalyst, be added 900 microlitres of ethyl alcohol and
In 100 microlitres of Nafion solutions (mass fraction of Nafion solution is 5%), ultrasound 0.5 hour is completely dispersed to catalyst, obtains
To uniform catalyst pulp.
0.2 mL of catalyst pulp for pipetting above-mentioned preparation is uniformly applied on the carbon paper of 1cm × 1cm, dry, as work
Make electrode, Ag/AgCl is used as reference electrode, platinum electrode to electrode.Linear volt-ampere curve test is using Shanghai occasion
The CHI760E electrochemical workstation of China, carries out in the H-type electrolytic cell of three-electrode system, and electrolyte is 0.1 mol/L KOH water
Solution first leads to nitrogen 0.5 hour before test, the nitrogen in electrolyte is made to reach saturation state.Sweep speed is 10 mV
s-1, Ag/AgCl is -1.0 ~ 0.2 V as the voltage set range under reference electrode, between Ag/AgCl and reversible hydrogen electrode RHE
Potential difference be 0.965 V.7200 s sampling analysis reaction result of cell reaction time carries out electricity under the conditions of different voltages and urges
Change reduction nitrogen ammonia synthesis reaction, the yield figure and drawing efficiency chart point of the synthesis ammonia in embodiment 1 under the conditions of different voltages
Not not as shown in Figure 3 and Figure 4.
Wherein ammonia content test method: drawing obtain the standard working curve of ammonia density first, and it is dense to prepare a series of differences
The ammonia spirit of degree, the ammonia spirit for pipetting 2 mL preparation respectively sequentially add 2 mL's in colorimetric cylinder, and into colorimetric cylinder
5% sodium citrate-salicylic acid solution, the 0.05 mol/L liquor natrii hypochloritis of 1 mL and 1% sodium nitroprusside solution of 0.2 mL, slightly
Chromogenic reaction occurs for the place of being protected from light that is placed on of concussion, takes out after 2 h, curve is scanned in spectrophotometer and reads wavelength
For the absorbance of 655 nm, and using deionized water as blank to get to different ammonia densities and absorbance corresponding relationship
Standard working curve.
Under different voltages after cell reaction, the electrolyte of 2 mL is pipetted respectively in colorimetric cylinder, and into colorimetric cylinder
Sequentially add the 1% of the 5% sodium citrate-salicylic acid solution of 2 mL, the 0.05 mol/L liquor natrii hypochloritis of 1 mL and 0.2 mL
Chromogenic reaction occurs for the place of being protected from light that is placed on of sodium nitroprusside solution, slight concussion, takes out after 2 h, is swept in spectrophotometer
It retouches curve and reads the absorbance that wavelength is 655 nm, bringing institute's measured data into ammonia standard working curve, that ammonia content can be obtained is dense
Degree.
In above-mentioned ammonia content test method, the preparation method of test fluid is as follows:
5% sodium citrate-salicylic preparation: the sodium hydroxide of 10.2030g is weighed in 250ml beaker, adds appropriate pure water
It makes it dissolve, then weighs the sodium citrate of 12.5000g respectively and 12.5000g salicylic acid solid is added in above-mentioned solution, fill
Divide and stir to dissolve, after dissolving and being cooled to room temperature, moves it in the volumetric flask of 25ml and carry out constant volume with pure water.
The preparation of 1% sodium nitroprusside solution: taking 1.0000g sodium nitroprusside solid in the beaker of 100ml, is added suitable
Amount pure water is dissolved, and is moved in 100ml volumetric flask and is carried out constant volume with pure water.
Embodiment 2:
1) the conductive black powder of the terephthalonitrile of 0.64g, the 2,6- pyridine dimethoxy nitrile of 0.64g and 3.2g is abundant in mortar
Ground and mixed obtains mixture A.From lower from the mixture A for being above sequentially placed 6.4g anhydrous zinc chloride, above-mentioned preparation in crucible
And 6.4g anhydrous zinc chloride (i.e. mixture A is placed between two layers of anhydrous zinc chloride powder)；
2) crucible of step 1) being placed in tube furnace, carries out high-temperature calcination under nitrogen protection, calcination temperature is 400 DEG C,
Calcination time is 40 hours, and the nitrogen flow being passed through in tube furnace is 50 mL/min.Calcined product successively uses 1 mol/L
Hydrochloric acid solution and deionized water distinguish stirring and washing 12 hours, the solid after cleaning be dried in vacuo at 60 DEG C 12h to get be total to
Valence organic frame support powder；
3) it takes 2) resulting covalent organic frame support powder 50mg and acetylacetone,2,4-pentanedione ruthenium 10.4mg to be put into mortar jointly, carries out
Be fully ground until be uniformly mixed, then carry out high-temperature calcination again in tube furnace under nitrogen protection, from room temperature with 3 DEG C/
Min is warming up to 300 DEG C, and calcines 3 hours at 300 DEG C, calcined product milli-Q water, and drying is urged to get target
Agent, i.e. the covalent organic frame material catalyst based on load Ru nano particle.
It is as follows that ammonia performance test is synthesized to the electro-catalysis for the catalyst that embodiment 2 obtains:
Weigh 4.0 mg based on load Ru nano particle covalent organic frame material catalyst, be added 900 microlitres of ethyl alcohol and
In 100 microlitres of Nafion solutions (mass fraction of Nafion solution is 5%), ultrasound 0.5 hour is completely dispersed to catalyst, obtains
To uniform catalyst pulp.
0.2 mL of catalyst pulp for pipetting above-mentioned preparation is uniformly applied on the carbon paper of 1cm × 1cm, dry, as work
Make electrode, Ag/AgCl is used as reference electrode, platinum electrode to electrode.Linear volt-ampere curve test is using Shanghai occasion
The CHI760E electrochemical workstation of China, carries out in the H-type electrolytic cell of three-electrode system, and electrolyte is 0.1 mol/L KOH water
Solution first leads to nitrogen 0.5 hour before test, the nitrogen in electrolyte is made to reach saturation state.Sweep speed is 10 mV
s-1, Ag/AgCl is -1.0 ~ 0.2 V as the voltage set range under reference electrode, between Ag/AgCl and reversible hydrogen electrode RHE
Potential difference be 0.965 V.7200 s sampling analysis reaction result of cell reaction time, sampling interval are set as 1 s, sensitivity
It is set as 0.1, electro-catalysis is carried out under the conditions of different voltages and restores nitrogen ammonia synthesis reaction, in embodiment 2 under the conditions of different voltages
Synthesis ammonia yield figure and draw efficiency chart difference it is as shown in Figure 3 and Figure 4.Ammonia content test method is the same as embodiment 1.
Embodiment 3:
It takes 50mg conductive black powder and 20.8mg acetylacetone,2,4-pentanedione ruthenium to be placed in mortar to be fully ground up to being uniformly mixed, then exist
High-temperature calcination is carried out under nitrogen protection in tube furnace, is warming up to 300 DEG C from room temperature with 3 DEG C/min, and calcine 3 at 300 DEG C
Hour, calcined product milli-Q water is dry to get final catalyst.
It is as follows that ammonia performance test is synthesized to the electro-catalysis for the catalyst that embodiment 3 obtains:
3 catalyst of embodiment for weighing 4.0 mg, be added 900 microlitres of ethyl alcohol and 100 microlitres of Nafion solutions (Nafion solution
Mass fraction be 5%) in, ultrasound 0.5 hour, be completely dispersed to catalyst, obtain uniform catalyst pulp.Pipette above-mentioned match
0.2 mL of catalyst pulp of system is uniformly applied on the carbon paper of 1cm × 1cm, dry, as working electrode, Ag/AgCl(3
Mol/L KCl) it is used as reference electrode, platinum electrode is used as to electrode.Linear volt-ampere curve test is using Shanghai Chen Hua
CHI760E electrochemical workstation carries out in the H-type electrolytic cell of three-electrode system, and electrolyte is that 0.1 mol/L KOH is water-soluble
Liquid first leads to nitrogen 0.5 hour before test, the nitrogen in electrolyte is made to reach saturation state.Sweep speed is 10 mV s-1,
Ag/AgCl is -1.0 ~ 0.2 V as the voltage set range under reference electrode, between Ag/AgCl and reversible hydrogen electrode RHE
Potential difference is 0.965 V.7200 s sampling analysis reaction result of cell reaction time, sampling interval are set as 1 s, and sensitivity is set
It is 0.1, electro-catalysis is carried out under the conditions of different voltages and restores nitrogen ammonia synthesis reaction, in embodiment 3 under the conditions of different voltages
It synthesizes the yield figure of ammonia and draws efficiency chart difference as shown in Figure 3 and Figure 4.Ammonia content test method is the same as embodiment 1.
Embodiment 4:
1) melamine of 2.00g and 3.2g conductive black powder are placed in mortar and are fully ground until being uniformly mixed, later
It is placed in porcelain boat, then carries out high-temperature calcination in tube furnace under nitrogen protection,
In 550 DEG C of high-temperature calcination 3h, C is finally obtained3N4Powder；
2) by C obtained by step 1)3N4Powder 50mg and acetylacetone,2,4-pentanedione ruthenium 20.8mg are put into mortar jointly, be fully ground straight
To being uniformly mixed, then carries out high-temperature calcination again in tube furnace under nitrogen protection, be warming up to from room temperature with 3 DEG C/min
300 DEG C, and calcined 3 hours at 300 DEG C, calcined product milli-Q water, it is dry to get final catalyst.
It is as follows that ammonia performance test is synthesized to the electro-catalysis for the catalyst that embodiment 4 obtains:
4 catalyst of embodiment for weighing 4.0 mg, be added 900 microlitres of ethyl alcohol and 100 microlitres of Nafion solutions (Nafion solution
Mass fraction be 5%) in, ultrasound 0.5 hour, be completely dispersed to catalyst, obtain uniform catalyst pulp.Pipette above-mentioned match
0.2 mL of catalyst pulp of system is uniformly applied on the carbon paper of 1cm × 1cm, dry, as working electrode, Ag/AgCl conduct
Reference electrode, platinum electrode are used as to electrode.Linear volt-ampere curve tests the CHI760E electrochemistry work using Shanghai Chen Hua
It stands, is carried out in the H-type electrolytic cell of three-electrode system, electrolyte is 0.1 mol/L KOH aqueous solution, is first led to before test
Nitrogen 0.5 hour, the nitrogen in electrolyte is made to reach saturation state.Sweep speed is 10 mV s-1, Ag/AgCl is as reference electricity
Voltage set range under extremely is -1.0 ~ 0.2 V, and the potential difference between Ag/AgCl and reversible hydrogen electrode RHE is 0.965 V.Electricity
7200 s sampling analysis reaction result of reaction time is solved, the sampling interval is set as 1 s, and sensitivity is set as 0.1, in different voltages item
Carry out electro-catalysis under part and restore nitrogen ammonia synthesis reaction, the yield figure of the synthesis ammonia in embodiment 4 under the conditions of different voltages and
Draw efficiency chart difference as shown in Figure 3 and Figure 4.Ammonia content method is tested with embodiment 1.
Embodiment 5:
Using Ru/C(Ru load capacity 5%) as the contrast sample of NRR reaction, performance test methods are as follows: weighing 4 mg
Ru/C is added in the centrifuge tube of 4mL, and 900 microlitres of ethyl alcohol and 100 microlitres of Nafion solution (quality of Nafion solution point are added
Catalyst is 5%), ultrasound 0.5 hour is fully dispersed in ethyl alcohol, obtains uniform catalyst pulp by number.
0.2 mL of catalyst pulp for pipetting above-mentioned preparation is uniformly applied on the carbon paper of 1cm × 1cm, dry, as work
Make electrode, Ag/AgCl is used as reference electrode, platinum electrode to electrode.Linear volt-ampere curve test is using Shanghai occasion
The CHI760E electrochemical workstation of China, carries out in the H-type electrolytic cell of three-electrode system, and electrolyte is 0.1 mol/L KOH water
Solution first leads to nitrogen 0.5 hour before test, the nitrogen in electrolyte is made to reach saturation state.Sweep speed is 10 mV
s-1, Ag/AgCl is -1.0 ~ 0.2 V as the voltage set range under reference electrode, between Ag/AgCl and reversible hydrogen electrode RHE
Potential difference be 0.965 V.7200 s sampling analysis reaction result of cell reaction time, sampling interval are set as 1 s, sensitivity
It is set as 0.1, electro-catalysis is carried out under the conditions of different voltages and restores nitrogen ammonia synthesis reaction, in embodiment 5 under the conditions of different voltages
Synthesis ammonia yield figure and draw efficiency chart difference it is as shown in Figure 3 and Figure 4.Ammonia content test method is the same as embodiment 1.
Under the conditions of different voltages, the comparison diagram of the yield of the electro-catalysis reduction nitrogen synthesis ammonia of 1 ~ 5 catalyst of embodiment
As shown in Figure 3.From figure 3, it can be seen that the catalytic activity of 1 ~ 2 electro-catalysis of embodiment reduction nitrogen ammonia synthesis reaction it is obvious it is excellent in
Embodiment 3 ~ 5.Under the conditions of different voltages, the faraday of the electro-catalysis reduction nitrogen ammonia synthesis reaction of 1 ~ 5 catalyst of embodiment
Efficiency comparative's figure is as shown in Figure 4.From fig. 4, it can be seen that faraday's effect of 1 ~ 2 electro-catalysis of embodiment reduction nitrogen ammonia synthesis reaction
Rate is obvious excellent in embodiment 3 ~ 5.
It can be seen that the catalyst of embodiment 3 ~ 5 is bright in being applied to catalytic electrochemical reduction nitrogen ammonia reaction process
Significant difference is in the catalyst of embodiment 1.Both embodiment 1 and embodiment 3 catalyst the difference is that, embodiment 1 is using mixing
The covalent organic frame material of miscellaneous conductive black is as carrier, and embodiment 3 directlys adopt conductive black as carrier, by property
The NRR performance for the catalyst that energy test discovery conductive black is prepared as carrier is not that very well, thus comparative illustration is of the invention
Make containing triazine ring and doped with the covalent organic frame carrier of conductive black and active component Ru with good concerted catalysis
With for the reaction of electrochemical reduction nitrogen ammonia with good catalytic effect.
Both embodiment 1 and embodiment 4 catalyst the difference is that, the load with embodiment 1 is prepared in embodiment 4
Body has the C of similar structure3N4Material, but C made from embodiment 43N4Material does not contain triazine ring structure.And embodiment 1 is made
The triazine ring in covalent organic frame material obtained has a large amount of unpaired electrons, so as to the growth of confinement Ru nano particle
Position and granular size also act as electronic structure between regulation Ru and carrier, and then influence the performance that catalyst is reacted in NRR,
And final catalyst made from embodiment 1 has non-perfect pattern (comparative diagram 1, Fig. 2 a and Fig. 2 b), can equally be formed not
With the triazine ring of position, these all have positive influence to catalyst performance.
Embodiment 5 uses the common business Ru/C catalyst of the prior art, from figs. 3 and 4 it can be seen that the present invention is made
Based on load Ru nano particle covalent organic frame material catalyst be applied to electrochemical reduction nitrogen ammonia reaction in,
Its catalytic performance is got well than the catalytic performance of business Ru/C catalyst.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated.
Claims (10)
1. a kind of preparation method of the covalent organic frame material catalyst based on load Ru nano particle, it is characterised in that including
Following steps:
1) it takes benzene derivative, pyridine derivate and conductive carbon material to be sufficiently mixed, obtains mixture A；From lower from upper in crucible
Three layers of powder are sequentially placed, first layer powder and third layer powder are base metal salt, and second layer powder is above-mentioned preparation
Mixture A；
2) crucible is placed in tube furnace, high-temperature calcination is carried out under nitrogen protection atmosphere, calcined product successively uses salt
Acid solution and deionized water stirring and washing, the solid after cleaning are dried in vacuo covalently have machine frame at a temperature of 40-100 DEG C
Frame support powder；
3) covalently organic frame support powder and ruthenium metal salt are put into mortar jointly obtained by step 2, be fully ground until
It is uniformly mixed, is subsequently placed in tube furnace and carries out again under nitrogen protection atmosphere high-temperature calcination, calcined product is used super
It is dry to get the covalent organic frame material catalyst based on load Ru nano particle after pure water.
2. a kind of preparation side of covalent organic frame material catalyst based on load Ru nano particle as described in claim 1
Method, it is characterised in that in step 1), benzene derivative is terephthalonitrile, benzonitrile or isophthalodinitrile；Pyridine derivate is 2,6-
Pyridine dimethoxy nitrile, biphenyl pyridine or 3- picoline, base metal salt are anhydrous zinc chloride, anhydrous sodium chloride, anhydrous potassium chloride
Or anhydrous aluminum chloride.
3. a kind of preparation of covalent organic frame material catalyst based on load Ru nano particle as described in claim 1
Method, it is characterised in that in step 1), take benzene derivative, pyridine derivate and conductive carbon material mass ratio be 1: 0.5 ~
1.5: 3 ~ 7, preferably 1: 1: 5；The gross mass of two layers of base metal salt in crucible and the mass ratio of mixture A are
2 ~ 3.5: 1, preferably 2.8: 1.
4. a kind of preparation side of covalent organic frame material catalyst based on load Ru nano particle as described in claim 1
Method, it is characterised in that in step 2, the temperature of high-temperature calcination is 300-500 DEG C, and the time of high-temperature calcination is 30 ~ 50h；The salt
The concentration of acid solution is 0.8 ~ 1.2mol/L.
5. a kind of preparation side of covalent organic frame material catalyst based on load Ru nano particle as described in claim 1
Method, it is characterised in that in step 3), ruthenium metal salt is acetylacetone,2,4-pentanedione ruthenium, three ruthenium trichlorides, nitrosyl nitrate ruthenium or 12 carbonyls
Three ruthenium of base.
6. a kind of preparation of covalent organic frame material catalyst based on load Ru nano particle as described in claim 1
Method, it is characterised in that in step 3), the mass ratio of covalent organic frame support powder and ruthenium metal salt is 5: 0.8 ~ 2.5.
7. a kind of preparation side of covalent organic frame material catalyst based on load Ru nano particle as described in claim 1
Method, it is characterised in that in step 3), the temperature of high-temperature calcination is 250 ~ 350 DEG C, and the time of high-temperature calcination is 2 ~ 4h.
8. the covalent organic frame material based on load Ru nano particle prepared by the method as described in claim 1 ~ 7 any one
Expect catalyst.
9. the covalent organic frame material catalyst as claimed in claim 8 based on load Ru nano particle is in catalytic electrochemical
Restore the application in nitrogen ammonia.
10. application as claimed in claim 9, it is characterised in that use two electrode system test devices, with platinum filament be to electrode,
The covalent organic frame material catalyst based on load Ru nano particle is coated on carbon paper and is used as working electrode, with nothing
Machine aqueous alkali is electrolyte, carries out the reaction of electro-catalysis reduction nitrogen ammonia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910804180.1A CN110479379B (en) | 2019-08-28 | 2019-08-28 | Covalent organic framework material catalyst based on loaded Ru nanoparticles and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910804180.1A CN110479379B (en) | 2019-08-28 | 2019-08-28 | Covalent organic framework material catalyst based on loaded Ru nanoparticles and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110479379A true CN110479379A (en) | 2019-11-22 |
| CN110479379B CN110479379B (en) | 2022-07-22 |
Family
ID=68555229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910804180.1A Active CN110479379B (en) | 2019-08-28 | 2019-08-28 | Covalent organic framework material catalyst based on loaded Ru nanoparticles and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110479379B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111545250A (en) * | 2020-05-21 | 2020-08-18 | 浙江工业大学 | Ruthenium catalyst with efficient electrocatalytic full-hydrolytic performance and application thereof |
| CN111841645A (en) * | 2020-08-31 | 2020-10-30 | 江南大学 | OER catalyst compounded by carbon nano tube and covalent organic framework |
| CN112111069A (en) * | 2020-09-30 | 2020-12-22 | 中国科学院生态环境研究中心 | Preparation method and application of palladium nanoparticle-supported benzothiazole-linked covalent organic framework material |
| CN112281185A (en) * | 2020-09-29 | 2021-01-29 | 河北科技大学 | Preparation method and application of hierarchical pore covalent organic framework compound and metal composite hydrogen evolution catalyst |
| CN113059175A (en) * | 2021-01-08 | 2021-07-02 | 中国石油大学(华东) | Preparation method of Au @ Ag @ AgCl nanoparticles and application of Au @ Ag @ AgCl nanoparticles in ammonia colorimetric detection |
| CN113151860A (en) * | 2021-04-28 | 2021-07-23 | 安徽大学 | Sulfur-doped carbon-coated iridium nanoparticle and preparation and application thereof |
| CN113802144A (en) * | 2020-09-29 | 2021-12-17 | 河北科技大学 | Preparation method and application of single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst |
| CN114733549A (en) * | 2022-04-22 | 2022-07-12 | 浙江工业大学 | Preparation method and application of double-nitrogen-group embedded carbon nano-framework |
| CN114768849A (en) * | 2022-04-14 | 2022-07-22 | 浙江工业大学 | Preparation method and application of layered sulfur-doped carbon-nitrogen copolymer |
| CN114808026A (en) * | 2022-03-11 | 2022-07-29 | 浙江大学衢州研究院 | Two-dimensional metal organic framework nanosheet supported noble metal monatomic catalyst and preparation method and application thereof |
| CN115487866A (en) * | 2021-06-18 | 2022-12-20 | 浙江大学 | Covalent organic framework material coupled nano metal catalyst and preparation method thereof |
| CN115850865A (en) * | 2022-12-29 | 2023-03-28 | 江阴瑞林精密机械制造有限公司 | Photovoltaic corrosion-resistant anti-aging polypropylene plate and preparation method thereof |
| CN116328845A (en) * | 2023-03-16 | 2023-06-27 | 兰州大学 | Pt unit point catalyst for olefin hydrosilylation and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3775380A (en) * | 1971-09-01 | 1973-11-27 | Texaco Inc | Polymerization of aromatic nitriles |
| CN107129583A (en) * | 2017-05-25 | 2017-09-05 | 西北师范大学 | The synthetic method of porous organic covalent frame material with triazine structure |
| WO2018111777A1 (en) * | 2016-12-12 | 2018-06-21 | The Regents Of The University Of California | Pore size engineering of porous carbonaceous materials using covalent organic frameworks |
| CN108976417A (en) * | 2018-06-05 | 2018-12-11 | 广东工业大学 | A kind of covalent organic polymer of triazine ring, electrode material and its preparation method and application |
| CN110075902A (en) * | 2019-05-22 | 2019-08-02 | 浙江工业大学 | A kind of deficiency covalent triazine frame material derived material catalyst and its preparation method and application |
-
2019
- 2019-08-28 CN CN201910804180.1A patent/CN110479379B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3775380A (en) * | 1971-09-01 | 1973-11-27 | Texaco Inc | Polymerization of aromatic nitriles |
| WO2018111777A1 (en) * | 2016-12-12 | 2018-06-21 | The Regents Of The University Of California | Pore size engineering of porous carbonaceous materials using covalent organic frameworks |
| CN107129583A (en) * | 2017-05-25 | 2017-09-05 | 西北师范大学 | The synthetic method of porous organic covalent frame material with triazine structure |
| CN108976417A (en) * | 2018-06-05 | 2018-12-11 | 广东工业大学 | A kind of covalent organic polymer of triazine ring, electrode material and its preparation method and application |
| CN110075902A (en) * | 2019-05-22 | 2019-08-02 | 浙江工业大学 | A kind of deficiency covalent triazine frame material derived material catalyst and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| ANNA KATHARINA BEINE等: "Selective production of glycols from xylitol over Ru on covalent triazine frameworks-suppressing decarbonylation reactions", 《GREEN CHEMISTRY》 * |
| FEI CHANG等: "Covalent triazine-based framework as an efficient catalyst support for ammonia decomposition", 《RSC ADVANCES》 * |
| T. H. ROD等: "Ammonia synthesis at low temperatures", 《JOURNAL OF CHEMICAL PHYSICS》 * |
| XIAOXI GUO等: "Recent progress in electrocatalytic nitrogen reduction", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111545250B (en) * | 2020-05-21 | 2023-04-18 | 浙江工业大学 | Ruthenium catalyst with efficient electrocatalytic full-hydrolytic performance and application thereof |
| CN111545250A (en) * | 2020-05-21 | 2020-08-18 | 浙江工业大学 | Ruthenium catalyst with efficient electrocatalytic full-hydrolytic performance and application thereof |
| CN111841645A (en) * | 2020-08-31 | 2020-10-30 | 江南大学 | OER catalyst compounded by carbon nano tube and covalent organic framework |
| CN112281185A (en) * | 2020-09-29 | 2021-01-29 | 河北科技大学 | Preparation method and application of hierarchical pore covalent organic framework compound and metal composite hydrogen evolution catalyst |
| CN113802143A (en) * | 2020-09-29 | 2021-12-17 | 河北科技大学 | Preparation method and application of hierarchical pore covalent organic framework compound and metal composite hydrogen evolution catalyst |
| CN113802144A (en) * | 2020-09-29 | 2021-12-17 | 河北科技大学 | Preparation method and application of single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst |
| CN112111069A (en) * | 2020-09-30 | 2020-12-22 | 中国科学院生态环境研究中心 | Preparation method and application of palladium nanoparticle-supported benzothiazole-linked covalent organic framework material |
| CN113059175B (en) * | 2021-01-08 | 2022-08-19 | 中国石油大学(华东) | Preparation method of Au @ Ag @ AgCl nanoparticles and application of Au @ Ag @ AgCl nanoparticles in ammonia gas colorimetric detection |
| CN113059175A (en) * | 2021-01-08 | 2021-07-02 | 中国石油大学(华东) | Preparation method of Au @ Ag @ AgCl nanoparticles and application of Au @ Ag @ AgCl nanoparticles in ammonia colorimetric detection |
| CN113151860A (en) * | 2021-04-28 | 2021-07-23 | 安徽大学 | Sulfur-doped carbon-coated iridium nanoparticle and preparation and application thereof |
| CN113151860B (en) * | 2021-04-28 | 2023-09-29 | 安徽大学 | Sulfur-doped carbon-coated iridium nanoparticle as well as preparation and application thereof |
| CN115487866A (en) * | 2021-06-18 | 2022-12-20 | 浙江大学 | Covalent organic framework material coupled nano metal catalyst and preparation method thereof |
| CN114808026A (en) * | 2022-03-11 | 2022-07-29 | 浙江大学衢州研究院 | Two-dimensional metal organic framework nanosheet supported noble metal monatomic catalyst and preparation method and application thereof |
| CN114768849A (en) * | 2022-04-14 | 2022-07-22 | 浙江工业大学 | Preparation method and application of layered sulfur-doped carbon-nitrogen copolymer |
| CN114768849B (en) * | 2022-04-14 | 2024-01-09 | 浙江工业大学 | Preparation method and application of lamellar sulfur-doped carbon-nitrogen copolymer |
| CN114733549A (en) * | 2022-04-22 | 2022-07-12 | 浙江工业大学 | Preparation method and application of double-nitrogen-group embedded carbon nano-framework |
| CN114733549B (en) * | 2022-04-22 | 2023-11-28 | 浙江工业大学 | Preparation method and application of dinitrogen group embedded carbon nano-frame |
| CN115850865A (en) * | 2022-12-29 | 2023-03-28 | 江阴瑞林精密机械制造有限公司 | Photovoltaic corrosion-resistant anti-aging polypropylene plate and preparation method thereof |
| CN116328845A (en) * | 2023-03-16 | 2023-06-27 | 兰州大学 | Pt unit point catalyst for olefin hydrosilylation and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110479379B (en) | 2022-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110479379A (en) | A kind of covalent organic frame material catalyst and its preparation method and application based on load Ru nano particle | |
| Yuan et al. | A universal synthesis strategy for single atom dispersed cobalt/metal clusters heterostructure boosting hydrogen evolution catalysis at all pH values | |
| CN106694007B (en) | A kind of single dispersion metal atom/graphene composite catalyst and its preparation method and application | |
| CN108325565B (en) | Multi-functional carbon-based base metal elctro-catalyst of one kind and its preparation method and application | |
| CN107587161B (en) | A kind of preparation method of rodlike NiFeSe/C electrolysis water catalyst | |
| Zhang et al. | Self-supported Ni2P nanosheets on low-cost three-dimensional Fe foam as a novel electrocatalyst for efficient water oxidation | |
| CN110075902A (en) | A kind of deficiency covalent triazine frame material derived material catalyst and its preparation method and application | |
| Zhang et al. | Ni3S2 nanowires grown on nickel foam as an efficient bifunctional electrocatalyst for water splitting with greatly practical prospects | |
| CN110038634A (en) | A kind of oxygen evolution reaction catalysts and its synthetic method based on MXene Yu metal organic framework compound composite construction | |
| CN108923051A (en) | A kind of nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle and its application | |
| CN109524678A (en) | A kind of analysis oxygen ferrocobalt-cobalt ferrite/nitrogen-doped nanometer carbon pipe composite catalyst and its preparation method and application | |
| CN108232210A (en) | A kind of high stability, low-load amount ultra-dispersed noble metal electrocatalyst preparation method | |
| CN111682223A (en) | Preparation of in-situ synthesized nitrogen-doped carbon sheet supported (Co, Ni, Fe) nanoparticle electrocatalyst | |
| Wang et al. | Ag loaded on layered perovskite H2SrTa2O7 to enhance the selectivity of photocatalytic CO2 reduction with H2O | |
| CN109908938A (en) | A kind of preparation method of Novel electrolytic water Oxygen anodic evolution catalyst Co@NC/CNT | |
| Zhang et al. | Ni-Mo based mixed-phase polyionic compounds nanorod arrays on nickel foam as advanced bifunctional electrocatalysts for water splitting | |
| CN106207205B (en) | A kind of fuel cell PtPd elctro-catalysts and preparation method thereof | |
| CN109082676B (en) | A kind of Pd/VN hollow nano-sphere elctro-catalyst and its preparation method and application | |
| CN110064406A (en) | A kind of alkaline solution Electrocatalytic Activity for Hydrogen Evolution Reaction agent V2O3- NiPt and its preparation method and application | |
| CN110354891A (en) | A kind of preparation method and application of the composite catalyst based on Ce-MOF | |
| CN105177621A (en) | Molybdenum-oxygen cluster modified hollow microspherical nickel disulfide catalyst and application thereof | |
| CN113611881A (en) | Atomic-level dispersed Fe/nitrogen-doped mesoporous carbon spheres and preparation method and application thereof | |
| Nie et al. | Pd doped Ni derived from Ni-Metal organic framework for efficient hydrogen evolution reaction in alkaline electrolyte | |
| Zhang et al. | Carbon-based active support for water oxidation electrocatalyst: Making full use of the available surface area | |
| Jia et al. | One-step synthesis of Co2P/NP co-doped porous carbon composites derived from soybean derivatives as acidic and alkaline HER electrocatalysts |
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 |