CN110479379B - Covalent organic framework material catalyst based on loaded Ru nanoparticles and preparation method and application thereof - Google Patents
Covalent organic framework material catalyst based on loaded Ru nanoparticles and preparation method and application thereof Download PDFInfo
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- CN110479379B CN110479379B CN201910804180.1A CN201910804180A CN110479379B CN 110479379 B CN110479379 B CN 110479379B CN 201910804180 A CN201910804180 A CN 201910804180A CN 110479379 B CN110479379 B CN 110479379B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 71
- 239000000463 material Substances 0.000 title claims abstract description 53
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 106
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 53
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 38
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 150000003222 pyridines Chemical class 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 7
- 239000012498 ultrapure water Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000003837 high-temperature calcination Methods 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 17
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- 238000012360 testing method Methods 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 13
- 150000001555 benzenes Chemical class 0.000 claims description 11
- 239000004570 mortar (masonry) Substances 0.000 claims description 9
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical group [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 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
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 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
- XNPMXMIWHVZGMJ-UHFFFAOYSA-N pyridine-2,6-dicarbonitrile Chemical group N#CC1=CC=CC(C#N)=N1 XNPMXMIWHVZGMJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- WKAXDAMWMOBXMP-UHFFFAOYSA-N 2,3-diphenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=C1 WKAXDAMWMOBXMP-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
- 239000011780 sodium chloride Substances 0.000 claims description 2
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 claims 1
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002923 metal particle 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
- 238000003786 synthesis reaction Methods 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 18
- 229910021607 Silver chloride Inorganic materials 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 15
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 15
- 239000002002 slurry Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229920000557 Nafion® Polymers 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000004832 voltammetry Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000001493 electron microscopy Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 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 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 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 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 229940083618 sodium nitroprusside Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013311 covalent triazine framework Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000010355 oscillation Effects 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
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229960004889 salicylic acid Drugs 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
- -1 sodium nitroferricyanide Chemical compound 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
- 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
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- B01J35/33—
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- B01J35/615—
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- 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 covalent organic framework material catalyst based on loaded Ru nano particles and a preparation method and application thereof, wherein the preparation method of the catalyst comprises the following steps: fully mixing the benzene derivative, the pyridine derivative and the conductive carbon material to obtain a mixture A, placing the mixture A and non-noble metal salt in a tubular furnace, calcining at high temperature in a nitrogen atmosphere, sequentially washing calcined products with hydrochloric acid solution and deionized water, and drying to obtain covalent organic framework carrier powder; and fully grinding the obtained covalent organic framework carrier powder and ruthenium metal salt until the covalent organic framework carrier powder and the ruthenium metal salt are uniformly mixed, placing the mixture in a tubular furnace, calcining the mixture at a high temperature in a nitrogen atmosphere, washing a calcined product with ultrapure water, and drying the washed product to obtain the covalent organic framework material catalyst based on the loaded Ru nano particles. The catalyst has the advantages of high specific surface area, larger pore diameter, small ruthenium metal particles loaded on covalent organic framework carrier powder, high dispersity and good catalytic activity when being applied to synthesizing ammonia by electrochemically reducing nitrogen.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a covalent organic framework material catalyst based on loaded Ru nanoparticles, and a preparation method and application thereof.
Background
Ammonia is an alkaline, colorless, lighter-than-air gas with an irritating odor. It is the most produced chemical worldwide and is the main raw material for manufacturing nitrogen fertilizers and compound fertilizers. In order to improve the nitrogen conversion rate and the economy of the ammonia synthesis process, the selection and use of the catalyst are crucial, and a great deal of research is now being conducted to find an electrochemical ammonia synthesis catalyst with more stable chemical and thermodynamic properties and good economic benefits. Many catalysts have been discovered continuously in research. Rod et al, which were the first to investigate the low-temperature electrochemical synthesis Of ammonia using the density functional theory, consider that low-temperature electrochemical synthesis Of ammonia on the surface Of an iron or ruthenium catalyst is feasible (Journal Of Chemical Physics, 2000, 112 (12): 5343-5347). The catalysts used in the current electrochemical synthesis of ammonia mainly comprise noble metal catalysts and non-noble metal catalysts, transition metal elements such as ruthenium, cobalt, lead and the like are commonly used in the noble metal catalysts and combined with a terygite carrier or conductive metal, and a cathode catalytic material is prepared by a common impregnation method. In order to find a method for synthesizing ammonia with high economic efficiency, a new method for synthesizing ammonia in large quantities is being developed in consideration of the great prospect that the increase of the ammonia production will bring (International Journal of Hydrogen Energy,2013,38 (34); Applied Catalysis B: Environmental, 2014: 152-) -153). At present, the research on the application of the supported catalyst based on the covalent organic framework in the aspect of electrocatalysis is less, and the catalytic activity of the catalyst is to be improved.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a covalent organic framework material catalyst based on loaded Ru nanoparticles, a preparation method and application thereof.
The preparation method of the covalent organic framework material catalyst based on the loaded Ru nanoparticles is characterized by comprising the following steps of:
1) fully mixing a benzene derivative, a pyridine derivative and a conductive carbon material to obtain a mixture A; sequentially placing three layers of powder in a crucible from bottom to top, wherein the first layer of powder and the third layer of powder are both non-noble metal salts, and the second layer of powder is the prepared mixture A;
2) placing the crucible in a tubular furnace, calcining at high temperature under the nitrogen protection atmosphere, sequentially stirring and cleaning a calcined product by hydrochloric acid solution and deionized water, and drying the cleaned solid in vacuum at the temperature of 40-100 ℃ to obtain covalent organic framework carrier powder;
3) putting the covalent organic framework carrier powder obtained in the step 2) and ruthenium metal salt into a mortar together, fully grinding until the covalent organic framework carrier powder and the ruthenium metal salt are uniformly mixed, then putting the mixture into a tubular furnace, carrying out high-temperature calcination again under the nitrogen protection atmosphere, washing the calcined product with ultrapure water, and drying to obtain the covalent organic framework material catalyst based on the loaded Ru nanoparticles.
The preparation method of the covalent organic framework material catalyst based on the loaded Ru nanoparticles is characterized in that in the step 1), benzene derivatives are terephthalonitrile, benzonitrile or isophthalonitrile; the pyridine derivative is 2, 6-pyridinedicarbonitrile, diphenylpyridine or 3-methylpyridine, and the non-noble metal salt is anhydrous zinc chloride, anhydrous sodium chloride, anhydrous potassium chloride or anhydrous aluminum chloride.
The preparation method of the covalent organic framework material catalyst based on the loaded Ru nanoparticles is characterized in that in the step 1), the mass ratio of the benzene derivative to the pyridine derivative to the conductive carbon material is 1: 0.5-1.5: 3-7, and the preferred mass ratio is 1: 1: 5; the ratio of the total mass of the two layers of non-noble metal salt in the crucible to the mass of the mixture A is 2-3.5: 1, preferably 2.8: 1.
The preparation method of the covalent organic framework material catalyst based on the loaded Ru nanoparticles is characterized in that in the step 2), the high-temperature calcination temperature is 300-500 ℃, and the high-temperature calcination time is 30-50 h; the concentration of the hydrochloric acid solution is 0.8-1.2 mol/L.
The preparation method of the covalent organic framework material catalyst based on the loaded Ru nanoparticles is characterized in that in the step 3), the ruthenium metal salt is ruthenium acetylacetonate, ruthenium trichloride, ruthenium nitrosyl nitrate or ruthenium dodecacarbonyl.
The preparation method of the covalent organic framework material catalyst based on the loaded Ru nanoparticles is characterized in that in the step 3), the mass ratio of the covalent organic framework carrier powder to the ruthenium metal salt is 5: 0.8-2.5.
The preparation method of the covalent organic framework material catalyst based on the loaded Ru nanoparticles is characterized in that in the step 3), the high-temperature calcination temperature is 250-350 ℃, and the high-temperature calcination time is 2-4 h.
A covalent organic framework material catalyst based on supported Ru nanoparticles prepared according to the above method.
The covalent organic framework material catalyst based on the loaded Ru nanoparticles is applied to the preparation of ammonia by catalytic electrochemical reduction of nitrogen.
The application of the covalent organic framework material catalyst based on the loaded Ru nanoparticles in the preparation of ammonia by catalytic electrochemical reduction of nitrogen is characterized in that a two-electrode system testing device is adopted, a platinum wire is used as a counter electrode, the covalent organic framework material catalyst based on the loaded Ru nanoparticles is coated on carbon paper to serve as a working electrode, and inorganic alkaline aqueous solution is used as electrolyte to carry out the reaction of preparing ammonia by electrocatalytic reduction of nitrogen.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
(1) in the preparation process of the catalyst, a mixture of a benzene derivative, a pyridine derivative and a conductive carbon material is placed between two layers of non-noble metal salt powder to form a sandwich structure, the non-metal salt is changed into a molten state in the high-temperature calcination process, the sandwich structure enables the molten non-metal salt to fully contact the mixture of the benzene derivative, the pyridine derivative and the conductive carbon material, the nitrogen-nitrogen triple bond in the benzene derivative and the pyridine derivative is opened by the molten non-metal salt under the action of ionic heat to form a triazine ring, so that a covalent organic framework material formed by conversion of the benzene derivative and the pyridine derivative under the high-temperature calcination contains the triazine ring structure, the covalent organic framework material containing the triazine ring structure is mixed with ruthenium metal salt, and the catalyst is obtained by one-pot high-temperature calcination, washing and drying; therefore, the triazine ring in the catalyst has a large number of unpaired electrons, so that the growth position and the particle size of Ru nanoparticles can be limited, the electronic structure between Ru and a covalent organic framework material carrier can be regulated and controlled, the active component Ru and the covalent organic framework material carrier have a concerted catalysis effect, and the triazine ring anchoring Ru effectively regulates and optimizes the electronic structures of the Ru and the covalent organic framework material carrier, so that the catalyst has a positive effect on attacking nitrogen-nitrogen triple bonds, and has good recycling stability and low price.
(2) The catalyst has the advantages of high specific surface area, larger pore diameter, small ruthenium metal particles loaded on covalent organic framework carrier powder, high dispersity and good mechanical strength. The catalyst can be applied to electrochemical reduction of nitrogen and has excellent electro-catalytic reduction performance. The preparation method of the catalyst is simple, does not need complex and expensive auxiliary equipment, has low noble metal consumption and low cost, is not easy to poison, is easy to regulate and control, is suitable for large-scale preparation, and has wide application prospect.
(3) In the preparation process of the catalyst, the conductive carbon material is doped for the purposes of: and the multi-pore channel of the conductivity and the structure of the prepared covalent organic framework material is improved. The covalent organic framework carrier prepared by the invention has a graphene-like structure, a better hole structure and a larger specific surface area, the content of Ru loaded on the covalent organic framework carrier is low, the Ru is uniformly distributed, more active sites are provided for reaction, and the covalent organic framework carrier is low in cost and good in stability.
Drawings
FIG. 1 is a projection electron microscopy micrograph of a covalent organic framework material obtained in example 1;
FIG. 2a is a projection electron microscopy observation at 50nm of a covalent organic framework material catalyst based on supported Ru nanoparticles obtained in example 1;
fig. 2b is a projection electron microscopy micrograph at 20nm of the Ru nanoparticle-supported covalent organic framework material catalyst obtained in example 1;
FIG. 3 is a graph comparing the yields of ammonia from electrochemical synthesis of catalysts of examples 1-5;
FIG. 4 is a graph showing a comparison of the Faraday efficiencies of the electrochemical ammonia synthesis reactions of the catalysts of examples 1 to 5.
Detailed Description
The invention is further illustrated with reference to the following specific examples, without limiting the scope of the invention thereto.
Example 1:
1) 0.64g of terephthalonitrile, 0.64g of 2, 6-pyridinedicarbonitrile, and 3.2g of conductive carbon black powder were sufficiently ground and mixed in a mortar to obtain a mixture A. 6.4g of anhydrous zinc chloride, the prepared mixture A and 6.4g of anhydrous zinc chloride are placed in the crucible from bottom to top in sequence (namely the mixture A is placed between two layers of anhydrous zinc chloride powder);
2) and (2) placing the crucible in the step 1) into a tubular furnace, and calcining at a high temperature under the protection of nitrogen, wherein the calcining temperature is 400 ℃, the calcining time is 40 hours, and the flow of nitrogen introduced into the tubular furnace is 50 mL/min. Respectively stirring and cleaning the calcined product by using 1 mol/L hydrochloric acid solution and deionized water for 12 hours, and drying the cleaned solid in vacuum at 60 ℃ for 12 hours to obtain covalent organic framework carrier powder (step 2 in example 1), wherein the covalent organic framework carrier powder is a material with a mesoporous pore structure and has a specific surface area of 110.4 m according to BET (surface area) test2(iv)/g, average pore diameter 10.9323 nm);
3) putting 50mg of the covalent organic framework carrier powder obtained in the step 2) and 20.8mg of ruthenium acetylacetonate into a mortar together, fully grinding until the materials are uniformly mixed, then carrying out high-temperature calcination in a tubular furnace under the protection of nitrogen, heating to 300 ℃ from room temperature at a rate of 3 ℃/min, calcining for 3 hours at the temperature of 300 ℃, washing the calcined product with ultrapure water, and drying to obtain the target catalyst, namely the covalent organic framework material catalyst based on the loaded Ru nanoparticles.
The result of observing the defective covalent triazine framework carrier material powder obtained in step 2) of example 1 by a projection electron microscope is shown in figure 1, and as can be seen from figure 1, the covalent organic framework material obtained in the example is in a two-dimensional fiber shape.
The covalent organic framework material catalyst based on supported Ru nanoparticles finally obtained in step 3) of example 1 was observed by projection electron microscopy, and the results are shown in fig. 2a and fig. 2 b. As can be seen from fig. 2a and 2b, some small metal Ru nanoparticles are uniformly dispersed on the catalyst, and the particle size of the small metal Ru nanoparticles is approximately in the range of 1 to 3 nm.
The electrocatalytic ammonia synthesis performance of the catalyst obtained in example 1 was tested as follows:
weighing 4.0 mg of covalent organic framework material catalyst based on the loaded Ru nanoparticles, adding the catalyst into 900 microliters of ethanol and 100 microliters of Nafion solution (the mass fraction of the Nafion solution is 5%), performing ultrasonic treatment for 0.5 hour, and obtaining uniform catalyst slurry after the catalyst is completely dispersed.
0.2 mL of the prepared catalyst slurry is transferred and uniformly coated on carbon paper of 1cm multiplied by 1cm, and the catalyst slurry is dried to be used as a working electrode, Ag/AgCl is used as a reference electrode, and a platinum wire electrode is used as a counter electrode. The linear voltammetry test adopts CHI760E electrochemical workstation of Shanghai Chenghua, and is carried out in an H-shaped electrolytic cell of a three-electrode system, the electrolyte is 0.1 mol/L KOH aqueous solution, and nitrogen is introduced for 0.5 hour before the test to ensure that the nitrogen in the electrolyte reaches a saturated state. The scanning rate is 10 mV s-1The voltage setting range of the Ag/AgCl used as a reference electrode is-1.0-0.2V, and the potential difference between the Ag/AgCl and the reversible hydrogen electrode RHE is 0.965V. The electrolysis reaction time was 7200 s, the reaction results were sampled and analyzed, the electrocatalytic reduction reaction of nitrogen to ammonia was performed under different voltage conditions, and the yield and the pull-up efficiency of ammonia synthesis under different voltage conditions in example 1 are shown in fig. 3 and 4, respectively.
The ammonia content test method comprises the following steps: firstly, drawing a standard working curve of ammonia concentration, preparing a series of ammonia water solutions with different concentrations, respectively transferring 2 mL of the prepared ammonia water solutions into a colorimetric tube, sequentially adding 2 mL of 5% sodium citrate-salicylic acid solution, 1 mL of 0.05 mol/L sodium hypochlorite solution and 0.2 mL of 1% sodium nitroprusside solution into the colorimetric tube, placing the colorimetric tube in a dark place for color development reaction after slight oscillation, taking out the colorimetric tube after 2 hours, scanning the curve in a spectrophotometer, reading the absorbance with the wavelength of 655 nm, and comparing the absorbance with deionized water as a blank to obtain the standard working curve with the corresponding relation between different ammonia concentrations and the absorbance.
After the electrolytic reaction under different voltages is finished, respectively transferring 2 mL of electrolyte into a colorimetric tube, sequentially adding 2 mL of 5% sodium citrate-salicylic acid solution, 1 mL of 0.05 mol/L sodium hypochlorite solution and 0.2 mL of 1% sodium nitroprusside solution into the colorimetric tube, slightly oscillating, placing the colorimetric tube in a dark place for color reaction, taking out the colorimetric tube after 2 hours, scanning a curve in a spectrophotometer, reading the absorbance with the wavelength of 655 nm, and bringing measured data into an ammonia standard working curve to obtain the ammonia content concentration.
In the method for testing the ammonia content, the preparation method of the test solution comprises the following steps:
preparation of 5% sodium citrate-salicylic acid: 10.2030g of sodium hydroxide is weighed into a 250ml beaker, a proper amount of pure water is added for dissolution, then 12.5000g of sodium citrate and 12.5000g of salicylic acid solid are respectively weighed and added into the solution, the solution is fully stirred for dissolution, and after the dissolution and the cooling to the room temperature, the solution is moved into a 25ml volumetric flask for constant volume by using pure water.
Preparation of 1% sodium nitroprusside solution: 1.0000g of sodium nitroferricyanide solid is taken to be placed in a 100ml beaker, a proper amount of pure water is added for dissolution, and the solution is moved to a 100ml volumetric flask for constant volume by using the pure water.
Example 2:
1) 0.64g of terephthalonitrile, 0.64g of 2, 6-pyridinedicarbonitrile, and 3.2g of conductive carbon black powder were sufficiently ground and mixed in a mortar to obtain a mixture A. 6.4g of anhydrous zinc chloride, the prepared mixture A and 6.4g of anhydrous zinc chloride are placed in the crucible from bottom to top in sequence (namely the mixture A is placed between two layers of anhydrous zinc chloride powder);
2) and (2) placing the crucible in the step 1) into a tubular furnace, and calcining at a high temperature under the protection of nitrogen, wherein the calcining temperature is 400 ℃, the calcining time is 40 hours, and the flow of nitrogen introduced into the tubular furnace is 50 mL/min. Respectively stirring and cleaning the calcined product by using 1 mol/L hydrochloric acid solution and deionized water for 12 hours, and vacuum-drying the cleaned solid for 12 hours at 60 ℃ to obtain covalent organic framework carrier powder;
3) taking 50mg of the covalent organic framework carrier powder obtained in the step 2) and 10.4mg of ruthenium acetylacetonate to be placed into a mortar together, fully grinding until the materials are uniformly mixed, then carrying out high-temperature calcination in a tube furnace under the protection of nitrogen, heating from room temperature to 300 ℃ at a speed of 3 ℃/min, calcining for 3 hours at the temperature of 300 ℃, washing a calcined product with ultrapure water, and drying to obtain a target catalyst, namely the covalent organic framework material catalyst based on the loaded Ru nano-particles.
The performance of the electrocatalytic ammonia synthesis of the catalyst obtained in example 2 was tested as follows:
weighing 4.0 mg of covalent organic framework material catalyst based on the loaded Ru nanoparticles, adding the covalent organic framework material catalyst into 900 microliters of ethanol and 100 microliters of Nafion solution (the mass fraction of the Nafion solution is 5%), carrying out ultrasonic treatment for 0.5 hour, and obtaining uniform catalyst slurry after the catalyst is completely dispersed.
0.2 mL of the prepared catalyst slurry is transferred and uniformly coated on carbon paper of 1cm multiplied by 1cm, and the catalyst slurry is dried to be used as a working electrode, Ag/AgCl as a reference electrode and a platinum wire electrode as a counter electrode. The linear voltammetry curve test adopts CHI760E electrochemical workstation of Shanghai Chenghua, and is carried out in an H-shaped electrolytic cell of a three-electrode system, the electrolyte is 0.1 mol/L KOH aqueous solution, and nitrogen is introduced for 0.5 hour before the test, so that the nitrogen in the electrolyte reaches a saturated state. The scanning rate is 10 mV s-1The voltage setting range of the Ag/AgCl used as a reference electrode is-1.0-0.2V, and the potential difference between the Ag/AgCl and the reversible hydrogen electrode RHE is 0.965V. The electrolytic reaction time was 7200 s, the reaction results were sampled and analyzed, the sampling interval was set to 1 s, the sensitivity was set to 0.1, the electrocatalytic reduction reaction of nitrogen to ammonia was performed under different voltage conditions, and the yield and the pull-up efficiency of ammonia synthesis under different voltage conditions in example 2 were shown in fig. 3 and 4, respectivelyAs shown. The ammonia content was measured as in example 1.
Example 3:
and (2) putting 50mg of conductive carbon black powder and 20.8mg of ruthenium acetylacetonate in a mortar, fully grinding until the conductive carbon black powder and the ruthenium acetylacetonate are uniformly mixed, then calcining at high temperature in a tubular furnace under the protection of nitrogen, heating to 300 ℃ from room temperature at a speed of 3 ℃/min, calcining for 3 hours at 300 ℃, washing a calcined product with ultrapure water, and drying to obtain the target catalyst.
The electrocatalytic ammonia synthesis performance of the catalyst obtained in example 3 was tested as follows:
weighing 4.0 mg of the catalyst of example 3, adding the catalyst into 900 microliter of ethanol and 100 microliter of Nafion solution (the mass fraction of the Nafion solution is 5%), and carrying out ultrasonic treatment for 0.5 hour until the catalyst is completely dispersed to obtain uniform catalyst slurry. 0.2 mL of the prepared catalyst slurry was transferred and uniformly coated on 1cm × 1cm carbon paper, dried, and used as a working electrode, Ag/AgCl (3 mol/L KCl) as a reference electrode, and a platinum wire electrode as a counter electrode. The linear voltammetry curve test adopts CHI760E electrochemical workstation of Shanghai Chenghua, and is carried out in an H-shaped electrolytic cell of a three-electrode system, the electrolyte is 0.1 mol/L KOH aqueous solution, and nitrogen is introduced for 0.5 hour before the test, so that the nitrogen in the electrolyte reaches a saturated state. The scanning rate is 10 mV s-1The voltage setting range of the Ag/AgCl used as a reference electrode is-1.0-0.2V, and the potential difference between the Ag/AgCl and the reversible hydrogen electrode RHE is 0.965V. The electrolysis reaction time was 7200 s, the reaction results were sampled and analyzed, the sampling interval was set to 1 s, the sensitivity was set to 0.1, the electrocatalytic reduction reaction for ammonia synthesis from nitrogen was performed under different voltage conditions, and the yield graph and the pull-up efficiency graph of the ammonia synthesis under different voltage conditions in example 3 are shown in fig. 3 and 4, respectively. The ammonia content was measured in the same manner as in example 1.
Example 4:
1) 2.00g of melamine and 3.2g of conductive carbon black powder were put in a mortar and sufficiently ground until they were uniformly mixed, and then put in a porcelain boat, followed by high-temperature calcination in a tube furnace under nitrogen protection,
calcining at 550 ℃ for 3h to finally obtain C3N4Powder;
2) subjecting C obtained in step 1) to3N4Putting 50mg of powder and 20.8mg of ruthenium acetylacetonate into a mortar together, fully grinding until the powder and the ruthenium acetylacetonate are uniformly mixed, then carrying out high-temperature calcination again in a tubular furnace under the protection of nitrogen, heating to 300 ℃ from room temperature at 3 ℃/min, calcining for 3 hours at 300 ℃, washing calcined products with ultrapure water, and drying to obtain the target catalyst.
The electrocatalytic ammonia synthesis performance of the catalyst obtained in example 4 was tested as follows:
weighing 4.0 mg of the catalyst of example 4, adding the catalyst into 900 microliter of ethanol and 100 microliter of Nafion solution (the mass fraction of the Nafion solution is 5%), and carrying out ultrasonic treatment for 0.5 hour until the catalyst is completely dispersed to obtain uniform catalyst slurry. 0.2 mL of the prepared catalyst slurry is transferred and uniformly coated on carbon paper of 1cm multiplied by 1cm, and the catalyst slurry is dried to be used as a working electrode, Ag/AgCl as a reference electrode and a platinum wire electrode as a counter electrode. The linear voltammetry test adopts CHI760E electrochemical workstation of Shanghai Chenghua, and is carried out in an H-shaped electrolytic cell of a three-electrode system, the electrolyte is 0.1 mol/L KOH aqueous solution, and nitrogen is introduced for 0.5 hour before the test to ensure that the nitrogen in the electrolyte reaches a saturated state. The scanning rate is 10 mV s-1The voltage setting range of the Ag/AgCl used as a reference electrode is-1.0-0.2V, and the potential difference between the Ag/AgCl and the reversible hydrogen electrode RHE is 0.965V. The electrolytic reaction time was 7200 s, the reaction results were sampled and analyzed, the sampling interval was set to 1 s, the sensitivity was set to 0.1, the reaction for synthesizing ammonia by electrocatalytic reduction of nitrogen was performed under different voltage conditions, and the yield graph and the pull-up efficiency graph of the synthetic ammonia under different voltage conditions in example 4 are shown in fig. 3 and 4, respectively. The ammonia content method was as in example 1.
Example 5:
the performance test method of the sample with Ru/C (5% loading Ru) as NRR reaction is as follows: weighing 4mg of Ru/C, adding the Ru/C into a 4mL centrifuge tube, adding 900 microliters of ethanol and 100 microliters of Nafion solution (the mass fraction of the Nafion solution is 5%), performing ultrasonic treatment for 0.5 hour, and completely dispersing the catalyst into the ethanol to obtain uniform catalyst slurry.
0.2 mL of the prepared catalyst slurry is transferred and uniformly coated on carbon paper of 1cm multiplied by 1cm, and the catalyst slurry is dried to be used as a working electrode, Ag/AgCl is used as a reference electrode, and a platinum wire electrode is used as a counter electrode. The linear voltammetry curve test adopts CHI760E electrochemical workstation of Shanghai Chenghua, and is carried out in an H-shaped electrolytic cell of a three-electrode system, the electrolyte is 0.1 mol/L KOH aqueous solution, and nitrogen is introduced for 0.5 hour before the test, so that the nitrogen in the electrolyte reaches a saturated state. The scanning rate is 10 mV s-1The voltage setting range of Ag/AgCl used as a reference electrode is-1.0-0.2V, and the potential difference between Ag/AgCl and the reversible hydrogen electrode RHE is 0.965V. The electrolysis reaction time was 7200 s, the reaction results were sampled and analyzed, the sampling interval was set to 1 s, the sensitivity was set to 0.1, the electrocatalytic reduction reaction for ammonia synthesis from nitrogen was performed under different voltage conditions, and the yield graph and the pull-up efficiency graph of the ammonia synthesis under different voltage conditions in example 5 are shown in fig. 3 and 4, respectively. The ammonia content was measured in the same manner as in example 1.
A comparison graph of the yields of ammonia synthesis from the electrocatalytic reduction of nitrogen for the catalysts of examples 1-5 under different voltage conditions is shown in FIG. 3. As can be seen from FIG. 3, the catalytic activity of the electrocatalytic reduction reaction of nitrogen to ammonia in examples 1-2 is significantly better than that in examples 3-5. The comparative faradaic efficiency of the electrocatalytic reduction nitrogen-ammonia synthesis reaction of the catalysts of examples 1-5 under different voltage conditions is shown in fig. 4. As can be seen from FIG. 4, the Faraday efficiencies of the electrocatalytic reduction reactions for ammonia synthesis from nitrogen in examples 1-2 are significantly better than those in examples 3-5.
It can be seen that the catalysts of examples 3-5 are significantly inferior to the catalyst of example 1 in the process of catalytic electrochemical reduction of nitrogen to ammonia. The difference between the catalysts of example 1 and example 3 is that example 1 adopts a covalent organic framework material doped with conductive carbon black as a carrier, while example 3 directly adopts conductive carbon black as a carrier, and performance tests show that the NRR performance of the catalyst prepared by using conductive carbon black as a carrier is not very good, so that comparison shows that the covalent organic framework carrier containing triazine rings and doped with conductive carbon black has good synergistic catalytic effect with active component Ru and good catalytic effect on ammonia production reaction by electrochemical reduction of nitrogen.
Example 1 and example 4 differ in that example 4 produces a catalyst C having a structure similar to the support of example 13N4Materials, but C from example 43N4The material does not contain a triazine ring structure. The triazine ring in the covalent organic framework material prepared in the embodiment 1 has a large number of unpaired electrons, so that the growth position and the particle size of the Ru nanoparticles can be limited, the electronic structure between Ru and the carrier can be regulated and controlled, and the performance of the catalyst in the NRR reaction can be influenced, the target catalyst prepared in the embodiment 1 has an imperfect shape (compare fig. 1, fig. 2a and fig. 2 b), and triazine rings at different positions can be formed, and the imperfect shape has positive influence on the performance of the catalyst.
Example 5 adopts a commercial Ru/C catalyst commonly used in the prior art, and as can be seen from fig. 3 and 4, the catalytic performance of the covalent organic framework material catalyst based on the supported Ru nanoparticles prepared by the invention is better than that of the commercial Ru/C catalyst when the covalent organic framework material catalyst is applied to the reaction of preparing ammonia by electrochemically reducing nitrogen.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (7)
1. The application of the covalent organic framework material catalyst based on the loaded Ru nanoparticles in the preparation of ammonia by catalytic electrochemical reduction of nitrogen is characterized in that the preparation method of the covalent organic framework material catalyst based on the loaded Ru nanoparticles comprises the following steps:
1) fully mixing a benzene derivative, a pyridine derivative and a conductive carbon material to obtain a mixture A; sequentially placing three layers of powder in a crucible from bottom to top, wherein the first layer of powder and the third layer of powder are both non-noble metal salts, and the second layer of powder is the prepared mixture A;
2) placing the crucible in a tubular furnace, calcining at high temperature under the nitrogen protection atmosphere, stirring and cleaning the calcined product with hydrochloric acid solution and deionized water in sequence, and drying the cleaned solid in vacuum at 40-100 ℃ to obtain covalent organic framework carrier powder;
3) putting the covalent organic framework carrier powder obtained in the step 2) and ruthenium metal salt into a mortar together, fully grinding until the covalent organic framework carrier powder and the ruthenium metal salt are uniformly mixed, then putting the mixture into a tubular furnace, carrying out high-temperature calcination again under the nitrogen protection atmosphere, washing the calcined product with ultrapure water, and drying to obtain the covalent organic framework material catalyst based on the loaded Ru nanoparticles;
in the step 1), the mass ratio of the benzene derivative, the pyridine derivative and the conductive carbon material is 1: 0.5-1.5: 3-7, and the mass ratio of the total mass of two layers of non-noble metal salts in the crucible to the mass of the mixture A is 2-3.5: 1;
in the step 3), the mass ratio of the covalent organic framework carrier powder to the ruthenium metal salt is 5: 0.8-2.5.
2. The use of the Ru nanoparticle-supported covalent organic framework catalyst for the catalytic electrochemical reduction of nitrogen to ammonia according to claim 1, wherein in step 1), the benzene derivative is terephthalonitrile, benzonitrile or isophthalonitrile; the pyridine derivative is 2, 6-pyridinedicarbonitrile, diphenylpyridine or 3-methylpyridine, and the non-noble metal salt is anhydrous zinc chloride, anhydrous sodium chloride, anhydrous potassium chloride or anhydrous aluminum chloride.
3. The application of the covalent organic framework material catalyst based on the Ru-supported nanoparticles in ammonia production through catalytic electrochemical reduction of nitrogen according to claim 1, wherein in the step 1), the benzene derivative, the pyridine derivative and the conductive carbon material are taken in a mass ratio of 1: 1: 5; the ratio of the total mass of the two layers of non-noble metal salts in the crucible to the mass of the mixture A was 2.8: 1.
4. The application of the covalent organic framework material catalyst based on the supported Ru nanoparticles in ammonia preparation by catalytic electrochemical reduction of nitrogen in the claim 1, wherein in the step 2), the high-temperature calcination temperature is 300-500 ℃, and the high-temperature calcination time is 30-50 h; the concentration of the hydrochloric acid solution is 0.8-1.2 mol/L.
5. The use of the Ru nanoparticle-supported covalent organic framework material catalyst in the catalytic electrochemical reduction of nitrogen to ammonia according to claim 1, wherein in step 3), the ruthenium metal salt is ruthenium acetylacetonate, ruthenium chloride trihydrate, ruthenium nitrosyl nitrate, or triruthenium dodecacarbonyl.
6. The application of the covalent organic framework material catalyst based on the Ru-supported nanoparticles in ammonia production through catalytic electrochemical reduction of nitrogen in claim 1 is characterized in that in the step 3), the high-temperature calcination temperature is 250-350 ℃, and the high-temperature calcination time is 2-4 h.
7. The application of the covalent organic framework material catalyst based on the supported Ru nanoparticles to ammonia production through catalytic electrochemical reduction of nitrogen, which is disclosed by claim 1, is characterized in that a two-electrode system testing device is adopted, a platinum wire is used as a counter electrode, the covalent organic framework material catalyst based on the supported Ru nanoparticles is coated on carbon paper to be used as a working electrode, and an inorganic alkaline aqueous solution is used as an electrolyte, so that the reaction of ammonia production through electrocatalytic reduction of nitrogen is carried out.
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