CN110227513B - Carbon-based supported metal phosphide catalyst and preparation method and application thereof - Google Patents
Carbon-based supported metal phosphide catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 62
- 239000002184 metal Substances 0.000 title claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 21
- 239000011574 phosphorus Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 229920005610 lignin Polymers 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 150000002989 phenols Chemical class 0.000 claims abstract description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005416 organic matter Substances 0.000 claims abstract description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 3
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 61
- 239000002243 precursor Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- 229960001867 guaiacol Drugs 0.000 claims description 29
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 239000004744 fabric Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 229920000557 Nafion® Polymers 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical group OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 5
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 5
- 238000005341 cation exchange Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000000467 phytic acid Substances 0.000 claims description 5
- 235000002949 phytic acid Nutrition 0.000 claims description 5
- 229940068041 phytic acid Drugs 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002503 iridium Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- 150000003303 ruthenium Chemical class 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 235000013824 polyphenols Nutrition 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000012298 atmosphere Substances 0.000 abstract description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- 239000000843 powder Substances 0.000 description 14
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 8
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- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 239000002029 lignocellulosic biomass Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JMFRWRFFLBVWSI-NSCUHMNNSA-N coniferol Chemical compound COC1=CC(\C=C\CO)=CC=C1O JMFRWRFFLBVWSI-NSCUHMNNSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- LZFOPEXOUVTGJS-ONEGZZNKSA-N trans-sinapyl alcohol Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O LZFOPEXOUVTGJS-ONEGZZNKSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- LZFOPEXOUVTGJS-UHFFFAOYSA-N cis-sinapyl alcohol Natural products COC1=CC(C=CCO)=CC(OC)=C1O LZFOPEXOUVTGJS-UHFFFAOYSA-N 0.000 description 1
- 229940119526 coniferyl alcohol Drugs 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical group N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- B01J35/33—
-
- 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
-
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Abstract
The invention discloses a carbon-based supported metal phosphide catalyst, a preparation method and application thereof, wherein the preparation process of the carbon-based supported metal phosphide catalyst comprises the following steps: after uniformly mixing the noble metal salt, deionized water and a phosphorus source, adding a nitrogen-containing organic matter, uniformly stirring, transferring the obtained solution into a polytetrafluoroethylene tank, carrying out hydrothermal reaction at 120-180 ℃ for 10-24 hours, cooling to room temperature after the reaction is finished, filtering the reaction solution, drying filter residues, placing the dried filter residues in a tubular furnace, heating to 700-900 ℃ from room temperature at the speed of 3-8 ℃/min under the atmosphere of nitrogen, keeping the temperature at the constant temperature for 1-4 hours, then naturally cooling to room temperature, respectively washing the calcined product with deionized water and absolute ethyl alcohol for 3-5 times, carrying out suction filtration, and drying the filter residues to obtain the carbon-based supported metal phosphide catalyst. The carbon-based supported metal phosphide catalyst prepared by the invention has lower cost, and has higher catalytic activity and stability when being used for the reaction of electrocatalytic hydrogenation of lignin phenolic compounds.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a carbon-based supported metal phosphide catalyst, and a preparation method and application thereof.
Background
With the continuous consumption of fossil energy, the global energy crisis is gradually increased. In order to solve the problem of increasingly serious energy shortage, people begin to search for new energy sources which can replace fossil energy. Lignocellulosic biomass has received increasing attention as the only renewable carbon energy source.
Lignocellulosic biomass is composed of carbohydrates (cellulose and hemicellulose), lignin, and other components such as proteins, inorganic substances, and the like. According to the concept of biorefinery, the final processing of lignocellulosic biomass is targeted to two of: (1) the ability to fractionate out the three major products and to produce bio-based products with the greatest added value through further conversion; (2) can produce biofuel, and the residue is a byproduct.
Lignin is the second most important component of lignocellulosic biomass after cellulose has been added. Lignin consists of three different precursors: coumaryl alcohol, coniferyl alcohol and sinapyl alcohol. Guaiacol structures can be found in cork materials and are obtained by the decomposition of phenylpropane structural units polymerized from coniferyl ester. Guaiacol, also known as o-hydroxyanisole, o-methoxyphenol, 2-methoxyphenol, is one of the main components of the fast pyrolysis product of lignocellulose, and is also a model compound of a lignin derivative monomer. Guaiacol is reduced to produce a wide variety of compounds, complete hydrodeoxygenation to cyclohexane and partial hydrodeoxygenation to oxygenates: phenol, methyl ether, cyclohexanol, and the like.
Noble metal Pt has better electrocatalytic guaiacol hydrogenation performance, and researches on Pt for guaiacol hydrogenation are carried out by a plurality of groups at present (Nanomaterials, 2019, 9 and 362; Molecular Catalysis, 2019, 467, 61-69; Fuel, 2019, 239, 1083-. But the rare reserves and high price of the noble metal Pt limit its widespread use. Moreover, pure Pt has poor stability, and the reactivity after reaction for over ten hours is greatly reduced.
Disclosure of Invention
The carbon-based supported metal phosphide catalyst prepared by the invention has lower cost, and has higher catalytic activity and stability when being used for the electrocatalytic hydrogenation reaction of lignin phenolic compounds.
The traditional catalyst Pt/C has the defects of rare metal Pt reserves and high price, so that the wide application of the traditional catalyst in the field of electrocatalytic hydrogenation is limited. In addition, in the catalytic reaction process of the catalyst Pt/C, Pt atoms are easy to agglomerate and fall off, so that the active sites of the electrocatalytic hydrogenation reaction are reduced, and the stability of the catalyst is poor. The invention introduces non-metal phosphorus element on the basis of noble metal. The combination of the metal powder and the noble metal can reduce the agglomeration phenomenon of the noble metal and improve the stability of the noble metal; non-metallic nitrogen is introduced into the carrier, so that the electronic structure of the carrier and the action between the carrier and an active site are changed, and the electrocatalytic hydrogenation capability is improved.
The preparation method of the carbon-based supported metal phosphide catalyst is characterized by comprising the following steps of:
1) adding noble metal salt, deionized water and a phosphorus source into a beaker, and stirring for 30-60 minutes to form a uniform solution;
2) adding a nitrogen-containing organic matter into the solution obtained in the step 1), and continuously stirring and dispersing for 30-120 minutes to uniformly disperse the nitrogen-containing organic matter in the solution to obtain a precursor solution;
3) transferring the precursor solution obtained in the step 2) into a polytetrafluoroethylene tank, carrying out hydrothermal reaction at the temperature of 120-180 ℃ for 10-24 hours, cooling to room temperature after the reaction is finished, filtering the reaction solution, and carrying out vacuum drying on the solid obtained by filtering at the temperature of 60-100 ℃ for 20-25 hours to obtain a metal phosphide precursor;
4) placing the metal phosphide precursor obtained in the step 3) into a tube furnace, heating the metal phosphide precursor to 700-900 ℃ from room temperature at the speed of 3-8 ℃/min under the nitrogen atmosphere, then keeping the temperature for 1-4 hours at constant temperature, and naturally cooling the metal phosphide precursor to room temperature to obtain a carbon-based loaded metal phosphide solid;
5) and 4) washing the carbon-based supported metal phosphide solid obtained in the step 4) with deionized water and absolute ethyl alcohol for 3-5 times respectively, performing suction filtration, placing filter residues in a vacuum drying oven, and drying at the temperature of 60-80 ℃ for 20-25 hours to obtain the carbon-based supported metal phosphide catalyst.
The preparation method of the carbon-based supported metal phosphide catalyst is characterized in that in the step 1), the noble metal salt is rhodium salt, iridium salt, palladium salt or ruthenium salt; the phosphorus source is phytic acid, phosphoric acid or phosphate, and the phosphate is sodium phosphate or sodium dihydrogen phosphate; in the step 2), the nitrogen-containing organic matter is melamine, urea or cyanamide.
The preparation method of the carbon-based supported metal phosphide catalyst is characterized in that the phosphorus source is phytic acid or phosphoric acid, the ratio of the mass of the noble metal salt to the volume of the phosphorus source is 5-10: 1, the unit of the mass is mg, and the unit of the volume is mL.
The preparation method of the carbon-based supported metal phosphide catalyst is characterized in that the phosphorus source is phosphate, and the mass ratio of the noble metal salt to the phosphorus source is 0.01-0.03: 1, preferably 0.01-0.015: 1.
The preparation method of the carbon-based supported metal phosphide catalyst is characterized in that the mass ratio of the noble metal salt to the nitrogen-containing organic matter is 0.01-0.1: 1, preferably 0.01-0.05: 1.
The preparation method of the carbon-based supported metal phosphide catalyst is characterized in that in the step 1), the ratio of the mass of the noble metal salt to the volume of the deionized water is 0.5-3: 1, preferably 1-2: 1, the unit of the mass is mg, and the unit of the volume is mL.
A carbon-based supported metal phosphide catalyst prepared according to the above-mentioned method.
The carbon-based supported metal phosphide catalyst is applied to the electrocatalytic hydrogenation reaction of lignin phenolic compounds.
The application of the carbon-based supported metal phosphide catalyst in the electrocatalytic hydrogenation reaction of the lignin phenolic compound is characterized by comprising the following steps:
s1: mixing the carbon-based supported metal phosphide catalyst with an ethanol solution of Nafion, performing ultrasonic dispersion, dripping the obtained dispersion liquid on carbon cloth, and drying to prepare a carbon cloth electrode;
s2: an H-shaped electrolytic tank is taken as a reaction container, and a cathode chamber and an anode chamber are separated by a cation exchange membrane; in the anode chamber, a platinum sheet is used as a counter electrode, and 0.1-2.0 mol/L acid solution is used as anolyte; and in the cathode chamber, taking the carbon cloth electrode obtained in the step S1 as a working electrode, taking a lignin phenolic compound as a reaction substrate, dissolving the lignin phenolic compound in 0.1-2.0 mol/L acid solution as catholyte, and carrying out electrocatalytic hydrogenation reaction on the catholyte under the stirring of 500-1000r/min to prepare the KA oil, wherein the reaction current is 10-30mA, the reaction voltage is 3-6V, the reaction temperature is 40-80 ℃, and the reaction time is 0.5-2 hours.
The application of the carbon-based supported metal phosphide catalyst in the electrocatalytic hydrogenation reaction of the lignin phenolic compound is characterized in that the acidic solution is an aqueous solution of sulfuric acid, nitric acid, hydrochloric acid, perchloric acid or phosphoric acid, preferably an aqueous solution of perchloric acid; the lignin phenolic compound is guaiacol.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
1) the novel carbon-based supported metal phosphide catalyst is synthesized by a simple and low-cost method, and the dosage of metal is reduced by doping phosphorus, so that the preparation cost of the catalyst is reduced; the metal phosphide is loaded on the carbon nitride structure, so that the using amount of the metal phosphide is reduced, and the cost is further reduced; the doping of the phosphorus element improves the reaction activity to a certain extent and improves the stability of the catalyst; the preparation method is simple, low in cost and easy to regulate and control; provides basic application research for the material in the field of electrocatalysis, and has wide application prospect.
2) In the preparation process of the catalyst, the noble metal salt and the phosphorus source are uniformly dissolved in deionized water, the noble metal salt and the phosphorus source are combined to form a metal phosphide precursor, then a nitrogen-containing organic matter is added to carry out hydrothermal reaction, a solid product obtained after the reaction is roasted, the nitrogen-containing organic matter is decomposed to form a nitrogen-doped carbon carrier material, and the metal phosphide precursor is converted into metal phosphide and loaded on the nitrogen-doped carbon carrier material. Because nitrogen has stronger electron withdrawing property than carbon, the catalyst prepared by the nitrogen-doped carbon carrier material can weaken the adsorption effect of active center metal phosphide of the catalyst on a reaction product of electrocatalytic hydrogenation when the catalyst is applied to the electrocatalytic hydrogenation reaction of a lignin phenol compound, is favorable for desorption of the reaction product under the condition of not influencing the adsorption effect of the active center of the catalyst on a reaction raw material, improves the efficiency of the electrocatalytic reaction and improves the selectivity of the reaction product.
3) In the catalyst prepared by the invention, the active component of the catalyst is metal phosphide, and after the phosphorus element and the metal element act, the metal can be effectively prevented from polymerizing in the electrocatalytic hydrogenation reaction, so that the metal keeps higher dispersion degree on a nitrogen-doped carbon carrier material, and the stability of the catalyst is improved.
Drawings
FIG. 1a is RhP obtained in example 12The transmission electron microscope observation picture of the @ NC catalyst at 0.2 μm;
FIG. 1b shows RhP obtained in example 12Observation of the @ NC catalyst by transmission electron microscope at 20 nm;
FIG. 2a shows the IrP obtained in example 22The observation picture of the @ NC catalyst under a transmission electron microscope at 0.5 μm;
FIG. 2b shows the IrP obtained in example 22Observation of the @ NC catalyst by transmission electron microscopy at 50 nm;
FIG. 3a is Pd obtained in example 35P2The observation picture of the @ NC catalyst under a transmission electron microscope at 0.5 μm;
FIG. 3b is Pd obtained in example 35P2Observation of the @ NC catalyst by a transmission electron microscope at 100 nm;
FIG. 4 shows RhP obtained in example 12A reaction result diagram of the @ NC catalyst used for preparing the KA oil by the electrocatalytic hydrogenation of the guaiacol;
FIG. 5 shows IrP obtained in example 22A reaction result diagram of the @ NC catalyst used for preparing the KA oil by the electrocatalytic hydrogenation of the guaiacol;
FIG. 6 shows Pd obtained in example 35P2A reaction result diagram of the @ NC catalyst used for preparing the KA oil by the electrocatalytic hydrogenation of the guaiacol;
FIG. 7 shows RhP obtained in example 12And the reaction result chart of preparing the KA oil by electrocatalytic hydrogenation of the guaiacol when the @ NC catalyst is repeatedly used for 20 times.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1: RhP2Synthesis of @ NC
1) Adding 50mg of rhodium nitrate and 50mL of deionized water into a 250mL beaker, stirring for dissolving, dropwise adding 5mL of phosphoric acid while continuously stirring, and stirring for 40 minutes to form a uniform aqueous solution;
2) adding 1g of cyanamide into the aqueous solution obtained in the step 1), and stirring for 75 minutes to uniformly disperse the cyanamide in the aqueous solution to obtain a precursor solution;
3) putting the precursor solution obtained in the step 2) into a polytetrafluoroethylene tank, carrying out hydrothermal reaction at the temperature of 150 ℃ for 20 hours, cooling to room temperature after the reaction, filtering the reaction liquid, and carrying out vacuum drying on the solid obtained by filtering at the temperature of 80 ℃ for 20 hours to obtain a rhodium phosphide precursor;
4) grinding the rhodium phosphide precursor obtained in the step 3) into powder, weighing 1g of rhodium phosphide precursor powder, transferring the powder into a tubular furnace, introducing nitrogen for 60 minutes, exhausting the air in the tubular furnace, heating to 900 ℃ at a speed of 5 ℃/min under the atmosphere of nitrogen, keeping the temperature at 900 ℃ for 2 hours, and then naturally cooling to room temperature to obtain RhP2@ NC solid;
5) RhP obtained in the step 4)2Washing the @ NC solid with water and absolute ethyl alcohol for 4 times respectively, filtering, placing the obtained filter residue in a vacuum drying oven, drying at 60 ℃ for 24 hours to obtain the carbon-based supported metal phosphide catalyst (marked as RhP)2@ NC catalyst). RhP obtained in example 12The transmission electron microscope observation patterns of the @ NC catalyst at 0.2 μm and 20nm are shown in FIGS. 1a and 1b, and from FIGS. 1a and 1b we can see that the metal is relatively uniformly distributed on the support. The P is combined with the metal Ru, so that the agglomeration among metal particles can be effectively prevented, and the stability is better.
RhP prepared in example 12The catalytic performance of the @ NC catalyst is tested by the following specific method:
mixing 8mg of RhP2Catalyst powder of @ NCMixing the powder with 0.9mL of anhydrous ethanol and 0.1mL of Nafion solution (the mass concentration of the Nafion solution is 5%), ultrasonically dispersing the mixture uniformly, and dripping the dispersion liquid uniformly on a 2X 2cm2And drying the carbon cloth with the same size to obtain the carbon cloth electrode.
An H-shaped electrolytic tank is taken as a reaction container, and a cathode chamber and an anode chamber are separated by a cation exchange membrane; in the anode chamber, a platinum sheet is used as a counter electrode, and 0.2mol/L perchloric acid aqueous solution is used as anolyte; in the cathode chamber, the carbon cloth electrode prepared above is used as a working electrode, guaiacol is used as a reaction substrate and dissolved in 0.2mol/L perchloric acid aqueous solution to be used as catholyte (the concentration of guaiacol in the catholyte is controlled at 10 mmol/L), the reaction of preparing KA oil through guaiacol electrocatalytic hydrogenation is carried out under the stirring of the catholyte for 600r/min (the stirring is carried out for eliminating the influence of external diffusion), the whole electrolytic tank is placed in a constant-temperature water bath to control the temperature of the reaction system to be 60 ℃, the reaction current to be 20mA, the voltage is kept between 3V and 6V, and the reaction time is 2 h. The reaction liquid is sampled and analyzed in the reaction process, the reaction result is shown in fig. 4, and it can be seen from fig. 4 that the guaiacol is basically completely converted when the reaction lasts for more than 60 minutes, and the main product is KA oil (the KA oil is composed of cyclohexanol and cyclohexanone). Firstly, guaiacol is hydrogenated into cyclohexanone, and then the cyclohexanone is further hydrogenated to generate cyclohexanol. After 2 hours of reaction, the conversion rate of guaiacol is 100%, and the selectivity of KA oil is 96.7% (in the reaction product, the sum of the selectivities of cyclohexanol and cyclohexanone is the selectivity of KA oil).
To verify RhP prepared in example 12The catalytic stability of the @ NC catalyst, the electrocatalytic hydrogenation reaction experiment was repeated on the catalyst after 1 reaction (total reaction time 2 hours), and the reaction results after 20 catalytic reactions (total reaction time 40 hours) are shown in FIG. 7. As can be seen from fig. 7, in the 20 th experiment of the catalyst recycling reaction, when the reaction time is about 100 minutes, the guaiacol is almost completely converted, and the main product is KA oil. After reacting for 2 hours, the conversion rate of guaiacol is 100 percent, and the selectivity of KA oil is 96.0 percent. The catalytic effect was not significantly reduced compared to the results of the 1 st reaction of the catalyst.
Example 2: IrP2Synthesis of @ NC
1) Adding 100mg of iridium tetrachloride and 50mL of deionized water into a 250mL beaker, stirring for dissolving, dropwise adding 10mL of phytic acid with 50% volume concentration while continuously stirring, and stirring for 30 minutes to form a uniform aqueous solution;
2) adding 2g of melamine into the aqueous solution obtained in the step 1), and stirring for 60 minutes to enable the melamine to be uniformly dispersed in the aqueous solution to obtain a precursor solution;
3) putting the precursor solution obtained in the step 2) into a polytetrafluoroethylene tank, carrying out hydrothermal reaction at 120 ℃ for 24 hours, cooling to room temperature after the reaction, filtering the reaction liquid, and carrying out vacuum drying on the solid obtained by filtering at 60 ℃ for 25 hours to obtain an iridium phosphide precursor;
4) grinding the iridium phosphide precursor obtained in the step 3) into powder, weighing 1g of iridium phosphide precursor powder, transferring the iridium phosphide precursor powder into a tubular furnace, introducing nitrogen for 50 minutes, exhausting the air in the tubular furnace, heating to 800 ℃ at a speed of 5 ℃/min under the atmosphere of nitrogen, keeping the temperature at 800 ℃ for 2.5 hours, and then naturally cooling to room temperature to obtain IrP2@ NC solid;
5) IrP obtained in the step 4)2Washing the @ NC solid with water and anhydrous ethanol for 4 times respectively, filtering, placing the obtained filter residue in a vacuum drying oven, and drying at 80 deg.C for 20 hr to obtain carbon-based supported metal phosphide catalyst (labeled as IrP)2@ NC catalyst). IrP obtained in example 22The transmission electron microscope observation diagrams of the @ NC catalyst at 0.5 μm and 50nm are shown in FIG. 2a and FIG. 2b, respectively, and it can be seen from FIG. 2a and FIG. 2b that the metal particles of uniform size are relatively uniformly distributed on the carrier. The P is combined with the metal Ir, so that the agglomeration among metal particles can be effectively prevented, and the stability is better.
IrP prepared in example 22The catalytic performance of the @ NC catalyst is tested by the following specific method:
mixing 8mg of IrP2Mixing the @ NC catalyst powder, 0.9mL of absolute ethyl alcohol and 0.1mL of Nafion solution (the mass concentration of the Nafion solution is 5 percent), uniformly dispersing by ultrasonic waves, and uniformly dispersing the dispersion liquidUniformly dripping at 2 × 2cm2And drying the carbon cloth with the same size to obtain the carbon cloth electrode.
An H-shaped electrolytic tank is taken as a reaction container, and a cathode chamber and an anode chamber are separated by a cation exchange membrane; in the anode chamber, a platinum sheet is used as a counter electrode, and 0.2mol/L perchloric acid aqueous solution is used as anolyte; in the cathode chamber, the carbon cloth electrode prepared above was used as a working electrode, guaiacol as a reaction substrate was dissolved in a 0.2mol/L aqueous solution of perchloric acid as a catholyte (the concentration of guaiacol in the catholyte was controlled at 10 mmol/L), the catholyte was stirred at 600r/min (stirring was performed to eliminate the effect of external diffusion), the whole electrolytic cell was placed in a thermostatic water bath to control the temperature of the reaction system at 60 ℃, the reaction current at 20mA, the voltage was maintained between 3 and 6V, and the reaction time was 2 hours. The reaction liquid is sampled and analyzed in the reaction process, the reaction result is shown in fig. 5, and it can be seen from fig. 5 that guaiacol is almost completely converted when the reaction lasts for 2 hours, and the main product is KA oil (the KA oil is composed of cyclohexanol and cyclohexanone). Firstly, guaiacol is hydrogenated into cyclohexanone, and then the cyclohexanone is further hydrogenated to generate cyclohexanol. After 2 hours of reaction, the conversion rate of guaiacol is 100%, and the selectivity of KA oil is 96.0% (in the reaction product, the sum of the selectivities of cyclohexanol and cyclohexanone is the selectivity of KA oil).
Example 3: pd5P2Synthesis of @ NC
1) Adding 75mg of palladium chloride and 70 mL of deionized water into a 250mL beaker, stirring for dissolving, dropwise adding 5g of sodium dihydrogen phosphate while continuously stirring, and stirring for 45 minutes to form a uniform aqueous solution;
2) adding 3g of urea into the aqueous solution obtained in the step 1), and stirring for 100 minutes to enable the urea to be uniformly dispersed in the aqueous solution to obtain a precursor solution;
3) putting the precursor solution obtained in the step 2) into a polytetrafluoroethylene tank, carrying out hydrothermal reaction at 180 ℃ for 10 hours, cooling to room temperature after the reaction, filtering the reaction solution, and carrying out vacuum drying on the solid obtained by filtering at 100 ℃ for 20 hours to obtain a palladium phosphide precursor;
4) grinding the palladium phosphide precursor obtained in the step 3) into powder,weighing 1g of palladium phosphide precursor powder, transferring the palladium phosphide precursor powder into a tubular furnace, introducing nitrogen for 30 minutes, exhausting air in the tubular furnace, heating to 700 ℃ at a speed of 5 ℃/min in the nitrogen atmosphere, keeping the temperature at 700 ℃ for 3 hours, and naturally cooling to room temperature to obtain Pd5P2@ NC solid;
5) pd obtained in the step 4)5P2Washing the @ NC solid with water and absolute ethyl alcohol for 3 times respectively, filtering, placing the obtained filter residue in a vacuum drying oven, and drying at 80 ℃ for 20 hours to obtain the carbon-based supported metal phosphide catalyst (marked as Pd)5P2@ NC catalyst). Pd obtained in example 35P2The observation views of 0.5 μm and 100nm for the transmission electron microscope of @ NC are shown in FIGS. 3a and 3b, respectively, and it can be seen from FIGS. 3a and 3b that the metal particles of uniform size are distributed relatively uniformly on the support. The P is combined with the metal Pd, so that the agglomeration among metal particles can be effectively prevented, and the stability is better.
Pd prepared in example 35P2The catalytic performance of the @ NC catalyst is tested by the following specific method:
mixing 8mg of Pd5P2Mixing @ NC catalyst powder, 0.9mL of absolute ethanol and 0.1mL of Nafion solution (the mass concentration of the Nafion solution is 5%), ultrasonically dispersing uniformly, and dripping the dispersion liquid on 2 x 2cm2And drying the carbon cloth with the same size to obtain the carbon cloth electrode.
An H-shaped electrolytic tank is taken as a reaction container, and a cathode chamber and an anode chamber are separated by a cation exchange membrane; in the anode chamber, a platinum sheet is used as a counter electrode, and 0.2mol/L perchloric acid aqueous solution is used as anolyte; in the cathode chamber, the carbon cloth electrode prepared above was used as a working electrode, guaiacol as a reaction substrate was dissolved in a 0.2mol/L aqueous solution of perchloric acid as a catholyte (the concentration of guaiacol in the catholyte was controlled at 10 mmol/L), the catholyte was stirred at 600r/min (stirring was performed to eliminate the effect of external diffusion), the whole electrolytic cell was placed in a thermostatic water bath to control the reaction system temperature at 40 ℃, the reaction current at 20mA, the voltage was maintained between 3 and 6V, and the reaction time was 2 hours. The reaction liquid is sampled and analyzed in the reaction process, the reaction result is shown in fig. 6, and it can be seen from fig. 6 that guaiacol is basically converted up to 110 minutes of reaction, and the main product is KA oil (the KA oil is composed of cyclohexanol and cyclohexanone). Firstly, guaiacol is hydrogenated into cyclohexanone, and then the cyclohexanone is further hydrogenated to generate cyclohexanol. After 2 hours of reaction, the conversion rate of guaiacol is 100%, and the selectivity of KA oil is 97.7% (in the reaction product, the sum of the selectivities of cyclohexanol and cyclohexanone is the selectivity of KA oil).
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 (14)
1. A preparation method of a carbon-based supported metal phosphide catalyst is characterized by comprising the following steps:
1) adding noble metal salt, deionized water and a phosphorus source into a beaker, and stirring for 30-60 minutes to form a uniform solution;
2) adding a nitrogen-containing organic matter into the solution obtained in the step 1), and continuously stirring and dispersing for 30-120 minutes to uniformly disperse the nitrogen-containing organic matter in the solution to obtain a precursor solution;
3) transferring the precursor solution obtained in the step 2) into a polytetrafluoroethylene tank, carrying out hydrothermal reaction at the temperature of 120-180 ℃ for 10-24 hours, cooling to room temperature after the reaction is finished, filtering the reaction solution, and carrying out vacuum drying on the solid obtained by filtering at the temperature of 60-100 ℃ for 20-25 hours to obtain a metal phosphide precursor;
4) placing the metal phosphide precursor obtained in the step 3) into a tube furnace, heating the metal phosphide precursor to 700-900 ℃ from room temperature at the speed of 3-8 ℃/min under the nitrogen atmosphere, then keeping the temperature for 1-4 hours at constant temperature, and naturally cooling the metal phosphide precursor to room temperature to obtain a carbon-based loaded metal phosphide solid;
5) and 4) washing the carbon-based supported metal phosphide solid obtained in the step 4) with deionized water and absolute ethyl alcohol for 3-5 times respectively, performing suction filtration, placing filter residues in a vacuum drying oven, and drying at the temperature of 60-80 ℃ for 20-25 hours to obtain the carbon-based supported metal phosphide catalyst.
2. The method for preparing the carbon-based supported metal phosphide catalyst according to claim 1, wherein in the step 1), the noble metal salt is rhodium salt, iridium salt, palladium salt or ruthenium salt; the phosphorus source is phytic acid, phosphoric acid or phosphate, and the phosphate is sodium phosphate or sodium dihydrogen phosphate; in the step 2), the nitrogen-containing organic matter is melamine, urea or cyanamide.
3. The method for preparing the carbon-based supported metal phosphide catalyst according to claim 2, wherein the phosphorus source is phytic acid or phosphoric acid, the ratio of the mass of the noble metal salt to the volume of the phosphorus source is 5-10: 1, the unit of mass is mg, and the unit of volume is mL.
4. The method for preparing the carbon-based supported metal phosphide catalyst according to claim 2, wherein the phosphorus source is phosphate, and the mass ratio of the noble metal salt to the phosphorus source is 0.01-0.03: 1.
5. The method for preparing the carbon-based supported metal phosphide catalyst according to claim 4, wherein the phosphorus source is phosphate, and the mass ratio of the noble metal salt to the phosphorus source is 0.01-0.015: 1.
6. The method of claim 2, wherein the mass ratio of the noble metal salt to the nitrogen-containing organic compound is 0.01-0.1: 1.
7. The method of claim 6, wherein the mass ratio of the noble metal salt to the nitrogen-containing organic compound is 0.01-0.05: 1.
8. The method of claim 2, wherein in step 1), the ratio of the mass of the noble metal salt to the volume of the deionized water is 0.5-3: 1, the unit of the mass is mg, and the unit of the volume is mL.
9. The method of claim 8, wherein in step 1), the ratio of the mass of the noble metal salt to the volume of the deionized water is 1-2: 1, the unit of the mass is mg, and the unit of the volume is mL.
10. A carbon-based supported metal phosphide catalyst prepared by the method of any one of claims 1 to 9.
11. The use of the carbon-based supported metal phosphide catalyst according to claim 10 in electrocatalytic hydrogenation of lignin phenolics.
12. Use according to claim 11, characterized in that it comprises the following steps:
s1: mixing the carbon-based supported metal phosphide catalyst with an ethanol solution of Nafion, performing ultrasonic dispersion, dripping the obtained dispersion liquid on carbon cloth, and drying to prepare a carbon cloth electrode;
s2: an H-shaped electrolytic tank is taken as a reaction container, and a cathode chamber and an anode chamber are separated by a cation exchange membrane; in the anode chamber, a platinum sheet is used as a counter electrode, and 0.1-2.0 mol/L acid solution is used as anolyte; and in the cathode chamber, taking the carbon cloth electrode obtained in the step S1 as a working electrode, taking a lignin phenolic compound as a reaction substrate, dissolving the lignin phenolic compound in 0.1-2.0 mol/L acid solution as catholyte, and carrying out electrocatalytic hydrogenation reaction on the catholyte under the stirring of 500-1000r/min to prepare the KA oil, wherein the reaction current is 10-30mA, the reaction voltage is 3-6V, the reaction temperature is 40-80 ℃, and the reaction time is 0.5-2 hours.
13. Use according to claim 12, characterized in that the acidic solution is an aqueous solution of sulfuric acid, nitric acid, hydrochloric acid, perchloric acid or phosphoric acid; the lignin phenolic compound is guaiacol.
14. Use according to claim 12, characterized in that the acidic solution is an aqueous solution of perchloric acid.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013134220A1 (en) * | 2012-03-06 | 2013-09-12 | Board Of Trustees Of Michigan State University | Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds |
CN106423233A (en) * | 2016-09-12 | 2017-02-22 | 天津大学 | Transition metal phosphide catalyst, preparing method and application to guaiacol hydrogenolysis reaction |
CN107029764A (en) * | 2017-03-20 | 2017-08-11 | 浙江工业大学 | A kind of preparation method and application of support type P Modification palladium catalyst |
CN107754840A (en) * | 2017-10-20 | 2018-03-06 | 天津工业大学 | One-step method prepares the N doping platinum nickel carbon electrochemical catalyst for Catalytic oxidation of ethanol |
CN108660479A (en) * | 2018-04-29 | 2018-10-16 | 浙江工业大学 | A kind of method that lignin-base phenolic compound electrocatalytic hydrogenation produces KA oil and its derivative |
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-
2019
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013134220A1 (en) * | 2012-03-06 | 2013-09-12 | Board Of Trustees Of Michigan State University | Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds |
CN106423233A (en) * | 2016-09-12 | 2017-02-22 | 天津大学 | Transition metal phosphide catalyst, preparing method and application to guaiacol hydrogenolysis reaction |
CN107029764A (en) * | 2017-03-20 | 2017-08-11 | 浙江工业大学 | A kind of preparation method and application of support type P Modification palladium catalyst |
CN107754840A (en) * | 2017-10-20 | 2018-03-06 | 天津工业大学 | One-step method prepares the N doping platinum nickel carbon electrochemical catalyst for Catalytic oxidation of ethanol |
CN108660479A (en) * | 2018-04-29 | 2018-10-16 | 浙江工业大学 | A kind of method that lignin-base phenolic compound electrocatalytic hydrogenation produces KA oil and its derivative |
Non-Patent Citations (2)
Title |
---|
Aqueous phase electrocatalysis and thermal catalysis for the hydrogenation of phenol at mild conditions;Yang Song et al.;《Applied Catalysis B: Environmental》;20151214;第128卷;第236-246页 * |
氮掺杂炭材料负载的纳米钯催化剂在催化加氢反应中的应用研究;徐旋;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20140815(第8期);第B014-49页 * |
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Application publication date: 20190913 Assignee: GUANGXI WUZHOU MICRO-MAGNET TECHNOLOGY Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980054260 Denomination of invention: A carbon based supported metal phosphide catalyst and its preparation method and application Granted publication date: 20211109 License type: Common License Record date: 20231227 |