CN110227513A - A kind of carbon-based carried metal phosphide catalyst and its preparation method and application - Google Patents
A kind of carbon-based carried metal phosphide catalyst and its preparation method and application Download PDFInfo
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- CN110227513A CN110227513A CN201910560963.XA CN201910560963A CN110227513A CN 110227513 A CN110227513 A CN 110227513A CN 201910560963 A CN201910560963 A CN 201910560963A CN 110227513 A CN110227513 A CN 110227513A
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- metal phosphide
- carried metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 58
- 239000002184 metal Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 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 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 19
- 239000010970 precious metal Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 229920005610 lignin Polymers 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 12
- 150000002989 phenols Chemical class 0.000 claims abstract description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 238000010792 warming Methods 0.000 claims abstract description 3
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 44
- 229960001867 guaiacol Drugs 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 239000004744 fabric Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229920000557 Nafion® Polymers 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 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
- 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
- 229910019142 PO4 Inorganic materials 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
- 239000004202 carbamide 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
- 239000010452 phosphate Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 230000004044 response Effects 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
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 229960004756 ethanol Drugs 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
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 150000003283 rhodium Chemical class 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract 2
- 238000002156 mixing Methods 0.000 abstract 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000013528 metallic particle Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- JMFRWRFFLBVWSI-NSCUHMNNSA-N coniferol Chemical compound COC1=CC(\C=C\CO)=CC=C1O JMFRWRFFLBVWSI-NSCUHMNNSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 239000007970 homogeneous dispersion Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229940119526 coniferyl alcohol Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical class CCCCC(C)=O QQZOPKMRPOGIEB-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
- 239000012696 Pd precursors Substances 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000004429 atom Chemical group 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
- 239000000470 constituent Substances 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- -1 hexamethylene Alcohol Chemical compound 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process 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
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 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
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of carbon-based carried metal phosphide catalysts and its preparation method and application, the preparation process of the carbon-based carried metal phosphide catalyst are as follows: precious metal salt, deionized water and phosphorus source are after mixing, itrogenous organic substance is added and stirs evenly, acquired solution is transferred in polytetrafluoroethyltank tank, in 120 DEG C -180 DEG C of hydro-thermal reactions 10-24 hours, it is cooled to room temperature after reaction, reaction solution is filtered, it is placed in tube furnace after filter residue and drying, under nitrogen atmosphere, 700-900 DEG C is warming up to from room temperature with the rate of 3 ~ 8 DEG C/min, then constant temperature is kept for 1-4 hours, then it is naturally cooling to room temperature, calcined product deionized water and dehydrated alcohol are respectively cleaned into 3-5 after, it filters, filter residue and drying is obtained into the carbon-based carried metal phosphide catalysis Agent.Cost is relatively low for carbon-based carried metal phosphide catalyst prepared by the present invention, and catalyst of the invention is in the reaction for lignin phenolic compound electrocatalytic hydrogenation, catalytic activity and stability with higher.
Description
Technical field
The invention belongs to electro-catalysis technical fields, and in particular to a kind of carbon-based carried metal phosphide catalyst and its preparation
Methods and applications.
Background technique
With the continuous consumption of fossil energy, global energy crisis is gradually aggravated.In order to solve the energy got worse
Shortage problem, people begin look for the new energy of alternative fossil energy.And as unique reproducible carbon energy, wood fibre
Cellulosic biomass receives people and more and more pays close attention to.
The composition of lignocellulose biomass include carbohydrate (cellulose and hemicellulose), lignin and other one
A little components, such as protein, inorganic substances.According to the concept of biorefining, the final editing objective of lignocellulose biomass
For following two: (1) three kinds of primary products can be fractionated out, and can have maximum add by further converting production
The biobased products of value；(2) it is able to produce bio-fuel, residue is by-product.
Lignin is the second important ingredient after lignocellulose biomass relaying cellulose.Lignin is different by three kinds
Presoma composition: tonquinol, coniferyl alcohol and sinapinic alcohol.Guaiacol structure can be found in vegetable cork, it can be by coniferyl alcohol
The phenylpropyl alcohol alkyl structure unit decomposition of polymerization obtains.Guaiacol also known as ortho-hydroxyanisole, o-methoxyphenol, 2- methoxyl group
Phenol is the modelling of one of main constituents of lignocellulosic rapid pyrolysis products and lignin derivative monomer
Close object.A variety of compounds can be generated after guaiacol reduction, complete hydrogenation deoxidation generates hexamethylene, and partial hydrogenation deoxidation can give birth to
At oxygenatedchemicals: phenol, methyl ether and cyclohexanol etc..
Precious metals pt has preferable electro-catalysis guaiacol Hydrogenation, has many seminars to expand Pt at present and is used for
Guaiacol add hydrogen research (Nanomaterials, 2019,9,362；Molecular Catalysis, 2019,
467, 61–69；Fuel, 2019, 239, 1083–1090；J. Phys. Chem. C, 2018, 122, 29180−
29189 etc.).But the rare reserves and fancy price of precious metals pt limit its extensive use.Moreover, pure Pt's is steady
Qualitative poor, reactivity substantially reduces after reacting for ten a few houres.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of carbon-based carried metal phosphides to be catalyzed
Agent and its preparation method and application, cost is relatively low for carbon-based carried metal phosphide catalyst prepared by the present invention, and carbon-based load
Metal phosphide catalyst is in for the reaction of lignin phenolic compound electrocatalytic hydrogenation, catalytic activity with higher and steady
It is qualitative.
Traditional catalyst Pt/C, since Pt metal reserves are more rare, price is higher, limits it in electrocatalytic hydrogenation
The extensive use in field.And catalyst Pt/C, in catalytic reaction process, Pt atom is easy to reunite, fall off, and reduces electricity and urges
The active site for changing hydrogenation reaction, causes its stability poor.The present invention introduces nonmetallic phosphorus member on the basis of noble metal
Element.By and noble metal combination, can be reduced the agglomeration of noble metal, improve its stability；It introduces in the carrier nonmetallic
Nitrogen changes the effect between the electronic structure and carrier and active sites of carrier, improves the ability of electrocatalytic hydrogenation.
A kind of preparation method of the carbon-based carried metal phosphide catalyst, it is characterised in that the following steps are included:
1) precious metal salt, deionized water and phosphorus source are added in beaker, stirs 30-60 minutes, forms uniform solution；
2) itrogenous organic substance is added into step 1) acquired solution, is persistently dispersed with stirring 30-120 minutes, keeps itrogenous organic substance equal
Disperse in the solution, to obtain precursor solution evenly；
3) precursor solution obtained by step 2 is transferred in polytetrafluoroethyltank tank, the hydro-thermal reaction at a temperature of 120 DEG C -180 DEG C
It 10-24 hours, is cooled to room temperature after reaction, reaction solution is filtered, filter obtained solid vacuum at a temperature of 60-100 DEG C
It is 20-25 hours dry, obtain metal phosphide presoma；
4) metal phosphide presoma obtained by step 3) is placed in tube furnace, under nitrogen atmosphere, from room temperature with 3 ~ 8 DEG C/
The rate of min is warming up to 700-900 DEG C, and then constant temperature is kept for 1-4 hours, is then naturally cooling to room temperature, obtains carbon-based load
Metal phosphide solid；
5) carbon-based carried metal phosphide solid deionized water and dehydrated alcohol obtained by step 4) respectively clean 3-5 after, filter,
Filter residue is placed in a vacuum drying oven, dries 20-25 hours at a temperature of 60-80 DEG C to get the carbon-based carried metal phosphorus is arrived
Compound catalyst.
The preparation method of a kind of carbon-based carried metal phosphide catalyst, it is characterised in that described in step 1)
Precious metal salt is rhodium salt, iridium salt, palladium salt or ruthenium salt；Phosphorus source is phytic acid, phosphoric acid or phosphate, and the phosphate is sodium phosphate
Or sodium dihydrogen phosphate；In step 2, the itrogenous organic substance is melamine, urea or cyanamide.
The preparation method of a kind of carbon-based carried metal phosphide catalyst, it is characterised in that phosphorus source is phytic acid
Or phosphoric acid, the ratio between quality and the volume of phosphorus source of precious metal salt are 5 ~ 10: 1, and the unit of quality is mg, the unit of volume
For mL.
The preparation method of a kind of carbon-based carried metal phosphide catalyst, it is characterised in that phosphorus source is phosphoric acid
The mass ratio of salt, precious metal salt and phosphorus source is 0.01 ~ 0.03: 1, preferably 0.01 ~ 0.015: 1.
A kind of preparation method of the carbon-based carried metal phosphide catalyst, it is characterised in that the precious metal salt with
The mass ratio of the itrogenous organic substance is 0.01 ~ 0.1: 1, preferably 0.01 ~ 0.05: 1.
The preparation method of a kind of carbon-based carried metal phosphide catalyst, it is characterised in that described in step 1)
The ratio between volume of the quality of precious metal salt and the deionized water is 0.5 ~ 3: 1, preferably 1 ~ 2: 1, and the unit of quality is
Mg, the unit of volume are mL.
The carbon-based carried metal phosphide catalyst prepared according to above-mentioned method.
The carbon-based carried metal phosphide catalyst answering in the reaction of lignin phenolic compound electrocatalytic hydrogenation
With.
The carbon-based carried metal phosphide catalyst answering in the reaction of lignin phenolic compound electrocatalytic hydrogenation
With, it is characterised in that the following steps are included:
S1: the carbon-based carried metal phosphide catalyst is mixed with the ethanol solution of Nafion, after ultrasonic disperse, by gained
Carbon cloth electrode is made after dry on carbon cloth in dispersant liquid drop；
S2: using H-type electrolytic cell as reaction vessel, cathode chamber and anode chamber are separated with cation-exchange membrane；In anode chamber, platinized platinum is made
For to electrode, the acid solution of 0.1-2.0 mol/L is as anolyte；In cathode chamber, using carbon cloth electrode obtained by step S1 as
Working electrode is dissolved in the acid solution of 0.1-2.0 mol/L by reaction substrate of lignin phenolic compound as cathode
Liquid under the stirring for carrying out 500-1000r/min to catholyte, carries out electrocatalytic hydrogenation reaction preparation KA oil, and the electric current of reaction is
10-30mA, response voltage 3-6V, reaction temperature are 40-80 DEG C, and the reaction time is 0.5-2 hours.
The carbon-based carried metal phosphide catalyst answering in the reaction of lignin phenolic compound electrocatalytic hydrogenation
It is the aqueous solution of sulfuric acid, nitric acid, hydrochloric acid, perchloric acid or phosphoric acid with, it is characterised in that the acid solution, preferably perchloric acid
Aqueous solution；The lignin phenolic compound is guaiacol.
By using above-mentioned technology, compared with prior art, beneficial effects of the present invention are as follows:
1) present invention synthesizes novel carbon-based carried metal phosphide catalyst by easy and lower-cost method, passes through
P elements are adulterated, metal consumption are reduced, to reduce catalyst preparation cost；Metal phosphide is carried on carbon N structure, is subtracted
The dosage of few metal phosphide, is further reduced cost；The doping of P elements improves reactivity to a certain extent, and
Improve catalyst stability；And preparation method is simple, at low cost, is easy to regulate and control；It is mentioned for such material in electro-catalysis field
Base application research has been supplied, has been had broad application prospects.
2) in the preparation process of catalyst of the present invention, precious metal salt and phosphorus source uniform dissolution are in deionized water, noble metal
Then salt and phosphorus source can be added itrogenous organic substance and carry out hydro-thermal reaction in conjunction with metal phosphide presoma is formed, will obtain after reaction
To solid product roasted, itrogenous organic substance is decomposed to form the carrier material of nitrogen-doped carbon, and metal phosphide presoma
It is converted into metal phosphide, and is supported on the carrier material of nitrogen-doped carbon.Since nitrogen has more stronger than carbon electron-withdrawing, nitrogen
The catalyst that the carrier material of doped carbon is prepared, catalyst are anti-in the electrocatalytic hydrogenation for being applied to lignin phenolic compound
At once, suction-operated of the activated centre metal phosphide of catalyst to electrocatalytic hydrogenation reaction product can be weakened, in not shadow
The activated centre of catalyst is rung to the desorption of reaction product under the suction-operated of reaction raw materials, is conducive to, and improves electrocatalytic reaction
Efficiency, and improve reaction product selectivity.
3) in catalyst prepared by the present invention, the active component of catalyst is metal phosphide, P elements and metallic element
After effect, metal can be effectively prevented and polymerize in electrocatalytic hydrogenation reaction, make metal in the carrier material of nitrogen-doped carbon
It is upper to keep higher dispersion degree, improve the stability of catalyst.
Detailed description of the invention
Fig. 1 a is the RhP obtained of embodiment 12Transmission electron microscope observation figure of the@NC catalyst under 0.2 μm；
Fig. 1 b is the RhP obtained of embodiment 12Transmission electron microscope observation figure of the@NC catalyst at 20nm；
Fig. 2 a is the IrP obtained of embodiment 22Transmission electron microscope observation figure of the@NC catalyst under 0.5 μm；
Fig. 2 b is the IrP obtained of embodiment 22Transmission electron microscope observation figure of the@NC catalyst at 50nm；
Fig. 3 a is the Pd obtained of embodiment 35P2Transmission electron microscope observation figure of the@NC catalyst under 0.5 μm；
Fig. 3 b is the Pd obtained of embodiment 35P2Transmission electron microscope observation figure of the@NC catalyst at 100nm；
Fig. 4 is the RhP obtained of embodiment 12@NC catalyst is used for the reaction result of guaiacol electrocatalytic hydrogenation KA oil
Figure；
Fig. 5 is the IrP obtained of embodiment 22@NC catalyst is used for the reaction result of guaiacol electrocatalytic hydrogenation KA oil
Figure；
Fig. 6 is the Pd obtained of embodiment 35P2@NC catalyst is used for the reaction result of guaiacol electrocatalytic hydrogenation KA oil
Figure；
Fig. 7 is the RhP obtained of embodiment 12When@NC catalyst repeats catalysis using the 20th time, guaiacol electro-catalysis is added
The reaction result figure of hydrogen KA oil.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment 1:RhP2The synthesis of@NC
1) 50mg rhodium nitrate is added in 250mL beaker and 5mL is added dropwise in lasting stirring in 50 mL deionized waters, stirring and dissolving
Phosphoric acid stirs 40 minutes and forms uniform aqueous solution；
2) 1g cyanamide is added into step 1) obtained aqueous solution, stirs 75 minutes, so that cyanamide is more evenly dispersed in water-soluble
In liquid, precursor solution is obtained；
3) precursor solution obtained by step 2 is put into polytetrafluoroethyltank tank, hydro-thermal reaction 20 hours at a temperature of 150 DEG C, instead
Should after be cooled to room temperature, reaction solution is filtered, filtering obtained solid be dried in vacuo 20 hours at a temperature of 80 DEG C, obtain phosphatization rhodium
Presoma；
4) phosphatization rhodium presoma obtained by step 3) is ground into powder, weighs 1g phosphatization rhodium precursor powder and is transferred to tube furnace
In, lead to 60 minutes nitrogen, the air in tube furnace is drained, in a nitrogen atmosphere, is heated to 900 DEG C with the speed of 5 DEG C/min
Afterwards, it is kept for 2 hours at 900 DEG C, is then naturally cooling to room temperature, obtains RhP2@NC solid；
5) by RhP obtained by step 4)2@NC solid water and dehydrated alcohol wash 4 times respectively, filter, obtained filter residue is placed in
It is 24 hours dry at 60 DEG C in vacuum oven, carbon-based carried metal phosphide catalyst is obtained (labeled as RhP2@NC is urged
Agent).The RhP obtained of embodiment 12Transmission electron microscope observation figure of the@NC catalyst under 0.2 μm and 20nm such as Fig. 1 a
With shown in Fig. 1 b, it will be seen that metal is relatively evenly distributed on carrier from shown in Fig. 1 a and Fig. 1 b.Pass through P and gold
Belong to Ru to combine, the reunion between metallic particles can be effectively prevented, to there is preferable stability.
The RhP that embodiment 1 is prepared2The catalytic performance of@NC catalyst is tested, and the specific method is as follows:
By 8mg RhP2(Nafion solution quality is dense for@NC catalyst fines, 0.9mL dehydrated alcohol and 0.1mL Nafion solution
For degree 5%) to mix, ultrasonic disperse is uniform, and homogeneous dispersion is dripped in 2 × 2cm2On the carbon cloth of size, it is dried to obtain carbon cloth electricity
Pole.
Using H-type electrolytic cell as reaction vessel, cathode chamber and anode chamber are separated with cation-exchange membrane；In anode chamber, platinized platinum
As to electrode, the high chloro acid solution of 0.2mol/L is as anolyte；In cathode chamber, using the carbon cloth electrode of above-mentioned preparation as
Working electrode is dissolved in the high chloro acid solution of 0.2 mol/L by reaction substrate of guaiacol as catholyte (catholyte
The concentration of middle guaiacol is controlled in 10mmol/L), catholyte is carried out (to stir and extend out to eliminate under the stirring of 600r/min
Dissipating influences), the reaction that the reaction of guaiacol electrocatalytic hydrogenation prepares KA oil is carried out, electrolytic cell is integrally placed in water bath with thermostatic control
To control 60 DEG C of temperature of reaction system, kinetic current 20mA, keep voltage between 3-6V, reaction time 2h.It reacted
To reaction solution sampling analysis in journey, reaction result as shown in figure 4, when being reacted to more than 60 minutes as can be seen from Figure 4, guaiacol
Completely, primary product is KA oily (KA oil is made of cyclohexanol and cyclohexanone) for conversion substantially.Guaiacol is by adding first
Hydrogen becomes cyclohexanone, and then cyclohexanone is further hydrogenated to cyclohexanol.Reaction 2 hours, the conversion ratio of guaiacol are 100%,
The selectivity of KA oil is the sum of the selectivity of both cyclohexanol and cyclohexanone in 96.7%(reaction product, the selection of as KA oil
Property).
In order to verify the RhP of the preparation of embodiment 12The catalytic stability of@NC catalyst, to above-mentioned reaction 1 time (when overall reaction
Between 2h) after catalyst carry out repeating electrocatalytic hydrogenation reaction experiment, it is anti-after catalyst reaction 20 times (total reaction time 40h)
Answer result as shown in Figure 7.From figure 7 it can be seen that being reacted to 100 minutes in catalyst recycling reaction the 20th time experiment
When left and right, guaiacol is substantially completely converted completely, and primary product is KA oil.Reaction 2 hours, the conversion ratio of guaiacol are
The selectivity of 100%, KA oil is 96.0%.Compared with the result of the 1st secondary response of catalyst, there is no significantly subtract catalytic effect
It is weak.
Embodiment 2:IrP2The synthesis of@NC
1) 100mg iridic chloride is added in 250mL beaker and 50 mL deionized waters, stirring and dissolving is added dropwise in lasting stirring
The phytic acid of 50% volumetric concentration of 10mL stirs 30 minutes and forms uniform aqueous solution；
2) 2g melamine is added into step 1) obtained aqueous solution, stirs 60 minutes, melamine is enable more equably to divide
It dissipates in aqueous solution, obtains precursor solution；
3) precursor solution obtained by step 2 is put into polytetrafluoroethyltank tank, hydro-thermal reaction 24 hours at a temperature of 120 DEG C, instead
Should after be cooled to room temperature, reaction solution is filtered, filtering obtained solid be dried in vacuo 25 hours at a temperature of 60 DEG C, obtain phosphatization iridium
Presoma；
4) phosphatization iridium presoma obtained by step 3) is ground into powder, weighs 1g phosphatization iridium precursor powder and is transferred to tube furnace
In, lead to 50 minutes nitrogen, the air in tube furnace is drained, in a nitrogen atmosphere, is heated to 800 DEG C with the speed of 5 DEG C/min
Afterwards, it is kept for 2.5 hours at 800 DEG C, is then naturally cooling to room temperature, obtains IrP2@NC solid；
5) by IrP obtained by step 4)2@NC solid water and dehydrated alcohol wash 4 times respectively, filter, obtained filter residue is placed in
It is 20 hours dry at 80 DEG C in vacuum oven, carbon-based carried metal phosphide catalyst is obtained (labeled as IrP2@NC is urged
Agent).The IrP obtained of embodiment 22Transmission electron microscope observation figure of the@NC catalyst under 0.5 μm and 50nm is respectively such as
Shown in Fig. 2 a and Fig. 2 b, it can be seen that metallic particles of uniform size is relatively evenly distributed on carrier from Fig. 2 a and Fig. 2 b.It is logical
P is crossed in conjunction with metal Ir, can effectively prevent the reunion between metallic particles, to there is preferable stability.
The IrP that embodiment 2 is prepared2The catalytic performance of@NC catalyst is tested, and the specific method is as follows:
By 8mg IrP2(Nafion solution quality is dense for@NC catalyst fines, 0.9mL dehydrated alcohol and 0.1mL Nafion solution
For degree 5%) to mix, ultrasonic disperse is uniform, and homogeneous dispersion is dripped in 2 × 2cm2On the carbon cloth of size, it is dried to obtain carbon cloth electricity
Pole.
Using H-type electrolytic cell as reaction vessel, cathode chamber and anode chamber are separated with cation-exchange membrane；In anode chamber, platinized platinum
As to electrode, the high chloro acid solution of 0.2mol/L is as anolyte；In cathode chamber, using the carbon cloth electrode of above-mentioned preparation as
Working electrode is dissolved in the high chloro acid solution of 0.2 mol/L by reaction substrate of guaiacol as catholyte (catholyte
The concentration of middle guaiacol is controlled in 10mmol/L), catholyte is carried out (to stir and extend out to eliminate under the stirring of 600r/min
Dissipating influences), electrolytic cell is integrally placed in water bath with thermostatic control to protect to control 60 DEG C of temperature of reaction system, kinetic current 20mA
Voltage is held between 3-6V, reaction time 2h.To reaction solution sampling analysis in reaction process, reaction result as shown in figure 5, from
Fig. 5 can be seen that when being reacted to 2 hours, and completely, primary product is that (KA oil is by cyclohexanol for KA oil to guaiacol for conversion substantially
It is formed with cyclohexanone).Guaiacol is by being hydrogenated into as cyclohexanone first, and then cyclohexanone is further hydrogenated to cyclohexanol.
Reaction 2 hours, the conversion ratio of guaiacol is that the selectivity of 100%, KA oil is cyclohexanol and hexamethylene in 96.0%(reaction product
The selectivity of the sum of selectivity of both ketone, as KA oil).
Embodiment 3:Pd5P2The synthesis of@NC
1) 75mg palladium chloride is added in 250mL beaker and 5g is added dropwise in lasting stirring in 70 mL deionized waters, stirring and dissolving
Sodium dihydrogen phosphate stirs 45 minutes and forms uniform aqueous solution；
2) 3g urea is added into step 1) obtained aqueous solution, stirs 100 minutes, so that urea is more evenly dispersed in water-soluble
In liquid, precursor solution is obtained；
3) precursor solution obtained by step 2 is put into polytetrafluoroethyltank tank, hydro-thermal reaction 10 hours at a temperature of 180 DEG C, instead
Should after be cooled to room temperature, reaction solution is filtered, filtering obtained solid be dried in vacuo 20 hours at a temperature of 100 DEG C, obtain phosphatization
Palladium presoma；
4) phosphatization palladium presoma obtained by step 3) is ground into powder, weighs 1g phosphatization palladium precursor powder and is transferred to tube furnace
In, lead to 30 minutes nitrogen, the air in tube furnace is drained, in a nitrogen atmosphere, is heated to 700 DEG C with the speed of 5 DEG C/min
Afterwards, it is kept for 3 hours at 700 DEG C, is then naturally cooling to room temperature, obtains Pd5P2@NC solid；
5) by Pd obtained by step 4)5P2@NC solid water and dehydrated alcohol wash 3 times respectively, filter, obtained filter residue is placed in
It is 20 hours dry at 80 DEG C in vacuum oven, carbon-based carried metal phosphide catalyst is obtained (labeled as Pd5P2@NC is urged
Agent).The Pd obtained of embodiment 35P2Transmission electron microscope observation figure of the@NC under 0.5 μm and 100nm is respectively such as Fig. 3 a
With shown in Fig. 3 b, it can be seen that metallic particles of uniform size is relatively evenly distributed on carrier from Fig. 3 a and Fig. 3 b.By P with
Metal Pd combines, and the reunion between metallic particles can be effectively prevented, to there is preferable stability.
The Pd that embodiment 3 is prepared5P2The catalytic performance of@NC catalyst is tested, and the specific method is as follows:
By 8mg Pd5P2(Nafion solution quality is dense for@NC catalyst fines, 0.9mL dehydrated alcohol and 0.1mL Nafion solution
For degree 5%) to mix, ultrasonic disperse is uniform, and homogeneous dispersion is dripped in 2 × 2cm2On the carbon cloth of size, it is dried to obtain carbon cloth electricity
Pole.
Using H-type electrolytic cell as reaction vessel, cathode chamber and anode chamber are separated with cation-exchange membrane；In anode chamber, platinized platinum
As to electrode, the high chloro acid solution of 0.2mol/L is as anolyte；In cathode chamber, using the carbon cloth electrode of above-mentioned preparation as
Working electrode is dissolved in the high chloro acid solution of 0.2 mol/L by reaction substrate of guaiacol as catholyte (catholyte
The concentration of middle guaiacol is controlled in 10mmol/L), catholyte is carried out (to stir and extend out to eliminate under the stirring of 600r/min
Dissipating influences), electrolytic cell is integrally placed in water bath with thermostatic control to protect to control 40 DEG C of temperature of reaction system, kinetic current 20mA
Voltage is held between 3-6V, reaction time 2h.To reaction solution sampling analysis in reaction process, reaction result as shown in fig. 6, from
Fig. 6 can be seen that when being reacted to 110 minutes, and conversion is over guaiacol substantially, and primary product is that (KA oil is by hexamethylene for KA oil
Pure and mild cyclohexanone composition).Guaiacol is by being hydrogenated into as cyclohexanone first, and then cyclohexanone is further hydrogenated to hexamethylene
Alcohol.Reaction 2 hours, the conversion ratio of guaiacol is that the selectivity of 100%, KA oil is cyclohexanol and ring in 97.7%(reaction product
The selectivity of the sum of selectivity of both hexanones, as KA oil).
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated.
Claims (10)
1. a kind of preparation method of carbon-based carried metal phosphide catalyst, it is characterised in that the following steps are included:
1) precious metal salt, deionized water and phosphorus source are added in beaker, stirs 30-60 minutes, forms uniform solution；
2) itrogenous organic substance is added into step 1) acquired solution, is persistently dispersed with stirring 30-120 minutes, keeps itrogenous organic substance equal
Disperse in the solution, to obtain precursor solution evenly；
3) precursor solution obtained by step 2 is transferred in polytetrafluoroethyltank tank, the hydro-thermal reaction at a temperature of 120 DEG C -180 DEG C
It 10-24 hours, is cooled to room temperature after reaction, reaction solution is filtered, filter obtained solid vacuum at a temperature of 60-100 DEG C
It is 20-25 hours dry, obtain metal phosphide presoma；
4) metal phosphide presoma obtained by step 3) is placed in tube furnace, under nitrogen atmosphere, from room temperature with 3 ~ 8 DEG C/
The rate of min is warming up to 700-900 DEG C, and then constant temperature is kept for 1-4 hours, is then naturally cooling to room temperature, obtains carbon-based load
Metal phosphide solid；
5) carbon-based carried metal phosphide solid deionized water and dehydrated alcohol obtained by step 4) respectively clean 3-5 after, filter,
Filter residue is placed in a vacuum drying oven, dries 20-25 hours at a temperature of 60-80 DEG C to get the carbon-based carried metal phosphorus is arrived
Compound catalyst.
2. a kind of preparation method of carbon-based carried metal phosphide catalyst according to claim 1, it is characterised in that step
It is rapid 1) in, the precious metal salt be rhodium salt, iridium salt, palladium salt or ruthenium salt；Phosphorus source is phytic acid, phosphoric acid or phosphate, the phosphorus
Hydrochlorate is sodium phosphate or sodium dihydrogen phosphate；In step 2, the itrogenous organic substance is melamine, urea or cyanamide.
3. a kind of preparation method of carbon-based carried metal phosphide catalyst according to claim 2, it is characterised in that institute
Stating phosphorus source is phytic acid or phosphoric acid, and the ratio between quality and the volume of phosphorus source of precious metal salt are 5 ~ 10: 1, and the unit of quality is
Mg, the unit of volume are mL.
4. a kind of preparation method of carbon-based carried metal phosphide catalyst according to claim 2, it is characterised in that institute
Phosphorus source is stated as phosphate, the mass ratio of precious metal salt and phosphorus source is 0.01 ~ 0.03: 1, preferably 0.01 ~ 0.015:
1。
5. a kind of preparation method of carbon-based carried metal phosphide catalyst according to claim 2, it is characterised in that institute
The mass ratio for stating precious metal salt and the itrogenous organic substance is 0.01 ~ 0.1: 1, preferably 0.01 ~ 0.05: 1.
6. a kind of preparation method of carbon-based carried metal phosphide catalyst according to claim 2, it is characterised in that step
It is rapid 1) in, the ratio between volume of the quality of the precious metal salt and the deionized water is 0.5 ~ 3: 1, preferably 1 ~ 2: 1, matter
The unit of amount is mg, and the unit of volume is mL.
7. carbon-based carried metal phosphide catalyst prepared by the method as described in claim 1 ~ 6 any one.
8. carbon-based carried metal phosphide catalyst as claimed in claim 7 is anti-in lignin phenolic compound electrocatalytic hydrogenation
Application in answering.
9. application as claimed in claim 8, it is characterised in that the following steps are included:
S1: the carbon-based carried metal phosphide catalyst is mixed with the ethanol solution of Nafion, after ultrasonic disperse, by gained
Carbon cloth electrode is made after dry on carbon cloth in dispersant liquid drop；
S2: using H-type electrolytic cell as reaction vessel, cathode chamber and anode chamber are separated with cation-exchange membrane；In anode chamber, platinized platinum is made
For to electrode, the acid solution of 0.1-2.0 mol/L is as anolyte；In cathode chamber, using carbon cloth electrode obtained by step S1 as
Working electrode is dissolved in the acid solution of 0.1-2.0 mol/L by reaction substrate of lignin phenolic compound as cathode
Liquid under the stirring for carrying out 500-1000r/min to catholyte, carries out electrocatalytic hydrogenation reaction preparation KA oil, and the electric current of reaction is
10-30mA, response voltage 3-6V, reaction temperature are 40-80 DEG C, and the reaction time is 0.5-2 hours.
10. application as claimed in claim 9, it is characterised in that the acid solution be sulfuric acid, nitric acid, hydrochloric acid, perchloric acid or
The aqueous solution of phosphoric acid, the preferably aqueous solution of perchloric acid；The lignin phenolic compound is guaiacol.
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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 |