CN111834642A - Organic matter electrocatalytic oxidation catalyst and preparation method and application thereof - Google Patents
Organic matter electrocatalytic oxidation catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- 230000003647 oxidation Effects 0.000 title claims abstract description 22
- 239000005416 organic matter Substances 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 150000003624 transition metals Chemical group 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003623 transition metal compounds Chemical group 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 239000011593 sulfur Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
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- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 13
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- 238000001035 drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
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- 239000010948 rhodium Substances 0.000 claims description 5
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- 239000002253 acid Substances 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
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- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 11
- 150000003384 small molecules Chemical group 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000002918 waste heat Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an organic electro-catalytic oxidation catalyst, and provides a preparation method of the catalyst and application of the catalyst in C, H, N, O micromolecule organic electro-catalytic oxidation. The catalyst is a transition metal compound loaded noble metal with a molecular formula of x1％M1x2％M2x3％M3/HyQaRbYcN3Wherein M is1、M2、M3Is a noble metal, x1％、x2％、x3% is the percentage content of noble metal in the total mass of the catalyst, wherein at most two values are 0, the rest values are 0.1-20%, Q, R, Y is transition metal, y value is 0-1, a + b + c is 1, N is one element of oxygen, nitrogen, carbon, phosphorus and sulfur. The organic electro-catalytic oxidation catalyst prepared by the method can greatly reduce the use amount of noble metals, can realize the decomposition of small molecules by repeatedly utilizing waste heat generated by the fuel cell, and improves the utilization rate of the fuel cell.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to an organic electro-catalytic oxidation catalyst, a preparation method thereof and application thereof in C, H, N, O micromolecular organic electro-catalytic oxidation.
Background
The hydrogen energy is the most ideal green energy in the 21 st century and has the characteristics of cleanness, high efficiency and high quality. C, H, N, O micromolecule liquid organic matters are used as fuel, so that the problems of storage, transportation and safety of hydrogen in the hydrogen fuel cell can be avoided. When the fuel cell works, C, H, N, O micromolecule liquid organic matters enter the flow channel from the anode flow field plate, then enter the anode catalyst through the anode diffusion layer, are oxidized under the action of the catalyst to release electrons and protons, and C, H, N, O micromolecule liquid organic matters after reaction are discharged from the anode. The electrons flow through an external circuit to do work, and the protons are transferred to the cathode through the solid electrolyte membrane. At the moment, oxygen or air enters the flow channel through the cathode flow field plate, enters the cathode catalyst layer through the cathode diffusion layer, and reacts with protons transferred from the anode in a combined manner to generate H2O, while consuming electrons transferred from the external circuit. Generation of H2O is discharged from the cathode in the form of water vapor or condensed water. At present, C, H, N, O catalysts for electrocatalytic oxidation of small-molecular organic matters are mainly precious metal materials such as Pd, Pt, Ru, Rh and the like, and are expensive and deficient in resources, so that development of a hydrogen production catalyst for electrolysis of water with low precious metal content, low cost and high efficiency is a research hotspot in the fields of energy, catalysis and materials.
Through long-term exploration and research, professor of Chenghangsong and teams thereof discover that a class of transition metal oxides has good addition/dehydrogenation performance and long cycle life, and the class of transition metal oxides becomes an electronic conductor after hydrogenation. The principle of electrocatalytic oxidation is similar to Hydrodeoxygenation (HDO), Hydrodenitrogenation (HDN) and Hydrodesulfurization (HDS), so that the material can be a high-efficiency and stable electrocatalytic oxidation catalyst.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides an organic electro-catalytic oxidation catalyst, a preparation method of the catalyst and application of the catalyst in the electro-catalytic oxidation of C, H, N, O small-molecule organic matters.
In order to achieve the above object, the present invention adoptsThe technical scheme is as follows: an electrocatalytic oxidation catalyst for organic matters, which is a transition metal compound loaded noble metal and has a molecular formula of x1％M1x2％M2x3％M3/HyQaRbYcN3Wherein M is1、M2、M3Is a noble metal, x1％、x2％、x3% is the percentage content of noble metal in the total mass of the catalyst, wherein at most two values are 0, the rest values are 0.1-20%, Q, R, Y is transition metal, y value is 0-1, a + b + c is 1, N is one element of oxygen, nitrogen, carbon, phosphorus and sulfur.
Further, M1、M2、M3Is one of ruthenium, rhodium, palladium, osmium, iridium and platinum.
Further, Q, R, Y is one element selected from scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, rhodium, osmium, tungsten, tantalum, and iridium.
A preparation method of an organic electro-catalytic oxidation catalyst comprises the following steps:
(1) weighing two or three transition metal acid ammonium salts and polyethylene glycol, stirring and mixing, and heating and stirring the mixed solution; after stirring, dropwise adding 10% dilute nitric acid to adjust the pH of the solution to 1-3;
(2) filling the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction; after the reaction is finished, carrying out suction filtration, washing the reactant to be neutral by using ultrapure water and ethanol, and fully drying at 60 ℃;
(3) calcining the dried product at high temperature for 1-5 h to obtain a metal oxide product;
(4) putting the product into a high-temperature high-pressure reaction kettle, and reacting to obtain transition metal oxide HxQaRbYcO3；
(5) The product H is reacted withxQaRbYcO3And NH3、H2/CH4、NaH2PO2Or calcining the sulfur powder at the high temperature of 350-700 ℃ for 2h to respectively prepare transition goldNitrogen, carbon, phosphorus, sulfide;
(6) putting noble metal salt and the transition metal oxygen, nitrogen, carbon, phosphorus or sulfide into a round-bottom flask, adding ethylene glycol and water, ultrasonically dispersing, reducing in an oil bath at 140-160 ℃ in a nitrogen atmosphere for 6-12 h, performing suction filtration, washing reactants to be neutral by ultrapure water, and fully drying at 60 ℃ to obtain a transition metal compound loaded noble metal x1％M1x2％M2x3％M3/HyQaRbYcN3。
Further, in the step 1, the mass ratio of the metal acid ammonium salt to the polyethylene glycol is 1:2,
further, in the step 1, the reaction conditions of the mixed solution are that the temperature is controlled to be 50-70 ℃, and the stirring time is controlled to be 24-72 hours.
Further, the hydrothermal reaction condition in the step 2 is that the temperature is 150-250 ℃, and the reaction time is 48-62 hours.
Further, the calcining temperature in the step 3 is 200-500 ℃.
Further, the reaction conditions of the step 4 are that the temperature is 150-500 ℃, the hydrogen pressure is 3MPa, and the heating reaction is carried out for 2-5 hours.
An application of organic electro-catalytic oxidation catalyst in the electro-catalytic oxidation reaction of small molecular organic matters.
The organic electro-catalytic oxidation catalyst prepared by the method can greatly reduce the use amount of noble metals, can realize the decomposition of small molecules by repeatedly utilizing waste heat generated by the fuel cell, and improves the utilization rate of the fuel cell.
Drawings
FIG. 1 is a diagram showing the construction of a test system according to example 3.
FIG. 2 is a polarization plot of the catalyst of example 4.
Detailed Description
In order to make the technical solutions better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only partial embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It should be noted that the terms "comprises" and "comprising," and any variations thereof, in the description and claims of this application and the above-described drawings, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1
(1) Weighing 10g of ammonium metatungstate and 10.8g of ammonium paramolybdate, stirring and mixing with polyethylene glycol, and stirring for 48h at 60 ℃; after stirring, dropwise adding dilute nitric acid with the mass ratio of 10% to adjust the pH of the solution to 2;
(2) filling the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 48 hours at the temperature of 200 ℃;
(3) after the hydrothermal reaction is finished, carrying out suction filtration, washing the reactant to be neutral by using ultrapure water and ethanol, and fully drying at 60 ℃;
(4) calcining the dried substance at high temperature for 5h to obtain a bimetal oxide product;
(5) putting the product into a high-temperature high-pressure reaction kettle, heating and reacting for 5 hours at the temperature of 150 ℃ and the hydrogen pressure of 3MPa to obtain H0.15Mo0.6W0.4O3。
(6) 100mg of the hydride was weighed into a round-bottomed flask, and 429. mu.L of 10mg/mL H was measured2PtCl6Putting the solution, 60mL of ethylene glycol and 40mL of ultrapure water into a round-bottom flask, performing ultrasonic dispersion for half an hour, stirring and performing oil bath reduction for 6 hours at 140 ℃ in a nitrogen atmosphere, performing suction filtration, washing a reactant to be neutral by using the ultrapure water, and sufficiently drying at 60 ℃ to obtain a binary transition metal oxide loaded noble metal 2% Pt/H0.15Mo0.6W0.4O3。
Example 2
(1) Weighing 10g of ammonium metatungstate, 10.8g of ammonium paramolybdate and 7.8g of nickel nitrate, stirring and mixing with polyethylene glycol, and stirring for 48h at 60 ℃; after stirring, dropwise adding dilute nitric acid with the mass ratio of 10% to adjust the pH of the solution to 2;
(2) filling the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 48 hours at the temperature of 200 ℃;
(3) after the hydrothermal reaction is finished, carrying out suction filtration, washing the reactant to be neutral by using ultrapure water and ethanol, and fully drying at 60 ℃;
(4) calcining the dried substance at high temperature for 5h to obtain a trimetal oxide product;
(5) putting the product into a high-temperature high-pressure reaction kettle, heating and reacting for 5 hours at the temperature of 150 ℃ and the hydrogen pressure of 3MPa to obtain H0.15Ni0.29Mo0.42W0.29O3；
(6) 100mg of the hydride was weighed into a round-bottomed flask, and 429. mu.L of 10mg/mL H was measured2PtCl6Solution, 168.3. mu.L of 10mg/mL PdCl2Putting the solution, 90mL of ethylene glycol and 60mL of ultrapure water into a round-bottom flask, performing ultrasonic dispersion for half an hour, stirring and performing oil bath reduction for 6 hours at 140 ℃ in a nitrogen atmosphere, performing suction filtration, washing a reactant to be neutral by using the ultrapure water, and sufficiently drying at 60 ℃ to obtain the ternary transition metal oxide loaded with the two noble metals, namely 2% Pt and 1% Pd/H0.15Ni0.29Mo0.42W0.29O3。
Example 3
(1) Weighing 10g of ammonium metatungstate, then stirring and mixing with polyethylene glycol, and stirring for 48h at 60 ℃; after stirring, dropwise adding dilute nitric acid with the mass ratio of 10% to adjust the pH of the solution to 2;
(2) filling the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 48 hours at the temperature of 200 ℃;
(3) after the hydrothermal reaction is finished, carrying out suction filtration, washing the reactant to be neutral by using ultrapure water and ethanol, and fully drying at 60 ℃;
(4) calcining the dried substance at high temperature for 5h to obtain a trimetal oxide product;
(5) putting the product into a high-temperature high-pressure reaction kettle, heating and reacting for 5 hours at the temperature of 150 ℃ and the hydrogen pressure of 3MPa to obtain WO3；
(6) Mixing WO3The mixture is put into a tube furnace,heating to 700 ℃, and preserving heat for 2h to obtain W2C。
(7) Weighing the above W2C100 mg in a round-bottomed flask, 429. mu.L of 10mg/mL H was measured2PtCl6Solution, 168.3. mu.L of 10mg/mL PdCl2Putting the solution, 90mL of ethylene glycol and 60mL of ultrapure water into a round-bottom flask, performing ultrasonic dispersion for half an hour, stirring and performing oil bath reduction for 6 hours at 140 ℃ in a nitrogen atmosphere, performing suction filtration, washing a reactant to be neutral by using the ultrapure water, and sufficiently drying at 60 ℃ to obtain the ternary transition metal oxide loaded with the two noble metals, namely 2% Pt and 1% Pd/W2C。
Example 4
1. 2％Pt/H0.15Mo0.6W0.4O3Method for preparing catalyst solution
9.4mg of 2% Pt/H was weighed0.15Mo0.6W0.4O3The catalyst (hereinafter referred to as catalyst) is dispersed in the mixed solution of 4mL of absolute ethyl alcohol and 1mL of deionized water, 1.6mg of conductive carbon black is added, and the mixture is subjected to ultrasonic treatment for 1 hour to uniformly disperse the catalyst.
2. Method for spraying electrode
(1) And (3) carbon paper treatment: cutting carbon paper with the size of 2.0cm multiplied by 2.0cm, and blowing off pollutants such as impurities on the carbon paper by using an ear washing ball.
(2) Spraying of an electrode: and (3) placing the carbon paper in the step (1) on a sample table of an electrostatic spraying instrument, pouring the uniformly dispersed catalyst solution into a syringe, placing the syringe in a sample chamber, and adjusting the spraying voltage and the spraying flow rate to enable the carbon paper to be sprayed in a mist shape and uniformly sprayed on each part of the carbon paper. And naturally drying the prepared carbon paper for subsequent testing. The spraying of the catalyst of the anode and the cathode is respectively carried out by the method.
3. Electrocatalytic oxidation performance test
(1) Building a single battery test system: the single cell testing system mainly comprises a single cell system, a fuel feeding and discharging system, an oxygen or air feeding and discharging system, a temperature control system, a software control system and the like, and the structure of the single cell testing system is shown in figure 1.
(2) Testing the performance of the fuel cell: testing platform soft using fuel cellThe control system makes the electronic load work in a constant current mode, continuously changes the load current to measure the output voltage value of the single cell under different current densities, and then obtains the I-V curve of the single cell by data processing and plotting. In the experimental process, the battery is heated through a temperature control system, the isopropanol micromolecule liquid organic matter is preheated through an oven, and the I-V curve test is carried out when the isopropanol micromolecule liquid organic matter is preheated to a set value. Setting the fuel flow to be 1mL/min, the oxygen flow to be 0.6mL/min, setting the current initial value to be 0A, setting the current final value based on the output voltage value to be 0.1V, setting each group of load current to correspond to the test time to be about 3min, stabilizing for 10s under the current load, and taking one group of data every 2 s. Selecting current density as gradient change according to polarization curve characteristics, sequentially increasing load current value until single cell voltage is reduced to about 0.1V, and finishing to obtain I-V curve as shown in FIG. 2, wherein the power density of the catalyst at 180 deg.C is 10mW/cm2(ii) a And after the experiment is finished, closing the test platform, discharging the isopropanol micromolecule organic solution in the pipeline, introducing nitrogen into the cathode of the single cell for purging, and closing the nitrogen after the cell is cooled to room temperature.
Although the present invention has been described with reference to the preferred embodiments, the embodiments and drawings are not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be defined by the claims of the present application.
Claims (10)
1. An electrocatalytic oxidation catalyst for organic matters, which is characterized in that: the catalyst is a transition metal compound loaded noble metal with a molecular formula of x1％M1x2％M2x3％M3/HyQaRbYcN3Wherein M is1、M2、M3Is a noble metal, x1％、x2％、x3% is the percentage content of noble metal in the total mass of the catalyst, wherein at most two values are 0, and the rest values are 0.1-20%,q, R, Y is transition metal, y is 0-1, a + b + c is 1, N is one of oxygen, nitrogen, carbon, phosphorus and sulfur.
2. The organic electrocatalytic oxidation catalyst as set forth in claim 1, wherein: the M is1、M2、M3Is one of ruthenium, rhodium, palladium, osmium, iridium and platinum.
3. The organic electrocatalytic oxidation catalyst as set forth in claim 1, wherein: q, R, Y is one element selected from scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, rhodium, osmium, tungsten, tantalum and iridium.
4. A method for preparing an electrocatalytic oxidation catalyst for organic matter according to any one of claims 1 to 3, characterized by comprising the steps of:
(1) weighing two or three transition metal acid ammonium salts and polyethylene glycol, stirring and mixing, and heating and stirring the mixed solution; after stirring, dropwise adding 10% dilute nitric acid to adjust the pH of the solution to 1-3;
(2) filling the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction; after the reaction is finished, carrying out suction filtration, washing the reactant to be neutral by using ultrapure water and ethanol, and fully drying at 60 ℃;
(3) calcining the dried product at high temperature for 1-5 h to obtain a metal oxide product;
(4) putting the product into a high-temperature high-pressure reaction kettle, and reacting to obtain transition metal oxide HxQaRbYcO3；
(5) The product H is reacted withxQaRbYcO3And NH3、H2/CH4、NaH2PO2Or calcining the sulfur powder at the high temperature of 350-700 ℃ for 2 hours to respectively prepare nitrogen, carbon, phosphorus and sulfide of the transition metal;
(6) charging noble metal salt and the above transition metal oxygen, nitrogen, carbon, phosphorus or sulfide into round-bottom flask, adding ethylene glycol and waterUltrasonically dispersing, carrying out oil bath reduction for 6-12 h at 140-160 ℃ in nitrogen atmosphere, carrying out suction filtration, washing reactants to be neutral by using ultrapure water, and fully drying at 60 ℃ to obtain a transition metal compound loaded noble metal x1％M1x2％M2x3％M3/HyQaRbYcN3。
5. The method of claim 4, wherein: in the step 1, the mass ratio of the metal acid ammonium salt to the polyethylene glycol is 1: 2.
6. The method of claim 4, wherein: the reaction condition of the mixed solution in the step 1 is that the temperature is controlled to be 50-70 ℃, and the stirring time is controlled to be 24-72 hours.
7. The method of claim 4, wherein: the hydrothermal reaction condition in the step 2 is that the temperature is 150-250 ℃, and the reaction time is 48-62 h.
8. The method of claim 4, wherein: the calcination temperature in the step 3 is 200-500 ℃.
9. The method of claim 4, wherein: the reaction conditions of the step 4 are that the temperature is 150-500 ℃, the hydrogen pressure is 3MPa, and the heating reaction is carried out for 2-5 h.
10. Use of an organic electrocatalytic oxidation catalyst according to any one of claims 1 to 3 in electrocatalytic oxidation reactions of small molecular organic species.
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