CN114430048A - Catalyst, preparation method thereof, membrane electrode and direct liquid fuel cell - Google Patents
Catalyst, preparation method thereof, membrane electrode and direct liquid fuel cell Download PDFInfo
- Publication number
- CN114430048A CN114430048A CN202011098596.5A CN202011098596A CN114430048A CN 114430048 A CN114430048 A CN 114430048A CN 202011098596 A CN202011098596 A CN 202011098596A CN 114430048 A CN114430048 A CN 114430048A
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- Prior art keywords
- catalyst
- carbon
- metal
- precursor
- carrier
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- 239000003054 catalyst Substances 0.000 title claims abstract description 155
- 239000007788 liquid Substances 0.000 title claims abstract description 71
- 239000000446 fuel Substances 0.000 title claims abstract description 43
- 239000012528 membrane Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 63
- 239000010953 base metal Substances 0.000 claims abstract description 56
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 53
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 37
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 105
- 239000010411 electrocatalyst Substances 0.000 claims description 74
- 239000002243 precursor Substances 0.000 claims description 58
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 36
- 239000003575 carbonaceous material Substances 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 229910021389 graphene Inorganic materials 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 23
- 238000003860 storage Methods 0.000 claims description 23
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 150000007522 mineralic acids Chemical class 0.000 claims description 19
- 239000012694 precious metal precursor Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 11
- 239000002041 carbon nanotube Substances 0.000 claims description 11
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- 239000012298 atmosphere Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
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- 239000007789 gas Substances 0.000 claims description 7
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- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 7
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- 238000002156 mixing Methods 0.000 claims description 6
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- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000003943 catecholamines Chemical class 0.000 claims description 5
- 238000009792 diffusion process Methods 0.000 claims description 5
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- 229910052721 tungsten Inorganic materials 0.000 claims description 5
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- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- 150000001721 carbon Polymers 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010970 precious metal Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 2
- SBVSDAFTZIVQEI-UHFFFAOYSA-N 2,3,4,4a,4b,5,6,7,8,8a,9,9a-dodecahydro-1h-carbazole Chemical compound C1CCCC2C3CCCCC3NC21 SBVSDAFTZIVQEI-UHFFFAOYSA-N 0.000 claims description 2
- ICBFNPPCXPMCBP-UHFFFAOYSA-N 2,5-dimethylpiperidine Chemical compound CC1CCC(C)NC1 ICBFNPPCXPMCBP-UHFFFAOYSA-N 0.000 claims description 2
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 claims description 2
- NNWUEBIEOFQMSS-UHFFFAOYSA-N 2-Methylpiperidine Chemical compound CC1CCCCN1 NNWUEBIEOFQMSS-UHFFFAOYSA-N 0.000 claims description 2
- RGHPCLZJAFCTIK-UHFFFAOYSA-N 2-methylpyrrolidine Chemical compound CC1CCCN1 RGHPCLZJAFCTIK-UHFFFAOYSA-N 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- JEGMWWXJUXDNJN-UHFFFAOYSA-N 3-methylpiperidine Chemical compound CC1CCCNC1 JEGMWWXJUXDNJN-UHFFFAOYSA-N 0.000 claims description 2
- KYINPWAJIVTFBW-UHFFFAOYSA-N 3-methylpyrrolidine Chemical compound CC1CCNC1 KYINPWAJIVTFBW-UHFFFAOYSA-N 0.000 claims description 2
- UZOFELREXGAFOI-UHFFFAOYSA-N 4-methylpiperidine Chemical compound CC1CCNCC1 UZOFELREXGAFOI-UHFFFAOYSA-N 0.000 claims description 2
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 claims description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002441 X-ray diffraction Methods 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000003976 azacycloalkanes Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- SBMSLRMNBSMKQC-UHFFFAOYSA-N pyrrolidin-1-amine Chemical compound NN1CCCC1 SBMSLRMNBSMKQC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000000034 method Methods 0.000 abstract description 47
- 230000003197 catalytic effect Effects 0.000 abstract description 45
- 230000008569 process Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 33
- 239000000243 solution Substances 0.000 description 29
- 229910052697 platinum Inorganic materials 0.000 description 26
- 210000004027 cell Anatomy 0.000 description 25
- 239000004094 surface-active agent Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 239000000693 micelle Substances 0.000 description 17
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 229910002837 PtCo Inorganic materials 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006356 dehydrogenation reaction Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- -1 amine compounds Chemical class 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 229910002836 PtFe Inorganic materials 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
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- 239000000758 substrate Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 239000012018 catalyst precursor Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
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- 239000003999 initiator Substances 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
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- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 description 1
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- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 description 1
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 description 1
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Images
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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
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
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- 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
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
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Abstract
The invention relates to the field of direct liquid fuel cells, and discloses a catalyst, a preparation method thereof, a membrane electrode and a direct liquid fuel cell, wherein the catalyst comprises a carbon-based carrier and metal nanoparticles loaded on the carbon-based carrier, wherein the metal nanoparticles exist in the form of intermetallic compounds formed by noble metals and base metals, and the content of the metal nanoparticles is 10-50 wt% and the content of the carbon-based carrier is 50-90 wt% based on the total mass of the catalyst. The catalyst has high catalytic activity in the direct liquid fuel catalysis process, and also has the advantages of strong anti-poisoning capacity, stable catalytic performance, long service life and the like.
Description
Technical Field
The invention relates to a direct liquid fuel cell, in particular to a catalyst and a preparation method thereof, a membrane electrode with the catalyst and a direct liquid fuel cell.
Background
At present, a number of hydrogen storage methods are reported: the methods of low-temperature liquid hydrogen storage, high-pressure gaseous hydrogen storage, metal alloy hydrogen storage, carbon material adsorption hydrogen storage, chemical hydride hydrogen storage, metal organic framework material hydrogen storage and the like are advanced to a certain extent, but further consideration needs to be given to the aspects of improving the mass hydrogen storage density, the volume hydrogen storage density, the energy efficiency, the safety, reducing the cost and the like. Therefore, it is critical to find a hydrogen storage method that is efficient, low cost, and scalable. Compared with numerous hydrogen storage technologies, the direct organic hydrogen storage liquid fuel cell has the advantages of high energy density, high theoretical energy conversion efficiency, green and renewable fuel, safe operation and the like, so that the research on the direct organic hydrogen storage liquid fuel cell has strategic significance for relieving the problems of current energy crisis, environmental pollution and the like.
In previous studies, US patent application US8338055 discloses a device that can generate electricity using organic hydrogen storage compounds. The device is similar to a proton exchange membrane fuel cell power generation system, and various organic micromolecules such as saturated cyclane, saturated azacyclane, alcohols, ethers and the like are used as fuels of the power generation device. The patent application states that this power plant requires the use of a catalyst for proper operation, but the type of catalyst that can be selected is not described in detail.
JapaneseScientists (chem. commun.2003, 609) tried to construct a micro fuel cell system using cyclohexane as organic fuel and oxygen as oxidant by using Nafion 117 as a proton exchange membrane, activated carbon as a catalyst carrier, and Pt as a cathode and an anode catalyst. The maximum output power of the micro fuel cell system is only 16mW cm-2Indicating that the electrocatalytic efficiency of Pt for cyclohexane is low.
Direct liquid fuels such as cyclohexane and the like can realize reversible reaction of dehydrogenation and hydrogenation under the condition of not changing a carbon skeleton, so that hydrogen storage is realized under the condition of hydrogenation, and hydrogen release is realized under the condition of dehydrogenation. However, the complete catalytic oxidation of the organic liquid is a multi-electron transfer process, the intermediate reaction is various, and the direct liquid fuel and the intermediate product have a strong adsorption effect on the catalyst and are easily accumulated on the surface of the catalyst, so that the activity of the catalyst is reduced, and the service life of the catalyst is shortened.
Therefore, the development of a catalyst for direct liquid fuel cells having high catalytic activity and anti-poisoning ability is an important issue in the development of current direct liquid fuel cell technologies.
Disclosure of Invention
The invention aims to solve the problems of low catalytic activity, weak anti-poisoning capability and short service life of a catalyst for a direct liquid fuel cell in the prior art, and provides the catalyst, a preparation method thereof, a membrane electrode and the direct liquid fuel cell.
In order to achieve the above object, a first aspect of the present invention provides a catalyst comprising a carbon-based support and metal nanoparticles supported on the carbon-based support, wherein the metal nanoparticles are present in the form of an intermetallic compound formed of a noble metal and a base metal, and the content of the metal nanoparticles is 10 to 50 wt% and the content of the carbon-based support is 50 to 90 wt%, based on the total mass of the catalyst.
In a second aspect, the present invention provides a method for preparing a catalyst, comprising the steps of: (1) dispersing a carbon-based carrier in an organic solvent containing inorganic acid for pretreatment to obtain a dispersion liquid containing the pretreated carrier; (2) mixing the dispersion liquid containing the pretreatment carrier with a precious metal precursor and a base metal precursor to load the precious metal precursor and the base metal precursor on the pretreatment carrier, and then separating and drying to obtain an electrocatalyst precursor; (3) the electrocatalyst precursor is calcined in an inert atmosphere.
The third aspect of the present invention provides a membrane electrode of a direct liquid fuel cell, including a proton exchange membrane, a catalyst attached to the surface of the proton exchange membrane, and a gas diffusion layer on the outer layer of the catalyst, where the catalyst is the catalyst of the first aspect and/or the catalyst prepared by the preparation method of the second aspect.
A fourth aspect of the invention provides a direct liquid fuel cell comprising a membrane electrode as described above and an organic liquid hydrogen storage solution.
Through the technical scheme, the catalyst has high content of metal nano particles, so that the catalyst has high activity in the application of direct liquid fuel catalytic dehydrogenation, and the metal nano particles exist in the form of intermetallic compounds formed by precious metals and base metals, so that the catalytic activity of the catalyst is further improved, the active centers formed by the precious metals and the base metals in the catalyst are not easy to poison, the catalyst is further high in poison resistance and stable in catalytic performance, and the service life of the catalyst is prolonged.
According to the invention, the carbon-based carrier is dispersed in an organic solvent containing inorganic acid for pretreatment, then the precious metal precursor and the base metal precursor are loaded on the pretreated carrier, and the obtained electrocatalyst precursor is roasted in an inert atmosphere, so that the obtained electrocatalyst not only has higher catalytic activity, but also has the advantages of stronger anti-poisoning capacity, stable catalytic performance, long service life and the like. The reason for this is probably because the step of dispersing the carbon-based carrier in the organic solvent containing the inorganic acid for pretreatment promotes the dispersion of the carbon-based carrier in the solvent and realizes the protonation of the carrier, enhances the acting force of the carrier and the metal precursor ions, and can hinder the hydrolysis of the metal precursor ions, thus improving the loading amount of the active component formed by the noble metal-base metal, further leading the noble metal ions and the base metal ions in the catalyst precursor to be more closely arranged, and further leading all the metal nanoparticles with catalytic activity in the catalyst to exist in the form of intermetallic compounds formed by the noble metal and the base metal. As mentioned above, on one hand, the catalytic activity of the catalyst is further improved, on the other hand, the active center formed by the noble metal-base metal in the catalyst is not easy to poison, the catalyst is further strong in poisoning resistance and stable in catalytic performance, and the service life of the catalyst is prolonged.
The catalyst of the invention can be applied to the membrane electrode of the direct liquid fuel cell, and further the direct liquid fuel cell can be obtained, and the catalyst has better application prospect in the field of the direct liquid fuel cell.
Drawings
FIG. 1 is a wide angle X-ray diffraction analysis of the catalysts of examples 1, 4 and 5;
FIG. 2 is a cyclic voltammogram of the membrane electrode obtained with the catalysts of example 1, example 4 and example 5;
FIG. 3 is a wide angle X-ray diffraction analysis chart of the catalyst in comparative example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, according to an aspect of the present invention, there is provided a catalyst comprising a carbon-based support and metal nanoparticles supported on the carbon-based support, wherein the metal nanoparticles are present in the form of an intermetallic compound formed of a noble metal and a base metal, and the content of the metal nanoparticles is 10 to 50 wt% and the content of the carbon-based support is 50 to 90 wt% based on the total mass of the catalyst.
In the invention, the existence state of the metal compound in the metal nano particles is tested by adopting wide-angle X-ray diffraction, and the metal nano particles exist in the form of the intermetallic compound formed by the noble metal and the base metal. Taking fig. 1 as an example, the PtCo catalyst observed only four diffraction peaks in the vicinity of 41 °, 48 °, 70 °, and 84 °. Actually, it is known from the standard sample of Pt that 4 absorption peaks of Pt originally appear at 39.5 °, 46.5 °, 67 ° and 82 °, and in combination with the standard absorption peaks of Pt, the 4 absorption peaks of Pt in the catalyst of the present invention are shifted to a high angle, and at the same time, no absorption peak appears at the position where the absorption peak of Co (44.2 °) appears in the diffraction pattern, indicating that the metal nanoparticles exist in the PtCo catalyst as an intermetallic compound formed from a noble metal (Pt) and a base metal (Co). Similarly, the strongest absorption peaks of Fe (44.6 °) and Zn (43.5 °) were not observed in the PtFe catalyst and PtZn catalyst, and the absorption peaks of Pt were shifted in the high-angle direction. In summary, in the catalyst obtained by the present invention, the base metals: the position of the strongest absorption peak of Co, Fe or Zn does not show the corresponding metal absorption peak, and the 4 absorption peaks of Pt are all shifted to high angles, which indicates that the metal nanoparticles in the present invention are all in the form of intermetallic compounds formed by noble metals (e.g., Pt) and base metals (e.g., Co, Fe, Zn, etc.).
Preferably, the catalyst has an X-ray diffraction curve in which the diffraction peak of the noble metal is shifted by 0.3 to 5 degrees in the high angle direction and does not have a diffraction peak corresponding to a base metal. Further preferably, the diffraction peak of the noble metal is shifted by 0.5 to 3 degrees toward the high angle direction. In this preferred embodiment, the catalyst exhibits better catalytic activity and catalytic stability.
According to the present invention, it is preferable that the content of the metal nanoparticles is 20 to 50 wt%, preferably 20 to 40 wt%, and the content of the carbon-based support is 50 to 80 wt%, preferably 60 to 80 wt%, based on the total mass of the catalyst.
According to the invention, the metal nanoparticles are preferably present in an amount of 20 to 40 wt.%, based on the total mass of the catalyst, and may for example be 20 wt.%, 22 wt.%, 24 wt.%, 26 wt.%, 28 wt.%, 30 wt.%, 32 wt.%, 34 wt.%, 36 wt.%, 38 wt.%, 40 wt.% and any value in between.
According to the present invention, the carbon-based support is preferably contained in an amount of 60 to 80 wt%, for example, 60 wt%, 62 wt%, 64 wt%, 66 wt%, 68 wt%, 70 wt%, 72 wt%, 74 wt%, 76 wt%, 78 wt%, 80 wt% and any value therebetween, based on the total mass of the catalyst.
And detecting the content of the metal nanoparticles in the prepared electrocatalyst by adopting an inductively coupled plasma atomic emission spectrometry (ICP-AES) method.
The inventors of the present invention have further found that in the case where the size of the metal nanoparticles is 2 to 10nm, the catalytic activity and anti-poisoning ability of the catalyst can be further improved, and the catalytic stability and service life of the catalyst can be further improved, and further preferably, the size of the metal nanoparticles is 2 to 5nm, which is why it is possible to further improve the effective contact of the catalyst with the direct liquid fuel in this case.
The size of the intermetallic compound nanoparticles can be calculated by utilizing the Shele formula and combining the half-peak width of a diffraction peak in an XRD spectrogram and the Shele formula.
According to the invention, the noble metal is Pt and/or Pd, and the base metal is at least one of transition metal elements of the fourth period, W and Mo; preferably, the base metal is at least one of Cu, W, Mo, Zn, Fe, Co, Ni and Mn; further preferably, the noble metal is Pt, and the base metal is Zn, Fe or Co, in which case, active centers of intermetallic compounds of Pt-Zn, Pt-Fe and Pt-Co can be formed, further improving the catalytic activity and poisoning resistance of the catalyst. Still more preferably, the atomic ratio of the noble metal to the base metal in the metal nanoparticles is from 0.5 to 5:1, preferably 1 to 3: 1; still more preferably, the atomic ratio of noble metal to base metal in the metal nanoparticles is 2-3: 1.
and detecting the atomic ratio of each element in the intermetallic compound by adopting X-ray photoelectron spectroscopy.
According to the present invention, the carbon-based carrier may be a carbon-based material that is at least one of carbon black, carbon nanotubes, graphene, two-dimensional carbon sheets, and graphene oxide; the material may also be at least one of carbon black modified by a nitrogen-containing polymer, carbon nanotubes, graphene, two-dimensional carbon sheets, and graphene oxide.
According to the present invention, in order to increase the loading amount of the metal nanoparticles and further increase the catalytic activity of the catalyst, preferably, the carbon-based support is at least one of carbon black modified by a nitrogen-containing polymer, a carbon nanotube, graphene, a two-dimensional carbon sheet, and graphene oxide.
According to the invention, the nitrogen-containing polymer is obtained by polymerizing at least one of pyrrole, thiophene, pyrrole derivatives, catecholamine and aromatic amine; further preferably, the nitrogen-containing polymer is obtained by polymerizing at least one of pyrrole, aniline, p-phenylenediamine, o-phenylenediamine, thiophene, m-phenylenediamine, 1,3, 5-triaminobenzene, and dopamine.
According to the present invention, it is preferable that the nitrogen-containing polymer is contained in the carbon-based support in an amount of 5 to 99 wt%, preferably 20 to 99 wt%, based on the total weight of the carbon-based support.
According to the present invention, a carbon-based support obtained from at least one of carbon black, carbon nanotube, graphene, two-dimensional carbon sheet, and graphene oxide modified with a nitrogen-containing polymer may be prepared using a conventional method, for example, the method disclosed in CN 101549304A: dispersing carbon materials into water, methanol or chloroform to prepare suspension, wherein the mass ratio of the suspension to the carbon materials is 1: 10-30; adding glacial acetic acid or hydrochloric acid to adjust pH to 1-4, and stirring at room temperature for 10-30 min; adding pyrrole or thiophene according to the mass ratio of the pyrrole or thiophene to the carbon material of 1: 4-1: 5, stirring for 5-10min, and then adding H with the concentration of 3-30 wt%2O2Or FeCl320-50ml of water solution is used as an initiator of polymerization reaction, and is stirred for 3-10h at room temperature; product ofWashing with warm deionized water, and vacuum drying to obtain the conductive polymer modified carbon carrier. The invention can be realized by a carbon-based carrier obtained by at least one of carbon black modified by a nitrogen-containing polymer, a carbon nano tube, graphene, a two-dimensional carbon sheet and graphene oxide, an electrocatalyst carrier described in CN202010599251.1 Chinese patent application, and a graphene/pyrrole polymer supercapacitor electrode material prepared by the preparation method of the graphene/pyrrole polymer supercapacitor electrode material disclosed in CN 104992851A.
According to the present invention, in order to further improve the catalytic activity of the obtained battery catalyst, it is preferable that the carbon-based support obtained from at least one of carbon black modified with a nitrogen-containing polymer, carbon nanotube, graphene, two-dimensional carbon sheet, and graphene oxide is the electrocatalyst support described in chinese patent application CN 202010599251.1. The electrocatalyst carrier comprises a carbon-based material with a sheet structure and a nitrogen-containing polymer layer coated on the surface of the carbon-based material, wherein mesopores are distributed on the nitrogen-containing polymer layer. Preferably, the electrocatalyst support has a specific surface area in the range from 100 to 400m2G (which may be 100m, for example)2/g、150m2/g、200m2/g、300m2/g、350m2/g、400m2/g, or any value between any two values), preferably from 150 to 300m2(ii) in terms of/g. Further preferably, the pore size of the mesopores is 5-15 nm; still more preferably, the shape of the mesopores is spherical or strip-shaped.
In the present invention, the specific surface area is measured by a BET nitrogen adsorption method.
In a preferred embodiment of the present invention, in order to further increase the content of hydrophilic groups in the support and, at the same time, increase the mass transfer efficiency of the carbon-based material in the support, thereby increasing the catalytic activity, the thickness of the nitrogen-containing polymer layer is 5 to 30nm (which may be, for example, 5nm, 8nm, 11nm, 14nm, 18nm, 22nm, 28nm, 30nm, or any value between any two values), preferably 8 to 20 nm.
In the invention, the surface appearance of the electrocatalyst carrier and the thickness of the sample are characterized by using a Bruker atomic force microscope.
Preferably, the content of the carbon-based material is 1-10% and the content of the nitrogen-containing polymer is 90-99% by mass percentage of the electrocatalyst carrier; preferably, the content of the carbon-based material is 4% to 8%, and the content of the nitrogen-containing polymer is 92% to 96%.
In the present invention, the content of the carbon-based material and the content of the nitrogen-containing polymer are measured by a thermogravimetric analysis method.
In the technical scheme, as long as the conditions of the invention are met, the catalytic activity of the electrocatalyst obtained by the carbon-based electrocatalyst carrier can be greatly improved. In order to increase the number of nitrogen-containing groups in the nitrogen-containing polymer and further increase the catalytic activity of the electrocatalyst, it is preferable that the nitrogen-containing polymer layer is obtained after polymerization of at least one of pyrrole, pyrrole derivatives, catecholamines, and aromatic amines. The pyrrole derivative is a compound obtained after a hydrogen group on a pyrrole ring is substituted by other groups, preferably, the substituted hydrogen group is an electron donating group, and the electron donating group is preferably a hydroxyl group and/or an amino group. By aromatic amine is meant an amine having one aromatic substituent, i.e. -NH2The aromatic hydrocarbon generally has one or more benzene rings, i.e., the nitrogen atom is directly bonded to a carbon atom of the benzene ring by a chemical bond, preferably, the aromatic hydrocarbon group bonded to the amino group in the aromatic amine is a benzene ring, and more preferably, the benzene ring contains a plurality of electron donating groups such as amino groups and/or hydroxyl groups. Catecholamines are amine compounds containing catechol (i.e., catechol) and include dopamine, norepinephrine and epinephrine and their derivatives. Still more preferably, the nitrogen-containing organic monomer is at least one of pyrrole, aniline, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, 1,3, 5-triaminobenzene and dopamine.
In a preferred embodiment of the invention, the amount of amino groups in the electrocatalyst support is from 7 to 28mmol/g (which may be, for example, 7mmol/g, 10mmol/g, 15mmol/g, 20mmol/g, 25mmol/g, 28mmol/g, or any value therebetween), preferably from 10 to 25 mmol/g. The content of amino groups refers to the content of all types of amino groups, including primary, secondary, tertiary, and the like.
The content of amino groups was measured by the Kjeldahl method.
Preferably, in the electrocatalyst carrier, the content of carbon element is 35-85%, the content of nitrogen element is 10-40%, the content of hydrogen element is 10-15%, and the content of oxygen element is 5-10% by mass percentage of the electrocatalyst carrier.
The content of each element in the electrocatalyst support was measured by a CHNS-932 element analyzer from Leco.
The size of the electrocatalyst support is not more than 30 μm, preferably not more than 20 μm, and more preferably 1-20 μm; among them, the thickness of the electrocatalyst support is 10 to 100nm, preferably 10 to 50nm, and more preferably 10 to 35 nm.
In a preferred embodiment of the invention, the electrocatalyst support is prepared by: (1) under the condition that the mass of a surfactant contained in a dispersion liquid is not less than the mass corresponding to the critical micelle concentration of the surfactant, contacting a carbon-based material with a liquid in which the surfactant and a nitrogen-containing organic monomer are dispersed to obtain a mixed liquid; (2) and (2) under the condition of polymerizing the nitrogen-containing organic monomer, contacting an initiator with the nitrogen-containing organic monomer in the mixed solution in the step (1).
In the above technical solution, under the condition that the mass of the surfactant contained in the dispersion is not less than the mass corresponding to the critical micelle concentration of the surfactant, the surfactant forms micelles in the solution, the micelles are adsorbed on the surface of the carbon-based material due to the adsorption effect of the carbon-based material, and the nitrogen-containing organic monomer having a nitrogen-containing group is further distributed on the surface of the micelles under the effect of the hydrophilic group of the surfactant to form an aggregate in which the nitrogen-containing organic monomer is distributed along the micelles. According to the preparation method of the electrocatalyst carrier provided by the invention, the surfactant is introduced into a polymerization system of the nitrogen-containing organic monomer and is attached to the surface of the carbon-based material in a micelle form, so that the adhesive force and the adhesive amount of the nitrogen-containing organic monomer on the surface of the carbon-based material are improved, the adhesive force and the adhesive amount of the nitrogen-containing polymer on the surface of the carbon-based material are improved, and the surfactant is removed after polymerization, so that a mesoporous structure is formed on the surface of the material, and the mesoporous structure is beneficial to improving the mass transfer efficiency in the catalytic reaction process and improving the catalytic performance of the final catalyst.
In the above technical solution, the present invention can be achieved as long as the surfactant forms micelles in water and can be adsorbed on the carbon-based material, and the micelles can further adsorb the nitrogen-containing organic monomer distributed along the micelles, and in order to further increase the number of mesopores, increase the specific surface area of the carrier, and further increase the catalytic activity of the catalyst, the surfactant is preferably a nonionic surfactant, and the surfactant is preferably at least one of alkylphenol ethoxylates, fatty acid polyoxyethylene esters, polyoxyethylene alkylamines, polyoxyethylene alkylolamides, and polyether surfactants; more preferably a polyether surfactant, and even more preferably a poloxamer type surfactant which is a polyoxyethylene polyoxypropylene ether block copolymer having the general formula HO (C) and at least one of Brj35, Brj56, Brj78, Brj76 and Brj97 manufactured by BASF2H4O)a(C3H6O)b(C2H4O)cH, wherein a is 2-130, c is 2-130, and b is 15-67; the polyoxyethylene content was 81.8. + -. 1.9% by weight. Still more preferably, the poloxamer-type surfactant is at least one of L64, P65, F68, P84, P108, P105, P123, P103, F127, F88, and F108 produced by basf; still more preferably at least one of F127, P123 and F108.
In order to further adjust the aperture and the length of the mesopores, increase the specific surface area of the carrier and further increase the catalytic activity of the catalyst, the mass content of the surfactant in the step (1) is 2 to 30 times, preferably 2 to 15 times, of the mass content corresponding to the critical micelle concentration of the surfactant.
In the present invention, the critical micelle concentration refers to the lowest concentration of surfactant molecules that associate in a solvent to form micelles. The surfactant can adsorb common monomolecular layer at interface in enrichment way, and when the surface adsorption reaches saturationAnd when the surfactant molecules cannot be enriched on the surface, the hydrophobic effect of the hydrophobic groups still strives to promote the hydrophobic group molecules to escape from the water environment, so that the surfactant molecules are self-polymerized in the solution, namely the hydrophobic groups are gathered together to form an inner core, and the hydrophilic groups face outwards to contact with water to form a shell, thereby forming the simplest micelle. The concentration of surfactant at the onset of micelle formation is referred to as the critical micelle concentration, abbreviated as CMC, and is usually expressed in mol/L or g/L. The method for measuring the critical micelle concentration is various, and the method is commonly used in a surface tension method, a conductivity method, a dye method, a dissolution increasing method, an osmotic pressure method, a pulse injection method, a fluorescence method, an ultrasonic adsorption method, a turbidity method, a pH value method, a rheology method, an ion selective electrode method, a cyclic voltammetry method and the like. Typical ionic surfactants have a CMC of approximately 10-2-10-3The CMC of the nonionic surfactant is 10 between mol/L-4mol/L is less than. For example, in the examples hereinafter, the CMC of F127 produced by Basff is 3g/L (30 ℃).
Preferably, the mass ratio of the carbon-based material, the surfactant, the nitrogen-containing organic monomer and the initiator is 1: 80-300: 10-40: 30-120;
preferably, the carbon-based material is used in an amount of 0.03 to 0.3mg with respect to 1mL of the solution in step (1).
Preferably, the contacting conditions in step (1) include: the temperature is 10-50 ℃ and the time is 0.5-4 h.
Preferably, the polymerization conditions in step (2) include: the temperature is 12-50 ℃ and the time is 3-36 h.
According to the present invention, preferably, the carbon-based material has a size of 50nm to 50 μm and a specific surface area of 50 to 1000m2(ii)/g; further preferably, the specific surface area is 300 to 1000m2(ii)/g; still more preferably, the carbon-based material has a specific surface area of 400 to 800m2In this case, the inventors of the present invention have found that the resulting catalyst has higher catalytic activity and higher poisoning resistance, and has a longer service life. The reason for this is probably that the specific surface area of the carbon-based material is 400 to 800m2In the case of/g, on the one hand, the uniformity of the loading of the metal nanoparticles can be further improved, and on the other handOn one hand, the adsorption effect of the catalyst on the direct liquid fuel and the product is moderate, and the activity reduction caused by the accumulation of the direct liquid fuel and the product can be further reduced, so that the service life of the catalyst is further prolonged.
According to the present invention, it is preferable that the carbon-based material has a specific surface area of 400 to 800m2A value of/g, for example 400m2/g，450m2/g，500m2/g，550m2/g，600m2/g，650m2/g，700m2/g，750m2/g，800m2G, and any value between any two values.
A second aspect of the present invention provides a method for preparing a catalyst, comprising the steps of: (1) dispersing a carbon-based carrier in an organic solvent containing inorganic acid for pretreatment to obtain a dispersion liquid containing the pretreated carrier; (2) mixing the dispersion liquid containing the pretreatment carrier with a precious metal precursor and a base metal precursor to load the precious metal precursor and the base metal precursor on the pretreatment carrier, and then separating and drying to obtain an electrocatalyst precursor; (3) the electrocatalyst precursor is calcined in an inert atmosphere.
As mentioned above, in the invention, the carbon-based carrier is dispersed in the organic solvent containing the inorganic acid for pretreatment, then the precious metal precursor and the base metal precursor are loaded on the pretreatment carrier, and the obtained electrocatalyst precursor is roasted in the inert atmosphere, so that the obtained electrocatalyst not only has higher catalytic activity, but also has the advantages of stronger anti-poisoning capacity, stable catalytic performance, long service life and the like. The reason for this is probably because the step of dispersing the carbon-based carrier in the organic solvent containing the inorganic acid for pretreatment promotes the dispersion of the carbon-based carrier in the solvent and realizes the protonation of the carrier, enhances the acting force of the carrier and the metal precursor ions, and can hinder the hydrolysis of the metal precursor ions, thus improving the loading amount of the active component formed by the noble metal-base metal, further leading the noble metal ions and the base metal ions in the catalyst precursor to be more closely arranged, and further leading all the metal nanoparticles with catalytic activity in the catalyst to exist in the form of intermetallic compounds formed by the noble metal and the base metal. As mentioned above, on one hand, the catalytic activity of the catalyst is further improved, on the other hand, the active center formed by the noble metal-base metal in the catalyst is not easy to poison, the catalyst is further strong in poisoning resistance and stable in catalytic performance, and the service life of the catalyst is prolonged.
The inventors of the present invention found that, compared to the prior art in which a catalyst precursor is partially reduced before calcination (for example, chinese patent document CN101976737B, sodium dihydrogen hypophosphite is added in the process of preparing the catalyst precursor), the catalyst precursor of the present invention does not need to undergo a reduction step in the preparation process, and does not need to add other auxiliary agents such as sodium dihydrogen hypophosphite to perform a preliminary reduction, and does not need to introduce other auxiliary agent ions, so that more active centers are formed in the catalyst, and a catalyst with higher activity is obtained.
According to the invention, the inorganic acid is a strong inorganic acid, which may be, for example, at least one of hydrochloric acid and/or hydrobromic acid; further preferred is hydrochloric acid.
According to the present invention, the organic solvent is at least one of an alcohol having 1 to 4 carbon atoms and tetrahydrofuran; the alcohol containing 1 to 4 carbon atoms may be a monohydric alcohol containing 1 to 4 carbon atoms, or a polyhydric alcohol containing 1 to 4 carbon atoms, and examples thereof include methanol, ethanol, ethylene glycol, n-propanol, isopropanol, glycerol, and n-butanol; in order to further improve the catalytic activity and catalytic performance stability of the obtained catalyst, preferably, the organic solvent is at least one of methanol, ethanol and tetrahydrofuran.
According to the invention, the concentration of the inorganic acid in the organic solvent is between 0.1 and 5mol L-1Preferably, the concentration of the inorganic acid in the organic solvent is 0.5 to 4.5mol L-1Further preferably, the concentration of the inorganic acid in the organic solvent is 0.8 to 3mol L-1(ii) a Still more preferably, the concentration of the inorganic acid in the organic solvent is 1 to 2mol L-1。
According to the invention, the concentration of the mineral acid in the organic solvent is preferably from 1 to 2mol L-1For example, it may be 1.0mol L-1，1.2mol L-1，1.4mol L-1，1.6mol L-1，1.8mol L-1，2.0mol L-1And any value between any two values. Wherein, in the case of using hydrochloric acid, the concentration of the inorganic acid in the organic solvent refers to the concentration of HCl in the solution.
In the above technical scheme, the organic solvent containing inorganic acid can be obtained by a conventional preparation method, for example, concentrated inorganic acid is added into the organic solvent. Taking a hydrochloric acid-ethanol solution as an example, the method for preparing the hydrochloric acid-ethanol solution comprises the following steps: and adding concentrated hydrochloric acid into ethanol according to a ratio to obtain a target hydrochloric acid-ethanol solution.
According to the present invention, the precious metal precursor and/or the base metal precursor in step (2) may be added in the form of powder, or may be added in the form of solution, as long as the precious metal precursor and/or the base metal precursor are/is finally dissolved in the mixed system of step (2), and the present invention can be achieved. Preferably, the precious metal precursor and/or the base metal precursor in step (2) are added to the dispersion containing the pretreated support in the form of respective precursor solutions.
According to the present invention, in order to further improve the catalytic activity of the obtained catalyst and the catalytic stability of the catalyst, it is preferable that the volume content of the organic solvent in the mixed system obtained by mixing in step (2) is 70 to 90%; in this case, the carbon-based material can be more dispersed, and the load of the metal on the pretreated carbon-based material can be increased.
The loading modes of the precious metal precursor and the base metal precursor can be flexibly adjusted, for example, continuous mixing can be adopted. In the invention, in order to further improve the preparation efficiency, the loading process is carried out under ultrasonic conditions, and the ultrasonic conditions can be flexibly adjusted, preferably, the ultrasonic frequency is 20-200kHz, and the ultrasonic time is 6-12 h.
According to the invention, the calcination conditions in step (3) include: the roasting temperature is 800-1000 ℃, preferably 850-950 ℃, and the roasting time is 1-4h, preferably 2-3 h.
According to the present invention, the inert atmosphere may be an inert gas or a mixed gas of an inert gas and a reducing gas such as hydrogen, and preferably, the inert gas is nitrogen and/or argon.
According to the present invention, preferably, the carbon-based carrier, the noble metal precursor and the base metal precursor are used in such amounts that the metal nanoparticles are contained in an amount of 20 to 50 wt% and the carbon-based carrier is contained in an amount of 50 to 80 wt%, based on the total mass of the catalyst.
The amount of the added elements can be adjusted within a wide range, and the mass ratio of the noble metal to the base metal in the mixed system in the step (2) is preferably 0.5 to 4, preferably 1.8 to 2.5: 1.
According to the invention, the molar ratio of the precious metal precursor and the base metal precursor is preferably 0.3-5: 1; preferably 1-5: 1; still further preferably, the concentration of the noble metal precursor in the mixed system in the step (2) is 8-24 mmol/L.
Still more preferably, the amount of the carbon-based carrier added in the step (1) is 10 to 25mg, preferably 10 to 20mg, relative to 10mL of the mixed system in the step (2).
According to the invention, the precious metal precursor and the base metal precursor are water-soluble metal salts corresponding to respective metal elements. For example, the precursor of Pt may be at least one of platinum acetate, platinum chloride, ammonium chloroplatinite, dinitrosoplatinum, chloroplatinic acid, and tetraammineplatinum chloride, preferably platinum chloride; the precursor of Zn can be at least one of zinc nitrate, zinc chloride, zinc sulfate and zinc acetate, and is preferably zinc chloride; the precursor of Fe can be at least one of ferrous acetate, ferrocene, ferric chloride and ferric sulfate, and is preferably ferric chloride; the precursor of Co can be carbonyl cobalt, cobalt acetate, cobalt chloride and cobalt nitrate, preferably cobalt chloride; the precursor of Cu can be at least one of copper sulfate, copper chloride and copper nitrate, and is preferably copper chloride; the precursor of W can be at least one of tungsten chloride, tungsten carbonyl, ammonium paratungstate and ammonium tungstate, and is preferably tungsten chloride; the precursor of Mo may be at least one of molybdenum pentachloride, molybdenum carbonyl and molybdic acid, and may be, for example, molybdenum pentachloride; the precursor of Ni may be at least one of nickel acetate, nickel nitrate, nickel sulfate, and nickel chloride, and may be, for example, nickel chloride; the precursor of Mn can be at least one of manganese chloride, manganese sulfate, manganese nitrate and manganese acetate; manganese chloride is preferred.
The manner in which the carbon-based carrier is dispersed in step (1) may be any conventional manner in the art according to the present invention, such as stirring, sonication, vortexing, and the like. Preferably, the conditions of the pretreatment in step (1) include: the temperature of the pretreatment is 25-40 ℃; and/or the time is 60-240 min.
According to the present invention, the separation and drying in step (2) can be performed by conventional methods in the art, for example, the separation can be performed by filtration, centrifugation, etc.; the drying mode is drying, natural air drying, etc., preferably, the drying condition is drying for 6-12h at 40-60 deg.C.
The third aspect of the present invention provides a membrane electrode of a direct liquid fuel cell, including a proton exchange membrane, a catalyst attached to the surface of the proton exchange membrane, and a gas diffusion layer on the outer layer of the catalyst, where the catalyst is the catalyst of the first aspect and/or the catalyst prepared by the preparation method of the second aspect.
The membrane electrode of the direct liquid fuel cell obtained by applying the catalyst disclosed by the invention not only has higher catalytic activity, but also has the advantages of stronger anti-poisoning capacity, stable catalytic performance, long service life and the like.
For direct liquid fuel cell membrane electrode acquisition, the electrocatalyst may be attached to the surface of the proton exchange membrane in a manner conventional in the art. The membrane electrode can be prepared, for example, by the method in CN 106784943A.
In a specific embodiment of the invention, the catalyst is coated on two sides of the electrode substrate by adopting a spraying mode; the coating mode can be selected from conventional spraying modes in the field such as ultrasonic spraying, pneumatic spraying or electrostatic spraying. The electrode substrate is typically a proton exchange membrane.
More preferably, the membrane electrode of the direct liquid fuel cell is prepared by a method such asThe following: the catalyst is coated on two sides of a proton exchange membrane by ultrasonic spraying, pneumatic spraying or electrostatic spraying to form a catalyst layer, and the coating amount of the catalyst is 1-10mg/cm2(ii) a And then the gas diffusion layer is fixed to the outside of the catalyst layer by means of hot pressing.
The gas diffusion layer can be carbon fiber paper, carbon fiber woven cloth, non-woven cloth and the like.
A fourth aspect of the invention provides a direct liquid fuel cell comprising a membrane electrode as described hereinbefore and an organic liquid hydrogen storage solution.
The direct liquid fuel cell obtained by applying the catalyst of the invention not only has higher catalytic activity, but also has the advantages of stronger anti-poisoning capability, stable catalytic performance, long service life and the like.
According to the invention, the direct liquid fuel cell can be obtained in a conventional manner in the prior art, for example, on the basis of the obtained membrane electrode, the direct liquid fuel can be used as a substrate, and the bipolar plate, the sealing member and the membrane electrode obtained by the invention can be further assembled to obtain the direct liquid fuel cell in combination with the prior art.
According to the invention, the organic liquid hydrogen storage liquid is an alkane having a saturated cyclic group which effects a reversible reaction of dehydrogenation and hydrogenation without changing the carbon skeleton, and according to the invention, preferably, the organic liquid hydrogen storage liquid is a saturated cycloalkane having at least one 5-6 membered ring and/or a saturated azacycloalkane having at least one 5-6 membered ring; further preferably, the organic liquid hydrogen storage liquid is at least one of methylcyclohexane, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole, perhydrocarbazole, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 2, 6-dimethylpiperidine, 2, 5-dimethylpiperidine, 1-methylpyrrolidine, 2-methylpyrrolidine, 3-methylpyrrolidine, 1-aminopyrrolidine, piperazine and perhydroimidazole.
The present invention will be described in detail below by way of examples. In the following examples, the content of metal nanoparticles in the prepared electrocatalyst was detected by inductively coupled plasma atomic emission spectrometry (ICP-AES); testing the existence state of the metal compound in the metal nanoparticles by adopting wide-angle X-ray diffraction; detecting the atomic ratio of each element in the intermetallic compound by adopting X-ray photoelectron spectroscopy; the dehydrogenation potential of the catalyst was measured using Cyclic Voltammetry (CV) method, with lower dehydrogenation potential meaning higher methylcyclohexane electrocatalytic activity. The raw materials of the invention are all commercial products except for special instructions.
Preparation example 1
Carbon-based supports were prepared using the method described in example 1 in CN 101549304A: 10 g of graphene oxide (size 1-20 μm, specific surface area 420 m)2/g) 100ml of methanol is added to prepare a suspension, 2g of glacial acetic acid is added to the suspension, the mixture is stirred for 20min at room temperature, and the pH value is adjusted to 1.0. 2.5g of pyrrole monomer was added and stirred for 7min, after which 30ml of 3 wt.% FeCl was added3The aqueous solution was used as an initiator for polymerization and stirred at room temperature (25 ℃ C.) for 3 hours. The product was washed with warm deionized water and dried at 90 ℃ for 12h under vacuum.
The content of polypyrrole in the carbon-based carrier is 20 wt% based on the total mass of the carbon-based carrier.
Preparation example 2
The preparation method of the carbon-based carrier described in example 1 of chinese patent application CN 202010599251.1:
(1) 40mg of graphene oxide (1-20 μm in size and 420m in specific surface area) was added to 300mL of a dispersion (deionized water as liquid) containing 5g of F127 (16.7 mg/mL)2/g) and 650mg of m-phenylenediamine (the concentration is 2.2mg/mL), stirring for 2 hours at 30 ℃ to enable the graphene oxide to be in contact with a dispersion liquid containing F127 and the m-phenylenediamine to obtain a mixed liquid;
(2) dropwise adding 50mL of aqueous solution containing 1.9g of ammonium peroxide into the mixed solution in the step (1), and reacting for 24 hours at 30 ℃ under the stirring condition;
(3) after the reaction is finished, separating the product from the mixed solution by centrifugation (the rotating speed is 3000rpm, the centrifugation time is 10min), re-dispersing the centrifuged product by deionized water, repeating the centrifugation procedure, cleaning the product, repeating the cleaning process for 3 times, and drying for 12h at 60 ℃.
In this preparation example, the content of the carbon-based material was 5.1% and the content of the nitrogen-containing polymer was 94.9% in terms of the mass percentage of the electrocatalyst support, based on the total weight of the electrocatalyst support. The size of the electrocatalytic carrier is 1-20 mu m, and the thickness is 28 nm; the electrocatalyst carrier has a mesoporous structure, the mesoporous aperture is about 11nm (as proved by a result of a scanning electron microscope), and the specific surface area of the carrier is 160m2(ii)/g; the content of amino groups in the electrocatalyst support was 17.5 mmol/g.
Example 1
(1) Dispersing 200mg of the carbon-based carrier obtained in preparation example 1 in 10mL of hydrochloric acid-ethanol solution with the concentration of 1mol/L by vortex oscillation for pretreatment for 100min, wherein the pretreatment temperature is 30 ℃, and obtaining a dispersion liquid containing the pretreated carrier;
(2) adding 3mL of 20mg/mL chloroplatinic acid solution and 280 mu L of 100mg/mL cobalt chloride aqueous solution into dispersion liquid containing a pretreatment carrier, dispersing for 6h by ultrasonic (frequency is 200kHz), separating by using reduced pressure suction filtration to obtain an electrocatalyst precursor adsorbed with metal ions, and drying for 12h at 40 ℃ to obtain the electrocatalyst precursor;
(3) and (3) carrying out high-temperature roasting treatment on the electrocatalyst precursor to obtain the electrocatalyst, wherein the roasting temperature is 900 ℃, the roasting time is 3h, and the roasting atmosphere is high-purity nitrogen.
Through the detection of an inductively coupled plasma spectrometer, the mass content of metal nano particles in the electrocatalyst is 30 wt% based on the total mass of the electrocatalyst, wherein the content of platinum element is 27.1 wt%, the content of cobalt element is 2.9 wt%, and the rest is a carrier.
The atomic ratio of Pt to Co in the intermetallic compound was 2.8 as detected by X-ray photoelectron spectroscopy: 1.
in order to characterize the crystalline state of the metal nanoparticles in the catalyst, a wide-angle X-ray diffraction test was used, and the result is shown in fig. 1, and the curve corresponding to PtCo is the XRD test curve of the electrocatalyst in this example. As is clear from the curve corresponding to PtCo in fig. 1, only a diffraction peak of metal platinum is observed in the sample, and no diffraction peak of Co metal or a compound thereof is observed. But the diffraction peak of the prepared electrocatalyst was shifted to a high angle direction compared to the standard peak position of Pt. This is because the Co doping causes the Pt — Pt bond length to be shortened, and the interplanar spacing to be shortened, so that the diffraction peak position is directed toward a high angle. Specifically, the PtCo catalyst observed only four diffraction peaks in the vicinity of 41 °, 48 °, 70 °, and 84 °. Actually, it is found from the standard sample of Pt that 4 absorption peaks of Pt originally appear at 39.5 °, 46.5 °, 67 ° and 82 °, and in combination with the standard absorption peaks of Pt, the 4 absorption peaks of Pt are shifted to a high angle, and in the diffraction pattern, no absorption peak is found at a position where an absorption peak of Co (44.2 °) is supposed to appear, indicating that the metal nanoparticles exist as an intermetallic compound formed of a noble metal (Pt) and a base metal (Co) in the PtCo catalyst.
By utilizing the Shele formula, the size of the intermetallic compound nano particles can be calculated to be 3.6nm by combining the half-peak width of a diffraction peak in an XRD spectrogram.
Example 2
(1) Dispersing 200mg of the carbon-based carrier obtained in preparation example 1 in 5mL of hydrochloric acid-ethanol solution with the concentration of 5mol/L by vortex oscillation for pretreatment for 240min, wherein the pretreatment temperature is 25 ℃, and obtaining a dispersion liquid containing the pretreated carrier;
(2) adding 5mL of 20mg/mL chloroplatinic acid solution and 280 mu L of 100mg/mL cobalt chloride aqueous solution into dispersion liquid containing a pretreatment carrier, dispersing for 8h by ultrasonic (frequency is 100kHz), separating by using reduced pressure suction filtration to obtain an electrocatalyst precursor adsorbed with metal ions, and drying for 10h at 50 ℃ to obtain the electrocatalyst precursor;
(3) and (3) carrying out high-temperature roasting treatment on the electrocatalyst precursor to obtain the electrocatalyst, wherein the roasting temperature is 1000 ℃, the roasting time is 1h, and the roasting atmosphere is high-purity nitrogen.
The catalyst in this example was examined in the same manner as in example 1, and it was found that the electrocatalyst had a metal nanoparticle content of 50 wt%, wherein the platinum content was 47.1 wt%, the cobalt content was 2.9 wt%, and the others were the carriers, based on the total mass of the catalyst; the atomic ratio of Pt to Co in the intermetallic compound was 4.9: 1.
in the wide-angle X-ray diffraction test, only the diffraction peak of metal platinum was observed in the sample, and no diffraction peak of Co metal or its compound was found, but the diffraction peak of the prepared electrocatalyst was shifted to a high angle direction compared to the standard peak position of Pt. Specifically, 4 diffraction peaks were observed in the PtCo catalyst only in the vicinity of 40.5 °, 47.2 °, 68.9 ° and 82.9 °, and the 4 absorption peaks of Pt were all shifted toward high angles, and in the diffraction pattern, no absorption peak was observed at the position where the absorption peak of Co (44.2 °) would have occurred, indicating that the metal nanoparticles are present in the PtCo catalyst in the form of an intermetallic compound formed of a noble metal (Pt) and a base metal (Co).
The size of the intermetallic compound nanoparticles can be calculated by utilizing the Sherle formula and combining the half-peak width of a diffraction peak in an XRD spectrogram, and the size of the intermetallic compound nanoparticles is 6.5 nm.
Example 3
(1) Dispersing 200mg of the carbon-based carrier obtained in preparation example 1 in 10mL of hydrochloric acid-ethanol solution with the concentration of 0.1mol/L by vortex oscillation for pretreatment for 60min, wherein the pretreatment temperature is 40 ℃, and obtaining a dispersion liquid containing the pretreated carrier;
(2) adding 1mL of 20mg/mL chloroplatinic acid solution and 280 mu L of 100mg/mL cobalt chloride aqueous solution into a dispersion liquid containing a pretreatment carrier, dispersing for 12h by ultrasonic (frequency is 20kHz), separating by using reduced pressure suction filtration to obtain an electrocatalyst precursor adsorbed with metal ions, and drying for 6h at 60 ℃ to obtain the electrocatalyst precursor;
(3) and (3) carrying out high-temperature roasting treatment on the electrocatalyst precursor to obtain the electrocatalyst, wherein the roasting temperature is 800 ℃, the roasting time is 4 hours, and the roasting atmosphere is high-purity nitrogen.
The catalyst in this example was examined in the same manner as in example 1, and it was found that the electrocatalyst had a metal nanoparticle content of 10 wt%, wherein the platinum element content was 7.1 wt%, the cobalt element content was 2.9 wt%, and the others were the carriers, based on the total mass of the catalyst; the atomic ratio of Pt to Co in the intermetallic compound was 0.7: 1.
in the wide-angle X-ray diffraction test, only the diffraction peak of metal platinum was observed in the sample, and no diffraction peak of Co metal or its compound was found, but the diffraction peak of the prepared electrocatalyst was shifted to a high angle direction compared to the standard peak position of Pt. Specifically, in the PtCo catalyst, 4 diffraction peaks were observed only in the vicinity of 41.5 °, 48.6 °, 71.1 ° and 85.2 °, and the 4 absorption peaks of Pt were all shifted toward high angles, and in the diffraction pattern, no absorption peak was observed at the position where the absorption peak of Co (44.2 °) was present, indicating that the metal nanoparticles are present in the form of an intermetallic compound formed of a noble metal (Pt) and a base metal (Co).
The size of the intermetallic compound nanoparticles can be calculated by utilizing a Sherle formula and combining the half-peak width of a diffraction peak in an XRD spectrogram, and the size of the intermetallic compound nanoparticles is 2.3 nm.
Example 4
The catalyst was prepared as in example 1 except that ferric chloride was used in place of cobalt chloride.
The catalyst in this example was examined in the same manner as in example 1, and it was found that the electrocatalyst had a metal nanoparticle content of 30 wt%, wherein the platinum element content was 27.4 wt%, the iron element content was 2.6 wt%, and the others were the carriers, based on the total mass of the catalyst; the atomic ratio of Pt to Fe in the intermetallic compound was 3.0: 1.
in order to characterize the crystalline state of the metal nanoparticles in the catalyst, we adopted a wide-angle X-ray diffraction test, and the result is shown in fig. 1, where the curve corresponding to PtFe is the XRD test curve of the electrocatalyst in this example; as is clear from the curve corresponding to PtFe in fig. 1, only a diffraction peak of metal platinum is observed in the sample, and no diffraction peak of Fe metal or a compound thereof is observed. But the diffraction peak of the prepared electrocatalyst was shifted to a high angle direction compared to the standard peak position of Pt. This is because the Pt — Pt bond length is shortened by the Fe doping, and the interplanar spacing is shortened accordingly, so that the diffraction peak position is shifted to a high angle direction. Specifically, the PtFe catalyst observed only 4 diffraction peaks near 40.8 °, 47.7 °, 69.4 °, and 83.2 °. Actually, it is found from the standard sample of Pt that 4 absorption peaks of Pt originally appear at 39.5 °, 46.5 °, 67 ° and 82 °, and in combination with the standard absorption peaks of Pt, the 4 absorption peaks of Pt are shifted to a high angle, and in a diffraction pattern, no absorption peak is found at a position where an absorption peak of Fe (44.6 °) is supposed to appear, indicating that the metal nanoparticles exist as an intermetallic compound formed of a noble metal (Pt) and a base metal (Fe) in the PtFe catalyst.
By utilizing the Shele formula, the size of the intermetallic compound nano particles can be calculated to be 3.2nm by combining the half-peak width of a diffraction peak in an XRD spectrogram.
Example 5
The catalyst was prepared as in example 1 except that zinc chloride was used instead of cobalt chloride.
The catalyst in this example was examined in the same manner as in example 1, and it was found that the electrocatalyst had a metal nanoparticle content of 30 wt%, in which the platinum element content was 26.9 wt%, the zinc element content was 3.1 wt%, and the others were the carriers, based on the total mass of the catalyst; the atomic ratio of Pt to Zn in the intermetallic compound was 2.9: 1.
in order to characterize the crystalline state of the metal nanoparticles in the catalyst, we adopted a wide-angle X-ray diffraction test, and the result is shown in fig. 1, where the curve corresponding to PtZn is the XRD test curve of the electrocatalyst in this example; as is clear from the curve corresponding to PtZn in fig. 1, only a diffraction peak of metal platinum is observed in the sample, and no diffraction peak of Fe metal or a compound thereof is observed. But the diffraction peak of the prepared electrocatalyst was shifted to a high angle direction compared to the standard peak position of Pt. This is because the doping of Zn causes a reduction in the Pt-Pt bond length and hence a reduction in the interplanar spacing, and therefore the diffraction peak position is shifted to a high angle direction. Specifically, the PtZn catalyst observed only 4 diffraction peaks in the vicinity of 40.5 °, 47.3 °, 69.0 °, and 83.0 °. Actually, it is found from the standard sample of Pt that 4 absorption peaks of Pt originally appear at 39.5 °, 46.5 °, 67 ° and 82 °, and in combination with the standard absorption peaks of Pt, the 4 absorption peaks of Pt are shifted to a high angle, and in the diffraction pattern, no absorption peak is found at a position where an absorption peak of Zn (43.5 °) is supposed to appear, indicating that the metal nanoparticles exist as an intermetallic compound formed of a noble metal (Pt) and a base metal (Zn) in the PtZn catalyst.
The size of the metal nanoparticles can be calculated to be 3.1nm by utilizing a Sherle formula and combining the half-peak width of a diffraction peak in an XRD spectrogram.
Example 6
The catalyst was prepared as in example 1 except that nickel chloride was used instead of cobalt chloride. After the verification, the method has the advantages that,
the catalyst in this example was examined in the same manner as in example 1, and it was found that the electrocatalyst had a metal nanoparticle content of 30 wt%, wherein the platinum element content was 27.1 wt%, the nickel element content was 2.9 wt%, and the others were the carriers, based on the total mass of the catalyst; the atomic ratio of Pt to Ni in the intermetallic compound was 2.8: 1.
by the wide-angle X-ray diffraction test, only the diffraction peak of metal platinum is observed in the sample, the diffraction peak of Ni metal or a compound thereof is not found, and the diffraction peak of the prepared electrocatalyst is shifted to a high-angle direction compared with the standard peak position of Pt. Specifically, the PtNi catalyst observed four diffraction peaks only in the vicinity of 40.8 °, 47.6 °, 69.6 °, and 83.3 °, and no absorption peak was observed at the position where the absorption peak of Ni (44.2 °) had been observed, indicating that the metal nanoparticles were present in the form of an intermetallic compound formed of a noble metal (Pt) and a base metal (Ni) in the PtNi catalyst.
Example 7
A catalyst was prepared by following the procedure in example 1, except that the 1mol/L hydrochloric acid-ethanol solution was replaced with the 0.05mol/L hydrochloric acid-ethanol solution in step (1).
With the wide-angle X-ray diffraction test, only four diffraction peaks near 40.4 °, 47.3 °, 69.4 °, and 84.3 ° of the diffraction peak of metal platinum were observed in the sample.
Example 8
A catalyst was prepared according to the procedure of example 1, except that 2mL of a 20mg/mL solution of chloroplatinic acid and 360. mu.L of an aqueous solution of 100mg/mL ferric chloride were used in place of 3mL of a 20mg/mL solution of chloroplatinic acid and 280. mu.L of an aqueous solution of 100mg/mL cobalt chloride in example 1.
When the catalyst was examined by the method of example 1, it was found that the electrocatalyst had a metal nanoparticle content of 20 wt%, wherein the platinum element content was 17.5 wt%, the iron element content was 2.5 wt%, and the others were carriers, based on the total mass of the catalyst; the atomic ratio of Pt to Fe in the intermetallic compound was 2.1: 1. the size of the intermetallic compound nanoparticles was 3.4 nm.
With the wide-angle X-ray diffraction test, only the diffraction peak of metal platinum was observed in the sample, and no diffraction peak of Fe metal or a compound thereof was found, specifically, four diffraction peaks were observed only in the vicinity of 41.3 °, 48.5 °, 70.3 ° and 84.1 ° for the PtFe catalyst.
Example 9
A catalyst was prepared according to the method of example 1, except that the carbon-based support of preparation example 2 was substituted for the carbon-based support of preparation example 1 used in example 1, and the other was the same as example 1.
With the wide-angle X-ray diffraction test, only the diffraction peak of metal platinum was observed in the sample, and no diffraction peak of Co metal or a compound thereof was found, specifically, four diffraction peaks were observed only in the vicinity of 41.2 °, 47.6 °, 71.1 ° and 83.5 ° for the PtCo catalyst.
Comparative example 1
200mg of a commercially available activated carbon carrier (XC-72R) was dispersed in 10mL of an ethanol solution, followed by addition of 3mL of a 20mg/mL chloroplatinic acid solution and 280. mu.L of a 100mg/mL aqueous solution of cobalt chloride and ultrasonic dispersion for 6 hours. And (3) putting the dispersion liquid into a watch glass, volatilizing for 48 hours at normal temperature, and treating the obtained product for 3 hours at 900 ℃ under the protection of nitrogen to obtain the electrocatalyst.
By adopting a wide-angle X-ray diffraction test, as shown in figure 3, the electrocatalyst prepared by the method cannot be matched with the diffraction peak of platinum or can be obtained by regularly shifting the diffraction peak of platinum, and the obtained product is not an intermetallic compound formed by Pt and Co. In addition, the diffraction peaks of this sample are sharper, indicating larger particle sizes in the control. The particle size was about 50nm as calculated by the Sherrer equation.
Comparative example 2
A catalyst was prepared according to the method of example 1, except that no carrier pretreatment step was performed, and the preparation of the electrocatalyst precursor was performed as follows:
adding 3mL of 20mg/mL chloroplatinic acid solution and 280 μ L of 100mg/mL cobalt chloride aqueous solution into 10mL hydrochloric acid-ethanol solution with the concentration of 1mol/L, adding 200mg of the carrier in the preparation example 1, dispersing for 6 hours by ultrasonic waves (the frequency is 15kHz), separating by reduced pressure suction filtration to obtain an electrocatalyst precursor adsorbed with metal ions, and drying for 12 hours at 40 ℃ to obtain the electrocatalyst precursor.
By using a wide-angle X-ray diffraction test, the diffraction pattern of the electrocatalyst prepared by the method is similar to that of FIG. 3, and the diffraction pattern cannot be matched with the diffraction peak of platinum or can be obtained by regular shift of the diffraction peak of platinum, which indicates that the obtained product is not an intermetallic compound formed by Pt and Co.
Comparative example 3
A catalyst was prepared according to the method of example 1, except that 0.6g of sodium dihydrogenphosphite was further added in step (2).
By using a wide-angle X-ray diffraction test, the diffraction pattern of the electrocatalyst prepared by the method is similar to that of FIG. 3, and the diffraction pattern cannot be matched with the diffraction peak of platinum or can be obtained by regular shift of the diffraction peak of platinum, which indicates that the obtained product is not an intermetallic compound formed by Pt and Co.
Application example
The Pt/C catalyst in this reference was replaced with the electrocatalysts of examples and comparative examples of the present invention described above with reference to the preparation of a membrane electrode in CN106784943A by the method of example 1 (fifth step to eighth step), and the coating amounts of the electrocatalysts were 2mg/cm in terms of the mass content of the metal element2。
On the basis of the obtained membrane electrode, direct liquid fuel is taken as a substrate, and a direct liquid fuel cell can be further assembled by combining a bipolar plate, a sealing member and the membrane electrode obtained by the invention with the prior art.
Detection example 1
To verify the catalytic activity of the catalysts of the invention, cyclic voltammetry tests were performed on the electrocatalysts:
selecting three-electrode system, respectively using the above-mentioned materialsThe membrane electrodes obtained with the catalysts of the examples and comparative examples were working electrodes, Ag/Ag+The electrode is used as a reference electrode, the graphite rod is used as a counter electrode, and methylcyclohexane is used as a test substrate. The scan rate was 10mV/s, and the test voltage interval was (-0.6) -0V.
Cyclic voltammograms of the membrane electrodes obtained with the catalysts of example 1, example 4 and example 5 are shown in figure 2. As can be seen from FIG. 2, the oxidation potentials of the electrocatalysts obtained in the examples, all of which are below-0.3V, are specified in Table 1, while the oxidation potential of methylcyclohexane of a pure platinum-coated electrode (i.e., the working electrode is a platinum wire) is-0.3V. The lower oxidation potential means higher electrocatalytic activity of methylcyclohexane, and thus the catalyst of the present invention exhibits superior catalytic performance. The catalytic performance of the catalysts of the specific examples and comparative examples is shown in table 1. The cyclic voltammogram of the membrane electrode obtained with the catalyst of comparative example 2 is shown in FIG. 3, and the results show that the electrooxidation dehydrogenation potential of the catalyst is shown in Table 1, and is higher than-0.3V, and the catalytic activity for the dehydrogenation of methylcyclohexane is poor.
Detection example 2
In order to characterize the working stability of the catalysts obtained according to the invention, the same substrates as in test example 1 were subsequently used and subjected to a cycling stability test. The test adopts a constant potential discharge method, the discharge voltage is 0.4V, the test duration is 12h, and the initial current density and the current density after the test for 12h are compared to calculate the current retention rate.
The results are shown in table 1, and it can be seen that the catalyst of the present invention has a high current retention rate, which indicates that the catalyst of the present invention has stable catalytic performance, good anti-poisoning effect, and a long service life.
TABLE 1
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A catalyst comprising a carbon-based support and metal nanoparticles supported on the carbon-based support, wherein the metal nanoparticles are present in the form of an intermetallic compound formed from a noble metal and a base metal, and the content of the metal nanoparticles is 10 to 50 wt% and the content of the carbon-based support is 50 to 90 wt%, based on the total mass of the catalyst.
2. The catalyst according to claim 1, wherein the metal nanoparticles are present in an amount of 20 to 50 wt.%, preferably 20 to 40 wt.%, and the carbon-based support is present in an amount of 50 to 80 wt.%, preferably 60 to 80 wt.%, based on the total mass of the catalyst;
preferably, the size of the metal nanoparticles is 2-10nm, preferably 3-5 nm;
preferably, the diffraction peaks of the noble metals in the X-ray diffraction curve of the catalyst are all shifted to the high-angle direction and do not have diffraction peaks corresponding to the base metals, and the diffraction peaks of the noble metals are preferably shifted to the high-angle direction by 0.3 to 5 degrees, and more preferably shifted to the high-angle direction by 0.5 to 3 degrees.
3. The catalyst according to claim 1 or 2, wherein the noble metal is Pt and/or Pd, and the base metal is at least one of a fourth period transition metal element, W and Mo;
preferably, the base metal is at least one of Cu, W, Mo, Zn, Fe, Co, Ni and Mn;
further preferably, the precious metal is Pt, and the base metal is Zn, Fe or Co;
still more preferably, the atomic ratio of the noble metal to the base metal in the metal nanoparticles is from 0.5 to 5:1, preferably 1 to 3: 1.
4. the catalyst according to any one of claims 1 to 3, wherein the carbon-based support is at least one of carbon black, carbon nanotubes, graphene, two-dimensional carbon sheets and graphene oxide and/or at least one of nitrogen-containing polymer-modified carbon black, carbon nanotubes, graphene, two-dimensional carbon sheets and graphene oxide;
preferably, the nitrogen-containing polymer is polymerized from at least one of pyrrole, pyrrole derivatives, catecholamines and aromatic amines;
preferably, the carbon-based material has a size of 50nm to 50 μm and a specific surface area of 50 to 1000m2/g。
5. A preparation method of a catalyst is characterized by comprising the following steps:
(1) dispersing a carbon-based carrier in an organic solvent containing inorganic acid for pretreatment to obtain a dispersion liquid containing the pretreated carrier;
(2) mixing the dispersion liquid containing the pretreatment carrier with a precious metal precursor and a base metal precursor to load the precious metal precursor and the base metal precursor on the pretreatment carrier, and then separating and drying to obtain an electrocatalyst precursor;
(3) the electrocatalyst precursor is calcined in an inert atmosphere.
6. The production method according to claim 5, wherein the inorganic acid is a strong inorganic acid, preferably at least one of hydrochloric acid and/or hydrobromic acid, and further preferably hydrochloric acid;
and/or the organic solvent is at least one of alcohol containing 1-4 carbon atoms and tetrahydrofuran, preferably at least one of methanol, ethanol and tetrahydrofuran;
further preferably, the concentration of the inorganic acid in the organic solvent is 0.1 to 5mol L-1。
7. The production method according to claim 5 or 6, wherein the precious metal precursor and/or the base metal precursor in step (2) is added to the dispersion containing the pretreatment support in the form of respective precursor solutions;
preferably, the volume content of the organic solvent in the mixed system obtained by mixing in the step (2) is 70-90%;
and/or, the roasting condition in the step (3) comprises: the roasting temperature is 800-1000 ℃, and the roasting time is 1-4 h; preferably, the inert atmosphere is nitrogen and/or argon;
preferably, the conditions of the pretreatment in step (1) include: the temperature is 25-40 ℃; and/or the time is 60-240 min.
8. The production method according to any one of claims 5 to 7, wherein the carbon-based carrier, the noble metal precursor and the base metal precursor are used in such amounts that the content of the metal nanoparticles is 20 to 50 wt% and the content of the carbon-based carrier is 50 to 80 wt%, based on the total mass of the catalyst;
preferably, the molar ratio of the precious metal precursor and the base metal precursor is 0.3-5: 1;
still further preferably, the concentration of the noble metal precursor in the mixed system in the step (2) is 8-24 mmol/L.
9. The production method according to any one of claims 5 to 8, wherein the carbon-based support is at least one of carbon black, carbon nanotubes, graphene, two-dimensional carbon sheets, graphene oxide, and/or at least one of nitrogen-containing polymer-modified carbon black, carbon nanotubes, graphene, two-dimensional carbon sheets, and graphene oxide;
the carbon-based carrier is preferably at least one of carbon black, carbon nano tubes, graphene, two-dimensional carbon sheets and graphene oxide modified by nitrogen-containing polymers; still further preferably, the nitrogen-containing polymer is obtained by polymerizing at least one of pyrrole, a pyrrole derivative, catecholamine, and an aromatic amine;
and/or the precious metal is Pt and/or Pd, the base metal is at least one of transition metal elements, W and Mo in the fourth period, and the precious metal precursor and the base metal precursor are water-soluble metal salts corresponding to the respective metal elements.
10. A membrane electrode of a direct liquid fuel cell, which is characterized by comprising a proton exchange membrane, a catalyst attached to the surface of the proton exchange membrane and a gas diffusion layer of the outer layer of the catalyst, wherein the catalyst is the catalyst of any one of claims 1 to 4 and/or the catalyst prepared by the preparation method of any one of claims 5 to 9;
preferably, the adhesion amount of the battery catalyst on the surface of the proton exchange membrane is 1-10mg/cm2。
11. A direct liquid fuel cell comprising the membrane electrode of claim 10 and an organic liquid hydrogen storage solution;
preferably, the organic liquid hydrogen storage liquid is a saturated cycloalkane containing at least one 5-6 membered ring and/or a saturated azacycloalkane containing at least one 5-6 membered ring;
further preferably, the organic liquid hydrogen storage liquid is at least one of methylcyclohexane, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole, perhydrocarbazole, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 2, 6-dimethylpiperidine, 2, 5-dimethylpiperidine, 1-methylpyrrolidine, 2-methylpyrrolidine, 3-methylpyrrolidine, 1-aminopyrrolidine, piperazine and perhydroimidazole.
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