CN115050972B - Polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst carrier and preparation method and application thereof - Google Patents
Polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst carrier and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 44
- 239000001257 hydrogen Substances 0.000 title claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 36
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 35
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 35
- 230000003647 oxidation Effects 0.000 title claims abstract description 28
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title claims abstract 7
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 16
- 239000000446 fuel Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000013110 organic ligand Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- -1 transition metal salt Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- QMXBEONRRWKBHZ-UHFFFAOYSA-N [Na][Mo] Chemical compound [Na][Mo] QMXBEONRRWKBHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- IWWXMZMHTZKRMT-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[K+].[W+4] Chemical compound P(=O)([O-])([O-])[O-].[K+].[W+4] IWWXMZMHTZKRMT-UHFFFAOYSA-K 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 6
- 238000004729 solvothermal method Methods 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract 1
- 239000013460 polyoxometalate Substances 0.000 description 28
- 150000002431 hydrogen Chemical class 0.000 description 27
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 9
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical group [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 125000002524 organometallic group Chemical group 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- OZGNYLLQHRPOBR-DHZHZOJOSA-N naftifine Chemical compound C=1C=CC2=CC=CC=C2C=1CN(C)C\C=C\C1=CC=CC=C1 OZGNYLLQHRPOBR-DHZHZOJOSA-N 0.000 description 4
- 229960004313 naftifine Drugs 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical class [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
Abstract
The invention is disclosed inA polyhedral carbon shell supported transition metal-based hydrogen oxidation catalyst carrier and a preparation method and application thereof are provided, belonging to the technical field of preparation of fuel cell anode electrocatalyst carriers. The catalyst is characterized in that a precursor of the metal organic framework is mixed with a polyoxometallate solution to obtain a precursor solution, the polyoxometallate is packaged in the metal framework of the polyhedral structure through a solvothermal synthesis technology, and the catalyst carrier is obtained through heat treatment after centrifugation. The electrode material obtained by the catalyst carrier has better hydrogen oxidation electrocatalytic capacity, and the limiting current density of hydrogen oxidation is close to 2.81mAcm ‑2 。
Description
Technical Field
The invention relates to a polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst carrier, and a preparation method and application thereof, and belongs to the technical field of preparation of fuel cell anode electrocatalyst carriers.
Background
Fuel cells, which do not require a combustion process due to their excellent performance, are not limited by the carnot cycle and are considered as an alternative power source in the near future. Among the various types of fuel cells, the most promising is a Proton Exchange Membrane Fuel Cell (PEMFC), which consists of two half reactions, an anodic oxidation reaction (HOR) and a cathodic Oxygen Reduction Reaction (ORR). For the HOR reaction, the noble metal Pt catalyst cannot be replaced, and the hydrogen obtained from the reforming fuel flow at present does not contain CO, and CO is easily adsorbed on the surface of Pt and occupies the surface active site of the Pt, so that the surface of Pt available for hydrogen adsorption is reduced, the utilization rate of Pt is reduced, and the performance of a battery is not ideal. Therefore, it is necessary to provide a catalyst support capable of introducing a transition metal-based nitrogen (carbon) compound, desorbing CO molecules from Pt surface, and improving CO tolerance of HOR.
Disclosure of Invention
The invention provides a polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst carrier, a preparation method and application thereof, wherein CO molecules can be desorbed from the surface of Pt by introducing transition metal-based nitrogen (carbon) compounds, and the CO tolerance performance of HOR is improved.
The technical scheme of the invention is as follows:
a preparation method of a polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst carrier comprises the following implementation steps:
step one, mixing an inorganic transition metal salt solution and an organic ligand solution, stirring the mixed solution for 2-12 hours at the temperature of 25-30 ℃, and performing centrifugal washing and vacuum drying treatment to obtain a metal organic frame precursor;
respectively dissolving a metal organic framework precursor and a polyacid oxyacid salt in an organic solvent, mixing the two solutions, and carrying out hydrothermal treatment on the mixed solution to obtain a reaction solution;
and thirdly, centrifugally washing the reaction liquid, then drying in vacuum, and performing heat treatment in a nitrogen atmosphere to obtain the polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst carrier.
Further limiting, stirring the mixed solution in the first step for 4-8 hours at the temperature of 25-30 DEG C
Further limited, in the first step, the inorganic transition metal salt is one or more of cobalt nitrate, zinc nitrate, copper nitrate or zirconium chloride, and the inorganic transition metal salt is mixed in any proportion.
Further defined, in the first step, the organic ligand is one or more than two of terephthalic acid, ethylenediamine tetraacetic acid or methylimidazole and is mixed in any proportion.
Further defined, the molar ratio of inorganic transition metal salt to organic ligand in the mixed liquor of step one is 1: (1-20).
Further defined, the molar ratio of inorganic transition metal salt to organic ligand in the mixed liquor of step one is 1: (1-15).
Further defined, the molar ratio of inorganic transition metal salt to organic ligand in the mixed liquor of step one is 1: (1-10).
Further defined, the concentration of the organic ligand in the mixed solution in the step one is 60 mmol/L-80 mmol/L.
Further defined, the concentration of the organic ligand in the mixed solution in the step one is 50mmol/L to 80mmol/L.
Further defined, the concentration of the organic ligand in the mixed solution in the step one is 60mmol/L to 80mmol/L.
Further defined, the organic solution in the inorganic transition metal salt solution and the organic ligand solution configured in the first step is anhydrous methanol or anhydrous ethanol.
Further limited, in the first step, the inorganic transition metal salt and the organic ligand are ultrasonically dispersed in the organic solvent under the condition of 400-2000W of power, and the ultrasonic dispersion treatment time is 5-60 min.
Further limited, in the first step, the inorganic transition metal salt and the organic ligand are ultrasonically dispersed in the organic solvent under the condition of 400-2000W of power, and the ultrasonic dispersion treatment time is 5-30 min.
Further defined, the centrifugal washing operation in the first step is as follows: centrifuging at 8000-10000 rad/min for 5-8 min, washing with anhydrous methanol or alcohol for 3-5 times.
Further defined, the conditions of the vacuum drying treatment in the first step are: vacuum drying at 60-80 deg.c for 10-14 hr.
Further selecting, in the second step, the polyoxometalate is one or more than two of phosphotungstic acid, phosphomolybdic acid, potassium tungsten phosphate and sodium molybdenum silicate, and mixing the above materials according to any proportion.
Further limited, the hydrothermal treatment temperature in the second step is 70-120 ℃ and the time is 4-8 h.
Further defined, the centrifugal washing operation in the second step comprises the following steps: centrifuging at 8000-10000 rad/min for 5-8 min, washing with anhydrous methanol or alcohol for 3-5 times.
Further defined, the heat treatment conditions in step three are: calcining for 2-4 h at 600-1000 ℃ under nitrogen atmosphere.
Further defined, the conditions of the vacuum drying treatment in the third step are: vacuum drying at 60-80 deg.c for 10-14 hr.
The invention also provides a catalyst carrier for the fuel cell, which is prepared by the preparation method.
The invention also provides application of the polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst carrier, wherein the carrier is used for a HOR anode electrocatalyst of a fuel cell after being loaded with transition metal to catalyze hydrogen oxidation reaction of the anode of the fuel cell.
Compared with the prior art, the method introduces the transition metal-based nitrogen (carbon) compound, can desorb CO molecules from the surface of Pt, and improves the CO tolerance of HOR. The method has the specific beneficial effects that:
(1) The method comprises the steps of packaging polyoxometallate in a prepared metal organic framework precursor by using a solvothermal synthesis method, and obtaining the polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst carrier after heat treatment after centrifugation. The catalyst has better hydrogen oxidation electrocatalytic capacity, and the limiting current density is close to 2.81mAcm -2 。
(2) According to the invention, a solvothermal synthesis method is utilized, and the prepared metal organic framework window is opened, so that polyoxometallate enters the metal organic framework, so that the polyhedral carbon shell supported transition metal-based hydrogen oxidation catalyst carrier is prepared, and has excellent HOR performance after Pt is supported.
(3) The polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst carrier prepared by the invention has transition metal-based nitrogen (carbon) compound, and can desorb CO molecules from the surface of Pt, so that the utilization rate of Pt is improved, and the performance of a battery is further improved.
(4) According to the preparation method, carbonization treatment is carried out in the process of preparing the polyhedral carbon shell-supported transition metal-based hydrogen oxidation catalyst carrier, so that the graphitization degree and the conductivity of the catalyst are effectively increased.
Drawings
FIG. 1 is an X-ray diffraction pattern of a polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst carrier prepared in example 1;
FIG. 2 is a scanning electron micrograph of a polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst support prepared in example 1;
FIG. 3 is a comparative graph of linear sweep voltammetry tests of polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst supports prepared in various examples;
FIG. 4 is a scanning electron micrograph of a polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst support prepared in example 2;
FIG. 5 is a scanning electron micrograph of a polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst support prepared in example 3;
FIG. 6 is a scanning electron micrograph of a polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst support prepared in comparative example 1;
FIG. 7 is a graph showing a comparative linear sweep voltammetry test of a polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst carrier prepared in example 1 and a polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst carrier prepared in comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
Example 1:
(1) Preparation of organometallic framework (ZIF-67) CoZn )
Dissolving 1.2g of zinc nitrate hexahydrate and 2.4g of cobalt nitrate hexahydrate in 400mL of ethanol, dissolving 4.1g of 2-methylimidazole in 400mL of ethanol, respectively carrying out ultrasonic treatment on the metal solution and the 2-methylimidazole solution for 30min, mixing, and stirring the mixed solution at 30 ℃ for 4h to formCentrifuging and washing once with distilled water at 8000rad/min, centrifuging and washing once with ethanol solvent, and drying at 80deg.C under vacuum for 12 hr to obtain metal organic frame, ZIF-67 CoZn ，ZIF-67 CoZn As a template for standby.
(2) Organometallic framework ZIF-67 of cobalt by solvothermal method CoZn The window is opened and Polyoxometalate (POM) is encapsulated inside the polyhedron:
0.15g of ZIF-67 obtained in step (1) was reacted with CoZn Dispersing in 50mL of methanol solution, dispersing 0.02g of sodium molybdenum silicate in 50mL of methanol solution, mixing the two solutions, transferring the mixed solution into a 100mL hydrothermal kettle, carrying out hydrothermal treatment at 120 ℃ for 8 hours, and cooling to room temperature after the reaction is finished to obtain a reaction solution. Washing the reaction solution with methanol solvent at 9000rad/min for 5min, and drying at 80deg.C under vacuum for 12 hr to obtain zinc metal organic frame ZIF-67 encapsulated by POM CoZn Abbreviated as POM@ZIF-67 CoZn 。
For the obtained POM@ZIF-67 CoZn As shown in FIG. 1, the result of the X-ray diffraction pattern characterization is that the POM@ZIF-67 was successfully obtained from FIG. 1 CoZn The carrier has introduced therein a transition metal based nitrogen (carbon) compound.
For the obtained POM@ZIF-67 CoZn As shown in FIG. 2, the microstructure is characterized, and as can be seen from FIG. 2, POM@ZIF-67 is obtained through assembly CoZn Is a catalyst similar to regular dodecahedron and has uniform particles.
(3) Calcination treatment
POM@ZIF-67 obtained in step (2) is subjected to CoZn Calcining for 2 hours in nitrogen atmosphere at 600 ℃ to obtain a polyhedral carbon shell supported transition metal-based hydrogen oxidation catalyst carrier, which is called Mo for short x Co x C-1 electrocatalyst support.
(4) Load Pt
50mg of the catalyst carrier obtained in the step (3) was uniformly dispersed in 50mL of water, and an appropriate amount of chloroplatinic acid solution was added. Then adding proper amount of 1MNaOH solution to adjust the pH to 8-9, and adding excessive NaBH 4 The solution is stirred for 3 to 5 hours with high intensity, filtered and striped at 60 DEG CDrying for 12h under the piece to obtain Pt/Mo x Co x C-1。
For Pt/Mo x Co x The C-1 electrocatalyst was subjected to electrochemical performance testing:
Pt/Mo x Co x The C-1 electrocatalyst, 5% naftifine solution and absolute ethanol were mixed and subjected to ultrasonic dispersion treatment, and the coated electrode was tested, and the results are shown in FIG. 3. As can be seen from FIG. 3, the limiting current density of the hydrogen oxidation reaction is approximately 2.81mAcm -2 。
Example 2:
this embodiment differs from embodiment 1 in that: when the ZIF-67 precursor is prepared, a small amount of zinc nitrate hexahydrate is not added, and the preparation process is as follows:
(1) Preparation of organometallic framework (ZIF-67) Co )
Dissolving 3.6g of cobalt nitrate hexahydrate in 400mL of ethanol, dissolving 4.1g of 2-methylimidazole in 400mL of ethanol, respectively carrying out ultrasonic treatment on a metal solution and the 2-methylimidazole solution for 30min, mixing, stirring the mixed solution for 4h at 30 ℃, centrifuging and washing once by using distilled water at 8000rad/min after precipitation, centrifuging and washing once by using an ethanol solvent, and then drying for 12h at 80 ℃ under vacuum to obtain a metal organic frame, namely ZIF-67 for short Co ，ZIF-67 Co As a template for standby.
(2) The cobalt organometallic framework ZIF-67 window was opened by solvothermal method, and Polyoxometalate (POM) was encapsulated inside the polyhedron:
0.15g of ZIF-67 obtained in step (1) was reacted with Co Dispersing in 50mL of methanol solution, dispersing 0.02g of sodium molybdenum silicate in 50mL of methanol solution, mixing the two solutions, transferring the mixed solution into a 100mL hydrothermal kettle, carrying out hydrothermal treatment at 120 ℃ for 8 hours, and cooling to room temperature after the reaction is finished to obtain a reaction solution. Washing the reaction solution with methanol solvent at 9000rad/min for 5min, and drying at 80deg.C under vacuum for 12 hr to obtain zinc metal organic frame ZIF-67 encapsulated by POM Co Abbreviated as POM@ZIF-67 Co 。
For the obtained POM@ZIF-67 Co Microstructure characterization was performed as shown in FIG. 4, consisting ofFIG. 4 shows that POM@ZIF-67 is obtained by assembly Co Is a catalyst similar to regular dodecahedron and has uniform particles.
(3) Calcination treatment
POM@ZIF-67 obtained in step (2) is subjected to Co Calcining for 2 hours in nitrogen atmosphere at 600 ℃ to obtain a polyhedral carbon shell supported transition metal-based hydrogen oxidation catalyst carrier, which is called Mo for short x Co x C-2 electrocatalyst support.
(4) Load Pt
50mg of the catalyst carrier obtained in the step (3) was uniformly dispersed in 50mL of water, and an appropriate amount of chloroplatinic acid solution was added. Then adding proper amount of 1MNaOH solution to adjust the pH to 8-9, and adding excessive NaBH 4 The solution is stirred for 3 to 5 hours with high intensity, filtered by suction, and dried for 12 hours at 60 ℃ to obtain Pt/Mo x Co x C-2。
For Pt/Mo x Co x The C-2 electrocatalyst was subjected to electrochemical performance testing:
Pt/Mo x Co x The C-2 electrocatalyst, 5% naftifine solution and absolute ethanol were mixed and subjected to ultrasonic dispersion treatment, and the coated electrode was tested, and the results are shown in FIG. 3. As can be seen from FIG. 3, the limiting current density of the hydrogen oxidation reaction is approximately 2.19mAcm -2 。
Example 3:
this embodiment differs from embodiment 1 in that: the prepared precursor is ZIF-8, and the specific preparation process is as follows:
(1) Preparation of organometallic frame (ZIF-8)
3.6g of zinc nitrate hexahydrate is dissolved in 400mL of ethanol, 4.1g of 2-methylimidazole is dissolved in 400mL of ethanol, the metal solution and the 2-methylimidazole solution are respectively treated by ultrasonic for 30min and then mixed, the mixed solution is stirred for 4h at 30 ℃, after precipitation is formed, the precipitate is centrifugally washed once by using distilled water at 8000rad/min, the precipitate is centrifugally washed once by using an ethanol solvent, and then drying is carried out for 12h at 80 ℃ under vacuum, so that a metal organic frame, namely ZIF-8 for short, is obtained, and ZIF-8 is used as a template for standby.
(2) The cobalt organometallic framework ZIF-8 window was opened by solvothermal method, and Polyoxometalate (POM) was encapsulated inside the polyhedron:
0.15g of ZIF-8 obtained in the step (1) is dispersed in 50mL of methanol solution, 0.02g of sodium molybdenum silicate is dispersed in 50mL of methanol solution, the two solutions are mixed, the mixed solution is transferred into a 100mL hydrothermal kettle, the hydrothermal treatment is carried out for 8 hours at 120 ℃, and after the reaction is finished, the reaction solution is cooled to room temperature, so that a reaction solution is obtained. The reaction solution is washed for 5min under 9000rad/min by using a methanol solvent, and dried under 80 ℃ vacuum for 12h, so that a zinc metal organic framework ZIF-8 encapsulated by POM (POM@ZIF-8 for short) is obtained.
The obtained POM@ZIF-8 is subjected to microstructure characterization, as shown in FIG. 5, and as can be seen from FIG. 5, the POM@ZIF-8 is a catalyst similar to a regular dodecahedron and is uniform in particles.
(3) Calcination treatment
Calcining the POM@ZIF-8 obtained in the step (2) for 2 hours in a nitrogen atmosphere at 600 ℃ to obtain a polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst carrier, which is called Mo for short x Co x C-3 electrocatalyst support.
(4) Load Pt
50mg of the catalyst carrier obtained in the step (3) was uniformly dispersed in 50mL of water, and an appropriate amount of chloroplatinic acid solution was added. Then adding proper amount of 1MNaOH solution to adjust the pH to 8-9, and adding excessive NaBH 4 The solution is stirred for 3 to 5 hours with high intensity, filtered by suction, and dried for 12 hours at 60 ℃ to obtain Pt/Mo x Co x C-3。
For Pt/Mo x Co x The C-3 electrocatalyst was subjected to electrochemical performance testing:
Pt/Mo x Co x The C-3 electrocatalyst, 5% naftifine solution and absolute ethanol were mixed and subjected to ultrasonic dispersion treatment, and the coated electrode was tested as shown in FIG. 3. As can be seen from FIG. 3, the limiting current density of the hydrogen oxidation reaction is approximately 0.30mAcm -2 。
Comparative example 1:
this comparative example differs from example 1 in that: the solvothermal treatment is not carried out, and the specific operation process is as follows:
(1) Preparation of organometallic framework (ZIF-67) CoZn )：
1.2g of zinc nitrate hexahydrate and 2.4g of cobalt nitrate hexahydrate are dissolved in 400mL of ethanol, 4.1g of 2-methylimidazole is dissolved in 400mL of ethanol, the zinc nitrate hexahydrate solution and the 2-methylimidazole solution are respectively treated by ultrasonic for 30min and then mixed, the mixed solution is stirred for 4h at 30 ℃, the precipitate is formed and then centrifugally washed once by using distilled water at 8000rad/min, and the ethanol solvent is used for centrifugally washing once, and then the mixture is dried for 12h at 80 ℃ under vacuum, so that a metal organic frame, which is called ZIF-8 for short, is obtained, and ZIF-8 is used as a template for standby.
(2) 0.15g of ZIF-67 obtained in the step (1) above was reacted CoZn Dispersing in 50mL methanol solution, dispersing 0.02g sodium molybdenum silicate in 50mL methanol solution, mixing the two solutions, stirring at room temperature for 8 hr, washing with methanol at 9000rad/min for 5min, and drying at 80deg.C under vacuum for 12 hr to obtain POM@ZIF-67 CoZn 。
For the obtained POM@ZIF-67 CoZn As shown in FIG. 6, the microstructure was characterized, and as can be seen from FIG. 6, POM@ZIF-67 CoZn The shapes are not uniform and are adhered to each other.
(3) Calcination treatment
Obtaining POM@ZIF-67 in the step (2) CoZn Calcining for 2h in nitrogen atmosphere at 600 ℃ to obtain Mo x Co x C-4 electrocatalyst support.
(4) Load Pt
50mg of the catalyst carrier obtained in the step (3) was uniformly dispersed in 50mL of water, and an appropriate amount of chloroplatinic acid solution was added. Then adding proper amount of 1MNaOH solution to adjust the pH to 8-9, and adding excessive NaBH 4 The solution is stirred for 3 to 5 hours with high intensity, filtered by suction, and dried for 12 hours at 60 ℃ to obtain Pt/Mo x Co x C-4。
For Pt/Mo x Co x The C-4 electrocatalyst was subjected to electrochemical performance testing:
Pt/Mo x Co x The C-4 electrocatalyst, 5% naftifine solution and absolute ethanol were mixed and subjected to ultrasonic dispersion treatment, and the coated electrode was tested as shown in FIG. 7. As can be seen from FIG. 7, the limiting current density of the hydrogen oxidation reaction is approximately 0.40mAcm -2 。
The above description is merely a preferred embodiment of the present invention, and since the person skilled in the art can make appropriate changes and modifications to the above-described embodiment, the present invention is not limited to the above-described embodiment, and some modifications and changes of the present invention should fall within the scope of the claims of the present invention.
Claims (5)
1. A method for preparing a fuel cell catalyst support, comprising the steps of:
step one, mixing an inorganic transition metal salt solution and an organic ligand solution, stirring the mixed solution for 2-12 hours at the temperature of 25-30 ℃, and performing centrifugal washing and vacuum drying treatment to obtain a metal organic frame precursor;
respectively dissolving the metal organic frame precursor and the polyoxometallate in an organic solvent, mixing the two solutions, and performing solvothermal treatment on the mixed solution to obtain a reaction solution;
step three, centrifugally washing the reaction liquid, then carrying out vacuum drying treatment, and carrying out heat treatment in a nitrogen atmosphere to obtain a polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst carrier;
in the first step, the inorganic transition metal salt is one or more than two of cobalt nitrate, zinc nitrate, copper nitrate and zirconium chloride which are mixed in any proportion; the organic ligand is one or more of terephthalic acid, ethylenediamine tetraacetic acid and methylimidazole which are mixed in any proportion;
the molar ratio of the inorganic transition metal salt to the organic ligand in the mixed solution in the step one is 1: (1-20);
the polyoxometallate in the second step is one or more than two of phosphotungstic acid, phosphomolybdic acid, potassium tungsten phosphate and sodium molybdenum silicate which are mixed in any proportion;
the solvent heat treatment temperature in the second step is 70-120 ℃ and the time is 4-8 h;
the heat treatment conditions in the third step are as follows: calcining for 2-4 h at 600-1000 ℃ under nitrogen atmosphere.
2. The method for producing a fuel cell catalyst carrier according to claim 1, wherein the concentration of the organic ligand in the mixed solution in the step one is 60mmol/L to 80mmol/L.
3. The method for preparing a fuel cell catalyst support according to claim 1, wherein the centrifugal washing in the first and third steps is performed by: centrifuging at 8000-10000 rad/min for 5-8 min, washing with anhydrous methanol or alcohol for 3-5 times.
4. The method for producing a fuel cell catalyst support according to claim 1, wherein the conditions of the vacuum drying treatment in the first and third steps are: vacuum drying at 60-80 deg.c for 10-14 hr.
5. A fuel cell catalyst support prepared by the method of claim 1, wherein the catalyst support is a polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst support, and the support is used for a fuel cell HOR anode electrocatalyst to catalyze the hydrogen oxidation reaction of a fuel cell anode after supporting transition metal.
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| JP2012239932A (en) * | 2011-05-16 | 2012-12-10 | Toyota Motor Corp | Manufacturing method for catalyst support |
| CN109126849A (en) * | 2017-06-28 | 2019-01-04 | 中国科学院大连化学物理研究所 | A method of preparing the monatomic catalyst of Ni-N-C |
| CN110102348A (en) * | 2019-05-23 | 2019-08-09 | 中国科学院上海硅酸盐研究所 | A kind of elctro-catalyst of hollow structure and preparation method thereof |
| CN113013427A (en) * | 2021-02-26 | 2021-06-22 | 华南理工大学 | High-performance electrocatalyst carrier derived based on Metal Organic Framework (MOF) material and preparation method thereof |
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| JP2012239932A (en) * | 2011-05-16 | 2012-12-10 | Toyota Motor Corp | Manufacturing method for catalyst support |
| CN109126849A (en) * | 2017-06-28 | 2019-01-04 | 中国科学院大连化学物理研究所 | A method of preparing the monatomic catalyst of Ni-N-C |
| CN110102348A (en) * | 2019-05-23 | 2019-08-09 | 中国科学院上海硅酸盐研究所 | A kind of elctro-catalyst of hollow structure and preparation method thereof |
| CN113013427A (en) * | 2021-02-26 | 2021-06-22 | 华南理工大学 | High-performance electrocatalyst carrier derived based on Metal Organic Framework (MOF) material and preparation method thereof |
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