CN115050972A - Polyhedral carbon shell layer loaded transition metal-based hydrogen oxidation catalyst carrier and preparation method and application thereof - Google Patents
Polyhedral carbon shell layer loaded transition metal-based hydrogen oxidation catalyst carrier and preparation method and application thereof Download PDFInfo
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- CN115050972A CN115050972A CN202210396340.5A CN202210396340A CN115050972A CN 115050972 A CN115050972 A CN 115050972A CN 202210396340 A CN202210396340 A CN 202210396340A CN 115050972 A CN115050972 A CN 115050972A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 41
- 239000001257 hydrogen Substances 0.000 title claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 34
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title claims abstract 4
- 239000000446 fuel Substances 0.000 claims abstract description 21
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 16
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 53
- 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 47
- 238000005406 washing Methods 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000013110 organic ligand Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000003756 stirring 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
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- -1 transition metal salt Chemical class 0.000 claims description 8
- 238000001291 vacuum drying Methods 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
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 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
- 239000007788 liquid Substances 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 238000011068 loading method Methods 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
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 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
- 238000004729 solvothermal method Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 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
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 28
- 235000019441 ethanol Nutrition 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002904 solvent Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 238000012512 characterization method Methods 0.000 description 5
- 125000002524 organometallic group Chemical group 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating 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
- 238000001816 cooling Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011056 performance test Methods 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
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 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 2
- 229960004313 naftifine Drugs 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 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
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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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
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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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
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
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- 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
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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
- H01M4/88—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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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Abstract
The invention discloses a polyhedral carbon shell layer loaded transition metal-based hydrogen oxidation catalyst carrier and a preparation method and application thereof, belonging to the technical field of preparation of fuel cell anode electrocatalyst carriers. The invention synthesizes a catalyst which encapsulates polyoxometallate in a metal framework with a three-dimensional polyhedral structure by a solvothermal synthesis technology, the catalyst can keep a hollow porous polyhedral structure after high-temperature calcination, specifically, a metal organic framework precursor is mixed with a polyoxometallate solution to obtain a precursor solution, meanwhile, the polyoxometallate is encapsulated in the metal framework with the polyhedral structure by the solvothermal synthesis technology, and a catalyst carrier is obtained by heat treatment after centrifugation. The electrode material obtained by using the catalyst carrier has better oxyhydrogen electrocatalysis capacity, and the ultimate current density of the oxyhydrogen is close to 2.81mAcm ‑2 。
Description
Technical Field
The invention relates to a polyhedral carbon shell layer loaded transition metal-based hydrogen oxidation catalyst carrier and a preparation method and application thereof, belonging to the technical field of preparation of fuel cell anode electrocatalyst carriers.
Background
The fuel cell is gradually brought into the sight of people due to its excellent performance, does not need a combustion process, is not limited by the carnot cycle, and is considered as an alternative power source in the near future. Among the various types of fuel cells, the most promising is the Proton Exchange Membrane Fuel Cell (PEMFC), which consists of two half-reactions, the anodic Hydrogen Oxidation Reaction (HOR) and the cathodic Oxygen Reduction Reaction (ORR). For the HOR reaction, a noble metal Pt catalyst cannot be substituted, but hydrogen obtained from reformed fuel flow at present cannot avoid containing CO, CO is easily adsorbed on the surface of Pt, occupies the surface active sites of the Pt, reduces the Pt surface available for hydrogen adsorption, reduces the utilization rate of Pt, and has unsatisfactory cell performance. Therefore, it is necessary to provide a catalyst support capable of introducing a transition metal-based nitrogen (carbide), desorbing CO molecules from the Pt surface, and improving CO tolerance of HOR.
Disclosure of Invention
The invention provides a polyhedral carbon shell layer loaded transition metal-based hydrogen oxidation catalyst carrier and a preparation method and application thereof.
The technical scheme of the invention is as follows:
a preparation method of a transition metal-based hydrogen oxidation catalyst carrier loaded on a polyhedral carbon shell layer comprises the following implementation steps:
mixing an inorganic transition metal salt solution and an organic ligand solution, stirring the mixed solution for 2-12 h at 25-30 ℃, and performing centrifugal washing and vacuum drying treatment to obtain a metal organic framework precursor;
respectively dissolving a metal organic framework precursor and polyoxometallate in an organic solvent, mixing the two solutions, and carrying out hydrothermal treatment on the mixed solution to obtain a reaction solution;
and step three, centrifugally washing the reaction solution, then drying in vacuum, and carrying out heat treatment in a nitrogen atmosphere to obtain the polyhedral carbon shell layer loaded transition metal-based hydrogen oxidation catalyst carrier.
Further limiting, in the step one, the mixed solution is stirred for 4 to 8 hours at the temperature of between 25 and 30 DEG C
Further limit, in the step one, the inorganic transition metal salt is one or more of cobalt nitrate, zinc nitrate, copper nitrate or zirconium chloride which are mixed in any proportion.
Further limiting, in the first step, the organic ligand is one or more of terephthalic acid, ethylene diamine tetraacetic acid or methylimidazole which are mixed according to any proportion.
Further limiting, the molar ratio of the inorganic transition metal salt to the organic ligand in the mixed solution in the first step is 1: (1-20).
More specifically, the molar ratio of the inorganic transition metal salt to the organic ligand in the mixed solution in the first step is 1: (1-15).
More specifically, the molar ratio of the inorganic transition metal salt to the organic ligand in the mixed solution in the first step is 1: (1-10).
Further limiting, the concentration of the organic ligand in the mixed solution in the first step is 60 mmol/L-80 mmol/L.
Further limiting, the concentration of the organic ligand in the mixed liquid in the first step is 50 mmol/L-80 mmol/L.
Further limiting, the concentration of the organic ligand in the mixed solution in the step one is 60 mmol/L-80 mmol/L.
Further limiting, the organic solution in the inorganic transition metal salt solution and the organic ligand solution prepared in the step one is absolute methanol or absolute ethanol.
Further limiting, in the step one, under the condition that the power is 400W-2000W, the inorganic transition metal salt and the organic ligand are dispersed in the organic solvent in an ultrasonic mode, and the ultrasonic dispersion treatment time is 5-60 min.
Further limiting, in the step one, under the condition that the power is 400W-2000W, the inorganic transition metal salt and the organic ligand are dispersed in the organic solvent in an ultrasonic mode, and the ultrasonic dispersion treatment time is 5-30 min.
Further limited, the operation process of the centrifugal washing in the first step is as follows: centrifuging for 5-8 min at 8000-10000 rad/min, wherein the washing liquid is absolute methanol or absolute ethanol, and the washing times are 3-5.
Further limiting, the conditions of the vacuum drying treatment in the step one are as follows: vacuum drying at 60-80 deg.c for 10-14 hr.
And further selecting the polyoxometallate in the step two as one or more of phosphotungstic acid, phosphomolybdic acid, potassium tungstophosphate and sodium molybdenum silicate to be mixed in any proportion.
Further limiting, the temperature of the water heat treatment in the second step is 70-120 ℃, and the time is 4-8 h.
Further limiting, the operation process of centrifugal washing in the second step is as follows: centrifuging for 5-8 min at 8000-10000 rad/min, wherein the washing liquid is absolute methanol or absolute ethanol, and the washing times are 3-5.
Further limited, the heat treatment conditions in the third step are as follows: calcining for 2-4 h at 600-1000 ℃ in nitrogen atmosphere.
Further limiting, the vacuum drying conditions in the third step are as follows: vacuum drying at 60-80 deg.c for 10-14 hr.
The invention also provides a catalyst carrier for a fuel cell, which is prepared by the preparation method.
The invention also provides an application of the transition metal-based hydrogen oxidation catalyst carrier loaded with the polyhedral carbon shell, and the carrier is used for a fuel cell HOR anode electrocatalyst to catalyze the hydrogen oxidation reaction of a fuel cell anode after loading the transition metal.
Compared with the prior art, the invention introduces the transition metal-based nitrogen (carbide), can desorb CO molecules from the Pt surface, and improves the CO tolerance of HOR. The method has the following specific beneficial effects:
(1) the invention uses a solvothermal synthesis method to encapsulate polyoxometallate in the prepared metal organic framework precursor, and obtains the polyhedral carbon shell layer loaded transition metal-based hydrogen oxidation catalyst carrier after thermal treatment after centrifugation. The catalyst has better hydrogen oxidation electrocatalysis capability and extremely highThe current limiting density is close to 2.81mAcm -2 。
(2) According to the invention, by utilizing a solvothermal synthesis method, the prepared metal organic framework window is opened, so that polyoxometallate enters the metal organic framework to prepare the transition metal-based hydrogen oxidation catalyst carrier loaded on the polyhedral carbon shell layer, and the carrier has excellent HOR performance after being loaded with Pt.
(3) The transition metal-based hydrogen oxidation catalyst carrier loaded on the polyhedral carbon shell layer, which is prepared by the invention, has transition metal-based nitride (carbide), can desorb CO molecules from the surface of Pt, improves the utilization rate of Pt, and then improves the performance of a battery.
(4) The invention carries out carbonization treatment in the process of preparing the polyhedral carbon shell layer loaded transition metal base hydrogen oxidation catalyst carrier, thereby effectively increasing the graphitization degree and the conductivity of the catalyst.
Drawings
FIG. 1 is an X-ray diffraction pattern of a polyhedral carbon shell-supported transition metal-based hydrogen oxidation catalyst support prepared in example 1;
FIG. 2 is a scanning electron micrograph of the polyhedral carbon shell-supported transition metal-based hydrogen oxidation catalyst support prepared in example 1;
FIG. 3 is a comparison graph of the linear sweep voltammetry tests of the polyhedral carbon shell-supported transition metal-based hydrogen oxidation catalyst support prepared in different examples;
FIG. 4 is a scanning electron micrograph of the polyhedral carbon shell-supported transition metal-based hydrogen oxidation catalyst support prepared in example 2;
FIG. 5 is a scanning electron micrograph of the polyhedral carbon shell-supported transition metal-based hydrogen oxidation catalyst support prepared in example 3;
FIG. 6 is a scanning electron micrograph of the polyhedral carbon shell-supported transition metal-based hydrogen oxidation catalyst support prepared in comparative example 1;
fig. 7 is a comparison graph of the linear sweep voltammetry test of the polyhedral carbon shell-supported transition metal-based hydrogen oxidation catalyst carrier prepared in example 1 and the polyhedral carbon shell-supported transition metal-based hydrogen oxidation catalyst carrier prepared in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
Example 1:
(1) preparation of organometallic frameworks (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 a metal solution and a 2-methylimidazole solution for 30min, mixing, stirring the mixed solution at 30 ℃ for 4h, forming a precipitate, carrying out centrifugal washing once by using distilled water at 8000rad/min, carrying out centrifugal washing once by using an ethanol solvent, and then carrying out drying for 12h at 80 ℃ under a vacuum condition to obtain a metal organic framework, namely ZIF-67 for short CoZn ，ZIF-67 CoZn And the template is used for standby.
(2) Organometallic framework ZIF-67 of cobalt by solvothermal method CoZn Opening a window, and encapsulating Polyoxometallate (POM) inside the polyhedron:
0.15g of ZIF-67 obtained in step (1) 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 8h, 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 80 deg.C under vacuum for 12h to obtain zinc metal organic framework ZIF-67 packaged by POM CoZn POM @ ZIF-67 for short CoZn 。
For the obtained POM @ ZIF-67 CoZn Performing X-ray diffraction pattern characterization, and obtaining the result shown in figure 1As shown in FIG. 1, POM @ ZIF-67 was successfully performed CoZn The transition metal based nitrogen (carbide) compound is introduced into the carrier.
For the obtained POM @ ZIF-67 CoZn Microstructure characterization was performed, as shown in FIG. 2, and as can be seen from FIG. 2, POM @ ZIF-67 was obtained by assembly CoZn Is a catalyst similar to a regular dodecahedron and has uniform particles.
(3) Calcination treatment
The POM @ ZIF-67 obtained in the step (2) CoZn Calcining for 2h at 600 ℃ in nitrogen atmosphere to obtain the polyhedral carbon shell loaded transition metal-based hydrogen oxidation catalyst carrier, Mo for short x Co x A C-1 electrocatalyst support.
(4) Loaded Pt
50mg of the catalyst carrier obtained in the step (3) was uniformly dispersed in 50mL of water, and an appropriate amount of a chloroplatinic acid solution was added. Then adding a proper amount of 1M NaOH solution to adjust the pH value to 8-9, and then adding excessive NaBH 4 Stirring the solution vigorously for 3-5 h, filtering, and drying at 60 ℃ for 12h to obtain Pt/Mo x Co x C-1。
For Pt/Mo x Co x Electrochemical performance test of the C-1 electrocatalyst:
mixing Pt/Mo x Co x The results of the ultrasonic dispersion treatment after mixing the C-1 electrocatalyst, the 5% naphthylene solution and the absolute ethyl alcohol, and the testing after coating the electrode are shown in FIG. 3. As can be seen from FIG. 3, the limiting current density of the hydrogen oxidation reaction is close to 2.81mAcm -2 。
Example 2:
the present example differs from example 1 in that: a small amount of zinc nitrate hexahydrate is not added during preparation of a ZIF-67 precursor, and the preparation process comprises the following steps:
(1) preparation of organometallic frameworks (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 the metal solution and the 2-methylimidazole solution for 30min, mixing, stirring the mixed solution at 30 ℃ for 4h, forming a precipitate, carrying out centrifugal washing once by using distilled water under the condition of 8000rad/min, and usingCentrifugally washing the ethanol solvent once, and drying the washed ethanol solvent for 12 hours at 80 ℃ under a vacuum condition to obtain a metal organic framework, namely ZIF-67 for short Co ，ZIF-67 Co And the template is used for standby.
(2) Opening a cobalt organometallic framework ZIF-67 window by a solvothermal method to encapsulate Polyoxometallate (POM) inside a polyhedron:
0.15g of ZIF-67 obtained in step (1) 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 8h, 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 80 deg.C under vacuum for 12h to obtain zinc metal organic framework ZIF-67 packaged by POM Co POM @ ZIF-67 for short Co 。
For the obtained POM @ ZIF-67 Co Microstructure characterization was performed, as shown in FIG. 4, and as can be seen from FIG. 4, POM @ ZIF-67 was obtained by assembly Co Is a catalyst similar to a regular dodecahedron and has uniform particles.
(3) Calcination treatment
The POM @ ZIF-67 obtained in the step (2) Co Calcining for 2h at 600 ℃ in nitrogen atmosphere to obtain the polyhedral carbon shell loaded transition metal-based hydrogen oxidation catalyst carrier, Mo for short x Co x A C-2 electrocatalyst support.
(4) Loaded Pt
50mg of the catalyst carrier obtained in the step (3) was uniformly dispersed in 50mL of water, and an appropriate amount of a chloroplatinic acid solution was added. Then adding a proper amount of 1M NaOH solution to adjust the pH value to 8-9, and then adding excessive NaBH 4 Stirring the solution vigorously for 3-5 h, filtering, and drying at 60 ℃ for 12h to obtain Pt/Mo x Co x C-2。
For Pt/Mo x Co x C-2 electrocatalyst was tested for electrochemical performance:
mixing Pt/Mo x Co x Mixing C-2 electrocatalyst, 5% naphthylene solution and absolute ethyl alcohol, and ultrasonic dispersingThe results of the test after coating the electrodes are shown in FIG. 3. FIG. 3 shows that the limiting current density of the hydrogen oxidation reaction is close to 2.19mAcm -2 。
Example 3:
this example differs from example 1 in that: the prepared precursor is ZIF-8, and the specific preparation process is as follows:
(1) preparation of organometallic Frames (ZIF-8)
Dissolving 3.6g of zinc 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 a 2-methylimidazole solution for 30min, mixing, stirring the mixed solution at 30 ℃ for 4h, carrying out centrifugal washing once by using distilled water at 8000rad/min after forming a precipitate, carrying out centrifugal washing once by using an ethanol solvent, and then carrying out drying at 80 ℃ for 12h under a vacuum condition to obtain a metal organic framework, namely ZIF-8 for short, and taking the ZIF-8 as a template for later use.
(2) Opening a cobalt organometallic framework ZIF-8 window by a solvothermal method to encapsulate Polyoxometallate (POM) inside a polyhedron:
dispersing 0.15g of ZIF-8 obtained in the step (1) 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 8h, and cooling to room temperature after the reaction is finished to obtain a reaction solution. And washing the reaction solution by using a methanol solvent for 5min under the condition of 9000rad/min, and drying for 12h under the vacuum condition of 80 ℃ to obtain the zinc metal organic framework ZIF-8 packaged by the POM, which is abbreviated as POM @ ZIF-8.
Microstructure characterization is carried out on the obtained POM @ ZIF-8, as shown in FIG. 5, as can be seen from FIG. 5, the POM @ ZIF-8 obtained by assembly is a catalyst which is approximately regular dodecahedron, and the particles are uniform.
(3) Calcination treatment
Calcining the POM @ ZIF-8 obtained in the step (2) for 2 hours at 600 ℃ in a nitrogen atmosphere to obtain a polyhedral carbon shell layer loaded transition metal base hydrogen oxidation catalyst carrier, which is Mo for short x Co x A C-3 electrocatalyst support.
(4) Loaded Pt
50mg of the catalyst carrier obtained in the step (3) was uniformly dispersed in 50mL of water, and an appropriate amount of a chloroplatinic acid solution was added. Then adding a proper amount of 1M NaOH solution to adjust the pH value to 8-9, and then adding excessive NaBH 4 Stirring the solution vigorously for 3-5 h, filtering, and drying at 60 ℃ for 12h to obtain Pt/Mo x Co x C-3。
For Pt/Mo x Co x Electrochemical performance test of the C-3 electrocatalyst:
mixing Pt/Mo x Co x The C-3 electrocatalyst, 5% naftifine solution and absolute ethyl alcohol were mixed, subjected to ultrasonic dispersion treatment, and tested after coating the electrode, as shown in FIG. 3. As can be seen from FIG. 3, the limiting current density of the hydrogen oxidation reaction is close to 0.30mAcm -2 。
Comparative example 1:
the comparative example differs from example 1 in that: the solvent thermal method treatment is not carried out, and the specific operation process is as follows:
(1) preparation of organometallic frameworks (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 zinc nitrate hexahydrate solution and the 2-methylimidazole solution for 30min, mixing the mixed solution at 30 ℃, stirring the mixed solution for 4h, forming a precipitate, carrying out centrifugal washing once by using distilled water at 8000rad/min, carrying out centrifugal washing once by using an ethanol solvent, and then carrying out drying for 12h at 80 ℃ under a vacuum condition to obtain a metal organic framework, namely ZIF-8 for short, wherein the ZIF-8 is used as a template for later use.
(2) 0.15g of ZIF-67 obtained in the above step (1) 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 8h, washing with methanol at 9000rad/min for 5min, and drying at 80 deg.C under vacuum for 12h to obtain POM @ ZIF-67 CoZn 。
For the obtained POM @ ZIF-67 CoZn Microstructure characterization was performed, as shown in FIG. 6, 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
POM @ ZIF-67 obtained in the step (2) CoZn Calcining for 2 hours at 600 ℃ in nitrogen atmosphere to obtain Mo x Co x A C-4 electrocatalyst support.
(4) Loaded Pt
50mg of the catalyst carrier obtained in the step (3) was uniformly dispersed in 50mL of water, and an appropriate amount of a chloroplatinic acid solution was added. Then adding a proper amount of 1M NaOH solution to adjust the pH value to 8-9, and then adding excessive NaBH 4 Stirring the solution vigorously for 3-5 h, filtering, and drying at 60 ℃ for 12h to obtain Pt/Mo x Co x C-4。
For Pt/Mo x Co x Electrochemical performance test of the C-4 electrocatalyst:
mixing 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 electrode was coated and tested as shown in fig. 7. FIG. 7 shows that the limiting current density of the hydrogen oxidation reaction is close to 0.40mAcm -2 。
The above embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to the above embodiments, and modifications and changes thereof may be made by those skilled in the art within the scope of the claims of the present invention.
Claims (10)
1. A preparation method of a fuel cell catalyst carrier is characterized by comprising the following steps:
mixing an inorganic transition metal salt solution and an organic ligand solution, stirring the mixed solution for 2-12 h at 25-30 ℃, and performing centrifugal washing and vacuum drying treatment to obtain a metal organic framework precursor;
respectively dissolving a metal organic framework precursor and polyoxometallate in an organic solvent, mixing the two solutions, and carrying out hydrothermal treatment on the mixed solution to obtain a reaction solution;
and step three, centrifugally washing the reaction solution, then drying in vacuum, and carrying out heat treatment in a nitrogen atmosphere to obtain the polyhedral carbon shell layer loaded transition metal-based hydrogen oxidation catalyst carrier.
2. The method for preparing a fuel cell catalyst carrier according to claim 1, wherein in the first step, the inorganic transition metal salt is one or more of cobalt nitrate, zinc nitrate, copper nitrate, and zirconium chloride mixed at an arbitrary ratio; the organic ligand is one or more than two of terephthalic acid, ethylene diamine tetraacetic acid or methylimidazole which are mixed in any proportion.
3. The method for producing a fuel cell catalyst carrier according to claim 1 or 2, wherein the molar ratio of the inorganic transition metal salt to the organic ligand in the mixed solution in the first step is 1: (1-20).
4. The method for preparing a fuel cell catalyst carrier according to claim 1, wherein the concentration of the organic ligand in the mixed solution in the first step is 60mmol/L to 80 mmol/L.
5. The method for preparing a fuel cell catalyst carrier according to claim 1, wherein the operation process of the centrifugal washing in the first and second steps is: centrifuging for 5-8 min at 8000-10000 rad/min, wherein the washing liquid is absolute methanol or absolute ethanol, and the washing times are 3-5.
6. The method for preparing a fuel cell catalyst carrier according to claim 1, wherein the conditions of the vacuum drying treatment in the first step and the third step are: vacuum drying at 60-80 deg.c for 10-14 hr.
7. The method for preparing a catalyst carrier for a fuel cell according to claim 1, wherein the polyoxometallate in the second step is one or more of phosphotungstic acid, phosphomolybdic acid, potassium tungstophosphate and sodium molybdenum silicate mixed in any proportion.
8. The method for preparing a fuel cell catalyst carrier according to claim 1, wherein the hydrothermal treatment temperature in the second step is 70 to 120 ℃ for 4 to 8 hours.
9. The method for producing a fuel cell catalyst carrier according to claim 1, characterized in that the heat treatment conditions in the third step are: calcining for 2-4 h at 600-1000 ℃ in nitrogen atmosphere.
10. A fuel cell catalyst support prepared according to the method of claim 1, wherein the support is used as a fuel cell HOR anode electrocatalyst, after loading of transition metal, to catalyse the hydrogen oxidation reaction of the fuel cell anode.
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| 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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| 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 |
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