CN117497779B - Preparation method and application of integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst - Google Patents
Preparation method and application of integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 99
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 49
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 48
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 43
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 38
- 239000002135 nanosheet Substances 0.000 title claims abstract description 29
- 239000007809 chemical reaction catalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000446 fuel Substances 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims description 11
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002064 nanoplatelet Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical group [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 3
- 229960001553 phloroglucinol Drugs 0.000 claims description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 125000006267 biphenyl group Chemical group 0.000 claims 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 229910001215 Te alloy Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000011865 Pt-based catalyst Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- VRLFOXMNTSYGMX-UHFFFAOYSA-N diphenyl ditelluride Chemical compound C=1C=CC=CC=1[Te][Te]C1=CC=CC=C1 VRLFOXMNTSYGMX-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method and application of an integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst. The preparation method comprises the following steps: dispersing a platinum precursor, a tellurium precursor, a reducing agent and a catalyst carrier in a solvent, uniformly mixing by ultrasonic, and reacting at a certain temperature to obtain an integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst; the catalyst is obtained by in-situ growth of uniform and clean two-dimensional platinum tellurium alloy nano-sheets on the surface of commercial carbon powder. The resulting catalyst has not only good stability, but also higher specific surface area and surface atom utilization, and the resulting catalyst has a clean surface, does not require excessive complicated post-treatment methods, and exhibits excellent FAOR activity and CO tolerance when applied to the anode FAOR of a direct formic acid fuel cell. In addition, the liquid phase method adopted by the invention has simple preparation process, thus having wide application prospect.
Description
Technical Field
The invention belongs to the field of formic acid oxidation catalyst synthesis, and particularly relates to a preparation method and application of an integrated carbon-supported platinum tellurium nanosheet formic acid oxidation catalyst.
Background
Fuel cells, which are a kind of storage medium, are novel energy technologies for converting chemical energy into electric energy, which exhibit advantages of high energy density, low cost, low safety risk, etc., and show great potential in terms of alleviation of carbon emission and energy crisis. Among them, formic acid has an important role in a Direct Formic Acid Fuel Cell (DFAFC) because of advantages of easy production, incombustibility, low cost, safety, easy storage, etc., and an anodic Formic Acid Oxidation Reaction (FAOR) is a key for determining a rate in a system, and an indirect dehydration process is usually easy to perform, so that carbon monoxide (CO) poisoning occurs. Thus, the preparation of electrocatalysts with high selectivity and high CO tolerance has been a focus of research in this area.
Platinum (Pt) is also an indispensable place in FAOR as the most widely used and effective electrocatalyst. However, due to the strong adsorption of CO, conventional Pt-based catalysts also cause CO poisoning in FAOR. In recent years, researchers have weakened CO adsorption by constructing a hexagonal phase Pt-based alloy catalyst to promote the direct dehydrogenation process of formic acid, wherein platinum tellurium (PtTe) alloys exhibit superior electrochemically active properties.
The low-dimensional material has high specific surface area and high surface atom utilization rate, so that in the preparation of PtTe alloy catalyst, researchers have spent a great deal of effort in precisely controlling the synthesis of specific morphology, and the morphology structures such as one-dimensional nanowires and two-dimensional nanoplatelets can be synthesized usually under the environments of various surfactants, structure directing agents, oleylamine and the like. Although morphology regulation can be successfully realized, a plurality of impurities which are difficult to treat cleanly are attached to the surface of the catalyst in the preparation process, and the problems of blocking intrinsic active sites, reducing the conductivity of the alloy catalyst and the like can be generated, so that the activity of FAOR is greatly influenced. In addition, the method cannot generally realize in-situ growth on the carbon carrier, and secondary loading is required, so that the binding force between the catalyst and the carrier is not strong enough, the problems of catalyst agglomeration and the like are easy to occur in the electrochemical process, and the performance is also greatly influenced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method and application of an integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst.
The first aspect of the invention provides a preparation method of an integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst, which comprises the following steps: dispersing the platinum precursor, tellurium precursor, reducing agent and catalyst carrier in a solvent, uniformly mixing by ultrasonic, reacting at a certain temperature, and purifying to obtain the integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst.
Preferably, the platinum precursor is platinum acetylacetonate or chloroplatinic acid.
Preferably, the tellurium precursor is any one of telluric acid, diphenyl ditelluride and Jiao Di potassium acid.
Preferably, the molar ratio of the platinum precursor to the tellurium precursor is 5-1: 1.
Preferably, the reducing agent is any one of phenol, hydroquinone, catechol, resorcinol and phloroglucinol.
Preferably, the mass ratio of the reducing agent to the platinum precursor to the tellurium precursor is 5-25: 2 to 12:11.
Preferably, the mass ratio of the catalyst carrier to the platinum precursor is 0.025-5: 0.02-8.
Preferably, the catalyst carrier is any one of carbon nano tube, ketjen black and cabot carbon.
Preferably, the solvent is any one of DMF (N, N-dimethylformamide) and DMAC (N, N-dimethylacetamide).
Preferably, the reaction temperature is 100-220 ℃, and the reaction time is 2-12 h.
Preferably, the purification treatment comprises: and sequentially centrifuging, washing and drying the reaction product.
Preferably, the washing solvent is one or a combination of ethanol and acetone.
Preferably, the drying temperature is 50-100 ℃ and the drying time is 1-24 h.
The second aspect of the invention provides an integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst prepared by the preparation method, which consists of a catalyst carrier carbon layer and platinum tellurium alloy nanosheets with uniform surface in-situ growth distribution.
The third aspect of the invention provides an application of the integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst as an anode electrocatalyst for a direct formic acid fuel cell in an anode FAOR of the direct formic acid fuel cell.
The invention has the following beneficial effects:
(1) The invention prepares the integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst by in-situ growth of a clean two-dimensional platinum tellurium alloy nanosheet (PtTe 2 nanosheets) on commercial carbon powder (serving as a catalyst carrier). The catalyst is directly grown on the surface of commercial carbon powder (serving as a catalyst carrier) in situ, so that the interaction force between the catalyst carrier and the platinum tellurium alloy nanosheets, namely the catalyst, can be improved, and the catalyst obtained by the method has better structural stability; meanwhile, the catalyst obtained by the invention exists in the form of nano sheets, so that the specific surface area and the surface atom utilization rate of the catalyst can be increased; furthermore, the catalyst is obtained by in-situ growth of the two-dimensional platinum tellurium nanosheets on the surface of the carbon carrier, and the surface is clean, and an excessive and complicated post-treatment method is not needed, so that the overall activity and CO tolerance of the Pt-based catalyst can be effectively improved.
(2) The catalyst obtained by the invention has certain universality in the aspect of catalyzing formic acid oxidation reaction, and catalysts with different uniformity degrees can be synthesized by adopting different reducing agents.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a TEM image of an integrated carbon-supported platinum tellurium nanoplatelets formic acid oxidation reaction catalyst prepared in example 1;
FIG. 2 is an X-ray diffraction pattern of the integrated carbon-supported platinum tellurium nanoplatelets formic acid oxidation reaction catalyst prepared in example 1;
FIG. 3 is an X-ray photoelectron spectrum of the integrated carbon-supported platinum tellurium nanoplatelets formic acid oxidation reaction catalyst prepared in example 1;
FIG. 4 is a linear sweep voltammogram (test interval 0.1-1.1V (vs. RHE), test rate 0.01V/s) for the integrated carbon-supported platinum-tellurium nanoplatelets formic acid oxidation catalyst prepared in examples 1-3 and commercial platinum carbon activated in 0.5M H 2SO4;
FIG. 5 is a linear sweep voltammogram (test interval 0.1-1.1V (vs. RHE)) of the integrated carbon-supported platinum-tellurium nanoplatelets formic acid oxidation catalyst prepared in examples 1-3 and commercial platinum-carbon 0.5M H 2SO4 +0.5M HCOOH for formic acid oxidation at a test rate of 0.01V/s.
Detailed Description
In the following description, for purposes of explanation and not limitation, specific details are set forth such as the particular system architecture, techniques, etc., in order to provide a thorough understanding of the embodiments of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details. The present invention will be described in detail with reference to examples.
Example 1
The preparation method of the integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst comprises the following steps: weighing 60mg of telluric acid, 100mg of platinum acetylacetonate, 220mg of catechol and 100mg of ketjen black, placing the materials in a reactor, adding 100mL of DMF (dimethyl formamide) into the reactor, placing the mixture in an ultrasonic instrument, and performing ultrasonic treatment for 30min to uniformly disperse; placing the dispersed mixture on an oil bath pot, reacting for 6 hours at 160 ℃ at a stirring rotation speed of 200rpm, and naturally cooling to room temperature; the reaction product was washed three times with ethanol and acetone mixture, and then dried overnight in an oven at 50℃to finally obtain a catalyst designated PtTe-c.
Example 2
The procedure was substantially the same as in experimental example 1, except that: the "catechol" was replaced by "phenol" and the final catalyst was obtained and designated PtTe-ph.
Example 3
The procedure was substantially the same as in experimental example 1, except that: the "catechol" was replaced by "phloroglucinol", and the final catalyst was obtained, designated PtTe-pg.
Example 4
The procedure was substantially the same as in experimental example 1, except that: the catalyst was finally obtained by replacing "60mg of telluric acid" with "229.6mg of telluric acid".
Example 5
The procedure was substantially the same as in experimental example 1, except that: the catalyst was finally obtained by replacing "60mg of telluric acid" with "46mg of telluric acid".
Example 6
The procedure was substantially the same as in experimental example 1, except that: the catalyst is finally obtained by replacing 100mg of platinum acetylacetonate and 100mg of ketjen black with 517mg of chloroplatinic acid and 100mg of carbon nano tubes.
Example 7
The procedure was substantially the same as in experimental example 1, except that: the reaction is carried out at 160 ℃ for 6 hours, and is replaced by the reaction at 100 ℃ for 12 hours, so that the catalyst is finally obtained.
The catalyst prepared in example 1, ptTe-c, was characterized to give TEM results, XRD results, and X-ray photoelectron spectroscopy results, as shown in FIGS. 1-3 and Table 1, respectively.
As can be seen from the results of fig. 1 (a) and fig. 1 (b), ptTe-c prepared in the examples are uniformly distributed on carbon powder (carrier) in a nano-sheet structure, and are uniformly dispersed; by measuring that the lattice spacing is 0.289nm and 0.202nm accords with PtTe 2 standard lattice spacing.
As can be seen intuitively from the results of fig. 2, the PtTe-c diffraction peaks obtained in example 1 correspond one-to-one to PtTe 2 standard cards, which indicates that PtTe-c obtained in example 1 has the presence of hexagonal phase platinum tellurium nanostructures.
As can be seen from FIGS. 3 (a) - (d) and the results in Table 1 below, the catalysts obtained in examples 1-3 all contained the presence of platinum, carbon and tellurium.
TABLE 1
The characterization result shows that the invention successfully synthesizes the integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst.
Electrochemical performance test
The following studies have been made on the application of the integrated carbon-supported platinum tellurium nanoplatelets formic acid oxidation reaction catalyst prepared in examples 1-3 as an anode electrocatalyst for direct formic acid fuel cells in anodes FAOR of direct formic acid fuel cells.
The method comprises the following specific steps: prior to preparing the working electrode, the catalyst, isopropyl alcohol, and naphthol (v: v=5:0.02) were mixed and ultrasonically dispersed until a uniform liquid was formed. A certain volume of solution is dripped on the polished working electrode, and the integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst and commercial platinum carbon are subjected to a linear scanning voltammetry test (the test interval is 0.1-1.1V (vs. RHE) and the test speed is 0.01V/s) in a rotating disc test, wherein the result is shown in FIG. 4;
in addition, the integrated carbon-supported platinum tellurium nanoplatelets formic acid oxidation reaction catalyst prepared in examples 1-3 and commercial platinum carbon were subjected to a linear sweep voltammetry test (test interval of 0.1-1.1V (vs. RHE), test rate of 0.01V/s) of formic acid oxidation in 0. M H 2SO4 +0.5M HCOOH in a rotating disk test, and the results are shown in FIG. 5.
As can be seen from the results of fig. 4, it was found by analysis that the catalyst obtained in the present invention did not exhibit a significant hydrogen region in CV, and that an oxidation peak of Te was also apparent, indicating that the present invention successfully produced platinum tellurium nanoplatelets.
As can be seen from the results of fig. 5, the catalyst obtained by the present invention has a higher current at 0.6V potential, which indicates that it is in a direct reaction path in formic acid oxidation, and the introduction of Te reduces the continuous Pt sites, resulting in reduced adsorption of CO intermediates, and promotes the direct reaction path. Compared with the traditional commercial platinum carbon, the catalyst obtained by the invention has excellent formic acid oxidation performance and selectivity, so that the catalyst prepared by the invention can be used on the anode FAOR of a formic acid fuel cell and has wide application prospect.
The present invention is not limited to the above-described specific embodiments, and various modifications may be made by those skilled in the art without inventive effort from the above-described concepts, and are within the scope of the present invention.
Claims (8)
1. The preparation method of the integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst is characterized by comprising the following steps of: dispersing a platinum precursor, a tellurium precursor, a reducing agent and a catalyst carrier in a solvent, uniformly mixing by ultrasonic, reacting at a certain temperature, and purifying to obtain a formic acid oxidation reaction catalyst;
The reducing agent is any one of phenol, hydroquinone, catechol, resorcinol and phloroglucinol; the mass ratio of the reducing agent to the platinum precursor to the tellurium precursor is 5-25: 2-12: 11;
the reaction temperature is 100-220 ℃, and the reaction time is 2-12 h.
2. The method for preparing the integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst of claim 1, wherein the platinum precursor is platinum acetylacetonate or chloroplatinic acid.
3. The method for preparing the integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst of claim 1, wherein the tellurium precursor is any one of telluric acid, diphenyl ditellum and Jiao Di potassium.
4. The method for preparing the integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst according to claim 1, wherein the molar ratio of the platinum precursor to the tellurium precursor is 5-1: 1.
5. The method for preparing the integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst according to claim 1, wherein the catalyst carrier is any one of carbon nanotubes, ketjen black and cabot carbon; the mass ratio of the catalyst carrier to the platinum precursor is 0.025-5: 0.02-8.
6. The method for preparing the integrated carbon-supported platinum tellurium nanosheet formic acid oxidation reaction catalyst according to claim 1, wherein the solvent is DMF or DMAC.
7. The integrated carbon-supported platinum tellurium nanosheets formic acid oxidation catalyst prepared by the preparation method of any one of claims 1 to 6.
8. The use of the integrated carbon-supported platinum tellurium nanoplatelets formic acid oxidation catalyst of claim 7 in an anode FAOR of a direct formic acid fuel cell.
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