CN116657175A - Synthesis and application of Pt atomic cluster cooperated with Pt single-atom electrocatalytic material - Google Patents
Synthesis and application of Pt atomic cluster cooperated with Pt single-atom electrocatalytic material Download PDFInfo
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- CN116657175A CN116657175A CN202310405105.4A CN202310405105A CN116657175A CN 116657175 A CN116657175 A CN 116657175A CN 202310405105 A CN202310405105 A CN 202310405105A CN 116657175 A CN116657175 A CN 116657175A
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- 238000003786 synthesis reaction Methods 0.000 title abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 239000005711 Benzoic acid Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- 229910007926 ZrCl Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000013207 UiO-66 Substances 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 239000010411 electrocatalyst Substances 0.000 abstract description 4
- 239000013110 organic ligand Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000012621 metal-organic framework Substances 0.000 abstract description 3
- 150000004032 porphyrins Chemical class 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- OQCRAXGQKOWHQI-UHFFFAOYSA-N [Pt].C(=O)(O)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 Chemical compound [Pt].C(=O)(O)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 OQCRAXGQKOWHQI-UHFFFAOYSA-N 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 229910003134 ZrOx Inorganic materials 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 229910021397 glassy carbon Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates to synthesis and application of a Pt atomic cluster and Pt single atom electro-catalytic material, wherein the Pt atomic cluster and the Pt single atom are anchored by using a porphyrin organic ligand with a metal center, and a carbon-based electro-catalyst is prepared by calcining. The porphyrin organic ligand adopted by the invention is 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin platinum (PtTCPP), is doped into MOF (UiO-66) and is used as a precursor for preparing the electrocatalyst, and the preparation process is mature and is suitable for commercial production. In order to obtain high performance Hydrogen Evolution Reactions (HERs), a composite electrocatalytic material (Pt) is obtained by co-embedding Pt clusters and Pt monoatoms into N-doped carbon materials using an in situ strategy SA ‑Pt AC ) So as to have respective advantages and even synergistic effect, realize the performance which can be compared with commercial Pt/C in the aspect of electrocatalytic hydrogen evolution,is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of electrocatalytic hydrogen evolution, in particular to synthesis and application of a Pt atomic cluster cooperated with Pt single-atom electrocatalytic material.
Background
Energy is an important material basis for human survival and development. It is well known that hydrogen energy has the advantages of very high energy density, renewable and pollution-free properties. The purity of hydrogen produced by electrolysis of water and hydrogen evolution can reach more than 99%, which is an important method for industrially preparing hydrogen. The method converts the electric energy into relatively stable chemical energy, does not generate other byproducts while obtaining the hydrogen, and is an important method which is friendly to the environment and realizes sustainable hydrogen storage. In this respect, the electrolysis of water is limited by the slow kinetics of the Hydrogen Evolution Reaction (HER), which is inefficient and energy-consuming. Therefore, the development of high-activity and durable electrocatalysts is a necessary path for accelerating the reactions and improving the energy conversion efficiency, and the research of catalytic materials has important significance for the electrocatalytic hydrogen production technology.
Metal Organic Frameworks (MOFs) are a material assembled orderly from metal nodes and organic ligands, with excellent specific surface area and functional tunability, considered important precursors for supporting metal species by pyrolysis to carbon-based materials. It is very important that the various organic ligands containing heteroatoms are good attachment sites for the individual metal atoms. In particular, the efficient chemical bonds between metal atoms and heteroatoms may enable anchoring of the metal atoms to reduce migration and aggregation during pyrolysis. The catalytic performance of electrocatalysts is generally determined primarily by two factors, including the number of catalytically active sites and the intrinsic activity of the individual active sites. Recent studies have shown that by reducing the size of the catalyst particles, the number of catalytically active sites and more exposed active surface area can be increased, and by tailoring the metal sites and electronic structures, the intrinsic properties of the metal sites can be enhanced. The catalyst particles are reduced to an atomic level, so that an effective way is provided for realizing the highest utilization efficiency of metal atoms and improving the intrinsic catalytic activity of the catalyst. In this regard, pt monoatomic and Pt cluster catalysts have attracted attention in recent years due to their greater geometry, electrochemical surface area, more exposed active sites, and maximized Pt utilization and low cost compared to Pt monoliths and Pt nanoparticles. However, it is known that the mass activity of noble metal catalysts currently used in the field of electrocatalytic hydrogen evolution is generally not high, which increases the production costs.
Therefore, the synthesis of a Pt atomic cluster cooperated with a Pt single-atom electrocatalytic material and the application of the Pt atomic cluster to electrocatalytic hydrogen evolution research are the directions of research of the technicians in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to synthesize the Pt atomic cluster coordinated Pt single-atom electro-catalytic material so as to solve the problems of high price, small storage capacity and large industrial use difficulty of the noble metal-based catalytic material in the prior art.
The invention also provides a preparation method of the Pt atomic cluster cooperated Pt single-atom electrocatalytic material, and the Pt electrocatalytic material can be prepared by the method.
The invention also provides an application of the Pt atomic cluster cooperated with the Pt single-atom electrocatalytic material, and the Pt electrocatalytic material prepared by the preparation method is suitable for electrocatalytic hydrogen evolution reaction under an acidic condition.
The technical scheme adopted by the invention is as follows:
a preparation method of a Pt atomic cluster cooperated with Pt single-atom electrocatalytic material comprises the following steps:
step 1) ZrCl 4 Terephthalic acid, benzoic acid and tetra-carboxyl phenyl porphyrin platinum are used as raw materials, and an intermediate PtTCPP@UIO-66 is prepared by a hydrothermal method;
step 2) calcining the intermediate PtTCPP@UIO-66 at high temperature to obtain the composite electrocatalytic material Pt SA -Pt AC 。
Wherein, in the step 1), the reaction temperature is 135 ℃ and the reaction time is 12 hours;
in the step 2), the calcining temperature is 800 ℃ and the calcining time is 2 hours;
the invention also provides application of the Pt atomic cluster and Pt single-atom electrocatalytic material, which is characterized in that the Pt atomic cluster and Pt single-atom electrocatalytic material is prepared by the method of claim 1; the Pt atomic cluster cooperated with the Pt single-atom electrocatalytic material is suitable for electrocatalytic hydrogen evolution application under an acidic condition and shows an excellent effect.
Compared with the prior art, the invention has the following advantages:
1. the preparation method of the Pt atomic cluster cooperated with the Pt single-atom electrocatalytic material provided by the invention enables the obtained composite electrocatalytic material Pt to be SA -Pt AC The morphology of PtTCPP@UIO-66 before calcination is maintained, and active sites can be fully exposed; the addition of PtTCPP provides an active site Pt on one hand, and the pyrrole N in the porphyrin structure anchors metal Pt on the other hand, so that aggregation of the metal Pt under high-temperature calcination is avoided to form nano particles.
2. The Pt atomic cluster cooperated with Pt single-atom electrocatalytic material prepared by the invention is suitable for electrocatalytic hydrogen evolution research under an acidic condition, and has excellent hydrogen evolution effect, ultrahigh Pt quality activity and stability.
Drawings
FIG. 1 is an XRD pattern for UIO-66 prepared in example 1.
FIG. 2 is an SEM image of UiO-66 prepared according to example 1.
FIG. 3 is an XRD pattern for ZrOx/C prepared in example 1.
FIG. 4 is an electrocatalytic hydrogen evolution graph of ZrOx/C prepared in example 1.
FIG. 5 is an SEM image of TCPP@UiO-66 prepared in example 2.
FIG. 6 is an XRD pattern for ZrOx/CN prepared in example 2.
FIG. 7 is an electrocatalytic hydrogen evolution graph of ZrOx/CN prepared in example 2.
FIG. 8 is an SEM image of PtTCPP@UIO-66 prepared in example 3.
FIG. 9 shows Pt prepared in example 3 SA -Pt AC SEM images of (a).
FIG. 10 shows Pt prepared in example 3 SA -Pt AC Is a XRD pattern of (C).
FIG. 11 shows Pt prepared in example 3 SA -Pt AC Electrocatalytic hydrogen evolution diagram of (2).
FIG. 12 shows Pt prepared in example 3 SA -Pt AC Is described.
Detailed Description
The invention will be further described with reference to the drawings and examples.
Example 1:
the preparation method of the ZrOx/C material comprises the following steps:
(1) ZrCl is added to 4 (0.39 mg), terephthalic acid (0.277 g), benzoic acid (6 g) were added to 20mL DMF and stirred for 30 minutes to dissolve the starting material sufficiently, which was then charged to the reaction vessel and reacted at 135℃for 12 hours. After the reaction is cooled, the solid is obtained by centrifugation, and is washed by DMF and ethanol for a plurality of times, and finally the UIO-66 is obtained by drying.
(2) 200mg of UIO-66 was in flow-through N 2 Calcining at 800 ℃ for 2 hours to obtain ZrOx/C.
Successful synthesis of UiO-66 can be seen from the XRD pattern of fig. 1, and the SEM pattern of fig. 2 shows that the morphology of the prepared UiO-66 exhibits an octahedral structure. It can be seen from fig. 3 that ZrOx is successfully formed after calcination, and that ZrOx crystal information is present.
The ZrOx/C material is used in electrocatalytic hydrogen evolution, and is concretely as follows:
(1) Preparation of the test electrode: 1mg of ZrOx/C material is weighed and added into 490uL of ethanol/water solution (volume ratio is 1:1), 10uL of Nafion solution is added, and then ultrasonic treatment is carried out for 30 minutes, so that the catalytic material is uniformly dispersed; and (3) dripping 4uL of the mixed solution subjected to ultrasonic treatment onto a glassy carbon electrode, and naturally airing the mixed solution for later use.
(2) Electrocatalytic hydrogen evolution test: a three-electrode test mode is selected, a reference electrode is a saturated calomel electrode, a counter electrode is a carbon rod electrode, a working electrode is a glassy carbon electrode loaded with a catalytic material, and an acidic electrolyte is 0.5M H 2 SO 4 。
FIG. 4 is a graph showing the electrocatalytic hydrogen evolution results of the ZrOx/C material prepared.
Example 2:
the preparation method of the ZrOx/CN material comprises the following steps:
(1) ZrCl is added to 4 (0.39 mg), terephthalic acid (0.277 g), benzoic acid (6 g) and TCPP (12 mg) were added to 20mL of DMF and stirred for 30 minutes to sufficiently dissolve the starting material, which was then charged into the reaction vessel and reacted at 135℃for 12 hours. After the reaction is cooled, the solid is obtained by centrifugation, and is washed by DMF and ethanol for a plurality of times, and finally, TCPP@UIO-66 is obtained by drying.
(2) 200mg TCPP@UIO-66 was added to the flow-through N 2 Calcining for 2 hours at 800 ℃ to obtain ZrOx/CN.
From the SEM image of FIG. 5, it can be seen that the morphology of the prepared TCPP@UIO-66 exhibited an octahedral structure. The XRD pattern of fig. 6 reflects ZrOx crystal information generated after calcination.
The prepared ZrOx/CN material is used in electrocatalytic hydrogen evolution, and specifically comprises the following steps:
(1) Preparation of the test electrode: 1mg of ZrOx/CN material is weighed and added into 490uL of ethanol/water solution (the volume ratio is 1:1), 10uL of Nafion solution is added, and then ultrasonic treatment is carried out for 30 minutes, so that the catalytic material is uniformly dispersed; and (3) dripping 4uL of the mixed solution subjected to ultrasonic treatment onto a glassy carbon electrode, and naturally airing the mixed solution for later use.
(2) Electrocatalytic hydrogen evolution test: a three-electrode test mode is selected, a reference electrode is a saturated calomel electrode, a counter electrode is a carbon rod electrode, a working electrode is a glassy carbon electrode loaded with a catalytic material, and an acidic electrolyte is 0.5M H 2 SO 4 。
FIG. 7 is a graph showing the electrocatalytic hydrogen evolution results of the ZrOx/CN material prepared.
Example 3:
Pt SA -Pt AC the preparation method of the material comprises the following steps:
(1) ZrCl is added to 4 (0.39 mg), terephthalic acid (0.277 g), benzoic acid (6 g) and PtTCPP (12 mg) were added to 20mL of DMF and stirred for 30 minutes to sufficiently dissolve the raw materials, which were then charged into a reaction vessel and reacted at 135℃for 12 hours. After the reaction is cooled, the mixture is centrifuged to obtain solid, and the solid is washed by DMF and ethanol for a plurality of times, and finally the PtTCPP@UIO-66 is obtained by drying.
(2) 200mg PtTCPP@UIO-66 was added to the flow-through N 2 Calcining at 800 ℃ for 2 hours to obtain Pt SA -Pt AC 。
From the SEM images of FIGS. 8 and 9, it can be seen that the morphology of PtTCPP@UIO-66 prepared exhibited an octahedral structure, and Pt was calcined at 800℃under high temperature SA -Pt AC Still in an octahedral structure. The XRD pattern of fig. 10 reflects ZrOx crystal information generated after calcination.
Pt to be prepared SA -Pt AC The material is used in electrocatalytic hydrogen evolution, and specifically comprises the following steps:
(1) Preparation of the test electrode: weigh 1mg Pt SA -Pt AC Adding the material into 490uL of ethanol/water solution (volume ratio is 1:1), adding 10uL of Nafion solution, and then carrying out ultrasonic treatment for 30 minutes to uniformly disperse the catalytic material; and (3) dripping 4uL of the mixed solution subjected to ultrasonic treatment onto a glassy carbon electrode, and naturally airing the mixed solution for later use.
(2) Electrocatalytic hydrogen evolution test: a three-electrode test mode is selected, and the reference electrode isSaturated calomel electrode, counter electrode is carbon rod electrode, working electrode is glass carbon electrode of load catalytic material, acid electrolyte is 0.5M H 2 SO 4 。
FIG. 11 shows the Pt preparation SA -Pt AC The electrocatalytic hydrogen evolution result graph of the material can be found to show excellent electrocatalytic hydrogen evolution effect, which is comparable to that of commercial 20wt% Pt/C. Fig. 12 is an electrocatalytic impedance test, which can be found to have smaller impedance characteristics.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the technical solution, and those skilled in the art should understand that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the present invention, and all such modifications and equivalents are included in the scope of the claims.
Claims (6)
1. The Pt atomic cluster cooperated with Pt single-atom electrocatalytic material synthesized by adopting in-situ strategy is characterized in that the electrocatalytic material is a composite electrocatalytic material Pt SA -Pt AC 。
2. A method for preparing a Pt atomic cluster and Pt single-atom electrocatalytic material according to claim 1, comprising the steps of:
step 1) ZrCl 4 Terephthalic acid, benzoic acid and tetra-carboxyl phenyl porphyrin platinum are used as raw materials, and an intermediate PtTCPP@UIO-66 is prepared by a hydrothermal method;
step 2) calcining the intermediate PtTCPP@UIO-66 at high temperature to obtain the composite electrocatalytic material Pt SA -Pt AC 。
3. The method for preparing the Pt atomic cluster coordinated Pt single-atom electrocatalytic material according to claim 2, wherein in the step 1), zrCl 4 The molar ratio of terephthalic acid, benzoic acid and PtTCPP was 1:1:20:0.05.
4. The method for preparing Pt atomic cluster co-Pt monoatomic electrocatalytic material according to claim 2, wherein in step 1), the raw materials are added into an organic solvent DMF, and after the raw materials are fully dissolved, they are loaded into a reaction kettle to react for 12 hours at 135 ℃.
5. The method for preparing Pt atomic cluster co-Pt monoatomic electrocatalytic material according to claim 2, wherein in step 2), the calcination temperature is 800 ℃ and the calcination time is 2h.
6. The application of the Pt atomic group and Pt single-atom electrocatalytic material is characterized in that the Pt atomic group and Pt single-atom electrocatalytic material prepared by the preparation method of any one of claims 2-5 is suitable for electrocatalytic hydrogen evolution reaction under an acidic condition.
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