CN114657598B - Core-shell structured catalyst and preparation method and application thereof - Google Patents
Core-shell structured catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- 239000011258 core-shell material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 claims description 170
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 162
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 147
- 229910052697 platinum Inorganic materials 0.000 claims description 70
- 229910052714 tellurium Inorganic materials 0.000 claims description 69
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 69
- 239000002923 metal particle Substances 0.000 claims description 52
- 239000002052 molecular layer Substances 0.000 claims description 51
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims description 51
- 150000002736 metal compounds Chemical class 0.000 claims description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims description 35
- 239000001257 hydrogen Substances 0.000 claims description 35
- 238000004519 manufacturing process Methods 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 22
- 238000005868 electrolysis reaction Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
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- 238000006073 displacement reaction Methods 0.000 claims description 9
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- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 239000010948 rhodium Substances 0.000 claims description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
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- 239000002904 solvent Substances 0.000 claims description 5
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- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001465 metallisation Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
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- 239000010419 fine particle Substances 0.000 claims description 3
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- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 claims description 2
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229940074360 caffeic acid Drugs 0.000 claims description 2
- 235000004883 caffeic acid Nutrition 0.000 claims description 2
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229940074391 gallic acid Drugs 0.000 claims description 2
- 235000004515 gallic acid Nutrition 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005289 physical deposition Methods 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims 3
- 235000019445 benzyl alcohol Nutrition 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 27
- 239000002073 nanorod Substances 0.000 description 61
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 28
- 239000011259 mixed solution Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000002484 cyclic voltammetry Methods 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
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- 238000003917 TEM image Methods 0.000 description 7
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- 239000002243 precursor Substances 0.000 description 7
- 231100000572 poisoning Toxicity 0.000 description 6
- 230000000607 poisoning effect Effects 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
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- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
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- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- VOADVZVYWFSHSM-UHFFFAOYSA-L sodium tellurite Chemical compound [Na+].[Na+].[O-][Te]([O-])=O VOADVZVYWFSHSM-UHFFFAOYSA-L 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
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- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic 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
-
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
Abstract
The application belongs to the technical field of catalytic materials, and particularly relates to a core-shell structure catalyst and a preparation method and application thereof.
Description
Technical Field
The application belongs to the technical field of catalytic materials, and particularly relates to a catalyst with a core-shell structure, and a preparation method and application thereof.
Background
Hydrogen is a green and environment-friendly renewable energy source, however, the practical application of electrochemical water decomposition hydrogen production in the prior art is limited by the oxygen evolution reaction of an anode, and has higher overpotential, and compared with the theoretical potential of the oxygen evolution reaction, the oxidation potential of methanol is lower, so that the high-efficiency production of hydrogen can be realized by combining the methanol oxidation and the hydrogen evolution, and the development of a catalyst with the double functions of the methanol oxidation and the hydrogen evolution has important significance.
In methanol oxidation and hydrogen evolution, platinum catalysts are currently considered the most effective single metal catalysts, however, the relative scarcity of platinum results in its high price, and platinum-based catalysts can produce some deleterious effects during electro-oxidation, such as surface poisoning, particle agglomeration, all of which can result in a reduced number of active sites available during methanol electrolysis, resulting in slow kinetics and poor durability, poor catalytic efficiency.
Disclosure of Invention
The purpose of the application is to provide a core-shell structure catalyst and a preparation method and application thereof, and aims to solve the problems of slow dynamics, poor durability, high cost and low utilization rate of a single metal catalyst to a certain extent.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a core-shell structured catalyst, including non-noble metal particles as an inner core and a shell layer covering the inner core, wherein a material of the shell layer includes a noble metal compound, and the noble metal compound contains a non-noble metal element, and the non-noble metal element includes at least a non-noble metal element contained in the non-noble metal particles.
In a second aspect, the present application provides a method for preparing a core-shell catalyst, including the steps of:
providing non-noble metal particles;
and forming a noble metal compound shell layer on the surface of the non-noble metal particles so as to coat the non-noble metal particles, thereby obtaining the catalyst with the core-shell structure.
In a third aspect, the application provides an application of the catalyst with the core-shell structure in catalyzing methanol electrolysis to prepare hydrogen.
According to the core-shell structure catalyst provided by the first aspect of the application, the use of noble metal can be reduced by taking non-noble metal as a core, more active sites can be exposed by taking a noble metal compound as a shell layer, meanwhile, the internal non-noble metal can be protected from corrosion in an electrochemical reaction, so that the stability of the catalyst is improved, and meanwhile, the electronic surface structures of the non-noble metal core and the noble metal compound shell layer can be adjusted by the electronic effect existing between the non-noble metal core and the noble metal compound shell layer, so that the utilization rate of the active sites of the catalytic reaction is improved.
According to the preparation method of the core-shell structure catalyst, the ultra-thin noble metal compound shell layer is formed on the surface of the non-noble metal particles, so that the utilization rate and the attachment rate of noble metal atoms are greatly improved, more active sites can be provided when the catalytic methanol electrolysis hydrogen production is performed, the catalyst utilization rate is improved, the preparation process is simple and convenient, no extremely toxic medicines and harsh production conditions are used, the preparation is easy, and the cost is low.
The application of the core-shell catalyst in catalyzing the hydrogen production by the methanol electrolysis provided by the third aspect of the application is that the core-shell catalyst has wide application potential in the field of the hydrogen production by the methanol electrolysis in view of the high-efficiency catalytic activity and stability of the core-shell catalyst, and can realize commercial large-scale production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly introduce the drawings that are needed in the embodiments or the description of the prior art, it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic view of a catalyst PtTe with a core-shell structure, in which a platinum telluride nano layer grows on the surface of a tellurium nanorod prepared in example 1 of the present application 2 XRD pattern of @ Te-A;
FIG. 2 is an SEM image of tellurium nanorods prepared in example 1 of the present application;
fig. 3 is an SEM and TEM image of a platinum telluride nano layer core-shell structure catalyst grown on the surface of a tellurium nanorod prepared in example 1 of the present application, wherein fig. a is an SEM image and fig. b is a TEM image;
FIG. 4 shows different thicknesses of platinum telluride nano-layer core-shell structured catalyst PtTe grown on the surface of tellurium nanorod prepared in example 2 of the present application 2 TEM image of @ Te-B;
FIG. 5 shows different thicknesses of platinum telluride nano-layer core-shell structured catalyst PtTe grown on the surface of tellurium nanorod prepared in example 3 of the present application 2 TEM image of @ Te-C;
FIG. 6 shows a PtTe catalyst with a core-shell structure of platinum telluride nano layers with different thicknesses grown on the surfaces of tellurium nanorods in example 4 of the present application 2 @Te-A，PtTe 2 @Te-B，PtTe 2 A comparison of cyclic voltammogram (a) and chronoamperometric test curve (b) for a commercial Pt-C catalyst in a mixed electrolyte of 1mol/L methanol and 1mol/L potassium hydroxide;
FIG. 7 shows a platinum telluride nano-layer core-shell structured catalyst PtTe grown on the surface of tellurium nanorods in example 4 of the present application 2 H of @ Te-A and commercial Pt-C catalyst in 1.0mol/L Potassium hydroxide solutionER Performance graphs (a) and PtTe 2 Polarization curve (b) control plot before and after 1000 CV cycles in 1mol/L sulfuric acid solution;
FIG. 8 shows a platinum telluride nano-layer core-shell structured catalyst PtTe grown on the surface of tellurium nanorods in example 4 of the present application 2 Catalytic electrolytic Hydrogen production Performance graphs (b) and PtTe for 1mol/L Potassium hydroxide solution and 1mol/L Potassium hydroxide and 1mol/L methanol Mixed solution, respectively, for Te-A and commercial Pt-C catalysts 2 A chronoamperometric test curve (b) for the @ Te-A catalyst in a 1mol/L potassium hydroxide and 1mol/L methanol mixed solution;
FIG. 9 shows a PtTe catalyst with a core-shell structure of platinum telluride nano layers of different thicknesses grown on the surfaces of tellurium nanorods in example 5 of the present application 2 @Te-A，PtTe 2 @Te-B，PtTe 2 A comparison of cyclic voltammogram (a) and chronoamperometric test curve (b) of a commercial Pt-C catalyst in a mixed electrolyte of methanol and sulfuric acid at a concentration of 1mol/L and 0.5 mol/L;
FIG. 10 shows a platinum telluride nano-layer core-shell structured catalyst PtTe grown on the surface of tellurium nanorods in example 5 of the present application 2 HER Performance graphs (a) and PtTe in 0.5mol/L sulfuric acid solution for @ Te-A and commercial Pt-C catalysts 2 Polarization curve (b) control plot before and after 1000 CV cycles in 0.5mol/L sulfuric acid solution for Te-A catalyst;
FIG. 11 shows a platinum telluride nano-layer core-shell structured catalyst PtTe grown on the surface of tellurium nanorods in example 5 of the present application 2 Catalytic electrolytic Hydrogen production Performance graphs (b) and PtTe for 0.5mol/L sulfuric acid solution and 0.5mol/L sulfuric acid and 1mol/L methanol Mixed solution, respectively, for Te-A and commercial Pt-C catalysts 2 Time current test curve (b) for Te-A catalyst in a mixed solution of 0.5mol/L sulfuric acid and 1mol/L methanol.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of an association object, which means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c" may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application in the examples and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the mass described in the specification of the embodiment of the present application may be a mass unit well known in the chemical industry field such as g, mg, g, kg.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
In methanol oxidation and hydrogen evolution, platinum catalysts are currently considered the most effective single metal catalysts, however, the relative scarcity of the noble metal platinum results in its high cost and platinum-based catalysts can produce some deleterious effects during electro-oxidation, such as surface poisoning, particle agglomeration, all of which can result in a reduced number of active sites available during methanol electrolysis, resulting in slow kinetics and poor durability. In view of the foregoing drawbacks of the prior art, a first aspect of the present application provides a catalyst with a core-shell structure, including non-noble metal particles as a core and a shell layer covering the core, where a material of the shell layer includes a noble metal compound, and the noble metal compound contains a non-noble metal element, and the non-noble metal element includes at least a non-noble metal element contained in the non-noble metal particles.
According to the core-shell structure catalyst provided by the first aspect of the application, the non-noble metal is used as the core, the use of noble metal can be reduced, the noble metal compound is used as the shell layer, more active sites can be exposed, the utilization rate of noble metal atoms is improved, meanwhile, the internal non-noble metal can be protected from corrosion in the electrochemical reaction, so that the stability of the catalyst is improved, and meanwhile, the electronic surface structures of the non-noble metal core and the noble metal compound shell layer can be adjusted by the electronic effect existing between the non-noble metal core and the noble metal compound shell layer, so that the utilization rate of the active sites of the catalytic reaction is improved.
In the embodiment of the application, the non-noble metal elements contained in the non-noble metal particles include but are not limited to tellurium, selenium, carbon and phosphorus, the noble metal elements in the noble metal compounds include but are not limited to platinum, ruthenium, rhodium, palladium and iridium, the non-noble metal particles and the noble metal simple substance form an ultrathin noble metal compound nano layer on the surfaces of the non-noble metal particles through electrostatic displacement reaction, and a strong core-shell interaction force is formed between a non-noble metal core and a noble metal shell layer, so that the catalyst with a core-shell structure has stronger stability.
In a further embodiment of the present application, the noble metal compound includes at least one of platinum telluride, ruthenium telluride, rhodium telluride, palladium telluride, and iridium telluride, in a specific embodiment of the present application, the non-noble metal particles are tellurium nanoparticles with an oxygen-philic characteristic, the noble metal simple substance is platinum with the best catalytic methanol hydrogen production effect, the core-shell structure catalyst provided in the embodiment of the present application uses the tellurium nanoparticles as a core, the platinum telluride nano layer as a shell, the problem of platinum atom aggregation is solved, the utilization rate and the attachment rate of the platinum atoms are greatly improved, in addition, the tellurium nanoparticles with the oxygen-philic characteristic are used as a noble metal carrier to provide an oxygen-containing substance with a low potential through a ligand effect, and the adsorption capability of CO poisoning substances generated in the alcohol oxidation reaction process is reduced through the downward movement of the d band center, so that poisoning is reduced, the activity of methanol electrolysis can be effectively promoted, and the activity and stability of the catalyst are further improved.
In the embodiment of the application, the particle size of the non-noble metal particles is 2 nm-5 nm, and the formed core-shell catalyst has large specific surface area and good catalytic efficiency. The thickness of the shell layer formed by the noble metal compound is 1-2 atomic layers of noble metal, so that the attachment rate and the utilization rate of noble metal are greatly improved, the catalytic efficiency is improved, and the cost is reduced.
In embodiments of the present application, the shape of the non-noble metal particles is not limited, including but not limited to rods, flakes, spheres, and irregular grains, and in particular embodiments of the present application, the non-noble metal particles are tellurium nanorods, which are simple in preparation process and easy to obtain.
A second aspect of the embodiment of the present application provides a method for preparing a catalyst with a core-shell structure, which is characterized by comprising the following steps:
s1: providing non-noble metal particles;
s2: and forming a noble metal compound shell layer on the surface of the non-noble metal particles so as to coat the non-noble metal particles, thereby obtaining the catalyst with the core-shell structure.
The preparation method of the core-shell structure catalyst provided by the second aspect of the embodiment of the application has the advantages of simple and convenient preparation process, no use of highly toxic medicines and harsh production conditions, easy preparation and low cost. An ultrathin noble metal compound shell layer is formed on the surface of the non-noble metal particles, so that the utilization rate and the attachment rate of noble metal atoms are greatly improved, meanwhile, a stronger core-shell interaction force is formed between the noble metal compound shell layer and the non-noble metal particle core, the electronic structure of the noble metal surface of an active ingredient can be regulated, more active sites can be provided when the catalytic methanol electrolysis hydrogen production is carried out, and the catalyst utilization rate is improved.
In the embodiment of the present application, in step S1, the non-noble metal particles include, but are not limited to, tellurium nanoparticles, selenium nanoparticles, carbon nanoparticles, and phosphorus nanoparticles, and the shape and preparation manner of the non-noble metal particles are not limited, in the specific embodiment of the present application, the non-noble metal particles are tellurium nanorods with an oxygen-philic property, the tellurium nanorods can be used as a noble metal carrier to provide a low-potential oxygen-containing substance through a ligand effect, and the adsorption capacity of CO poisoning substances generated in the alcohol oxidation reaction process is reduced through the downward shift of the d-band center, so that poisoning is reduced, the activity of methanol electrolysis is effectively promoted, and the activity and stability of the catalyst are further improved. Tellurium nanorods can be produced in the following manner, but are not limited to:
s11: dispersing sodium tellurite into glycol solution, stirring uniformly, and adding hydrazine hydrate and polyvinylpyrrolidone to obtain a first mixed solution;
s12: transferring the first mixed solution obtained in the step S11 into a microwave high-pressure synthesis reaction kettle, sealing, performing microwave synthesis and performing hydrothermal reaction to obtain a second mixed solution;
s13: and (3) carrying out suction filtration on the second mixed solution after the hydrothermal reaction is finished, flushing and precipitating the product by using acetone and ultrapure water, and carrying out vacuum drying to obtain the tellurium nanorods.
In the embodiment of the present application, in step S2, a noble metal compound shell layer is formed on the surface of the non-noble metal fine particles, comprising the steps of:
s21: carrying out noble metal deposition treatment on the surfaces of the non-noble metal particles to obtain noble metal @ non-noble metal particles,
s22: and carrying out electrostatic displacement reaction on the noble metal@non-noble metal particles, and forming a noble metal compound shell layer on the surfaces of the non-noble metal particles to obtain the catalyst with the core-shell structure.
The noble metal compound shell layer is a noble metal compound nano layer, and the noble metal simple substance @ non-noble metal particles represent a core-shell structure material taking non-noble metal particles as cores and noble metal simple substances as shells; the noble metal simple substance on the surface of the non-noble metal particles forms a noble metal compound nano layer in situ to obtain a noble metal compound nano layer@a core-shell structure catalyst of the non-noble metal particles, namely a core-shell structure material with the noble metal compound nano layer as a shell and the non-noble metal particles as cores.
In step S21, in embodiments of the present application, the noble metal deposition process includes, but is not limited to, a chemical reduction deposition process, a physical deposition process, and in further embodiments of the present application, the chemical reduction deposition process includes the steps of:
s211: mixing non-noble metal particles, a reducing agent and a reducing solvent to obtain a suspension;
s212: and (3) dropwise adding a soluble noble metal source into the suspension liquid and carrying out reduction reaction treatment to obtain noble metal simple substance @ non-noble metal particles.
The chemical reduction method is adopted to slowly deposit noble metal simple substances on the surfaces of the non-noble metal particles to form an ultrathin noble metal layer, so that the problem of noble metal atom aggregation in the process of reducing a noble metal precursor in the prior art can be solved, and the utilization rate and the attachment rate of noble metals are greatly improved.
In step S211, in the embodiment of the present application, the reducing agent includes, but is not limited to, ascorbic acid, sodium citrate, gallic acid, and caffeic acid, and in the embodiment of the present application, ascorbic acid is selected as the reducing agent to reduce the noble metal, and meanwhile, the pH of the solution may be adjusted, so as to reduce the reduction rate of the noble metal, so that the simple substance of the noble metal is slowly deposited on the surface of the non-noble metal particles, thereby forming an ultrathin noble metal layer, avoiding aggregation of noble metal atoms, and improving the utilization rate and the adhesion rate of the noble metal.
In embodiments of the present application, the reducing solvent includes, but is not limited to, ethylene glycol, benzyl alcohol, formic acid, and in embodiments of the present application, ethylene glycol is selected as the reducing solvent for reducing the precious metal in the soluble precious metal source to deposit it onto the surface of the non-precious metal particles.
In step S212, in the embodiment of the present application, the soluble noble metal source includes, but is not limited to, a soluble platinum source, a soluble ruthenium source, a soluble rhodium source, a soluble palladium source, a soluble iridium source, platinum, ruthenium, rhodium, palladium, and iridium may be used as the single metal catalyst, and in the further embodiment of the present application, the soluble noble metal source is selected from a soluble platinum source, and platinum is the single metal catalyst with the best effect in the catalytic electrolysis hydrogen production in the prior art, and the soluble platinum source includes, but is not limited to, chloroplatinic acid, potassium chloroplatinate, platinum acetylacetonate, or potassium chloroplatinic acid.
In the embodiment of the application, the mass ratio of the tellurium nanoparticles to the platinum in the soluble platinum source is 2-4:0.1, so as to prepare the platinum telluride nano layers with different thicknesses.
In the embodiment of the application, the dropping treatment and the reduction reaction treatment are performed simultaneously, and when a soluble noble metal source is dropped, noble metal is reduced to be simple substance to deposit on the surfaces of non-noble metal particles, the dropping treatment is specifically to drop by drop, so that the deposition rate of the noble metal simple substance is slowed down, a thinner noble metal simple substance layer is obtained, and the attachment rate and the utilization rate of the noble metal simple substance are improved.
In a specific embodiment of the present application, step S21 may be performed in the following manner, but is not limited to:
dispersing 40mg of tellurium nanorods in 50 ml of ethylene glycol solution, magnetically stirring uniformly, and adding 200 mg of ascorbic acid into the solution to obtain a tellurium nanorod suspension;
167. Mu.l of an aqueous solution of chloroplatinic acid having a platinum content of 30 mg/ml was added dropwise to the above suspension to obtain a Pt@Te suspension.
In step S22, in the embodiment of the present application, the treatment manner of the electrostatic displacement reaction includes, but is not limited to, microwave high-pressure treatment, water bath heating treatment, and oil bath heating treatment, so that the non-noble metal elementary substance core and the noble metal elementary substance layer on the surface thereof perform the electrostatic displacement reaction, and the noble metal compound nano layer is formed on the surface of the non-noble metal nano particle in situ. In a further embodiment of the present application, the formation treatment of the noble metal compound nano layer adopts microwave high-pressure treatment, which has the advantages of fast reaction speed, mild reaction condition, high reaction efficiency, and the like, and the prepared noble metal compound nano layer has higher purity, narrow particle size distribution and uniform morphology, and in the specific embodiment of the present application, the microwave power of the microwave high-pressure treatment is 400-800W, the pressure is 2-5 MPa, and the treatment duration is 2-4 h.
In the embodiment of the application, after the noble metal compound nano layer is formed by the electrostatic displacement reaction, the catalyst with the core-shell structure is subjected to post-treatment, wherein the post-treatment comprises suction filtration water washing treatment and vacuum drying treatment, and the suction filtration water washing treatment is used for removing impurities. In a further embodiment of the present application, the drying temperature of the vacuum drying treatment is 60 ℃ to 80 ℃, the drying time is 10 to 12 hours, the oxygen content is low when the vacuum drying treatment is performed under low pressure, the vacuum drying treatment can prevent the material to be dried from oxidative deterioration, the drying speed is high, and valuable and useful components in the dried material can be effectively recovered.
In a specific embodiment of the present application, step S22 may be performed in the following manner, but is not limited to:
s221: transferring the Pt@Te suspension obtained in the step S21 into a 100 ml microwave high-pressure synthesis reaction kettle, and carrying out microwave high-pressure synthesis reaction for 3 hours under the conditions of 800W and 3 MPa;
s222: filtering the solution after the S221 reaction, flushing the product with ethanol and deionized water, and vacuum drying the flushed product at 60 ℃ for 12 hours to obtain a core-shell catalyst, which is named PtTe 2 @Te-A。
In a third aspect, the present application provides the use of the above-described core-shell structured catalyst for catalyzing the electrolysis of methanol to produce hydrogen in alkaline and acidic electrolytes.
The application of the core-shell catalyst in catalyzing the hydrogen production by the methanol electrolysis provided by the third aspect of the application is that the core-shell catalyst has wide application potential in the field of the hydrogen production by the methanol electrolysis in view of the high-efficiency catalytic activity and stability of the core-shell catalyst, and can realize commercial large-scale production.
In order that the details and operations of the above embodiments of the present application may be clearly understood by those skilled in the art, and that the advanced performances of the core-shell catalyst and the preparation method and application of the embodiments of the present application may be significantly reflected, the following examples are given to illustrate the above technical solutions.
Example 1
The tellurium simple substance nano rod is prepared by adopting the existing method, and specifically comprises the following steps:
(1) 200 mg of sodium tellurite is dispersed into 20 ml of glycol solution, and after being stirred evenly by magnetic force, 2 ml of hydrazine hydrate and 100 mg of polyvinylpyrrolidone are added;
(2) Transferring the mixed solution obtained in the step (1) into a 50 milliliter microwave high-pressure synthesis reaction kettle, sealing, and carrying out microwave synthesis for 4 hours under 700W and 3.5 MPa;
(3) And (3) carrying out suction filtration on the mixed solution after the hydrothermal reaction is finished, flushing and precipitating the product by using acetone and ultrapure water, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the tellurium simple substance nanorod.
Fig. 1 is an XRD spectrum of the elemental tellurium nanorods prepared in example 1. The characteristic diffraction peak intensity of the tellurium nanorods is higher, the characteristic diffraction peak width is narrower, and the tellurium nanorods have good crystallinity. Fig. 2 is an SEM image of the elemental tellurium nanorods prepared in example 1. The figure shows that the prepared tellurium nanorods have uniform length and thickness, smooth surface and better dispersion.
PtTe of platinum telluride nano layer core-shell structure catalyst grown on tellurium nano rod surface 2 Preparation of @ Te-A. The tellurium nanorod prepared by the method is used as a carrier, the reduction preparation of the platinum telluride nano layer is carried out on the surface of the tellurium nanorod, and the platinum telluride nano layer core-shell structure catalyst grown on the surface of the tellurium nanorod is obtained through the electrostatic displacement reaction between platinum and tellurium, and the specific steps are as follows:
(1) Dispersing 40mg tellurium nanorods in 50 ml of ethylene glycol solution, magnetically stirring uniformly, and adding 200 mg of ascorbic acid into the solution;
(2) To the mixed solution obtained in the step (1), 167. Mu.l of an aqueous solution of chloroplatinic acid having a platinum content of 30 mg/ml was added dropwise;
(3) Transferring the suspension obtained in the step (2) into a 100 milliliter microwave high-pressure synthesis reaction kettle, and carrying out microwave high-pressure synthesis reaction for 3 hours under the conditions of 800W and 3 MPa;
(4) Filtering the solution after the reaction in the step (3), washing the product by ethanol and deionized water, and vacuum drying the washed product at 60 ℃ for 12 hours, wherein the obtained product is PtTe 2 @Te-A。
FIG. 3 shows a platinum telluride nano-layer core-shell structure catalyst PtTe grown on the surface of a tellurium nano-rod 2 XRD pattern of @ Te-A. From the figure, it can be seen that the simple substance tellurium diffraction peak is weakened, and the diffraction peak of platinum telluride appears, indicating successful preparation of the platinum telluride nano layer. Wherein FIG. 3a shows a platinum telluride nano-layer core-shell structure catalyst PtTe grown on the surface of the prepared tellurium nanorod 2 SEM image of @ Te-A, from which it can be seen that the tellurium nanorod surface roughness increases, indicating the presence of a platinum telluride nano layer on the tellurium nanorod surface; FIG. 3b shows a platinum telluride nano-layer core-shell structure catalyst PtTe grown on the surface of the prepared tellurium nanorod 2 From the high-power TEM image of Te-A, it can be clearly seen that the platinum telluride nano layer grown on the surface of tellurium nano rod has a thickness of only a few nanometers and is uniformly distributed.
Example 2
PtTe of platinum telluride nano layer core-shell structure catalyst grown on tellurium nano rod surface 2 Preparation of @ Te-B, wherein the tellurium nanorods were prepared by the method of example 1, the specific steps were as follows:
(1) Dispersing 30mg tellurium nanorods in 50 ml of ethylene glycol solution, magnetically stirring uniformly, and adding 200 mg of ascorbic acid into the solution;
(2) To the mixed solution obtained in the step (1), 167. Mu.l of an aqueous solution of chloroplatinic acid having a platinum content of 30 mg/ml was added dropwise;
(3) Transferring the suspension obtained in the step (2) into a 100 milliliter microwave high-pressure synthesis reaction kettle, and carrying out microwave high-pressure synthesis reaction for 3 hours under the conditions of 800W and 3 MPa;
(4) Filtering the solution after the reaction in the step (3), washing the product by ethanol and deionized water, and vacuum drying the washed product at 60 ℃ for 12 hours, wherein the obtained product is PtTe 2 @Te-B。
FIG. 4 shows a platinum telluride nano layer catalyst PtTe grown on the surface of the prepared tellurium nanorods 2 TEM image of @ Te-B. As the proportion of the metal platinum in the raw materials is increased, a thicker platinum telluride nano layer is formed on the surface of the tellurium nanorod. Thus, from the figure it can be seen that the nanolayer thickness of the tellurium nanorod surface is the platinum telluride nanolayer in fig. 3 b.
Example 3
PtTe of platinum telluride nano layer core-shell structure catalyst grown on tellurium nano rod surface 2 Preparation of @ Te-C, wherein the tellurium nanorods were prepared by the method of example 1, the specific steps were as follows:
(1) Dispersing 20mg of tellurium nanorods in 50 ml of ethylene glycol solution, magnetically stirring uniformly, and adding 200 mg of ascorbic acid into the solution;
(2) To the mixed solution obtained in the step (1), 167. Mu.l of an aqueous solution of chloroplatinic acid having a platinum content of 30 mg/ml was added dropwise;
(3) Transferring the suspension obtained in the step (2) into a 100 milliliter microwave high-pressure synthesis reaction kettle, and carrying out microwave high-pressure synthesis reaction for 3 hours under the conditions of 800W and 3 MPa;
(4) Filtering the solution after the reaction in the step (3), washing the product by ethanol and deionized water, and vacuum drying the washed product at 60 ℃ for 12 hours, wherein the obtained product is PtTe 2 @Te-C。
FIG. 5 shows a platinum telluride nano-layer core-shell structure catalyst PtTe grown on the surface of the prepared tellurium nanorod 2 TEM image of @ Te-C. As the proportion of the metal platinum in the raw materials is further increased, after the platinum telluride nano layer is formed on the surface of the tellurium nano rod, the redundant platinum is continuously reduced into platinum nanoThe nano particles are loaded on the surface of the tellurium nano rod. Thus, as can be seen from the figures, more distinct platinum nanoparticles were found on the tellurium nanorod surface compared to fig. 3b and 4 a.
Further, in order to verify the advancement of the catalyst with the core-shell structure in the embodiment of the application, the application test of the catalyst with the core-shell structure in the hydrogen production by methanol electrolysis is performed in the following manner.
Example 4
The application of the platinum telluride nano-layer core-shell structure catalyst grown on the surface of the tellurium nano-rod in catalyzing alkaline electrolyte for preparing hydrogen by methanol electrolysis:
the catalytic alkaline electrolyte methanol oxidation reaction is carried out on an electrochemical workstation, a standard three-electrode system is adopted, the catalytic alkaline electrolyte methanol oxidation reaction is carried out at normal temperature (25 ℃), the electrolyte is a mixed solution of 1mol/L methanol and 1mol/L potassium hydroxide, the electrolyte for the catalytic alkaline electrolyte methanol electrolysis hydrogen production is a mixed solution of 1mol/L potassium hydroxide and 1mol/L methanol and 1mol/L potassium hydroxide, the surface of a glass carbon electrode polished by alumina is used as a working electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, a carbon rod is used as a counter electrode, and the specific process is that: 2 mg of the platinum telluride nano-layer core-shell structure catalyst with different thicknesses, which is grown on the surface of the tellurium nano-rod and is prepared in the embodiment 1 and the embodiment 2, and 0.5 mg of carbon black (Vulcan XC 72) are respectively added into 475 microliter of ethanol and 25 microliter of Nafion mixed solution, the catalyst ink with good dispersion is prepared by uniformly dispersing the catalyst ink in an ultrasonic manner, 10 microliter of the catalyst ink is dripped on the surface of a working electrode, after drying, cyclic voltammetry scanning is carried out at a scanning speed of 50mV/s between-1 and 0.2V, and a constant current timing test of 7000 seconds is carried out at a potential of-0.3V vs. HER testing in catalytic alkaline electrolyte was cyclic voltammetry at 5mV/s scan rate between 0 and-0.3V, electrolytic hydrogen production in 1mol/L potassium hydroxide solution was cyclic voltammetry at 5mV/s scan rate between 0 and 1.8V, electrolytic hydrogen production in 1mol/L methanol and 1mol/L potassium hydroxide mixed solution was cyclic voltammetry at 5mV/s scan rate between 0 and 1.3V, and constant current timing test was performed at-0.284V vs. SCE potential for 12 hours.
FIG. 6 shows a platinum telluride nano-layer core-shell structured catalyst PtTe grown on the surface of a tellurium nanorod 2 @Te-A,PtTe 2 @Te-B，PtTe 2 Cyclic voltammogram (a) and chronoamperometric test curve (b) of Te-C and commercial Pt-C catalysts in a mixed solution of 1mol/L methanol and 1mol/L potassium hydroxide. As can be seen from FIG. 6, the platinum telluride nano layer core-shell structured catalyst PtTe of different thickness grown on the tellurium nanorod surface of the present invention compared with the commercial Pt-C catalyst 2 @Te-A，PtTe 2 @Te-B and PtTe 2 The @ Te-C has higher catalytic activity and stability in catalyzing alkaline methanol oxidation reactions, wherein PtTe is prepared from optimal precursor ratios 2 The @ Te-A catalyst has proper nano-layer thickness, so that the catalyst performance and stability are best.
FIG. 7 shows a platinum telluride nano-layer core-shell catalyst PtTe grown on the surface of a tellurium nanorod 2 HER performance profile and PtTe in 1mol/L Potassium hydroxide solution for @ Te-A and commercial Pt-C catalysts 2 Polarization curve (b) for catalyst @ Te-A in 1mol/L potassium hydroxide solution before and after 1000 CV cycles. As can be seen from FIG. 7, the current density reaches 10mA/cm in the catalytic hydrogen evolution reaction 2 PtTe at the time 2 The overpotential of the catalyst at Te-A is smaller than that of the Pt-C catalyst, and after 1000 CV cycles, the overpotential of the catalyst is only slightly increased, which shows that PtTe prepared with the optimal precursor proportion 2 The catalyst at Te-A has good catalytic performance and stability.
FIG. 8 shows a platinum telluride nano-layer core-shell structured catalyst PtTe grown on the surface of a tellurium nanorod 2 Electrolysis Hydrogen production Performance graph and PtTe for 1mol/L Potassium hydroxide solution and 1mol/L Potassium hydroxide and 1mol/L methanol Mixed solution, respectively, of Te-A and commercial Pt-C catalysts 2 Timing current test curve (b) for @ Te-a catalyst. As can be seen from FIG. 8, when the current density reaches 10mA/cm in a 1mol/L potassium hydroxide solution 2 PtTe at the time 2 The potential of the @ Te-A catalyst is relatively small compared to the Pt-C catalyst. And after adding methanol solution, ptTe 2 The @ Te-A catalyst had a current density of 10mA/cm 2 The potential at the time is minimum, and PtTe 2 After 12 hours of timing current test, the catalyst at Te-A has very small current density decay, which indicates PtTe prepared with optimal precursor proportion 2 The performance and stability of the electrolytic hydrogen production of the Te-A in the mixed solution of 1mol/L potassium hydroxide and 1mol/L methanol are good.
Example 5
The application of the platinum telluride nano-layer core-shell structure catalyst grown on the surface of the tellurium nano-rod in catalyzing the hydrogen production by the electrolysis of methanol in an acid electrolyte:
the catalytic acid electrolyte methanol oxidation reaction is carried out on an electrochemical workstation, a standard three-electrode system is adopted, the catalytic acid electrolyte is a mixed solution of 1mol/L methanol and 0.5mol/L sulfuric acid, the catalytic acid electrolyte methanol electrolysis hydrogen production electrolyte is a mixed solution of 0.5mol/L sulfuric acid and 1mol/L methanol respectively, the surface of a glassy carbon electrode polished by alumina is used as a working electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, and a carbon rod is used as a counter electrode, and the specific process is that: 2 mg of the platinum telluride nano-layer core-shell structure catalyst with different thicknesses and grown on the surface of the tellurium nano-rod prepared in the example 1, the example 2 and 0.5 mg of carbon black (Vulcan XC 72) are respectively added into 475 microliter of ethanol and 25 microliter of Nafion mixed solution, the catalyst ink with good dispersion is prepared by uniformly dispersing by ultrasonic, 10 microliter of catalyst ink is dripped on the surface of a working electrode, after drying, cyclic voltammetry scanning is carried out at a scanning speed of 50mV/s between-0.2 and 1V, and a constant current timing test of 7000 seconds is carried out at a 0.6V vs. HER testing in catalytic acid electrolytes was performed by cyclic voltammetry at a scan rate of 5mV/s between 0 and-0.3V, electrolytic hydrogen production in 0.5mol/L sulfuric acid solution was performed by cyclic voltammetry at a scan rate of 5mV/s between 0 and 1.8V, electrolytic hydrogen production in a mixed solution of 0.5mol/L sulfuric acid and 1mol/L methanol was performed by cyclic voltammetry at a scan rate of 5mV/s between 0 and 1.3V, and constant current timing testing was performed at-0.275 Vvs. SCE potential for 12 hours.
FIG. 9 is telluriumPlatinum telluride nano-layer core-shell structure catalyst double-function PtTe grown on nano rod surface 2 @Te-A，PtTe 2 @Te-B，PtTe 2 Cyclic voltammograms (a) and chronoamperometric tests (b) of Te-C and commercial Pt-C catalysts in a mixed solution of 1mol/L methanol and 0.5mol/L sulfuric acid. As can be seen from FIG. 9, the platinum telluride nano layer bi-functional catalyst PtTe of different thickness grown on the tellurium nanorod surface of the present invention compared to the commercial Pt-C catalyst 2 @Te-A，PtTe 2 @Te-B and PtTe 2 The @ Te-C also has higher catalytic activity and stability in catalyzing acidic methanol oxidation reaction, and PtTe prepared by optimal precursor proportion 2 The @ Te-A catalyst has proper nano-layer thickness, so that the catalyst performance and stability are best.
FIG. 10 shows a platinum telluride nano-layer core-shell structured catalyst PtTe grown on the surface of a tellurium nanorod 2 HER Performance graphs (a) and PtTe in 0.5mol/L sulfuric acid solution for @ Te-A and commercial Pt-C catalysts 2 Polarization curve (b) control of catalyst @ Te-A in 0.5mol/L sulfuric acid solution before and after 1000 CV cycles. As can be seen from FIG. 10, the current density reaches 10mA/cm in the catalytic hydrogen evolution reaction 2 PtTe at the time 2 The overpotential of the catalyst at Te-A is smaller than that of the Pt-C catalyst, and after 1000 CV cycles, the overpotential of the catalyst is only slightly increased, which shows that PtTe prepared with the optimal precursor proportion 2 The catalyst at Te-A has good catalytic performance and stability.
FIG. 11 shows a platinum telluride nano-layer core-shell structured catalyst PtTe grown on the surface of a tellurium nanorod 2 Electrolysis Hydrogen production Performance graphs (a) and PtTe for 0.5mol/L sulfuric acid solution and 0.5mol/L sulfuric acid and 1mol/L methanol mixed solution, respectively, of Te-A and commercial Pt-C catalysts 2 Timing current test curve (b) for @ Te-a catalyst. As can be seen from FIG. 11, when the current density reaches 10mA/cm in a 0.5mol/L sulfuric acid solution 2 PtTe at the time 2 The potential of the @ Te-A catalyst is relatively small compared to the Pt-C catalyst. And after adding methanol solution, ptTe 2 The @ Te-A catalyst had a current density of 10mA/cm 2 The potential at the time is minimum, and PtTe 2 After 12 hours of chronoamperometric testing of the @ Te-a catalyst,the current density decay was small, indicating that PtTe prepared with optimal precursor ratio 2 The catalyst Te-A has good electrolytic hydrogen production performance and stability in a mixed solution of 1mol/L potassium hydroxide and 1mol/L methanol.
The foregoing description of the preferred embodiment of the present invention is not intended to limit the invention to the particular form disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (7)
1. The preparation method of the core-shell structure catalyst is characterized by comprising the following steps of:
providing non-noble metal particles;
forming a noble metal compound shell layer on the surface of the non-noble metal particles so as to coat the non-noble metal particles, thereby obtaining a core-shell structure catalyst;
the non-noble metal particles are tellurium nano particles;
the noble metal compound shell layer is a noble metal compound nano layer;
forming the noble metal compound shell layer on the surface of the non-noble metal fine particles, comprising the steps of:
carrying out noble metal deposition treatment on the surfaces of the non-noble metal particles to obtain noble metal@non-noble metal particles,
carrying out electrostatic displacement reaction on the noble metal@non-noble metal particles, and forming a noble metal compound shell layer on the surfaces of the non-noble metal particles to obtain a core-shell structure catalyst;
the treatment mode of the electrostatic displacement reaction comprises at least one of microwave high-pressure treatment, water bath heating treatment and oil bath heating treatment;
the core-shell structured catalyst comprises non-noble metal particles serving as a core and a shell layer coating the core, wherein the material of the shell layer comprises a noble metal compound, the noble metal compound contains non-noble metal elements, and the non-noble metal elements at least comprise the non-noble metal elements contained in the non-noble metal particles;
the noble metal element in the noble metal compound comprises at least one of platinum, ruthenium, rhodium, palladium and iridium;
the non-noble metal particles and the noble metal simple substance form an ultrathin noble metal compound nano layer on the surfaces of the non-noble metal particles through electrostatic displacement reaction;
the noble metal compound comprises at least one of platinum telluride, ruthenium telluride, rhodium telluride, palladium telluride and iridium telluride.
2. The method according to claim 1, wherein,
the particle size of the non-noble metal particles is 2 nm-5 nm; and/or
The thickness of the shell layer is 1-2 atomic layers of noble metal; and/or
The shape of the non-noble metal fine particles is at least one of a rod shape, a sheet shape, a sphere shape, and an irregular particle shape.
3. The production method according to claim 1, wherein the noble metal deposition treatment comprises at least one of a chemical reduction deposition treatment and a physical deposition treatment; and/or
And after the noble metal compound shell layer is formed, carrying out post-treatment on the core-shell structure catalyst, wherein the post-treatment comprises suction filtration water washing treatment and vacuum drying treatment.
4. The preparation method according to claim 3, wherein the microwave power of the microwave high-pressure treatment is 400-800W, the pressure is 2-5 MPa, and the treatment time is 2-4 hours; and/or
The drying temperature of the vacuum drying treatment is 60-80 ℃ and the drying time is 10-12 h; and/or
The chemical reduction deposition treatment comprises the following steps:
mixing the non-noble metal particles, the reducing agent and the reducing solvent to obtain suspension,
and (3) dropwise adding a soluble noble metal source into the suspension liquid and carrying out reduction reaction treatment to obtain the noble metal@non-noble metal particles.
5. The method according to claim 4, wherein the reducing agent comprises at least one of ascorbic acid, sodium citrate salt, gallic acid, and caffeic acid; and/or
The reducing solvent comprises at least one of glycol, benzyl alcohol and formic acid;
the soluble noble metal source comprises at least one of a soluble platinum source, a soluble ruthenium source, a soluble rhodium source, a soluble palladium source and a soluble iridium source.
6. The method of claim 5, wherein the soluble platinum source comprises at least one of chloroplatinic acid, potassium chloroplatinate, platinum acetylacetonate, or potassium chloroplatinite.
7. The application of the core-shell catalyst prepared by the preparation method according to any one of claims 1-6 in catalyzing methanol electrolysis to prepare hydrogen.
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| CN111715245A (en) * | 2019-03-21 | 2020-09-29 | 扬州大学 | Based on high catalytic activity and crystalline RuTe2The electrolytic water catalyst and the preparation method thereof |
| CN112103520A (en) * | 2020-09-24 | 2020-12-18 | 扬州大学 | Anode catalyst of alcohol fuel cell |
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| CN111715245A (en) * | 2019-03-21 | 2020-09-29 | 扬州大学 | Based on high catalytic activity and crystalline RuTe2The electrolytic water catalyst and the preparation method thereof |
| CN110061246A (en) * | 2019-04-18 | 2019-07-26 | 扬州大学 | The preparation method of core-shell structure Te@metal electro-oxidizing-catalyzing agent |
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