CN115138362A - Metal-hydroxyl cluster modified noble metal catalyst and application thereof - Google Patents
Metal-hydroxyl cluster modified noble metal catalyst and application thereof Download PDFInfo
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- CN115138362A CN115138362A CN202210821173.4A CN202210821173A CN115138362A CN 115138362 A CN115138362 A CN 115138362A CN 202210821173 A CN202210821173 A CN 202210821173A CN 115138362 A CN115138362 A CN 115138362A
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- metal
- hydroxide
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- electrocatalyst
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 title abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 76
- 239000002184 metal Substances 0.000 claims abstract description 76
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 36
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 36
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 17
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000004108 freeze drying Methods 0.000 claims abstract description 10
- 238000007710 freezing Methods 0.000 claims abstract description 10
- 230000008014 freezing Effects 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 229910052707 ruthenium Inorganic materials 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 claims description 7
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- -1 transition metal salt Chemical class 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 26
- 238000007254 oxidation reaction Methods 0.000 abstract description 18
- 150000002431 hydrogen Chemical class 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 3
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- 239000003513 alkali Substances 0.000 abstract description 2
- 238000004873 anchoring Methods 0.000 abstract description 2
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- 239000004964 aerogel Substances 0.000 description 14
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- 208000005374 Poisoning Diseases 0.000 description 8
- 150000003303 ruthenium Chemical class 0.000 description 8
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
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- 230000000607 poisoning effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
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- QVGXLLKOCUKJST-NJFSPNSNSA-N oxygen-18 atom Chemical compound [18O] QVGXLLKOCUKJST-NJFSPNSNSA-N 0.000 description 3
- XLYOFNOQVPJJNP-NJFSPNSNSA-N ((18)O)water Chemical compound [18OH2] XLYOFNOQVPJJNP-NJFSPNSNSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- VSANUNLQSRKIQA-UHFFFAOYSA-K trichlororuthenium hexahydrate Chemical compound O.O.O.O.O.O.Cl[Ru](Cl)Cl VSANUNLQSRKIQA-UHFFFAOYSA-K 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
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- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- 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
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- 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
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- C25B11/097—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 comprising two or more noble metals or noble metal alloys
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Abstract
The invention relates to a metal-hydroxide cluster modified noble metal catalyst and application thereof. The invention realizes the anchoring of the metal-oxyhydrogen clusters dispersed at the atomic level on the surface of the noble metal nano particles, thereby constructing a novel and high-performance electrocatalyst. The method utilizes a strong alkali and strong reducing sodium borohydride solution to quickly reduce a noble metal precursor and simultaneously deposit an atomically dispersed metal-oxyhydrogen cluster, and the method is prepared by freezing and freeze-drying through liquid nitrogen. The atomically dispersed metal-hydroxide clusters are anchored on the metal surface to construct rich interface active sites, and the unique atomic interface structure activates oxygen species in the metal-hydroxide clusters, so that hydrogen adsorption is optimized, water dissociation is promoted, and the barrier of speed limiting steps in the hydrogen oxidation reaction and the water decomposition reaction is reduced. In addition, the metal-hydroxide cluster on the surface of the metal can also effectively inhibit the agglomeration of metal species in the catalytic process and promote the oxidation of carbon monoxide, thereby improving the stability and the anti-poisoning capability of the catalyst.
Description
Technical Field
The invention belongs to the technical field of electrocatalyst preparation, and particularly relates to a metal-hydroxide cluster modified noble metal catalyst and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The electrolytic water device can store renewable electric energy in hydrogen through electrocatalytic water decomposition reaction, and then the generated hydrogen is converted into electric energy again in the fuel cell device through the mode of hydrogen oxidation. Anion exchange membrane water electrolysis devices (AEMWEs) and Anion Exchange Membrane Fuel Cells (AEMFCs) are important technologies to drive the above-described hydrogen cycle because their operating environment is less corrosive than their corresponding acid operating devices, and therefore a low cost catalyst can be used. However, the reaction kinetics of hydrogen evolution and hydrogen oxidation reactions in alkaline media are much lower than those in acidic environments, which severely hampers the development of high performance hydrogen energy conversion devices. Therefore, the design of the high-performance alkaline hydrogen electro-catalyst and the promotion of the understanding of the alkaline hydrogen electro-catalytic mechanism have important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a metal-hydroxyl cluster modified noble metal catalyst and application thereof.
Optimization of the surface or electronic structure of the electrocatalyst will balance the adsorption of intermediates to a large extent, thereby improving its electrocatalytic activity and anti-poisoning performance. In this regard, strategies such as doping or alloying and heterojunction engineering have been widely used to improve the activity and durability of electrocatalysts. By combining the structural characteristics of the monatomic alloy and the heterojunction catalyst, the invention designs the noble metal catalyst of metal-hydroxide cluster (M1 (OH) x) with dispersed surface anchoring atoms, which is used for accelerating the reaction kinetics of hydrogen electrocatalysis. Taking chromium-hydroxide clusters as an example, the isolated chromium-hydroxide clusters on the metal surface can maximize the number of interface active sites, create abundant active oxygen species, optimize hydrogen adsorption and promote the dissociation of water. Therefore, the electrocatalytic hydrogen oxidation and hydrogen evolution activity of the catalyst is far higher than that of an unmodified ruthenium nanoparticle catalyst. In addition, the chromium-hydroxide cluster is also beneficial to removing carbon monoxide molecules and inhibiting the aggregation of metal species in the catalytic process, and has excellent anti-poisoning performance and catalytic stability. The strategy provided by the invention is superior to the design strategy of the common heterostructure and alloy catalyst, and compared with the traditional mechanism taking surface metal as an active site, the catalytic system constructed by the invention presents a remarkably different catalytic mechanism.
Specifically, the technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a metal-hydroxide cluster modified noble metal electrocatalyst, which is a hydrogen evolution/oxidation reaction electrocatalyst, having noble metal nanoparticles as a substrate, supporting metal-hydroxide clusters dispersed at atomic level.
In a second aspect of the present invention, there is provided a method for preparing a metal-hydroxide cluster-modified ruthenium electrocatalyst, comprising the steps of:
(1) Mixing an easily reducible metal precursor and a difficultly reducible transition metal salt precursor in water to obtain a mixed solution;
(2) Dripping a certain amount of sodium borohydride aqueous solution into the mixed solution, and obtaining metal gel after the reaction is finished;
(3) And freezing the metal gel by liquid nitrogen, and freeze-drying to obtain the target catalyst.
In a third aspect of the invention, there is provided the use of the metal-hydroxide cluster modified noble metal electrocatalyst in the fuel cell and water splitting fields.
One or more technical schemes in the invention have the following beneficial effects:
(1) The metal-hydroxide cluster anchored on the metal surface can not only maximize the number of interface active sites, but also activate oxygen species in the metal-hydroxide cluster at the atomic level, so that the metal-hydroxide cluster has high catalytic activity.
(2) And oxygen species in the metal-oxyhydrogen cluster have higher negative charge and proton affinity, can optimize the adsorption of hydrogen on the surface of the noble metal, and can also act with hydrogen in water molecules to promote the dissociation of water, thereby being beneficial to enhancing the reaction kinetics of hydrogen oxidation and hydrogen evolution.
(3) The metal-hydroxide cluster has the function of inhibiting the aggregation of metal species in a catalytic process on one hand, and the active oxygen species of the metal-hydroxide cluster can promote the oxidation of carbon monoxide on the other hand, so that the poisoning of noble metals by the carbon monoxide is inhibited. Therefore, the selection of the metal-hydroxide cluster in the present invention contributes to the enhancement of the catalytic stability and the poisoning resistance of the catalyst as a whole.
(4) The atomic-level dispersed metal-hydroxyl cluster modified noble metal electrocatalyst provided by the invention has the advantages of high stability, high activity and low cost, and the preparation method is simple and easy to control.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, are included to provide a further understanding of the application, and the description of the exemplary embodiments and illustrations of the application are intended to explain the application and are not intended to limit the application.
FIG. 1 is an XRD pattern for example 1;
FIG. 2 is the EELS surface distribution map of example 1;
FIG. 3 is an EXAFS map in example 1;
FIG. 4 is a LSV curve for hydrogen hydroxide in example 1;
FIG. 5 is an anti-poisoning LSV curve of example 1;
FIG. 6 is the hydrogen evolution LSV curve of example 1;
FIG. 7 is a LSV curve for hydrogen hydroxide in example 2.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
A metal-hydroxide cluster modified noble metal electrocatalyst is a hydrogen oxidation and hydrogen evolution reaction electrocatalyst, noble metal nanoparticles are used as a substrate, and metal-hydroxide clusters dispersed in atomic scale are anchored on the surface to construct abundant atomic scale interface active sites. The noble metal nano particles are one or more of platinum, ruthenium, iridium, rhodium, gold, silver and palladium; the metal-hydroxide cluster is selected from metal-hydroxide clusters based on chromium, manganese, zinc, niobium and zirconium and metal-hydroxide clusters mixed by two or three of the metal-hydroxide clusters, preferably, the metal-hydroxide cluster is chromium-hydroxide cluster;
further, in the metal-hydroxide cluster modified noble metal electrocatalyst, the mass percentage of chromium metal is 0.6 to 2.2wt%, preferably 1.1wt%.
Metal (hydr) oxide nanoparticles or clusters are commonly used in alkaline water splitting and hydro-oxidation reactions, mainly due to their excellent ability to adsorb water and hydroxyl radicals. However, these nanoscale metal (hydr) oxides have a limited number of interfacial active sites and are not conducive to regulating hydrogen adsorption on metal substrates. By constructing the metal-oxyhydrogen clusters dispersed at the atomic level on the surface of the metal substrate, not only is the formation of a large number of atomic level interface sites facilitated, but also the activity of the metal-oxyhydrogen clusters can be activated. In particular, the broken metal-metal bond can create abundant active oxyhydrogen clusters on isolated metal atoms, which helps to achieve regulation of hydrogen intermediates in hydrogen participation reactions, thereby promoting hydrogen oxidation and hydrogen evolution reaction kinetics.
According to the invention, through constructing the atomically dispersed metal-hydroxide clusters on the surface of the noble metal, on one hand, the problem of metal species agglomeration existing in the catalytic reaction process can be effectively solved, and on the other hand, the atomically dispersed metal-hydroxide clusters can also promote the oxidation of carbon monoxide on the surface of the metal, so that the anti-poisoning capability of the catalyst is improved.
In one embodiment of the present invention, a method for preparing a metal-hydroxide cluster-modified noble electrocatalyst, comprises:
(1) Mixing an easily reducible metal precursor and a difficultly reducible transition metal salt precursor in water to obtain a mixed solution;
(2) Dripping sodium borohydride solution into the mixed solution until the reaction is finished to obtain metal gel;
(3) And freezing the metal gel in liquid nitrogen, and then carrying out freeze drying.
The preparation method provided by the invention is simple, the obtained electrocatalyst nano particles are mutually crosslinked into a hierarchical porous structure, the appearance is in a metal aerogel form, the average size of the particles is 2.4nm, the surfaces of the particles are covered with uniformly distributed metal-oxyhydrogen clusters, and the mononuclear clusters are favorable for exerting the catalytic activity of an atomic-level interface to the maximum extent.
Further, in the step (1), the easily reducible metal includes platinum, ruthenium, iridium, rhodium, gold, silver, palladium and the like, and the easily reducible metal precursor includes a mixture of one or more of the above metals in any proportion, preferably, ruthenium chloride hydrate, chloroplatinic acid and potassium chloroiridate; the difficult-to-reduce transition metal comprises chromium, manganese, zinc, niobium, zirconium and the like, the difficult-to-reduce metal precursor comprises one or a mixture of several metals in any proportion, and preferably, chromium chloride hexahydrate and zinc chloride.
Further, in the step (1), in the mixed solution, the concentration of the easy-to-reduce metal precursor is 5mg/mL, and the concentration of the difficult-to-reduce metal precursor is 0.15-1.2mg/mL, preferably 0.6mg/mL; further, the mixing is carried out by means of ultrasound, and the ultrasound time is 0.2-1h, preferably, 0.5h.
Further, in the step (2), the concentration of sodium borohydride is 0.5-2mol/L, preferably 1mol/L; in order to ensure strong alkali and strong reduction environment, the adding amount of the sodium borohydride is far higher than the dosage of the metal salt precursor, and the concentration of the sodium borohydride in the mixed solution can be 30-80mg/mL, for example, the concentration of the sodium borohydride can be 75.6mg/mL.
Further, adding the sodium borohydride solution into the mixed solution of ruthenium chloride and chromium chloride at a constant speed, and finishing the addition within 3 min;
further, stopping the reaction when no bubbles emerge;
further, obtaining metal gel after the reaction is finished, and washing the metal gel by deionized water;
further, in the step (3), the metal gel obtained in the step (2) is put into liquid nitrogen, frozen for 10min, taken out and freeze-dried in a freeze-dryer for 24h, and finally a sample in a metal aerogel state is obtained.
In one embodiment of the invention, the application of the atomic-level dispersed metal-hydroxide cluster modified electrocatalyst in the fields of fuel cells and water decomposition is to use the electrocatalyst as an anode hydrogen oxidation catalyst and a cathode hydrogen evolution catalyst, so that the reaction rate can be increased, the problems of agglomeration, poisoning and the like of noble metal particles in the reaction process can be avoided, and the catalytic reaction activity, the toxicity resistance and the durability can be improved.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
An atomic-scale dispersed chromium-hydroxide cluster modified ruthenium electrocatalyst is prepared by the following specific steps:
step 1) preparation of metal gel: first, 100mg of ruthenium chloride hydrate and 12mg of chromium chloride hexahydrate were dissolved in 20mL of deionized water and sonicated for 30min. Then, 4mL of an aqueous solution of sodium borohydride (1 mol/L) was injected into the above solution under vigorous stirring until no air bubbles were formed, and then the resulting metal gel was washed with deionized water to completely remove unreacted ions.
Step 2) preparing metal aerogel: and putting the metal gel into liquid nitrogen, freezing for 10min, taking out, and freeze-drying in a freeze dryer for 24h to obtain a metal aerogel sample.
This example carried out XRD characterization of an atomically dispersed chromium-hydroxide cluster modified ruthenium electrocatalyst, e.g., asAs shown in fig. 1, only the diffraction peak of crystalline ruthenium was detected, and the diffraction peak of chromium-based crystal was not detected. The ruthenium surface is anchored with atomically dispersed chromium-oxyhydrogen clusters, as shown in FIG. 2. The simultaneous radiation X-ray absorption spectrum test shows that the chromium in the chromium-hydroxide cluster is coordinated with 5 oxygen atoms and 1 ruthenium atom, as shown in figure 3. Before electrochemical test, the glassy carbon electrode is continuously polished by aluminium oxide powder with the grain diameter of 50nm, and then cleaned by ethanol and water to obtain a clean surface. 0.4mg of catalyst sample, 1.6mg of carbon black, 0.49mL of ethanol and 10 mul of Nafion (5%) solution are ultrasonically mixed into uniform slurry, the slurry is taken out and is dropwise coated on a glassy carbon electrode with the diameter of 5mm, and the metal loading is 60ug cm -2 And after slow drying at room temperature, the obtained product is used as a working electrode for electrochemical test. Electrochemical tests were performed in a five-port electrochemical cell equipped with a three-electrode system using a Chi 760E electrochemical workstation, in which a carbon rod and a mercury/mercury oxide electrode were used as the counter and reference electrodes, respectively. The electrolyte is 0.1M potassium hydroxide aqueous solution, and is saturated by nitrogen or hydrogen for 30 minutes before testing, and simultaneously, gas is continuously introduced for saturation in the testing process. The polarization curve is tested by Linear Sweep Voltammetry (LSV) with a sweep rate of 2mV s -1 . Before this test, the working electrode was first measured at 200mV s -1 The scanning speed of the scanning device is circularly scanned for 5 times between-0.1V and-0.3V. In this example, the half-wave potential and exchange current density of the atomic-level dispersed chromium-hydroxide cluster modified ruthenium catalyst for catalyzing hydrogen oxidation reach 20mV and 5.8mA cm -2 As shown in fig. 4. The test of carbon monoxide poisoning resistance is the same as the test of the hydrogen oxidation polarization curve, and is different from the test of continuously introducing a certain amount of carbon monoxide into a hydrogen saturated 0.1M potassium hydroxide solution. The atomic-scale dispersed chromium-hydroxide cluster-modified ruthenium electrocatalyst in this example exhibited good resistance to carbon monoxide poisoning, with only a slight decay in the presence of carbon monoxide, as shown in figure 5. The atomic-scale dispersed chromium-hydroxide cluster modified ruthenium catalyst of this example reached 11.6mA cm at 50mV overpotential -2 The hydrogen evolution reaction current of (2) is shown in FIG. 6.
Comparative example 1:
obtained without addition of chromium chloridePure ruthenium nanoparticles as a control catalyst, and the same as in example 1, were subjected to the performance test of the hydrogen oxidation reaction, and as shown in FIG. 4, it can be seen that the half-wave potential and the exchange current density of the ruthenium nanoparticle electrocatalyst were 88mV and 0.26mA cm -2 The performance is significantly lower than that of ruthenium electrocatalysts anchored with chromium-oxyhydrogen clusters. The ruthenium nanoparticle catalyst completely lost activity in the presence of carbon monoxide, indicating its poor resistance to poisoning, as shown in figure 5. In the present example, the hydrogen evolution reaction current of the ruthenium nanoparticle catalyst under 50mV overpotential is 0.71mA cm -2 Significantly lower than the atomically dispersed chromium-hydroxide cluster modified ruthenium catalyst, as shown in figure 6.
Example 2:
an atomic-scale dispersed chromium-hydroxide cluster modified platinum electrocatalyst is prepared by the following steps:
step 1) preparation of metal gel: first, 0.366mmol of chloroplatinic acid and 12mg of chromium chloride hexahydrate were dissolved in 20mL of deionized water and sonicated for 30min. Then, 4mL of an aqueous solution of sodium borohydride (1 mol/L) was injected into the above solution under vigorous stirring until no air bubbles were formed, and then the resulting metal gel was washed with deionized water to completely remove unreacted ions.
Step 2) preparing the metal aerogel: and (3) putting the metal gel into liquid nitrogen, freezing for 10min, taking out, and freeze-drying in a freeze dryer for 24h to finally obtain a metal aerogel sample.
In this example, the obtained platinum electrocatalyst modified by atomically dispersed chromium-hydroxide clusters was subjected to electrocatalytic hydrogen oxidation test, which was performed in the same manner as in example 1. The half-wave potential of the platinum electrocatalyst surface-anchored with atomically dispersed chromium-hydroxide clusters in this example was up to 30mV, as shown in fig. 7.
Comparative example 2:
pure platinum nanoparticles obtained without chromium chloride as a control catalyst, and the rest of the same conditions as in example 1 were subjected to a hydrogen oxidation reaction performance test, as shown in fig. 7, it can be seen that the half-wave potential of the platinum nanoparticle electrocatalyst is 45mV, and the performance is significantly lower than that of the platinum electrocatalyst anchored with chromium-oxyhydrogen clusters.
Example 3:
an atomically dispersed chromium-hydroxyl cluster modified iridium electrocatalyst is prepared by the following steps:
step 1) preparation of metal gel: first, 0.366mmol of potassium chloroiridate and 12mg of chromium chloride hexahydrate were dissolved in 20mL of deionized water and sonicated for 30min. Then, 4mL of an aqueous solution of sodium borohydride (1 mol/L) was injected into the above solution under vigorous stirring until no air bubbles were formed, and then the resulting metal gel was washed with deionized water to completely remove unreacted ions.
Step 2) preparing metal aerogel: and (3) putting the metal gel into liquid nitrogen, freezing for 10min, taking out, and freeze-drying in a freeze dryer for 24h to finally obtain a metal aerogel sample. Comparative example 3:
the pure iridium nanoparticles obtained without chromium chloride addition were used as control catalysts and were otherwise identical to those of example 1.
Example 4:
an atomically dispersed chromium-hydroxide cluster modified platinum/ruthenium alloy electrocatalyst is prepared by the following specific steps:
step 1) preparation of metal gel: first, 50mg of ruthenium chloride hydrate, 94.8mg of chloroplatinic acid, and 12mg of chromium chloride hexahydrate were dissolved in 20mL of deionized water and sonicated for 30min. Then, 4mL of an aqueous solution of sodium borohydride (1 mol/L) was injected into the above solution under vigorous stirring until no air bubbles were formed, and then the resulting metal gel was washed with deionized water to completely remove unreacted ions.
Step 2) preparing the metal aerogel: and putting the metal gel into liquid nitrogen, freezing for 10min, taking out, and freeze-drying in a freeze dryer for 24h to obtain a metal aerogel sample. Comparative example 4:
the platinum/ruthenium alloy nanoparticles obtained without chromium chloride addition were used as a control catalyst, and the rest was the same as in example 1.
Example 5:
an atomic-level dispersed zinc-hydroxyl cluster modified ruthenium electrocatalyst is prepared by the following specific steps:
step 1) preparation of metal gel: first, 100mg of ruthenium chloride hexahydrate and 2.25mg of zinc chloride were dissolved in 20mL of deionized water and sonicated for 30min. Then, 4mL of an aqueous solution of sodium borohydride (1 mol/L) was injected into the above solution under vigorous stirring until no air bubbles were formed, and then the resulting metal gel was washed with deionized water to completely remove unreacted ions.
Step 2) preparing metal aerogel: and (3) putting the metal gel into liquid nitrogen, freezing for 10min, taking out, and freeze-drying in a freeze dryer for 24h to finally obtain a metal aerogel sample. Comparative example 5:
the same procedure as in example 1 was repeated except that pure ruthenium nanoparticles obtained without zinc chloride addition were used as a control catalyst.
Example 6:
a preparation method of a heavy oxygen marked chromium-hydroxide cluster modified ruthenium electrocatalyst.
This example is essentially the same as example 1, except that: changing the deionized water to heavy oxygen (O) 18 ) And (3) water. Step 1) preparation of metal gel: first, 10mg of ruthenium chloride hydrate and 1.2mg of chromium chloride hexahydrate were dissolved in 2mL of heavy oxygen water and sonicated for 0.5h. Then, 0.4mL of a solution of sodium borohydride (1M) in heavy oxygen in water was injected into the above solution under vigorous stirring until no bubbles were formed, followed by washing the resulting metal gel with heavy oxygen water to completely remove unreacted ions. Step 2) preparing metal aerogel: and putting the metal gel into liquid nitrogen, freezing for 10min, taking out, and freeze-drying in a freeze dryer for 24h to obtain a metal aerogel sample.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A metal-hydroxide cluster modified noble metal electrocatalyst is characterized in that noble metal nanoparticles are used as a substrate, and metal-hydroxide clusters which are dispersed in atomic scale are anchored on the surface of the noble metal nanoparticles; the noble metal nano particles are one or more of platinum, ruthenium, iridium, rhodium, gold, silver and palladium; the metal-hydroxide cluster is selected from the group consisting of metal-hydroxide clusters based on chromium, manganese, zinc, niobium, zirconium and mixtures of two or three thereof, and preferably, is a chromium-hydroxide cluster.
2. The metal-hydroxide cluster-modified noble metal electrocatalyst according to claim 1, characterized in that the mass percentage of chromium metal in the metal-hydroxide cluster-modified noble metal electrocatalyst is between 0.6 and 2.2 wt.%, preferably 1.1 wt.%.
3. A method for preparing a metal-hydroxide cluster-modified noble electrocatalyst according to claim 1 or 2, comprising the steps of:
(1) Mixing an easily reducible metal precursor and a difficultly reducible transition metal salt precursor in water to obtain a mixed solution;
(2) Dripping sodium borohydride solution into the mixed solution until the reaction is finished to obtain metal gel;
(3) The metal gel was frozen in liquid nitrogen and subsequently freeze-dried.
4. The preparation method according to claim 3, wherein in step (1), the easily reducible metal comprises one or more of platinum, ruthenium, iridium, rhodium, gold, silver and palladium, preferably, the easily reducible metal precursor comprises one or more of ruthenium chloride hydrate, chloroplatinic acid and potassium chloroiridate; the difficult-to-reduce transition metal comprises one or more of chromium, manganese, zinc, niobium and zirconium, and preferably, the difficult-to-reduce metal precursor comprises one or more of chromium chloride hexahydrate and zinc chloride.
5. The process according to claim 3, wherein in step (1), the concentration of the easily reducible metal precursor in the mixed solution is 5mg/mL, and the concentration of the hardly reducible metal precursor is 0.15 to 1.2mg/mL, preferably 0.6mg/mL.
6. The process according to claim 3, wherein in step (1), the mixing is carried out by means of sonication for a period of 0.2 to 1 hour, preferably 0.5 hour.
7. The process according to claim 3, wherein in the step (2), the concentration of sodium borohydride is 0.5 to 2mol/L, preferably 1mol/L.
8. The preparation method according to claim 3, wherein in the step (2), the sodium borohydride solution is added into the mixed solution of ruthenium chloride and chromium chloride at a constant speed, and the addition is completed within 3 min; and stopping the reaction until no bubbles emerge.
9. The method according to claim 3, wherein the metal gel is obtained after the reaction is completed and washed with deionized water; and (3) putting the metal gel obtained in the step (2) into liquid nitrogen, freezing for 10min, taking out, and freeze-drying in a freeze dryer for 24 h.
10. Use of the metal-hydroxide cluster-modified electrocatalyst according to claim 1 or 2 in the field of fuel cells and water splitting.
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