CN112077334A - 一种过渡金属掺杂钌铑合金的制备方法及其应用 - Google Patents
一种过渡金属掺杂钌铑合金的制备方法及其应用 Download PDFInfo
- Publication number
- CN112077334A CN112077334A CN202010917568.5A CN202010917568A CN112077334A CN 112077334 A CN112077334 A CN 112077334A CN 202010917568 A CN202010917568 A CN 202010917568A CN 112077334 A CN112077334 A CN 112077334A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- ruthenium
- rhodium
- rhodium alloy
- trichloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 58
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 58
- 229910000629 Rh alloy Inorganic materials 0.000 title claims abstract description 44
- YPPQDPIIWDQYRY-UHFFFAOYSA-N [Ru].[Rh] Chemical compound [Ru].[Rh] YPPQDPIIWDQYRY-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 10
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 9
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 9
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims abstract description 8
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 3
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 3
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 239000011651 chromium Substances 0.000 description 16
- 229910052804 chromium Inorganic materials 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 13
- 229910052759 nickel Inorganic materials 0.000 description 13
- 229910017052 cobalt Inorganic materials 0.000 description 11
- 239000010941 cobalt Substances 0.000 description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 10
- 239000011572 manganese Substances 0.000 description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- 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 description 8
- 238000003917 TEM image Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 6
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B01J35/23—
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
本发明提供一种过渡金属掺杂钌铑合金的制备方法，所述制备方法包括下述步骤：将双分子表面活性剂与三氯化钌、三氯化铑、过渡金属无机盐进行反应得到过渡金属掺杂钌铑合金。本发明所得过渡金属掺杂钌铑合金作为电催化剂能够高效催化燃料电池中的析氢和析氧反应。
Description
技术领域
本发明涉及电催化剂技术领域，具体涉及一种过渡金属掺杂钌铑合金的制备方法及其应用。
背景技术
随着世界能源需要和环境问题的日益增加，寻找清洁能源迫在眉睫。近年来，氢燃料电池的开发利用，进一步拓宽了能源领域的研究范围。在电-氢能源体系中，电化学分解水起到桥梁和纽带作用，通过电能将太阳能、风能、潮汐能等转化成化学能。电化学分解水具有操作简单、制氢效率高、产品纯度高等优点，引起了人们的广泛关注。
电化学分解水是利用电能将水分子分解成氢气和氧气的过程。电解水包括阴极的析氢反应和样机的析氧反应。而在设计氢燃料电池的过程中，提高析氢反应（HER）的反应效率（降低HER过电位）成为商业化应用的关键。文献研究表明，Pt-基金属催化剂具有最小HER过电位，最高的反应效率，然而Pt价值昂贵，限制了催化剂的广泛应用，因此开发低成本，高性能及高稳定性电催化剂是目前氢燃料电池亟待解决的问题。
发明内容
针对现有技术存在的技术问题，本发明提供一种过渡金属掺杂钌铑合金的制备方法以及应用，所得过渡金属掺杂钌铑合金具有优异的析氢和析氧性能，能够作为电催化剂高效催化燃料电池中的析氢和析氧反应。
本发明提供的一种过渡金属掺杂钌铑合金的制备方法, 所述制备方法包括下述步骤：将双分子表面活性剂与三氯化钌、三氯化铑、过渡金属无机盐进行反应得到过渡金属掺杂钌铑合金。
优选地，所述制备方法包括下述具体步骤：将双分子表面活性剂、三氯化钌、三氯化铑和过渡金属无机盐加入蒸馏水和乙二醇溶液的混合液中，加入苯甲酸溶液，升温后恒温反应，反应物经分散沉降、离心分离、真空干燥后得到过渡金属掺杂钌铑合金。
优选地，所述双分子表面活性剂为聚乙二醇-b-聚丙二醇-b-聚乙二醇。
优选地，所述恒温反应中，反应温度为140-150 ℃，反应时间为12 h。
优选地，所述过渡金属无机盐为六水合氯化钴、四水合氯化锰、乙酰丙酮铁、乙酰丙酮镍、乙酰丙酮铬中的一种。
优选地，所述三氯化钌、三氯化铑、过渡金属无机盐的摩尔比为1：2：1。
优选地，所述分散沉降中，依次采用蒸馏水与无水乙醇进行分散沉降。
本发明还公开了一种将所述制备方法制得的过渡金属掺杂钌铑合金作为燃料电池析氢反应的电催化剂的应用。
与现有技术相比，本发明具有以下有益效果：
1、本发明针对现有技术的不足，提供一种过渡金属掺杂钌铑合金的制备方法，所得的过渡金属掺杂钌铑合金作为电催化剂具有优异的析氢和析氧性能，能够高效催化燃料电池中的析氢和析氧反应。
2、由文献报道可知，尺寸均一的金属纳米颗粒裸露较多活性位点参与电催化反应。本发明利用双分子表面活性剂优选聚乙二醇-b-聚丙二醇-b-聚乙二醇控制纳米片的中空结构，利用苯甲酸释放的CO进一步限域控制金属纳颗粒的结构，制得的过渡金属调控贵金属的复合纳米颗粒具有优异的析氢性能，能够高效催化燃料电池中的析氢反应，同时水热法具有工艺简单，反应温度低，适合于批量生产的工业化特点，对于可再生能源技术发展具有重要的指导意义。商用催化剂Pt-C价格高昂，本发明采用贵金属与非贵金属杂化的方式，降低了所需成本，能够有效得到尺寸均一的纳米颗粒催化剂，其电催化析氢性能在碱性条件下甚至超越了商用铂碳，具有良好的应用发展前景，对于可再生能源技术发展具有重要的指导意义。
附图说明
图1为本发明实施例1-5得到的过渡金属（钴、锰、铁、镍、铬）掺杂钌铑合金的XRD图。
图2为本发明实施例1得到的过渡金属钴掺杂钌铑合金的XPS图。
图3为本发明实施例2得到的过渡金属锰掺杂钌铑合金的XPS图。
图4为本发明实施例3得到的过渡金属铁掺杂钌铑合金的XPS图。
图5为本发明实施例4得到的过渡金属镍掺杂钌铑合金的XPS图。
图6为本发明实施例5得到的过渡金属铬掺杂钌铑合金的XPS图。
图7为本发明实施例1-5得到的过渡金属（钴、锰、铁、镍、铬）掺杂钌铑合金的TEM图。
图8为本发明实施例1-5得到的过渡金属（钴、锰、铁、镍、铬）掺杂钌铑合金的OER性能测试图。
图9为本发明实施例1-5得到的过渡金属（钴、锰、铁、镍、铬）掺杂钌铑合金的HER性能测试图。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体图示，进一步阐述本发明。
实施例1
一种过渡金属钴掺杂钌铑合金的制备方法，操作步骤如下：室温下，称量0.0200g聚乙二醇-b-聚丙二醇-b-聚乙二醇、0.0332g（0.16mmol）三氯化钌（RuCl3•xH2O）粉末、0.0670g（0.32mmol）三氯化铑（RhCl3•xH2O）粉末和0.16mmol乙酰丙酮钴加入20mL二次蒸馏水和4mL乙二醇溶液的混合液中，加入0.0130g苯甲酸溶于12mL二次蒸馏水后的苯甲酸溶液，将所得反应体系转移至反应釜后放入烘箱中，逐步升温至150℃，保温12 h至反应结束。待反应釜自然冷却至室温，分别加入适量二次蒸馏水和无水乙醇分散沉降后，离心分离固体，将所得固体洗涤后得到黑色产物，将所得黑色产物在真空干燥箱里真空干燥过夜后，得到过渡金属掺杂钌铑合金。
实施例2
一种过渡金属锰掺杂钌铑合金的制备方法，将实施例1中的乙酰丙酮钴换成四水合氯化锰，温度替换成140℃，其他操作均与实施例1相同。
实施例3
一种过渡金属铁掺杂钌铑合金的制备方法，将实施例1中的乙酰丙酮钴换成乙酰丙酮铁，温度替换成145℃，其他操作均与实施例1相同。
实施例4
一种过渡金属镍掺杂钌铑合金的制备方法，将实施例1中的乙酰丙酮钴换成乙酰丙酮镍，其他操作均与实施例1相同。
实施例5
一种过渡金属铬掺杂钌铑合金的制备方法，将实施例1中的乙酰丙酮钴换成乙酰丙酮铬，其他操作均与实施例1相同。
对实施例1-5得到的过渡金属（钴、锰、铁、镍、铬）掺杂钌铑合金采用X射线衍射仪（XRD）和X射线光电子能谱分析（XPS）表征其组份和结构；采用扫描电子显微镜（TEM）分析其尺寸、形貌和微结构，结果分别如图1-7所示；图1为样品的XRD图，XRD显示其主要产物为立方晶系，主要峰位于面心立方Rh（JCPDS#88-2334）和Ru（JCPDS#88-2333）；图2-6为样品的XPS图，从图中可以看出Rh、Ru均为0价金属；图7为样品的TEM图，其中，（a）为过渡金属钴掺杂钌铑合金的TEM图；（b）为过渡金属铁掺杂钌铑合金的TEM图；（c）为过渡金属锰掺杂钌铑合金的TEM图；（d）为过渡金属镍掺杂钌铑合金的TEM图；（e）为过渡金属铬掺杂钌铑合金的TEM图，从图中可以看出样品为尺寸均一的颗粒；基于上述分析可知，所述方法得到的产物为过渡金属（钴、锰、铁、镍、铬）掺杂的RuRh2合金纳米颗粒。
试验例1
对实施例1-5得到的过渡金属（钴、锰、铁、镍、铬）掺杂钌铑合金进行电化学实验，所述电化学实验在辰华CHI660E型电化学工作站上进行，采用标准的三电极测试体系，相应的工作电极为实施例1-5所获取的过渡金属（钴、锰、铁、镍、铬）掺杂钌铑合金作为电催化剂的铂碳电极，对电极为石墨棒电极，参比电极为银/氯化银（Ag/AgCl）（0.1989 Vvs.RHE）。本试验例所有的电势均相对于RHE，所有电化学测试均在25℃条件下进行。每次实验时，所有的修饰电极均在N2饱和的1.0mol/L KOH溶液中进行测试。电化学实验前，取4μL的过渡金属（钴、锰、铁、镍、铬）掺杂钌铑合金分散溶液（5 mg/mL）滴在铂碳电极上，全部滴完后烘干，再滴加2μL0.1%的萘酚溶液覆盖在催化剂表面，烘干备用。检测结果如图8、9所示，在相同电流密度下比较过电位的大小，过电位越小，析氢和析氧的催化活性越高。在同等碱性环境下，10mA/cm2 时商用铂碳的过电位为30 mV，实施例1-5得到的过渡金属（钴、锰、铁、镍、铬）掺杂钌铑合作为电催化剂的过电位分别为8 mV（Co）、24.3 mV（Mn）、24.3 mV（Fe）、29.4 mV（Ni）、32.6 mV（Cr）。在同等碱性环境下，10 mA/cm2 时商用二氧化钌的过电位为300 mV，实施例1-5得到的过渡金属（钴、锰、铁、镍、铬）掺杂钌铑合作为电催化剂对应的过电位分别为310 mV（Co）、328 mV（Mn）、313 mV（Fe）、321 mV（Ni）、280 mV（Cr）。总体来看，过渡金属（钴、锰、铁、镍、铬）调控RuRh合金的复合材料在析氢和析氧反应过程中都能够表现出优异的催化活性，其中钴最优。
总之，过渡金属掺杂钌铑合金作为电催化剂经检测性能好，能够高效催化燃料电池中的析氢和析氧反应，同时利用水热法可控合成的过渡金属掺杂钌铑合金作为电催化剂，具有工艺简单，反应温度低，适合于批量生产的工业化特点，对于可再生能源技术发展具有重要的指导意义。
以上仅为本发明的实施方式，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构，直接或间接运用在其他相关的技术领域，均同理在本发明的专利保护范围之内。
Claims (8)
1.一种过渡金属掺杂钌铑合金的制备方法,其特征在于，所述制备方法包括下述步骤：将双分子表面活性剂与三氯化钌、三氯化铑、过渡金属无机盐进行反应得到过渡金属掺杂钌铑合金。
2.如权利要求1所述的制备方法，其特征在于，所述制备方法包括下述具体步骤：将双分子表面活性剂、三氯化钌、三氯化铑和过渡金属无机盐加入蒸馏水和乙二醇溶液的混合液中，加入苯甲酸溶液，升温后恒温反应，反应物经分散沉降、离心分离、真空干燥后得到过渡金属掺杂钌铑合金。
3.如权利要求1或2所述的制备方法，其特征在于，所述双分子表面活性剂为聚乙二醇-b-聚丙二醇-b-聚乙二醇。
4.如权利要求2所述的制备方法，其特征在于，所述恒温反应中，反应温度为140-150℃，反应时间为12 h。
5.如权利要求1或2所述的制备方法，其特征在于，所述过渡金属无机盐为六水合氯化钴、四水合氯化锰、乙酰丙酮铁、乙酰丙酮镍、乙酰丙酮铬中的一种。
6.如权利要求1或2所述的制备方法，其特征在于，所述三氯化钌、三氯化铑、过渡金属无机盐的摩尔比为1：2：1。
7.如权利要求2所述的制备方法，其特征在于，所述分散沉降中，依次采用蒸馏水与无水乙醇进行分散沉降。
8.一种将权利要求1-7任一项所述制备方法制得的过渡金属掺杂钌铑合金作为燃料电池析氢反应的电催化剂的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010917568.5A CN112077334A (zh) | 2020-09-03 | 2020-09-03 | 一种过渡金属掺杂钌铑合金的制备方法及其应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010917568.5A CN112077334A (zh) | 2020-09-03 | 2020-09-03 | 一种过渡金属掺杂钌铑合金的制备方法及其应用 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112077334A true CN112077334A (zh) | 2020-12-15 |
Family
ID=73731622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010917568.5A Pending CN112077334A (zh) | 2020-09-03 | 2020-09-03 | 一种过渡金属掺杂钌铑合金的制备方法及其应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112077334A (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115196697A (zh) * | 2022-08-04 | 2022-10-18 | 北京化工大学 | 过渡金属掺杂的氧化钌纳米材料、其制备方法及用途 |
| CN115354360A (zh) * | 2022-10-24 | 2022-11-18 | 中国科学院过程工程研究所 | 一种掺杂型铂基催化剂及其制备方法与应用 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008134939A1 (en) * | 2007-05-08 | 2008-11-13 | Synfuels China Technology Co., Ltd. | Transition metal nano-catalyst, its preparation method and its use in fischer-tropsch synthetic reaction |
| CN104607184A (zh) * | 2015-01-22 | 2015-05-13 | 燕山大学 | 一种高活性藤缠树结构Pt-Rh合金纳米催化剂及制备方法 |
| CN106784903A (zh) * | 2016-12-28 | 2017-05-31 | 清华大学深圳研究生院 | 用于燃料电池催化剂的铂‑过渡金属合金纳米晶制备方法 |
| CN108554421A (zh) * | 2018-03-22 | 2018-09-21 | 北京化工大学 | 一种过渡金属掺杂铱基纳米枝晶电催化剂的制备方法 |
| CN110756819A (zh) * | 2019-10-11 | 2020-02-07 | 南京晓庄学院 | 一种钌铑合金纳米环的制备方法和应用 |
| CN111129508A (zh) * | 2019-12-17 | 2020-05-08 | 一汽解放汽车有限公司 | 一种过渡金属掺杂的铂碳催化剂及其制备方法和用途 |
| CN111545218A (zh) * | 2020-04-23 | 2020-08-18 | 华南理工大学 | 一种新型高分散过渡金属掺杂的RuO2/C复合材料及制备方法 |
-
2020
- 2020-09-03 CN CN202010917568.5A patent/CN112077334A/zh active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008134939A1 (en) * | 2007-05-08 | 2008-11-13 | Synfuels China Technology Co., Ltd. | Transition metal nano-catalyst, its preparation method and its use in fischer-tropsch synthetic reaction |
| CN104607184A (zh) * | 2015-01-22 | 2015-05-13 | 燕山大学 | 一种高活性藤缠树结构Pt-Rh合金纳米催化剂及制备方法 |
| CN106784903A (zh) * | 2016-12-28 | 2017-05-31 | 清华大学深圳研究生院 | 用于燃料电池催化剂的铂‑过渡金属合金纳米晶制备方法 |
| CN108554421A (zh) * | 2018-03-22 | 2018-09-21 | 北京化工大学 | 一种过渡金属掺杂铱基纳米枝晶电催化剂的制备方法 |
| CN110756819A (zh) * | 2019-10-11 | 2020-02-07 | 南京晓庄学院 | 一种钌铑合金纳米环的制备方法和应用 |
| CN111129508A (zh) * | 2019-12-17 | 2020-05-08 | 一汽解放汽车有限公司 | 一种过渡金属掺杂的铂碳催化剂及其制备方法和用途 |
| CN111545218A (zh) * | 2020-04-23 | 2020-08-18 | 华南理工大学 | 一种新型高分散过渡金属掺杂的RuO2/C复合材料及制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| 历嘉云等: "过渡金属钌、铑配合物在室温离子液体中催化硅氢加成反应的研究", 《化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115196697A (zh) * | 2022-08-04 | 2022-10-18 | 北京化工大学 | 过渡金属掺杂的氧化钌纳米材料、其制备方法及用途 |
| CN115196697B (zh) * | 2022-08-04 | 2024-02-02 | 北京化工大学 | 过渡金属掺杂的氧化钌纳米材料、其制备方法及用途 |
| CN115354360A (zh) * | 2022-10-24 | 2022-11-18 | 中国科学院过程工程研究所 | 一种掺杂型铂基催化剂及其制备方法与应用 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Ultrafine Rh nanocrystals decorated ultrathin NiO nanosheets for urea electro-oxidation | |
| Arshad et al. | Recent advances in electrocatalysts toward alcohol-assisted, energy-saving hydrogen production | |
| Maiyalagan et al. | Role of the morphology and surface planes on the catalytic activity of spinel LiMn1. 5Ni0. 5O4 for oxygen evolution reaction | |
| Xiong et al. | Catalytic activity of Pt–Ru alloys synthesized by a microemulsion method in direct methanol fuel cells | |
| CN113774422A (zh) | 一种应用于电解水的PdCuFeCoNi高熵合金纳米颗粒催化剂的制备方法 | |
| Xu et al. | A facile strategy for the synthesis of NiSe@ CoOOH core-shell nanowires on nickel foam with high surface area as efficient electrocatalyst for oxygen evolution reaction | |
| Li et al. | Carbon-supported Pt-RuCo nanoparticles with low-noble-metal content and superior catalysis for ethanol oxidization | |
| Wang et al. | Dissolution reconstruction of electron-transfer enhanced hierarchical NiSx-MoO2 nanosponges as a promising industrialized hydrogen evolution catalyst beyond Pt/C | |
| Tang et al. | Multifunctional carbon-armored Ni electrocatalyst for hydrogen evolution under high current density in alkaline electrolyte solution | |
| CN113684498B (zh) | 一种单原子合金催化剂的制备方法及应用 | |
| CN111957336A (zh) | 一种ZIF-8衍生的Fe-N-C氧还原电催化剂的制备方法 | |
| Huang et al. | Chelating agent assisted heat treatment of carbon supported cobalt oxide nanoparticle for use as cathode catalyst of polymer electrolyte membrane fuel cell (PEMFC) | |
| CN113437314A (zh) | 氮掺杂碳负载低含量钌和Co2P纳米粒子的三功能电催化剂及其制备方法和应用 | |
| CN112002915B (zh) | 一种氧电极双功能催化剂、制备方法及应用 | |
| CN112077334A (zh) | 一种过渡金属掺杂钌铑合金的制备方法及其应用 | |
| CN114164452B (zh) | 一种制备超薄钒酸钴纳米片负载金属单原子催化剂的方法 | |
| Alcaide et al. | Supporting PtRh alloy nanoparticle catalysts by electrodeposition on carbon paper for the ethanol electrooxidation in acidic medium | |
| Yin et al. | Construction of superhydrophilic metal-organic frameworks with hierarchical microstructure for efficient overall water splitting | |
| Zhang et al. | Amorphous mixed Ir–Mn oxide catalysts for the oxygen evolution reaction in PEM water electrolysis for H2 production | |
| Zeng et al. | Accelerated oxygen evolution enabled by encapsulating hybrid CoOx/RuO2 nanoparticle with nanoporous carbon | |
| Souza et al. | NaNbO3 microcubes decorated with minimum Pd and maximum performance for Alkaline Direct Ethanol Fuel Cell applications | |
| CN110681407A (zh) | Fe掺杂Co1.11Te2@NCNTFs纳米复合材料及其制备方法 | |
| CN112725828B (zh) | IrRu基多元合金氧析出催化剂及其制备方法 | |
| Salarizadeh et al. | Comparison of methanol oxidation reaction process for NiCo2O4/X (X= rGO, MWCNTs, HCNs) nanocatalyst | |
| Zhai et al. | One-pot fabrication of Nitrogen-doped graphene supported binary palladium-sliver nanocapsules enable efficient ethylene glycol electrocatalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |