CN109012673A - 一种析氧催化剂的制备方法及应用 - Google Patents
一种析氧催化剂的制备方法及应用 Download PDFInfo
- Publication number
- CN109012673A CN109012673A CN201810763850.5A CN201810763850A CN109012673A CN 109012673 A CN109012673 A CN 109012673A CN 201810763850 A CN201810763850 A CN 201810763850A CN 109012673 A CN109012673 A CN 109012673A
- Authority
- CN
- China
- Prior art keywords
- oxygen
- separating catalyst
- application
- mesoporous carbon
- nickel cobalt
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- -1 nickel cobalt metal oxide Chemical class 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000004458 analytical method Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 10
- 229910003266 NiCo Inorganic materials 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- CZAYMIVAIKGLOR-UHFFFAOYSA-N [Ni].[Co]=O Chemical compound [Ni].[Co]=O CZAYMIVAIKGLOR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
-
- 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
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本申请涉及一种析氧催化剂及其制备方法和应用，该析氧催化剂由镍钴金属氧化物与介孔碳组成，其中，所述镍钴金属氧化物在介孔碳上形成；该析氧催化剂具有良好的热稳定性和析氧催化活性。
Description
技术领域
本申请涉及电催化水分解析氧技术领域，具体涉及一种析氧催化剂及其制备方法和应用。
背景技术
全球变暖和气候变化问题受到广泛关注，研究人员致力于开发成本更低，环境友好，相对无毒的电催化剂。电化学水分解是产生清洁燃料的实用且环境友好的方法，水分解包括阳极析氧反应(OER)和阴极析氢反应，其具有严重的过电势要求，在实际应用中受到很大限制，特别是OER过程中固有的慢动力学和多电子转移步骤，显著影响能量转换效率。目前为止，氧化铱(IrO2)或氧化钌(RuO2)是最先进的OER催化剂，然而由于它们的稀缺性和较高的成本，使得其在实际工业中的广泛应用受到阻碍，因此，水分解的关键问题主要是研究活性高和成本低的催化剂。
在过去的几十年中，过渡金属氧化物在碱性电解质中得到广泛研究，并被认为是有效的水分解候选电催化剂。基于铁(Fe)、钴(Co)和镍(Ni)氧化物的许多材料作为有效的OER电催化剂已经引起了很多关注。
发明内容
本申请提供了一种基于介孔碳(OMC)的镍氧化物/钴氧化物的析氧催化剂及其制备方法和应用，该催化剂具有显著提高的析氧催化活性，该催化剂在碱性条件下使用，能够使电解水反应可以在较小的外加偏压下高效进行并保持长时间的稳定性。
本申请是通过如下技术方案实现的：
一方面，本申请提供了一种析氧催化剂，其由镍钴金属氧化物与介孔碳复合而成，其中，所述镍钴金属氧化物在介孔碳上形成。
进一步地，所述镍钴金属氧化物为纳米颗粒，其平均中粒径为3-8nm。
进一步地，所述镍钴金属氧化物为CoO和NiO。
进一步地，所述NiO和CoO的摩尔比是1：2。
进一步地，所述析氧催化剂的结构为NiCo2O3@OMC。
另一方面，本申请提供了一种制备上述析氧催化剂的方法，所述方法包括：
(1)将介孔碳粉末加入硝酸，水浴，离心洗涤，得介孔碳；
(2)将六水合硝酸镍(Ni(NO3)2〃6H2O)和六水合硝酸钴(Co(NO3)2〃6H2O)按照一定的摩尔比称取，溶解于有机溶剂中；
(3)用有机溶剂将步骤(1)的介孔碳转移到步骤(2)的溶液中，搅拌并超声，然后搅拌至干，得到粉末；
(4)将步骤(3)的粉末放在管式炉中，氩气气氛煅烧。
进一步地，在步骤(1)中，所述水浴温度为60℃；
进一步地，在步骤(1)中，所述水浴时间为30min；
进一步地，在步骤(1)中，所述硝酸的浓度为2M；
进一步地，在步骤(1)中，所述硝酸的用量为5mL；
进一步地，在步骤(2)中，所述硝酸镍和硝酸钴的摩尔比为1：2；
进一步地，在步骤(2)中，所述有机溶剂为乙醇；
进一步地，在步骤(3)中，所述搅拌时间为10min；
进一步地，在步骤(3)中，所述超声时间为2h；
进一步地，在步骤(4)中，所述煅烧温度为350℃；
进一步地，在步骤(4)中，所述煅烧时间为6h。
又一方面，本申请还提供了一种光电解水或可再生燃料或电解产氢装置，其含有上述析氧催化剂。
再一方面，本申请还提供了析氧催化剂在碱性电解水中的应用。
此外，本申请还提供了上述析氧催化剂在析氧反应中的应用；或者，上析氧催化剂在光电解水、可再生燃料电池和电解产氢装置中的应用。
此外，本申请还提供了上述析氧催化剂在析氧反应中的应用；或者，上述析氧催化剂在光电解水、可再生燃料电池和电解产氢装置中的应用。
钴基氧化物由于其活性高、价格低、稳定性好，被认为是最有前途的OER电催化剂，本申请发明人在以Fe、Zn、Cu和Ni等金属离子试图提高钴基氧化物的催化活性的实验中首次发现，在这些材料中，Ni可以使钴基氧化物具有更好的电子导电性和大量的水分解活性位点。而且，Ni和Co物质可以与水反应形成M-O(M＝Ni或Co)键，并因此促进水分解。除此之外，具有OER性能的Ni-Co氧化物材料优于任何单一氧化物(Ni或Co)，且本申请发明人发现当该镍钴氧化物为NiCo2O3(NiO和CoO的摩尔比为1：2)时，效果最好。此外，本申请将镍钴氧化物NiCo2O3(NiO和CoO的摩尔比为1：2)创新性地与介孔碳合用，使介孔碳容纳和固定镍钴氧化物，尤其本申请的镍钴氧化物NiCo2O3(NiO和CoO的摩尔比为1：2)纳米颗粒在介孔碳上形成的技术方案，既避免了金属氧化物导电性不足限制其在实际中的广泛应用的缺陷，也提高了析氧催化剂的整体性能，比如在应用时的比表面积大、孔隙率适宜及稳定性高。
此外，与现有技术相比，本申请的显著优点在于：
1、本申请的制备方法具有工艺简单、成本低廉、便于实现工业化生产等优势，在本申请较温和的条件下，可有效控制合成尺寸大小均一，分散度良好的纳米级基于介孔碳的二元金属氧化物催化剂NiCo2O3@OMC(NiO和CoO的摩尔比为1：2)，该催化剂经过锻烧后仍可保持原貌，具有良好的热稳定性。
2、本申请的镍钴二元过渡金属氧化物析氧电催化剂NiCo2O3@OMC(NiO和CoO的摩尔比为1：2)相较于传统单金属氧化物电催化剂拥有更高的析氧催化活性，此外，将镍钴二元过渡金属氧化物NiCo2O3负载到导电性更强，比表面积更大的介孔碳上(镍钴氧化物NiCo2O3纳米颗粒在介孔碳上形成)，通过两者的协同作用进一步提高了催化剂的析氧催化活性。
附图说明
以下，结合附图来详细说明本申请的实施方案，其中：
图1为依据本申请制备的镍钴氧化物的高分辨TEM图像；
图2为依据本申请制备的镍钴氧化物的XRD图谱；
图3为在常温下，在三电极体系中进行电化学测试，以1M NaOH溶液为电解液，0.567mg/cm2本申请的基于介孔碳的镍钴氧化物(NiCo2O3@OMC，a)、镍钴氧化物与介孔碳混合(NiCo2O3+OMC，b)以及原始OMC(c)为催化剂，进行线性伏安扫描得到的极化曲线图；
图4为依据本申请制备的基于介孔碳的镍钴氧化物(NiCo2O3@OMC)作为析氧电催化剂，在1.5V(vs RHE)恒电位下进行水分解析氧的稳定性测试结果。
具体实施方式
下面结合具体实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件或按照制造厂商所建议的条件。
除非另行定义，文中所使用的所有专业与科学用语与本领域熟练人员所熟悉的意义相同。此外，任何与所记载内容相似或均等的方法及材料皆可应用于本申请方法中。文中所述的较佳实施方法与材料仅作示范之用。
实施例1
(1)100mg OMC加入5mL 2M的硝酸水浴60℃ 30min，离心洗涤一次，得到介孔碳。
(2)六水合硝酸镍和六水合硝酸钴按照1：2的摩尔比称取，溶解于5mL无水乙醇。
(3)用5mL乙醇将步骤(1)的OMC转移到步骤(2)的溶液中，搅拌10min，再超声2h，然后搅拌至干，得到粉末。(搅拌到最后，样品会有点潮，可以在该步骤完成后进行烘干)。
(4)将步骤(3)的粉末放在管式炉中，氩气气氛350℃恒温煅烧6h。
物性表征：
图1显示了实施例1制备得到的NiCo2O3@OMC的高分辨TEM图像。
如图1所示，在OMC上形成了镍钴氧化物，并且镍钴氧化物颗粒的平均中粒径为3-8nm。
OMC和NiCo2O3@OMC析氧催化剂的XRD谱图如图2所示。
OMC的XRD图仅在27°2θ处有一个拓宽的衍射峰，表明OMC的无定形特征。而NiCo2O3@OMC具有三种宽的衍射图案，其可以被索引到CoO(JCPDS 89-7099)和NiO(JCPDS 89-3080)，且暗示了CoO和NiO的纯度。
实施例2 NiCo2O3@OMC催化剂的催化活性考评
以1M NaOH为电解质溶液，Ag/AgCl为参比电极，铂网为对电极，玻碳电极为工作电极，扫速为5mV/s，在AUTOLAB PGSTAT302N电化学工作站上做线性扫描伏安(LSV)测试，如图3所示。采用实施例1制备出的NiCo2O3@OMC催化剂(0.567mg/cm2)在碱性电解质溶液中10mA/cm2电流密度下的电位为1.51V，则相应的过电位为280mV，显著优于NiCo2O3+OMC(1200mV)和OMC(1300mV)
实施例3 NiCo2O3@OMC催化剂在恒电位下的电催化稳定性考评
如图4所示，以1M NaOH为电解质溶液，Ag/AgCl为参比电极，铂网为对电极，玻碳电极为工作电极，恒电位1.5V下测其电化学稳定性，经过20000s的测试，电流下降了25.7％，表明实施例1制备出的NiCo2O3@OMC催化剂具有良好的稳定性。
Claims (9)
1.一种析氧催化剂，其由镍钴金属氧化物与介孔碳复合而成，其中，所述镍钴金属氧化物在介孔碳上形成。
2.根据权利要求1所述的析氧催化剂，其特征在于，所述镍钴金属氧化物为纳米颗粒，其平均中粒径为3-8nm。
3.根据权利要求1或2所述的方法，其特征在于，所述镍钴金属氧化物为CoO和NiO；
进一步地，所述NiO和CoO的摩尔比是1：2。
4.根据权利要求1至3中任一项所述的析氧催化剂，其特征在于，所述析氧催化剂的结构为NiCo2O3@OMC。
5.一种制备权利要求1至4中任一项所述的析氧催化剂的方法，所述方法包括：
(1)将介孔碳粉末加入硝酸，水浴，离心洗涤，得介孔碳；
(2)将六水合硝酸镍和六水合硝酸钴按照一定的摩尔比称取，溶解于有机溶剂中；
(3)用有机溶剂将步骤(1)的介孔碳转移到步骤(2)的溶液中，搅拌并超声，然后搅拌至干，得到粉末；
(4)将步骤(3)的粉末放在管式炉中，氩气气氛煅烧。
6.根据权利要求5所述的方法，其特征在于，在步骤(1)中，所述水浴温度为60℃；
进一步地，在步骤(1)中，所述水浴时间为30min；
进一步地，在步骤(1)中，所述硝酸的浓度为2M；
进一步地，在步骤(1)中，所述硝酸的用量为5mL；
进一步地，在步骤(2)中，所述六水合硝酸镍和六水合硝酸钴的摩尔比为1：2；
进一步地，在步骤(2)中，所述有机溶剂为乙醇；
进一步地，在步骤(3)中，所述搅拌时间为10min；
进一步地，在步骤(3)中，所述超声时间为2h；
进一步地，在步骤(4)中，所述煅烧温度为350℃；
进一步地，在步骤(4)中，所述煅烧时间为6h。
7.一种光电解水或可再生燃料或电解产氢装置，其含有权利要求1至4中任一项所述的析氧催化剂。
8.权利要求1至4中任一项所述的析氧催化剂在碱性电解水中的应用。
9.权利要求1至4中任一项所述的析氧催化剂在析氧反应中的应用；或者，权利要求1至4中任一项所述的析氧催化剂在光电解水、可再生燃料电池和电解产氢装置中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810763850.5A CN109012673B (zh) | 2018-07-12 | 2018-07-12 | 一种析氧催化剂的制备方法及应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810763850.5A CN109012673B (zh) | 2018-07-12 | 2018-07-12 | 一种析氧催化剂的制备方法及应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109012673A true CN109012673A (zh) | 2018-12-18 |
| CN109012673B CN109012673B (zh) | 2021-08-03 |
Family
ID=64641116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810763850.5A Expired - Fee Related CN109012673B (zh) | 2018-07-12 | 2018-07-12 | 一种析氧催化剂的制备方法及应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109012673B (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112058267A (zh) * | 2020-09-18 | 2020-12-11 | 合肥工业大学 | 一种氧空位修饰的多孔镍钴氧化物纳米带材料及制备方法和应用 |
| CN113941331A (zh) * | 2021-10-29 | 2022-01-18 | 青岛科技大学 | 一种稳定催化剂表面Ni3+活性位点的方法及应用 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104364423A (zh) * | 2012-04-13 | 2015-02-18 | 丹麦技术大学 | 用于h2o电解或将co2和h2o转化为燃料的高性能可逆电化电池 |
| CN104801307A (zh) * | 2015-04-17 | 2015-07-29 | 中国科学院上海高等研究院 | 过渡金属氢氧化物-石墨烯氧化物复合材料及其制备与应用 |
| CN105289617A (zh) * | 2015-11-11 | 2016-02-03 | 东华大学 | 一种钴酸镍/碳纳米管复合催化剂及其制备和应用 |
| CN107393725A (zh) * | 2017-06-20 | 2017-11-24 | 中国科学院福建物质结构研究所 | 一种多孔导电的碳材料负载NiCo2O4复合材料及其制法和应用 |
-
2018
- 2018-07-12 CN CN201810763850.5A patent/CN109012673B/zh not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104364423A (zh) * | 2012-04-13 | 2015-02-18 | 丹麦技术大学 | 用于h2o电解或将co2和h2o转化为燃料的高性能可逆电化电池 |
| CN104801307A (zh) * | 2015-04-17 | 2015-07-29 | 中国科学院上海高等研究院 | 过渡金属氢氧化物-石墨烯氧化物复合材料及其制备与应用 |
| CN105289617A (zh) * | 2015-11-11 | 2016-02-03 | 东华大学 | 一种钴酸镍/碳纳米管复合催化剂及其制备和应用 |
| CN107393725A (zh) * | 2017-06-20 | 2017-11-24 | 中国科学院福建物质结构研究所 | 一种多孔导电的碳材料负载NiCo2O4复合材料及其制法和应用 |
Non-Patent Citations (2)
| Title |
|---|
| 李朋喜: "有序介孔碳负载过渡金属氧化物催化剂的合成及电催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 车倩等: "有序介孔碳负载NiCo2O4电极的制备及其超电容性能", 《物理化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112058267A (zh) * | 2020-09-18 | 2020-12-11 | 合肥工业大学 | 一种氧空位修饰的多孔镍钴氧化物纳米带材料及制备方法和应用 |
| CN113941331A (zh) * | 2021-10-29 | 2022-01-18 | 青岛科技大学 | 一种稳定催化剂表面Ni3+活性位点的方法及应用 |
| CN113941331B (zh) * | 2021-10-29 | 2023-12-22 | 青岛科技大学 | 一种稳定催化剂表面Ni3+活性位点的方法及应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109012673B (zh) | 2021-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108325565B (zh) | 一种多功能碳基非贵金属电催化剂及其制备方法和应用 | |
| Lin et al. | In situ growth of single-layered α-Ni (OH) 2 nanosheets on a carbon cloth for highly efficient electrocatalytic oxidation of urea | |
| Chen et al. | Inlay of ultrafine Ru nanoparticles into a self-supported Ni (OH) 2 nanoarray for hydrogen evolution with low overpotential and enhanced kinetics | |
| Gong et al. | High-performance bifunctional flower-like Mn-doped Cu7. 2S4@ NiS2@ NiS/NF catalyst for overall water splitting | |
| CN110227496A (zh) | 一种纳米片组成的微球状Fe掺杂二硫化三镍纳米结构材料、制备方法及应用 | |
| CN108893756B (zh) | 一种Ni3N NSs/NF纳米球的合成方法及其应用 | |
| Wang et al. | F-decoration-induced partially amorphization of nickel iron layered double hydroxides for high efficiency urea oxidation reaction | |
| CN110280275A (zh) | 一种Fe掺杂四硒化三镍纳米棒/纳米片分级阵列结构材料、制备方法及其应用 | |
| CN109794264A (zh) | 一种微米花球状高性能全解水双功能电催化剂FeOOH/Ni3S2的制备方法 | |
| CN107749483A (zh) | 一种用于氢空燃料电池阴极材料的催化剂及其制备方法 | |
| CN114457374B (zh) | 一种v掺杂硒化亚铜纳米片组装的纳米管阵列结构材料、制备方法及其应用 | |
| CN108048868A (zh) | 一种氮化钼纳米棒电极材料及其制备方法和应用 | |
| He et al. | P-doped nickel sulfide nanosheet arrays for alkaline overall water splitting | |
| Jiang et al. | Highly efficient hydrogen evolution reaction of Co 3 O 4 supports on N-doped carbon nanotubes in an alkaline solution | |
| CN112877725A (zh) | 一种钌/氧化钌修饰的氮掺杂石墨烯三维复合材料及其制备方法和应用 | |
| Lv et al. | Energy-efficient hydrogen production via electrochemical methanol oxidation using a bifunctional nickel nanoparticle-embedded carbon prism-like microrod electrode | |
| CN108126703A (zh) | 绣球状CuZnOX纳米材料的制备方法及其在电催化中的应用 | |
| Shen et al. | Highly active bifunctional catalyst: Constructing FeWO4-WO3 heterostructure for water and hydrazine oxidation at large current density | |
| Yu et al. | Nickel foam derived nitrogen doped nickel sulfide nanowires as an efficient electrocatalyst for the hydrogen evolution reaction | |
| Zhao et al. | Enhanced electrocatalytic activity of FeNi alloy quantum dot-decorated cobalt carbonate hydroxide nanosword arrays for effective overall water splitting | |
| Hao et al. | Preparation of quaternary FeCoMoCu metal oxides for oxygen evolution reaction | |
| CN109012673A (zh) | 一种析氧催化剂的制备方法及应用 | |
| Jian et al. | Hydrothermal Synthesized Co-Ni 3 S 2 Ultrathin Nanosheets for Efficient and Enhanced Overall Water Splitting | |
| CN109939707A (zh) | 磷化二钴@钨酸镍核壳异质结材料及其制备方法与应用 | |
| Fu et al. | NiFe-CN catalysts derived from the solid-phase exfoliation of NiFe-layered double hydroxide for CO 2 electroreduction |
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 | ||
| CB02 | Change of applicant information |
Address after: 266100 Hongkong East Road, Laoshan District, Qingdao, Shandong Province, No. 7 Applicant after: QINGDAO University Address before: 266061 No. 7, Hong Kong East Road, Qingdao, Shandong Applicant before: QINGDAO University |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210803 |