CN113930803B - 一种氮碳负载钴钌纳米粒子全解水电催化材料及其制备方法 - Google Patents
一种氮碳负载钴钌纳米粒子全解水电催化材料及其制备方法 Download PDFInfo
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- VLWBWEUXNYUQKJ-UHFFFAOYSA-N cobalt ruthenium Chemical compound [Co].[Ru] VLWBWEUXNYUQKJ-UHFFFAOYSA-N 0.000 title claims abstract description 21
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- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 16
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 239000010431 corundum Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910052573 porcelain Inorganic materials 0.000 claims description 8
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- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 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 claims description 3
- YHGGQZOFJGJAMR-UHFFFAOYSA-N cyclopenta-1,3-diene ruthenium Chemical compound C1=CC=CC1.C1=CC=CC1.[Ru] YHGGQZOFJGJAMR-UHFFFAOYSA-N 0.000 claims description 3
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical group [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000005868 electrolysis reaction Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000010411 electrocatalyst Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 3
- 229910000457 iridium oxide Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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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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Abstract
本发明公开了一种氮碳负载钴钌纳米粒子全解水电催化材料及其制备方法,通过溶剂热法合成CoRu‑ZIF‑67前驱体,然后在氢氩气气氛中热解生成CoRu/NC全解水电催化剂,制备出微观形貌为规则的十二面体,棱角分明,表面粗糙,面微向内凹陷的氮碳负载钴钌纳米粒子全解水电催化材料,该方法制备的CoRu/NC电催化剂具有高效的活性,具备良好的稳定性,并且合成方法简单,条件温和,在实现低负载贵金属钌的同时,表现出低于商业贵金属催化剂铂和氧化铱全解水的过电位,成本对比纯贵金属电催化剂有大幅度降低,具有很好的应用前景和极大的商业化潜力。
Description
技术领域
本发明属于电催化全解水的技术领域,具体涉及一种氮碳负载钴钌纳米粒子全解水电催化材料及其制备方法。
背景技术
目前应用最广泛的能源物质石油、煤和天然气等不可再生的化石能源,这些化石能源的大量消耗引起了一些环境问题,能源危机也随之到来,为应对这些危机与问题,急需寻找一种可再生清洁能源。
氢气能量密度大,来源广泛且对环境友好,是一种理想的可再生清洁能源。目前工业制氢技术中,化石燃料制氢、工业副产物制氢以及甲醇重整制氢,虽然工艺较成熟,但是制氢原料不可再生,且制氢过程产生的副产物对环境不友好,而电解水制氢技术,制氢原料为可再生的水,制氢纯度高,制氢过程无污染,并且所用电能来源广泛,潮汐能、地热能、水的势能等可再生能源转化的电能均可用于发电,所以电解水制氢技术是一项具有巨大应用前景的制氢技术,但是电解水过程中的析氢析氧反应缓慢的动力学限制了其电解速率,所以需要使用电催化剂来提高反应动力学从而提高电解水速率。
目前商用的电催化剂主要为贵金属铂、铱、钌及其氧化物,虽然其具有卓越的电催化活性,但是其低储量和高昂的价格限制了其大规模应用。开发低成本高活性的电催化剂成为当下研究热点。
发明内容
针对现有技术存在的不足,本发明的目的在于提供一种氮碳负载钴钌纳米粒子全解水电催化材料及其制备方法,该方法制备的CoRu/NC电催化剂具有极低的电解水过电位,具备高效的活性和良好的稳定性,并且合成方法简单,条件温和,与商用贵金属电催化剂相比具有低成本优势,表现出突出的工业化应用优势。
为了实现上述目的,本发明采用以下技术方案予以实现:
一种氮碳负载钴钌纳米粒子全解水电催化材料的制备方法,包括如下步骤:
1)首先称取分析纯的钴源、钌源和2-甲基咪唑溶于40~80ml的甲醇中搅拌至溶解形成钴离子浓度为0.05~0.5mol/L,钌离子浓度为0.005~0.25mol/L和2-甲基咪唑浓度为0.1~2mol/L的溶液A;
2)在A溶液中加入1~3g十六烷基三甲基溴化铵并用保鲜膜密封后移入水热釜,在120~200℃下溶剂热6~18h,水热釜冷却至室温后抽滤并洗涤、冷冻干燥,合成的蓬松的深紫色粉末为CoRu-ZIF-67前驱体;
3)取200~500mg的CoRu-ZIF-67粉体铺在刚玉瓷舟中置于充满氢氩气气氛的管式炉中,以2~5℃/min的升温速率,自室温升温至600~900℃,保温1~3h,以10℃/min的降温速率降至300℃,然后自然降温至室温,生成的黑色粉体为氮掺杂碳负载的钴钌纳米颗粒(CoRu/NC)。
本发明还具有以下技术特征:
优选的,所述的钴源为硝酸钴、氯化钴或乙酰丙酮钴;
所述的钌源为乙酰丙酮钌、十二羰基三钌或二茂钌。
优选的,所述步骤1)中的搅拌为在30~50℃温度下磁力搅拌。
优选的,所述步骤2)中洗涤为用无水乙醇和去离子水各洗涤2~4遍。
优选的,所述步骤2)中冷冻干燥为在-30~-40℃温度下冷冻干燥24~48h。
本发明还保护一种如上所述的制备方法制备的氮碳负载钴钌纳米粒子全解水电催化材料,微观形貌为规则的十二面体,棱角分明,表面粗糙,面微向内凹陷。
本发明与现有技术相比,具有如下技术效果:
本发明制备的CoRu/NC材料,采用溶剂热法合成的CoRu-ZIF-67前躯体具备尺寸均一,形貌可调控等优点,在氢氩气保护气氛中对前驱体进行热解生成CoRu/NC电催化剂,该制备方法条件温和,工艺可靠,实现工业化生产的可行性高;
本发明所提出的制备方法合成的CoRu/NC,CoRu纳米粒子的协同增强作用提高了电催化全解水的活性,降低了反应过电位,表现出高的全解水效率,氮掺杂的多孔碳基底具有较强的电子传输能力,有利于水分子的吸附,促进了电解水反应进行,表现出高效的活性,并且碳的包覆为活性中心提供了一定的保护,增强了电解水过程中催化剂的结构稳定性;
本发明所提出的制备方法合成的CoRu/NC,在实现低负载贵金属钌的同时,表现出低于商业贵金属催化剂铂和氧化铱全解水的过电位,成本对比纯贵金属电催化剂有大幅度降低,具有很好的应用前景和极大的商业化潜力。
附图说明
图1为实施例1制备的CoRu/NC的X射线衍射图;
图2为实施例1制备的CoRu/NC的SEM图;
图3为实施例1制备的CoRu/NC的全解水LSV图。
具体实施方式
以下结合实施例对本发明的具体内容做进一步详细解释说明。
实施例1:
1)首先,称取0.582g分析纯的Co(NO3)2•6H2O、0.07968g分析纯的C15H21O6Ru和0.3284g C4H6N2溶于40ml的甲醇中在30℃磁力搅拌形成溶液A;
2)在A溶液中加入1g十六烷基三甲基溴化铵(CTAB)并用保鲜膜密封在40℃磁力搅拌60min后移入水热釜,在120℃下溶剂热18h,水热釜冷却至室温后抽滤并用无水乙醇和去离子水各洗涤2遍后在-30℃冷冻干燥24h合成的蓬松的深紫色粉末为CoRu-ZIF-67前驱体;
3)取200mg的CoRu-ZIF-67粉体铺在刚玉瓷舟中置于充满氢氩气气氛的管式炉中,以2℃/min的升温速率,自室温升温至600℃保温3h,以10℃/min的降温速率降至300℃然后自然降温至室温,生成的黑色粉体为氮掺杂碳负载的钴钌纳米颗粒(CoRu/NC)。
实施例2:
1)首先,称取3.492g分析纯的Co(NO3)2•6H2O、3.586g分析纯的C15H21O6Ru和4.105gC4H6N2溶于60ml的甲醇中在40℃磁力搅拌形成溶液A;
2)在A溶液中加入1.5g十六烷基三甲基溴化铵(CTAB)并用保鲜膜密封在50℃磁力搅拌40min后移入水热釜,在160℃下溶剂热12h,水热釜冷却至室温后抽滤并用无水乙醇和去离子水各洗涤3遍后在-35℃冷冻干燥36h合成的蓬松的深紫色粉末为CoRu-ZIF-67前驱体;
3)取300mg的CoRu-ZIF-67粉体铺在刚玉瓷舟中置于充满氢氩气气氛的管式炉中,以3℃/min的升温速率,自室温升温至700℃保温2h,以10℃/min的降温速率降至300℃然后自然降温至室温,生成的黑色粉体为氮掺杂碳负载的钴钌纳米颗粒(CoRu/NC)。
实施例3:
1)首先,称取11.641g分析纯的Co(NO3)2•6H2O、7.968g分析纯的C15H21O6Ru和13.136g C4H6N2溶于80ml的甲醇中在50℃磁力搅拌形成溶液A;
2)在A溶液中加入2g十六烷基三甲基溴化铵(CTAB)并用保鲜膜密封在60℃磁力搅拌60min后移入水热釜,在200℃下溶剂热6h,水热釜冷却至室温后抽滤并用无水乙醇和去离子水各洗涤4遍后在-38℃冷冻干燥48h合成的蓬松的深紫色粉末为CoRu-ZIF-67前驱体;
3)取500mg的CoRu-ZIF-67粉体铺在刚玉瓷舟中置于充满氢氩气气氛的管式炉中,以5℃/min的升温速率,自室温升温至900℃保温1h,以10℃/min的降温速率降至300℃然后自然降温至室温,生成的黑色粉体为氮掺杂碳负载的钴钌纳米颗粒(CoRu/NC)。
实施例4:
1)首先,称取11.641g分析纯的Co(NO3)2•6H2O、7.968g分析纯的C15H21O6Ru和13.136g C4H6N2溶于70ml的甲醇中在50℃磁力搅拌形成溶液A;
2)在A溶液中加入3g十六烷基三甲基溴化铵(CTAB)并用保鲜膜密封在50℃磁力搅拌30min后移入水热釜,在180℃下溶剂热8h,水热釜冷却至室温后抽滤并用无水乙醇和去离子水各洗涤3遍后在-40℃冷冻干燥30h合成的蓬松的深紫色粉末为CoRu-ZIF-67前驱体;
3)取400mg的CoRu-ZIF-67粉体铺在刚玉瓷舟中置于充满氢氩气气氛的管式炉中,以5℃/min的升温速率,自室温升温至800℃保温1.5h,以10℃/min的降温速率降至300℃然后自然降温至室温,生成的黑色粉体为氮掺杂碳负载的钴钌纳米颗粒(CoRu/NC)。
实施例5:
1)首先,称取5.1928g分析纯的氯化钴、4.2633g分析纯的十二羰基三钌和13.136gC4H6N2溶于80ml的甲醇中在50℃磁力搅拌形成溶液A;
2)在A溶液中加入2g十六烷基三甲基溴化铵(CTAB)并用保鲜膜密封在60℃磁力搅拌60min后移入水热釜,在200℃下溶剂热6h,水热釜冷却至室温后抽滤并用无水乙醇和去离子水各洗涤4遍后在-38℃冷冻干燥48h合成的蓬松的深紫色粉末为CoRu-ZIF-67前驱体;
3)取500mg的CoRu-ZIF-67粉体铺在刚玉瓷舟中置于充满氢氩气气氛的管式炉中,以5℃/min的升温速率,自室温升温至900℃保温1h,以10℃/min的降温速率降至300℃然后自然降温至室温,生成的黑色粉体为氮掺杂碳负载的钴钌纳米颗粒(CoRu/NC)。
实施例6:
1)首先,称取14.2482g分析纯的乙酰丙酮钴、4.6252g分析纯的二茂钌和13.136gC4H6N2溶于70ml的甲醇中在50℃磁力搅拌形成溶液A;
2)在A溶液中加入3g十六烷基三甲基溴化铵(CTAB)并用保鲜膜密封在50℃磁力搅拌30min后移入水热釜,在180℃下溶剂热8h,水热釜冷却至室温后抽滤并用无水乙醇和去离子水各洗涤3遍后在-40℃冷冻干燥30h合成的蓬松的深紫色粉末为CoRu-ZIF-67前驱体;
3)取400mg的CoRu-ZIF-67粉体铺在刚玉瓷舟中置于充满氢氩气气氛的管式炉中,以5℃/min的升温速率,自室温升温至800℃保温1.5h,以10℃/min的降温速率降至300℃然后自然降温至室温,生成的黑色粉体为氮掺杂碳负载的钴钌纳米颗粒(CoRu/NC)。
图1为实施例1制备的CoRu/NC的X射线衍射图,CoRu/NC的X射线衍射图显示在25°附近出现一个凸起,这是因为石墨化碳的生成,38.4°和42.1°的衍射峰分别归属于Ru(PDF#06-0663)的(100)晶面和(002)晶面,44.1°左右的衍射峰归属于Co(PDF#15-0806)的(111)晶面和Ru(PDF#06-0663)的(101)晶面,说明有Co和Ru的生成。
图2为实施例1制备的CoRu/NC的SEM图,从CoRu/NC的SEM图中可以看出微观形貌为规则的十二面体,棱角分明,表面粗糙,面微向内凹陷,这是由于升温过程中结合水的挥发、有机溶剂的挥发造成、碳的石墨化过程中键的断裂造成,表面粗糙度增加有利于亲水和吸附,有利于催化反应的进行。
图3为实施例1制备的CoRu/NC的全解水LSV图,CoRu/NC的全解水LSV曲线显示10mA cm-2(该标准对应的太阳能制氢效率为12.3%)的过电位仅为270mV,小于商业铂碳和氧化铱全解水(10 mA cm-2的过电位为357mV),说明CoRu/NC的全解水催化性能优于商业化铂碳和氧化铱,具有更高的全解水效率。
需要说明的是,以上内容是对本发明所作的进一步详细说明,不能认定本发明的具体实施方式仅限于此,对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干简单的推演或替换,都应当视为属于本发明由所提交的权利要求书确定的保护范围。
Claims (5)
1.一种氮碳负载钴钌纳米粒子全解水电催化材料的制备方法,其特征在于,包括如下步骤:
1)首先称取分析纯的钴源、钌源和2-甲基咪唑溶于40~80ml的甲醇中搅拌至溶解形成钴离子浓度为0.05~0.5mol/L,钌离子浓度为0.005~0.25mol/L和2-甲基咪唑浓度为0.1~2mol/L的溶液A;
2)在A溶液中加入1~3g十六烷基三甲基溴化铵并用保鲜膜密封后移入水热釜,在120~200℃下溶剂热6~18h,水热釜冷却至室温后抽滤并洗涤、冷冻干燥,合成的蓬松的深紫色粉末为CoRu-ZIF-67前驱体;
3)取200~500mg的CoRu-ZIF-67粉体铺在刚玉瓷舟中置于充满氢氩气气氛的管式炉中,以2~5℃/min的升温速率,自室温升温至600~900℃,保温1~3h,以10℃/min的降温速率降至300℃,然后自然降温至室温,生成的黑色粉体为氮掺杂碳负载的钴钌纳米颗粒;
所述的钴源为硝酸钴、氯化钴或乙酰丙酮钴;
所述的钌源为乙酰丙酮钌、十二羰基三钌或二茂钌。
2.如权利要求1所述的氮碳负载钴钌纳米粒子全解水电催化材料的制备方法,其特征在于,所述步骤1)中的搅拌为在30~50℃温度下磁力搅拌。
3.如权利要求1所述的氮碳负载钴钌纳米粒子全解水电催化材料的制备方法,其特征在于,所述步骤2)中洗涤为用无水乙醇和去离子水各洗涤2~4遍。
4.如权利要求1所述的氮碳负载钴钌纳米粒子全解水电催化材料的制备方法,其特征在于,所述步骤2)中冷冻干燥为在-30~-40℃温度下冷冻干燥24~48h。
5.一种如权利要求1-4中任一项所述的制备方法制备的氮碳负载钴钌纳米粒子全解水电催化材料,其特征在于,微观形貌为规则的十二面体,棱角分明,表面粗糙,面微向内凹陷。
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