泡沫镍负载Co-MoC@N-CNS/CNT作为自支撑电极用于全水分解

doi:10.1016/S1872-2067(19)63406-6

催化学报 ›› 2019, Vol. 40 ›› Issue (9): 1352-1359.DOI: 10.1016/S1872-2067(19)63406-6

泡沫镍负载Co-MoC@N-CNS/CNT作为自支撑电极用于全水分解

邢江南^a, 林斐^a, 黄柳韬^a, 司玉昌^b, 王一菁^a, 焦丽芳^a

a 南开大学化学学院先进能源材料化学教育部重点实验室, 天津 300071;
b 中国人民武装警察部队后勤学院, 天津 300309

收稿日期:2019-03-31 出版日期:2019-09-18 发布日期:2019-07-06
通讯作者: 焦丽芳, 司玉昌
基金资助:
国家自然科学基金（51622102，51571124，21421001）；高等学校学科创新引智计划（111计划，B12015）；天津市自然科学基金（18ZXJMTG00040，16PTSYJC00030）；中央高校基本科研业务费专项资金.

Coupled cobalt-doped molybdenum carbide@N-doped carbon nanosheets/nanotubes supported on nickel foam as a binder-free electrode for overall water splitting

Jiangnan Xing^a, Fei Lin^a, Liutao Huang^a, Yuchang Si^b, Yijing Wang^a, Lifang Jiao^a

a Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Renewable Energy Conversion and Storage Center, College of Chemistry, Nankai University, Tianjin 300071, China;
b Logistics University of People's Armed Police Force, Tianjin 300309, China

Received:2019-03-31 Online:2019-09-18 Published:2019-07-06
Contact: S1872-2067(19)63406-6
Supported by:
This work was financially supported by the National Natural Science Foundation of China (51622102, 51571124, 21421001), the 111 Project (B12015), the Natural Science Foundation of Tianjin (18ZXJMTG00040, 16PTSYJC00030), and the Fundamental Research Funds for the Central Universities.

摘要/Abstract

摘要： 在众多的过渡金属催化剂中，碳化钼因具有类贵金属电子结构、高电子导电性、宽pH适用范围，优异的催化活性和稳定性等优点受到科研工作者的广泛关注.密度泛函理论计算（DFT）得出的"火山图"表明碳化钼具有较强的氢吸附能，而Co具有较弱的氢吸附能.已有报道指出将Co与碳化钼化学耦合能够促使其展现相对适中的氢吸附能，从而提高材料的本征催化活性.此外，碳化钼很少被认为是一种氧析出反应催化剂，而Co则被广泛认为是高效且稳定的碱性水分解析氧催化剂.基于此，我们提出化学耦合Co与碳化钼能够同时提升材料的析氧催化性能.值得一提的是，自支撑材料可直接用作工作电极以避免粘结剂（覆盖活性位，阻碍催化过程中传质的发生，增加电子转移阻抗）的使用.然而，目前关于自支撑碳化钼催化剂的研究鲜有报道.
本文采用简单的水热法制备了泡沫镍负载钴掺杂碳化钼耦合的碳纳米片和碳纳米管（Co-MoC@N-CNS/CNT）自支撑电极.通过X射线粉末衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）、X射线和紫外光电子能谱（XPS、UPS）等表征手段对产物形貌结构进行了表征，利用电化学工作站对其水分解催化性能进行了研究.通过调控前驱体制备时的钴源浓度得到了一系列不同Co掺杂量的样品.UPS测试表明，Co成功掺杂到MoC晶体结构中能够显著增加其费米能级附近的电子密度，从而优化其HER动力学.与纯相的MoC和Co单质相比，掺杂后样品的催化活性得到显著提升.其优异的电化学活性可归结为如下几点：（1）2D纳米片和1D纳米线交错形成的3D纳米结构可有效暴露更多的活性位点和促进电子转移；（2） Co掺杂能够优化MoC晶体结构费米能级附近的电子结构，从而提升其HER动力学；（3） N-CNS/CNT不仅能够保护Co和MoC免于碱性腐蚀，还能促进纳米颗粒和碳基质间快速的电子传递.
上述结果表明，通过合理设计碳化钼的组成和纳米结构可获得具有高活性和稳定性的双功能催化剂，为高性能催化剂的开发和利用开辟了新的途径.

关键词: 碳化钼, 钴掺杂, 自支撑电极, 全水分解

Abstract: In an attempt to develop low-cost, non-noble-metal bifunctional electrocatalysts for water electrolysis in alkaline media, cobalt-doped molybdenum carbide@N-doped carbon nanosheets/nanotubes were fabricated by using C₃N₄ as the carbon source on a 3D porous nickel foam substrate. Benefiting from the optimized electronic structure and enhanced mass and charge transport, as well as the 3D conducting pathway, Mo_xCo_y@N-CNSs/CNTs shows superior performance towards both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline medium. The optimal electrocatalyst is Mo₂Co₁@N-CNSs/CNTs, which reveals a current density of 10 mA cm^-2 at the low overpotentials of 99 mV and 300 mV for the HER and OER, respectively, and a relatively low cell voltage (1.63 V) for the overall water electrolysis. The method of optimizing the composition and nanostructure of a material provides a new avenue for the development and utilization of high-performance electrocatalysts.

Key words: Molybdenum carbide, Cobalt doping, Self-supported electrode, Overall water splitting

邢江南, 林斐, 黄柳韬, 司玉昌, 王一菁, 焦丽芳. 泡沫镍负载Co-MoC@N-CNS/CNT作为自支撑电极用于全水分解[J]. 催化学报, 2019, 40(9): 1352-1359.

Jiangnan Xing, Fei Lin, Liutao Huang, Yuchang Si, Yijing Wang, Lifang Jiao. Coupled cobalt-doped molybdenum carbide@N-doped carbon nanosheets/nanotubes supported on nickel foam as a binder-free electrode for overall water splitting[J]. Chinese Journal of Catalysis, 2019, 40(9): 1352-1359.

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泡沫镍负载Co-MoC@N-CNS/CNT作为自支撑电极用于全水分解

Coupled cobalt-doped molybdenum carbide@N-doped carbon nanosheets/nanotubes supported on nickel foam as a binder-free electrode for overall water splitting

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