催化学报

催化学报 ›› 2021, Vol. 42 ›› Issue (12): 2306-2312.DOI: 10.1016/S1872-2067(21)63903-7

• 论文 • 上一篇    下一篇

N,O共修饰的Ni纳米颗粒/氮掺杂介孔碳CO2高效电还原催化剂

王敏†, 解琦†, 陈会敏, 刘光波, 崔学晶, 姜鲁华*()   

  1. 青岛科技大学材料科学与工程学院纳米材料与电催化实验室, 山东青岛266042
  • 收稿日期:2020-12-12 接受日期:2020-12-12 出版日期:2021-12-18 发布日期:2021-09-10
  • 通讯作者: 姜鲁华
  • 作者简介:第一联系人：

    †共同第一作者.

  • 基金资助:
    山东省泰山学者项目(ts201712046);山东省重点研发项目(2019JZZY010905);山东省自然科学基金(ZR2020MB025)

Surface regulated Ni nanoparticles on N-doped mesoporous carbon as an efficient electrocatalyst for CO2 reduction

Min Wang†, Qi Xie†, Huimin Chen, Guangbo Liu, Xuejing Cui, Luhua Jiang*()   

  1. Nanomaterials and Electrocatalysis Laboratory, College of Materials and Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China
  • Received:2020-12-12 Accepted:2020-12-12 Online:2021-12-18 Published:2021-09-10
  • Contact: Luhua Jiang
  • About author:* Tel/Fax: +86-532-84022907; E-mail: luhuajiang@qust.edu.cn
    First author contact:

    †These authors contributed equally to this work.

  • Supported by:
    This work was supported by Taishan Scholar Program of Shandong Province(ts201712046);Key Research and Development Programme of Shandong Province(2019JZZY010905);Natural Science Foundation of Shandong Province(ZR2020MB025)

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摘要：

利用可再生电力能源将CO2电还原(CO2RR)为高附加值燃料和化学品(CO、甲酸盐和碳氢化合物等)是一种高效、绿色的CO2资源化利用新技术. 然而,由于CO2分子中双键难以活化, 且存在析氢竞争反应, 即使对于CO2电还原为CO这一简单反应, 除少数贵金属(Au、Ag和Pd及其合金)外, 当前大多数电催化剂对产物CO的选择性和活性仍较低. 因此, 开发高效、稳定且廉价的CO2RR催化剂具有重要意义.

过渡金属Ni储量高、成本低, 是潜在的CO2RR催化剂. 然而, 受限于Ni对*H及*CO等中间物种相对强的吸附能力, Ni基催化剂催化生成产物CO的活性和选择性较低. 近年来研究表明, 通过对Ni基材料进行表面修饰, 可以调控Ni表面与中间物种的吸附强度, 从而有效提升Ni基催化剂对CO2RR反应的活性和选择性.

鉴于此, 本文通过N, O共调控的策略对负载于N掺杂介孔碳上的Ni纳米颗粒进行表面修饰, 制得的N,O-Ni/CMK3催化剂能够高效、高选择性地将CO2电还原为CO. X射线衍射、高角度环形暗场扫描透射电子显微镜和X射线光电子能谱等表征结果表明, N,O-Ni/CMK3中的Ni纳米颗粒由金属Ni核和N掺杂的NiO壳组成, 即Ni纳米颗粒表面被N,O共调控, 这种独特的表面使其表现出与金属Ni不同的CO2RR催化性能. 电化学测试结果表明, 在0.5 M KHCO3电解液中, N,O-Ni/CMK3催化剂表现出较好的选择性(生成CO法拉第效率达97%)、活性(CO分电流密度为13.01 mA cm‒1)和转换频率(4.25 s‒1). 表征结果表明, N, O共同调控的Ni是该催化反应的活性中心. 此外, 得益于N,O共调控的Ni表面, N,O-Ni/CMK3催化剂比O调控的Ni催化剂具有更好的电化学稳定性.

本文通过调节Ni催化剂的表面化学环境来调控催化剂与反应中间物种的吸附强度, 显著提高了Ni基催化剂对CO2RR反应的催化活性和CO选择性, 为开发高活性、高选择性的过渡金属催化剂提供了新思路.

关键词: CO2电还原反应, Ni纳米颗粒, N掺杂的介孔碳, 表面调控, 高选择性

Abstract:

Low cost, highly selective and efficient electrocatalysts for CO2 reduction reaction (CO2RR) is crucial for lowering the global carbon footprint and mitigating energy shortages. Here, we first report a highly selective and efficient electrocatalyst for CO2RR to CO using a surface-regulated Ni nanoparticles supported on N-doped CMK-3 (N,O-Ni/CMK3). Compared with most Ni metal catalysts previously reported with severe competitive hydrogen evolution during the CO2RR, the N,O-Ni/CMK3 catalyst presents a superior CO faradaic efficiency of about 97%, a high CO partial current density (13.01 mA cm-1) and turnover frequency (4.25 s-1). The comprehensive characterization provides evidence that the N,O co-regulated Ni acts as the active center. Taking advantage of the N, O co-regulated chemical environment, N,O-Ni/CMK3 also displays a decent stability at negative potentials. Our work paves a novel approach for developing transition metal catalysts for CO2RR with enhanced activity and selectivity via regulating surface chemical environment.

Key words: CO2 electro-reduction reaction, Ni nanoparticle, N-doped mesoporous carbon, Surface regulation, High selectivity