Shanyong Chen , Tao Luo , Xiaoqing Li , Kejun Chen , Qiyou Wang , Junwei Fu , Kang Liu , Chao Ma , Ying-Rui Lu , Hongmei Li , Kishan S. Menghrajani , Changxu Liu , Stefan A. Maier , Ting-Shan Chan , Min Liu
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引用次数: 0
Abstract
Metal-nitrogen-carbon single-atom catalysts (SACs) have emerged as promising candidates for electrocatalytic CO2 reduction reaction. However, the perpendicular orbital within planar metal site mainly interacts with *COOH, resulting in inferior CO2 activation. Inspired by reaction-driven active configuration, here we propose to upshift nickel single-atom away from nitrogen-carbon substrate, prominently promoting the interaction between CO2 and other d orbitals besides . Theoretical and experimental analyses reveal that upshifting nickel site away substrate induces , , and to hybridize with CO2, expediting CO2 conversion to *COOH. The planar and out-of-plane Ni-N sites are formed on carbon nanosheet (Ni1-N/CNS) and curved nanoparticle (Ni1-N/CNP), respectively, which is verified by X-ray absorption fine structure spectroscopy. Impressively, the Ni1-N/CNP presents CO Faradaic efficiency of 96.4 % at 500 mA cm−2 and energy conversion efficiency of 79.8 % in flow cell, outperforming Ni1-N/CNS and most SACs. This work highlights the simulation of reaction-driven active sites for efficient electrocatalysis.
金属-氮-碳单原子催化剂(SAC)已成为电催化二氧化碳还原反应的理想候选催化剂。然而,平面金属位点内垂直的 dz2 轨道主要与 *COOH 相互作用,导致 CO2 活化效果不佳。受反应驱动活性构型的启发,我们在此提出将镍单原子从氮碳基质上移,从而显著促进 CO2 与 dz2 以外的其他 d 轨道之间的相互作用。理论和实验分析表明,镍单原子远离基质会诱导 dxz、dyz 和 dz2 与 CO2 发生杂化,从而加速 CO2 向 *COOH 的转化。碳纳米片(Ni1-N/CNS)和弯曲纳米粒子(Ni1-N/CNP)上分别形成了平面和平面外的镍-N位点,X射线吸收精细结构光谱验证了这一点。令人印象深刻的是,Ni1-N/CNP 在 500 mA cm-2 时的 CO 法拉第效率为 96.4%,在流动池中的能量转换效率为 79.8%,优于 Ni1-N/CNS 和大多数 SAC。这项工作强调了模拟反应驱动活性位点以实现高效电催化。
期刊介绍:
Nano Energy is a multidisciplinary, rapid-publication forum of original peer-reviewed contributions on the science and engineering of nanomaterials and nanodevices used in all forms of energy harvesting, conversion, storage, utilization and policy. Through its mixture of articles, reviews, communications, research news, and information on key developments, Nano Energy provides a comprehensive coverage of this exciting and dynamic field which joins nanoscience and nanotechnology with energy science. The journal is relevant to all those who are interested in nanomaterials solutions to the energy problem.
Nano Energy publishes original experimental and theoretical research on all aspects of energy-related research which utilizes nanomaterials and nanotechnology. Manuscripts of four types are considered: review articles which inform readers of the latest research and advances in energy science; rapid communications which feature exciting research breakthroughs in the field; full-length articles which report comprehensive research developments; and news and opinions which comment on topical issues or express views on the developments in related fields.