TY - JOUR
T1 - Design of reaction-driven active configuration for enhanced CO2 electroreduction
AU - Chen, Shanyong
AU - Luo, Tao
AU - Li, Xiaoqing
AU - Chen, Kejun
AU - Wang, Qiyou
AU - Fu, Junwei
AU - Liu, Kang
AU - Ma, Chao
AU - Lu, Ying Rui
AU - Li, Hongmei
AU - Menghrajani, Kishan S.
AU - Liu, Changxu
AU - Maier, Stefan A.
AU - Chan, Ting Shan
AU - Liu, Min
N1 - Funding Information:
This study was financially supported by the Natural Science Foundation of China (Grant No. 21872174, 22002189, 22308387 and U1932148), International Science and Technology Cooperation Program (Grant No. 2017YFE0127800), Guangdong Basic and Applied Basic Research Foundation (Nos. 2021A1515110907 and 2023A1515011935), Ministry of Science and Technology, Taiwan (MOST 111-2113-M-213-001). The authors gratefully thank the National Synchrotron Radiation Research Center (NSRRC, the TLS 01C1 and TLS 16A1 beamlines, Taiwan) for XAFS measurement. We are grateful for resources from the High Performance Computing Center of Central South University. S.A.M. acknowledges the EPSRC Catalytic Plasmonics Programme (EP/W017075/1) and the Lee-Lucas Chair in Physics.
Funding Information:
This study was financially supported by the Natural Science Foundation of China (Grant No. 21872174, 22002189, 22308387 and U1932148), International Science and Technology Cooperation Program (Grant No. 2017YFE0127800), Guangdong Basic and Applied Basic Research Foundation (Nos. 2021A1515110907 and 2023A1515011935). The authors gratefully thank the National Synchrotron Radiation Research Center (NSRRC, the TLS 01C1 and TLS 16A1 beamlines, Taiwan) for XAFS measurement. We are grateful for resources from the High Performance Computing Center of Central South University. S.A.M. acknowledges the EPSRC Catalytic Plasmonics Programme (EP/W017075/1) and the Lee-Lucas Chair in Physics.
Publisher Copyright:
© 2024
PY - 2024/9
Y1 - 2024/9
N2 - Metal-nitrogen-carbon single-atom catalysts (SACs) have emerged as promising candidates for electrocatalytic CO2 reduction reaction. However, the perpendicular dz2 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 dz2. Theoretical and experimental analyses reveal that upshifting nickel site away substrate induces dxz, dyz, and dz2 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.
AB - Metal-nitrogen-carbon single-atom catalysts (SACs) have emerged as promising candidates for electrocatalytic CO2 reduction reaction. However, the perpendicular dz2 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 dz2. Theoretical and experimental analyses reveal that upshifting nickel site away substrate induces dxz, dyz, and dz2 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.
KW - 3d orbital tuning
KW - CO2 activation
KW - CO2 electroreduction
KW - Reaction-driven reconstruction
KW - Single-atom catalyst
UR - http://www.scopus.com/inward/record.url?scp=85195572211&partnerID=8YFLogxK
U2 - 10.1016/j.nanoen.2024.109873
DO - 10.1016/j.nanoen.2024.109873
M3 - Article
AN - SCOPUS:85195572211
SN - 2211-2855
VL - 128
JO - Nano Energy
JF - Nano Energy
IS - Part A
M1 - 109873
ER -
