密度泛函理论
化学
X射线光电子能谱
无机化学
材料科学
结晶学
计算化学
化学工程
工程类
作者
Ying Zhang,Hailei Jiang,Anuj Kumar,Hongchuan Zhang,Zongge Li,Tongxin Xu,Yuan Pan,Yaqun Wang,Zhiming Liu,Guoxin Zhang,Yan Zhang
摘要
Abstract Design of supportive atomic sites with a controllably adjusted coordinating environment is essential to advancing the reduction of CO 2 to value‐added fuels and chemicals and to achieving carbon neutralization. Herein, atomic Ni (Zn) sites that are uniquely coordinated with ternary Zn (Ni)/N/O ligands were successfully decorated on formamide‐derived porous carbon nanomaterials, possibly forming an atomic structure of Ni(N 2 O 1 )‐Zn(N 2 O 1 ), as studied by combining X‐ray photoelectron spectroscopy and X‐ray absorption spectroscopy. With the mediation of additional O coordination, the Ni–Zn dual site induces significantly decreased desorption of molecular CO. The NiZn‐NC decorated with rich Ni(N 2 O 1 )‐Zn(N 2 O 1 ) sites remarkably gained >97% CO Faraday efficiency over a wide potential range of ‒0.8 to ‒1.1 V (relative to reversible hydrogen electrode). Density functional theory computations suggest that the N/O dual coordination effectively modulates the electronic structure of the Ni–Zn duplex and optimizes the adsorption and conversion properties of CO 2 and subsequent intermediates. Different from the conventional pathway of using Ni as the active site in the Ni–Zn duplex, it is found that the Ni‐neighboring Zn sites in the Ni(N 2 O 1 )‐Zn(N 2 O 1 ) coordination showed much lower energy barriers of the CO 2 protonation step and the subsequent dehydroxylation step.
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