催化作用
酞菁
电化学
选择性
吸附
极性效应
替代(逻辑)
过渡金属
材料科学
金属
组合化学
化学
结晶学
光化学
纳米技术
电极
有机化学
物理化学
计算机科学
程序设计语言
作者
Weiwei Zhu,Suqin Liu,Kuangmin Zhao,Guanying Ye,Kui Huang,Zhen He
出处
期刊:Small
[Wiley]
日期:2023-09-15
卷期号:20 (4)
标识
DOI:10.1002/smll.202306144
摘要
Electron-donating/-withdrawing groups (EDGs/EWGs) substitution is widely used to regulate the catalytic performance of transition-metal phthalocyanine (MPc) toward electrochemical CO2 reduction, but the corresponding structure-activity relationships and regulation mechanisms are still ambiguous. Herein, by investigating a series of substitution-functionalized MPc (MPc-X), this work reveals a double-volcano-like relationship between the electron-donating/-withdrawing abilities of the substituents and the catalytic activities of MPc-X. The weak-EDG/-EWG substitution enhances whereas the strong-EDG/-EWG substitution mostly lowers the CO selectivity of MPc. Experimental and calculation results demonstrate that the electronic properties of the substituents influence the symmetry and energy of the highest occupied molecular orbitals of MPc-X, which in turn determine the CO2 adsorption/activation and lead to diverse CO2 reduction pathways on the EWG or EDG substituted MPc via different CO2 adsorption modes. This work provides mechanism insights that could be guidance for the design and regulation of molecular catalysts.
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