Revealing a Double-Volcano-Like Structure-Activity Relationship for Substitution-Functionalized Metal-Phthalocyanine Catalysts toward Electrochemical CO2 Reduction.
Revealing a Double-Volcano-Like Structure-Activity Relationship for Substitution-Functionalized Metal-Phthalocyanine Catalysts toward Electrochemical CO2 Reduction.
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DOI：
10.1002/smll.202306144
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发表时间：
2023-09
期刊：
影响因子：
13.3
通讯作者：
Weiwei Zhu;Suqin Liu;Kuangmin Zhao;Guanying Ye;Kui Huang;Zhen He
中科院分区：
文献类型：
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作者：
Weiwei Zhu;Suqin Liu;Kuangmin Zhao;Guanying Ye;Kui Huang;Zhen He
供电子/吸电子基团（EDGs/EWG）取代被广泛用于调节过渡金属酞菁（MPc）对CO2电化学还原的催化性能，但其构效关系和调控机制尚不明确。本文通过对一系列取代基功能化的MPc（MPc-X）的研究，揭示了取代基的供/吸电子能力与MPc-X催化活性之间的双火山式关系。弱EDG/-EWG取代提高了MPc的CO选择性，而强EDG/-EWG取代降低了MPc的CO选择性。实验和计算结果表明，取代基的电子性质影响MPc-X分子最高占据轨道的对称性和能量，从而决定了CO2的吸附/活化，并导致EWG或EDG取代MPc通过不同的CO2吸附模式实现不同的CO2还原途径.这一工作为分子催化剂的设计和调控提供了机理上的指导。
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.