High current density microkinetic and electronic structure analysis of CO2 reduction using Co and Fe complexes on gas diffusion electrode
High current density microkinetic and electronic structure analysis of CO2 reduction using Co and Fe complexes on gas diffusion electrode
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DOI：
10.1016/j.checat.2022.03.010
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发表时间：
2022-04
期刊：
影响因子：
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通讯作者：
Xiaofei Lu;B. Dereli;Tatsuya Shinagawa;M. Eddaoudi;L. Cavallo;K. Takanabe
中科院分区：
文献类型：
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作者：
Xiaofei Lu;B. Dereli;Tatsuya Shinagawa;M. Eddaoudi;L. Cavallo;K. Takanabe
为满足工业应用对高电流密度的要求，采用气体扩散电极研究了Co或Fe配合物电催化CO2还原为CO的反应机理.我们的实验和理论计算结果一致表明，铁基分子催化剂表现出更积极的氧化还原电位相关的CO2电催化，但不利于脱附所产生的CO，特别是在高过电位，未能实现可观的反应速率。不同的是，异质化的钴基分子复合物被发现是宽容的高覆盖率的CO在稳定状态下的活性位点上，并实现了超过100 mA cm− 2的速度向独家CO的演变。密度泛函理论计算不仅揭示了四苯基卟啉和酞菁在电催化CO2还原过程中的非无害氧化还原反应，而且证实了Co和Fe配合物之间独特的反应途径，特别是CO2和CO吸附的能量学.
Reaction mechanisms of electrocatalytic CO2reduction into CO over Co or Fe complexes were examined using gas diffusion electrodes to meet the requirement of high current densities for industrial deployment. Our experimental and theoretical calculation results consistently revealed that the Fe-based molecular catalysts exhibited more positive redox potentials relevant to CO2electrocatalysis but disfavored the desorption of generated CO, especially at high overpotentials, failing to achieve appreciable reaction rates. Distinctively, the heterogenized Co-based molecular complexes were found to be tolerant to the high coverage of CO at steady state on the active site and achieved rates exceeding 100 mA cm−2toward exclusive CO evolution. Density-functional theory calculations not only disclosed the redox non-innocent tetraphenylporphyrins and phthalocyanines during electrocatalytic CO2reduction but also corroborated the energetics, especially for CO2and CO adsorption, accounting for distinctive reaction pathways between Co and Fe complexes.