Primary- and secondary-sphere effects of amine substituent position on rhenium bipyridine electrocatalysts for CO2 reduction
Primary- and secondary-sphere effects of amine substituent position on rhenium bipyridine electrocatalysts for CO2 reduction
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胺取代基位置对联吡啶铼电催化剂 CO2 还原的初级和次级影响
DOI：
10.1016/j.poly.2022.115933
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发表时间：
2022
期刊：
影响因子：
2.6
通讯作者：
Marinescu, Smaranda C.
中科院分区：
文献类型：
--
作者：
Hellman, Ashley N.;Intrator, Jeremy A.;Choate, Jeremiah C.;Velazquez, David A.;Marinescu, Smaranda C.
众所周知，具有生物启发部分的电催化剂为化石燃料燃烧产物如二氧化碳有效转化为增值产物提供了有利的品质。本文提出了一类在联吡啶骨架的4，4 ′-，5，5 ′-和6，6 ′-位上带有NH 2侧基的Re（bpy）（CO）3Cl电催化剂，目的是确定初级和次级球相互作用对CO2还原为CO的影响。CO2下的循环伏安研究表明，6，6 ′-NH 2-Re的催化起始电位更正，这表明在催化过程中，可用的侧质子与金属中心的接近是有益的。控制电位电解研究表明，与6，6 ′-NH 2-Re类似，4，4 ′-NH 2-Re的法拉第效率（FE）与催化电位相关，在−2.40 V时达到最大值91%。该FE大于6，6 ′-NH 2-Re的观察值，但发生在更负的电位下。通过密度泛函理论（DFT）计算比较了这些配合物的HOMO-LUMO能隙，确定了4，4 ′-NH 2-Re > 6，6 ′-NH 2-Re > 5，5 ′-NH 2-Re的趋势。Mulliken电子布居分析表明，6，6 ′-NH 2-Re金属中心的电子密度高于其相关同系物，这与电解研究结果一致，电解研究表明6，6 ′-NH 2-Re更有利于CO2还原。最后，重要的是适当地平衡各种催化参数以提供最大的总催化活性。
It is well-established that electrocatalysts with biologically inspired moieties provide advantageous qualities for the efficient transformation of fossil fuel combustion products, such as carbon dioxide, into value-added products. Herein, we present a family of Re(bpy)(CO)3Cl electrocatalysts with pendant NH2groups in the 4,4′-, 5,5′-, and 6,6′-positions of the bipyridine backbone with the objective of determining the effects of combined primary- and secondary-sphere interactions on the reduction of CO2to CO. Cyclic voltammetry studies under CO2indicate that the catalytic onset potential is more positive for 6,6′-NH2-Re, indicating that proximity of the available pendant protons to the metal center is beneficial during catalysis. Controlled potential electrolysis studies demonstrate that, similar to 6,6′-NH2-Re, 4,4′-NH2-Re displays a dependence of Faradaic efficiency (FE) on catalytic potential, reaching a maximum FECOof 91% at −2.40 V. This FE is greater than that observed for 6,6′-NH2-Re but occurs at a more negative potential. Density functional theory (DFT) calculations were performed to compare the HOMO-LUMO gap of these complexes, and the following trend of 4,4′-NH2-Re > 6,6′-NH2-Re > 5,5′-NH2-Re was determined. Mulliken electron population analysis indicates a greater degree of electron density on the metal center for 6,6′-NH2-Re compared to its related congeners, in agreement with the electrolysis studies which illustrate a more favorable CO2reduction for 6,6′-NH2-Re. Ultimately, it is important that the various catalytic parameters are properly balanced to provide the greatest overall catalytic activity.
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DOI：
--
发表时间：
2021
期刊：
影响因子：
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作者：
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影响因子：
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