Redox “Innocence” of Re(I) in Electrochemical CO 2 Reduction Catalyzed by Nanographene–Re Complexes
Redox “Innocence” of Re(I) in Electrochemical CO 2 Reduction Catalyzed by Nanographene–Re Complexes
复制标题
纳米石墨烯-Re配合物催化电化学CO 2 还原中Re(I)的氧化还原“无罪”
DOI：
10.1021/acs.inorgchem.8b01092
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发表时间：
2018
影响因子：
4.6
通讯作者：
Li, Liang-shi
中科院分区：
文献类型：
--
作者：
Schaugaard, Richard N.;Raghavachari, Krishnan;Li, Liang-shi
提高电催化CO2转化为有用化学品的能源效率是一个重大的科学挑战。最近，我们报道了使用胶体纳米石墨烯作为二亚胺配体来形成分子复合物Re（diimine）（CO）3Cl来应对这一挑战，从而显著提高了CO2还原潜力。在这项工作中，我们使用理论计算来研究纳米石墨烯配体在还原和反应途径中的作用。值得注意的是，我们的研究结果表明，金属中心仅仅提供了一个CO2的结合位点和纳米石墨烯配体与基底之间的电子转移管道，而不是在过程中改变其自身的氧化态。因此，尽管其具有多种氧化态，但Re在由纳米石墨烯复合物催化的CO2还原中是氧化还原“无辜的”。
Improving energy efficiency of electrocatalytic CO2conversion to useful chemicals poses a significant scientific challenge. Recently we reported on using a colloidal nanographene as the diimine ligand to form a molecular complex Re(diimine)(CO)3Cl to tackle this challenge, leading to significantly improved CO2reduction potential. In this work, we use theoretical computations to investigate the roles of the nanographene ligand in the reduction and the reaction pathways. Remarkably, our results show that the metal center merely provides a binding site for CO2and a conduit for electron transfer between the nanographene ligand and the substrate instead of changing its own oxidation state in the processes. Thus, despite its multiple oxidation states, the Re is redox “innocent” in the CO2reduction catalyzed by the nanographene complex.