Tuning the Coordination Microenvironment of Central Fe Active Site to Boost Water Electrolysis and Oxygen Reduction Activity
Tuning the Coordination Microenvironment of Central Fe Active Site to Boost Water Electrolysis and Oxygen Reduction Activity
复制标题
调节中心铁活性位点的协调微环境以促进水电解和氧还原活性
作者：
Shuhua Wang;Baibiao Huang;Ying Dai;Wei Wei
在多相催化中，单原子催化剂是许多反应的前沿和重要原型，揭示内在的结构-活性关系是目前的一项关键任务，但仍然具有挑战性。本文采用第一性原理计算方法研究了铁卟啉中FeXYiN 3-i（X，Y = B，C，O，P和S; i= 0，1）基团的水电解和氧还原性能，旨在揭示调节活性金属原子的配位微环境如何以及为什么能够提高活性。可以得出结论，打破配位壳层对称性打破了公认的标准标度关系，调整了O吸附行为，从而优化了析氧反应（OER）活性，例如，达到0.17V的极低过电位。结合铁原子的自旋构型和配位场理论，可以很好地解释OER活性的显著提高。本文强调了中心金属原子配位微环境在电催化研究中的重要意义。
In heterogeneous catalysis, single-atom catalysts are the frontier and important prototypes for many reactions, and revealing the intrinsic structure-activity relationship is presently a critical task, but remains challenging. In this work, water electrolysis and oxygen reduction performances of FeXYi N3 -i (X, Y = B, C, O, P and S; i= 0, 1) moiety in Fe-porphyrin are studied by the first-principles calculations, aiming at unraveling how and why tuning the coordination microenvironment of the active metal atom can improve the activity. It can be concluded that breaking the coordination shell symmetry breaks the well-accepted standard scaling relationship, adjusts O adsorption behavior and thus optimizes the oxygen evolution reaction (OER) activity, for example, to an extremely low overpotential of 0.17V. In combination with the Fe atom spin configuration and ligand field theory, the dramatically improved OER activity can be well explained. In the present work, the significance of the coordination microenvironment of central metal atom in studies of electrocatalysis is highlighted.