Main group elements in electrochemical hydrogen evolution and carbon dioxide reduction
Main group elements in electrochemical hydrogen evolution and carbon dioxide reduction
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电化学析氢和二氧化碳还原的主族元素
DOI：
10.1039/d3cc03606e
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发表时间：
2023
影响因子：
4.9
通讯作者：
Jiang, Jianbing “Jimmy”
中科院分区：
文献类型：
--
作者：
Sinha, Soumalya;Jiang, Jianbing “Jimmy”
主族元素以其在有机金属化学中的多功能反应性而闻名，包括CO2插入和H2活化。然而，包含主族元素活性位点的电催化剂尚未被广泛开发用于活化CO2或产生H2。最近，研究集中在基于主族元素的电催化剂上，其在与燃料形成反应相关的氧化还原体系中具有活性。这些研究已经确定，基于重主族元素的电催化剂的催化性能通常与基于过渡金属的电催化剂的催化性能相似。我们的小组最近报道了在分子催化剂的设计中包括主族元素的范围，并探索了它们在氧化还原催化中的应用，例如在两个质子（H+）和两个电子（e-）耦合时产生H2。这篇专题文章概述我们在开发活性位含主族元素的分子电催化剂方面的研究工作。此外，我们强调了它们对速率决定步骤的影响，从而提高了多H +/多e-转移催化的反应速率和产物选择性。特别是，我们专注于我们最近报道的分子Sn或Sb为中心的大环化合物的电催化析氢反应（HER）的性能，以及它们的机制如何类似于过渡金属为基础的电催化剂。此外，我们讨论了CO2还原反应（CO2 RR），另一个有前途的燃料形成反应，并强调最近的进展，包括主族元素的CO2 RR。虽然主族元素被发现在分子催化剂的活性位点处并且被嵌入电极材料中以用于研究HER，但是带有主族元素的分子催化剂通常不用于CO2 RR。然而，主族元素通过充当助催化剂来辅助CO2 RR。例如，碱金属和碱土金属离子（例如，Li+、Na+、K+、Rb+、Cs+、Mg 2+、Ca 2+和Ba 2+）因其刘易斯酸性而闻名，其影响CO2 RR的热力学景观和产物选择性。相反，第13、14和15族中的元素主要用作催化材料制备中的掺杂剂。总之，本文确定了主族元素为基础的分子电催化剂和材料HER和CO2 RR。
Main-group elements are renowned for their versatile reactivities in organometallic chemistry, including CO2 insertion and H2 activation. However, electrocatalysts comprising a main-group element active site have not yet been widely developed for activating CO2 or producing H2. Recently, research has focused on main-group element-based electrocatalysts that are active in redox systems related to fuel-forming reactions. These studies have determined that the catalytic performances of heavier main-group element-based electrocatalysts are often similar to those of transition-metal-based electrocatalysts. Our group has recently reported the scope of including the main-group elements in the design of molecular catalysts and explored their applications in redox catalysis, such as the generation of H2 upon coupling of two protons (H+) and two electrons (e−). This feature article summarizes our research efforts in developing molecular electrocatalysts comprising main-group elements at their active sites. Furthermore, we highlight their influence on the rate-determining step, thereby enhancing the reaction rate and product selectivity for multi-H+/multi-e− transfer catalysis. Particularly, we focus on the performance of our recently reported molecular Sn- or Sb-centered macrocycles for electrocatalytic H2 evolution reaction (HER) and on how their mechanisms resemble those of transition-metal-based electrocatalysts. Moreover, we discuss the CO2 reduction reaction (CO2RR), another promising fuel-forming reaction, and emphasize the recent progress in including the main-group elements in the CO2RR. Although the main-group elements are found at the active sites of the molecular catalysts and are embedded in the electrode materials for studying the HER, molecular catalysts bearing main-group elements are not commonly used for CO2RR. However, the main-group elements assist the CO2RR by acting as co-catalysts. For example, alkali and alkaline earth metal ions (e.g., Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, and Ba2+) are known for their Lewis acidities, which influence the thermodynamic landscape of the CO2RR and product selectivity. In contrast, the elements in groups 13, 14, and 15 are primarily used as dopants in the preparation of catalytic materials. Overall, this article identifies main-group element-based molecular electrocatalysts and materials for HER and CO2RR.