Main group elements in electrochemical hydrogen evolution and carbon dioxide reduction
Main-group elements are renowned for their versatile reactivities in organometallic chemistry, including CO 2 insertion and H 2 activation. However, electrocatalysts comprising a main-group element active site have not yet been widely developed for activating CO 2 or producing H 2 . Recently, resear...
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Veröffentlicht in: | Chemical communications (Cambridge, England) England), 2023-10, Vol.59 (79), p.11767-11779 |
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Sprache: | eng |
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Zusammenfassung: | Main-group elements are renowned for their versatile reactivities in organometallic chemistry, including CO
2
insertion and H
2
activation. However, electrocatalysts comprising a main-group element active site have not yet been widely developed for activating CO
2
or producing H
2
. 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 H
2
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 H
2
evolution reaction (HER) and on how their mechanisms resemble those of transition-metal-based electrocatalysts. Moreover, we discuss the CO
2
reduction reaction (CO
2
RR), another promising fuel-forming reaction, and emphasize the recent progress in including the main-group elements in the CO
2
RR. 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 CO
2
RR. However, the main-group elements assist the CO
2
RR by acting as co-catalysts. For example, alkali and alkaline earth metal ions (
e.g.
, Li
+
, Na
+
, K
+
, Rb
+
, Cs
+
, Mg
2+
, Ca
2+
, and Ba
2+
) are known for their Lewis acidities, which influence the thermodynamic landscape of the CO
2
RR 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 CO
2
RR.
Main group elements are promising for developing electrochemical |
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ISSN: | 1359-7345 1364-548X |
DOI: | 10.1039/d3cc03606e |