Department of Chemistry, Tsinghua University, Beijing 100084, China.
State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China.
Chem Commun (Camb). 2022 Jan 20;58(7):897-907. doi: 10.1039/d1cc06254a.
Oxidation reactions provide a wide range of important chemicals in industry; however, most of these chemicals are produced from fossil feedstocks. As a candidate of oxygen evolution reaction (OER), the electrooxidation of biomass platform chemicals instead of a petroleum source offers a sustainable and atom-economic avenue toward organic oxygenates, with additional benefits when coupled with renewable electricity driven processes. This highlight article describes the representative examples in this nascent area, including oxidative dehydrogenation, coupling, and cleavage. We classify the examples into inner-sphere and outer-sphere electrode reactions based on the classical electrocatalysis concept for better understanding of the reaction mechanism. Moreover, we highlight the recent progress in oxidative biomass electrorefining inner-sphere anodic reactions, which are strongly dependent on the nature of the electrode material. Particularly, the understanding of the formation of reactive oxygen species, adsorption of substrates, and reconstruction of anode materials is presented. Finally, the existing challenges and perspectives are discussed.
氧化反应为工业提供了广泛的重要化学品；然而，这些化学品大多是由化石原料生产的。作为氧析出反应 (OER) 的候选物，生物质平台化学品的电化学生产代替石油资源为有机含氧物提供了一条可持续和原子经济的途径，当与可再生电力驱动的过程结合时，还具有额外的好处。本文重点介绍了这一新兴领域的代表性实例，包括氧化脱氢、偶联和断裂。我们根据经典的电催化概念将这些实例分为内球和外球电极反应，以便更好地理解反应机制。此外，我们还重点介绍了氧化生物质电精炼中内球阳极反应的最新进展，该反应强烈依赖于电极材料的性质。特别是，介绍了活性氧物种的形成、底物的吸附和阳极材料的重构的理解。最后，讨论了存在的挑战和展望。
