Electrocatalytic organic synthesis has attracted considerable research attention because it is an efficient and eco-friendly strategy for converting energy sources to value-added chemicals. Defect engineering is a promising strategy for regulating the electronic structure and charge density of electrocatalysts. It endows electrocatalysts with excellent physical and physicochemical properties and optimizes the adsorption energy of the reaction intermediates to reduce the kinetic barriers of the electrosynthesis reaction. Herein, the recent advances related to the use of electrocatalysts for organic synthesis with respect to defects are systematically reviewed. The roles of defects in anodic and cathodic reactions, such as the syntheses of alkanes, alkenes, alcohols, aldehydes, amides, and carboxylic acids, are reviewed. Furthermore, the relationship between the defective structure and electrocatalytic activity is discussed by combining experimental results and theoretical calculations. Finally, the challenges, opportunities, and development prospects of defective electrocatalysts are examined to promote the development of the field of electrocatalytic organic synthesis. This review is expected to help understand the vital role of defects in catalytic processes and the controllable synthesis of efficient electrocatalysts for the production of high-value chemicals.

Electrocatalytic valorization of biomass derivatives can be powered by electricity generated from renewable sources such as solar and wind energy. A shift from centralized, high-temperature, and energy-intensive processes to decentralized, low-temperature conversions is achieved, which meets the requirement of sustainable energy generation. This approach provides an efficient, green, and additive-free strategy for biomass derivative valorization, in which product selectivity could be easily regulated by the applied potential and electrocatalyst utilized. However, a scale-up application is still far from being completed due to the inability of conversion rates and selectivity to meet the industrialization requirements. A better understanding of the reaction mechanism and the development of high-efficiency and high-selectivity electrocatalysts are required to pave the path toward larger industrialization applications. Herein, we summarize the recent research progress in the electrocatalytic oxidation and hydrogenation of platform compounds such as furanic compounds and glycerol. In the literature, these three research areas are integrated to realize the scale-up application of the processes as mentioned above. The investigations of the mechanism are based on in situ techniques, theoretical calculations, and advanced electrocatalyst studies. Finally, the challenges and prospects in this topic are described. We expect that this review will provide the fundamental understanding and design guidelines to achieve efficient and high-selectivity catalysts and further facilitate the scale-up application of the electrocatalytic conversion of biomass derivatives.

Gas-involving electrochemical reactions, like oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER), are critical processes for energy-saving, environment-friendly energy conversion and storage technologies which gain increasing attention. The development of according electrocatalysts is key to boost their electrocatalytic performances. Dramatic efforts have been put into the development of advanced electrocatalysts to overcome sluggish kinetics. On the other hand, the electrode interfaces-architecture construction plays an equally important role for practical applications because these imperative electrode reactions generally proceed at triple-phase interfaces of gas, liquid electrolyte, and solid electrocatalyst. A desirable architecture should facilitate the complicate reactions occur at the triple-phase interfaces, which including mass diffusion, surface reaction and electron transfer. In this review, we will summarize some design principles and synthetic strategies for optimizing triple-phase interfaces of gas-involving electrocatalysis systematically, based on the electrode reaction process at the three-phase interfaces. It can be divided into three main optimization directions: exposure of active sites, promotion of mass diffusion and acceleration of electron transfer. Furthermore, we especially highlight several remarkable works with comprehensive optimization about specific energy conversion devices, including metal-air batteries, fuel cells, and water-splitting devices are demonstrated with superb efficiency. In the last section, the perspectives and challenges in the future are proposed.