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Developing robust electrocatalysts and advanced devices is important for electrochemical carbon dioxide (CO2) reduction toward the generation of valuable chemicals. We present herein a carbon‐confined indium oxide electrocatalyst for stable and efficient CO2 reduction. The reductive corrosion of oxidative indium to the metallic state during electrolysis could be prevented by carbon protection, and the applied carbon layer also optimizes the reaction intermediate adsorption, which enables both high selectivity and activity for CO2 reduction. In a liquid‐phase flow cell, the formate selectivity exceeds 90 % in a wide potential window from −0.8 V to −1.3 V vs. RHE. The continuous production of ca. 0.12 M pure formic acid solution is further demonstrated at a current density of 30 mA cm−2 in a solid‐state electrolyte mediated reactor. This work provides significant concepts in the parallel development of electrocatalysts and devices for carbon‐neutral technologies.

Oxygen electrocatalysis is of great significance in electrochemical energy conversion and storage. Many strategies have been adopted for developing advanced oxygen electrocatalysts to promote these technologies. In this invited contribution, recent progress in understanding the oxygen electrochemistry from theoretical and experimental aspects is summarized. The major categories of oxygen electrocatalysts, namely, noble‐metal‐based compounds, transition‐metal‐based composites, and nanocarbons, are successively discussed for oxygen reduction and evolution. Design strategies of various oxygen electrocatalysts and their relationship on the structure–activity–performance are comprehensively addressed with the perspectives. Finally, the challenge and outlook for advanced oxygen electrocatalysts are discussed toward energy conversion and storage technologies.

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Efficient and robust platinum-carbon electrocatalysts are of great significance for the long-term service of high-performance fuel cells. Here, we report a Pt alloy integrated in a cobalt-nitrogen-nanocarbon matrix by a multiscale design principle for efficient oxygen reduction reaction. This Pt integrated catalyst demonstrates an increased mass activity, 11.7 times higher than that of commercial Pt catalyst, and retains a stability of 98.7% after 30,000 potential cycles. Additionally, this integrated catalyst delivers a current density of 1.50 A cm−2 at 0.6 V in the hydrogen-air fuel cell and achieves a power density of 980 mW cm−2. Comprehensive investigations demonstrate that the synergistic contribution of components and structure in the platinum-carbon integrated catalyst is responsible for the high-efficiency ORR in fuel cells.

Inheritance and transformation: an in situ topological transformed NiCoFe-MOF nanosheet electrocatalyst exhibits highly efficient activity for water oxidation in an anion exchange membrane water electrolyzer.

Oxygen electrocatalysts are of great importance for the air electrode in zinc-air batteries (ZABs). Owing to the high specific surface area, controllable pore size and unsaturated metal active sites, metal–organic frameworks (MOFs) derivatives have been widely studied as oxygen electrocatalysts in ZABs. To date, many strategies have been developed to generate efficient oxygen electrocatalysts from MOFs for improving the performance of ZABs. In this review, the latest progress of the MOF-derived non-noble metal–oxygen electrocatalysts in ZABs is reviewed. The performance of these MOF-derived catalysts toward oxygen reduction, and oxygen evolution reactions is discussed based on the categories of metal-free carbon materials, single-atom catalysts, metal cluster/carbon composites and metal compound/carbon composites. Moreover, we provide a comprehensive overview on the design strategies of various MOF-derived non-noble metal–oxygen electrocatalysts and their structure-performance relationship. Finally, the challenges and perspectives are provided for further advancing the MOF-derived oxygen electrocatalysts in ZABs.

The rational design and development of highly efficient oxygen evolution reaction (OER) electrocatalysts is vital for the application of renewable energy devices. Recently, the strategy of defect engineering draws much attention due to its positive effect on regulating the electronic structure, and thus, promoting the electrocatalytic performance of various materials. In this review, the main focus is on the cation vacancy defects of transition metal‐based electrocatalysts; the latest progress in cation vacancy defect engineering for the electrocatalytic OER is summarized. The different effects of cation vacancy defects on OER are well discussed together with the reaction mechanism, mainly including improving the conductivity, optimizing the adsorption of key intermediates, guiding the surface reconstruction to form active species, and enhancing the long‐term stability. Then, methods to construct cation vacancy defects on different electrocatalysts and the characterization of cation vacancies are systematically introduced. Finally, the remaining challenges and future prospects of cation vacancy defect engineering for promoting OER performance are further proposed.