Herein, we report hierarchical 3D NiMn-layered double hydroxide (NiMn-LDHs) shells grown on conductive silver nanowire (Ag NWs) cores as efficient, low-cost, and durable oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) bifunctional electrocatalysts for metal–air batteries. The hierarchical 3D architectured Ag NW@NiMn-LDH catalysts exhibit superb OER/ORR activities in alkaline conditions. The outstanding bifunctional activities of Ag NW@NiMn-LDHs are essentially attributed to increasing both site activity and site populations. The synergistic contributions from the hierarchical 3D open-pore structure of the LDH shells, improved electrical conductivity, and small thickness of the LDHs shells are associated with more accessible site populations. Moreover, the charge transfer between Ag cores and metals of LDH shells and the formation of defective and distorted sites (less coordinated Ni and Mn sites) strongly enhance the site activity. Thus, Ag NW@NiMn-LDH hybrids exhibit a 0.75 V overvoltage difference between ORR and OER with excellent durability for 30 h, demonstrating the distinguished bifunctional electrocatalyst reported to date. Interestingly, the homemade rechargeable Zn–air battery using the hybrid Ag NW@NiMn-LDHs (1:2) catalyst as the air electrode exhibits a charge–discharge voltage gap of ∼0.77 V at 10 mA cm–2 and shows excellent cycling stability. Thus, the concept of the hierarchical 3D architecture of Ag NW@NiMn-LDHs considerably advances the practice of LDHs toward metal–air batteries and oxygen electrocatalysts.

Developing efficient and durable bifunctional electrocatalysts for oxygen reduction and evolution reaction (ORR/OER) is highly desirable in energy conversion and storage systems. This study prepares nickel–ruthenium layered double hydroxide (NiRu-LDHs) nanosheets subjected to decoration with conductive silver nanoparticles (Ag NP/NiRu-LDHs), which interestingly induce their multivacancies associated with catalytic site activity and populations. The as-prepared Ag NP/NiRu-LDH shows excellent catalytic activity toward both OER and ORR features with low onset overpotentials of 0.21 V and −0.27 V, respectively, with a 0.76 V potential gap between OER potential at 10 mA cm–2 and ORR potential at −3 mA cm–2, demonstrating that it is the preeminent bifunctional electrocatalyst reported to date. Compared with pristine NiRu-LDHs, the resulting Ag NP/NiRu-LDHs nanosheets require only an overpotential of 0.31 V to deliver 10 mA cm–2 with excellent durability. The superb bifunctional performance of Ag NP/NiRu-LDH is ascribed to the formation of multivacancies, mutual benefits of synergistic effect between metal LDHs and silver nanoparticles, and increased accessible active sites together with site activity are the key to the perceived performance. This work provides a new strategy to decorate LDHs and to engineer multivacancies to enhance site activity and populations simultaneously as ORR/OER bifunctional electrocatalysts.

Electrochemical energy storage and conversion devices play a key role in the development of clean, sustainable, and efficient energy systems to meet the sustainable growth of our society. However, challenging issues including the sluggish kinetics of oxygen electrode reactions involving the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are present, limiting the implementation of devices such as metal‐air batteries, water electrolyzers, and regenerative fuel cells. In this review, various monometallic and bimetallic transition metal oxides (TMOs) and hydroxides are summarized in terms of their application for ORR/OER, in which the merits and demerits of various precious metal and carbon‐based metal oxide materials are discussed, with requirements for better electrocatalysts and catalyst support being introduced as well. Following this, different approaches to improve catalytic activity such as the introduction of doping and defects, the manipulation of crystal facets, and the engineering of supports, compositions, and morphologies are summarized in which TMOs with improved ORR/OER catalytic activities can be synthesized, further improving the speed, stability, and polarization of electrochemical energy storage and conversion devices. Finally, perspectives into the improvement of performance and the better understanding of ORR/OER mechanisms for bifunctional electrocatalysts using in situ spectroscopic techniques and density functional theory calculations are also discussed.

Among many alternatives, CO2 electroreduction (CO2ER) is an emerging technology to alleviate its level in the atmosphere and simultaneously to produce essential products containing high energy density using various electrocatalysts. Cu‐based mono‐ and bimetallics are electrocatalysts of concerns in this work due to the material's abundance and versatility. Intrinsic factors affecting the CO2ER are first analyzed, whereby understanding and characterizing the surface features of electrocatalysts are addressed. An X‐ray absorption spectroscopy‐based methodology is discussed to determine electronic and structural properties of electrocatalyst surface which allows the prediction of reaction mechanism and establishing the correlation with reduction products. The selectivity and faradaic efficiency of products highly depend on the quality of surface modification. Preparation and modification of electrocatalyst surfaces through various techniques are critical to increase the number of activity sites and the corresponding site activity. Mechanisms of CO2ER are complicate and thus are discussed in accordance with main products of interests. The authors try to concisely compile the most interesting, recent, and reasonable ideas that are agreeable to experimental results. Finally, this review provides an outlook for designing better Cu and Cu‐based bimetallic catalysts to obtain selective products through CO2ER.

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