Metallic bismuth (Bi) shows great promise in electrocatalytic CO2 reduction into formate. However, the direct synthesis of active and stable Bi electrocatalysts remains a grand challenge. Herein, we present an in-plane confined hydrogen-reduction strategy for in situ growth of edge-modified Bi nanoribbons, which enables enhanced and stable reduction of CO2 into formate. Density functional theory calculations suggest that the synergistic effect of a preferentially exposed (113) facet and abundant Bi–O edge sites can contribute to a reduced formation energy for the formate intermediate. Moreover, in situ Raman characterizations reveal the Bi–O edge sites can remain stable during the reaction. Consequently, the Bi nanoribbons exhibit a high formate Faradaic efficiency of over 95% in a wide potential window. More impressively, a negligible degradation in selectivity and activity after more than 100 h of continuous operation can be achieved. This work provides a feasible strategy for fabricating robust catalysts for efficient CO2 reduction.

Aqueous zinc (Zn)-ion batteries have attracted increasing attentions owing to their low cost and intrinsic safety. Nevertheless, the sluggish kinetics at subzero temperatures severely exacerbate the Zn dendrite growth, which hinders their implementation in cold environments. By virtue of high activity and maximum exposure of single atoms, Bi−N 4 moieties were fabricated to serve as Zn nucleation sites to increase Zn nucleation kinetics toward high-rate and low-temperature Zn metal batteries. Benefiting from the boosted kinetics, the Bi−N 4 species render a highly reversible and dendrite-free Zn plating/stripping behavior at 5 mA cm −2 with an average Coulombic efficiency of 99.4% over 1600 cycles at −30 °C, as well as a prolonged life up to 600 cycles in symmetric cells. Low-temperature full cells were also demonstrated with nearly 100% capacity retention after cycling at 0.5 A g −1 for 1400 cycles. This work shows the feasibility of single atoms in manipulating nucleation behaviors toward low-temperature metal batteries.

Metallic bismuth (Bi) holds great promise in efficient conversion of carbon dioxide (CO2) into formate, yet the complicated synthetic routes and unobtrusive performance hinder the practical application. Herein, a facile galvanic‐cell deposition method is proposed for the rapid and one‐step synthesis of Bi nanodendrites. Compared to the traditional deposition method, it is found that the special galvanic‐cell configuration can promote the exposure of low‐angle grain boundaries. X‐ray absorption spectroscopy, in situ characterizations and theoretical calculations indicate the electronical structures can be greatly tailored by the grain boundaries, which can facilitate the CO2 adsorption and intermediate formation. Consequently, the grain boundary‐enriched Bi nanodendrites exhibit a high selectivity toward formate with an impressively high production rate of 557.2 µmol h‐1 cm‐2 at −0.94 V versus reversible hydrogen electrode, which outperforms most of the state‐of‐the‐art Bi‐based electrocatalysts with longer synthesis time. This work provides a straightforward method for rapidly fabricating active Bi electrocatalysts, and explicitly reveals the critical effect of grain boundary in Bi nanostructures on CO2 reduction.

Electrochemical carbon dioxide (CO2) reduction into value‐added products holds great promise in moving toward carbon neutrality but remains a grand challenge due to lack of efficient electrocatalysts. Herein, the nucleophilic substitution reaction is elaborately harnessed to synthesize carbon nanoplates with a FeN4O configuration anchored onto graphene substrate (FeN4OC/Gr) through covalent linkages. Density functional theory calculations demonstrate the unique configuration of FeN4O with one oxygen (O) atom in the axial direction not only suppresses the competing hydrogen evolution reaction, but also facilitates the desorption of *CO intermediate compared with the commonly planar single‐atomic Fe sites. The FeN4OC/Gr shows excellent performance in the electroreduction of CO2 into carbon monoxide (CO) with an impressive Faradaic efficiency of 98.3% at −0.7 V versus reversible hydrogen electrode (RHE) and a high turnover frequency of 3511 h−1. Furthermore, as a cathode catalyst in an aqueous zinc (Zn)‐CO2 battery, the FeN4OC/Gr achieves a high CO Faradaic efficiency (≈91%) at a discharge current density of 3 mA cm−2 and long‐term stability over 74 h. This work opens up a new route to simultaneously modulate the geometric and electronic structure of single‐atomic catalysts toward efficient CO2 conversion.

In article number 2300801, Huan Wang and co-workers report a graphene-supported Fe-N 4 O-C nanoplates electrocatalyst that drives a rechargeable Zn-CO 2 battery with energy supply and highly efficient conversion of CO 2 into CO, an important one-carbon building block for the synthesis of long-chain compounds.