Motivated by in silico predictions that Co,Rh, and Ir dopants would lead to low overpotentials to improve OER activity of Ni-based hydroxides,wereport here an experimental confirmation on the altered OER activities for as eries of metals (Mo,W ,F e, Ru, Co,Rh, Ir) doped into g-NiOOH. The in situ electrical conductivity for metal doped g-NiOOH correlates well with the trend in enhanced OER activities. Density functional theory (DFT) calculations were used to rationalizethe in situ conductivity of the key intermediate states of metal doped g-NiOOH during OER. The simultaneous increase of OER activity with intermediate conductivity was later rationalized by their intrinsic connections to the double exchange (DE) interaction between adjacent metal ions with various do rbital occupancies,s erving as an indicator for the key metal-oxoradical character,and an effective descriptor for the mechanistic evaluation and theoretical guidance in design and screening of efficient OER catalysts.

Selective oxidation to synthesize nitriles is critical for feedstock manufacturing in the chemical industry. Current strategies typically involve substitutions of alkyl halides with toxic cyanides or the use of strong oxidation reagents (oxygen or peroxide) under ammoxidation/oxidation conditions, setting considerable challenges in energy efficiency, sustainability, and production safety. Herein, we demonstrate a facile, green, and safe electrocatalytic route for selective oxidation of amines to nitriles under ambient conditions, assisted by the anodic water oxidation on metal-doped α-Ni­(OH)2 (a typical oxygen evolution reaction catalyst). By controlling the balance between co-adsorption of the amine molecule and hydroxyls on the catalyst surface, we demonstrate that Mn doping significantly promotes the subsequent chemical oxidation of amines, resulting in Faradaic efficiencies of 96% for nitriles under ≥99% conversion. This anodic oxidation is further coupled with cathodic hydrogen evolution for overall atomic economy and additional green energy production.

Single-atom catalysts represent a unique catalytic system with high atomic utilization and tunable reaction pathway. Despite current successes in their optimization and tailoring through structural and synthetic innovations, there is a lack of dynamic modulation approach for the single-atom catalysis. Inspired by the electrostatic interaction within specific natural enzymes, here we show the performance of model single-atom catalysts anchored on two-dimensional atomic crystals can be systematically and efficiently tuned by oriented external electric fields. Superior electrocatalytic performance have been achieved in single-atom catalysts under electrostatic modulations. Theoretical investigations suggest a universal “onsite electrostatic polarization” mechanism, in which electrostatic fields significantly polarize charge distributions at the single-atom sites and alter the kinetics of the rate determining steps, leading to boosted reaction performances. Such field-induced on-site polarization offers a unique strategy for simulating the catalytic processes in natural enzyme systems with quantitative, precise and dynamic external electric fields.

Electrochemical organic synthesis has attracted increasing attentions as a sustainable and versatile synthetic platform. Quantitative assessment of the electro‐organic reactions, including reaction thermodynamics, electro‐kinetics, and coupled chemical processes, can lead to effective analytical tool to guide their future design. Herein, we demonstrate that electrochemical parameters such as onset potential, Tafel slope, and effective voltage can be utilized as electro‐descriptors for the evaluation of reaction conditions and prediction of reactivities (yields). An “electro‐descriptor‐diagram” is generated, where reactive and non‐reactive conditions/substances show distinct boundary. Successful predictions of reaction outcomes have been demonstrated using electro‐descriptor diagram, or from machine learning algorithms with experimentally‐derived electro‐descriptors. This method represents a promising tool for data‐acquisition, reaction prediction, mechanistic investigation, and high‐throughput screening for general organic electro‐synthesis.

Electrocatalytic conversion of carbon dioxide to high-value fuels and chemical feedstocks represents a promising solution toward carbon neutrality. Ongoing efforts have been directed to the development of high-performance, mass production, and cost-efficient catalysts, which, in turn, requires a more precise understanding of the operando details of the catalytic interface and fine control over the reaction pathway. Here, we report that a two-dimensional (2D) monolayer Bi2WO6 with high bismuth exposure demonstrates excellent performance for the electrocatalytic conversion of CO2 to formic acid, including the high Faradic efficiency (FE) over a broad potential range (over 90% from 0.9 to 1.3 V vs RHE, >98% FE at 1.0 V vs RHE) and a high current density over 250 mA/cm2 in a flow cell equipped with a gas diffusion electrode (>97% FE). The distinct reaction pathway observed in the electrocatalytic process, in contrast to the photocatalytic reactions, was investigated by density functional theory. Additionally, the mechanistic investigation further elucidates in operando phase transition to a “metallic intermediate state” on monolayer Bi2WO6 during the electrocatalytic process, providing the experimental evidence to the basis of satisfying performance from all Bi-based catalysts in CO2 reduction.