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Carbon dioxide electroreduction (CO2RR) is a sustainable way of producing carbon‐neutral fuels. Product selectivity in CO2RR is regulated by the adsorption energy of reaction‐intermediates. Here, we employ differential phase contrast‐scanning transmission electron microscopy (DPC‐STEM) to demonstrate that Sn heteroatoms on a Ag catalyst generate very strong and atomically localized electric fields. In situ attenuated total reflection infrared spectroscopy (ATR‐IR) results verified that the localized electric field enhances the adsorption of *COOH, thus favoring the production of CO during CO2RR. The Ag/Sn catalyst exhibits an approximately 100 % CO selectivity at a very wide range of potentials (from −0.5 to −1.1 V, versus reversible hydrogen electrode), and with a remarkably high energy efficiency (EE) of 76.1 %. [ABSTRACT FROM AUTHOR]

Ruthenium (Ru)‐based catalysts, with considerable performance and desirable cost, are becoming highly interesting candidates to replace platinum (Pt) in the alkaline hydrogen evolution reaction (HER). The hydrogen binding at Ru sites (Ru−H) is an important factor limiting the HER activity. Herein, density functional theory (DFT) simulations show that the essence of Ru−H binding energy is the strong interaction between the 4dz2 orbital of Ru and the 1s orbital of H. The charge transfer between Ru sites and substrates (Co and Ni) causes the appropriate downward shift of the 4dz2 ‐band center of Ru, which results in a Gibbs free energy of 0.022 eV for H* in the RuCo system, much lower than the 0.133 eV in the pure Ru system. This theoretical prediction has been experimentally confirmed using RuCo alloy‐nanosheets (RuCo ANSs). They were prepared via a fast co‐precipitation method followed with a mild electrochemical reduction. Structure characterizations reveal that the Ru atoms are embedded into the Co substrate as isolated active sites with a planar symmetric and Z‐direction asymmetric coordination structure, obtaining an optimal 4dz2 modulated electronic structure. Hydrogen sensor and temperature program desorption (TPD) tests demonstrate the enhanced Ru−H interactions in RuCo ANSs compared to those in pure Ru nanoparticles. As a result, the RuCo ANSs reach an ultra‐low overpotential of 10 mV at 10 mA cm−2 and a Tafel slope of 20.6 mV dec−1 in 1 M KOH, outperforming that of the commercial Pt/C. This holistic work provides a new insight to promote alkaline HER by optimizing the metal‐H binding energy of active sites. [ABSTRACT FROM AUTHOR]

Atomically dispersed transition metal sites have been extensively studied for CO2 electroreduction reaction (CO2RR) to CO due to their robust CO2 activation ability. However, the strong hybridization between directionally localized d orbits and CO vastly limits CO desorption and thus the activities of atomically dispersed transition metal sites. In contrast, s‐block metal sites possess nondirectionally delocalized 3s orbits and hence weak CO adsorption ability, providing a promising way to solve the suffered CO desorption issue. Herein, we constructed atomically dispersed magnesium atoms embedded in graphitic carbon nitride (Mg‐C3N4) through a facile heat treatment for CO2RR. Theoretical calculations show that the CO desorption on Mg sites is easier than that on Fe and Co sites. This theoretical prediction is demonstrated by experimental CO temperature program desorption and in situ attenuated total reflection infrared spectroscopy. As a result, Mg‐C3N4 exhibits a high turnover frequency of ≈18 000 per hour in H‐cell and a large current density of −300 mA cm−2 in flow cell, under a high CO Faradaic efficiency ≥90 % in KHCO3 electrolyte. This work sheds a new light on s‐block metal sites for efficient CO2RR to CO. [ABSTRACT FROM AUTHOR]

Alkaline HER, Atomic Charge Distribution, Interfacial Water Orientation, Single-Atom Site, Water Dissociation In their Research Article (e202300873), Emiliano Cortés et al. designed an atomically asymmetric local electric field using Ir-Ru dizygotic single-atom sites (IrRu DSACs) to optimize the dissociation process by tuning the H SB 2 sb O adsorption configuration and orientation. Keywords: Alkaline HER; Atomic Charge Distribution; Interfacial Water Orientation; Single-Atom Site; Water Dissociation EN Alkaline HER Atomic Charge Distribution Interfacial Water Orientation Single-Atom Site Water Dissociation 1 1 1 06/20/23 20230626 NES 230626 B Alkaline water electrolysis b is a promising technology for hydrogen production, but the slow water dissociation process limits the kinetics of the hydrogen evolution reaction (HER). [Extracted from the article]