Hongyang Su

Electrocatalysts with single metal atoms as active sites have received increasing attention owing to their high atomic utilization efficiency and exotic catalytic activity and selectivity. This review aims to provide a comprehensive summary on the recent development of such single-atom electrocatalysts (SAECs) for various energy-conversion reactions. The discussion starts with an introduction of the different types of SAECs, followed by an overview of the synthetic methodologies to control the atomic dispersion of metal sites and atomically resolved characterization using state-of-the-art microscopic and spectroscopic techniques. In recognition of the extensive applications of SAECs, the electrocatalytic studies are dissected in terms of various important electrochemical reactions, including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), carbon dioxide reduction reaction (CO2RR), and nitrogen reduction reaction (NRR). Examples of SAECs are deliberated in each case in terms of their catalytic performance, structure-property relationships, and catalytic enhancement mechanisms. A perspective is provided at the end of each section about remaining challenges and opportunities for the development of SAECs for the targeted reaction.

Abstract As electron transfer to CO 2 is generally considered to be the critical step during the activation of CO 2 , it is important to develop approaches to engineer the electronic properties of catalysts to improve their performance in CO 2 electrochemical reduction. Herein, we developed an efficient strategy to facilitate CO 2 activation by introducing oxygen vacancies into electrocatalysts with electronic‐rich surface. ZnO nanosheets rich in oxygen vacancies exhibited a current density of −16.1 mA cm −2 with a Faradaic efficiency of 83 % for CO production. Based on density functional theory (DFT) calculations, the introduction of oxygen vacancies increased the charge density of ZnO around the valence band maximum, resulting in the enhanced activation of CO 2 . Mechanistic studies further revealed that the enhancement of CO production by introducing oxygen vacancies into ZnO nanosheets originated from the increased binding strength of CO 2 and the eased CO 2 activation.

Abstract Efforts have been devoted to achieving a highly efficient artificial synthesis of ammonia (NH 3 ). Reported herein is a novel Fe‐MoS 2 catalyst with Fe atomically dispersed onto MoS 2 nanosheets, imitating natural nitrogenase, to boost N 2 electroreduction into NH 3 at room temperature. The Fe‐MoS 2 nanosheets exhibited a faradic efficiency of 18.8 % with a yield rate of 8.63 μg mg cat. −1 h −1 for NH 3 at −0.3 V versus the reversible hydrogen electrode. The mechanism study revealed that the electroreduction of N 2 was promoted and the competing hydrogen evolution reaction was suppressed by decorating the edge sites of S in MoS 2 with the atomically dispersed Fe, resulting in high catalytic performance for the electroreduction of N 2 into NH 3 . This work provides new ideas for the design of catalysts for N 2 electroreduction and strengthens the understanding about N 2 activation over Mo‐based catalysts.

Abstract As electron transfer to CO 2 is generally considered to be the critical step during the activation of CO 2 , it is important to develop approaches to engineer the electronic properties of catalysts to improve their performance in CO 2 electrochemical reduction. Herein, we developed an efficient strategy to facilitate CO 2 activation by introducing oxygen vacancies into electrocatalysts with electronic‐rich surface. ZnO nanosheets rich in oxygen vacancies exhibited a current density of −16.1 mA cm −2 with a Faradaic efficiency of 83 % for CO production. Based on density functional theory (DFT) calculations, the introduction of oxygen vacancies increased the charge density of ZnO around the valence band maximum, resulting in the enhanced activation of CO 2 . Mechanistic studies further revealed that the enhancement of CO production by introducing oxygen vacancies into ZnO nanosheets originated from the increased binding strength of CO 2 and the eased CO 2 activation.

Mastery over the structure of materials at nanoscale can effectively tailor and control their catalytic properties, enabling enhancement in both activity and durability. We report a size-controlled synthesis of novel Pt-Cu hierarchical trigonal bipyramid nanoframes (HTBNFs). The obtained nanocrystals looked like a trigonal bipyramid on the whole, composed of similar ordered frame structural units. By varying the amount of KI involved in the reaction, HTBNFs with variable sizes from 110 to 250 nm could be obtained. In addition, the structure of HTBNFs could be preserved only in a limited range of the Pt/Cu feeding ratio. Relative to the commercial Pt/C, these Pt-Cu HTBNFs with different Pt/Cu ratio exhibited enhanced electrocatalytic activity toward formic acid oxidation reaction as much as 5.5 times in specific activity and 2.1 times in mass activity. The excellent electrocatalytic activity and better durability are due to the unique structure of HTBNFs and probably synergetic effects between Pt and Cu.