High‐Curvature Transition‐Metal Chalcogenide Nanostructures with a Pronounced Proximity Effect Enable Fast and Selective CO₂ Electroreduction

Abstract

A considerable challenge in the conversion of carbon dioxide into useful fuels comes from the activation of CO2 to CO2.− or other intermediates, which often requires precious‐metal catalysts, high overpotentials, and/or electrolyte additives (e.g., ionic liquids). We report a microwave heating strategy for synthesizing a transition‐metal chalcogenide nanostructure that efficiently catalyzes CO2 electroreduction to carbon monoxide (CO). We found that the cadmium sulfide (CdS) nanoneedle arrays exhibit an unprecedented current density of 212 mA cm−2 with 95.5±4.0 % CO Faraday efficiency at −1.2 V versus a reversible hydrogen electrode (RHE; without iR correction). Experimental and computational studies show that the high‐curvature CdS nanostructured catalyst has a pronounced proximity effect which gives rise to large electric field enhancement, which can concentrate alkali‐metal cations resulting in the enhanced CO2 electroreduction efficiency.

Recent Advances in Strategies for Improving the Performance of CO2 Reduction Reaction on Single Atom Catalysts

“…Cu and Cu‐based materials are some of the most attractive catalysts in ECR because their abundant products in ECR, [19c,73] and so are Cu SACs. [ 44,74,75 ] Cu SACs could mainly generate C 1 products.…”

“…[ 17 ] An optimal catalyst for the ECR not only owns high selectivity for the target products at low overpotential but also allows a large current density and long‐term stability in practical application [3c,18] . With mature sythesis methods and exact structure, metal‐based catalysts including Au, Ag, and Cu [ 19 ] are attractive for fundamental studies as well as for the actual implementation in an electrolyzer. Metal‐based catalyst can be divided into four groups according to the main ECR products, [17c,20] primarily through d‐band theory and diverse binding energy between catalyst and specific chemical intermediates.…”

Semimetal 1H‐SnS2 Enables High‐Efficiency Electroreduction of CO2 to CO

“…Electrochemical CO 2 reduction reaction (CO 2 RR) into value‐added chemicals is a promising reaction to solve the problems of greenhouse effect and energy shortage. [ 22–30 ] Products generated from CO 2 RR are diverse, spanning from two‐electron transferred products, including carbon monoxide (CO) and formic acid (HCOOH), to deeply reduced products such as ethylene (C 2 H 4 ). [ 26–30 ] However, among these products, CO is particularly important because it is more advantageous in kinetics to use H 2 O as the reaction medium to realize the conversion of CO to fuels.…”

“…[ 26–30 ] However, among these products, CO is particularly important because it is more advantageous in kinetics to use H 2 O as the reaction medium to realize the conversion of CO to fuels. [ 27 ] In fact, the 1T‐SnS 2 has been reported as the best catalyst candidate for CO 2 RR. [ 12–18 ] For example, the main product of ultrathin SnS 2 monolayer catalysts in CO 2 RR is HCOOH with a high Faradaic efficiency (FE) of 94 ± 5%, and its FE also related to SnS 2 thickness.…”

A Mn-N3 single-atom catalyst embedded in graphitic carbon nitride for efficient CO2 electroreduction

“…Novel catalysts are strongly desirable to simultaneously obtain a high Faradaic efficiency (FE) and high current density of target products 3 . Among the various products of CO 2 RR, CO is one of the most practical targets, since it can be used to prepare synthetic fuels and chemicals via a downstream Fischer-Tropsch process [4][5][6][7] . Electrocatalysts based on manganese (Mn), the third most abundant transition metal in Earth's crust, have been reported as catalysts for the CO 2 RR, including Mn oxides 8 , Mn complexes 9 , Mn single-atom catalysts (SACs) [10][11][12][13] , and so on.…”