Engineering Electronic Structure of Stannous Sulfide by Amino‐Functionalized Carbon: Toward Efficient Electrocatalytic Reduction of CO₂ to Formate

Abstract

Engineering electronic structure to enhance the binding energies of reaction intermediates in order to achieve a high partial current density can lead to increased yield of target products. Herein, amino‐functionalized carbon is used to regulate the electronic structure of tin‐based catalysts to enhance activity of CO2 electroreduction. The hollow nanotubes composed of SnS (stannous sulfide) nanosheets are modified with amino‐functionalized carbon layers, achieving a highest formate Faraday efficiency of 92.6% and a remarkable formate partial current density of 41.1 mA cm−2 (a total current density of 52.1 mA cm−2) at a moderate overpotential of 0.9 V versus reversible hydrogen electrode, as well as a good stability. Density functional theory calculations demonstrate that the superior activity is attributed to the synergistic effect among SnS and Aminated‐C in increasing the adsorption energies of the key intermediates and accelerating the charge transfer rate.

Recent Progress of Sn‐Based Derivative Catalysts for Electrochemical Reduction of CO2

“…According to the energy barrier to be overcome as needed, the rate‐determining step (RDS) on SnO was the process of HCOO* formation; apart from this, the process of HCOO* hydrogenation to form *HCOOH was the RDS for SnO 2 and Sn 3 O 4 . Liu and coworkers [ 35 ] explored the effect of an amino‐functionalized carbon layer on the catalytic activity of SnS from the perspective of the difference in adsorption energy caused by the change of electronic structure. According to DFT calculations, the free energy to form an OCHO* intermediate was significantly decreased after combining with the amino‐functionalized carbon layer (Figure 2d), which led to a significant increase in the catalytic selectivity of formic acid.…”

“…SnS 2 in the reduction process effectively stabilizes the intermediate () and enhances the stability of the catalyst. In 2020, Liu and coworkers [ 35 ] reported a hollow nanorod that was formed by amino‐functionalized carbon‐modified SnS nanosheets. After the amino modification, the current density and formic acid productivity of the SnS catalysts were remarkably enhanced.…”

“…g) Calculated adsorption energies of reaction intermediates. [35] Copyright 2020, WILEY-VCH. N atoms was transferred to the surface of the Sn atom ( Figure 2g).…”

Engineering Heterostructured Nanocatalysts for CO2 Transformation Reactions: Advances and Perspectives

“…Although the study of electrocatalytic and thermocatalytic CO 2 conversion based on hierarchical hollow heterostructures is relatively limited compared with CO 2 photocatalysis reduction, some typical reports are given in this part. Liu and co‐workers [83b] meticulously prepared hierarchical nanotubes (SnS/Aminated‐C) made up of stannous sulfide (SnS) nanosheets covered by amino‐functionalized carbon layers (Aminated‐C) by a modified hard‐template method. SnS/Aminated‐C holds a highest formate and CO faradaic efficiency closely 100 % with an appreciable partial current density of formate (41.1 mA cm −2 ) with a mild overpotential (900 mV vs. RHE), as well as good long‐time stability.…”

A generalized amino-modification strategy to boost CO2 electroreduction current density of single-atom catalysts to industrial application level

“…8,17,18,[45][46][47][48] Researches in the field of CO2 adsorption show that amine-modified carbon materials can significantly enhance adsorption capacity of CO2, [49][50][51] and moreover, combining with amino-modified carbon materials can enhance CO2RR activity of transition metals. 13,42,52,53 M-N/C catalysts can be regarded as a kind of carbon material co-doped with transition metal atoms (M) and nitrogen atoms (N), therefore, it can be reasonably inferred that catalytic activity of CO2RR can be effectively increased by modifying the carbon supports in M-N/C catalysts with amino groups such as -NH2.…”