Nano-crumples induced Sn-Bi bimetallic interface pattern with moderate electron bank for highly efficient CO2 electroreduction

Abstract

CO2 electroreduction reaction offers an attractive approach to global carbon neutrality. Industrial CO2 electrolysis towards formate requires stepped-up current densities, which is limited by the difficulty of precisely reconciling the competing intermediates (COOH* and HCOO*). Herein, nano-crumples induced Sn-Bi bimetallic interface-rich materials are in situ designed by tailored electrodeposition under CO2 electrolysis conditions, significantly expediting formate production. Compared with Sn-Bi bulk alloy and pure Sn, this Sn-Bi interface pattern delivers optimum upshift of Sn p-band center, accordingly the moderate valence electron depletion, which leads to weakened Sn-C hybridization of competing COOH* and suitable Sn-O hybridization of HCOO*. Superior partial current density up to 140 mA/cm2 for formate is achieved. High Faradaic efficiency (>90%) is maintained at a wide potential window with a durability of 160 h. In this work, we elevate the interface design of highly active and stable materials for efficient CO2 electroreduction.

Zn‐Sb Bimetallic Electrocatalyst Enhances the Conversion of CO2 to Formate

“…According to the d‐band center theory, a downshift of the d‐band center of Sb, which is beneficial to weaken the free energy barrier of reaction intermediate [36] . This to some extent links the hybridization match of metal d‐band electronic structure with the energy level of adsorbates, and consequently, the binding strength of reaction intermediates [37] . As a result, surface electronic structure manipulation facilitates the activity and selectivity of ECO 2 RR to formate.…”

“…[36] This to some extent links the hybridization match of metal d-band electronic structure with the energy level of adsorbates, and consequently, the binding strength of reaction intermediates. [37] As a result, surface electronic structure manipulation facilitates the activity and selectivity of ECO 2 RR to formate. Similar tuning of d band by the existence of metal-to-metal interaction can be easily found in PdÀ Zn, [26] AuÀ Cu, [38] PdAg [36b] and PdAu, [39] and PdNi.…”

Interfacial engineering of heterostructured Fe-Ni3S2/Ni(OH)2nanosheets with tailored d-band center for enhanced oxygen evolution catalysis

“…3c). 38 It is generally accepted that the upshift (higher) of the d-band center related to the Fermi level decreases the electron filling of antibonding states, which causes a stronger interaction between electrochemically active sites and OER intermediates (OH*, OOH*, and O*), which is positively associated with the OER activity. 39 Therefore, the formation of a heterojunction facilitates the adsorption of OER intermediates and obtains better performance, which is the main reason why the Fe-Ni 3 S 2 /Ni(OH) 2 exhibits high catalytic performance and low activation energy.…”

“…3c). 38 It is generally accepted that the upshift (higher) of the d-band center related to the Fermi level decreases the electron filling of antibonding states, which causes a stronger interaction between electrochemically active sites and OER intermediates (OH*, OOH*, and O*), which is positively associated with the OER…”

In situ construction of 3D low-coordinated bismuth nanosheets@Cu nanowire core–shell nanoarchitectures for superior CO2 electroreduction activity

“…4,5 In this respect, some metal-based cathodic electro-catalysts, including In, Pb, Sn, and Bi, have been used for CO 2 RR to produce HCOOH. [5][6][7][8][9][10][11][12] However, expensive or high toxic materials are not conducive to further applications. By contrast, Sn and Bi are the catalysts for the production of HCOOH with the advantages of low-cost and environmental friendliness.…”