Controllable CO2 electrocatalytic reduction via ferroelectric switching on single atom anchored In2Se3 monolayer

Abstract

Efficient and selective CO2 electroreduction into chemical fuels promises to alleviate environmental pollution and energy crisis, but it relies on catalysts with controllable product selectivity and reaction path. Here, by means of first-principles calculations, we identify six ferroelectric catalysts comprising transition-metal atoms anchored on In2Se3 monolayer, whose catalytic performance can be controlled by ferroelectric switching based on adjusted d-band center and occupation of supported metal atoms. The polarization dependent activation allows effective control of the limiting potential of CO2 reduction on TM@In2Se3 (TM = Ni, Pd, Rh, Nb, and Re) as well as the reaction paths and final products on Nb@In2Se3 and Re@In2Se3. Interestingly, the ferroelectric switching can even reactivate the stuck catalytic CO2 reduction on Zr@In2Se3. The fairly low limiting potential and the unique ferroelectric controllable CO2 catalytic performance on atomically dispersed transition-metals on In2Se3 clearly distinguish them from traditional single atom catalysts, and open an avenue toward improving catalytic activity and selectivity for efficient and controllable electrochemical CO2 reduction reaction.

Progress on Emerging Ferroelectric Materials for Energy Harvesting, Storage and Conversion

“…[304,305] Inspired by the ideal surface geometry, Ju et al predicted that the catalytic activity and selectivity of transition-metal atoms anchored α-In 2 Se 3 (TM@In 2 Se 3 , TM = Ni, Pd, Rh, Nb, or Re) used for CO 2 RR can be controlled by FE switching through adjusting the d-band center and occupation of supported metal atoms. [306,307]…”

“…Reproduced according to the terms of the CC‐BY license. [ 306 ] Copyright 2021, The authors, published by Springer Nature.…”

“…predicted that the catalytic activity and selectivity of transition‐metal atoms anchored α‐In 2 Se 3 (TM@In 2 Se 3 , TM = Ni, Pd, Rh, Nb, or Re) used for CO 2 RR can be controlled by FE switching through adjusting the d ‐band center and occupation of supported metal atoms. [ 306,307 ] By forming bidentate C‐TM‐O species, the strong hybridization of O p and TM d orbitals and charge transfer ensure chemical capture of the inert CO 2 on the TM@In 2 Se 3 surfaces. The activation degrees on opposite FE surfaces are manifested by different ∠OCO angles of the CO 2 molecules (Figure 10d,e).…”

“…d-g) Differential charge density plots (In-purple, Se-green) and partial density of states of CO 2 adsorbed on Pd@P↓-In 2 Se 3 (d,e) and Pd@P↑-In 2 Se 3 (f,g), respectively. Reproduced according to the terms of the CC-BY license [306]. Copyright 2021, The authors, published by Springer Nature.…”

Janus Mo2P3 Monolayer as an Electrocatalyst for Hydrogen Evolution

“…On the other hand, the Janus structure usually leads to inherent polarization, as observed in WSSe and In 2 Se 3 , which have shown remarkably high HER activity in photocatalytic water splitting 64,65 and CO 2 reduction. 66 For Mo 2 P 3 , the two kinds of P atoms have distinct charges (−0.30 for P 1 and −0.09 for P 2 ). Thus, P 1 atoms are fully used in both individual and average processes, and the utilization of P 2 atoms is up to 10/16.…”