Selective exposure of (111) crystal plane in Pd49Ag30Te4 by Tb doping to weaken Pd - C bond and promote electroreduction of CO2 to CO.

ABSTRACT

Employing electric energy to convert carbon dioxide (CO2) into valuable small molecules is a potentially practical method in energy storage and greenhouse gas alleviation. A huge challenge for electrocatalytic CO2 reduction is to reduce overpotential to improve energy efficiency. Herein, we demonstrate that doping alloy Pd49Ag30Te4 (PAT) with rare-earth element Tb is beneficial for selective exposure of (111) crystal plane, which is a highly active crystal plane for producing carbon monoxide (CO). The as-prepared Tb2.9PAT exhibited high electrocatalytic performance with 95.7 % CO faradic efficiency at - 0.8 V (vs RHE), far exceeding that of PAT, and coupled with good durability. In situ spectral study and theoretical calculations disclose that the introduction of Tb regulates the d-band center of PAT alloy, weakens the Pd - C bonding ability, and promotes the desorption of *CO in the rate-determining step. This study provides a method for doping induced selective exposure of crystal face, which provides new idea for improving catalytic performance.