Asymmetric Oxo‐Bridged ZnPb Bimetallic Electrocatalysis Boosting CO₂‐to‐HCOOH Reduction

Abstract

Electrochemical CO 2 reduction (ECR) is one of the promising CO 2 recycling technologies sustaining the natural carbon cycle and offering more sustainable higher-energy chemicals. Zn-and Pb-based catalysts have improved formate selectivity, but they suffer from relatively low current activities considering the competitive CO selectivity on Zn. Here, lead-doped zinc (Zn(Pb)) electrocatalyst is optimized to efficiently reduce CO 2 to formate, while CO evolution selectivity is largely controlled. Selective formate is detected with Faradaic efficiency (FE HCOOH ) of ≈95% at an outstanding partial current density of 47 mA cm -2 in a conventional H-Cell. Zn(Pb) is further investigated in an electrolyte-fed device achieving a superior conversion rate of ≈100 mA cm -2 representing a step closer to practical electrocatalysis. The in situ analysis demonstrates that the Pb incorporation plays a crucial role in CO suppression stem from the generation of the Pb-O-C-O-Zn structure rather than the CO-boosted Pb-O-C-Zn. Density functional theory (DFT) calculations reveal that the alloying effect tunes the adsorption energetics and consequently modifies the electronic structure of the system for an optimized asymmetric oxo-bridged intermediate. The alloying effect between Zn and Pb controls CO selectivity and achieves a superior activity for a selective CO 2 -to-formate reduction.

Selective electrochemical reduction of CO2 on compositionally variant bimetallic Cu–Zn electrocatalysts derived from scrap brass alloys

“…It is well-established in the literature that Zn-based electrocatalysts tend to produce HCOO − as a liquid product, which is also observed with our brass electrocatalysts upon HPLC analysis of the electrolyte 26 , 64 , 65 . The results in Fig.…”

Decoration of PdAg Dual-Metallic Alloy Nanoparticles on Z-Scheme α-Fe2O3/CdS for Manipulable Products via Photocatalytic Reduction of Carbon Dioxide

“…The sample, Ag/AgCl, and Pt wire were employed as the working electrode, reference electrode, and counter electrode, respectively. The potential vs. RHE was determined using the equation, from which the E(RHE) = E(Ag/AgCl) + 0.964 V (Mohamed et al, 2022) E(RHE) 0.197 + 0.0591pH + E Ag AgCl .…”

Bionic Construction of Helical Bi2O3 Microfibers for Highly Efficient CO2 Electroreduction

“…[1][2][3][4][5] Catalyst is generally considered as the primary factor in determining the real application of eCO 2 R to formate. Up to date, numerous elements [6,7] have been studied as catalysts for eCO 2 R to formate, such as Pb, [8,9] In, [10][11][12] Sn, [13][14][15][16] Bi, [17][18][19] Cu, [20,21] and so on. Among them, the Bi-based catalysts are well known due to their low cost and non-toxicity.…”