Exclusive Formation of Formic Acid from CO₂ Electroreduction by a Tunable Pd‐Sn Alloy

Abstract

Conversion of carbon dioxide (CO ) into fuels and chemicals by electroreduction has attracted significant interest, although it suffers from a large overpotential and low selectivity. A Pd-Sn alloy electrocatalyst was developed for the exclusive conversion of CO into formic acid in an aqueous solution. This catalyst showed a nearly perfect faradaic efficiency toward formic acid formation at the very low overpotential of -0.26 V, where both CO formation and hydrogen evolution were completely suppressed. Density functional theory (DFT) calculations suggested that the formation of the key reaction intermediate HCOO* as well as the product formic acid was the most favorable over the Pd-Sn alloy catalyst surface with an atomic composition of PdSnO , consistent with experiments.

Catholyte‐Free Electrocatalytic CO2 Reduction to Formate

“…[1][2][3][4] There are several electrochemical pathways to convert CO 2 into valuable products, [1,5,6] among which formic acid or formate has received particular attention over the past few years because the CO 2 Ri nto formic acid is regarded as as uitable reaction for industrial scale production. Interestingly,as the reaction temperature rises from 303 Kto363 K, the partial current density (PCD) of formate improves more than two times with 52.9 mA cm À2 ,despite the decrease in CO 2 solubility.…”

“…Interestingly,as the reaction temperature rises from 303 Kto363 K, the partial current density (PCD) of formate improves more than two times with 52.9 mA cm À2 ,despite the decrease in CO 2 solubility. [2,[10][11][12][13] Despite these significant results,t heir kinetics of CO 2 Rconversion into formate is still limited by the low CO 2 concentration in electrolytes.I nr ecent years,s ome research groups reported remarkable improvement in the current density of CO 2 Rt of ormate using gas diffusion electrodes (GDEs) with metal nanoparticles. [1][2][3][4] There are several electrochemical pathways to convert CO 2 into valuable products, [1,5,6] among which formic acid or formate has received particular attention over the past few years because the CO 2 Ri nto formic acid is regarded as as uitable reaction for industrial scale production.…”

“…[1][2][3][4] There are several electrochemical pathways to convert CO 2 into valuable products, [1,5,6] among which formic acid or formate has received particular attention over the past few years because the CO 2 Ri nto formic acid is regarded as as uitable reaction for industrial scale production. [1][2][3][4] There are several electrochemical pathways to convert CO 2 into valuable products, [1,5,6] among which formic acid or formate has received particular attention over the past few years because the CO 2 Ri nto formic acid is regarded as as uitable reaction for industrial scale production.…”

Boosting Electrochemical Reduction of CO2 at a Low Overpotential by Amorphous Ag‐Bi‐S‐O Decorated Bi0 Nanocrystals

“…After electrochemical pre-treatment, this Ag 0.95 BiS 0.75 O 3.1 nanorod was converted into Bi 0 nanocrystals attached by amorphous substance composed of Ag,Bi, S, and O( the whole synthesis procedure is shown in Figure 1a). Ther esults of transmission electron microscopy (TEM), X-ray diffraction (XRD), high-resolution TEM (HRTEM), high-angle annular dark-field scanning TEM (HAADF-STEM), and energy-dispersive X-ray spectroscopy (EDS;S upporting Information, Figures S2-S4 10 .T he shifting of Ag 3d, Bi 4f,S2p,a nd S2s peaks to higher binding energies (X-ray photoelectron spectroscopy (XPS);S upporting Information, Figures S9, S10) suggests the formation of AgÀO, BiÀO, and SÀO bonds in AgBi-500b and Bi-500b.F inally,X PS analysis illustrates the composition of AgBi-500b and Bi-500b to be Ag 0.95 BiS 0.75 O 3.1 and BiS 0.68 O 2.7 (Supporting Information, Table S1). AgBiS 2 nanorods (Supporting Information, Figure S1) were first synthesized and then annealed in air at 200 8 8Co r 500 8 8C, and the obtained samples were named as AgBi-200b and AgBi-500b ("b" means before electrochemical pre-treatment), respectively (seeing Supporting Information for more details).…”

Enhancing Activity and Reducing Cost for Electrochemical Reduction of CO2 by Supporting Palladium on Metal Carbides

“…[12,13] Producing syngas via simultaneous CO 2 RR and hydrogen evolution reaction (HER) realizes CO 2 utilization and chemical feedstock production using renewable energy sources,w hich has shown promising prospects and drawn increasing attentions. [16][17][18][19][20] Previous work reported the CO 2 RR on commercial Pd/C catalyst and the in situ formation of PdH on bulk Pd particles during CO 2 RR. [16][17][18][19][20] Previous work reported the CO 2 RR on commercial Pd/C catalyst and the in situ formation of PdH on bulk Pd particles during CO 2 RR.…”