Intercalated Gold Nanoparticle in 2D Palladium Nanosheet Avoiding CO Poisoning for Formate Production under a Wide Potential Window

Abstract

The electrochemical CO 2 reduction into formate acid over Pd-based catalysts under a wide potential window is a challenging task; CO poisoning commonly occurring on the vulnerable surface of Pd must be overcome. Herein, we designed a twodimensional (2D) AuNP-in-PdNS electrocatalyst, in which the Au nanoparticles are intercalated in Pd nanosheets, for formate production under a wide potential window from −0.1 to −0.7 V versus a reversible hydrogen electrode. Based on the X-ray absorption spectra (XAS) characterizations, CO accumulation detection, and CO stripping voltammetry measurements, we observed that the intercalated Au nanoparticles could effectively avoid the CO formation and boost the formate production on the Pd nanosheet surface by regulating its electronic structure.

Recent advances in nanoscale engineering of Pd-based electrocatalysts for selective CO2 electroreduction to formic acid/formate

“…In recent years, researchers have devoted tremendous efforts to finely designing highperformance Pd-based electrocatalysts through alloying. A variety of bimetallic Pd alloys with other transition metals, such as tin (Sn) [31,97] , silver (Ag) [33,40,68] , gold (Au) [73,98,99] , copper (Cu) [67,100,101] , bismuth (Bi) [34,74] , lead (Pb) [102] , etc., have been synthesized and displayed enhanced catalytic performance for CO 2 -to-formic acid/formate conversion.…”

High‐Dispersive Pd Nanoparticles on Hierarchical N‐Doped Carbon Nanocages to Boost Electrochemical CO2 Reduction to Formate at Low Potential

“…The high FE formate of >95% is presented in a wide window of −0.05-0.30 V at nearzero potentials with the maximum J formate of 10.3 mA cm −2 at −0.25 V. The excellent CO 2 RR performance of Pd/hNCNCs-9, especially the J formate , locates at the top level of Pd-based materials reported to date (Figure 2d; Figure S9, Supporting Information). [14,[17][18][19]27] The Pd/hNCNCs-9 also exhibits good stability with the maintained FE formate of >90% in 8 h (Figure S10, Supporting Information).…”

“…However, the Pd‐based CO 2 RR catalysts are beset by the resource scarcity and high price, as well as the low partial current density for formate ( J formate < 5 mA cm −2 ). [ 16 ] Alloying Pd with other metals (e.g., Au, [ 14a,17 ] Ag, [ 14b,18 ] Bi [ 19 ] ) is usually adopted to achieve high J formate for promoting the formate yield and meanwhile maintain the high FE formate . Unfortunately, this strategy is also accompanied by an increase in the applied potential (e.g., AuPd alloy: FE formate = 98% at −0.6 V).…”

“…Unfortunately, this strategy is also accompanied by an increase in the applied potential (e.g., AuPd alloy: FE formate = 98% at −0.6 V). [ 17 ] To maintain the low‐potential advantage of Pd, it is worthy of attempting to expose more active sites and regulate electronic structure of Pd catalyst by optimizing the supports. [ 20 ] The hierarchical carbon‐based nanocages developed by our group feature the merits of high conductivity, large specific surface area, co‐existing micro‐meso‐macropores and easy N‐doping, [ 21 ] which favors the exposure of active sites to increase Pd utilization, the regulation of electronic structure of Pd by N dopants to tune the reactants adsorption/desorption, and the acceleration of mass/charge transfer kinetics to enhance the reaction rate.…”