Boosting CO₂ Electrochemical Reduction with Atomically Precise Surface Modification on Gold Nanoclusters

Abstract

Thiolate‐protected gold nanoclusters (NCs) are promising catalytic materials for the electrochemical CO2 reduction reaction (CO2RR). In this work an atomic level modification of a Au23 NC is made by substituting two surface Au atoms with two Cd atoms, and it enhances the CO2RR selectivity to 90–95 % at the applied potential between −0.5 to −0.9 V, which is doubled compared to that of the undoped Au23. Additionally, the Cd‐doped Au19Cd2 exhibits the highest CO2RR activity (2200 mA mg−1 at −1.0 V vs. RHE) among the reported NCs. This synergetic effect between Au and Cd is remarkable. Density‐functional theory calculations reveal that the exposure of a sulfur active site upon partial ligand removal provides an energetically feasible CO2RR pathway. The thermodynamic energy barrier for CO formation is 0.74 eV lower on Au19Cd2 than on Au23. These results reveal that Cd doping can boost the CO2RR performance of Au NCs by modifying the surface geometry and electronic structure, which further changes the intermediate binding energy. This work offers insights into the surface doping mechanism of the CO2RR and bimetallic synergism.

Homoleptic Alkynyl‐Protected Ag15 Nanocluster with Atomic Precision: Structural Analysis and Electrocatalytic Performance toward CO2 Reduction

“…Figure 1 c presents the simulated absorbance spectrum of [Ag 15 (C≡C−CH 3 ) 12 ] + along with the experimental one. To simplify the calculation, all C≡C‐ t Bu ligands are replaced with C≡C−CH 3 , which has been regarded as a common choice in the simulation of organic ligand‐protected clusters [32–37] . Note that this simplified treatment of the side groups has been demonstrated to show negligible effect on the electronic, optical, and catalytic behaviors when compared to the experimental bulky ligands, since the main optical transition and the catalytic active sites mainly derive from the metals, while the contributions from the side groups of the ligands are less significant.…”

Controllable synthesis and electrocatalytic applications of atomically precise gold nanoclusters

“…107 It has been reported that Au-based materials show high selectivity towards CO formation because the *CO intermediates on gold are relatively weak. 108 31 increased to 96% at -0.57 V for the electrocatalytic reduction of CO 2 to CO (Figure 12a and 12b), and the results exhibited that the partial current density of CO for Au 47 Cd 2 (TBBT) 31 is more negative than the Au 44 (TBBT) 28 nanocluster and the Au NPs (Figure 12c, Figure 12d) showed that electrocatalytic durability of Au 47 Cd 2 (TBBT) 31 is superiour to other materials. Most importantly, the results confirm that the CO 2 RR ability of Au 47 Cd 2 (TBBT) 31 is superior.…”

Catalytic Conversion of C 1 Molecules on Atomically Precise Metal Nanoclusters

“…54. Copyright (2019) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.driven CO 2 conversion over Au nanoclusters (Figure23) 55.…”