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

Abstract

We report the fabrication of homoleptic alkynyl‐protected Ag15(C≡C‐tBu)12+ (abbreviated as Ag15) nanocluster and its electrocatalytic properties toward CO2 reduction reaction. Crystal structure analysis reveals that Ag15 possesses a body‐centered‐cubic (BCC) structure with an Ag@Ag8@Ag6 metal core configuration. Interestingly, we found that Ag15 can adsorb CO2 in the air and spontaneously self‐assembled into one‐dimensional linear material during the crystal growth process. Furthermore, Ag15 can convert CO2 into CO with a faradaic efficiency of ca. 95.0 % at −0.6 V and a maximal turnover frequency of 6.37 s−1 at −1.1 V along with excellent long‐term stability. Finally, density functional theory (DFT) calculations disclosed that Ag15(C≡C‐tBu)11+ with one alkynyl ligand stripping off from the intact cluster can expose the uncoordinated Ag atom as the catalytically active site for CO formation.

Functionalized Ag with Thiol Ligand to Promote Effective CO2 Electroreduction

“…It is worth noting here that the Ag NP synthesized in this work already exhibits a promising catalytic performance toward the CO 2 R compared to the state-of-the-art Ag nanoparticle based system, 35−37 due to its properties of ultrasmall particle size, rich surface defects, and grain boundaries (Figure S8). 16,17,38 The above comparison suggests that the superior catalytic performance of re-AgS 4 likely does not originate from the structural modification, at least not significantly.…”

A Bimetallic Ag/Ti‐Based Coordination Polymer as a Catalyst for Electrocatalytic CO2 Reduction and Selective Sulfide Oxidation

“…As revealed in Figure 4C, {TiAg 2 } displays high faraday efficiency (FE) toward CO (more than 41 %) under all different potentials (À 0.58 V to À 1.18 V), and a maximum FE of about 90.3 % was observed at À 0.88 V. The maximum TOF value for CO is 658 h À 1 at À 1.08 V. The FE value of {TiAg 2 } is indeed comparable to that of many Ag-based nanomaterials catalysts. [28][29][30][31] {TiAg 2 } not only shows excellent FE, but also stays robust during electrochemical reduction of CO 2 for a long time. Under all potentials from À 0.58 V to À 1.18 V for 1 hour of electrolysis, {TiAg 2 } maintained a steady current density (Figure 4C).…”

All-alkynyl-protected coinage metal nanoclusters: from synthesis to electrocatalytic CO2reduction applications

“…In 2021, our group reported the structure analysis and eCO 2 RR performance of the smallest all-alkynyl-protected [Ag 15 (CRC t Bu) 12 ] + (abbreviated as Ag 15 ) nanocluster. 89 As shown in Fig. 8a, Ag 15 possesses a body-centered-cubic (bcc) structure with an Ag@Ag 8 @Ag 6 metal core configuration.…”