Electrochemical CO₂ reduction catalyzed by atomically precise alkynyl-protected Au₇Ag₈, Ag₉Cu₆, and Au₂Ag₈Cu₅ nanoclusters: probing the effect of multi-metal core on selectivity

Abstract

Doping metal nanoclusters (NCs) with another metal usually leads to superior catalytic performance toward CO2 reduction reaction (CO2RR), yet elucidating the metal core effect is still challenging. Herein, we report...

Body-Centered-Cubic-Kernelled Ag15Cu6 Nanocluster with Alkynyl Protection: Synthesis, Total Structure, and CO2 Electroreduction

“…In this case, H* also prefers to bind to the Ag–Cu bridge site (Figure S20). Moreover, according to the recent work by Tang and co-workers, the comparable PDS energetics for the CO (0.40 eV) and formate (0.54 eV) formation on the ligand-removed Ag 9 Cu 6 result in an unsatisfactory FE and product selectivity, which is consistent with our experimental observation that Ag 15 Cu 6 exhibits a much better activity and selectivity toward CO production over the Ag 9 Cu 6 cluster.…”

“…Inspired by the recent researches on alkynyl-stabilized clusters for electrocatalytic reaction, , we predicted that local ligand removal exposes undercoordinated metal atoms, which may serve as the key reaction centers. Since the clusters are supported on carbon, removal of an alkynyl ligand is anticipated not to cause significant structural changes.…”

“…The electrochemical CO 2 reduction reaction (eCO 2 RR) holds great promise in the implementation of the carbon neutrality since it can convert CO 2 into value-added chemicals and fuels with the integration of renewable electricity, ambient reaction conditions, and tunable product selectivity. , Atomically precise metal nanoclusters, as new model electrocatalysts for eCO 2 RR, not only demonstrate promising catalytic performance but also enable the mechanistic investigations at the atomic level. ,, Gold nanoclusters stabilized by different ligands, including thiolates, phosphines, carbenes, alkynyls, and amidinates, have been extensively used for eCO 2 RR studies, revealing that the composition, core and surface structure, and ligand shell play a critical role in obtaining high faradaic efficiency (FE). ,,− Furthermore, doping of gold clusters with heteroatoms (e.g., Cd, Pt, and Ag) has been found to alter the electronic structure of the cluster and optimize the binding energies of the reaction intermediates, thereby enhancing the performance of eCO 2 RR. − The multi-metal core in the alkynyl-protected Au 7 Ag 8 , Ag 9 Cu 6 , and Au 2 Ag 8 Cu 5 clusters is found to significantly influence the product selectivity . Notably, only a handful of Cu and Ag clusters are employed for eCO 2 RR, ,, which may be due to the predominant competitive H 2 evolution, indicating the need for the design and synthesis of new nanoclusters of Ag, Cu, or their alloys for eCO 2 RR.…”

Platonic and Archimedean solids in discrete metal-containing clusters

“…490 A series of similar alloy M 15 + (Ag 9 Cu 6 , Au 7 Ag 8 , and Au 2 Ag 8 Cu 5 ) is also available. 491–493…”

Insight into the Role of Copper in the Transformation of a [Ag25(2,5-DMBT)16(DPPF)3]+ Nanocluster: Doping or Oxidation

“…Recently, alteration of the compositions of NCs has been recognized as an efficient approach for realizing the structural transformation of NCs. , This strategy can induce a significant structural transformation and make the transformation process more manageable. Therein, doping heterometallic atoms into a NC is more desirable because the synergistic effect between different metals can significantly affect the properties of the doping products even though the initial structural framework has not been changed. − On the basis of the reactions between NCs and heterometallic atoms, alloying NCs have been prepared in previous works, − especially the Au–Cu − or Ag–Cu − NCs. In these cases, copper is chosen because of its economy, and, in addition, it can react with NCs in two ways: (i) replacing the original metal atoms without changing the structural framework of parent NCs (which occurred in most copper-based alloy NCs); − (ii) initiating structural transformation of the parent NC, such as the size conversion from Au 25 to Au 44 and from Au 21 to Au 21– x Cu x in a different configuration. , Recently, related research works focusing on the effect of Cu 2+ on the charge states of NCs have been carried out by our group .…”