Atomically precise M ₁₅ (M = Au/Ag/Cu) alloy nanoclusters: Structural analysis, optical and electrocatalytic CO ₂ reduction properties

Abstract

Herein, the overall structure of a nanocluster coprotected by phosphine and mercaptan ligands [Au 7 Ag 8 (SPh) 6 ((p-OMePh) 3 P) 8 ]NO 3 (Au 7 Ag 8 ) was reported. For comparison, a previously reported nanocluster with the same structure, but a different metal composition, [Au 13 Cu 2 (TBBT) 6 ((p-ClPh) 3 P) 8 ]SbF 6 (Au 13 Cu 2 ), was synthesized. In addition, their optical and electrocatalytic CO 2 reduction properties were comprehensively compared. The results reveal that the photoluminescence quantum yield (PLQY) of the Ag-doped Au 7 Ag 8 nanocluster is 1.62%, which is seven times greater than that of the Cu-doped Au 13 Cu 2 nanocluster (PLQY = 0.23%). Furthermore, the Au 13 Cu 2 nanocluster demonstrates significantly enhanced catalytic selectivity for CO, with a CO Faradaic efficiency ranging from 79.7% to 90.4%, compared with that of the Au 7 Ag 8 nanocluster (CO Faradaic efficiency: 67.2%-77.7%) within a potential range of 0.5 to −1.1 V. From structural analyses, the superior CO selectivity of Au 13 Cu 2 is attributed to the copper dopant.

Boosting urea synthesis in simulated flue gas electroreduction by adjusting W–W electronic properties

“…Compared with W 18 O 49 @ZIF-8, the smaller EIS value of Cu–W 18 O 49 @ZIF-8 indicates an advantage for electronic transfer. 66–69 Meanwhile, the high density of electrocatalytic active sites resulting from the multi-porosity structure should also contribute to the high yield of urea.…”

An Au5Ag12(SR)9(dppf)4 alloy nanocluster: structural determination and optical property and photothermal conversion investigation

“…The synthesis of the Au 7 Ag 8 nanocluster was conducted with minor adjustments to a previously documented procedure. 52 HAuCl 4 ·4H 2 O (0.20 g mL −1 , 300 μL, 0.15 mmol) and AgNO 3 (90 mg, 0.53 mmol, dissolved in 2 mL of H 2 O) were sequentially introduced into a mixture containing 5 mL of ethyl alcohol and 15 mL of CH 2 Cl 2 , followed by vigorous agitation. After stirring for 5 minutes, ( p -OMePh) 3 P (160 mg, 0.45 mmol) and PhSH (0.24 mL, 2.34 mmol) were added successively to the reaction mixture, resulting in a change in the solution color from brown to light-yellow.…”

“…Compared with Au 5 Ag 11 (SPhMe 2 ) 8 (dppoe) 2 (Au 5 Ag 11 ), Au 4 Ag 13 (SPhMe 2 ) 9 (dppm) 3 (Au 4 Ag 13 ), and [Au 7 Ag 8 (SPh) 6 ((PhOMe) 3 P) 8 ]NO 3 (Au 7 Ag 8 ), which share an icosahedral M 13 core and a similar metal content, Au 5 Ag 12 demonstrates the highest photothermal conversion performance. 52,54,57 Upon excitation at 808 nm in 0.1 mM CHCl 3 solution, Au 5 Ag 12 exhibits a notable temperature rise of 9 °C within 270 s, surpassing the increases observed in Au 5 Ag 11 , Au 4 Ag 13 , and Au 7 Ag 8 under identical conditions. The persistence of Au 5 Ag 12 's structure after five photothermal cycles is noteworthy.…”

“…50,51 This approach not only contributes to the scientific understanding of nanomaterials but also paves the way for the development of more efficient and versatile photothermal agents. In recent years, a variety of alloy nanoclusters, including the families of M 15 , 29,52,53 M 16 , 54,55 and M 17 , 56,57 have been synthesized, laying the groundwork for further investigation into the properties of clusters.…”

Mo4+-Doped CuS Nanosheet-Assembled Hollow Spheres for CO2 Electroreduction to Ethanol in a Flow Cell

“…Utilizing renewable electricity to catalyze CO 2 reduction reaction (CO 2 RR) into value-added chemicals can effectively promote the sustainable development of carbon circular economy. − Of all CO 2 RR products, multicarbon (C 2+ ) species are more attractive on account of their high energy density and economic value. − Especially, ethanol, as a C 2 liquid product with convenient transportation and storage, is extensively utilized as a raw material for chemical synthesis, a solvent, a fuel, and an additive for gasoline, and so on. Cu-based materials are the main catalysts for CO 2 RR to ethanol, which mostly profit by Cu δ+ species (0 < δ <2) with medium electron-donating ability to bond C atoms with positive charge for C–C coupling. , However, Cu δ+ active species often experience in situ electroreduction during CO 2 RR, limiting the adsorption of *CO intermediate and C–C coupling, consequently, decreasing the activity and selectivity for ethanol production, especially at large current densities.…”