Electrocatalysis on Atomically Precise Metal Nanoclusters

Seong, Hoeun; Choi, Woojun; Jo, Yongsung

doi:10.1002/9781119788676.ch5

Cited by 4 publications

(1 citation statement)

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“…Unlike in discrete monometallic systems, the active site steric environment in APNCs is shaped by the coordination sphere on several adjacent metal atoms, resulting in an enzyme-like binding pocket that can be manipulated to control access and release of substrates and products. 26 Moreover, the configuration and number of core atoms can be known precisely and varied systematically to improve catalyst performance. 9,27- 30 Finally, APNCs incorporate a high density of active surface sites, leading to possible enhancement of turnover frequencies relative to analogous surfaces.…”

Section: Introductionmentioning

confidence: 99%

Ditopic ligand effects on solution-phase equilibria and electrochemistry of atomically precise copper chalcogenide nanoclusters

Trenerry,

Bailey

2024

Preprint

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Atomically precise copper chalcogenide nanoclusters are an exceptionally diverse class of nanomaterials with potential applications in chemiluminescence, sensing, and catalysis. However, most previously reported nanoclusters have been characterized exclusively in the solid state, leaving open questions as to their stability and function in solution. In this work, we report the first detailed solution-phase investigation of speciation, electrochemistry, and decomposition of atomically precise [Cu12S6] supported by a series of mono- and ditopic alkyldiphenylphosphines PPh2R (R = Et, -(CH2)5-, -(CH2)8-). While electronically identical, this series of ligands features monotopic and ditopic binding modes spanning zero, one, or three axes of the [Cu12S6] core, facilitating an in-depth examination of the impact of phosphine binding topology on solution behaviour. We find that binding topology dictates the extent of speciation, with complete solution stability being afforded through use of the longer octane chelate dppo (1,8-bis(diphenylphosphino)octane). Thus, the 1H and DOSY NMR spectra of [Cu12S6(dppo)4] indicate a rigid, stereochemically locked ligand configuration in which substantial stabilizing CH---S interactions are present. Meanwhile, electrochemical analysis coupled with DFT calculations indicates that the [Cu12S6] core undergoes a quasireversible one-electron oxidation at –0.50 V vs Fc0/+. In contrast, prolonged air exposure or treatment with chemical oxidants results in cluster degradation with formation of phosphine sulfide byproducts. This work demonstrates both progress and challenges in controlling the solution-phase behaviour and redox chemistry of phosphine-supported copper chalcogenide nanoclusters.

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Section: Introductionmentioning

confidence: 99%

Ditopic ligand effects on solution-phase equilibria and electrochemistry of atomically precise copper chalcogenide nanoclusters

Trenerry,

Bailey

2024

Preprint

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Atomically precise metal nanoclusters for energy conversion

Seong,

Lee

2024

Bulletin Korean Chem Soc

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Atomically precise metal nanoclusters (NCs) have emerged as a new frontier in electrocatalysis, enabling the study of electrocatalytic reactions on well‐defined stable surfaces and rational electrocatalyst design based on atomic‐level tailoring. In this review, we focus on the recent applications of these NCs to energy conversion reactions, including those involved in water splitting (hydrogen and oxygen evolution reactions), fuel cell operation (oxygen reduction and hydrogen oxidation reactions), and electrochemical CO2 reduction. Emblematic examples are used to highlight the roles of different NC parts, for example, core metal and surrounding ligands, and the significance of the electrode substrate. Finally, we discuss the perspectives of the future development and implementation of NC‐based energy conversion systems.

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