Charge state-dependent catalytic activity of [Au₂₅(SC₁₂H₂₅)₁₈] nanoclusters for the two-electron reduction of dioxygen to hydrogen peroxide

Abstract

The electrochemical production of H2O2 from O2 catalyzed by [Au25(SC12H25)18] was studied as a function of the charge state (-1, 0 and +1). Maximum H2O2 production (∼90%) was obtained from the negatively charged clusters (Au25(-)) due to the efficient electron transfer from the anionic Au25(-) cluster into the LUMO (π*) of O2.

Ultrasmall Palladium Nanoclusters as Effective Catalyst for Oxygen Reduction Reaction

“…[1][2][3] As eries of gold nanoclusters with atomicp recision have been successfully achieved with size-focusing andl igand-exchange-induced transformation methods, [4] some of which have been crystallographically solved. [5][6][7][8][9] Owing to the quantum size effect, ultrasmall nanoclusters show distinct properties as comparedt olarger gold nanoparticles andh old great promise in catalysis, [10][11][12] sensing, [13,14] energy, [15][16][17][18][19][20] and many other applications.…”

“…Herein, we report ao ne-phase method for the synthesis of thiolate-protected palladium nanoclusters with less than 20 palladium atoms protected by the 4-tert-butylbenzenethiolate ligand.M atrix-assisted laser desorption ionization (MALDI) mass spectrometry (MS) determined the nanoclusters to have am ass of approximately 5kDa. Its estimated formula is Pd [13][14][15][16][17] (SR) [18][19][20][21][22] (R = Ph-tBu) based upon the combined mass The recent prosperity of ultrasmall gold nanoclustersm akesi t desirable to expand the family of clusters to other metals. Here, we presentaone-phase approachf or synthesizing thiolate-protected palladium nanoclustersw ith am ass of approximately 5kDa.…”

“…Kinetic investigation indicates a direct four-electron oxygen reduction pathway for both ligand-on and ligand-off palladium nanoclusters, which constitutes the enhancement of power generation compared to the two-electron reduction pathway, [16] giving rise to hydrogen peroxide.…”

Catalytic Amplification of Au144 Nanocluster Collisions by Hydrogen Evolution Reaction

“…The size and charge state of NCs are essential factors influencing their catalytic activities, as demonstrated for oxygen and carbon dioxide electroreductions at Au nanoclusters. [6,7,[9][10][11] The atomic NCs typically exhibit high monodispersity [12] and well-defined molecular composition. [7] While larger NPs with long-chain capping ligands tend to be catalytically inert; [8] the NCs capped with a long chain surfactant can effectively catalyze surface reactions, though the activation mechanism in this case is largely unknown.…”

Synthesis of Protein-Directed Orange/Red-Emitting Copper Nanoclusters via Hydroxylamine Hydrochloride Reduction Approach and Their Applications on Hg2+ Sensing

“…[1][2][3][4] Since the size of MNCs is comparable to the Fermi wavelength of an electron, they exhibit discrete energy levels and molecule-like properties such as size-tunable electronic transitions and strong luminescence properties. [5][6][7] MNCs have been applied to practical applications in cell imaging, [8][9][10][11][12][13] ion sensing, [14][15][16][17][18] catalysis, [19][20][21][22] etc. In the past few years, extensive studies are concentrated on the synthesis of luminescent noble metals (i.e., Au, Ag and Pt) NCs, using various kinds of templates.…”