Reversible Switching of Catalytic Activity by Shuttling an Atom into and out of Gold Nanoclusters

Abstract

It is challenging to control the catalyst activation and deactivation by removal and addition of only one central atom, as it is almost impossible to precisely abstract an atom from aconventional catalyst and analyze its catalysis.Here we report that the loss of one central atom in Au 25 (resulting in Au 24 ) enhances the catalytic activity in the oxidation of methane compared to the original Au 25 .M ore importantly,t he activity can be readily switched through shuttling the central atom into Au 24 and out of Au 25 .This work will serve as astarting point for design rules on howt oc ontrol catalytic performance of ac atalyst by an atom alteration.

Controllable Conversion of CO2on Non‐Metallic Gold Clusters

“…[9][10][11][12][13][14][15] Specifically,they can be used to explore how the catalytic performance can be tailored by only one atom alteration. [16,17] They can also circumvent the sluggish kinetics of electron transfer for non-photosynthetic bacteria to enable photosynthesis of acetic acid from CO 2 . [18] Such studies are typically impossible for traditional metallic catalysts.…”

“…For example, these clusters provide exciting opportunities to map out the explicit structure‐property relationship and allow for identification of active sites with atomic precision . Specifically, they can be used to explore how the catalytic performance can be tailored by only one atom alteration . They can also circumvent the sluggish kinetics of electron transfer for non‐photosynthetic bacteria to enable photosynthesis of acetic acid from CO 2 .…”

Core Charge Density Dominated Size‐Conversion from Au6P8 to Au8P8Cl2

“…To date, the size‐conversion of several atomically precise MNCs upon treating with heating (e.g., Au 25 →Au 38 and Au 25 →Au 22 ), ligands (e.g., Au 38 →Au 36 , Au 13 →Au 25 , Au 25 →Au 23 ), pH changes (e.g., Au 25 →Au 23 , Au 16 ↔Au 18 , Au 18 →Au 22 ), and different solvents (e.g., Au 25 →Au 24 , Au 6 →Au 7 , Au 8 , Au 11 , etc.) have been reported .…”

Reactivity and Lability Modulated by a Valence Electron Moving in and out of 25‐Atom Gold Nanoclusters

“…[4][5][6][7][8][9] Coupled with operando spectroscopy and theoretical studies,v ery fundamental understanding of catalysis is expected at the single-atom or single-electron level. [10][11][12] Atomically precise Au n (SR) m (abbreviated as Au n hereafter) nanoclusters possess free valence electrons,w hich typically differ from the organometallic complexes,a nd have been used as model catalysts for establishing the relationship between catalytic properties and atomic-level structures,a swell as identifying the active sites of catalysts based on nanoclusters. [13][14][15][16][17][18][19][20][21] Within this field, Au 25 is ap ioneer in opening up new horizons in catalysis science.…”