On the Roles of Electron Transfer in Catalysis by Nanoclusters and Nanoparticles

Abstract

Electron transfer plays a major role in chemical reactions and processes, and this is particularly true of catalysis by nanomaterials. The advent of metal nanoparticle (NP) catalysts, recently including atomically precise nanoclusters (NCs) as parts of nanocatalyst devices has brought increased control of the relationship between NP and NC structures and their catalytic functions. Consequently, the molecular definition of these new nanocatalysts has allowed a better understanding and management of various kinds of electron transfer involved in the catalytic processes. This Minireview brings a chemist's view of several major aspects of electron-transfer functions concerning NPs and NCs in catalytic processes. Particular focus concerns the role of NPs and NCs as electron reservoirs and light-induced antenna in catalytic processes from H 2 generation to more complex reactions and sustainable energy production.

A Career in Catalysis: Didier Astruc

“…A mixed coinage metal cluster Au 4 Cu 4 was found to capture a key intermediate, Au 4 Cu 4 –π-alkyne, of the CuAAC “click” reaction without alkyne deprotonation to a σ,π-alkynyl intermediate despite the common belief according to which the alkyne would be deprotonated first before undergoing the CuAAC reaction . Didier had already extended the function of electron reservoirs in redox catalysis to Au and PdNPs, , and given the crucial role of electron transfer in cluster catalysis, he recently examined this role with late transition-metal atomically precise clusters …”

“…This catalytic activity was controlled by acid–base equilibrium; i.e., it was enhanced by base and stopped by acid, so that H 2 was delivered on command from its precursor. , The presence of a plasmonic metal in the alloyed nanocomposite is known to induce visible-light acceleration of some reactions. , Although Au did not catalyze ammonia borane or sodium borohydride hydrolysis, alloying Au with a late transition metal sometimes favored the reaction, but strong positive effects were obtained in the presence of visible light that boosted the reaction because of the hot electron transfer generated in the fs time scale from plasmonic Au to the active metal-substrate site of the transition-metal catalyst . In most of these systems, hydrogen production was used in situ for alkene hydrogenation with the same nanocatalyst (one pot) or Pd/C, a process that had been shown by the Astruc group early on to proceed stepwise (one H atom after the other). − …”

Emerging Prospects of Nanozymes for Antibacterial and Anticancer Applications

“…Several nanoscale materials are known for their fascinating properties which pave the way for various attractive applications [ 1 , 2 ]. It is well known that due to the high surface-to-volume ratio of nanoparticles, they can function as efficient heterogeneous catalysts [ 3 , 4 ]. This catalytic behavior is also observed in the biological domain, where certain nanoparticles can mimic the function of natural enzymes, which can be attributed to both the intrinsic composition and surface properties of the nanoparticles.…”

High‐Efficient Ultrathin PdCuMo Porous Nanosheets with Abundant Defects for Oxygen Reduction Reaction

“…Among the reported non-Pt catalysts, Pd has attracted much attention because Pd has the same number of electrons in the outermost layer and similar chemical properties to Pt. [8][9][10][11][12] Moreover, Pd owns the superior ability to resist CO poisoning. Although Pd has become an effective substitute for Pt-based catalysts, it's hard to design a single-metal Pd catalyst with good catalytic activity because the oxygen adsorption energy of monometallic Pd is high, and the binding of oxygen on the surface of Pd is very strong.…”

“…Among the reported non‐Pt catalysts, Pd has attracted much attention because Pd has the same number of electrons in the outermost layer and similar chemical properties to Pt [8–12] . Moreover, Pd owns the superior ability to resist CO poisoning.…”