Interplay between Chemical Transformations and Atomic Structure in Nanocrystals and Nanoclusters

Han, Haixiang; Yao, Yuan; Robinson, Richard D.

doi:10.1021/acs.accounts.0c00704

Cited by 30 publications

(25 citation statements)

References 72 publications

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“…Metal NCs are composed of the same metal atoms as observed in conventional metal nanocrystals, but they demonstrate distinct physicochemical properties from metal nanocrystals in light of complicated electronic structure at the atomic level. − This leads us to consider the intrinsic charge transport correlation between atomically precise metal NCs and metal nanocrystals in photoredox catalysis, which would significantly bridge the gap between these two metal nanomaterials for solar energy conversion. To this end, Au(0)Au(I)@GSH NCs and plasmonic citrate-capped Au nanoparticles (NPs) building blocks are progressively and periodically integrated with each other on the wide-band gap metal oxide framework (e.g., TiO 2 ) via a facile and easily accessible layer-by-layer (LbL) assembly strategy at ambient conditions (Figure d), which retains the structural stability of metal NCs.…”

Section: Metal Ncs-based Solar Energy Conversionmentioning

confidence: 99%

Solar-Powered Photocatalysis and Photoelectrocatalysis over Atomically Precise Metal Nanoclusters

Liu

Xiao

2021

J. Phys. Chem. C

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Atomically precise metal nanoclusters (NCs) have garnered enduring interest in account of peculiar atomic stacking mode, discrete energy band structure, and abundant active sites, which are distinct from conventional metal nanocrystals. Nonetheless, research works on metal NCs-based photosystems are still in the infant stage in terms of generic light-induced instability, deficiency of metal NCs with photosensitization effect to trigger photoredox catalysis, and a complicated interfacial charge transport process. Herein, we concisely overview the latest concerted endeavors in constructing metal NCs-based photosystems for heterogeneous photocatalysis and photoelectrochemical water splitting with particular emphasis focusing on elucidating the charge transfer characteristics of metal NCs. Moreover, objective discussion and personal opinions on quintessential works are specifically provided. Future perspectives and challenges of metal NCsbased photosystems are eventually highlighted. We hope this perspective article would inspire ongoing interest in unleashing the emerging potentials of atomically precise metal NCs for solar energy conversion.

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Section: Metal Ncs-based Solar Energy Conversionmentioning

confidence: 99%

Solar-Powered Photocatalysis and Photoelectrocatalysis over Atomically Precise Metal Nanoclusters

Liu

Xiao

2021

J. Phys. Chem. C

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“…Postsynthetic chemical transformation, a novel synthetic method, is an interesting and emerging method for obtaining materials with desired characteristics and involves the use of presynthesized nanoparticles (NPs) as starting materials. 4,5 Through postsynthetic transformations, such as ion exchange, 6,7 galvanic exchange, 8 and redox addition reactions, 4,9 foreign elements are exchanged with the original elements or introduced to presynthesized NPs, with new derivatives produced with various compositions, 8 crystal phases, 10 and structures 6 that are not accessible using direct synthetic routes. Several studies have applied postsynthetic transformations based on metal, 9 metal chalcogenide, 6 and metal oxide 7 NPs; however, studies utilizing metal phosphides as starting materials for postsynthetic transformation are lacking because the metal and metalloid atoms are strongly bonded, 11,12 which restricts the metal elements that can be used (Cu, In, Ga, etc.).…”

Section: Introductionmentioning

confidence: 99%

“…Despite the advantages of colloidal synthesis, including monodispersity 1 and solution processability, 3 there is a high demand for advanced synthetic routes for new nanomaterials with tailored electronic, optical, and structural properties. Postsynthetic chemical transformation, a novel synthetic method, is an interesting and emerging method for obtaining materials with desired characteristics and involves the use of presynthesized nanoparticles (NPs) as starting materials 4,5 . Through postsynthetic transformations, such as ion exchange, 6,7 galvanic exchange, 8 and redox addition reactions, 4,9 foreign elements are exchanged with the original elements or introduced to presynthesized NPs, with new derivatives produced with various compositions, 8 crystal phases, 10 and structures 6 that are not accessible using direct synthetic routes.…”

Section: Introductionmentioning

confidence: 99%

Transition‐metal‐incorporated molybdenum phosphide nanocatalysts synthesized through post‐synthetic transformation for the hydrogen evolution reaction

Kim

Park

Lee

et al. 2022

Intl J of Energy Research

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Summary Post‐synthetic chemical transformation is a recently emerging nanomaterial manufacturing method for obtaining materials with precisely modulated properties. Through post‐synthetic transformation methods, foreign elements are exchanged or incorporated into presynthesized nanoparticles (NPs). However, metal phosphides have not been primarily used as starting materials because of their strong bonding characteristics. In this study, we synthesized bimetallic transition metal phosphide (TMP) NPs through a cation addition reaction using amorphous molybdenum phosphide (MoP) as the starting material, which is a promising catalyst for the hydrogen evolution reaction (HER). The additional metal elements, namely Co and Ni, were successfully incorporated into the parent MoP NPs, which led to only marginal changes in size or shape, even after 12 hours of reaction. Because morphological factors strongly influence catalytic activity, nanocatalysts with identical morphologies provide a direct comparison among NPs with various chemical properties. The Co‐ and Ni‐incorporated MoP NPs exhibited significantly enhanced catalytic activities for the HER, with similar electrochemically active surface areas. In particular, Co‐1.5 h‐MoP showed the highest HER activity (167 mV at −10 mA cm−2) and durability among the samples in 0.5 M H2SO4. Such an improvement in catalytic activity through the cation addition reaction may be ascribed to the difference in the electronegativities of the original and newly added metal cations, as confirmed by X‐ray photoelectron spectroscopy (XPS), resulting in abundant metal‐P bonding and oxidation resistivity. This study provides a new advanced platform for directly analyzing the inherent characteristics of nanomaterials for diverse applications, especially electrocatalysis.

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“…Well‐defined, atomically precise metal nanoclusters (NCs) protected by ligands in the size range of tens to hundreds of metal atoms (equivalent to 1–3 nm in core diameter) would be perfect candidates for catalysis because the activity and selectivity could be controlled through the size, morphology, composition, surface charge and surface ligand of the nanocluster [1,2] . Most importantly, the structure‐activity relationship at the atomic level, insights into molecular activation, detailed mechanisms and the identification and modification of the active sites of such nanoclusters are possible because of their well‐defined crystallographically characterized structure [3,4] . To date, various structurally characterized NCs have been used for catalytic, photocatalytic and electrocatalytic reactions [5,6] .…”

Section: Introductionmentioning

confidence: 99%

Tetrametallic Copper Complex to Nanoscale Copper: Selective and Switchable Dehydrogenation‐Hydrogenation under Light

Pratihar

Sarmah

Shelte

et al. 2021

Chemistry A European J

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A discrete, photoactive, ultrafine copper nanocluster of fewer than hundreds of atoms with stimuli‐responsive switchable redox‐active states is highly desired to control two different antagonistic reactions. Herein, a mixed‐valent tetrametallic copper complex (C‐1) of N−O‐N Schiff base ligand is disclosed, in which the five different Cu−Cu interactions were used to generate photoactive nanoscale copper [LCu0n, S‐1] through the reduction of coordinated imine to the amine of C‐1. The presence of a ligand provides stability and helps to homogenize the material (S‐1) in the organic solvent. The cluster showed stimuli (O2/light)‐responsive switching between its reduced (S‐1) and oxidized [LCu0n−mCuOm, S‐2] states that allows it to serve as a highly and poorly active (bistate, relative rate >5–12 fold) catalyst for the dehydrogenation of alcohols to aldehydes and hydrogenation of nitroaromatics to amino aromatics under the light.

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Interplay between Chemical Transformations and Atomic Structure in Nanocrystals and Nanoclusters

Cited by 30 publications

References 72 publications

Solar-Powered Photocatalysis and Photoelectrocatalysis over Atomically Precise Metal Nanoclusters

Solar-Powered Photocatalysis and Photoelectrocatalysis over Atomically Precise Metal Nanoclusters

Transition‐metal‐incorporated molybdenum phosphide nanocatalysts synthesized through post‐synthetic transformation for the hydrogen evolution reaction

Tetrametallic Copper Complex to Nanoscale Copper: Selective and Switchable Dehydrogenation‐Hydrogenation under Light

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