Plasmon-Mediated Electron Injection from Au Nanorods into MoS2: Traditional versus Photoexcitation Mechanism

Zhang, Zhaosheng; Liu, Lihong; Fang, Wei‐Hai; Long, Run; Tokina, Marina V.; Prezhdo, Oleg V.

doi:10.1016/j.chempr.2018.02.025

Cited by 104 publications

(107 citation statements)

References 85 publications

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“…The methodology has been applied successfully to study photoexcitation dynamics in a broad range of systems, including TiO 2 , 30 , 31 and it interfaces with electron donors, 32 − 35 metal halide perovskites, 36 − 38 and so on. 39 − 42 …”

Section: Methodsmentioning

confidence: 99%

Water Splitting with a Single-Atom Cu/TiO₂ Photocatalyst: Atomistic Origin of High Efficiency and Proposed Enhancement by Spin Selection

Cheng

Fang

Long

et al. 2021

JACS Au

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Anatase TiO 2 is an intensely investigated photocatalytic material due to its abundance and chemical stability. However, it suffers from weak light harvesting and low photocatalytic efficiency. Experiments show that light absorption and photocatalytic properties can be enhanced simultaneously by TiO 2 doping with well-dispersed Cu atoms, forming a single-atom catalyst (Cu/TiO 2 ) that can be used for solar water splitting and other applications. By performing ab initio nonadiabatic molecular dynamics simulations, we demonstrate that Cu/TiO 2 is inactive before light irradiation due to rapid electron–hole recombination via both shallow and deep traps. Surprisingly, the shallow trap is more detrimental to the Cu/TiO 2 performance than the deep trap because it couples better to free carriers. After light irradiation, leading to electron transfer and Cu/TiO 2 protonation, the shallow trap is eliminated, and a local distortion around the Cu atom stabilizes the deep trap state on the Cu d-orbital, decoupling it from free charges and giving rise to high photocatalytic hydrogen generation activity. We further demonstrate that the photocatalytic performance of Cu/TiO 2 can be enhanced by spin selection, achievable experimentally via optical intersite spin transfer or chiral semiconductor coating. Both H adsorption and spin selection enhance charge carrier lifetimes by an order of magnitude. The spin selection mechanism does not require formation of the H species, which necessitates concurrent sources of electrons and protons and which is intrinsically unstable because water splitting involves frequent proton shuffling. Our results rationalize the experimental observations at the atomistic level, provide mechanistic insights into operation of single atom photocatalysis, and demonstrate that spin selection can be used to develop advanced and efficient systems for solar energy conversion.

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Section: Methodsmentioning

confidence: 99%

Water Splitting with a Single-Atom Cu/TiO₂ Photocatalyst: Atomistic Origin of High Efficiency and Proposed Enhancement by Spin Selection

Cheng

Fang

Long

et al. 2021

JACS Au

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“…One effective approach is to construct a heterostructure of plasmonic metal and semiconductor, in which an interfacial electric field exists at the plasmon-semiconductor interface, facilitating the effective separation of the generated hot electrons and holes. It has been reported that plasmonic metals (gold and silver) have been combined with many semiconductor materials, including TiO2 [74], zinc oxide (ZnO) [75], CdS [76], molybdenum disulfide (MoS2) [77], silver halides (AgX) [78], and bismuth oxide halides (BiOX) (X = Cl, Br, I) [79]. The obtained heterostructures showed enhanced photocatalytic performances, due to the improved charge separation.…”

Section: Hot Hole-involved Photochemistry At Plasmonsemiconductor Intmentioning

confidence: 99%

Plasmon-generated hot holes for chemical reactions

Zhang

Jia

et al. 2020

Nano Res.

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Plasmonic nanostructures have been widely used for photochemical conversions due to their unique and easy-tuning optical properties in visible and near-infrared range. Compared with the plasmon-generated hot electrons, the hot holes usually have a shorter lifetime, which makes them more difficult to drive redox reactions. This review focuses on the photochemistry driven by the plasmon-generated hot holes. First, we discuss the generation and energy distribution of the plasmon-generated hot carriers, especially hot holes. Then, the dynamics of the hot holes are discussed at the interface between plasmonic metal and semiconductor or adsorbed molecules. Afterwards, the utilization of these hot holes in redox reactions is reviewed on the plasmon-semiconductor heterostructures as well as on the surface of the molecule-adsorbed plasmonic metals. Finally, the remaining challenges and future perspectives in this field are presented. This review will be helpful for further improving the efficiency of the photochemical reactions involving the plasmon-generated hot holes and expanding the applications of these hot holes in varieties of chemical reactions, especially the ones with high conversion rate and selectivity.

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“…[14,15] Since these values are below the optical bandgap of MoS 2 (1.8 eV for a monolayer), a clever tuning of the PR spectral position, by appropriately changing the metal nanostructure dimensions or aspect ratio, can also potentially lead to sub-bandgap photon harvesting. According to a theoretical study, [16] charge transfer at the Au/MoS 2 interface efficiently competes with the onset of nonradiative carrier thermalization in gold and occurs via a traditional incoherent two-step process (i.e., without interfacial charge-transfer character) involving PRs decay in free hot electrons and injection above the Schottky barrier on ≈100 fs Hybrid plasmonic-semiconductor assemblies are receiving considerable attention due to the possibility to achieve hot-carrier-based photodetection. In this context, 2D transition metal dichalcogenides (TMDs) coupled to metal nanostructures are very promising.…”

Section: Introductionmentioning

confidence: 99%

Evidence of Plasmon Enhanced Charge Transfer in Large‐Area Hybrid Au–MoS₂ Metasurface

Camellini

Mazzanti

Mennucci

et al. 2020

Advanced Optical Materials

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Hybrid plasmonic‐semiconductor assemblies are receiving considerable attention due to the possibility to achieve hot‐carrier‐based photodetection. In this context, 2D transition metal dichalcogenides (TMDs) coupled to metal nanostructures are very promising. However, the plasmon‐to‐TMD carrier injection process is extremely challenging to achieve and even to reveal in a clear‐cut way. Herein, a report of multiple transient absorption ultrafast measurements, with tunable pump excitation, enabling quantitative comparison between the ultrafast behavior of metal nanostructures, TMDs, and their assembly is shown. This allows to provide the evidence of plasmon‐enhanced charge injection from Au nanostripes to a rippled‐shaped molybdenum disulfide (MoS2) few‐layer nanosheet. Finite element method numerical simulations and modeling of the transient optical response corroborate the charge transfer mechanism, showing that the experimental data cannot be described in terms of the thermomodulational nonlinearity of gold nanostripes or by simple superposition of metal and semiconductor responses. The sample is obtained by a self‐organization process on a large area; this demonstrates that plasmon‐enhanced photon harvesting exploiting hot‐electron injection can be achieved on a large area (approximately cm2) surface and provides a substantial advancement toward scalable ultrathin photodetection devices based on hot‐electrons technology.

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Plasmon-Mediated Electron Injection from Au Nanorods into MoS2: Traditional versus Photoexcitation Mechanism

Cited by 104 publications

References 85 publications

Water Splitting with a Single-Atom Cu/TiO₂ Photocatalyst: Atomistic Origin of High Efficiency and Proposed Enhancement by Spin Selection

Water Splitting with a Single-Atom Cu/TiO₂ Photocatalyst: Atomistic Origin of High Efficiency and Proposed Enhancement by Spin Selection

Plasmon-generated hot holes for chemical reactions

Evidence of Plasmon Enhanced Charge Transfer in Large‐Area Hybrid Au–MoS₂ Metasurface

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Plasmon-Mediated Electron Injection from Au Nanorods into MoS2: Traditional versus Photoexcitation Mechanism

Cited by 104 publications

References 85 publications

Water Splitting with a Single-Atom Cu/TiO2 Photocatalyst: Atomistic Origin of High Efficiency and Proposed Enhancement by Spin Selection

Water Splitting with a Single-Atom Cu/TiO2 Photocatalyst: Atomistic Origin of High Efficiency and Proposed Enhancement by Spin Selection

Plasmon-generated hot holes for chemical reactions

Evidence of Plasmon Enhanced Charge Transfer in Large‐Area Hybrid Au–MoS2 Metasurface

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Product

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Water Splitting with a Single-Atom Cu/TiO₂ Photocatalyst: Atomistic Origin of High Efficiency and Proposed Enhancement by Spin Selection

Water Splitting with a Single-Atom Cu/TiO₂ Photocatalyst: Atomistic Origin of High Efficiency and Proposed Enhancement by Spin Selection

Evidence of Plasmon Enhanced Charge Transfer in Large‐Area Hybrid Au–MoS₂ Metasurface