Mechanistic Insights into Photocatalyzed Hydrogen Desorption from Palladium Surfaces Assisted by Localized Surface Plasmon Resonances

Spata, Vincent A.; Carter, Emily A.

doi:10.1021/acsnano.8b00352

Cited by 67 publications

(94 citation statements)

References 74 publications

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“…In this case, population of the hybridized Pd and H atom orbitals brings the system to an excited state and results in smaller activation barriers along the reaction pathway compared to the ground state (Supplementary Fig. 8 ) 41 . Therefore, the increased absorption cross-section throughout the Pd cube expedites the phase transformation.…”

Section: Discussionmentioning

confidence: 99%

In-situ observation of plasmon-controlled photocatalytic dehydrogenation of individual palladium nanoparticles

et al. 2018

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Plasmonic nanoparticle catalysts offer improved light absorption and carrier transport compared to traditional photocatalysts. However, it remains unclear how plasmonic excitation affects multi-step reaction kinetics and promotes site-selectivity. Here, we visualize a plasmon-induced reaction at the sub-nanoparticle level in-situ and in real-time. Using an environmental transmission electron microscope combined with light excitation, we study the photocatalytic dehydrogenation of individual palladium nanocubes coupled to gold nanoparticles with sub-2 nanometer spatial resolution. We find that plasmons increase the rate of distinct reaction steps with unique time constants; enable reaction nucleation at specific sites closest to the electromagnetic hot spots; and appear to open a new reaction pathway that is not observed without illumination. These effects are explained by plasmon-mediated population of excited-state hybridized palladium-hydrogen orbitals. Our results help elucidate the role of plasmons in light-driven photochemical transformations, en-route to design of site-selective and product-specific photocatalysts.

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Section: Discussionmentioning

confidence: 99%

In-situ observation of plasmon-controlled photocatalytic dehydrogenation of individual palladium nanoparticles

et al. 2018

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“…with localized surface plasmon resonance (LSPR), which could not only broaden the light absorption range, but also inject hot electrons into the conduction band (CB) of the neighboring semiconductor and suppress the recombination of charge carriers. [ 17–20 ] Moreover, radiative energy transfer from the metal LSPR to the neighbor semiconductor could take place through near‐field electromagnetic resonant. [ 21,22 ] In the construction of metal/semiconductor Schottky junction, the geometrical configuration has a significant influence on their performance.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Piezo‐Photoelectric Catalysis with Oriented Carrier Migration in Asymmetric Au−ZnO Nanorod Array

Xiang

Liu

et al. 2020

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147

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Current photocatalytic semiconductors often have low catalytic performance due to limited light utilization and fast charge carrier recombination. Formation of Schottky junction between semiconductors and plasmonic metals can broaden the light absorption and facilitate the photon‐generated carriers separation. To further amplify the catalytic performance, herein, an asymmetric gold‐zinc oxide (Asy‐Au−ZnO) nanorod array is rationally designed, which realizes the synergy of piezocatalysis and photocatalysis, as well as spatially oriented electron−hole pairs separation, generating a significantly enhanced catalytic performance. In addition to conventional properties from noble metal/semiconductor Schottky junction, the rationally designed heterostructure has several additional advantages: 1) The piezoelectric ZnO under light and mechanical stress can directly generate charge carriers; 2) the Schottky barrier can be reduced by ZnO piezopotential to enhance the injection efficiency of hot electrons from Au nanoparticles to ZnO; 3) the unique asymmetric nanorod array structure can achieve a spatially directed separation and migration of the photon‐generated carriers. When ultrasound and all‐spectrum light irradiation are exerted simultaneously, the Asy‐Au−ZnO reaches the highest catalytic efficiency of 95% in 75 min for dye degradation. It paves a new pathway for designing unique asymmetric nanostructures with the synergy of photocatalysis and piezocatalysis.

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“…[147][148][149] In particular, DFT embedding approaches 150 such as the frozen density embedding have shown to be able to accurately describe photoinduced processes in complex systems combining mutichromophoric aggregates and biological matrices, 151 and were also used to describe plasmon-assisted photocatalysis. 152 Up to now, however, there are no doubts that the multiscale approach is still unbeatable in terms of efficiency and it will remain so for many years. We believe that the multiscale approach will stay even longer; its unique "control" of the different parts of the system through the selection of the optimal boundaries and the switch on/off for the interactions between them, is in fact an extremely effective tool.…”

Section: Discussionmentioning

confidence: 99%

Multiscale modelling of photoinduced processes in composite systems

2019

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| In the last decades, the quantum mechanical modeling has moved from isolated molecules made of few atoms, to large supramolecular aggregates embedded in complex environments. This has been made possible by the important progress achieved by multiscale models based on the integration of QM methods with classical descriptions. One of the first example of this integration is represented by continuum solvation models that starting from the eighties of the last century have been largely and successfully applied to predict properties and processes of solvated molecules. Almost in the same years, another alternative classical description, based on Molecular Mechanics (MM) has been coupled to QM methods to give the hybrid QM/MM approach. Since their first formulations, these QM/classical models have seen an enormous development in terms of accuracy, robustness and generalizability. This progress has allowed their application to systems of increasing complexity and to processes never faced before within a QM framework. An important example of such an achievement is represented by the novel insights reached in the fundamental understanding and the possible exploitation of photoinduced processes in biomolecules, nanomaterials and, more in general, composite systems where different "objects" of molecular, nano and mesoscopic scale are coupled together. In this review, we highlight the potentials and the limitations of such modeling, thereby showing which developments are still needed to definitely make the QM-based multiscale strategy the gold-standard for explaining the outputs of novel advanced spectroscopic techniques and predicting the outcome of light-activated events in composite systems. The multiscale strategiesIn the years, two main strategies to combine QM descriptions of the target and classical models of the environment, have been proposed. Interestingly, their first formulations date back to the same years, namely the end of the seventies of the previous century. [8][9][10] The two strategies refer to continuum and discrete (or atomistic) descriptions of the environment, respectively. In the latter case, the atoms of the environment (or group of atoms in coarser grained versions of the model) are treated through a Molecular Mechanics (MM) force field (FF). [11][12][13][14][15] In the former case, instead, the atomic nature of the environment is lost and a continuum description in terms of macroscopic properties is introduced instead. 16-18 Despite this huge "modellistic" difference, the two formulations present important common elements when reconsidered from the point of view of the QM target. In any case, for simplicity's sake two separate presentations will be given. QM/continuum. If the environment loses its atomic nature, an effective description has to be introduced which is based on some macroscopic properties. This is exactly what is done in continuum models where the target sees the environment as an infinite dielectric medium characterized by a (generally) frequency and position dependent permittivit...

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Mechanistic Insights into Photocatalyzed Hydrogen Desorption from Palladium Surfaces Assisted by Localized Surface Plasmon Resonances

Cited by 67 publications

References 74 publications

In-situ observation of plasmon-controlled photocatalytic dehydrogenation of individual palladium nanoparticles

In-situ observation of plasmon-controlled photocatalytic dehydrogenation of individual palladium nanoparticles

Enhanced Piezo‐Photoelectric Catalysis with Oriented Carrier Migration in Asymmetric Au−ZnO Nanorod Array

Multiscale modelling of photoinduced processes in composite systems

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