Reactivating Catalytic Surface: Insights into the Role of Hot Holes in Plasmonic Catalysis

Peng, Tianhuan; Miao, Junjian; Gao, Zhen; Zhang, Linjuan; Gao, Yi; Chen, Fan; Li, Di

doi:10.1002/smll.201703510

Cited by 39 publications

(39 citation statements)

References 58 publications

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“…The roles of holes in photocatalytic processes are typically complicated. 47 because SiC is an n-type semiconductor. In this process, SiC provides low-energy electrons to Au and receives hot electrons from Au.…”

Section: Resultsmentioning

confidence: 99%

Synergistic Effect of Segregated Pd and Au Nanoparticles on Semiconducting SiC for Efficient Photocatalytic Hydrogenation of Nitroarenes

Hao

Guo

Sankar

et al. 2018

ACS Appl. Mater. Interfaces

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Efficient catalytic hydrogenation of nitroarenes to anilines with molecular hydrogen at room temperature is still a challenge. In this study, this transformation was achieved by using a photocatalyst of SiC-supported segregated Pd and Au nanoparticles. Under visible-light irradiation, the nitrobenzene hydrogenation reached a turnover frequency as high as 1715 h at 25 °C and 0.1 MPa of H pressure. This exceptional catalytic activity is attributed to a synergistic effect of Pd and Au nanoparticles on the semiconducting SiC, which is different from the known electronic or ensemble effects in Pd-Au catalysts. This kind of synergism originates from the plasmonic electron injection of Au and the Mott-Schottky contact at the interface between Pd and SiC. This three-component system changes the electronic structures of the SiC surface and produces more active sites to accommodate the active hydrogen that spills over from the surface of Pd. These active hydrogen species have weaker interactions with the SiC surface and thus are more mobile than on an inert support, resulting in an ease in reacting with the N═O bonds in nitrobenzene absorbed on SiC to produce aniline.

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Section: Resultsmentioning

confidence: 99%

Synergistic Effect of Segregated Pd and Au Nanoparticles on Semiconducting SiC for Efficient Photocatalytic Hydrogenation of Nitroarenes

Hao

Guo

Sankar

et al. 2018

ACS Appl. Mater. Interfaces

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“…Surface plasmon resonance (SPR) excited the illuminated AuNPs to decay into energetic hot electrons. Hot electron transfer (HET) can promote many chemical reactions [ 59 , 60 , 61 ], including the dissociation of hydrogen [ 62 ], activation of oxygen [ 63 ], and electrocatalytic hydrogen evolution [ 64 ]. On the other hand, our group proposed an innovative method to create plasmon-activated water (PAW), which is prepared by treating deionized (DI) water with resonantly excited AuNPs [ 23 , 65 , 66 ].…”

Section: Introductionmentioning

confidence: 99%

Therapeutics for Inflammatory-Related Diseases Based on Plasmon-Activated Water: A Review

Yang

Liu

2018

IJMS

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It is recognized that the properties of liquid water can be markedly different from those of bulk one when it is in contact with hydrophobic surfaces or is confined in nano-environments. Because our knowledge regarding water structure on the molecular level of dynamic equilibrium within a picosecond time scale is far from completeness all of water’s conventionally known properties are based on inert “bulk liquid water” with a tetrahedral hydrogen-bonded structure. Actually, the strength of water’s hydrogen bonds (HBs) decides its properties and activities. In this review, an innovative idea on preparation of metastable plasmon-activated water (PAW) with intrinsically reduced HBs, by letting deionized (DI) water flow through gold-supported nanoparticles (AuNPs) under resonant illumination at room temperature, is reported. Compared to DI water, the created stable PAW can scavenge free hydroxyl and 2,2-diphenyl-1-picrylhydrazyl radicals and effectively reduce NO release from lipopolysaccharide-induced inflammatory cells. Moreover, PAW can dramatically induce a major antioxidative Nrf2 gene in human gingival fibroblasts. This further confirms its cellular antioxidative and anti-inflammatory properties. In addition, innovatively therapeutic strategy of daily drinking PAW on inflammatory-related diseases based on animal disease models is demonstrated, examples being chronic kidney disease (CKD), chronic sleep deprivation (CSD), and lung cancer.

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“…[1][2][3][4] Hot charge carriers, including hot electrons and hot holes, generated by plasmonic illuminations play synergistic roles in enhancing catalytic performance. [5][6][7] However, determining activation energies and rate limiting step under illumination condition and exploring the contribution of hot carrier reduced activation barrier is still rare and controversy. 1,8 For example, El-Sayed and coworkers found that the activation barrier for hexacyanoferrate (III) reduction on Au NPs was slightly higher under visible light excitation than that in the dark, even though the reaction rate was accelerated under light.…”

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confidence: 99%

Single-Molecular Catalysis Identifying Activation Energy of the Intermediate Product and Rate-Limiting Step in Plasmonic Photocatalysis

Miao

Peng

et al. 2020

Nano Lett.

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Plasmon mediated photocatalysis provides a novel strategy for harvesting solar energy. Identification of rate determining step and its activation energy in plasmon mediated photocatalysis plays critical roles for understanding the contribution of hot carriers that facilitates rational designing catalysts with integrated high photo-chemical conversion efficiency and catalytic performance. However, it remains a challenge due to a lack of research tools with spatiotemporal resolution that capable of capturing intermediates. In this work, we used a single molecular fluorescence approach to investigate a localized surface plasmon resonance (LSPR) enhanced photocatalytic reaction with sub-turnover resolution. By introducing variable temperature as an independent parameter in plasmonic photocatalysis, the activation energies of tandem reaction steps, including intermediate generation, product generation and product dissociation, were clearly differentiated, and intermediates generation was found to be the rate-limiting step. Remarkably, the cause of plasmon enhanced catalysis performance was found to be its ability of lowering the activation energy of intermediates generation. This study gives new insight into the photo-chemical energy conversion pathways in plasmon enhanced photocatalysis and sheds light on designing high performance plasmonic catalysts. File list (2) download file view on ChemRxiv Main text-20191220.docx (2.01 MiB) download file view on ChemRxiv SI-20191220.docx (2.40 MiB)

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Reactivating Catalytic Surface: Insights into the Role of Hot Holes in Plasmonic Catalysis

Cited by 39 publications

References 58 publications

Synergistic Effect of Segregated Pd and Au Nanoparticles on Semiconducting SiC for Efficient Photocatalytic Hydrogenation of Nitroarenes

Synergistic Effect of Segregated Pd and Au Nanoparticles on Semiconducting SiC for Efficient Photocatalytic Hydrogenation of Nitroarenes

Therapeutics for Inflammatory-Related Diseases Based on Plasmon-Activated Water: A Review

Single-Molecular Catalysis Identifying Activation Energy of the Intermediate Product and Rate-Limiting Step in Plasmonic Photocatalysis

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