Plasmon-mediated photodecomposition of NH3 via intramolecular charge transfer

Zhang, Yimin; Meng, Weite; Chen, Daqiang; Zhang, Lili; Li, Shunfang; Meng, Sheng

doi:10.1007/s12274-021-4021-8

Cited by 10 publications

(8 citation statements)

References 65 publications

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“…The fastest homolysis occurs for TEMPO-St-NH 2 , where the HOMO energy is closer to the E f of Au, leading to the active hybridization of electronic states between AA and AuNPs. A similar mechanism was observed by other researchers. ,,,− However, we noticed that only mechanism 5.3 could be sensitive to the HOMO energy of the AAs; therefore, through the three currently accepted mechanisms, we consider the mechanism of intramolecular excitation as the most suitable for our system.…”

Section: Resultssupporting

confidence: 71%

Uncovering the Role of Chemical and Electronic Structures in Plasmonic Catalysis: The Case of Homolysis of Alkoxyamines

et al. 2023

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The local surface plasmon resonances of gold nanoparticles have the potential to create alternative pathways for organic chemical reactions. These transformations depend on various physical factors, such as the temperature, illumination regime, and nanoparticle type. However, the role of chemical factors associated with organic reactants, including the molecular structure, electronic effects, and bonding with the metal surface, is often underestimated. To explore the role of these chemical factors, we synthesized five alkoxyamines (AAs) with different chemical and electronic structures and used electron paramagnetic resonance spectroscopy to study the kinetics of plasmon-induced homolysis. The kinetic data revealed that the rate constant (k d) for plasmon-assisted homolysis is dependent on the highest occupied molecular orbital (HOMO) energy of the AAs, which cannot be described by the kinetic parameters or activation energies observed in thermal homolysis experiments. The proximity of the HOMO to the Fermi energy (E f) of Au led to a more active decrease in the energy required to excite the adsorbate. The observed trend in k d indicates that the intramolecular excitation mechanism plays a key role instead of other commonly accepted mechanisms, which is supported by DFT calculations, spectroscopic characterization, and numerous control experiments. The intramolecular excitation mechanism is the most relevant explanation for the plasmon-induced homolysis of AAs. This observation suggests that the electronic structures of the organic molecules may play a key role in other related reactions used to study the mechanisms of plasmon catalysis.

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Section: Resultssupporting

confidence: 71%

Uncovering the Role of Chemical and Electronic Structures in Plasmonic Catalysis: The Case of Homolysis of Alkoxyamines

et al. 2023

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“…Many studies have shown that hot carriers generated by plasmon decay can effectively drive chemical reactions. [19][20][21] For instance, Christopher et al proved that plasmonic nanostructures of silver can concurrently utilize low-intensity visible light and thermal energy to drive catalytic oxidation reactions at low temperatures. 22 Wu et al investigated the mechanism for photoinduced H 2 dissociation on Au clusters.…”

Section: Introductionmentioning

confidence: 99%

Real-time dynamic simulation of laser-induced N₂ dissociation on two-dimensional graphene sheets

Chen

Cheng

Zhang

2023

Phys. Chem. Chem. Phys.

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“…The Intergovernmental Panel for Climate Change affirmed this in its most recent report and anticipated the global surface temperature to surpass the warming of 2 °C in the coming decades unless there is any work on rapid and sustained reduction works describing plasmon-assisted bond dissociation/activation reactions predict the ease of chemical transformation in plasmonic chemistry. Bao et al [15] quantified the reaction pathways and energetics for ammonia decomposition on Cu (111) surface, whereas Zheng et al [16] demonstrated that intramolecular charge transfer dominates the NH 3 photodissociation process on Ag nanoclusters. This way, plasmon-generated charge carriers have excellent capability to drive thermodynamically and kinetically challenging reactions by altering their respective potential landscape.…”

Section: Introductionmentioning

confidence: 99%

“…[ 15 ] quantified the reaction pathways and energetics for ammonia decomposition on Cu (111) surface, whereas Zheng et al. [ 16 ] demonstrated that intramolecular charge transfer dominates the NH 3 photodissociation process on Ag nanoclusters. This way, plasmon‐generated charge carriers have excellent capability to drive thermodynamically and kinetically challenging reactions by altering their respective potential landscape.…”

Section: Introductionmentioning

confidence: 99%

Recent Progress and Challenges in Plasmon‐Mediated Reduction of CO₂ to Chemicals and Fuels

Mittal

Ahlawat

Rao

2022

Adv Materials Inter

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Meanwhile, global energy demands also continue to rise. In such a situation, inspiration from nature's process of photosynthesis can be taken to target both the challenges, and artificial systems can be employed that recycle atmospheric CO 2 into valuable hydrocarbon fuels. [2,3] At the outset, artificial photosynthesis seems a straightforward and sustainable approach. However, conversion of CO 2 into value-added chemicals such as, carbon monoxide (CO), formic acid (HCOOH), methanol (CH 3 OH), methane (CH 4 ), and other C 2+ products is an endergonic process, involving a significant positive change in Gibbs free energy. [4] Also, kinetics and product selectivity are major challenges to tackle. While the energy barriers might be surpassed by thermal or electrical energy input to catalysts, economic feasibility, product yields, and selectivity are complex factors. A better strategy is to utilize solar energy to drive the thermodynamically uphill reactions and produce chemical fuels in a renewable and sustainable way. Moreover, the light excitation of catalysts allows more controlled CO 2 reduction. Nanotechnology in this scenario provides myriad opportunities to develop photocatalysts that produce electron-hole pairs upon light illumination and carry out the required chemical transformation. Semiconductor materials, mainly titania (TiO 2 ), have dominated the photocatalysis field but pose constraints regarding limited visible light absorption (while visible light constitutes ≈46% of the sunlight) and other factors. [5][6][7][8] As such, the quest to develop an efficient alternative has recently led to the emergence of photocatalysts consisting of plasmonic metal nanoparticles, mainly Au, Ag, Cu, and Al, that can harvest visible light with high optical cross-section and serve as a platform for surface catalyzed reactions. [9][10][11][12][13] Plasmonic nanostructures exhibit strong interaction with the incident electromagnetic radiation and trigger localized surface plasmon resonance (LSPR), leading to enhancement of local electric fields and subsequent generation of energetic charge carriers and heat that can be exploited in tremendous applications of chemical transformation. [14] The energetic charge carriers are generated with a non-equilibrium distribution, and their potential energy depends upon the electronic band structure of the nanomaterial. This regulates their overall contribution to the chemical reaction's free energy and the extent of activation of the reactants. Recent theoretical and experimentalThe realization of the strong interaction of plasmonic nanostructures with electromagnetic radiation, subdiffraction-limit field localization, and unusually high field enhancement enables immense opportunities to harness visible light in the field of photocatalysis. Plasmon-induced energetic charge carriers allow the metal nanostructures to catalyze surface reactions with selective pathways that are rather a holy grail of thermal catalysis. An intriguing application of plasmonic photocatalysis includes sequestr...

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Plasmon-mediated photodecomposition of NH3 via intramolecular charge transfer

Cited by 10 publications

References 65 publications

Uncovering the Role of Chemical and Electronic Structures in Plasmonic Catalysis: The Case of Homolysis of Alkoxyamines

Uncovering the Role of Chemical and Electronic Structures in Plasmonic Catalysis: The Case of Homolysis of Alkoxyamines

Real-time dynamic simulation of laser-induced N₂ dissociation on two-dimensional graphene sheets

Recent Progress and Challenges in Plasmon‐Mediated Reduction of CO₂ to Chemicals and Fuels

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Plasmon-mediated photodecomposition of NH3 via intramolecular charge transfer

Cited by 10 publications

References 65 publications

Uncovering the Role of Chemical and Electronic Structures in Plasmonic Catalysis: The Case of Homolysis of Alkoxyamines

Uncovering the Role of Chemical and Electronic Structures in Plasmonic Catalysis: The Case of Homolysis of Alkoxyamines

Real-time dynamic simulation of laser-induced N2 dissociation on two-dimensional graphene sheets

Recent Progress and Challenges in Plasmon‐Mediated Reduction of CO2 to Chemicals and Fuels

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Product

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About

Real-time dynamic simulation of laser-induced N₂ dissociation on two-dimensional graphene sheets

Recent Progress and Challenges in Plasmon‐Mediated Reduction of CO₂ to Chemicals and Fuels