Metal Core–Shell Nanoparticle Supercrystals: From Photoactivation of Hydrogen Evolution to Photocorrosion

Fan, Yun; Walls, Michael; Salzemann, Caroline; Noël, Jean‐Marc; Kanoufi, Frédéric; Courty, Alexa; Lemineur, Jean‐François

doi:10.1002/adma.202305402

“…Furthermore, our results are supported by a recent article demonstrating that the transfer of hot electrons across a Pt shell from an Au core depends on the shell thickness because according to density functional theory (DFT) calculations, hot electrons can only travel a very short distance in metals (<1 nm) . Thus, to compensate for the low light harvesting of dispersed Ag@Pt NPs, we have considered in a recently published paper their 3D organization into colloidal supercrystals (SCs) in order to promote coupling between the NPs and an enhancement of the local electromagnetic field, which strongly depends on the inter-NP distance and which leads to the creation of a hot spot accelerating the generation of localized hot electrons . We obtained evidence of the plasmonic photocatalytic activity of supported Ag@Pt SCs, particularly in the context of hydrogen evolution reaction (HER) …”

Section: Resultsmentioning

confidence: 99%

“…42 Thus, to compensate for the low light harvesting of dispersed Ag@Pt NPs, we have considered in a recently published paper their 3D organization into colloidal supercrystals (SCs) in order to promote coupling between the NPs and an enhancement of the local electromagnetic field, which strongly depends on the inter-NP distance and which leads to the creation of a hot spot accelerating the generation of localized hot electrons. 43 We obtained evidence of the plasmonic photocatalytic activity of supported Ag@Pt SCs, particularly in the context of hydrogen evolution reaction (HER). 43 3.4.…”

Section: Catalytic Activity Of Ag@pt Npsmentioning

confidence: 99%

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Colloidal Ag@Pt Core–Shell Nanoparticles for the Catalytic Reduction of Nitrophenol

Fan,

Salzemann,

Tremblay

et al. 2024

ACS Appl. Nano Mater.

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Bimetallic nanoparticles (NPs) composed of two metal elements have attracted much interest due to the possibility of synergistically enhancing the catalytic performance of nanocatalysts. In this context, we have recently reported the seed-mediated growth of bimetallic core−shell NPs combining a plasmonic metal Ag as a core and a catalytic metal Pt as a shell with fine control of the core size and shell thickness. Here, we report a detailed study of the catalytic properties of our Ag@Pt core−shell NPs through a model reaction of the reduction of 4-nitrophenol (4-NP) in 4-aminophenol (4-AP) in the presence of NaBH 4 , where the Pt shell thickness can be tuned from 1 to 6 atomic layers by adjusting the ratio of the Pt precursor to Ag seed concentration. First, we optimized the catalytic performance of pure Ag NPs by showing the role played by protons. We showed that the addition of an aqueous HCl or H 2 SO 4 solution improves the catalytic conversion rate due to the addition of H + . Furthermore, we showed that under light irradiation the presence of halide increases the catalytic efficiency of the Ag NPs by a photorecycling of Ag and the generation of hot electrons. We then evidenced that the bimetallic system is more catalytically active than its monometallic counterparts, highlighting how the synergy between the two metals crucially depends on both the thickness of the Pt shell and the size of the Ag core. The best conditions were found with four Pt atomic layers, which is attributed to a favorable electronic coupling between the Pt shell and the Ag core. Nevertheless, the effect of the irradiation on the catalytic activity of Ag@Pt NPs remains moderate, probably due to localized surface plasmon resonance damping by the Pt shell. Finally, the Ag@Pt NPs showed good stability and could be reused after running three recycling cycles, thus opening perspectives for the rational design of core−shell nanocatalysts with controlled shell morphologies.

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Unlocking Single Particle Anisotropy in Real‐Time for Photoelectrochemistry Processes at the Nanoscale

Lu,

Wang,

Chen

et al. 2024

Angewandte Chemie

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The key to rationally and rapidly designing high‐performance materials is the monitoring and comprehension of dynamic processes within individual particles in real‐time, particularly to gain insight into the anisotropy of nanoparticles. The intrinsic property of nanoparticles typically varies from one crystal facet to the next under realistic working conditions. Here, we introduce the operando collision electrochemistry to resolve the single silver nanoprisms (Ag NPs) anisotropy in photoelectrochemistry. We directly identify the effect of anisotropy on the plasmonic‐assisted electrochemistry at the single NP/electrolyte interface. The statistical collision frequency shows that heterogeneous diffusion coefficient among crystal facets facilitates Ag NPs to undergo direction‐dependent mass transfer toward the gold ultramicroelectrode. Subsequently, the current amplitudes of transient events indicate that anisotropy enables variations in dynamic interfacial electron transfer behaviors during photothermal processes. The results presented here demonstrate that the measurement precision of collision electrochemistry can be extended to the sub‐nanoparticle level, highlighting the potential for high‐throughput material screening with comprehensive kinetics information at the nanoscale.

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Unlocking Single Particle Anisotropy in Real‐Time for Photoelectrochemistry Processes at the Nanoscale

Lu,

Wang,

Chen

et al. 2024

Angew Chem Int Ed

0

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The key to rationally and rapidly designing high‐performance materials is the monitoring and comprehension of dynamic processes within individual particles in real‐time, particularly to gain insight into the anisotropy of nanoparticles. The intrinsic property of nanoparticles typically varies from one crystal facet to the next under realistic working conditions. Here, we introduce the operando collision electrochemistry to resolve the single silver nanoprisms (Ag NPs) anisotropy in photoelectrochemistry. We directly identify the effect of anisotropy on the plasmonic‐assisted electrochemistry at the single NP/electrolyte interface. The statistical collision frequency shows that heterogeneous diffusion coefficient among crystal facets facilitates Ag NPs to undergo direction‐dependent mass transfer toward the gold ultramicroelectrode. Subsequently, the current amplitudes of transient events indicate that anisotropy enables variations in dynamic interfacial electron transfer behaviors during photothermal processes. The results presented here demonstrate that the measurement precision of collision electrochemistry can be extended to the sub‐nanoparticle level, highlighting the potential for high‐throughput material screening with comprehensive kinetics information at the nanoscale.

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Metal Core–Shell Nanoparticle Supercrystals: From Photoactivation of Hydrogen Evolution to Photocorrosion

Cited by 4 publications

References 49 publications

Colloidal Ag@Pt Core–Shell Nanoparticles for the Catalytic Reduction of Nitrophenol

Colloidal Ag@Pt Core–Shell Nanoparticles for the Catalytic Reduction of Nitrophenol

Unlocking Single Particle Anisotropy in Real‐Time for Photoelectrochemistry Processes at the Nanoscale

Unlocking Single Particle Anisotropy in Real‐Time for Photoelectrochemistry Processes at the Nanoscale

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