Tailoring the aluminum nanocrystal surface oxide for all-aluminum-based antenna-reactor plasmonic photocatalysts

Bayles, Aaron; Fabiano, Catherine J.; Shi, Chuqiao; Yuan, Lin; Yuan, Yigao; Craft, Nolan; Jacobson, Christian R.; Dhindsa, Parmeet; Ogundare, Adebola; Mendez Camacho, Yelsin; Chen, Banghao; Robatjazi, Hossein; Han, Yimo; Strouse, Geoffrey F.; Nordlander, Peter; Everitt, Henry O.; Halas, Naomi J.

doi:10.1073/pnas.2321852121

Cited by 3 publications

(1 citation statement)

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“…Another mode for generating nanoheterostructures via postsynthetic modification is to leverage the molecular surface chemistry of the starting NP substrate. − In this approach, one may use NP surface chemistry to modulate the flux of the precursor to the NP surface and block, slow, and/or facilitate growth at particular sites. The use of NP surface chemistry to direct metal deposition has been well-studied in the modification of metal NP substrates ,− but is not yet established for metal chalcogenide particle substrates, although these particles are of high interest for incorporation into nanoheterostructures.…”

Section: Introductionmentioning

confidence: 99%

Influence of Surface Chemistry on Metal Deposition Outcomes in Copper Selenide-Based Nanoheterostructure Synthesis

Sen,

Millheim,

Gordon

et al. 2024

Langmuir

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The use of nanoparticle surface chemistry to direct metal deposition has been well-studied in the modification of metal nanoparticle substrates but is not yet well-established for metal chalcogenide particle substrates, although integration of these particles into nanoheterostructures is of high interest. In this report, we investigate the effect of Cu2–x Se surface chemistry on the morphology of metal deposition on these plasmonic semiconductor nanoparticles. Specifically, we functionalize Cu2–x Se nanoparticles with a suite of 12 different ligands and investigate how different aspects of the ligand structure do or do not impact the morphology and extent of subsequent metal deposition on the Cu2–x Se surface. Surprisingly, our results indicate that the morphology of the resulting metal deposits and the extent of metal deposition onto the existing Cu2–x Se particle substrate are indistinguishable for the majority of ligands tested. An exception to these findings is observed for particles functionalized by quaternary alkylammonium bromides, which exhibit statistically distinct metal deposition patterns compared to all other ligands tested. We hypothesize that this unique behavior is due to a cooperative binding mechanism of the quaternary alkylammonium bromides to the surface of copper selenide. Taken together, these results yield both new strategies for controlling postsynthetic modification of copper selenide nanoparticles and also reveal limitations of surface chemistry-based approaches for this system.

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Section: Introductionmentioning

confidence: 99%

Influence of Surface Chemistry on Metal Deposition Outcomes in Copper Selenide-Based Nanoheterostructure Synthesis

Sen,

Millheim,

Gordon

et al. 2024

Langmuir

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Deciphering the Photocatalysis Mechanism of Semimetallic Bismuth Nanoparticles

Hoffman,

Hennes,

Lyu

2024

J. Phys. Chem. C

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Metallic nanoparticle photocatalysts have been developed in various catalytic systems over the past few decades, including diverse noble and non-noble metals with plasmonic properties. The hot-carrier-induced mechanism is one of the most appealing pathways as it can provide energetic electrons or holes for driving thermodynamically unfavorable reactions or increasing the reaction rate. In this work, we evaluate the photocatalytic performance of semimetallic bismuth nanoparticles and offer detailed mechanistic interpretations in terms of hot carriers and interband transitions. The photocatalyzed nitrophenol reduction with sodium borohydride serves as a model reaction, and a wavelength-dependent study reveals the contribution of hot carriers. It is demonstrated that light irradiation under shorter wavelengths could produce deeper hot holes in bismuth nanoparticles, which can be quenched more effectively by hole scavengers, thus facilitating the electron-transfer process and resulting in larger apparent reaction rate constants. The observed photocatalysis enhancement accounts for the unique band structure with an extremely small band gap and exclusive interband absorption in the visible region. This proof-of-concept work offers a different perspective on the photocatalysis mechanism of bismuth nanoparticles and could help us better understand the role of hot carriers involved in photocatalysis, especially with interband transitions.

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