Multimetallic post-synthetic modifications of copper selenide nanoparticles

Sen, Riti; Gordon, Tyler Masato; Millheim, Shelby Liz; Smith, Jacob Harrison; Gan, Xing Yee; Millstone, Jill E.

doi:10.1039/d3nr00441d

Cited by 4 publications

(6 citation statements)

References 53 publications

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“…Are design rules additive, or does one process change the course of the second? Combining cation exchange and metal deposition allowed us to uncover the design rules for cooperation of these PSTs. , Multigeneration cation exchange suggests that new behaviors are likely to emerge . Regioselectivity is directed by similarities in crystal structure along different directions , but the introduction of interfaces creates disordered areas where new cations are rapidly introduced .…”

Section: Transforming Nanomaterialsselecting High-impact Research Ar...mentioning

confidence: 99%

Nanomaterials Research at a Primarily Undergraduate Institution: Transforming Nanorods, Undergraduate Research Communities, and Infrastructure

Plass,

Krebs,

Morford

et al. 2024

ACS Nanosci. Au

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Undergraduate research transforms student’s conceptions of themselves as scientists and encourages participation and retention in science, technology, engineering, and mathematics (STEM) fields. Many barriers exist to carrying out scientifically impactful undergraduate research in nanomaterials at primarily undergraduate institutions (PUIs). Here, we share several practices and design principles that demonstrate pathways to overcome these barriers. Design of modular research projects with low entry barriers is essential. Postsynthetic transformation of nanoparticles is a field that enables such design and has been used successfully to advance nanoscience research while being achievable within undergraduate laboratories. Relatively large, inclusive research communities can be supported through the creation of opportunities with peer- and near-peer mentoring. We also share emerging strategies for enabling routine undergraduate access to transmission electron microscopy, which is one of the most mainstream characterization techniques in nanoscience yet is frequently absent from the infrastructure at undergraduate-focused institutions.

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Section: Transforming Nanomaterialsselecting High-impact Research Ar...mentioning

confidence: 99%

Nanomaterials Research at a Primarily Undergraduate Institution: Transforming Nanorods, Undergraduate Research Communities, and Infrastructure

Plass,

Krebs,

Morford

et al. 2024

ACS Nanosci. Au

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“…There is a large and growing interest in the creation of metal–semiconductor hybrid nanomaterials because of their unique properties and applications including in photocatalysis, − optoelectronics, , and biological imaging/diagnostics. − To efficiently match structure with function, there has been sustained interest in establishing synthetic methods for precise control of their morphology. − A particularly successful approach for tuning these heterostructures has been postsynthetic modification of starting nanoparticle (NP) substrates. − There are several advantages to postsynthetic modification strategies for tuning nanoheterostructure morphology including the improved ability to tailor interfaces within the structure such as interface size, composition, number, and/or extent (e.g., gradient). Strategies such as cation/anion exchange and galvanic replacement have led to remarkably complex structures, ,,,− with both established and still studied new physical and chemical behaviors of interest. − …”

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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“…6,9 Selection between cation exchange and metal deposition on Cu 2−x Se follows design rules based on the compatibility of the lattice structures. 10,11 A particularly complex case reviewed by Kolny-Olesiak 12 nanostructures by acting as catalysts, seeds, or through cation exchange.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Ion exchange and directed growth processes, which are two of the most common methods for making heterostructured nanoparticles, often employ similar reagents and reaction conditions and thus can be in direct competition with one another. For example, directed growth of CdS arms on a range of seeds occurs simultaneously with cation exchange of the core. , Selection between cation exchange and metal deposition on Cu 2– x Se follows design rules based on the compatibility of the lattice structures. , A particularly complex case reviewed by Kolny-Olesiak details how copper sulfide precursors result in numerous hybrid nanostructures by acting as catalysts, seeds, or through cation exchange.…”

Section: Introductionmentioning

confidence: 99%

Temperature-Dependent Selection of Reaction Pathways, Reactive Species, and Products during Postsynthetic Selenization of Copper Sulfide Nanoparticles

Hole,

Luo,

Garcia

et al. 2023

Chem. Mater.

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Rational design of elaborate, multicomponent nanomaterials is important for the development of many technologies such as optoelectronic devices, photocatalysts, and ion batteries. Combination of metal chalcogenides with different anions, such as in CdS/CdSe structures, is particularly effective for creating heterojunctions with valence band offsets. Seeded growth, often coupled with cation exchange, is commonly used to create various core/shell, dot-in-rod, or multipod geometries. To augment this library of multichalcogenide structures with new geometries, we have developed a method for postsynthetic transformation of copper sulfide nanorods into several different classes of nanoheterostructures containing both copper sulfide and copper selenide. Two distinct temperature-dependent pathways allow us to select from several outcomes�rectangular, faceted Cu 2−x S/Cu 2−x Se core/shell structures, nanorhombuses with a Cu 2−x S core, and triangular deposits of Cu 2−x Se or Cu 2−x (S,Se) solid solutions. These different outcomes arise due to the evolution of the molecular components in solution. At lower temperatures, slow Cu 2−x S dissolution leads to concerted morphology change and Cu 2−x Se deposition, while Se-anion exchange dominates at higher temperatures. We present detailed characterization of these Cu 2−x S−Cu 2−x Se nanoheterostructures by transmission electron microscopy (TEM), powder X-ray diffraction, energy-dispersive X-ray spectroscopy, and scanning TEM−energy-dispersive spectroscopy. Furthermore, we correlate the selenium species present in solution with the roles they play in the temperature dependence of nanoheterostructure formation by comparing the outcomes of the established reaction conditions to use of didecyl diselenide as a transformation precursor.

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Multimetallic post-synthetic modifications of copper selenide nanoparticles

Abstract: Here, we find that cation exchange and metal deposition outcomes are insensitive to either synthetic approach or metal mixture. However, extent and composition of the added metals varies with both metal combination and synthetic approach.

Cited by 4 publications

References 53 publications

Nanomaterials Research at a Primarily Undergraduate Institution: Transforming Nanorods, Undergraduate Research Communities, and Infrastructure

Nanomaterials Research at a Primarily Undergraduate Institution: Transforming Nanorods, Undergraduate Research Communities, and Infrastructure

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

Temperature-Dependent Selection of Reaction Pathways, Reactive Species, and Products during Postsynthetic Selenization of Copper Sulfide Nanoparticles

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