Supramolecular Precursors for the Synthesis of Anisotropic Cu<sub>2</sub>S Nanocrystals

Bryks, Whitney; Wette, Melissa; Velez, Nathan R.; Hsu, Su Wen; Tao, Andrea R.

doi:10.1021/ja500786p

Cited by 77 publications

(119 citation statements)

References 23 publications

(38 reference statements)

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“…Cabot and co‐workers have proposed an oriented attachment pathway through which hexagonal nanodisks form hexagonal Cu 2− x S bifrustums and eventually hexagonal bipyramids . Other groups have presented evidence that Cu thiolate lamellar complexes act as both Cu precursors and shape‐templating agents . Recent work has demonstrated that the crystallographic phase and composition of Cu 2− x S NCs (see Section 2.1) can be controlled by proper choice of reaction parameters (namely, temperature, molar ratio of Cu/S, and volume ratio between the noncoordinating solvent 1‐octadecene and the ligand oleylamine) .…”

Section: Binary Copper Chalcogenidesmentioning

confidence: 99%

Prospects of Colloidal Copper Chalcogenide Nanocrystals

2016

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Over the past few years, colloidal copper chalcogenide nanocrystals (NCs) have emerged as promising alternatives to conventional Cd and Pb chalcogenide NCs. Owing to their wide size, shape, and composition tunability, Cu chalcogenide NCs hold great promise for several applications, such as photovoltaics, lighting and displays, and biomedical imaging. They also offer characteristics that are unparalleled by Cd and Pb chalcogenide NCs, such as plasmonic properties. Moreover, colloidal Cu chalcogenide NCs have low toxicity, potentially lower costs, and excellent colloidal stability. This makes them attractive materials for the large-scale deployment of inexpensive, sustainable, and environmentally benign solution-processed devices. Nevertheless, the synthesis of colloidal Cu chalcogenide NCs, especially that of ternary and quaternary compositions, has yet to reach the same level of mastery as that available for the prototypical Cd chalcogenide based NCs. This review provides a concise overview of this rapidly advancing field, sketching the state of the art and highlighting the key challenges. We discuss recent developments in the synthesis of size-, shape-, and composition-controlled NCs of Cu chalcogenides, with emphasis in strategies to circumvent the limitations arising from the need to precisely balance the reactivities of multiple precursors in synthesizing ternary and quaternary compositions. In this respect, we show that topotactic cation-exchange reactions are a promising alternative route to complex multinary Cu chalcogenide NCs and hetero-NCs, which are not attainable by conventional routes. The properties and potential applications of Cu chalcogenide NCs and hetero-NCs are also addressed.

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Section: Binary Copper Chalcogenidesmentioning

confidence: 99%

Prospects of Colloidal Copper Chalcogenide Nanocrystals

2016

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“…The peak at the low-angle window is from the thiol−metal complex, as this has already been established in the literature. 63 However, samples obtained after 10 min had all peaks including wurtzite CIS, Au, and thiol complex. With the increase of time, it was observed that the intensity of the thiol complex peak in first window gradually decreased, and that of CIS in second and third window increased.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Hybrid Dot–Disk Au-CuInS₂ Nanostructures as Active Photocathode for Efficient Evolution of Hydrogen from Water

et al. 2016

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The synthesis of hybrid 0D-2D dot−disk Au-CIS heterostructures is enabled through nucleating wurtzite ternary I−III−VI CuInS 2 (CIS) semiconductor nanostructures on cubic Au particles via thiol-activated interface reactions. Chemistry of formation of these unique hybrid metal− semiconductor nanostructures is established by correlating successive X-ray diffraction patterns and microscopic images. Furthermore, these nanostructures are explored as an efficient photocathode material for photoelectrochemical (PEC) production of hydrogen from water. Although CIS nanostructures are extensively used as PEC active materials for solar-tohydrogen conversion, the coupled structures with Au for their exciton−plasmon coupling is observed in producing a higher photocurrent with efficient evolution of hydrogen. In the comparison of materials properties, it is observed that the cathodic photocurrent, onset potential, and the half-cell solar-to-hydrogen efficiency (HC-STH) are recorded to be superior to all CISbased photocathodes reported up to the current time. These results suggest that designing proper heterostructured functional materials can enhance the hydrogen production in the PEC cell and would be helpful for the ongoing technological needs for a greener way of generating and storing hydrogen energy. ■ INTRODUCTIONHydrogen evolution from solar water splitting, a possible alternative way of generating green energy, is on the forefront of current research. 1−6 In this aspect, photoelectrochemical (PEC) solar-to-hydrogen conversion remains as a promising approach and has been studied extensively. 1,7−14 The performance of the PEC cell and the efficiency of hydrogen evolution typically depend on the effectiveness of the involved photoactive electrode material. Among these, semiconducting nanomaterials having absorption in the solar spectrum, high excitonic coefficient, and high charge carrier mobility are more focused. 15−17 Moreover, electrodes are also designed following proper band engineering with other materials for feasible transfer of the photoexcited electron to water. 15,17−20 In recent developments, even success has been obtained to a large extent for improving the PEC cell performance using different nanomaterials, but finding more efficient and stable materials for boosting the cathodic current and enhancing the efficiency of hydrogen evolution in a single building block are still in demand.Among the different developed functional photoactive materials, noble metal−semiconductor heterostructures have recently emerged as ideal photocatalytic materials where the semiconductor generates the charge carriers and metal acts as a sink for trapping the electron. 21−32 For the case of metal Au, the electron transfer is even more facilitated as the surface plasmon of Au couples with semiconductor exciton and enhances the excited state lifetime of the photoelectron. 33−38 Among the semiconductor counter parts, for high carrier mobility and high extinction coefficient, multinary materials are recently more focused. 22,23,35,3...

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“…Isotropic to hexagonal columnar phase transition was observed during solvent evaporation and in the columnar phase the discs were not periodically ordered within the columns [101]. Bryks et al demonstrated that self-assembly of copper alkanethiolates results liquid crystalline mesophase [102]. Well-ordered copper sulfide nanodiscs have been prepared by processing the copper alkanethiolates from their LC phase.…”

Section: Liquid Crystalline Nanodiscsmentioning

confidence: 99%

Liquid Crystalline Anisotropic Nanoparticles: From Metallic and Semiconducting Nanoparticles to Carbon Nanomaterials

Bisoyi

2015

Anisotropic Nanomaterials

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Anisotropic nanomaterials made of metals, semiconductors, or carbon are of special interest for their mechanical, electrical, magnetic, optical, chemical and other spectacular properties in the bottom-up fabrication of advanced functional materials and devices in the field of nanoscience and nanotechnology. To widen their applicability, it is necessary to process these anisotropic building blocks into different well-defined assembly structures with preferred orientations. This chapter deals with the liquid crystalline properties of one-and two-dimensional (1D and 2D) anisotropic nanoparticles such as nanorods, nanotubes, nanodiscs and graphene derivatives. The different strategies developed for the realization of liquid crystal phases from metallic, semiconducting and carbon based anisotropic nanoparticles have been discussed. High performance materials and devices fabricated by processing via liquid crystalline route of these materials have also been highlighted.

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Supramolecular Precursors for the Synthesis of Anisotropic Cu₂S Nanocrystals

Cited by 77 publications

References 23 publications

Prospects of Colloidal Copper Chalcogenide Nanocrystals

Prospects of Colloidal Copper Chalcogenide Nanocrystals

Hybrid Dot–Disk Au-CuInS₂ Nanostructures as Active Photocathode for Efficient Evolution of Hydrogen from Water

Liquid Crystalline Anisotropic Nanoparticles: From Metallic and Semiconducting Nanoparticles to Carbon Nanomaterials

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Supramolecular Precursors for the Synthesis of Anisotropic Cu2S Nanocrystals

Cited by 77 publications

References 23 publications

Prospects of Colloidal Copper Chalcogenide Nanocrystals

Prospects of Colloidal Copper Chalcogenide Nanocrystals

Hybrid Dot–Disk Au-CuInS2 Nanostructures as Active Photocathode for Efficient Evolution of Hydrogen from Water

Liquid Crystalline Anisotropic Nanoparticles: From Metallic and Semiconducting Nanoparticles to Carbon Nanomaterials

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Supramolecular Precursors for the Synthesis of Anisotropic Cu₂S Nanocrystals

Hybrid Dot–Disk Au-CuInS₂ Nanostructures as Active Photocathode for Efficient Evolution of Hydrogen from Water