Nanocrystal Heterostructures Based On Halide Perovskites and Lead–Bismuth Chalcogenides

Rusch, Pascal; Toso, Stefano; Ivanov, Yurii P.; Marras, Sergio; Divitini, Giorgio; Manna, Liberato

doi:10.1021/acs.chemmater.3c02503

Cited by 4 publications

(2 citation statements)

References 51 publications

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“…Hence, instead of one-to-one facets of each semiconductor, multiple options of connections are created. While this work under communication, Manna and co-workers reported a similar heterostructure having common Pb in both perovskite and metal sulfide counter parts following clusters mediated synthesis approach. , However, these were prismatic core versus rods and remained confined to one particular facet orientation unlike what we have reported here for perovskite dot and Pb–Bi–S rod nanocrystal heterostructures. Hence, such cases remained rare, particularly in halide perovskites, where such types of heterostructure formation indeed faced tremendous difficulties in bringing ionic and covalent crystals together in a single building block.…”

Section: Resultscontrasting

confidence: 44%

Perovskite-Chalcogenide Epitaxial Heterostructures: Possibility of Multiple Axial Orientations of CsPbBr₃ Nanocrystals on PbBi₂S₄ Nanorods

Patra,

Jagadish,

Shyamal

et al. 2024

Chem. Mater.

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The chemistry of designing epitaxial perovskite-chalcogenide nanocrystal heterostructures still could not be established yet in spite of significant successes in understanding both perovskite and chalcogenide nanostructures formation. Interfacing the ionic–covalent bonding at the junction of both remains the major obstacle for establishing the seamless formation of such nanostructures. Keeping the compatibility of Bi(III) ions with Pb(II) in different lead halide perovskite nanocrystals, herein, multiple possibilities of interface junctions of ionic CsPbBr3 and covalent PbBi2S4 sulfide nanocrystals are reported. Creating the common Pb(II) sublattice structures in this system indeed helped in designing such a wide possibility of nanocrystal heterostructures, and this supported the connection of CsPbBr3 polyhedral nanocrystals with PbBi2S4 nanorods in different orientations. While epitaxial heterostructure formations are typically observed with the interface of specific facets of two nanoscale materials, here, for perovskites, this provides multiple options of different facets combination. This concept remained important for fundamental understanding in creating junctions of ionic–covalent crystals and also helped in establishing the method for designing halide perovskite-chalcogenide nanocrystal heterostructures. Such interface junctions, where defects are mostly generated due to halide deficiency, quench the optical emission, but, in contrary, enhance the catalytic activities.

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Section: Resultscontrasting

confidence: 44%

Perovskite-Chalcogenide Epitaxial Heterostructures: Possibility of Multiple Axial Orientations of CsPbBr₃ Nanocrystals on PbBi₂S₄ Nanorods

Patra,

Jagadish,

Shyamal

et al. 2024

Chem. Mater.

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“…Incorporating surface functional groups and capping layers onto quantum dots (QDs) and NCs allows for harnessing the high activity of small-sized halide perovskite photocatalysts without compromising stability [194]. Moreover, the strategic construction of heterojunctions, specifically type-II and Z-scheme, at the nano and sub-nanoscale within porous semiconductor networks holds significant promise for revitalizing perovskitebased photocatalysis, ensuring heightened performance on both the activity and stability fronts [179,[195][196][197][198].…”

Section: Discussionmentioning

confidence: 99%

Photocatalysis Based on Metal Halide Perovskites for Organic Chemical Transformations

Jagadeeswararao,

Galian,

Pérez-Prieto

2023

Nanomaterials

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Heterogeneous photocatalysts incorporating metal halide perovskites (MHPs) have garnered significant attention due to their remarkable attributes: strong visible-light absorption, tuneable band energy levels, rapid charge transfer, and defect tolerance. Additionally, the promising optical and electronic properties of MHP nanocrystals can be harnessed for photocatalytic applications through controlled crystal structure engineering, involving composition tuning via metal ion and halide ion variations, dimensional tuning, and surface chemistry modifications. Combination of perovskites with other materials can improve the photoinduced charge separation and charge transfer, building heterostructures with different band alignments, such as type-II, Z-scheme, and Schottky heterojunctions, which can fine-tune redox potentials of the perovskite for photocatalytic organic reactions. This review delves into the activation of organic molecules through charge and energy transfer mechanisms. The review further investigates the impact of crystal engineering on photocatalytic activity, spanning a diverse array of organic transformations, such as C–X bond formation (X = C, N, and O), [2 + 2] and [4 + 2] cycloadditions, substrate isomerization, and asymmetric catalysis. This study provides insights to propel the advancement of metal halide perovskite-based photocatalysts, thereby fostering innovation in organic chemical transformations.

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Nanocrystal Heterostructures Based on Halide Perovskites and Metal Sulfides

Livakas,

Zito,

Ivanov

et al. 2024

J. Am. Chem. Soc.

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We report the synthesis of nanocrystal heterostructures composed of CsPbCl 3 and PbS domains sharing an epitaxial interface. We were able to promote the growth of a PbS domain (in competition with the more commonly observed Pb 4 S 3 Cl 2 one) on top of the CsPbCl 3 domain by employing Mn 2+ ions, the latter most likely acting as scavengers of Cl − ions. Complete suppression of the Pb 4 S 3 Cl 2 domain growth was then achieved by additionally selecting an appropriate sulfur source (bis(trimethylsilyl)sulfide, which also acted as a scavenger of Cl − ions) and reaction temperature. In the heterostructures, emission from the perovskite domain was quenched, while emission from the PbS domain was observed, pointing to a type-I band alignment, as confirmed by calculations. These heterostructures, in turn, could be exploited to prepare second-generation heterostructures through selective ion exchange on the individual domains (halide ion exchange on CsPbCl 3 and cation exchange on PbS). We demonstrate the cases of Cl − → Br − and Pb 2+ → Cu + exchanges, which deliver CsPbBr 3 −PbS and CsPbCl 3 −Cu 2-x S epitaxial heterostructures, respectively.

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Nanocrystal Heterostructures Based On Halide Perovskites and Lead–Bismuth Chalcogenides

Cited by 4 publications

References 51 publications

Perovskite-Chalcogenide Epitaxial Heterostructures: Possibility of Multiple Axial Orientations of CsPbBr₃ Nanocrystals on PbBi₂S₄ Nanorods

Perovskite-Chalcogenide Epitaxial Heterostructures: Possibility of Multiple Axial Orientations of CsPbBr₃ Nanocrystals on PbBi₂S₄ Nanorods

Photocatalysis Based on Metal Halide Perovskites for Organic Chemical Transformations

Nanocrystal Heterostructures Based on Halide Perovskites and Metal Sulfides

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Nanocrystal Heterostructures Based On Halide Perovskites and Lead–Bismuth Chalcogenides

Cited by 4 publications

References 51 publications

Perovskite-Chalcogenide Epitaxial Heterostructures: Possibility of Multiple Axial Orientations of CsPbBr3 Nanocrystals on PbBi2S4 Nanorods

Perovskite-Chalcogenide Epitaxial Heterostructures: Possibility of Multiple Axial Orientations of CsPbBr3 Nanocrystals on PbBi2S4 Nanorods

Photocatalysis Based on Metal Halide Perovskites for Organic Chemical Transformations

Nanocrystal Heterostructures Based on Halide Perovskites and Metal Sulfides

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Perovskite-Chalcogenide Epitaxial Heterostructures: Possibility of Multiple Axial Orientations of CsPbBr₃ Nanocrystals on PbBi₂S₄ Nanorods

Perovskite-Chalcogenide Epitaxial Heterostructures: Possibility of Multiple Axial Orientations of CsPbBr₃ Nanocrystals on PbBi₂S₄ Nanorods