Phase Evolution, Polymorphism, and Catalytic Activity of Nickel Dichalcogenide Nanocrystals

The nickel chalcogenide family contains multiple phases, each with varying properties that can be applied to an expansive range of industrially relevant processes. Specifically, pyrite-type NiS2 and NiSe2 have been used as electrocatalysts for oxygen or hydrogen evolution reactions. These pyrites have also been used in batteries and solar cells due to their optoelectronic and transport properties. The phase evolution of pyrite NiS2 and polymorphism of NiSe2 have briefly been studied in the literature, but there has been limited work focusing on the phase transformations within each of these two systems. Using experiments and calculations, we detail how pyrite NiS2 nanocrystals decompose into hexagonal α-NiS, and how the synthesis of pyrite NiSe2 nanocrystals is affected by the presence of two polymorphs, a metastable orthorhombic marcasite phase and a more stable cubic pyrite phase. Each reaction can be controlled by fine-tuning the reaction parameters, including temperature, time, and the precursor identity and concentration. Interestingly, both NiS2 and NiSe2 nanopyrites are active catalysts in the selective reduction of nitrobenzene to aniline, in agreement with other catalysts containing an fcc (sub) lattice. Our results demonstrate a feasible, logical process for synthesizing nanocrystalline pyrites without common byproducts or impurities. This work can help in solving a major problem suspected in preventing pyrite FeS2 and similar materials from large-scale use: the presence of small amounts of secondary phases and impurities.This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Chemistry of Materials, copyright © 2022 American Chemical Society after peer review. To access the final edited and published work see DOI: 10.1021/acs.chemmater.1c03557. Posted with permission

Alkaline-Earth Chalcogenide Nanocrystals: Solution-Phase Synthesis, Surface Chemistry, and Stability

Increasing demand for effective energy conversion materials and devices has renewed interest in semiconductors comprised of earth-abundant and biocompatible elements. Alkaline-earth sulfides doped with rare earth ions are versatile optical materials. However, relatively little is known about controlling the dimensionality, surface chemistry, and inherent optical properties of the undoped versions of alkaline-earth mono- and polychalcogenides. We describe the colloidal synthesis of alkaline-earth chalcogenide nanocrystals through the reaction of metal carboxylates with carbon disulfide or selenourea. Systematic exploration of the synthetic phase space allows us to tune particle sizes over a wide range using a mixture of commercially available carboxylate precursors. Solid-state NMR spectroscopy confirms the phase purity of the selenide compositions. Surface characterization reveals that bridging carboxylates and amines preferentially terminate the surface of the nanocrystals. While these materials are colloidally stable in the mother solution, the selenides are susceptible to oxidation over time, eventually degrading to selenium metal through polyselenide intermediates. As part of these investigations, we have developed the colloidal syntheses of barium di- and triselenides, two among few reported nanocrystalline alkaline-earth polychalcogenides. Electronic structure calculations reveal that both materials are indirect band gap semiconductors. The colloidal chemistry presented here may enable the synthesis of more complex, multinary chalcogenide materials containing alkaline-earth elements.This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication as Roth, Alison N., Yunhua Chen, Marquix AS Adamson, Eunbyeol Gi, Molly Wagner, Aaron J. Rossini, and Javier Vela. "Alkaline-Earth Chalcogenide Nanocrystals: Solution-Phase Synthesis, Surface Chemistry, and Stability." ACS nano 16, no. 8 (2022): 12024-12035. Copyright 2022 American Chemical Society after peer review. To access the final edited and published work see DOI:10.1021/acsnano.2c02116. Posted with permission. DOE Contract Number(s): AC02-07CH11358

Azo(xy) vs Aniline Selectivity in Catalytic Nitroarene Reduction by Intermetallics: Experiments and Simulations

Intermetallic nanoparticles are promising catalysts in hydrogenation and fuel cell technologies. Much is known about the ability of intermetallic nanoparticles to selectively reduce nitro vs alkene, alcohol, or halide functional groups; less is known about their selectivity toward aniline vs azo or azoxy condensation products that result from the reduction of a nitro group alone. Because azo(xy)arenes bear promise as dyes, chemical stabilizers, and building blocks to functional materials but can be difficult to isolate, developing high surface area nanoparticle catalysts that display azo(xy) selectivity is desirable. To address this question, we studied a family of nanocrystalline group 10 metal (Pd, Pt)- and group 14 metal (Ge, Sn, Pb)-containing intermetallics─Pd2Ge, Pd2Sn, Pd3Sn2, Pd3Pb, and PtSn─in the catalytic reduction of nitroarenes. In contrast to monometallic Au, Pt, and Pd nanoparticles and ″random″ PdxSn1 – x nanoalloys, which are selective for aniline, nanoparticles of atomically precise intermetallic Pd2Ge, Pd2Sn, Pd3Sn2, and PtSn prefer an indirect condensation pathway and have a high selectivity for the azo(xy) products. The only exception is Pd3Pb, the most active among the intermetallic nanoparticles studied here, which is instead selective for aniline. Employing a novel application of molecular dynamics─based on machine learned potentials within a DeePMD framework─to heterogeneous catalysis, we are able to identify key reaction species on the different types of catalysts employed, furthering our understanding of the unique selectivity of these materials. By demonstrating how intermetallic nanoparticles can be as active yet more selective than other more traditional catalysts, this work provides new physical insights and opens new opportunities in the use of these materials in other important chemical transformations and applications.This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review. To access the final edited and published work see DOI: 10.1021/acs.jpcc.1c08569. DOE Contract Number(s): AC02-07CH11358. Posted with permission

Ternary ACd4P3 (A = Na, K) Nanostructures via a Hydride Solution-Phase Route

Complex pnictides such as I–II4–V3 compounds (I = alkali metal; II = divalent transition metal; V = pnictide element) display rich structural chemistry and interesting optoelectronic properties, but can be challenging to synthesize using traditional high-temperature solid-state synthesis. Soft chemistry methods can offer control over particle size, morphology, and properties. However, the synthesis of multinary pnictides from solution remains underdeveloped. Here, we report the colloidal hot-injection synthesis of ACd4P3 (A = Na, K) nanostructures from their alkali metal hydrides (AH). Control studies indicate that NaCd4P3 forms from monometallic Cd0 seeds and not from binary Cd3P2 nanocrystals. IR and ssNMR spectroscopy reveal tri-n-octylphosphine oxide (TOPO) and related ligands are coordinated to the ternary surface. Computational studies show that competing phases with space group symmetries R3̅m and Cm differ by only 30 meV/formula unit, indicating that synthetic access to either of these polymorphs is possible. Our synthesis unlocks a new family of nanoscale multinary pnictide materials that could find use in optoelectronic and energy conversion devices.This article is published as Medina-Gonzalez, Alan M., Philip Yox, Yunhua Chen, Marquix AS Adamson, Maranny Svay, Emily A. Smith, Richard D. Schaller, Aaron J. Rossini, and Javier Vela. "Ternary ACd4P3 (A= Na, K) Nanostructures via a Hydride Solution-Phase Route." ACS Materials Au 1, no. 2 (2021): 130-139. DOI: 10.1021/acsmaterialsau.1c00018. Copyright 2021 The Author(s). Attribution-NonCommercial-ShareAlike 4.0 (CC BY-NC-SA 4.0). DOE Contract Number(s): AC02-07CH11358; AC02-06CH11357. Posted with permission

Solution-Grown Ternary Semiconductors: Nanostructuring and Stereoelectronic Lone Pair Distortions in I–V–VI2 Materials

Alkali pnictogen dichalcogenides─I–V–VI2 or APnCh2─have been identified as promising semiconducting materials for energy conversion devices. However, the controlled nanoscale synthesis and our understanding of the effects of cation ordering and stereochemically active lone pairs on the structures of these ternary compounds remain underdeveloped. Here, we use solution-phase chemistry to synthesize a family of APnCh2 materials, including LiSbSe2, NaSbS2, NaSbSe2, NaBiS2, and NaBiSe2. Our approach utilizes alkali metal hydrides (AH) or carboxylates, A(O2CR), PnPh3, and elemental chalcogens as synthetic precursors and oleylamine or 1-octadecene as solvents. Synthetic manipulation via fine-tuning of reaction temperature enables control over the degree of ordering caused by the Sb 5s2 lone pair-induced distortions in NaSbS2. Pair distribution function analysis demonstrates that the structure of the Sb-containing phases deviates much more from a disordered rock salt structure than that of the Bi-containing phases. This local distortion, induced by the Sb lone pair, leads to a previously unreported noncentrosymmetric NaSbS2 crystal structure, which is additionally supported by second-harmonic generation measurements. Infrared and multinuclear solid-state NMR spectroscopies show that oleylamine or chelating carboxylates and, in some cases, unreacted precursors (LiH and PnPh3) remain bound to the nanocrystalline surfaces. A deeper understanding of the local atomic environment, long-range ordering, surface chemistry, and optoelectronic properties of these materials may speed up their fundamental study and application.This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication as Medina-Gonzalez, Alan M., Philip Yox, Yunhua Chen, Marquix AS Adamson, Bryan A. Rosales, Maranny Svay, Emily A. Smith et al. "Solution-Grown Ternary Semiconductors: Nanostructuring and Stereoelectronic Lone Pair Distortions in I–V–VI2 Materials." Chemistry of Materials 34, no. 16 (2022): 7357-7368. Copyright 2022 American Chemical Society after peer review. To access the final edited and published work see DOI: 10.1021/acs.chemmater.2c01410. Posted with permission. DOE Contract Number(s): AC02-07CH11358; AC02-06CH11357; 1905066