Ligand conversion in nanocrystal synthesis: the oxidation of alkylamines to fatty acids by nitrate

Ligands are a fundamental part of nanocrystals. They control and direct nanocrystal syntheses and provide colloidal stability. Bound ligands also affect the nanocrystals’ chemical reactivity and electronic structure. Surface chemistry is thus crucial to understand nanocrystal properties and functionality. Here, we investigate the synthesis of metal oxide nanocrystals (CeO2-x, ZnO, and NiO) from metal nitrate precursors, in the presence of oleylamine ligands. Surprisingly, the nanocrystals are capped exclusively with a fatty acid instead of oleylamine. Analysis of the reaction mixtures with nuclear magnetic resonance spectroscopy revealed several reaction byproducts and intermediates that are common to the decomposition of Ce, Zn, Ni, and Zr nitrate precursors. Our evidence supports the oxidation of alkylamine and formation of a carboxylic acid, thus unraveling this counterintuitive surface chemistry.Postprint (published version

Exploiting the Lability of Metal Halide Perovskites for Doping Semiconductor Nanocomposites

Cesium lead halides have intrinsically unstable crystal lattices and easily transform within perovskite and nonperovskite structures. In this work, we explore the conversion of the perovskite CsPbBr3 into Cs4PbBr6 in the presence of PbS at 450 °C to produce doped nanocrystal-based composites with embedded Cs4PbBr6 nanoprecipitates. We show that PbBr2 is extracted from CsPbBr3 and diffuses into the PbS lattice with a consequent increase in the concentration of free charge carriers. This new doping strategy enables the adjustment of the density of charge carriers between 1019 and 1020 cm-3, and it may serve as a general strategy for doping other nanocrystal-based semiconductors.M.C. has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Grant Agreement No. 665385. ICN2 acknowledges funding from Generalitat de Catalunya 2017 SGR 327. ICN2 is supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2017-0706) and is funded by the CERCA Programme/Generalitat de Catalunya. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 823717 – ESTEEM3. M.V.K. acknowledges the support by the European Research Council under the Horizon 2020 Framework Program (ERC Consolidator Grant SCALE-HALO Grant Agreement No. 819740) and by FET-OPEN project no. 862656 (DROP-IT)

The importance of surface adsorbates in solution-processed thermoelectric materials: the case of SnSe

Solution synthesis of particles emerges as an alternative to prepare thermoelectric materials with less demanding processing conditions than conventional solid-state synthetic methods. However, solution synthesis generally involves the presence of additional molecules or ions belonging to the precursors or added to enable solubility and/or regulate nucleation and growth. These molecules or ions can end up in the particles as surface adsorbates and interfere in the material properties. This work demonstrates that ionic adsorbates, in particular Na+ ions, are electrostatically adsorbed in SnSe particles synthesized in water and play a crucial role not only in directing the material nano/microstructure but also in determining the transport properties of the consolidated material. In dense pellets prepared by sintering SnSe particles, Na remains within the crystal lattice as dopant, in dislocations, precipitates, and forming grain boundary complexions. These results highlight the importance of considering all the possible unintentional impurities to establish proper structure–property relationships and control material properties in solution-processed thermoelectric materials.Peer ReviewedPostprint (author's final draft

Exploiting the lability of metal halide perovskites for doping semiconductor nanocomposites

Cesium lead halides have intrinsically unstable crystal lattices and easily transform within perovskite and nonperovskite structures. In this work, we explore the conversion of the perovskite CsPbBr into CsPbBr in the presence of PbS at 450 °C to produce doped nanocrystal-based composites with embedded CsPbBr nanoprecipitates. We show that PbBr is extracted from CsPbBr and diffuses into the PbS lattice with a consequent increase in the concentration of free charge carriers. This new doping strategy enables the adjustment of the density of charge carriers between 10 19 and 10 20 cm -3, and it may serve as a general strategy for doping other nanocrystal-based semiconductors

Defect Engineering in Solution-Processed Polycrystalline SnSe Leads to High Thermoelectric Performance [Dataset]

29 pages. -- Content: The tracking process of adsorption of CdSe species on the SnSe surface; XRD patterns of SnSe and SnSe-x%CdSe nanocomposites; SEM images of SnSe-3%CdSe nanocomposites at the different stages; SEM images of annealed SnSe-x%CdSe nanopowders; Grain size evolution study for bare SnSe and SnSe-3%CdSe; SEM images at different magnifications of SnSe and SnSe-3%CdSe pellets; EBSD microstructure of SnSe and SnSe-3%CdSe pellets; XRD pattern of recrystallized CdSe; SEM images of annealed SnSe powder at 350°C; EDS elemental mapping for SnSe-3%CdSe; Surface treatment; Thermogravimetric analyses; SnSe-CdSe phase diagram; High-temperature XRD analyses of SnSe and SnSe-3%CdSe; Lattice parameters and unit cell volume of SnSe-3%PbS pellet; TE properties of SnSe-CdSe samples with different content of CdSe; Band structure changes in SnSe induced by the CdSe NPs; TE properties of SnSe and SnSe-3%CdSe measured in parallel direction; Heat capacity Cp of SnSe-3%CdSe; Percentage variations in the TE properties of SnSe-x%CdSe compared to SnSe; Lattice thermal conductivity (κL) calculation; Literature comparison; TEM images of SnSe-3%CdSe sample; Material stability and repeatability; Cylindrical pellet cutting; Theoretical zT prediction; Pellet density and composition; References.SnSe has emerged as one of the most promising materials for thermoelectric energy conversion due to its extraordinary performance in its single-crystal form and its low-cost constituent elements. However, to achieve an economic impact, the polycrystalline counterpart needs to replicate the performance of the single crystal. Herein, we optimize the thermoelectric performance of polycrystalline SnSe produced by consolidating solution-processed and surface-engineered SnSe particles. In particular, the SnSe particles are coated with CdSe molecular complexes that crystallize during the sintering process, forming CdSe nanoparticles. The presence of CdSe nanoparticles inhibits SnSe grain growth during the consolidation step due to Zener pinning, yielding a material with a high density of grain boundaries. Moreover, the resulting SnSe–CdSe nanocomposites present a large number of defects at different length scales, which significantly reduce the thermal conductivity. The produced SnSe–CdSe nanocomposites exhibit thermoelectric figures of merit up to 2.2 at 786 K, which is among the highest reported for solution-processed SnSe.Peer reviewe

ISTA Thesis

High-performance semiconductors rely upon precise control of heat and charge transport. This can be achieved by precisely engineering defects in polycrystalline solids. There are multiple approaches to preparing such polycrystalline semiconductors, and the transformation of solution-processed colloidal nanoparticles is appealing because colloidal nanoparticles combine low cost with structural and compositional tunability along with rich surface chemistry. However, the multiple processes from nanoparticle synthesis to the final bulk nanocomposites are very complex. They involve nanoparticle purification, post-synthetic modifications, and finally consolidation (thermal treatments and densification). All these properties dictate the final material’s composition and microstructure, ultimately affecting its functional properties. This thesis explores the synthesis, surface chemistry and consolidation of colloidal semiconductor nanoparticles into dense solids. In particular, the transformations that take place during these processes, and their effect on the material’s transport properties are evaluated

Alginate/porous silica matrices for the encapsulation of living organisms: tunable properties for biosensors, modular bioreactors, and bioremediation devices

The encapsulation of living cells within inorganic silica hydrogels is a promising strategy for the design of biosensors, modular bioreactors, and bioremediation devices, among other interesting applications, attracting scientific and technological interest. These host-guest multifunctional materials (HGFM) combine synergistically specific biologic functions of their guest with those of the host matrix enhancing their performance. Although inorganic immobilization hosts present several advantages over their (bio)polymer-based counterparts in terms of chemical and physical stability, the direct contact of cells with silica precursors during synthesis and the constraints imposed by the inorganic host during operating conditions have proved to influence their biological response. Recently we proposed an alternative two-step procedure including a pre-encapsulation in biocompatible polymers such as alginates in order to confer protection to the biological guest during the inorganic and more cytotoxic synthesis. By means of this procedure, whole cultures of microorganisms remain confined in small liquid volumes generated inside the inorganic host, providing near conventional liquid culture conditions. Moreover, the fact of protecting the biological guest during the synthesis of the host, allows extending the synthesis parameters beyond biocompatible conditions, tuning the microstructure of the matrix. In turn, the microstructure (porosity at the nanoscale, radius of gyration of particles composing the structure, and fractal dimension of particle clusters) is determinant of macroscopic parameters, such as optical quality and transport properties that govern the encapsulation material´s performance. Here we review the most interesting applications of the two-step procedure, making special emphasis on the optimization of optical, transport and mechanical properties of the host as well as in the interaction with the guest during operation conditions.Fil: Perullini, Ana Mercedes. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Calcabrini, Mariano. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Jobbagy, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Aldabe, Sara Alfonsina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentin

Solution-processed inorganic thermoelectric materials: Opportunities and challenges

Thermoelectric technology requires synthesizing complex materials where not only the crystal structure but also other structural features such as defects, grain size and orientation, and interfaces must be controlled. To date, conventional solid-state techniques are unable to provide this level of control. Herein, we present a synthetic approach in which dense inorganic thermoelectric materials are produced by the consolidation of well-defined nanoparticle powders. The idea is that controlling the characteristics of the powder allows the chemical transformations that take place during consolidation to be guided, ultimately yielding inorganic solids with targeted features. Different from conventional methods, syntheses in solution can produce particles with unprecedented control over their size, shape, crystal structure, composition, and surface chemistry. However, to date, most works have focused only on the low-cost benefits of this strategy. In this perspective, we first cover the opportunities that solution processing of the powder offers, emphasizing the potential structural features that can be controlled by precisely engineering the inorganic core of the particle, the surface, and the organization of the particles before consolidation. We then discuss the challenges of this synthetic approach and more practical matters related to solution processing. Finally, we suggest some good practices for adequate knowledge transfer and improving reproducibility among different laboratories

Ligand Conversion in Nanocrystal Synthesis: The Oxidation of Alkylamines to Fatty Acids by Nitrate

Ligands are a fundamental part of nanocrystals. They control and direct nanocrystal syntheses, and provide colloidal stability. Bound ligands also affect the nanocrystals’ chemical reactivity and electronic structure. Surface chemistry is thus crucial to understand nanocrystal properties and functionality. Here, we investigate the synthesis of metal oxide nanocrystals (CeO2-x, ZnO, and NiO) from metal nitrate precursors, in the presence of oleylamine ligands. Surprisingly, the nanocrystals are capped exclusively with a fatty acid instead of oleylamine. Analysis of the reaction mixtures with nuclear magnetic resonance spectroscopy revealed several reaction byproducts and intermediates that are common to the decomposition of Ce, Zn, Ni and Zr nitrate precursors. Our evidence supports the oxidation of alkylamine and formation of a carboxylic acid, thus unraveling this counterintuitive surface chemistry

Ligand Conversion in Nanocrystal Synthesis: The Oxidation of Alkylamines to Fatty Acids by Nitrate

Ligands are a fundamental part of nanocrystals. They control and direct nanocrystal syntheses and provide colloidal stability. Bound ligands also affect the nanocrystals’ chemical reactivity and electronic structure. Surface chemistry is thus crucial to understand nanocrystal properties and functionality. Here, we investigate the synthesis of metal oxide nanocrystals (CeO2-x, ZnO, and NiO) from metal nitrate precursors, in the presence of oleylamine ligands. Surprisingly, the nanocrystals are capped exclusively with a fatty acid instead of oleylamine. Analysis of the reaction mixtures with nuclear magnetic resonance spectroscopy revealed several reaction byproducts and intermediates that are common to the decomposition of Ce, Zn, Ni, and Zr nitrate precursors. Our evidence supports the oxidation of alkylamine and formation of a carboxylic acid, thus unraveling this counterintuitive surface chemistry