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The pyrovanadates ß-Mn2V2O7 and ß-Cu2V2O7 were previously investigated as photoanode materials for water splitting. Neither of them, however, was found to be sufficiently active. In this work, we predict the properties of these two structurally similar pyrovanadates upon Cu/Mn substitution in their corresponding lattices via density functional theory calculations to explore the suitability of their band structure for water splitting and to assess their ease of synthesis. We predict that a concentration of up to 20% Cu and Mn into ß-Mn2V2O7 and ß-Cu2V2O7, respectively, leads to a narrowing of the bandgap, which, in the former case, is experimentally confirmed by UV-vis spectroscopy. Calculations in the intermediate composition range, however, yield nearly constant bandgaps. Moreover, we predict the materials with higher substitution levels to be increasingly difficult to synthesize, implying that low substitution levels are most relevant in terms of bandgaps and ease of synthesis.
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The classical nucleation theory (CNT) is the most common theoretical framework used to explain particle formation. However, nucleation is a complex process with reaction pathways which are often not covered by the CNT. Herein, we study the formation mechanism of copper nanospheres using inâ situ X-ray absorption and scattering measurements. We reveal that their nucleation involves coordination polymer lamellae as pre-nucleation structures occupying a local minimum in the reaction energy landscape. Having learned this, we achieved a superior monodispersity for Cu nanospheres of different sizes. This report exemplifies the importance of developing a more realistic picture of the mechanism involved in the formation of inorganic nanoparticles to develop a rational approach to their synthesis.
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The ability to tune thin oxide coatings by wet-chemistry is desirable for many applications, yet it remains a key synthetic challenge. In this work, we introduce a general colloidal atomic layer deposition (c-ALD) synthesis to grow an alumina shell with tunable thickness around nanocrystalline cores of various compositions spanning from ionic semiconductors (i.e., CsPbX3, with X = Br, I, Cl) to metal oxides and metals (i.e., CeO2 and Ag). The distinctive characteristics of each core (i.e., emission, facile surface functionalization, stability) allowed us to optimize and to elucidate the chemistry of the c-ALD process. Compared to gas-phase ALD, this newly developed synthesis has the advantage of preserving the colloidal stability of the nanocrystalline core while controlling the shell thickness from 1 to 6 nm. As one example of the opportunities offered by the growth of a thin oxide shell, we study the anion exchange reaction in the CsPbX3 perovskites nanocrystals by in situ X-ray diffraction, which had been impeded so far by the instability of this class of materials and by the fast exchange kinetics.
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Understanding nucleation phenomena is crucial across all branches of physical and natural sciences. Colloidal nanocrystals are among the most versatile and tunable synthetic nanomaterials. While huge steps have been made in their synthetic development, synthesis by design is still impeded by the lack of knowledge of reaction mechanisms. Here, we report on the investigation of the reaction intermediates in high temperature syntheses of copper nanocrystals by a variety of techniques, including X-ray absorption at a synchrotron source using a customized in situ cell. We reveal unique insights into the chemical nature of the reaction intermediates and into their role in determining the final shape of the metal nanocrystals. Overall, this study highlights the importance of understanding the chemistry behind nucleation as a key parameter to predict synthetic pathways for shape-controlled nanocrystals.
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The reduction of six mixed-oxide samples containing 14, 24, 35, 46, 54, and 62 mol % Pu was studied in situ by X-ray diffraction. The samples were first oxidized in air and subsequently reduced in a controlled atmosphere corresponding to a stoichiometric composition with an O/M = 2.00. After oxidation, we observed two structures, one cubic and one orthorhombic, MO2+x and M3O8-z. The two phases were subsequently reduced back to their stoichiometric O/M = 2.00 in a controlled atmosphere. The plutonium contents of the two resulting cubic structures differed from the initial one. We conclude that strong cation transport took place during oxidation, according to the shape of the tie lines in the biphasic MO2+x/M4O9-M3O8-z domain. The resulting overall O/M after oxidation was estimated. We propose the shape of the tie lines in the aforementioned biphasic domain and suggest a maximal plutonium solubility in the M3O8 structure at 8 ± 2 mol % (Pu/U + Pu) at 1573 K.
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The oxidation products and kinetics of two sets of mixed uranium-plutonium dioxides containing 14%, 24%, 35%, 46%, 54%, and 62% plutonium treated in air were studied by means of in situ X-ray diffraction (XRD) from 300 to 1773 K every 100 K. The first set consisted of samples annealed 2 weeks before performing the experiments. The second one consisted of powdered samples that sustained self-irradiation damage. Results were compared with chosen literature data and kinetic models established for UO2. The obtained diffraction patterns were used to determine the temperature of the hexagonal M3O8 (M for metal) phase formation, which was found to increase with Pu content. The maximum observed amount of the hexagonal phase in wt % was found to decrease with Pu addition. We conclude that plutonium stabilizes the cubic phases during oxidation, but the hexagonal phase was observed even for the compositions with 62 mol % Pu. The results indicate that self-irradiation defects have a slight impact on the kinetics of oxidation and the lattice parameter even after the phase transformation. It was concluded that the lattice constant of the high oxygen phase was unaffected by the changes in the overall O/M when it was in equilibrium with small quantities of M3O8. We propose that the observed changes in the high oxygen cubic phase lattice parameter are a result of either cation migration or an increase in the miscibility of oxygen in this phase. The solubility of Pu in the hexagonal phase was estimated to be below 14 mol % even at elevated temperatures.
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Metal nanoparticles are currently used in a variety of applications, ranging from life sciences to nanoelectronic devices to gas sensors. In particular, the use of palladium nanoparticles is gaining increasing attention due to their ability to catalyze the rapid dissociation of hydrogen, which leads to an excellent response in hydrogen-sensing applications. However, current palladium-nanoparticle-based sensors are hindered by the presence of hysteresis upon hydride formation and decomposition, as this hysteresis limits sensor accuracy. Here, we present a robust colloidal synthesis for palladium-gold alloy nanoparticles and demonstrate their hysteresis-free response when used for hydrogen detection. The obtained colloidal particles, synthesized in an aqueous, room-temperature environment, can be tailored to a variety of applications through changing the size, ratio of metals, and surface stabilization. In particular, the variation of the viscosity of the mixture during synthesis resulted in a highly tunable size distribution and contributed to a significant improvement in size dispersity compared to the state-of-the-art methods.
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Grains constitute the building blocks of polycrystalline materials and their boundaries determine bulk physical properties like electrical conductivity, diffusivity and ductility. However, the structure and evolution of grains in nanostructured materials and the role of grain boundaries in reaction or phase transformation kinetics are poorly understood, despite likely importance in catalysis, batteries and hydrogen energy technology applications. Here we report an investigation of the kinetics of (de)hydriding phase transformations in individual Pd nanoparticles. We find dramatic evolution of single particle grain morphology upon cyclic exposure to hydrogen, which we identify as the reason for the observed rapidly slowing sorption kinetics, and as the origin of the observed kinetic compensation effect. These results shed light on the impact of grain growth on kinetic processes occurring inside nanoparticles, and provide mechanistic insight in the observed kinetic compensation effect.
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Copper vanadates have been proposed as promising photoanodes for water-splitting photoelectrochemical cells, but their performance has recently been shown to be severely limited. To understand this behavior, we study the electronic structure and the optical properties of ß-Cu2V2O7 both experimentally and computationally. The measured absorption spectrum shows an absorption peak at 1.5 eV followed by the onset of an apparent continuum at 2.26 eV, as generally found for this class of materials. We perform calculations within the framework of the QS GWÌ method and the Bethe-Salpeter equation while including effects of magnetic ordering, nuclear quantum motion, and thermal vibrations. We demonstrate the occurrence of two kinds of excitons with high binding energies upon optical excitation in ß-Cu2V2O7, which account for the first absorption peak and the lower edge of the apparent continuum. The results are confirmed by photoluminescence measurements, where sub-band-gap emissions are found for both excitons. These results provide an explanation for the low photocatalytic efficiencies of copper vanadates, despite the favorable size of their optical band gaps.
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Nanocrystal-seeded synthesis relies on the reaction of nanocrystal seeds with a molecular precursor and it can be regarded as the link between sol-gel and solid-state chemistries. This synthesis approach aims at accessing compositionally complex materials, yet to date its full potential remains unexploited. Herein, surface oxidized Cu nanocrystal seeds with diameters from 6 nm to 70 nm are reacted with vanadium acetylacetonate to form ß-Cu2V2O7 with a tunable grain size ranging from 29 nm to 63 nm. In situ X-ray diffraction measurements evidence the occurrence of a solid-state reaction between the NC seeds and the vanadium oxide formed during the annealing. The variation of the ion diffusion lengths, the homogeneity of the precursor solution and the number of nucleation sites with the NC seed size explains the lower formation temperature, the smaller grain size and the higher grain size monodispersity of ß-Cu2V2O7 as the seed size decreases. Finally, the tunability afforded by the nanocrystal-seeded synthesis provides a unique opportunity to correlate the photoelectrochemical performance with the grain size in a size regime close to the charge carrier diffusion length of ß-Cu2V2O7 (20-40 nm). The net photocurrent density peaks when the grain size is 39 nm by reaching 0.23 mA cm-2 at 1.23 V vs. RHE in the presence of a hole scavenger. While still far from the theoretical limit, this result overcomes the current state-of-the-art for ß-Cu2V2O7. An interesting double fold increase in the photocurrent is found in mixed phase ß-Cu2V2O7/CuV2O6 samples, suggesting that nanostructuring and heterostructuring are beneficial to the performance.