Exploration of anion effects in solvothermal synthesis using in situ X-ray diffraction.

Solvothermal synthesis presents a facile and highly flexible approach to chemical processing and it is widely used for preparation of micro- and nanosized inorganic materials. The large number of synthesis parameters in combination with the richness of inorganic chemistry means that it is difficult to predict or design synthesis outcomes, and it is demanding to uncover the effect of different parameters due to the sealed and complex nature of solvothermal reactors along with the time demands related to reactor cleaning, sample purification, and characterization. This study explores the effect on formation of crystalline products of six common anions in solvothermal treatment of aqueous and ethanolic precursors. Three different cations are included in the study (Mn2+, Co2+, Cu2+) representing chemical affinities towards different regions of the periodic table with respect to the hard soft acid base (HSAB) classification and the Goldschmidt classification. They additionally belong to the commonly used 3d transition metals and display a suitable variety in solvothermal chemistry to highlight anion effects. The results of the solvothermal in situ experiments demonstrate a clear effect of the precursor anions, with respect to whether crystallization occurs or not and the characteristics of the formed phases. Additionally, some of the anions are shown to be redox active and to influence the formation temperature of certain phases which in turn relates to the observed average crystallite sizes.

Stabilizing tetragonal ZrO2 nanocrystallites in solvothermal synthesis.

Phase-pure tetragonal ZrO2 nanoparticles have been prepared under simple solvothermal synthesis conditions using different types of alcohols as solvents and studied using in situ X-ray scattering. The variation of tetragonal/monoclinic phase ratios within the produced powders was directly correlated with the amount of in situ generated water from solvent dehydration during the syntheses. By controlling the dehydration kinetics, either choosing primary alcohols of varying thermal stability or by changing synthesis temperatures, it is possible to selectively tune this tetragonal/monoclinic phase ratio.

Unveiling the formation mechanism of PbxPdy intermetallic phases in solvothermal synthesis using in situ X-ray total scattering.

Pd possesses attractive catalytic properties and nano-structuring is an obvious way to enhance catalytic activity. Alloying Pd with Pb has been shown to enhance the catalytic effect of alcohol oxidation. Further optimization of the catalytic effect can be accomplished by controlling the particle size and key to this is understanding the formation mechanism. By monitoring solvothermal syntheses using in situ X-ray total scattering, this study unveils the formation mechanism of PbxPdy intermetallic nanoparticles. The formation occurs through a multi-step mechanism. Initially, Pd nanoparticles are formed, followed by incorporation of Pb into the Pd-structure, thus forming PbxPdy intermetallic nanoparticles. By varying the reaction time and temperature, the incorporation of Pb can be controlled, thereby tailoring the phase outcome. Based on the in situ solvothermal syntheses, ex situ autoclave syntheses were performed, resulting in the synthesis of Pb3Pd5 and Pb9Pd13 with a purity above 93%. The catalytic effect of these intermetallic phases towards the hydrogen evolution reaction (HER) is assessed. It is found that Pd, Pb3Pd5, and Pb9Pd13 have comparable stabilities, however, the overpotential increases with increasing amounts of Pb.

Pair Distribution Function from Liquid Jet Nanoparticle Suspension using Femtosecond X-ray Pulses.

X-ray scattering data measured on femtosecond timescales at the SACLA X-ray Free Electron Laser (XFEL) facility on a suspension of HfO2 nanoparticles in a liquid jet were used for pair distribution function (PDF) analysis. Despite a non-optimal experimental setup resulting in a modest Qmax of ~8 Å-1 , a promising PDF was obtained. The main features were reproduced when comparing the XFEL PDF to a PDF obtained from data measured at the PETRA III synchrotron light source. Refining structural parameters such as unit cell dimension and particle size from the XFEL PDF provided reliable values. Although the reachable Qmax limited the obtainable information, the present results indicate that good quality PDFs can be obtained on femtosecond timescales if the experimental conditions are further optimized. The study therefore encourages a new direction in ultrafast structural science where structural features of amorphous and disordered systems can be studied.

A reactor for time-resolved X-ray studies of nucleation and growth during solvothermal synthesis.

Understanding the nucleation and growth mechanisms of nanocrystals under hydro- and solvothermal conditions is key to tailoring functional nanomaterials. High-energy and high-flux synchrotron radiation is ideal for characterization by powder X-ray diffraction and X-ray total scattering in real time. Different versions of batch-type cell reactors have been employed in this work, exploiting the robustness of polyimide-coated fused quartz tubes with an inner diameter of 0.7 mm, as they can withstand pressures up to 250 bar and temperatures up to 723 K for several hours. Reported here are recent developments of the in situ setups available for general users on the P21.1 beamline at PETRA III and the DanMAX beamline at MAX IV to study nucleation and growth phenomena in solvothermal synthesis. It is shown that data suitable for both reciprocal-space Rietveld refinement and direct-space pair distribution function refinement can be obtained on a timescale of 4 ms.

In situ X-ray diffraction study of the solvothermal formation mechanism of gallium oxide nanoparticles.

Gallium oxides are of broad interest due to their wide band gaps and attractive photoelectric properties. Typically, the synthesis of gallium oxide nanoparticles is based on a combination of solvent-based methods and subsequent calcination, but detailed information about solvent based formation processes is lacking, and this limits the tailoring of materials. Here we have examined the formation mechanisms and crystal structure transformations of gallium oxides during solvothermal synthesis using in situ X-ray diffraction. γ-Ga2O3 readily forms over a wide range of conditions. In contrast, ß-Ga2O3 only forms at high temperatures (T > 300 °C), and it is always preceded by γ-Ga2O3, indicating that γ-Ga2O3 is a crucial part of the formation mechanism of ß-Ga2O3. The activation energy for formation of ß-Ga2O3 from γ-Ga2O3 is determined to be 90-100 kJ mol-1 in ethanol, water and aqueous NaOH based on kinetic modelling of phase fractions obtained from multi-temperature in situ X-ray diffraction data. At low temperatures GaOOH and Ga5O7OH form in aqueous solvent, but these phases are also obtained from γ-Ga2O3. Systematic exploration of synthesis parameters such as temperature, heating rate, solvent and reaction time reveal that they all affect the resulting product. In general, the solvent based reaction paths are different from reports on solid state calcination studies. This underlines that the solvent is an active part of the solvothermal reactions and to a high degree determines different formation mechanisms.

A Machine-Learning-Based Approach for Solving Atomic Structures of Nanomaterials Combining Pair Distribution Functions with Density Functional Theory.

Determination of crystal structures of nanocrystalline or amorphous compounds is a great challenge in solid-state chemistry and physics. Pair distribution function (PDF) analysis of X-ray or neutron total scattering data has proven to be a key element in tackling this challenge. However, in most cases, a reliable structural motif is needed as a starting configuration for structure refinements. Here, an algorithm that is able to determine the crystal structure of an unknown compound by means of an on-the-fly trained machine learning model, which combines density functional theory calculations with comparison of calculated and measured PDFs for global optimization in an artificial landscape, is presented. Due to the nature of this landscape, even metastable configurations and stacking disorders can be identified.

Zr4+ solution structures from pair distribution function analysis.

The structures of metal ions in solution constitute essential information for obtaining chemical insight spanning from catalytic reaction mechanisms to formation of functional nanomaterials. Here, we explore Zr4+ solution structures using X-ray pair distribution function (PDF) analysis across pH (0-14), concentrations (0.1-1.5 M), solvents (water, methanol, ethanol, acetonitrile) and metal sources (ZrCl4, ZrOCl2·8H2O, ZrO(NO3)2·xH2O). In water, [Zr4(OH)8(OH2)16]8+-tetramers are predominant, while non-aqueous solvents contain monomeric complexes. The PDF analysis also reveals second sphere coordination of chloride counter ions to the aqueous tetramers. The results are reproducible across data measured at three different beamlines at the PETRA-III and MAX IV synchrotron light sources.

Synthesis of Phase-Pure Thermochromic VO2 (M1).

A highly reproducible, simple, and inexpensive synthesis method for obtaining phase-pure thermochromic monoclinic VO2 (M1) is presented. Vanadium(III) oxide and ammonium metavanadate were used as starting materials and no additional reducing agents are required. Heating a mixture of these two components under an argon atmosphere at 750 °C for 2-4 h provides the direct formation of VO2 (M1) without detectable impurity phases. The formation reaction of VO2 (M1) was studied using in situ powder X-ray diffraction (PXRD), where a pressed pellet of the precursor material was heated during the continuous collection of PXRD data on a two-dimensional detector. The formation takes place via at least two crystalline intermediate phases where the first forms at 170-185 °C (likely an ammonium and oxygen deficient (NH4)1-δVO3-δ phase), and the second at 230 °C (likely a more disordered phase due to the increased background intensity). We assume that the solid-state reaction between the unknown but likely disordered vanadate phase and vanadium(III) oxide starts at 395 °C in concert with the appearance of several other unknown crystalline phases. At 610-750 °C, phase-pure rutile VO2 (P42/mnm) is obtained, which upon cooling converts to monoclinic VO2 (M1). The product composition, microstructure, and homogeneity are characterized by Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. The synthesized VO2 (M1) has a sharp reversible insulator-to-metal transition at 71.3 °C during heating and 59.5 °C during cooling, as characterized using differential scanning calorimetry, and resistivity and magnetic property measurements.

Unravelling the complex formation mechanism of HfO2 nanocrystals using in situ pair distribution function analysis.

Hafnia, HfO2, which is a wide band gap semiconducting oxide, is much less studied than the chemically similar zirconia (ZrO2). Here, we study the formation of hafnia nanocrystals from hafnium tetrachloride in methanol under solvothermal conditions (248 bar, 225-450 °C) using complementary in situ powder X-ray diffraction (PXRD) and Pair Distribution Function (PDF) analysis. The main structural motif of the precursor solution (HfCl4 dissolved in methanol) is a Hf oxide trimer with very similar local structure to that of m-HfO2. Different measurements on precursor solutions show large intensity variation for the Hf-Cl correlations signifying different extents of HCl elimation. A few seconds of heating lead to a correlation appearing at 3.9 Å corresponding to corner-sharing Hf-polyhedra in a disordered solid matrix. During the next minutes (depending on temperature) the disordered structure rearranges and the nearest neighbour Hf-Hf distance contracts while the Hf-O coordination number increases. After approximately 90 seconds (at T = 250 °C) the structural rearrangement terminates and 1-2 nm nanocrystals of m-HfO2 nucleate. Initially the m-HfO2 nanocrystals have significant disorder as reflected in large Hf atomic displacement parameter (ADP) values, but as the nanocrystals grow to 5-6 nm in size during extended heating, the Hf ADPs decrease toward the values obtained for ordered bulk structures. The nanocrystal growth is not well modelled by the Johnson-Mehl-Avrami expression reflecting that multiple complex chemical processes occur during this highly nonclassical nanocrystal formation under solvothermal conditions.