Espen D. Bøjesen

Revealing the mechanisms behind SnO2 nanoparticle formation and growth during hydrothermal synthesis: an in situ total scattering study.

The formation and growth mechanisms in the hydrothermal synthesis of SnO(2) nanoparticles from aqueous solutions of SnCl(4)·5H(2)O have been elucidated by means of in situ X-ray total scattering (PDF) measurements. The analysis of the data reveals that when the tin(IV) chloride precursor is dissolved, chloride ions and water coordinate octahedrally to tin(IV), forming aquachlorotin(IV) complexes of the form [SnCl(x)(H(2)O)(6-x)]((4-x)+) as well as hexaaquatin(IV) complexes [Sn(H(2)O)(6-y)(OH)(y)]((4-y)+). Upon heating, ellipsoidal SnO(2) nanoparticles are formed uniquely from hexaaquatin(IV). The nanoparticle size and morphology (aspect ratio) are dependent on both the reaction temperature and the precursor concentration, and particles as small as ~2 nm can be synthesized. Analysis of the growth curves shows that Ostwald ripening only takes place above 200 °C, and in general the growth is limited by diffusion of precursor species to the growing particle. The c-parameter in the tetragonal lattice is observed to expand up to 0.5% for particle sizes down to 2-3 nm as compared to the bulk value. SnO(2) nanoparticles below 3-4 nm do not form in the bulk rutile structure, but as an orthorhombic structural modification, which previously has only been reported at pressures above 5 GPa. Thus, adjustment of the synthesis temperature and precursor concentration not only allows control over nanoparticle size and morphology but also the structure.

Understanding the Formation and Evolution of Ceria Nanoparticles Under Hydrothermal Conditions

Supercritical growth: The formation and evolution of ceria nanoparticles during hydrothermal synthesis was investigated by in situ total scattering and powder diffraction. The nucleation of pristine crystalline ceria nanoparticles originated from previously unknown cerium dimer complexes. The nanoparticle growth was highly accelerated under supercritical conditions.

In Situ Total X‐Ray Scattering Study of WO3 Nanoparticle Formation under Hydrothermal Conditions

Pair distribution function analysis of in situ total scattering data recorded during formation of WO3 nanocrystals under hydrothermal conditions reveal that a complex precursor structure exists in solution. The WO6 polyhedra of the precursor cluster undergo reorientation before forming the nanocrystal. This reorientation is the critical element in the formation of different hexagonal polymporphs of WO3.

Mechanisms for iron oxide formation under hydrothermal conditions: an in situ total scattering study.

The formation and growth of maghemite (γ-Fe2O3) nanoparticles from ammonium iron(III) citrate solutions (C(6)O(7)H(6) · xFe(3+) · yNH(4)) in hydrothermal synthesis conditions have been studied by in situ total scattering. The local structure of the precursor in solution is similar to that of the crystalline coordination polymer [Fe(H(2)cit(H2O)](n), where corner-sharing [FeO(6)] octahedra are linked by citrate. As hydrothermal treatment of the solution is initiated, clusters of edge-sharing [FeO(6)] units form (with extent of the structural order <5 Å). Tetrahedrally coordinated iron subsequently appears, and as the synthesis continues, the clusters slowly assemble into crystalline maghemite, giving rise to clear Bragg peaks after 90 s at 320 °C. The primary transformation from amorphous clusters to nanocrystallites takes place by condensation of the clusters along the corner-sharing tetrahedral iron units. The crystallization process is related to large changes in the local structure as the interatomic distances in the clusters change dramatically with cluster growth. The local atomic structure is size dependent, and particles smaller than 6 nm are highly disordered. The final crystallite size (<10 nm) is dependent on both synthesis temperature and precursor concentration.

Evolution of atomic structure during nanoparticle formation.

The complete structural transformation of ionic species in the precursor solution, over an amorphous solid and finally into crystalline nanoparticles, is elucidated by in situ investigations under supercritical solvothermal conditions.

The chemistry of nucleation

Nucleation phenomena are of critical importance in numerous areas of science and everyday life. For decades the prevailing models to explain nucleation have been based on thermodynamic arguments without consideration of the chemical nature of the specific system. Even though newer models have included system-dependent variables, the quantitative atomistic differences are largely ignored. As a consequence, nucleation processes are treated on a “particle” or “monomer” level without discussion of the true atomic scale “chemistry of nucleation”. In the past couple of years, in situ studies of solvothermal reactions have considerably changed the experimental insight into nucleation phenomena, and especially the measurement of X-ray total scattering data and the subsequent pair distribution function analysis have proven to be vital tools. Here we discuss in situ results obtained for ten different material systems, and show that nucleation of nanoparticles in solvothermal reactions expose a fascinating chemical richness spanning from mono-metal to complex polymer precursor species, which, through a specific system-dependent multistep reaction mechanism, develop into pristine nanocrystals. It is argued that it is time to introduce a paradigm shift in the general nucleation theory and move away from the “one model fits all” to a chemistry-based approach rooted in atomic scale insight.

Crystal structure, microstructure and electrochemical properties of hydrothermally synthesised LiMn2O4

The hydrothermal synthesis method offers an environmentally benign way of synthesizing Li-ion battery materials with strong control of particle size and morphology, and thereby also the electrochemical performance. Here we present an in depth investigation of the crystal structure, microstructure and electrochemical properties of hydrothermally synthesized LiMn2O4, which is a widely used cathode material. A range of samples were synthesized by a simple, single-step hydrothermal route, and the products were characterized by elaborate Rietveld refinement of powder X-ray diffraction data, electron microscopy and electrochemical analysis. A distinct bimodal crystallite size distribution of LiMn2O4 was formed together with a Mn3O4 impurity. At high LiOH concentration the layered LixMnyO2 phase was formed. The crystallite sizes and impurity weight fractions were found to be highly synthesis dependent, and the amount of spinel impurity phase was found to correlate with deterioration of the electrochemical performance. The Mn3O4 phase can be very difficult to quantify in standard powder X-ray diffraction and due to peak overlap and X-ray fluorescence impurity levels of more than 10% are easily hidden. Furthermore, the spinel LiMn2O4 phase can easily be mistaken for the layered LixMnyO2 phase. The present study therefore highlights the importance of thorough structural characterization in studies of battery materials.

Towards atomistic understanding of polymorphism in the solvothermal synthesis of ZrO

Varying atomic short-range order is correlated with the ratio of the monoclinic (m) to tetragonal (t) phase in ZrO2 nanoparticle formation by solvothermal methods. Reactions from Zr oxynitrate in supercritical methanol and Zr acetate in water (hydrothermal route) were studied in situ by X-ray total scattering. Irrespective of the Zr source and solvent, the structure of the precursor in solution consists of edge-shared tetramer chains. Upon heating, the nearest-neighbor Zr-O and Zr-Zr distances shorten initially while the medium-range connectivity is broken. Depending on the reaction conditions, the disordered intermediate transforms either rapidly into m-ZrO2, or more gradually into mixed m- and t-ZrO2 with a concurrent increase of the shortest Zr-Zr distance. In the hydrothermal case, the structural similarity of the amorphous intermediate and m-ZrO2 favors the formation of almost phase-pure m-ZrO2 nanoparticles with a size of 5 nm, considerably smaller than the often-cited critical size below which the tetragonal is assumed to be favoured. Pair distribution function analysis thus unravels ZrO2 phase formation on the atomic scale and in this way provides a major step towards understanding polymorphism of ZrO2 beyond empirical approaches.

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The hydrothermal synthesis of magnetic strontium hexaferrite (SrFe12O19) nanocrystallites was followed in situ using synchrotron powder X-ray diffraction. For all the studied temperatures, the formation of SrFe12O19 happened through an intermediate crystalline phase, identified as the so-called six-line ferrihydrite (FeOOH). The presence of FeOOH has been overlooked in previous studies on hydrothermally synthesized SrFe12O19, despite the phase having a non-trivial influence on the magnetic properties of the final material. The chemical synthesis was successfully reproduced ex situ in a custom-designed batch-type reactor that resembles the experimental conditions of the in situ setup, while allowing larger quantities of material to be produced. The agreement in phase composition between the two studies reveals comparability between both experimental setups. Hexagonal platelet morphology is confirmed for SrFe12O19 combining Rietveld refinements of powder X-ray diffraction (PXRD) data with transmission electron microscopy (TEM). Room temperature magnetization curves were measured on the nanopowders prepared ex situ. The magnetic properties are discussed in the context of the influence of phase composition and crystallite size.

nanoparticles

In situ powder X-ray diffraction (PXRD) is a powerful characterization tool owing to its ability to provide time-resolved information about phase composition, crystal structure and microstructure. The application of high-flux synchrotron X-ray beams and the development of custom-built reactors have facilitated second-scale time-resolved studies of nanocrystallite formation and growth during solvothermal synthesis. The short exposure times required for good time resolution limit the data quality, while the employed high-temperature–high-pressure reactors further complicate data acquisition and treatment. Based on experience gathered during ten years of conducting in situ studies of solvothermal reactions at a number of different synchrotrons, a compilation of useful advice for conducting in situ PXRD experiments and data treatment is presented here. In addition, the reproducibility of the employed portable in situ PXRD setup, experimental procedure and data analysis is evaluated. This evaluation is based on repeated measurements of an LaB6 line-profile standard throughout 5 d of beamtime and on the repetition of ten identical in situ synchrotron PXRD experiments on the hydrothermal formation of γ-Fe2O3 nanocrystallites. The study reveals inconsistencies in the absolute structural and microstructural values extracted by Rietveld refinement and whole powder pattern modelling of the in situ PXRD data, but also illustrates the robustness of trends and relative changes in the extracted parameters. From the data, estimates of the effective errors and reproducibility of in situ PXRD studies of solvothermal nanocrystallite formation are provided.