Kirsten M. Ø. Jensen

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.

Experimental setup for in situ X-ray SAXS/WAXS/ PDF studies of the formation and growth of nanoparticles in near- and supercritical fluids

The growing interest in inorganic nanoparticles for a wide range of applications is spurring a need for synthesis methods that allow a highly specific tailoring of material properties. Synthesis in supercritical fluids holds great promise for solving this problem, but so far the fundamental chemical processes taking place under these conditions are to a large extent unknown. Here the design, construction and application of a versatile experimental setup are reported; this setup enables in situ synchrotron small-angle X-ray scattering/wide-angle X-ray scattering/pair distribution function (SAXS/WAXS/PDF) studies of the formation and growth of nanoparticles under supercritical fluid conditions.

In Situ Studies of Solvothermal Synthesis of Energy Materials

Solvothermal and hydrothermal synthesis, that is, synthesis taking place in a solvent at elevated temperature and pressure, is a powerful technique for the production of advanced energy materials as it is versatile, cheap, and environmentally friendly. However, the fundamental reaction mechanisms dictating particle formation and growth under solvothermal conditions are not well understood. In order to produce tailor-made materials with specific properties for advanced energy technologies, it is essential to obtain an improved understanding of these processes and, in this context, in situ studies are an important tool as they provide real time information on the reactions taking place. Here, we present a review of the use of powder diffraction and total scattering methods for in situ studies of synthesis taking place under solvothermal and hydrothermal conditions. The experimental setups used for in situ X-ray and neutron studies are presented, and methods of data analysis are described. Special attention is given to the methods used to extract structural information from the data, for example, Rietveld refinement, whole powder pattern modelling and pair distribution function analysis. Examples of in situ studies are presented to illustrate the types of chemical insight that can be obtained.

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.

Real‐time synchrotron powder X‐ray diffraction study of the antisite defect formation during sub‐ and supercritical synthesis of LiFePO4 and LiFe1−xMnxPO4 nanoparticles

In situ synchrotron powder X-ray diffraction (PXRD) is used to study the formation of LiFePO4 nanoparticles during hydrothermal synthesis from LiOH, H3PO4, and two different iron precursors, FeSO4 and (NH4)2Fe(SO4)2. Furthermore, the synthesis of Li(Fe1−xMnx)PO4 (x = 0.25, 0.50 and 0.75) from LiOH, H3PO4 and FeSO4/MnSO4 is studied. The reactions involve an unknown intermediate phase, which is not the previously observed intermediate NH4FePO4·H2O. The intermediate phase quickly transforms into LiFePO4 and Li(Fe1−xMnx)PO4 even at rather low temperatures. The presence of ammonium enhances the formation of LiFePO4, and it also leads to a significant reduction in the concentration of Li–Fe antisite defects. The in situ PXRD technique allows one to follow the influence of time, temperature and manganese doping on the antisite defect concentration, and it is shown that even under supercritical conditions a reaction time of several minutes is required to suppress the defects. This makes flow synthesis of defect-free LiFePO4 and Li(Fe1−xMnx)PO4 nanoparticles challenging.

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.

Polymorphism in magic-sized Au144(SR)60 clusters

Ultra-small, magic-sized metal nanoclusters represent an important new class of materials with properties between molecules and particles. However, their small size challenges the conventional methods for structure characterization. Here we present the structure of ultra-stable Au144(SR)60 magic-sized nanoclusters obtained from atomic pair distribution function analysis of X-ray powder diffraction data. The study reveals structural polymorphism in these archetypal nanoclusters. In addition to confirming the theoretically predicted icosahedral-cored cluster, we also find samples with a truncated decahedral core structure, with some samples exhibiting a coexistence of both cluster structures. Although the clusters are monodisperse in size, structural diversity is apparent. The discovery of polymorphism may open up a new dimension in nanoscale engineering.

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.

Watching Nanoparticles Form: An In Situ (Small‐/Wide‐Angle X‐ray Scattering/Total Scattering) Study of the Growth of Yttria‐Stabilised Zirconia in Supercritical Fluids

Understanding nanoparticle-formation reactions requires multi-technique in situ characterisation, since no single characterisation technique provides adequate information. Here, the first combined small-angle X-ray scattering (SAXS)/wide-angle X-ray scattering (WAXS)/total-scattering study of nanoparticle formation is presented. We report on the formation and growth of yttria-stabilised zirconia (YSZ) under the extreme conditions of supercritical methanol for particles with Y(2)O(3) equivalent molar fractions of 0, 4, 8, 12 and 25 %. Simultaneous in situ SAXS and WAXS reveals a quick formation (seconds) of sub-nanometre amorphous material forming larger agglomerates with subsequent slow crystallisation (minutes) into nanocrystallites. The amount of yttria dopant is shown to strongly affect the crystallite size and unit-cell dimensions. At yttria-doping levels larger than 8 %, which is known to be the stoichiometry with maximum ionic conductivity, the strain on the crystal lattice is significantly increased. Time-resolved nanoparticle size distributions are calculated based on whole-powder-pattern modelling of the WAXS data, which reveals that concurrent with increasing average particle sizes, a broadening of the particle-size distributions occur. In situ total scattering provides structural insight into the sub-nanometre amorphous phase prior to crystallite growth, and the data reveal an atomic rearrangement from six-coordinated zirconium atoms in the initial amorphous clusters to eight-coordinated zirconia atoms in stable crystallites. Representative samples prepared ex situ and investigated by transmission electron microscopy confirm a transformation from an amorphous material to crystalline nanoparticles upon increased synthesis duration.