Nina Lock

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.

Biomolecule-Assisted Hydrothermal Synthesis and Self-Assembly of Bi2Te3 Nanostring-Cluster Hierarchical Structure

A simple biomolecule-assisted hydrothermal approach has been developed for the fabrication of Bi(2)Te(3) thermoelectric nanomaterials. The product has a nanostring-cluster hierarchical structure which is composed of ordered and aligned platelet-like crystals. The platelets are approximately 100 nm in diameter and only approximately 10 nm thick even though a high reaction temperature of 220 degrees C and a long reaction time of 24 h were applied to prepare the sample. The growth of the Bi(2)Te(3) hierarchical structure appears to be a self-assembly process. Initially, Te nanorods are formed using alginic acid as both reductant and template. Subsequently, Bi(2)Te(3) grows in a certain direction on the surface of the Te rods, resulting in the nanostring structure. The nanostrings further recombine side-by-side with each other to achieve the ordered nanostring clusters. The particle size and morphology can be controlled by adjusting the concentration of NaOH, which plays a crucial role on the formation mechanism of Bi(2)Te(3). An even smaller polycrystalline Bi(2)Te(3) superstructure composed of polycrystalline nanorods with some nanoplatelets attached to the nanorods is achieved at lower NaOH concentration. The room temperature thermoelectric properties have been evaluated with an average Seebeck coefficient of -172 microV K(-1), an electrical resistivity of 1.97 x 10(-3) Omegam, and a thermal conductivity of 0.29 W m(-1) K(-1).

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.

Interrelation between atomic switching disorder and thermoelectric properties of ZrNiSn half-Heusler compounds

The interrelation between atomic switching disorder and thermoelectric properties in the half-Heusler alloy ZrNiSn was investigated. ZrNiSn samples were prepared by a time-efficient levitation melting and spark plasma sintering procedure. High-resolution synchrotron radiation powder X-ray diffraction shows that a single phase half-Heusler compound has been obtained. Trace impurities were detected after annealing at 970 K for 5 days. Rietveld refinements were carried out for both unannealed and annealed ZrNiSn samples to study the possible structural disorders. It is found that the generally accepted Zr/Sn antisite defects are not likely to exist. Instead, the refinements revealed interstitial fractional occupancy of Ni on the (½, ½, ½) site, which is normally empty in the half-Heusler phases, but filled in full Heusler materials. The electrical conductivity and Seebeck coefficient from 300 to 900 K of the unannealed and annealed ZrNiSn displayed no obvious distinction, and the room temperature electrical resistivity and absolute Seebeck coefficient of the annealed ZrNiSn even decreased slightly compared to those of the unannealed one, which implies no obvious Zr/Sn disorder transition during the annealing procedure. A slight increase in the thermal conductivity was observed after a long time annealing, possibly due to reduced Ni atomic disorder.

Experimental determination of core electron deformation in diamond

Synchrotron powder X-ray diffraction data are used to determine the core electron deformation of diamond. Core shell contraction inherently linked to covalent bond formation is observed in close correspondence with theoretical predictions. Accordingly, a precise and physically sound reconstruction of the electron density in diamond necessitates the use of an extended multipolar model, which abandons the assumption of an inert core. The present investigation is facilitated by negligible model bias in the extraction of structure factors, which is accomplished by simultaneous multipolar and Rietveld refinement accurately determining an atomic displacement parameter (ADP) of 0.00181 (1) Å(2). The deconvolution of thermal motion is a critical step in experimental core electron polarization studies, and for diamond it is imperative to exploit the monatomic crystal structure by implementing Wilson plots in determination of the ADP. This empowers the electron-density analysis to precisely administer both the deconvolution of thermal motion and the employment of the extended multipolar model on an experimental basis.

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.

Scrutinizing negative thermal expansion in MOF-5 by scattering techniques and ab initio calculations

Complementary experimental techniques and ab initio calculations were used to determine the origin and nature of negative thermal expansion (NTE) in the archetype metal-organic framework MOF-5 (Zn(4)O(1,4-benzenedicarboxylate)(3)). The organic linker was probed by inelastic neutron scattering under vacuum and at a gas pressure of 175 bar to distinguish between the pressure and temperature responses of the framework motions, and the local structure of the metal centers was studied by X-ray absorption spectroscopy. Multi-temperature powder- and single-crystal X-ray and neutron diffraction was used to characterize the polymeric nature of the sample and to quantify NTE over the large temperature range 4-400 K. Ab initio calculations complement the experimental data with detailed information on vibrational motions in the framework and their correlations. A uniform and comprehensive picture of NTE in MOF-5 has been drawn, and we provide direct evidence that the main contributor to NTE is translational transverse motion of the aromatic ring, which can be dampened by applying a gas pressure to the sample. The linker motion is highly correlated rather than local in nature. The relative energies of different framework vibrations populated in MOF-5 are suggested by analysis of neutron diffraction data. We note that the lowest-energy motion is a librational motion of the aromatic ring which does not contribute to NTE. The libration is followed by transverse motion of the linker and the carboxylate group. These motions result in unit-cell contraction with increasing temperature.

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.

Highly Selective Deethylation of Rhodamine B on Prepared in Supercritical Fluids

Pure phase anatase TiO2 nanoparticles with sizes of 5–8 nm and varying crystallinity were synthesized in supercritical isopropanol/water using a continuous flow reactor. Their photodegradation of rhodamine B (RhB) was evaluated under visible light irradiation. The as-prepared TiO2 nanoparticles show much higher photodegradation efficiencies than commercial Degussa P25 TiO2. Moreover, the photodegradation of RhB on the as-prepared TiO2 follows a different process from that on P25 TiO2, quicker N-deethylation and slower cleavage of conjugated chromophore structure. Based on PXRD, TEM, and BET measurements, these two photodegradation properties have been explained by the physicochemical properties of TiO2.

Zn migration during spark plasma sintering of thermoelectric Zn4Sb3

The phase homogeneity of spark plasma sintered thermoelectric Zn4Sb3 pellets along the pressing direction has been studied by potential Seebeck microprobe scanning and spatially resolved x-ray diffraction. Significant variations in the Seebeck coefficient reflect presence of different crystalline phases. The emergence of the ZnSb phase at the bottom of the pellet and metallic Zn impurity at the top explains the variation in the Seebeck coefficients. Quantitative phase distributions along the pressing axis were determined from the Rietveld refinements of spatially resolved x-ray diffraction patterns. These reveal a migration of highly mobilized Zn atoms under the direct current applied during spark plasma sintering.