Additive-mediated size control of MOF nanoparticles

A fast synthesis approach toward sub-60 nm sized MOF nanoparticles was developed by employing auxiliary additives. Control over the size of HKUST-1 and IRMOF-3 particles was gained by adjusting the concentration and type of stabilizers. Colloidal solutions of the MOFs were used for the formation of optically homogeneous thin films by spin-coating

Revealing kinetically tuned atomic pathways for interfacial strain relaxation

Strain at interfaces may profoundly impact the microstructure and properties of materials; thus, it is a major consideration when designing and engineering materials. Dislocation formation is a commonly known mechanism to release mismatch strain at solid-solid interfaces. However, it is still unclear about how materials accommodate interfacial strain under drastically accelerated structural transformation kinetics, since it is extremely challenging to directly observe the atomic structure evolution of fast-propagating interfaces. Utilizing liquid phase transmission electron microscopy (TEM), we have achieved atomic-scale imaging of hydrogen-induced phase transformations of palladium nanocrystals with different transformation speeds. Our observation reveals that the fast phase transformation occurs with an expanded interface of mixed $\alpha$- and $\beta$-$\mathrm{PdH}_x$ phases, and tilting of (020) planes to accommodate mismatch strain. In contrast, slow phase transformations lead to sharp interfaces with slipping misfit dislocations. Our kinetic Monte Carlo simulations show that fast phase transformation pushes the system far-from-equilibrium, generically roughening the interface; however, a smooth boundary minimizes strain near-equilibrium. Unveiling the atomic pathways of transformations from near-equilibrium to far-from-equilibrium, which was previously possible only computationally, this work holds significant implications for engineering microstructure of materials through modulating solid-solid transformations in a wide range of kinetics.Comment: 6 pages, 4 figures, plus Methods and Supplementary Note

Template-free synthesis of novel, highly-ordered 3D hierarchical Nb₃O₇(OH) superstructures with semiconductive and photoactive properties

3D hierarchical Nb3O7(OH) mesocrystals can be formed by self-organization from nanometer sized building blocks. The present study focuses on the synthesis and detailed investigation of mesocrystals, which can be achieved from a one-step, template-free hydrothermal synthesis approach. The obtained cubic superstructures consist of a periodic nanowire-network and combine a large surface area, high crystallinity, with a band gap of 3.2 eV and photocatalytic activity. Their easy processability in combination with the named excellent properties makes them promising candidates for a large number of applications. These include photochemical and photophysical devices where the Nb3O7(OH) mesocrystals can be used as electrode material since they are semiconducting and possess a large surface area. Generally the forces involved in the self-organized formation of mesocrystals are not fully understood. In this regard, the assembly of the Nb3O7(OH) mesocrystals was investigated in-depth applying transmission electron microscopy, scanning electron microscopy, UV/Vis measurements and electron energy-loss spectroscopy. Based on the achieved results a formation mechanisms is proposed, which expands the number of mechanisms for mesocrystal formation reported in literature. In addition, our study reveals different types of nanowire junctions and investigates their role at the stabilization of the networks

Heat-Induced Phase Transformation of Three-Dimensional Nb₃O₇(OH) Superstructures: Effect of Atmosphere and Electron Beam

Nanostructured niobium oxides and hydroxides are potential candidates for photochemical applications due to their excellent optical and electronic properties. In the present work the thermal stability of Nb₃O₇(OH) superstructures prepared by a simple hydrothermal approach is investigated at the atomic scale. Transmission electron microscopy and electron energy-loss spectroscopy provide insights into the phase transformation occurring at elevated temperatures and probe the effect of the atmospheric conditions. In the presence of oxygen, H₂O is released from the crystal at temperatures above 500 °C, and the crystallographic structure changes to H-Nb₂O₅. In addition to the high thermal stability of Nb₃O₇(OH), the morphology was found to be stable, and first changes in the form of a merging of nanowires are not observed until 850 °C. Under reducing conditions in a transmission electron microscope and during electron beam bombardment, an oxygen-deficient phase is formed at temperatures above 750 °C. This transformation starts with the formation of defects in the crystal lattice at 450 °C and goes along with the formation of pores in the nanowires which accommodate the volume differences of the two crystal phases

Theoretical and Experimental Study on the Optoelectronic Properties of Nb₃O₇(OH) and Nb₂O₅ Photoelectrodes

Nb₃O₇(OH) and Nb₂O₅ nanostructures are promising alternative materials to conventionally used oxides, e.g. TiO₂, in the field of photoelectrodes in dye-sensitized solar cells and photoelectrochemical cells. Despite this important future application, some of their central electronic properties such as the density of states, band gap, and dielectric function are not well understood. In this work, we present combined theoretical and experimental studies on Nb₃O₇(OH) and H–Nb₂O₅ to elucidate their spectroscopic, electronic, and transport properties. The theoretical results were obtained within the framework of density functional theory based on the full potential linearized augmented plane wave method. In particular, we show that the position of the H atom in Nb₃O₇(OH) has an important effect on its electronic properties. To verify theoretical predictions, we measured electron energy-loss spectra (EELS) in the low loss region, as well as, the O–K and Nb–M₃ element-specific edges. These results are compared with corresponding theoretical EELS calculations and are discussed in detail. In addition, our calculations of thermoelectric conductivity show that Nb₃O₇(OH) has more suitable optoelectronic and transport properties for photochemical application than the calcined H–Nb₂O₅ phase

Atomic dynamics of electrified solid–liquid interfaces in liquid-cell TEM

Electrified solid-liquid interfaces (ESLIs) play a key role in various electrochemical processes relevant to energy1-5, biology6 and geochemistry7. The electron and mass transport at the electrified interfaces may result in structural modifications that markedly influence the reaction pathways. For example, electrocatalyst surface restructuring during reactions can substantially affect the catalysis mechanisms and reaction products1-3. Despite its importance, direct probing the atomic dynamics of solid-liquid interfaces under electric biasing is challenging owing to the nature of being buried in liquid electrolytes and the limited spatial resolution of current techniques for in situ imaging through liquids. Here, with our development of advanced polymer electrochemical liquid cells for transmission electron microscopy (TEM), we are able to directly monitor the atomic dynamics of ESLIs during copper (Cu)-catalysed CO2 electroreduction reactions (CO2ERs). Our observation reveals a fluctuating liquid-like amorphous interphase. It undergoes reversible crystalline-amorphous structural transformations and flows along the electrified Cu surface, thus mediating the crystalline Cu surface restructuring and mass loss through the interphase layer. The combination of real-time observation and theoretical calculations unveils an amorphization-mediated restructuring mechanism resulting from charge-activated surface reactions with the electrolyte. Our results open many opportunities to explore the atomic dynamics and its impact in broad systems involving ESLIs by taking advantage of the in situ imaging capability

Titanium Doping and Its Effect on the Morphology of Three-Dimensional Hierarchical Nb₃O₇(OH) Nanostructures for Enhanced Light-Induced Water Splitting

This study presents a simple method that allows us to modify the composition, morphological, and surface properties of three-dimensional hierarchical Nb₃O₇(OH) superstructures, resulting in strongly enhanced photocatalytic H₂ production. The superstructures consist of highly ordered nanowire networks and self-assemble under hydrothermal conditions. The presence of titanium affects the morphology of the superstructures, resulting in increased surface areas for higher doping levels. Up to 12 at. % titanium is incorporated into the Nb₃O₇(OH) crystal lattice via substitution of niobium at its octahedral lattice sites. Further titanium excess results in the formation of niobium-doped TiO₂ plates, which overgrow the surface of the Nb₃O₇(OH) superstructures. Photoluminescence spectroscopy indicates fewer charge recombination processes near the surface of the nanostructures with an increasing titanium concentration in the crystal lattice. The combination of larger surface areas with fewer quenching sites at the crystal surface yields higher H₂ evolution rates for the doped samples, with the rate being doubled by incorporation of 5.5 ± 0.7 at. % Ti

Model for Hydrothermal Growth of Rutile Wires and the Associated Development of Defect Structures

Crystal defects play a major role in determining the electrical properties of semiconductors. Hydrothermally grown TiO₂ rutile nanowire arrays are frequently used as electrodes in photovoltaic devices. However, they exhibit a characteristic defect structure that may compromise performance. A detailed scanning and transmission electron microscopy study of these defects reveals their internal structure and is suggestive at their origin. We propose an anisotropic layer-by-layer growth model, which combined with steric effects and Coulombic repulsion on high atom-density facets, can explain the observed V-shaped defect cascade in the nanowires