(Al,Mg)3La: a new phase in the Mg-Al-La system.

During an investigation of the Mg-rich end of the Mg-Al-La system, a new ternary phase with the composition of (Al,Mg)3La was identified. The crystal structure of this phase was determined by conventional X-ray powder diffraction and transmission electron microscopy analysis and refined using high-resolution X-ray powder diffraction. The (Al,Mg)3La phase is found to have an orthorhombic structure with a space group of C2221 and lattice parameters of a = 4.3365 (1) Å, b = 18.8674 (4) Šand c = 4.4242 (1) Å, which is distinctly different from the binary Al3La phase (P63/mmc). The resolved structure of the (Al,Mg)3La phase is further verified by high-angle annular dark-field scanning transmission electron microscopy.

Aqueous Synthesis of High-Quality Cu2ZnSnS4 Nanocrystals and Their Thermal Annealing Characteristics.

Copper zinc tin sulfide (CZTS) nanocrystal inks are promising candidates for the development of cheap, efficient, scalable, and nontoxic photovoltaic (PV) devices. However, optimization of the synthetic chemistry to achieve these goals remains a key challenge. Herein we describe a single-step, aqueous-based synthesis that yields high-quality CZTS nanocrystal inks while also minimizing residual organic impurities. By exploiting simultaneous redox and crystal formation reactions, square-platelet-like CZTS nanocrystals stabilized by Sn2S64- and thiourea are produced. The CZTS synthesis is optimized by using a combination of inductively coupled plasma analysis, Raman spectroscopy, Fourier transform infrared spectroscopy, and synchrotron powder X-ray diffraction to assess the versatility of the synthesis and identify suitable composition ranges for achieving phase-pure CZTS. It is found that mild heat treatment between 185 and 220 °C is most suitable for achieving this because this temperature range is sufficiently high to thermalize existing ligands and ink additives while minimizing tin loss, which is problematic at higher temperatures. The low temperatures required to process these nanocrystal inks to give CZTS thin films are readily amenable to production-scale processes.

Chemical vapour deposition of zeolitic imidazolate framework thin films.

Integrating metal-organic frameworks (MOFs) in microelectronics has disruptive potential because of the unique properties of these microporous crystalline materials. Suitable film deposition methods are crucial to leverage MOFs in this field. Conventional solvent-based procedures, typically adapted from powder preparation routes, are incompatible with nanofabrication because of corrosion and contamination risks. We demonstrate a chemical vapour deposition process (MOF-CVD) that enables high-quality films of ZIF-8, a prototypical MOF material, with a uniform and controlled thickness, even on high-aspect-ratio features. Furthermore, we demonstrate how MOF-CVD enables previously inaccessible routes such as lift-off patterning and depositing MOF films on fragile features. The compatibility of MOF-CVD with existing infrastructure, both in research and production facilities, will greatly facilitate MOF integration in microelectronics. MOF-CVD is the first vapour-phase deposition method for any type of microporous crystalline network solid and marks a milestone in processing such materials.

Biomimetic Replication of Microscopic Metal-Organic Framework Patterns Using Printed Protein Patterns.

It is demonstrated that metal-organic frameworks (MOFs) can be replicated in a biomimetic fashion from protein patterns. Bendable, fluorescent MOF patterns are formed with micrometer resolution under ambient conditions. Furthermore, this technique is used to grow MOF patterns from fingerprint residue in 30 s with high fidelity. This technique is not only relevant for crime-scene investigation, but also for biomedical applications.

Biomimetic mineralization of metal-organic frameworks as protective coatings for biomacromolecules.

Enhancing the robustness of functional biomacromolecules is a critical challenge in biotechnology, which if addressed would enhance their use in pharmaceuticals, chemical processing and biostorage. Here we report a novel method, inspired by natural biomineralization processes, which provides unprecedented protection of biomacromolecules by encapsulating them within a class of porous materials termed metal-organic frameworks. We show that proteins, enzymes and DNA rapidly induce the formation of protective metal-organic framework coatings under physiological conditions by concentrating the framework building blocks and facilitating crystallization around the biomacromolecules. The resulting biocomposite is stable under conditions that would normally decompose many biological macromolecules. For example, urease and horseradish peroxidase protected within a metal-organic framework shell are found to retain bioactivity after being treated at 80 °C and boiled in dimethylformamide (153 °C), respectively. This rapid, low-cost biomimetic mineralization process gives rise to new possibilities for the exploitation of biomacromolecules.

In situ synchrotron X-ray diffraction investigation of the evolution of a PbO2/PbSO4 surface layer on a copper electrowinning Pb anode in a novel electrochemical flow cell. Corrigendum.

Figures 7 and 8 of the article by Clancy et al. [(2015), J. Synchrotron Rad. 22, 366-375] are corrected.

In situ synchrotron X-ray diffraction investigation of the evolution of a PbO2/PbSO4 surface layer on a copper electrowinning Pb anode in a novel electrochemical flow cell.

This paper describes the quantitative measurement, by in situ synchrotron X-ray diffraction (S-XRD) and subsequent Rietveld-based quantitative phase analysis and thickness calculations, of the evolution of the PbO2 and PbSO4 surface layers formed on a pure lead anode under simulated copper electrowinning conditions in a 1.6 M H2SO4 electrolyte at 318 K. This is the first report of a truly in situ S-XRD study of the surface layer evolution on a Pb substrate under cycles of galvanostatic and power interruption conditions, of key interest to the mining, solvent extraction and lead acid battery communities. The design of a novel reflection geometry electrochemical flow cell is also described. The in situ S-XRD results show that ß-PbO2 forms immediately on the anode under galvanostatic conditions, and undergoes continued growth until power interruption where it transforms to PbSO4. The kinetics of the ß-PbO2 to PbSO4 conversion decrease as the number of cycles increases, whilst the amount of residual PbO2 increases with the number of cycles due to incomplete conversion to PbSO4. Conversely, complete transformation of PbSO4 to ß-PbO2 was observed in each cycle. The results of layer thickness calculations demonstrate a significant volume change upon PbSO4 to ß-PbO2 transformation.

MOF positioning technology and device fabrication.

Metal organic frameworks (MOFs) offer the highest surface areas per gram of any known material. As such, they epitomise resource productivity in uses where specific surface area is critical, such as adsorption, storage, filtration and catalysis. However, the ability to control the position of MOFs is also crucial for their use in devices for applications such as sensing, delivery, sequestration, molecular transport, electronics, energy production, optics, bioreactors and catalysis. In this review we present the current technologies that enable the precise positioning of MOFs onto different platforms. Methods for permanent localisation, dynamic localisation, and spatial control of functional materials within MOF crystals are described. Finally, examples of devices in which the control of MOF position and functionalisation will play a major technological role are presented.

A furnace and environmental cell for the in situ investigation of molten salt electrolysis using high-energy X-ray diffraction.

This paper describes the design, construction and implementation of a relatively large controlled-atmosphere cell and furnace arrangement. The purpose of this equipment is to facilitate the in situ characterization of materials used in molten salt electrowinning cells, using high-energy X-ray scattering techniques such as synchrotron-based energy-dispersive X-ray diffraction. The applicability of this equipment is demonstrated by quantitative measurements of the phase composition of a model inert anode material, which were taken during an in situ study of an operational Fray-Farthing-Chen Cambridge electrowinning cell, featuring molten CaCl(2) as the electrolyte. The feasibility of adapting the cell design to investigate materials in other high-temperature environments is also discussed.