WO3 thin layers with nanometer-scale periodicity were prepared by evaporation-induced self-assembly (EISA) using a novel amphiphilic block-copolymer template (poly(ethylene-co-butylene)-block-poly(ethylene oxide)). The evolution of the mesoporous ordered network and the crystallinity of the framework were monitored by 2D-SAXS, WAXS, SEM, XPS, and porosimetry. By annealing the films, the pore-wall crystallinity is adjusted between fully amorphous and highly crystalline without mesostructural degradation. Thus, the crystalline-film framework is composed of phase-pure monoclinic WO3 nanoparticles (12-14 nm in size). Furthermore, heat treatment transforms the originally spherical mesopores into ellipsoids, resulting in a unidirectionally shrunken, but still well-defined and fully accessible bcc mesopore architecture. The influence of mesoporosity and crystallinity on electrochemical/electrochromic characteristics was addressed by monitoring electrochemical features and the absorption changes during Li insertion/extraction (repetitive potentiostatic cycling). Both the amorphous and crystalline mesoporous films possess electrochromic response times on the order of only seconds, which are attributable to the facilitated insertion of guest ions due to shortening of the diffusion path lengths. Also, the insertion/extraction reversibility of crystalline WO3 layers with 3D mesoporosity is improved compared to amorphous ones and reaches values close to 100%.

Electrochromic tungsten oxide (WO 3 ) thin films with nanometer-scale porosity have been synthesized via a sol-gel procedure making use of evaporation-induced self-assembly. According to wide-angle X-ray scattering data combined with electrochemical analyses, the degree of crystallinity ranging from fully amorphous to 100% crystalline can be adjusted by straightforward annealing. The three-dimensional cubic pore structure is thereby almost not affected. Aside from the material characterization, in this work we specifically focus on the overall electrochemical and electrochromic behavior (coloration efficiency, charge capacity, etc.) upon changes in the operating temperature. As a main result, only the mesoporous highly crystalline WO 3 films display long-term cycling stability under realistic environmental conditions. We further demonstrate that sufficient crystallinity is needed to ensure stability of the inherent electrochemical properties at high operating temperatures (up to 70 °C). Thus, only the WO 3 films with a highly crystalline framework exhibit almost unchanged electrochemical/electrochromic characteristics after prolonged potentiostatic cycling and exposure to elevated operating temperatures. In contrast, amorphous and partially crystalline films suffer from irreversible performance degradation due to structural modifications.

In September 2018, the First European Workshop on Metal Phosphonates Chemistry brought together some prominent researchers in the field of metal phosphonates and phosphinates with the aim of discussing past and current research efforts and identifying future directions. The scope of this perspective article is to provide a critical overview of the topics discussed during the workshop, which are divided into two main areas: synthesis and characterisation, and applications. In terms of synthetic methods, there has been a push towards cleaner and more efficient approaches. This has led to the introduction of high-throughput synthesis and mechanochemical synthesis. The recent success of metal–organic frameworks has also promoted renewed interest in the synthesis of porous metal phosphonates and phosphinates. Regarding characterisation, the main advances are the development of electron diffraction as a tool for crystal structure determination and the deployment of in situ characterisation techniques, which have allowed for a better understanding of reaction pathways. In terms of applications, metal phosphonates have been found to be suitable materials for several purposes: they have been employed as heterogeneous catalysts for the synthesis of fine chemicals, as solid sorbents for gas separation, notably CO2 capture, as materials for electrochemical devices, such as fuel cells and rechargeable batteries, and as matrices for drug delivery.

Silica thin films with variable pore hierarchy (different combinations of small meso‐, large meso‐, and macropores) were produced via evaporation induced self‐assembly in a one‐pot synthesis. A suitable block copolymer and an ionic liquid served as porogens for the generation of different types of mesopores whereas polymethylmethacrylate particles were used as macrotemplate. The silica architectures were characterized by various state‐of‐the‐art techniques, such as 2D‐SAXS, TEM, SEM, AFM, krypton and nitrogen sorption. Moreover, electrochemical functionalization was utilized as a tool to study the hierarchy‐property relationship. Thus, hierarchically porous films prepared on FTO‐coated glass were post‐synthetically silylated and electrochemically active ferrocene groups subsequently grafted onto the pore walls. Cyclic voltammetry was used to monitor the induced electrochemical activity as a function of variations in the pore hierarchy. It turned out that multimodal pore systems possess a relatively higher electrochemical response due to better connection between the pores and higher surface area.