Hybrid polyoxometalate materials for photo(electro-) chemical applications

Dye-sensitized solar cells (DSSCs) are the third generation of photovoltaic cells developed by Gratzel and O’Regan. They have the characteristics of low cost, simple manufacturing process, tunable optical properties, and higher photoelectric conversion efficiency (PCE). With an ever increasing energy crisis, there is an urgent need to develop highly efficient, environmentally benign, and energy-saving cell materials. Polyoxometalates (POMs), a kind of molecular inorganic quasi-semiconductor, are promising candidates for use in different parts of DSSCs due to their excellent photosensitivity, redox, and catalytic properties, as well as their relative stability. Following a brief introduction to the development of DSSCs and the potential virtues of POMs in DSSCs, we attempt to make some generalizations about the energy level regulation of POMs that is the underlying theoretical basis for their application in DSSCs, and then we summarize the research progress of POMs in DSSCs in recent years. This is organized in terms of the properties of POMs, namely, electron acceptor, photosensitivity, redox and catalysis, based on the accumulation of our research into POMs over many years. Meanwhile, in view of the fact that the properties of POMs depend primarily on their electronic structural diversity, we keep this point in mind throughout the article with a view to revealing their structure–property relationships. Finally we provide a short summary and remarks on the future outlook. This review may be of interest to synthetic chemists devoted to designing POMs with specific structures, and researchers engaged in the extension of POMs to photoelectric materials.

Polyoxometalates in dye-sensitized solar cells

In order to relieve current energy crisis and the related environment pollutions arising with fossil fuel, the development and application of sustainable and clean energy, such as solar and hydrogen, is anticipated as a prospective issue. It is urgent and significant to develop and construct various energy storage and conversion technologies and materials for the generation and utilization of clean energy sources. Polyoxometalates (POMs), a class of metal oxide polyanion clusters, can serve as outstanding candidates in energy-related fields like electrocatalysis, rechargeable battery, photocatalysis, and proton conduction, based on their plentiful redox property, semiconductor-like feature and acidity. Here, the selected recent and significant advances in the development of POM-based materials for sustainable and clean energy conversion and storage are reviewed and summarized, and special emphases are shown to the applications of POMs as platforms for hydrogen production, water oxidation, carbon dioxide reduction, Li-ion rechargeable batteries, supercapacitors, proton-exchange membrane fuel cells, dye-sensitized solar cells and so on. The results obtained from different catalytic/energy storage systems have been compared and we try to give a better understanding on catalytic reactivity-catalysts structure correlation as well as to put a picture for the rational design of electrochemical electrodes.

Polyoxometalate-based materials for sustainable and clean energy conversion and storage

Polyoxometalates (POMs) are molecular metal oxide clusters that feature a broad range of structures and functionalities, making them one of the most versatile classes of inorganic molecular materials. They have attracted widespread attention in homogeneous catalysis. Due to the challenges associated with their aggregation, precipitation, and degradation under operational conditions and to extend their scope of applications, various strategies of depositing POMs on heterogeneous substrates have been developed. Recent ground-breaking developments in the materials chemistry of supported POM composites are summarized and links between molecular-level understanding of POM-support interactions and macroscopic effects including new or optimized reactivities, improved stability, and novel function are established. Current limitations and future challenges in studying these complex composite materials are highlighted, and cutting-edge experimental and theoretical methods that will lead to an improved understanding of synergisms between POM and support material from the molecular through to the nano- and micrometer level are discussed. Future development in this fast-moving field is explored and emerging fields of research in POM heterogenization are identified.

/pdf/polyoxometalates-on-functional-substrates-concepts-synergies-u1odwl8oyb.pdf

Polyoxometalates on Functional Substrates: Concepts, Synergies, and Future Perspectives.

Electrochemistry of Polyoxometalates: From Fundamental Aspects to Applications

Thermoplastic polyurethane/titania/polydopamine(TPU/TiO2/PDA) 3-D porous composite foam with outstanding oil/water separation performance and photocatalytic dye degradation

For exploration of the effects of polyoxometalate on the photoelectrochemical properties of cadmium sulfide (CdS), a composite film of poly(allylamine hydrochloride)-modified CdS (CdS-PAH) and polyoxometalate (K6P2W18O62) has been prepared by the layer-by-layer self-assembly method. The thin film was characterized by UV–vis spectroscopy, infrared spectra, X-ray diffraction, X-ray photoelectron spectroscopy, atomic force microscopy, and scanning electron microscopy. Both photocurrent transient measurement and current–voltage curves displayed that the photocurrent response and power conversion efficiency of the CdS-PAH/P2W18 composite film were markedly enhanced in comparison with those of the single CdS-PAH film. Furthermore, CdS-PAH/P2W18 film exhibited higher photocurrent response intensity than the simple sum of individual components, and polyoxometalate (P2W18) could act as the photoinduced electron transfer shuttle to efficiently suppress electron–hole recombination in CdS. Such a mechanism was furthe...

Effects of Dawson-Type Tungstophosphate on Photoelectrochemical Responses of Cadmium Sulfide Composite Film

A comparative study on photoelectrochemical performance of TiO2 photoanodes enhanced by different polyoxometalates

Nanocomposite film of TiO2 nanotube and polyoxometalate towards photocatalytic degradation of nitrobenzene

A novel type of Janus polyvinylidene fluoride/deacetylated cellulose acetate (PVDF/D‐CA) nanofiber membrane with multifunctional application is successfully fabricated by sequential electrospinning. The morphology, chemical composition, surface wettability, oil–water separation performance, and unidirectional liquid transmission capability have been systematically analyzed. It has asymmetric wettability property in air and in liquid systems for its bottom and top sides. It can be used as a water‐removing, or oil‐removing substance for oil–water mixture and emulsion under a harsh environment only under gravity driving force (DF) by simply switching the different sides. It possesses on‐demand water and oil collection ability, and moisture‐wicking performance due to its switchable permeation and unidirectional liquid transmission capability. Its multifunction application can be easy to control by adjusting the thickness of the top and bottom sides through controlling the electrospinning time. Its excellent mechanical property, chemical stability, durability under harsh environment and outstanding anti‐pollution ability endow the membrane with powerful cyclic stability and reusability.

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/admi.202201550

Design and Modification of Janus Polyvinylidene Fluoride/Deacetylated Cellulose Acetate Nanofiber Membrane and its Multifunctionality

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