Titanium dioxide, TiO₂, is an important photocatalytic material that exists as two main polymorphs, anatase and rutile. The presence of either or both of these phases impacts on the photocatalytic performance of the material. The present work reviews the anatase to rutile phase transformation. The synthesis and properties of anatase and rutile are examined, followed by a discussion of the thermodynamics of the phase transformation and the factors affecting its observation. A comprehensive analysis of the reported effects of dopants on the anatase to rutile phase transformation and the mechanisms by which these effects are brought about is presented in this review, yielding a plot of the cationic radius versus the valence characterised by a distinct boundary between inhibitors and promoters of the phase transformation. Further, the likely effects of dopant elements, including those for which experimental data are unavailable, on the phase transformation are deduced and presented on the basis of this analysis.

Materials derived from metal–organic frameworks (MOFs) have demonstrated exceptional structural variety and complexity and can be synthesized using low‐cost scalable methods. Although the inherent instability and low electrical conductivity of MOFs are largely responsible for their low uptake for catalysis and energy storage, a superior alternative is MOF‐derived metal‐based derivatives (MDs) as these can retain the complex nanostructures of MOFs while exhibiting stability and electrical conductivities of several orders of magnitude higher. The present work comprehensively reviews MDs in terms of synthesis and their nanostructural design, including oxides, sulfides, phosphides, nitrides, carbides, transition metals, and other minor species. The focal point of the approach is the identification and rationalization of the design parameters that lead to the generation of optimal compositions, structures, nanostructures, and resultant performance parameters. The aim of this approach is to provide an inclusive platform for the strategies to design and process these materials for specific applications. This work is complemented by detailed figures that both summarize the design and processing approaches that have been reported and indicate potential trajectories for development. The work is also supported by comprehensive and up‐to‐date tabular coverage of the reported studies.

The present work describes the effects of water on Fe-doped nanoparticulate CeO₂, produced by flame spray pyrolysis, which is a critical environmental issue because CeO₂ is not stable in typical atmospheric conditions. It is hygroscopic and absorbs ~29 wt % water in the bulk when exposed to water vapor but, more importantly, it forms a hydrated and passivating surface layer when immersed in liquid water. In the latter case, CeO₂ initially undergoes direct and/or reductive dissolution, followed by the establishment of a passivating layer calculated to consist of ~69 mol % solid CeO₂·2H₂O and ~30 mol % gelled Ce(OH)₄. Under static flow conditions, a saturated boundary layer also forms but, under turbulent flow conditions, this is removed. While the passivating hydrated surface layer, which is coherent probably owing to the continuous Ce(OH)₄ gel, would be expected to eliminate the photoactivity, this does not occur. This apparent anomaly is explained by the calculation of (a) the thermodynamic stability diagrams for Ce and Fe; (b) the speciation diagrams for the Ce⁴⁺-H₂O, Ce³⁺-H₂O, Fe³⁺-H₂O, and Fe²⁺-H₂O systems; and (c) the Pourbaix diagrams for the Ce-H₂O and Fe-H₂O systems. Furthermore, consideration of the probable effects of the localized chemical and redox equilibria owing to the establishment of a very low pH (<0) at the liquid-solid interface also is important to the interpretation of the phenomena. These factors highlight the critical importance of the establishment of the passivating surface layer and its role in photocatalysis. A model for the mechanism of photocatalysis by the CeO₂ component of the hydrated phase CeO₂·2H₂O is proposed, explaining the observation of the retention of photocatalysis following the apparent alteration of the surface of CeO₂ upon hydration. The model involves the generation of charge carriers at the outer surface of the hydrated surface layer, followed by the formation of radicals, which decompose organic species that have diffused through the boundary layer, if present.

Increasing demands in minimization of fire risks and meeting fire safety requirements by polymers require advances in knowledge of flame-retardant materials suitable for use in fire-retardancy applications. The present work represents the seminal review of alginate/polymer-based materials as flame retardants. Alginates are suitable for this application as they represent alternatives to petroleum-based polymer feedstocks. The content of the present work is structured into four sections: synthesis and structure, including alginate synthesis and modification by polymeric conjugation; properties, including four-stage mechanism of thermal degradation; applications, including commercial information on alginates and polymers; and flame retardancy, including comprehensive summaries of test methods and published data, discussion of key parameters, eight fire retardancy mechanisms, four char generation mechanisms, and extensive quantitative analysis of polymer char formation. The final section culminates in a first-principles approach to the prediction of quantitative polymer char formation. The goal of the review is to provide guidance for the application of alginates and alginates conjugated with fire-retardant polymers as a new generation flame retardant material.

The morphologies of ceria nanocrystals play an essential role in determining their redox and catalytic performances in many applications, yet the effects of synthesis variables on the formation of ceria nanoparticles of different morphologies and their related growth mechanisms have not been systematised. The design of these morphologies is underpinned by a range of fundamental parameters, including crystallography, optical mineralogy, the stabilities of exposed crystallographic planes, CeO_2−x stoichiometry, phase equilibria, thermodynamics, defect equilibria, and the crystal growth mechanisms. These features are formalised and the key analytical methods used for analysing defects, particularly the critical oxygen vacancies, are surveyed, with the aim of providing a source of design parameters for the synthesis of nanocrystals, specifically CeO_2−x. However, the most important aspect in the design of CeO_2−x nanocrystals is an understanding of the roles of the main variables used for synthesis. While there is a substantial body of data on CeO_2−x morphologies fabricated using low cerium concentrations ([Ce]) under different experimental conditions, the present work fully maps the effects of the relevant variables on the resultant CeO_2−x morphologies in terms of the commonly used raw materials [Ce] (and [NO₃ ⁻] in Ce(NO₃)₃·6H₂O) as feedstock, [NaOH] as precipitating agent, temperature, and time (as well as the complementary vapour pressure). Through the combination of consideration of the published literature and the generation of key experimental data to fill in the gaps, a complete mechanistic description of the development of the main CeO_2−x morphologies is illustrated. Further, the mechanisms of the conversion of nanochains into the two variants of nanorods, square and hexagonal, have been elucidated through crystallographic reasoning. Other key conclusions for the crystal growth process are the critical roles of (1) the formation of Ce(OH)₄ crystallite nanochains as the precursors of nanorods and (2) the disassembly of the nanorods into Ce(OH)₄ crystallites and NO₃ ⁻-assisted reassembly into nanocubes (and nanospheres) as an unrecognised intermediate stage of crystal growth.