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This document is the Accepted Manuscript version of a Published Work that appeared in final form inACS Sustainable Chemistry and Engineering, copyright © 2023 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acssuschemeng.2c06573. Hydrogen is a promising fossil-fuel alternative fuel owing to its environmentally neutral emissions and high energy density. However, the need for purified water and external power are critical hindrances to the implementation of hydrogen production. The present work demonstrates the potential to overcome these shortcomings through piezo-photocatalysis of seawater using defective BaTiO3–x (BTO) nanoparticles. This material was made piezoelectrically active by a straightforward annealing process under different atmospheres, including O2, N2, Ar, or H2, the latter of which caused Ti4+ ¿ Ti(4–x)+ multiple reductions and structural distortions that stabilize piezoelectric tetragonal domains. A suite of experimental techniques was employed to reveal the effects of reduction on the energy band structure. A substantial piezoelectric effect and the presence of self-polarization were confirmed by piezoresponse force microscopy, while simulation work clarified the role of vibrations on band bending deriving from the self-polarization. The hydrogen evolution through photocatalysis, piezocatalysis, and piezo-photocatalysis over the defective BaTiO3–x nanoparticles was characterized with deionized (DI) water, simulated seawater, and natural seawater. A promising HER with a rate of 132.4 µmol/g/h was achieved using DI water through piezo-photocatalysis without a cocatalyst. In contrast, a substantial HER rate of 48.7 µmol/g/h was obtained for natural seawater, despite the deleterious impact of dissolved ions. The present work offers new perspectives for large-scale green H2 production using abundant natural resources with a conventional piezoelectric material that is readily available but still affected by the ions dissolved in seawater.

The lead-free piezoelectric material sodium bismuth titanate (NBT, Na0.5Bi0.5TiO3) has attracted considerable attention owing to its promising dielectric, piezoelectric, and electrical properties. However, the literature on the binary subsystems is contradictory and there are only limited data for the ternary system. The present work surveys all of the reports of the binary subsystems Bi2O3 – TiO2 and Na2O – TiO2 and synthesizes these data into inclusive revised versions. The compatibilities for the ternary system Na2O – Bi2O3 – TiO2 were determined experimentally, thus enabling the construction of a complete isothermal section at 800 °C. The compatibilities associated with the problematic binary subsystem Na2O – Bi2O3, which experiences extreme volatilisation, were determined through the generation of the absent standard-state thermodynamic functions for the relevant binary and ternary phases, thus providing a full suite of thermodynamic data for this system. The thermodynamic stability diagrams for Na2O, Bi2O3, and TiO2 thus were calculated. The isothermal section also addresses the contradictions in the literature concerning the formation of solid solutions of Bi12TiO20-x / Bi12-xTi1+xO20+0.5x, pyrochlore (Bi2Ti2O7 / NawBi2-xTi2-yO7-z), BTO (Bi4Ti3O12 / NaxBi4Ti3O12+0.5x), and NBT (Na0.5Bi0.5TiO3 / Bi1±xNaxTiO3.5±x). Further, it was observed that the congruent melting point of NBT, which was determined to be 1225 °C, was preceded by the onset of gradual structural destabilization at 940 °C. Also, the NBT rhombohedral → tetragonal phase transformation was observed at an onset temperature of ∼250 °C. The present work thus provides platform data for the fabrication and reactivities of materials in the ternary system Na2O – Bi2O3· TiO2 and its binary subsystems.

Uniformly codoped anatase TiO2 thin films of varying (equal) Mo and Cr concentrations (≤1.00 mol% for each dopant) were fabricated using sol-gel spin coating and deposited on fused silica substrates. All films were annealed at 450 °C for 2 h to recrystallise anatase. Undoped anatase films have been subjected to dual ion implantation for the first time, using Mo, Cr, and sequential Mo + Cr at 1 × 1014 atoms/cm2. The films were characterised by GAXRD, AFM, SIMS, XPS, and UV–Vis and the performance was assessed by dye degradation. Despite the volumetric doping by sol-gel and the directional doping by ion implantation, neither method resulted in homogeneous dopant distributions. Both methods caused decreasing crystallinities and associated partial amorphisation. The XPS signal of the uniformly codoped films is dominated by undissolved dopant ions, which is not the case for the ion-implanted films. Increasing Ti valences are attributed to the fully oxidised condition of the Ti4+ ions that diffuse to the surface from Ti vacancy formation compared to the Ti valence of the bulk lattice, which contains Ti3+. Increasing O valence is attributed to the electronegativity of O2−, which is higher than that of Ti4+. Detailed structural mechanisms for the solubility and energetics mechanisms involve the initial formation of Mo and Cr interstitials that fill the two voids adjacent to the central Ti ion in the TiO6 octahedron, followed by integrated solid solubility (ISS) and intervalence/multivalence charge transfer (IVCT/MVCT). The sequential order of the last two is reversed for the two different doping methods. These two effects are likely to be the source of synergy, if any, between the two dopant ions. The photocatalytic performances of the uniformly codoped films are relatively poor and correlate well with the band gap (Eg). The performances of the ion-implanted films do not correlate with the Eg, where TiO2–Mo performs poorly but TiO2–Cr and TiO2–Mo–Cr outperform the undoped film. These results are interpreted in terms of the competition between the effects of Mo doping, which causes partial amorphisation and/or blockage of active sites, and Cr doping, which may cause Mo–Cr synergism, Cr-based heterojunction formation, and/or improved charge-carrier separation owing to the surface-deposition nature of ion implantation.

TiO2 coatings were fabricated by anodization of Ti6Al4V in 1 M H3PO4 or H2SO4, at room temperature at 120 V for 10 min, and followed by annealing at 300° or 500 °C for 8 h. Analyses include mineralogy (GAXRD, Raman), chemistry (XPS), morphology and microstructure (FESEM, FIB, 3D confocal microscopy), thermodynamic, optical (UV–Vis), and photocatalytic performance (MB degradation). The present work highlights factors that govern the nature of the materials and their performance. The influence of the oxidation strength of the acid is pervasive in that it impacts on the crystallinity, microstructural homogeneity, coating thickness, Ti3+ concentration, gas generation during arcing to form pores, and resultant pore size and distribution density. A key observation is that the pores form a subsurface network of variable continuity, which has a significant impact on the surface area and associated density of photocatalytically active sites, access by liquids and gases inside the coating, penetration depth of incident radiation, gas condensation, and residual liquid trapping. These data and the related thermodynamic analyses of the acids, anodization processes, and oxidation processes facilitate the generation of schematic models for the anodization mechanisms and the resultant surface, bulk, and microstructural effects that dominate the photocatalytic performance.

Oxide perovskites have emerged as an important class of materials with important applications in many technological areas, particularly thermocatalysis, electrocatalysis, photocatalysis, and energy storage. However, their implementation faces numerous challenges that are familiar to the chemist and materials scientist. The present work surveys the state-of-the-art by integrating these two viewpoints, focusing on the critical role that defect engineering plays in the design, fabrication, modification, and application of these materials. An extensive review of experimental and simulation studies of the synthesis and performance of oxide perovskites and devices containing these materials is coupled with exposition of the fundamental and applied aspects of defect equilibria. The aim of this approach is to elucidate how these issues can be integrated in order to shed light on the interpretation of the data and what trajectories are suggested by them. This critical examination has revealed a number of areas in which the review can provide a greater understanding. These include considerations of (1) the nature and formation of solid solutions, (2) site filling and stoichiometry, (3) the rationale for the design of defective oxide perovskites, and (4) the complex mechanisms of charge compensation and charge transfer. The review concludes with some proposed strategies to address the challenges in the future development of oxide perovskites and their applications.

Summary of ROS-dependent and ROS-independent anticancer effects of Ce-based nanoparticles in the cellular environment, categorized according to materials-based and radiation-assisted effects.

Thin films of anatase codoped with 0.01 mol% Co and 0.01 mol% Mo up to 5.00 mol% Co and 5.00 mol% Mo were fabricated by spin coating on soda-lime-silica glass substrates. The films subsequently were calcined in air at 450 °C for 2 h. The mineralogical, chemical, morphological, topographical, optical, and photocatalytic properties of the films were investigated in order to assess the factors and mechanisms affecting the photocatalytic properties. The analytical techniques included glancing angle X-ray diffraction, X-ray photoelectron spectrometry, atomic force microscopy, UV–Vis spectrophotometry, and methylene blue photodegradation. A key determinant of the data was the solubility limit of the dopants, particularly Co. When this was exceeded (≥0.30 mol%), the formation of undetectable precipitates commenced blockage of the active sites, thereby reducing the photocatalytic performance. The initial precursor cation valences altered from Co2+ and Mo5+ to Co2+/Co3+ and Mo4+/Mo5+ upon interstitial solid solution. The absence of charge-compensating Ti3+/Ti4+ redox indicates that charge compensation for the codoping was by IVCT through the reaction Co2+ + Mo5+ ↔ Co3+ + Mo4+. While the three dominant factors affecting the band gap were crystallinity, grain size, and precipitation, the band gap did not dominate the photocatalytic performance or its kinetics. These were reduced by blockage of the active sites by dopant precipitates and, to a lesser extent, from contamination from the cations from the substrate. These phases were the dominant factor in decreasing the optical transmission and thus increasing the band gap through the absorption, reflection, and scattering mechanisms of these grains; the crystallinity and grain size were of secondary importance.

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 appl...

Anatase thin films spin coated on soda–lime–silica (SLS) glass and unpolished (001) rutile were annealed at 200–550 °C for 8 h, followed by GAXRD, Raman, XPS, SIMS, AFM, TEM, UV–Vis, ellipsometry, and MB dye degradation. Films on SLS substrates annealed at 200–350 °C were amorphous but those annealed at 450°–550 °C consisted of anatase; the rutile substrates gave epitaxial rutile films. Annealing caused diffusion of glass ions into the films and counterdiffusion of Ti into the glass substrates. The decrease in glass ion concentrations during aqueous MB testing shows that grain boundary diffusion occurred. The AFM, TEM, and UV–Vis data were affected by the substrate topographies, where SLS was smooth and rutile was rough/uneven. Decreasing Eg in the anatase films with increasing annealing temperature was attributed to increasing crystallinity (heterogeneous nucleation) while the same effect in the rutile films was attributed to the substrate topography (homogeneous nucleation). The anatase films photocatalytically outperformed the rutile films; this was attributed to the potential to form midgap states from oxygen vacancy formation and/or Ti vacancy formation (deriving from the Ti counter-diffusion). However, the deep energy levels of these defects suggest that the performance is dominated by the crystallinity and blockage of the active sites.

Facet engineering is a new method of materials design with considerable potential for many technological applications. The present work uses DFT calculations to understand how this strategy can be ...

Electrocatalytic activities of electrodes for water splitting generally are assessed in terms of current density normalisation on the basis of geometric area. However, this approach does not involve the effects of surface microstructure which often is rough. The present work examines this disagreement through the electrochemical characterisation of thermally treated carbon fibre paper in which the current density is normalised comparatively by geometric area, BET specific surface area and electrochemical active surface area (ECSA). The results show that the geometric area provides a nominal means of assessing the electrocatalytic activity. Since BET is effective in assessing the physical surface area, it provides a superior indication. However, ECSA provides the most discriminating means of assessment and reflects the intrinsic electrochemical activity.

Precise control over the morphology of nanomaterials is critical yet challenging. The present work reports an efficient approach to tailor the architecture of nanostructures. The process involves rapid disassembly/reassembly of an unstable metal-based coordination polymer (MCP) by controlling the kinetics of the reassembly process. The synthesis procedure delivers unprecedented polycrystalline nanostructures, e.g., holey 2D CeO2−x nanosheets, with precisely tailored thicknesses in the range of 10–100 nm, and hollow 3D pseudo-octahedra and spheres. The consequent high surface areas and pore volumes, short diffusion distances, and high defect densities of the holey 2D CeO2−x indicate significant densities of active sites. This holey architecture exhibits rapid CO conversion and outstanding solar light photocatalytic performance. This approach of directed assembly offers a template-free, controllable, and cost-effective approach to achieve engineered CeO2−x architectures, which are nearly impossible through existing approaches.

The present work reports a detailed mechanistic interpretation of the role of the solubility of dopants and resultant midgap defect energies in band gap engineering. While there is a general perception that a single dopant is associated with single solubility and defect mechanisms, in reality, the potential for multiple solubility and defect mechanisms requires a more nuanced interpretation. Similarly, Kroger–Vink defect equilibria assume that stoichiometries during substitutional and interstitial solid solubility as well as Schottky and Frenkel pair formation are compensated by the diffusion of matrix ions to the grain boundaries or surface. However, this approach does not allow the possibility that stoichiometry is uncompensated, where diffusion of the matrix ion to lattice interstices occurs, followed by charge compensation by redox of this ion. Consequently, a modified defect equilibria formalism has been developed in order to allow description of this situation. Experimental data for the structural, chemical, semiconducting, and photocatalytic properties as a function of doping level are correlated with conceptual structural models, a comprehensive energy band diagram, and the corresponding defect equilibria. These correlations reveal the complex mechanisms of the interrelated solubility and defect formation mechanisms, which change significantly and irregularly as a function of small changes in doping level. The analyses confirm that the assumption of single mechanisms of solid solubility and defect formation may be simplifications of more complex processes. The generation of (1) a matrix of complementary characterisation and analytical data, (2) the calculation of a complete energy band diagram, (3) consideration of charge compensation mechanisms and redox beyond the limitations of Kroger–Vink approaches, and (4) the development of models of corresponding structural analogies combine to create a new approach to interpret and explain experimental data. These strategies allow deconstruction of these complex issues and thus targeting of optimal and possibly unique doping levels to achieve lattice configurations that may be energetically and structurally unfavorable. These approaches then can be applied to other doped semiconducting systems.

Inorganic nanoparticles for drug delivery in cancer treatment offer many potential advantages because they can maximize therapeutic effect through targeting ligands while minimizing off-target side-effects through drug adsorption and infiltration. Although inorganic nanoparticles were introduced as drug carriers, they have emerged as having the capacity for combined therapeutic capabilities, including anticancer effects through cytotoxicity, suppression of oncogenes and cancer cell signaling pathway inhibition. The most promising advanced strategies for cancer therapy are as synergistic platforms for RNA interference (siRNA, miRNA, shRNA) and as synergistic drug delivery agents for the inhibition of cancer cell signaling pathways. The present work summarizes relevant current work, the promise of which is suggested by a projected compound annual growth rate of ∼ 20% for drug delivery alone.

Metal oxide pseudocapacitors are limited by low electrical and ionic conductivities. The present work integrates defect engineering and architectural design to exhibit, for the first time, intercalation pseudocapacitance in CeO

The present work reports data for TiO2 thin films on borosilicate glass and (001) single-crystal TiO2, annealed at 200–550 °C for 8 h. Characterization included GAXRD, laser Raman microspectroscopy, AFM, UV–Vis, XPS, SIMS, TEM, ellipsometry, and methylene blue (MB) dye degradation. The substrate determined the TiO2 polymorph that formed, while the annealing temperature and boron contamination from the substrate determined most of the associated properties. The films on glass substrates were amorphous following annealing at 200 °C but were anatase at higher temperatures. The films on rutile exhibited epitaxial growth at all annealing temperatures. Annealing caused diffusion of glass component elements into the films and counterdiffusion of Ti into the glass substrates. Since aqueous MB testing caused decreased glass ion concentrations, the diffusion mechanism is via the grain boundaries. Volatilization of boron occurred during annealing at 550 °C. The morphological features dominated the optical properties; the anatase films exhibited high transmissions and low reflectances, while the rutile films exhibited the converse. The band gap decreased slightly with increasing annealing temperatures, reflecting increasing crystallinity. The refractive indices showed an anomalous trend of decrease with increasing annealing temperature and associated crystallinity; this is attributed to the effects of boron volatilization and associated air-filled pore formation. Although the anatase films outperformed the rutile films, the effect of annealing temperature is likely to have been dominant in that it determined the relative extents of crystallinity, grain size, RMS roughness, optical indirect band gap, and oxygen vacancy concentration.

CeO2, TiO2, and CeO2–TiO2 layered thin films of different compositions were deposited on polished fused silica glass substrates using spin coating and then annealed at 550 °C for 1 h. Poorly crystalline fluorite-type CeO2 and anatase-type TiO2 were the only phases detected. The valence effects for Ce are attributed to intervalence charge transfer (IVCT) while those for TiO2 are attributed to simultaneous Ti4+ → Ti3+ redox and IVCT. Contamination of the grain boundaries by Si from the substrate is likely to have contributed to blockage of surface-active sites. While the roughnesses of the former thin films exhibited the expected direct correlation with the grain size, those of the latter two types of thin films showed a converse relation, suggesting that the grain boundaries of the layered TiO2 thin films included a recrystallized CeO2–TiO2 invariant point liquid and/or a CeO2–TiO2–SiO2 glass. These would have derived from the other sources of grain boundary contamination, which are Si contamination from the substrate and/or exsolved CeO2 beyond the solubility limit of TiO2. The UV–Vis spectra demonstrated two principal types of curves, with the CeO2 and higher TiO2 concentration giving typical spectra with sharp absorption edges while those of the lower TiO2 concentration indicated highly defective nanostructures with diffuse absorption edges. These data support the conclusion that CeO2 initially decreases the Eg by enhancing nucleation and recrystallization through defect formation but subsequently increases the Eg through supersaturation and consequent lattice distortion. The CeO2 thin films exhibited much worse photocatalytic performances than those of the TiO2 thin films, although no significant differences between the TiO2 thin films and the CeO2–TiO2 layered thin films were apparent, which probably resulted from the competing effects of blockage of the active sites on the grain boundaries and the extent of recrystallization of the thin film phases, the latter of which is more significant.

Methanol decomposition is a promising method for hydrogen production. However, the performance of current catalysts for this process is not sufficient for commercial applications. In this work, methanol adsorption on the CeO2 low-index surfaces is studied by density functional theory (DFT). The results show that methanol always dissociates spontaneously on the (100) surface, whereas dissociation on the (110) surface is site-selective; dissociation does not occur at all on the (111) surface, where only weak physisorption is found. The results confirm that surfaces with higher energies are more catalytically active. Analysis of the surface geometries shows that the dominant factors for the dissociation of methanol are the degree of undercoordination and the charges of the surface ions. The adsorption energy of each methanol molecule decreases with increasing coverage and there is a transition threshold between dissociative and associative adsorption. The present work indicates that a strategy to design catalysts with high activity is to maximize exposure of surfaces on which the ions have a high degree of undercoordination and a strong tendency to donate/accept electrons. The results demonstrate the importance of appropriately selecting and controlling exposed facets and particle morphology for optimizing catalyst performance.

The present work reports a new method for the green chemical synthesis of biomaterials using an integrated, room-temperature, aqueous, chemical technique involving surfactant-free precipitation of ...

Mo3+- or Mo5+-doped TiO2 sol-gel thin films (≤0.100 mol%) were spin coated on fused silica glass substrates and annealed at 450 °C for 2 h. The effect of the valence of the dopant precursor is significant to the nanostructural development and resultant properties. Mo3+ or Mo5+ doping yields converse trends with doping level, thus reflecting the competing influences of lattice distortion and destabilization (dominating Mo3+ doping) and nucleation and recrystallization (dominating Mo5+ doping). Mo doping results in oxidation of Mo3+ and reduction of Mo5+, both of which alter to Mo(5−x)+, as well as oxidation of Ti3+ to Ti(4+x)+; all of these result in V O • • annihilation. Although the absorption edges were largely indistinguishable, Mo3+ doping causes a red shift and Mo5+ doping causes a blue shift. These data suggest that the performances are controlled by the synergistic effects of crystallinity, surface area, and band gap, with the latter's exhibiting the dominant effect. This suggests that the defect structure governs the photocatalytic performance but also that the defect chemistry at these low annealing temperatures is indicative of nonequilibrium conditions, thereby explaining the significance of the dopant valence.

Mo-doped TiO2 [≤ 0.20 wt% Mo; ≤ 0.10 mol% (metal basis)] with conjugated polyvinyl alcohol (TiO2/C-PVA) composite thin films was prepared by sol–gel dip coating on polished fused SiO2 substrates, followed by annealing at 180 °C for 4 h. These conditions were sufficient for solid solubility, despite the unusually low annealing temperature. The annealed thin films consisted of homogeneously distributed individual and slightly agglomerated anatase grains in a continuous C-PVA matrix characterized by the carbon double bond formed upon conjugation. The films exhibited drying shrinkage cracks, which increased consistently in extent with increasing Mo-doping concentration, effectively increasing the number of exposed TiO2 particles. Mo addition enhanced anatase nucleation, recrystallization, and growth at lower doping concentrations (up to ≤ 0.10 wt%), thereby increasing crystallinity. However, increasing doping levels (> 0.10 wt%) appeared to exceed the solubility limit, resulting in supersaturation and significant lattice destabilization. Mo-doping also caused the Ti2p XPS peaks to shift to lower binding energies and the Mo3d peaks to shift to higher binding energies. These data are consistent with thermodynamically unstable Ti4+ → Ti3+ conversion and thermodynamically stable Mo5+ → Mo6+ conversion, which are interpreted in terms of intervalence charge transfer (IVCT), in which charge compensation is achieved through majority Ti4+ → Ti3+ reduction plus Mo5+ → Mo6+ oxidation. Ti3+ concentration also reflects a direct correlation with the Mo-doping concentration and resultant IVCT within the Mo solubility limit and a reverse effect upon supersaturation. There is a correlation with the Eg but this can be attributed to recrystallization rather than a semiconducting effect. No effect of midgap state formation from enhancement of the $$ {\text{V}}_{\text{O}}^{ \cdot \cdot } $$ concentration is expected because IVCT is a redox effect only and dissolution of Mo5+ or Mo6+ would generate Ti vacancies. The methylene blue dye degradation data exhibited the same trend but at a significant level (90.6% degradation), thus indicating that the mechanism dominating the photocatalytic performance is the recrystallization of the anatase and/or the modification of the semiconducting properties induced by Mo-doping, as indicated by the trends in band gap.

The architectural design of nanocatalysts plays a critical role in the achievement of high densities of active sites but current technologies are hindered by process complexity and limited scaleability. The present work introduces a rapid, flexible, and template-free method to synthesize three-dimensional (3D), mesoporous, CeO

Of the utmost importance of chirality in organic compounds and drugs, the present work reports structure-chirality relationship of three steroidal quinoxalines, which were synthesised by condensing diaminobenzenes with cholestenone. All the compounds were purified and characterised by varying analytical tools prior to their chiroptical analysis by circular dichroism (CD) technique. The substituent groups on quinoxalines contributed to determining the chiroptical properties of the compounds. The positive Cotton effects have been observed in the CD spectra of unsubstituted and methyl-substituted quinoxalines, which indicated their P helicity. Importantly, chloro-substituent on quinoxalines produced different CD behaviour, which can be attributed to the presence of three lone pairs of electrons on Cl atom. The present work provides guidelines for determining the chiral properties of steroidal quinoxalines, which can be useful to design and develop potential molecules of biological importance.

Hypothesis The air-solution interface of supersaturated calcium hydrogen carbonate (Ca(HCO3)2) represents the highest saturation state due to evaporation/CO2-degassing, where calcite crystals are expected to nucleate and grow along the interface. Hence, it should be possible to form a free-standing mineral-only calcium carbonate (CaCO3) microfilm at the air-solution interface of Ca(HCO3)2. The air-solution interface of phosphate buffered saline (PBS) could represent a phase boundary to introduce a hybrid microstructure of CaCO3 and carbonate-rich dicalcium hydroxide phosphate (carbonate-rich hydroxylapatite). Experiments Supersaturated Ca(HCO3)2 was prepared at high pressure and heated to form CaCO3 microfilms, which were converted to bone-like microfilms at the air-solution interface of PBS by dissolution-recrystallisation. The microfilms were characterised by scanning electron microscopy, 3D confocal microscopy, atomic force microscopy, Fourier transform infrared spectroscopy, laser Raman microspectroscopy, and X-ray photoelectron spectroscopy. An in situ X-ray diffraction (XRD) system that simulates the aforementioned interfacial techniques was developed to elucidate the microfilms formation mechanisms. Findings The CaCO3 and bone-like microfilms were free-standing, contiguous, and crystalline. The bone-like microfilms exhibited a hybrid structure consisting of a surface layer of remnant calcite and a carbonate-rich hydroxylapatite core of plates. The present work shows that the air-solution interface can be used to introduce hybrid microstructures to mineral microfilms.

The present work analyses the effects of curing temperature (25&deg, 40&deg, 60 &deg, C for 24 h), silicate modulus Ms value (1.5, 1.7, 2.0), and slag content (10, 20, 30, 40 wt%) on the compressive strength development (1, 7, 14, 28 days) of low-alkali geopolymer mortars with matrices from fly ash and blast furnace slag. These data were used to generate predictive models for 28-day compressive strength as a function of curing temperature and slag content. While the dominant variable for the 1-day compressive strength was the curing temperature, the slag content was dominant for the 28-day compressive strength. The ratio of the 1-day and 28-day compressive strengths as a function of curing temperature, Ms value, and slag content allows prediction of the maximal possible curing temperature and shows cold-weather casting to present an obstacle to setting. These data also allow prediction of the 28-day compressive strength using only the 1-day compressive strength.

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, CeO2-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 CeO2-x. However, the most important aspect in the design of CeO2-x nanocrystals is an understanding of the roles of the main variables used for synthesis. While there is a substantial body of data on CeO2-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 CeO2-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 CeO2-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.

The major downsides of cement manufacturing are the high CO2 emissions and high energy usage. Geopolymers, which are fabricated by activation of blends of fly ash (FA) and ground granulated blast furnace slag (GGBFS) using an alkaline activator, offer a promising solution to this issue. However, to enhance the replacement of cement in construction applications, geopolymer compositions have to be designed such that they can be activated on site by just adding water, similar to how cements are used. Therefore, the present work uses solid sodium metasilicate (MS, Na2SiO3) as the alkaline activator in order to design an add-water-style FA/GGBFS-based geopolymer composition. These compositions were designed by optimising the binder (FA/GGBFS) ratio, Na2SiO3/binder ratio, and water/binder ratio individually to assess the effects of these parameters on the setting times and mechanical (flexural and compressive) strengths over extended curing times (three months). The major factors affecting the strength development and setting times (initial and final) were the amounts of GGBFS and Na2SiO3, with the former demonstrating the more dominant effect. The consistent strength development with curing time was attributed to calcium aluminium silicate hydrate (CASH) gel formation in the early curing times which was affected by the slag addition levels, and sodium aluminium silicate hydrate (NASH) gel formation at later curing times which was influenced by the metasilicate addition levels. The metasilicate amounts were observed to impact on CASH gel formation in early stage curing. Geopolymer compositions with FA/GGBFS ratio of 35/65 and MS/water ratios of 0.2 showed high compressive strengths of ~70 MPa at 28 days, which are superior to values seen in conventional ordinary Portland cement (OPC) mixes for the same curing times.

Metal oxide pseudocapacitors are limited by low electrical and ionic conductivities. The present work integrates defect engineering and architectural design to exhibit, for the first time, intercalation pseudocapacitance in CeO2–x. An engineered chronoamperometric electrochemical deposition is used to synthesize 2D CeO2–x nanoflakes as thin as ~12 nm. Through simultaneous regulation of intrinsic and extrinsic defect concentrations, charge transfer and charge–discharge kinetics with redox and intercalation capacitances together are optimized, where reduction increases the gravimetric capacitance by 77% to 583 F g–1, exceeding the theoretical capacitance (562 F g–1). Mo ion implantation and reduction processes increase the specific capacitance by 133%, while the capacitance retention increases from 89 to 95%. The role of ion-implanted Mo6+ is critical through its interstitial solid solubility, which is not to alter the energy band diagram but to facilitate the generation of electrons and to establish the midgap states for color centers, which facilitate electron transfer across the band gap, thus enhancing n-type semiconductivity. Critically, density functional theory simulations reveal, for the first time, that the reduction causes the formation of ordered oxygen vacancies that provide an atomic channel for ion intercalation. These channels enable intercalation pseudocapacitance but also increase electrical and ionic conductivities. In addition, the associated increased active site density enhances the redox such that the 10% of the Ce3+ available for redox (surface only) increases to 35% by oxygen vacancy channels. These findings are critical for any oxide system used for energy storage systems, as they offer both architectural design and structural engineering of materials to maximize the capacitance performance by achieving accumulative surface redox and intercalation-based redox reactions during the charge/discharge process.

Removal of rare earth elements (REEs) from industrial wastewater is a continual challenge. To date, several approaches to the synthesis of nanoadsorbants for this application have been reported, although these are characterized by insufficient adsorption capacity and limitations in cycling stability. The present work reports the fabrication and performance of hierarchical hybrid transition metal oxide (TMO) nanowires deposited on carbon fibers. An ordered assembly of hybrid TMO nanowires exhibits an outstanding adsorbance of 1000 mg·g-1 of REEs with 93% recyclability. This superior performance is attributed to the unique mesoporous architecture of the nanowires, which exhibits a high surface area of 122 cm3·g-1. Further, rapid adsorption/desorption of the REEs reveals minimal morphological alteration and hence high structural stability of these hybrid TMO nanowires after multiple cycles. The ready accessibility of the adsorption sites at crystallite boundaries and the surfaces as well as rapid adsorption of the REEs on the mesoporous nanostructure facilitate considerable adsorption capacity, improved structural stability, and extended cyclability, all of which suggest the potential for this material in REE extraction.

The present work applies a focal point of materials-related issues to review the major case studies of electron transport layers (ETLs) of metal halide perovskite solar cells (PSCs) that contain graphene-based materials (GBMs), including graphene (GR), graphene oxide (GO), reduced graphene oxide (RGO), and graphene quantum dots (GQDs). The coverage includes the principal components of ETLs, which are compact and mesoporous TiO2, SnO2, ZnO and the fullerene derivative PCBM. Basic considerations of solar cell design are provided and the effects of the different ETL materials on the power conversion efficiency (PCE) have been surveyed. The strategy of adding GBMs is based on a range of phenomenological outcomes, including enhanced electron transport, enhanced current density-voltage (J-V) characteristics and parameters, potential for band gap (Eg) tuning, and enhanced device stability (chemical and environmental). These characteristics are made complicated by the variable effects of GBM size, amount, morphology, and distribution on the nanostructure, the resultant performance, and the associated effects on the potential for charge recombination. A further complication is the uncertain nature of the interfaces between the ETL and perovskite as well as between phases within the ETL.

The mechanistic effects of long-term γ irradiation on the mineralogical, microstructural, structural, physical, and chemical properties of 40 wt% blast furnace slag + 60 wt% fly ash geopolymer pastes have been examined. Ambient curing for 28 days during normal equilibration was followed by exposure to 60Co irradiation (1574, 4822, 10,214 kGy). The material characteristics are controlled largely through the competing mechanisms of beneficial equilibration at initial lower dosages, which enhances gelation and crosslinking, and detrimental equilibration at subsequent higher dosages, which causes structural and microstructural destabilisation. Irradiation for 2 months (1574 kGy) increases the compressive strength ~45% (~57 to ~83 MPa) through conversion of less-crosslinked (Q0/Q1/Q1′) to more-crosslinked (Q2/Q3/Q4) silicate species. The transition between these regimes occurs after ~5 months of irradiation (~4000 kGy). Beyond this, the rates of beneficial equilibration and detrimental equilibration equalise upon completion of normal geopolymerisation. Additional geopolymerisation from γ irradiation is controlled by the rate-limiting release of Si4+ from the unreacted aluminosilicates and silicates and their rapid incorporation in the geopolymer network. The aqueous leaching of the geopolymer pastes is not affected significantly by γ irradiation. These data reveal the potential for these materials as intermediate-level wasteforms that can outperform Portland cement-based materials.

The effects of curing temperature, blast furnace slag content, and Ms on the initial and final setting times, and compressive strengths of geopolymer paste and mortars are examined. The present work demonstrates that ambient-cured geopolymer pastes and mortars can be fabricated without requiring high alkalinity activators or thermal curing, provided that the ratios of Class F fly ash (40&ndash, 90 wt%), blast furnace slag (10&ndash, 60 wt%), and low alkalinity sodium silicate (Ms = 1.5, 1.7, 2.0) are appropriately balanced. Eighteen mix designs were assessed against the criteria for setting time and compressive strength according to ASTM C150 and AS 3972. Using these data, flexible and reproducible mix designs in terms of the fly ash/slag ratio and Ms were mapped and categorised. The optimal mix designs are 30&ndash, 40 wt% slag with silicate modulus (Ms) = 1.5&ndash, 1.7. These data were used to generate predictive models for initial and final setting times and for ultimate curing times and ultimate compressive strengths. These projected data indicate that compressive strengths &gt, 100 MPa can be achieved after ambient curing for &gt, 56 days of mixes of &ge, 40 wt% slag.

The application of nanoparticulate therapies for cancer depends largely on the uptake and redox activity of the particles. The present work reports the fabrication of different morphologies of nanoceria (CeO2−x) as nanooctahedra (NO), nanorods (NR), and nanocubes (NC) by hydrothermal synthesis at different temperatures (100 °C, 180 °C) of solutions of 0.05 M Ce(NO3)3·6H2O and different concentrations of NaOH (0.01 M, 6.00 M). The characteristics of these nanomorphologies are compared in terms of the crystallinity (XRD), grain size (TEM), surface area (BET), tendency to agglomerate, and the oxygen vacancy concentration ([VO••]) as reflected by the [Ce3+]/[Ce4+] ratio (XPS). The effects of these parameters on the potential cellular uptake are canvassed, suggesting that the nonpolarity of the {111} planes of NO and NR facilitate the preferential uptake of these nanomorphologies. These experimental variables then were normalized through the use of NC as a model substrate for the functionalization using gum arabic (GA) and collagen in order to assess their roles in enhancing redox activity. Both the unfunctionalized and functionalized NC were noncytotoxic in in vitro tests with Kuramochi ovarian cancer cells. However, the antioxidant behavior of the collagen-functionalized NC was superior to that of the unfunctionalized NC, which was superior to that of the controls. These results demonstrate that, while the intrinsic VO•• of CeO2−x enhance the destruction of reactive oxygen species (ROS), functionalization by gum arabic and collagen crosslinking as extrinsic additions to the system enhances ROS destruction to an even greater extent. The antioxidant behavior and potential to neutralize superoxide and hydroxyl radicals of these materials offers new potential for the improvement of nanoparticulate cancer therapies.

CeO2 films doped with 0–9 mol% Ga/Mn were fabricated by spin coating on 3D-printed Ti6Al4V, calcined at 650 °C for 2 h, and characterised by TEM, FESEM, 3D laser scanning confocal microscopy, GAXRD, and XPS. The results depend on the roles of several factors: (1) Sol-gel precursor viscosity affected pore filling and surface coverage. (2) Lattice contraction and resultant intervalence charge transfer increased the Ce3+ concentration as a minority effect. (3) Substitutional solid solubility and associated redox charge compensation controlled the defect equilibria, which highlight the majority role of this solid solubility mechanism in decreasing the Ce3+ concentration. (4) Electronegativity played a negligible role in affecting the valences but was important in initiating intervalence charge transfer. (5) Multivalence charge transfer combined electron exchanges between film matrix, dopants, and Ti substrate. The present work provides a foundation to interpret the effects of extrinsic effects from both dopant and substrate on the properties of films.