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Fe-based potassium Prussian blue analogues (K-PBAs) are traditionally used as K-ion battery cathodes. Interestingly, K-PBAs are appealing cathodes for Na-ion batteries (NIBs), due to the increased cation intercalation voltage compared to Na-PBAs. In such a hybrid NIB cell, where Na+ is in the electrolyte and K+ is in the PBA cathode, cation intercalation and electrochemical performance of the cathode can be significantly affected by [Fe(CN)6]4- anion vacancy. This work studies the effect of [Fe(CN)6]4- anion vacancy in K-PBAs on regulating K+/Na+ intercalation mechanism in hybrid NIB cells, by comparing two K-PBA cathodes with different vacancy contents. Experimental and computational results demonstrate that introducing a level of anion vacancy can maximize the number of K+ intercalation sites and enhance K+ diffusion in the PBA framework. This facilitates K+ intercalation and suppresses Na+ intercalation, resulting in a K+-dominated and high-discharge-voltage ion storage process in the hybrid NIB cell. The K-PBA cathode with 20% anion vacancy delivers 127 mAh g-1 at 50 mA g-1 and 63 mAh g-1 at 500 mA g-1, as well as retains 87% and 77% capacity after 100 and 300 cycles, respectively. It completely outperforms the counterpart with 7% anion vacancy, which exhibits increased Na+ intercalation but overall deteriorated ion storage. Our results show the promise of hybrid battery systems and the crucial role of vacancy regulation in designing electrode materials for these systems.

Fe-based potassium Prussian blue analogues (K-PBAs) are traditionally used as K-ion battery cathodes. Interestingly, K-PBAs are appealing cathodes for Na-ion batteries (NIBs), due to the increased cation intercalation voltage compared to Na-PBAs. In such a hybrid NIB cell, where Na+ is in the electrolyte and K+ is in the PBA cathode, cation intercalation and electrochemical performance of the cathode can be significantly affected by [Fe(CN)6]4- anion vacancy. This work studies the effect of [Fe(CN)6]4- anion vacancy in K-PBAs on regulating K+/Na+ intercalation mechanism in hybrid NIB cells, by comparing two K-PBA cathodes with different vacancy contents. Experimental and computational results demonstrate that introducing a level of anion vacancy can maximize the number of K+ intercalation sites and enhance K+ diffusion in the PBA framework. This facilitates K+ intercalation and suppresses Na+ intercalation, resulting in a K+-dominated and high-discharge-voltage ion storage process in the hybrid NIB cell. The K-PBA cathode with 25% anion vacancy delivers 127 mAh g-1 at 50 mA g-1 and 63 mAh g-1 at 500 mA g-1, as well as retains 87% and 77% capacity after 100 and 300 cycles, respectively. It completely outperforms the counterpart with 7% anion vacancy, which exhibits increased Na+ intercalation but overall deteriorated ion storage. Our results show the promise of hybrid battery systems and the crucial role of vacancy regulation in designing electrode materials for these systems.

Usually, VO2 films prepared by a magnetron sputtering method exhibit good durability and excellent solar modulation efficiency (ΔTsol). However, its undesirable low-temperature luminous transmittan...

Copper containing materials are widely used in a range of catalytic applications. Here, we report the use of Cu K-edge high resolution XANES to determine the local site symmetry of copper ions during the thermal treatment of a Cu-Cr-Fe oxide catalyst. We exploited the Cu K-edge XANES spectral features, in particular the correlation between area under the pre-edge peak and its position to determine the local environment of Cu2+ ions. The information gained from this investigation rules out the presence of Cu2+ ions in a tetrahedral or square planar geometry, a mixture of these sites, or in a reduced oxidation state. Evidence is presented that the Cu2+ ions in the Cu-Cr-Fe oxide system are present in a distorted octahedral environment.

Metal organic frameworks (MOFs) constructed from metal ions/clusters and organic linkers have led to new porous luminescent materials and, thus, have attracted much attention. But their photoluminescence quantum yields (PLQYs) are not high and the photoluminescence mechanism is still unclear. In order to solve this problem, in this work, zeolitic imidazolate framework-8 (ZIF-8, a kind of MOF) composite films containing small molecules of acetic acid were successfully prepared on a glass substrate via a sol–gel method, and they exhibited a high PLQY of 54.42%. Compared with pure ZIF-8 film, the obtained ZIF-8 composite film presented a significant enhancement in blue light emission. Moreover, the PLQY of the ZIF-8 composite film can be controlled to a certain extent via adjusting the molar ratio of the ligands to the zinc source. Among them, ZIF-8 film prepared at a molar ratio of 2.5 : 1 showed higher transmittance, and the fluorescence quantum efficiency reached 54.42%, which may be attributed to electron transfer between acetic acid as an electron-donor and the ZIF-8 structure caused by their relatively strong hydrogen bonding interactions. This work may provide new insights into the enhanced fluorescence of MOF materials for light-emitting applications.

Cu2O is an attractive photocathode for important renewable energy reactions such as water splitting and CO2 reduction. Electrodeposition is commonly used to deposit Cu2O films on conductive substrates due to its simplicity and consistency. However, structural descriptors, linking electrodeposition parameters, film structure and the catalytic properties are elusive. A variety of Cu2O films reported by many research groups would often display vastly different electronic properties and catalytic activity, while appear indistinguishable under common characterisation tools. In this work, we take a systematic look into electrochemically deposited Cu2O and investigate the impact of deposition parameters towards the bulk and surface chemistry of the deposited film. Specifically, we employ high resolution XANES for thorough quantitative analysis of the Cu2O films, alongside more common characterisation methods like XRD, SEM and Raman spectroscopy. Photoelectrochemical (PEC) studies reveal an unexpected trend, where the highest PEC activity appears to correlate with the amount of Cu2+ content. Other factors which also affect the PEC activity and stability are film thickness and crystallite grain size. Our study shows that the use of high resolution XANES, though not perfect due to possible self-absorption issue, is apt for extracting compositional descriptor in concentrated thin film samples from the pre-edge energy position analysis. This descriptor can serve as a guide for future development of more active Cu2O based films for wide range of PEC processes as well as for solar cell applications.

The formation of silver and Au@Ag core@shell nanoparticles via reduction of AgNO3 by trisodium citrate was followed using in situ X-ray absorption near-edge structure (XANES) spectroscopy and time-resolved UV-visible (UV-vis) spectroscopy. The XANES data were analyzed through linear combination fitting, and the reaction kinetics were found to be consistent with first-order behavior with respect to silver cations. For the Au@Ag nanoparticles, the UV-vis data of a lab-scale reaction showed a gradual shift in dominance between the gold- and silver-localized surface plasmon absorbance bands. Notably, throughout much of the reaction, distinct gold and silver contributions to the UV-vis spectra were observed; however, in the final product, the contributions were not distinct.

Zinc sulfide is an important wide-band gap semi-conductor and dithiocarbamate complexes [Zn(S2CNR2)(2)] find widespread use as single-source precursors for the controlled synthesis of ZnS nanoparticulate modifications. Decomposition of [Zn((S2CNBu2)-Bu-i)(2)] in oleylamine gives high aspect ratio wurtzite nanowires, the average length of which was increased upon addition of thiuram disulfide to the decomposition mixture. To provide further insight into the decomposition process, X-ray absorption spectroscopy (XAS) of [Zn(S2CNMe2)(2)] was performed in the solid-state, in non-coordinating xylene and in oleylamine. In the solid-state, dimeric [Zn(S2CNMe2)(2)](2) was characterised in accord with the single crystal X-ray structure, while in xylene this breaks down into tetrahedral monomers. In situ XAS in oleylamine (RNH2) shows that the coordination sphere is further modified, amine binding to give five-coordinate [Zn(S2CNMe2)(2)(RNH2)]. This species is stable to ca. 70 degrees C, above which amine dissociates and at ca. 90 degrees C decomposition occurs to generate ZnS. The relatively low temperature onset of nanoparticle formation is associated with amine-exchange leading to the in situ formation of [Zn(S2CNMe2)(S2CNHR)] which has a low temperature decomposition pathway. Combining these observations with the previous work of others allows us to propose a detailed mechanistic scheme for the overall process.

Operando X-ray absorption spectroscopy (XAS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and mass spectrometry (MS) provide complementary information on the catalyst structure, surface reaction mechanisms and activity relationships. The powerful combination of the techniques has been the driving force to design and engineer suitable spectroscopic operando reactors that can mitigate limitations inherent to conventional reaction cells and facilitate experiments under kinetic regimes. Microreactors have recently emerged as effective spectroscopic operando cells due to their plug-flow type operation with no dead volume and negligible mass and heat transfer resistances. Here we present a novel microfabricated reactor that can be used for both operando XAS and DRIFTS studies. The reactor has a glass-silicon-glass sandwich-like structure with a reaction channel (3000 μm × 600 μm; width × depth) packed with a catalyst bed (ca. 25 mg) and placed sideways to the X-ray beam, while the infrared beam illuminates the catalyst bed from the top. The outlet of the reactor is connected to MS for continuous monitoring of the reactor effluent. The feasibility of the microreactor is demonstrated by conducting two reactions: i) combustion of methane over 2 wt% Pd/Al2O3 studied by operando XAS at the Pd K-edge and ii) CO oxidation over 1 wt% Pt/Al2O3 catalyst studied by operando DRIFTS. The former shows that palladium is in an oxidised state at all studied temperatures, 250, 300, 350, 400 °C and the latter shows the presence of linearly adsorbed CO on the platinum surface. Furthermore, temperature-resolved reduction of palladium catalyst with methane and CO oxidation over platinum catalyst are also studied. Based on these results, the catalyst structure and surface reaction dynamics are discussed, which demonstrate not only the applicability and versatility of the microreactor for combined operando XAS and DRIFTS studies, but also illustrate the unique advantages of the microreactor for high space velocity and transient response experiments.

The effect of Pd loading on the redox characteristics of a ceria support was examined using in situ Pd K-edge XAS, Ce L-3-edge XAS and in situ X-ray diffraction techniques. Analysis of the data obtained from these techniques indicates that the onset temperature for the partial reduction of Ce(iv) to Ce(iii), by exposure to H-2, varies inversely with the loading of Pd. Whilst the onset and completion temperatures of the reduction of Ce(iv) to Ce(iii) are different, both samples yield the same maximal fraction of Ce(iii) formation independent of Pd loading. Furthermore, the partial reduction of Ce is found to be concurrent with the reduction of PdO and demonstrated that the presence of metallic Pd is necessary for the reduction of the CeO2 support. Upon passivation by room temperature oxidation, a full oxidation of the reduced ceria support was observed. However, only a mild surface oxidation of Pd was identified. The mild passivation of the Pd is found to lead to a highly reactive sample upon a second reduction by H-2. The onset of the reduction of Pd and Ce has been demonstrated to be independent of the Pd loading after a mild passivation with both samples exhibiting near room temperature reduction in the presence of H-2.

The reaction between ceria and hydrogen has been subject to numerous theoretical and experimental studies because of its importance as a catalytic material. Here, we present dynamic and reversible evolution of the cerium oxidation states observed through X-ray absorption spectroscopy experiments in addition to the investigation of associated lattice expansion and contraction through X-ray diffraction and PDF methods. Employing a novel calculation of the temperature dependence of the Gibbs free energy through consideration of the relationship between the instantaneous thermal lattice expansion and the rate of change of the cerium oxidation state, the unusual redox chemistry is reported here. This unusual behavior is interpreted to be due to the formation of a metastable cerium oxyhydride as suggested.

Here, we report the use of Li2Mn(SO4)2 as a potential energy storage material and describe its route of synthesis and structural characterization over one electrochemical cycle. Li2Mn(SO4)2 is synthesized by ball milling of MnSO4·H2O and Li2SO4·H2O and characterized using a suite of techniques, in particular, ex situ X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy on the Mn and S K-edges to investigate the electronic and local geometry around the absorbing atoms. The prepared Li2Mn(SO4)2 electrodes undergo electrochemical cycles to different potential points on the charge–discharge curve and are then extracted from the cells at these points for ex situ structural analysis. Analysis of X-ray absorption spectroscopy (both near and fine structure part of the data) data suggests that there are minimal changes to the oxidation state of Mn and S ions during charge–discharge cycles. However, X-ray photoelectron spectroscopy analysis suggests that there are changes in the oxidation state of Mn, which appears to be different from the conclusion drawn from X-ray absorption spectroscopy. This difference in results during cycling can thus be attributed to electrochemical reactions being dominant at the surface of the Li2Mn(SO4)2 particles rather than in the bulk.

Here we report a high-pressure investigation into the structural and magnetic properties of the double perovskite La2NiMnO6 using neutron scattering over a temperature range of 4.2–300 K at ambient...

Nanoparticulate iron sulfides have many potential applications and are also proposed to be prebiotic catalysts for the reduction of CO2 to biologically important molecules, thus the development of reliable routes to specific phases with controlled sizes and morphologies is important. Here we focus on the use of iron dithiocarbamate complexes as single source precursors (SSPs) to generate greigite and pyrrhotite nanoparticles. Since these minerals contain both iron(iii) and iron(ii) centres, SSPs in both oxidation states, [Fe(S2CNR2)(3)] and cis-[Fe(CO)(2)(S2CNR2)(2)] respectively, have been utilised. Use of this Fe(ii) precursor is novel and it readily loses both carbonyls in a single step (as shown by TGA measurements) providing an in situ source of the extremely air-sensitive Fe(ii) dithiocarbamate complexes [Fe(S2CNR2)(2)]. Decomposition of [Fe(S2CNR2)(3)] alone in oleylamine affords primarily pyrrhotite, although by careful control of reaction conditions (ca. 230 degrees C, 40-50 nM SSP) a window exists in which pure greigite nanoparticles can be isolated. With cis-[Fe(CO)(2)(S2CNR2)(2)] we were unable to produce pure greigite, with pyrrhotite formation dominating, a similar situation being found with mixtures of Fe(ii) and Fe(iii) precursors. In situ X-ray absorption spectroscopy (XAS) studies showed that heating [Fe((S2CNBu2)-Bu-i)(3)] in oleylamine resulted in amine coordination and, at ca. 60 degrees C, reduction of Fe(iii) to Fe(ii) with (proposed) elimination of thiuram disulfide (S2CNR2)(2). We thus carried out a series of decomposition studies with added thiuram disulfide (R = Bu-i) and found that addition of 1-2 equivalents led to the formation of pure greigite nanoparticles between 230 and 280 degrees C with low SSP concentrations. Average particle size does not vary significantly with increasing concentration, thus providing a convenient route to ca. 40 nm greigite nanoparticles. In situ XAS studies have been carried out and allow a decomposition pathway for [Fe((S2CNBu2)-Bu-i)(3)] in oleylamine to be established; reduction of Fe(iii) to Fe(ii) reduction triggers substitution of the secondary amide backbone by oleylamine (RNH2) resulting in the in situ formation of a primary dithiocarbamate derivative [Fe(RNH2)(2)(S2CNHR)(2)]. This in turn extrudes RNCS to afford molecular precursors of the observed FeS nanomaterials. The precise role of thiuram disulfide in the decomposition process is unknown, but it likely plays a part in controlling the Fe(iii)-Fe(ii) equilibrium and may also act as a source of sulfur allowing control over the Fe : S ratio in the mineral products.

Copper containing materials are widely used in a range of catalytic applications. Here, we report the use of Cu K-edge high resolution XANES to determine the local site symmetry of copper ions during the thermal treatment of a Cu-Cr-Fe oxide catalyst. We exploited the Cu K-edge XANES spectral features, in particular the correlation between area under the pre-edge peak and its position to determine the local environment of Cu2+ ions. The information gained from this investigation rules out the presence of Cu2+ ions in a tetrahedral or square planar geometry, a mixture of these sites, or in a reduced oxidation state. Evidence is presented that the Cu2+ ions in the Cu-Cr-Fe oxide system are present in a distorted octahedral environment.

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In situ studies on the physical and chemical properties of Au in inverse ceria alumina supported catalysts have been conducted between 295 and 623 K using high energy resolved fluorescence detection X-ray absorption near edge spectroscopy and X-ray total scattering. Precise structural information is extracted on the metallic Au phase present in a 0.85 wt% Au containing inverse ceria alumina catalyst (ceria/Au/alumina). Herein evidence for the formation of an Au hydride species at elevated temperature is presented. Through modelling of total scattering data to extract the thermal properties of Au using Gruneisen theory of volumetric thermal expansion it proposed that the Au Hydride formation occurs synergistally with the formation of a cerium oxyhydride. The temperature reversible nature, whilst remaining in a reducing atmosphere, demonstrates the activation of hydrogen without consumption of oxygen from the supporting ceria lattice.

Organometallic coordination polymers (OMCPs) are a promising class of thermoelectric materials with high electrical conductivities and thermal resistivities. The design criteria for these materials, however, remain elusive and so far material modifications have been focused primarily on the nature of the metal cation to tune the thermoelectric properties. Herein, an alternative approach is described by synthesizing new organic ligands for OMCPs, allowing modulation of the thermoelectric properties of the novel OMCP materials over several orders of magnitude, as well as controlling the polarity of the Seebeck coefficient. Extensive material purification combined with spectroscopy experiments and calculations furthermore reveal the charge‐neutral character of the polymer backbones. In the absence of counter‐cations, the OMCP backbones are composed of air‐stable, ligand‐centered radicals. The findings open up new synthetic possibilities for OMCPs by removing structural constraints and putting significant emphasis on the molecular structure of the organic ligands in OMCP materials to tune their thermoelectric properties., The authors gratefully acknowledge Dr. Mark Baxendale for the use of the MMR Seebeck instrument, as well as Dr. Shibo Xi for the support and assistance provided during the XANES measurements. Z.L., T.L. and J.L. acknowledge the support from Chinese Scholarship Council (CSC). B.C.S. acknowledges funding by the Leverhulme Trust (Grant RF‐2017‐655\4) and the EPSRC (EP/P007767/1). M.A.Z. acknowledges the UK Engineering and Physical Sciences Research Council (EPSRC) for funding (Grant EP/N004884/1, Integration of Computation and Experiment for Accelerated Materials Discovery). B.C.S. and M.A.Z. acknowledge the EPSRC (Grant EP/R034540/1, Defect Functionalized Sustainable Energy Materials: From Design to Devices Application). O.F. acknowledges the support of The Royal Society (UF140372). The authors at ICMAB would like to acknowledge financial support from the Spanish Ministry of Science, Innovation and Universities through the “‘Severo Ochoa”' Program for Centers of Excellence in R&D (SEV‐2015‐0496), PGC2018‐095411‐B‐I00, and MAT2017‐ 90024‐P, and from the European Research Council (ERC) under grant agreement no. 648901. J. P. J. has received financial support through the “la Caixa” INPhINIT Fellowship Grant (Grant code: LCF/BQ/IN17/11620035). L.P. acknowledges a Newton Fellowship from the Royal Society for funding (grant reference NF170361). The use of the UCL Legion, Myriad, and Grace High Performance Computing Facilities (Legion@UCL, Myriad@UCL and Grace@UCL) is acknowledged in the production of this work. Computational work was also performed on the ARCHER UK National Supercomputing Service, via our membership of the UK's HEC Materials Chemistry Consortium, funded by EPSRC (EP/L000202 and EP/R029431), and the UK Materials and Molecular Modelling Hub, which is partially funded by EPSRC (EP/P020194/1).

The strong directing effects and difficulties in the removal of organic based surfactants makes the templated synthesis of nanoparticles in solid porous structures of defined molecular sizes such as SBA-15, without the use of surfactants, considerably attractive. However, the effects of their internal surface structures, adsorption affinities, and lattice mismatch on the particle morphology grown therein have not been fully appreciated. Here, we report the internal surface of the silica preferentially hosts isolated tetrahedrally coordinated oxidic Zn species on the molecular walls of the SBA-15 channels from wet impregnated Zn2+ and Pt2+ species. This leads to a less thermodynamically stable but kinetically controlled configuration of atomic zinc deposition on core platinum nanoparticles with unique confined lattice changes and surface properties to both host and guest structures at the interface upon reduction of the composite. This method for the formation templated nanoparticles may generate interest in forming new tunable materials as dehydrogenation catalysts.

Methane activation under moderate conditions and with good selectivity for value-added chemicals still remains a huge challenge. Here, we present a highly selective catalyst for the transformation of methane to methanol composed of highly dispersed iron species on titanium dioxide. The catalyst operates under moderate light irradiation (close to one Sun) and at ambient conditions. The optimized sample shows a 15% conversion rate for methane with an alcohol selectivity of over 97% (methanol selectivity over 90%) and a yield of 18 moles of alcohol per mole of iron active site in just 3 hours. X-ray photoelectron spectroscopy measurements with and without xenon lamp irradiation, light-intensity-modulated spectroscopies, photoelectrochemical measurements, X-ray absorption near-edge structure and extended X-ray absorption fine structure spectra, as well as isotopic analysis confirm the function of the major iron-containing species—namely, FeOOH and Fe2O3, which enhance charge transfer and separation, decrease the overpotential of the reduction reaction and improve selectivity towards methanol over carbon dioxide production. Methanol synthesis from methane is a promising route to valorize this abundant natural gas, but existing thermal processes require harsh reaction conditions. Now, a photocatalytic approach based on TiO2-supported iron oxide species is described, which affords methanol in high yield and selectivity at ambient conditions.

A Pd-promoted Re/SiO2 catalyst was prepared by sequential impregnation and compared to monometallic Pd/SiO2 and Re/SiO2. All samples were characterized by electron microscopy, H2 and CO chemisorption, H2 temperature-programmed reduction, and in-situ X-ray absorption spectroscopy at the Re LIII and Pd K-edges. The samples were also tested in the reduction of propionic acid to 1-propanol and propionaldehyde at 433 K in 0.1-0.2 MPa H2. Whereas monometallic Pd was inactive for carboxylic acid reduction, monometallic Re catalyzed aldehyde formation, but only after high-temperature pre-reduction that produced metallic Re. When Pd was present with Re in a bimetallic catalyst, Pd facilitated the reduction of Re in H2 to ~4+ oxidation state at modest temperatures, producing an active catalyst for the conversion of propionic acid to 1-propanol. Under the conditions of this study, the orders of reaction in propionic acid and H2 were approximately zero and one, respectively. Transient kinetic analysis of the carboxyl...

In situ electron microscopy, tomography, photoluminescence, and X-ray absorption spectroscopy were utilized to monitor and explain the formation and growth of internal pores within ZnO nanorods. Careful examination using electron microscopy and tomography indicate that nanosized internal pores start appearing within the individual solution-grown ZnO nanorods upon exposure to 200 °C. The pore volume growth rate is proportional to the heat treatment time, indicating that the process is diffusion controlled, akin to a reverse Ostwald ripening-like process. A manageable pore growth rate of 1.4–4.4 nm3·min−1 was observed at 540 °C, suggesting that the effective control over internal porosity can be achieved by carefully controlling the heat-treatment profile. Mechanistic studies using X-ray absorption spectroscopy indicated that the pore formation is linked to the significant reduction of the number of zinc vacancies after heat treatment. An optimum condition exists where most of the native surface defects are removed, while the bulk defects are contained within the internal pores. It is also demonstrated that the internal porosity can be exploited to improve the visible light absorption of ZnO. A combination of the lower defect density and improved light absorption of the heat-treated ZnO films thus lead to an increase in the photoelectrochemical response of more than 20× compared to that of the as-grown ZnO.

Catalytic combustion of ventilation air methane (VAM) is a potential solution for abatement of this greenhouse gas. In this study, we evaluate the combustion of VAM (with methane concentrations below 1%) spanning over 100 h time on stream (TOS) during reaction over a Pd/HZSM-5 catalyst. The aim is to understand the structural changes that lead to catalyst deactivation. We observe the formation of carbonaceous deposits even under oxygen-rich conditions, which are an important contributor to deactivation. X-ray absorption spectroscopic (XAS) investigation shows that, in addition to carbon deposits, the growth of Pd oxide clusters leads to a reduced number of accessible sites and in turn intrinsic activity. STEM-EDS analysis disclosed the presence of the carbonaceous deposit on the surface of the used catalyst, and TGA confirmed the presence of different carbon species on the used catalyst under very lean conditions. Structural changes show that Pd–O/acid–base interactions have a significant influence on the...

As a very promising thermochromic material, VO2 (M/R) (Monoclinic/Rutile) has not been widely applied in smart windows due to its intrinsic low solar modulation (ΔTsol) and low luminous transmission (Tlum). To address this issue, porous structures have been introduced into the VO2 film. Herein, mesoporous VO2 powders with pore size of about 2–10 nm were synthesized using cotton as template by hydrothermal methods. The pore and crystal size of the synthesized VO2 powders can be reliably controlled by the hydrothermal temperature. The mesoporous VO2 powders were mixed with PVP to prepare the VO2-based nanocomposite films by spin coating. The VO2-based films show a better performance between ΔTsol and Tlum than that appeared in previous reports. Especially, a larger pore size could lead to a higher visible transmittance and a larger crystal size would facilitate the enhancement in the solar modulation. In this sense, the VO2-based film obtained at the hydrothermal temperature of 180 °C exhibits an outstanding thermochromic performance with ΔTsol of 12.9% and Tlum up to 56.0% due to a larger crystal size and pore size. Therefore, this synthetic route shows a potential method for the application of mesoporous VO2 powders for solar control coatings.

A method of quantitative phase analysis using valence band X-ray photoelectron spectra is presented and applied to the analysis of TiO2 anatase-rutile mixtures. The valence band spectra of pure TiO2 polymorphs were measured, and these spectral shapes used to fit valence band spectra from mixed phase samples. Given the surface sensitive nature of the technique, this yields a surface phase fraction. Mixed phase samples were prepared from high and low surface area anatase and rutile powders. In the samples studied here, the surface phase fraction of anatase was found to be linearly correlated with photocatalytic activity of the mixed phase samples, even for samples with very different anatase and rutile surface areas. We apply this method to determine the surface phase fraction of P25 powder. This method may be applied to other systems where a surface phase fraction is an important characteristic.

Vanadium(IV) oxide thin films were synthesized via atmospheric pressure chemical vapor deposition by the reaction between vanadium(IV) chloride and ethyl acetate at 550 °C. The substrate was varied with films being deposited on glass, SnO2, and F-doped SnO2. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, UV–vis spectroscopy, scanning electron microscopy, and X-ray absorption near-edge structure. The influence of the electronic contribution of the substrate on the deposited VO2 film was found to be key to the functional properties observed. Highly electron-withdrawing substituents, such as fluorine, favored the formation of V5+ ions in the crystal lattice and so reduced the thermochromic properties. By considering both the structural and electronic contributions of the substrate, it is possible to establish the best substrate choices for the desired functional properties of the VO2 thin films synthesized.

Hierarchical TS-1 zeolite was successfully prepared using chitosan as a sacrificial template. The X-ray diffraction showed that the presence of chitosan with the synthesis precursor had no deleterious effect on the crystallinity and phase purity of this zeolite. X-ray absorption spectroscopy at the Ti K-edge, FTIR and Raman spectroscopies revealed the titanium ions in the zeolite structure have predominantly tetrahedral coordination. However, it appears that the higher chitosan content in the synthesis gel imparted some hydrophilic character to the TS-1 system. Furthermore, the technique adopted for the preparation of the synthesis gel – e.g partially dried or fully dried – appears to affect the amount of framework titanium in the zeolite structure. The calcined form of the chitosan templated TS-1 zeolites exhibited higher cyclohexene conversion compared to the TS-1 material synthesised without this template, but these catalysts showed lower selectivity for cyclohexene epoxide.

Nanoparticles with nominal structures of Au@Ag (core@shell) and Au@Ag@Au (core@shell@shell) were prepared using the sequential citrate reduction technique and characterized using routine characterization techniques, including transmission electron microscopy. X-ray absorption spectroscopy was then carried out on the samples, and extended X-ray absorption fine structure (EXAFS) analysis was used to determine the structure of the systems. The results of the routine techniques and the X-ray absorption spectroscopy were then compared. EXAFS analysis of the nanoparticles with the Au@Ag structure revealed very limited bimetallic interactions, supporting the assignment of a core@shell structure. EXAFS analysis of the nanoparticles with Au@Ag@Au structure showed an increased proportion of bimetallic interactions. Based on the colloid composition, the other characterization techniques and the chemistry of the system, these nanoparticles were interpreted as having an Au@Au/Ag-alloy structure. The EXAFS analyses corroborated the other characterization techniques and enabled the determination of the average-structure of the entire sample.

With the objective of moving towards the commercialisation of Fe-based high voltage cathode Li2Fe(SO4)2, the effect of fluorinated binder (polyvinylidene fluoride – PVDF) and non-fluorinated binder (polyacrylonitrile – PAN) was evaluated. First, the redox mechanism involved in the cycling of Li2Fe(SO4)2 cathode in the presence of these two binders was investigated through ex situ X-ray Absorption Spectroscopy (XAS) studies which can directly determine oxidation state changes of the Fe ion during the charge–discharge process. Subsequently, the effect of the binders on the cycling and rate performance was evaluated. In the present work, consistent cycling performance with discharge capacity of 60 mA h g−1 was recorded at low current rate of C/15. However, it was noted that at high charging rate the cell with binder retained only 29% of the discharge capacity in comparison to the cell without binder. This was attributed to the high charge transfer resistance of binders through cyclic voltammogram and electrochemical impedance spectroscopy studies. This in turn suggests the requirement of high conductivity binders for such sulphate based electrodes.

Different morphologies and sizes of VO2(D) particles were synthesised via hydrothermal synthesis using ammonium metavanadate (NH4VO3) or vanadium pentoxide (V2O5) as a vanadium precursor. By adjusting the concentration of vanadium precursors and the pH of the starting solution, a variety of morphologies and sizes of VO2(D) particles from 20 nm to 3 μm could be produced. A flower-shape morphology was obtained under strongly acidic conditions, passing through star-shape particles of 1 μm at pH 2.5 and finally obtaining homogeneous round balls of around 3 μm at pH 6.9. Nanoparticles were produced hydrothermally using V2O5 as a precursor and hydrazine as a reducing agent. The transition from VO2(D) to thermochromic VO2(R) in micron scale particles occurred at 350 °C under vacuum. However, the nanoparticles of VO2(D) had a significantly lower VO2(D) to thermochromic VO2(R) transition temperature of 165 °C after annealing for only a few minutes. This is, to our knowledge, the lowest annealing temperature and time reported in the literature in order to obtain a thermochromic VO2 material via another VO2 phase. After the conversion of VO2(D) microparticles to thermochromic VO2(R), the metal to insulator transition temperature is 61 ± 1 °C for the heating cycle and 53 ± 1 °C for the cooling cycle. However, VO2(R) nanoparticles showed a significantly reduced metal insulator transition temperature of 59 ± 1 °C and 42 ± 1 °C for the cooling cycle lower than that reported in the literature for bulk VO2. This is important due to the need for having a compound with a switching temperature closer to room temperature to be used in smart window devices for energy consumption. W-VO2(D) star shape microparticle samples were prepared using 2–7 at% of the dopant (using ammonium metavanadate as a precursor), although unexpectedly this does not seem to be a viable route to a reduced metal to insulator transition in this system.

The electronic properties of antimony-doped anatase (TiO2) thin films deposited via aerosol assisted chemical vapour deposition were investigated by a range of spectroscopic techniques. The incorporation of Sb(V) into the TiO2 lattice was characterised by X-ray absorption spectroscopy and resulted in n-type conductivity, with a decrease in sheet resistance by four-orders of magnitude compared to that of undoped TiO2 films. The films with the best electrical properties displayed charge carrier concentrations of ca. 1 × 1020 cm−3 and a specific resistivity as low as 6 × 10−2 Ω cm. Doping also resulted in an orange colouration of the films that became progressively stronger with increasing Sb content. X-ray photoelectron spectroscopy showed that substantial segregation of Sb(III) to the surface of the film was associated with the appearance of lone pair surface states lying above the top of the main O 2p valence band. The pronounced visible region absorption in the films is attributed to transitions from the Sb(III) states at surface and grain boundary interfaces into the conduction band. The segregation of Sb leads to p-type surface layers at high doping levels and limits the mobility in this new conducting oxide.

Here we report a high-pressure investigation into the structural and magnetic properties of the double perovskite La

Nanoparticulate iron sulfides have many potential applications and are also proposed to be prebiotic catalysts for the reduction of CO

Use of in situ combined x-ray diffraction and x-ray absorption spectroscopy for the study of the thermal decomposition of zinc peroxide to zinc oxide is reported here. Comparison of data extracted from both x-ray diffraction (XRD) and x-ray absorption spectroscopy (XAS) with thermo gravimetric analysis (TGA) enabled us to follow the nature of the conversion of ZnO2 to ZnO. A temperature range between 230 °C and 350 °C appears to show that a very poorly crystalline ZnO is formed prior to the formation of an ordered ZnO material. Both the decrease in white line intensity in the Zn K-edge XANES and resulting lower coordination numbers estimated from analysis of the Zn K-edge data of ZnO heated at 500 °C, in comparison to bulk ZnO, suggest that the ZnO produced by this method has significant defects in the system.

VO2 films are widely considered as one of the most suitable material to act as smart windows. Although this system is able to function, the durability of the film has been an issue as the surface of the films may oxidize by converting V4+ to V5+. To overcome this problem, attempt is made to coat the VO2 film with ZnO, which can assist by creating a resistance layer to prevent further oxidation of VO2. Here, VO2/ZnO bilayer film was prepared by a facile method comprised of spin-coating and dip-coating process and shows excellent durability, and in particular. the solar modulation efficiency (△Tsol) maintaining ca 89.9% (from 17.8% to 16.0%) after 300 days in a humid environment, however, the △Tsol of pure VO2 film is decreased from 11.8% to 4.1%. Also, the VO2/ZnO bilayer exhibits an enhanced thermochromic property of visible transmittance (Tlum = 55.7 ± 2.1%) and △Tsol (17.1 ± 1.4%) which is 1.49 times higher than that of pure VO2 film (△Tsol = 11.5 ± 0.4%). The enhancement in the thermochromic performance and durability is probably attributed to the anti-reflection and protection of ZnO layer. Therefore, this work can provide an effective way to optimize thermochromic property for practical application of VO2-based smart windows.

Time-resolved combined scattering and spectroscopic techniques were used to understand in detail the formation of cordierite ceramic from two sources, (a) zeolite B and (b) cordierite glass systems. Time-resolved in situ combined EXAFS/XRD (at the Zn K-edge) investigation of the zinc oxide mixed zeolite B reveal that a series of transformations occur before the formation of cordierite ceramic. In particular the study revealed that addition of small amounts of zinc oxide promote the transformation of cordierite, through the formation of ZnAl2O4, at lower temperatures compared to the system without zinc oxide. Using in situ time-resolved SAXS/WAXS technique chromium doped in the cordierite glass system was investigated which revealed that, in addition to the formation of phase pure cordierite phase some amount of MgCr2O4 spinel phase are also produced.

This study focused on the study of titanium sites, their local structure and reactivities in nanoporous titanosilicates frameworks by using in situ X-ray absorption spectroscopy. XANES provides the information on the oxidation state of the titanium species as well as their change in coordination geometry during de- and re-hydration. Results from in situ XANES studies shows that TS-1 is much more hydrophobic than TiAl or TiFe systems. Pre-edge features of Ti K-edge XANES spectra of these materials also suggested that TiIV is the dominant Ti coordination in dehydrated system whilst TiVI is the dominant in the re-hydrated one.

In this combined in situ XAFS, DRIFTS, and Mossbauer study, we elucidate the changes in structural, electronic, and local environments of Fe during pyrolysis of the metal organic framework Fe-BTC toward highly active and stable Fischer–Tropsch synthesis (FTS) catalysts (Fe@C). Fe-BTC framework decomposition is characterized by decarboxylation of its trimesic acid linker, generating a carbon matrix around Fe nanoparticles. Pyrolysis of Fe-BTC at 400 °C (Fe@C-400) favors the formation of highly dispersed epsilon carbides (e′-Fe2.2C, dp = 2.5 nm), while at temperatures of 600 °C (Fe@C-600), mainly Hagg carbides are formed (χ-Fe5C2, dp = 6.0 nm). Extensive carburization and sintering occur above these temperatures, as at 900 °C the predominant phase is cementite (θ-Fe3C, dp = 28.4 nm). Thus, the loading, average particle size, and degree of carburization of Fe@C catalysts can be tuned by varying the pyrolysis temperature. Performance testing in high-temperature FTS (HT-FTS) showed that the initial turnover fr...