High Throughput Synthesis and Screening of Oxygen Reduction Catalysts in the MTiO₃ (M = Ca, Sr, Ba) Perovskite Phase Diagram

A library of 66 perovskite BaxSryCazTiO3 (x + y + z = 1) samples (ca. three grams per sample) was made in ca. 14 h using a high-throughput continuous hydrothermal flow synthesis system. The as-synthesized samples were collected from the outlet of the process and then cleaned and freeze-dried before being evaluated individually as oxygen reduction catalysts using a rotating disk electrode testing technique. To establish any correlations between physical and electrochemical characterization data, the as-synthesized samples were investigated using analytical methods including BET surface area, powder X-ray diffraction (PXRD) and in selected cases, transmission electron microscopy (TEM). The aforementioned approach was validated as being able to quickly identify oxygen reduction catalysts from new libraries of electrocatalysts

Photocatalytic water disinfection by simple and low-cost monolithic and heterojunction ceramic wafers

In this work, the photocatalytic disinfection of Escherichia coli (E. coli) using dual layer ceramic wafers, prepared by a simple and low-cost technique, was investigated. Heterojunction wafers were prepared by pressing TiO2 and WO3 powders together into 2 layers within a single, self-supported monolith. Data modelling showed that the heterojunction wafers were able to sustain the formation of charged species (after an initial "charging" period). In comparison, a wafer made from pure TiO2 showed a less desirable bacterial inactivation profile in that the rate decreased with time (after being faster initially). The more favourable kinetics of the dual layer system was due to superior electron-hole vectorial charge separation and an accumulation of charges beyond the initial illumination period. The results demonstrate the potential for developing simplified photocatalytic devices for rapid water disinfection

Combinatorial Performance Mapping of Near-NMC111 Li-ion Cathodes

A combinatorial library of twenty-three, phase pure, near-NMC111 (LiNi0·33Mn0·33Co0·33O2) compositions were synthesised and their electrochemical performance, was mapped (in lithium ion half-cells). Each of the 23 compositions was made in series, using a two-step process of 1) a rapid initial continuous hydrothermal precipitation, followed by 2) solid state lithiation. The 23 lithiated NMC samples were then subjected to analytical methods including electron microscopy (selected samples), Powder X-ray Diffraction and electrochemical tests in half cell Li-ion configurations versus Li metal. A sample with a Ni:Mn:Co (NMC) ratio of 39:28:33, revealed a specific capacity of 150 mA h g−1 at a C/20 rate, which was 63 and 43% greater capacity than NMC111 and NMC433 samples produced in this work, respectively. The sample with NMC ratio 47:25:28, showed the best capacity retention characteristics, retaining 70% of its C/20 capacity at 1C, after 40 cycles. Further analysis of all the samples by cyclic voltammetry and electrochemical impedance spectroscopy, allowed compositional mapping of diffusion coefficients. Overall, the mapping data revealed a gradual change of properties across compositional space, which has validated our combinatorial approach and allowed identification of the optimum performing near-NMC111 cathode materials

In situ spectroscopic monitoring of CO2 reduction at copper oxide electrode

Copper oxide modified electrodes were investigated as a function of applied electrode potential using in situ infrared spectroscopy and ex situ Raman and X-ray photoelectron spectroscopy. In deoxygenated KHCO3 electrolyte bicarbonate and carbonate species were found to adsorb to the electrode during reduction and the CuO was reduced to Cu(I) or Cu(0) species. Carbonate was incorporated into the structure and the CuO starting material was not regenerated on cycling to positive potentials. In contrast, in CO2 saturated KHCO3 solution, surface adsorption of bicarbonate and carbonate was not observed and adsorption of a carbonato-species was observed with in situ infrared spectroscopy. This species is believed to be activated, bent CO2. On cycling to negative potentials, larger reduction currents were observed in the presence of CO2; however, less of the charge could be attributed to the reduction of CuO. In the presence of CO2 CuO underwent reduction to Cu2O and potentially Cu, with no incorporation of carbonate. Under these conditions the CuO starting material could be regenerated by cycling to positive potentials

Al-, Ga-, and In-doped ZnO thin films via aerosol assisted CVD for use as transparent conducting oxides

Al-, Ga-, and In-doped ZnO thin films were deposited on glass substrates by aerosol assisted chemical vapour deposition (AACVD) at a deposition temperature of 450 °C. The air-stable compound zinc acetylacetonate [Zn(acac)2] was used as a Zn source, whilst for the dopants of Al, Ga and In, the corresponding trichloride was used. Methanol solutions of the metal salts were used as precursor solutions and N2 carrier gas was used for the aerosol. Films were grown in approximately 30 min and were synthesised using dopant values of 5, 10, 15 and 20 mol.% (with respect to the Zn) in the precursor solution. XRD analysis showed that the films were wurtzite ZnO. XPS analysis confirmed the presence of the dopants in the films. Several of the films showed high transparency (>80%) in the visible range, and low resistivity (∼10−3 Ω cm)

Scaling aerosol assisted chemical vapour deposition: Exploring the relationship between growth rate and film properties

Thin films of fluorine doped tin oxide were deposited, by an aerosol assisted chemical vapour deposition route, to study the effect of scaling the growth rate. The effect of precursor concentration on the growth rate of the films and the properties of deposited films were compared. The films were characterised by X-ray diffraction, scanning electron microscopy, UV/vis spectroscopy, X-ray photoelectron spectroscopy and Hall effect measurements. A maximum film growth rate of ca. 100 nm min− 1 was observed, which is significantly faster than previously reported aerosol assisted studies. This method shows the ability of aerosol assisted methods to deliver high growth rates whilst maintaining the ease of doping and control over stoichiometry

Thermocatalytic syntheses of highly defective hybrid nano-catalysts for photocatalytic hydrogen evolution

Defects play important roles in many catalytic processes, particularly for photocatalytic processes in semiconductors as they can alter the band structures and affect the excited electron–hole recombination pathways/lifetimes of semiconductors. In this report, we described the development of a facile route to the production of highly defective photocatalysts. Firstly, organic species were bound onto the surface of a metal oxide semiconductor catalyst, followed by a relatively low temperature ageing in N2, to remove the organics and to attract oxygen molecules from the surface, generating oxygen vacancies. In particular, we introduced a co-catalyst during the syntheses, which acted as a thermocatalyst to promote full oxidation of the organics, leaving more oxygen vacancies at the surface and to form intimate heterojunctions with host-catalysts to further drive the photocatalytic hydrogen evolution. The hydrogen evolution rate for our developed NiO–TiO2 defective heterojunctions in a sacrificial system was measured at ca. 1.41 mmol g−1 h−1, which was much higher than those of comparable catalysts reported in the literature (that generally display hydrogen evolution rates <0.4 mmol g−1 h−1). Computational simulation, together with other analytical techniques, suggested that the generated surface oxygen vacancies could induce a series of impurity energy levels within the VBM and CBM of TiO2 that narrowed the electron transmission gap in the TiO2 and acted as active sites for the reaction between adsorbed H2O and photoinduced trapped electrons to produce H2

Highly efficient electro-reduction of CO2 to formic acid by nano-copper

Ultra-fine copper(II) oxide nanoparticles were used for the electrocatalytic reduction of CO2 to formic acid at high Faradaic efficiencies. The nanoparticles were directly synthesised via continuous hydrothermal flow synthesis (CHFS) process, which used water as a solvent and reagent. The as-prepared nanoparticles were subsequently formulated into Nafion based inks. For the electroreduction of CO2, the influence of Nafion fraction on the Faradaic efficiencies and overpotential (for formic acid production), was explored over a wide potential range. The highest Faradaic efficiency for formic acid production (61%) was observed with a 25 wt% Nafion fraction, at a potential of −1.4 V vs. Ag/AgCl. Some insights into the significant increase in Faradaic efficiency for the production of formic acid with the optimum Nafion content, was elucidated with electrochemical impedance spectroscopy

High-Throughput Synthesis, Screening, and Scale-Up of Optimized Conducting Indium Tin Oxides

A high-throughput optimization and subsequent scale-up methodology has been used for the synthesis of conductive tin-doped indium oxide (known as ITO) nanoparticles. ITO nanoparticles with up to 12 at % Sn were synthesized using a laboratory scale (15 g/hour by dry mass) continuous hydrothermal synthesis process, and the as-synthesized powders were characterized by powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray analysis, and X-ray photoelectron spectroscopy. Under standard synthetic conditions, either the cubic In2O3 phase, or a mixture of InO(OH) and In2O3 phases were observed in the as-synthesized materials. These materials were pressed into compacts and heat-treated in an inert atmosphere, and their electrical resistivities were then measured using the Van der Pauw method. Sn doping yielded resistivities of ∼10(-2) Ω cm for most samples with the lowest resistivity of 6.0 × 10(-3) Ω cm (exceptionally conductive for such pressed nanopowders) at a Sn concentration of 10 at %. Thereafter, the optimized lab-scale composition was scaled-up using a pilot-scale continuous hydrothermal synthesis process (at a rate of 100 g/hour by dry mass), and a comparable resistivity of 9.4 × 10(-3) Ω cm was obtained. The use of the synthesized TCO nanomaterials for thin film fabrication was finally demonstrated by deposition of a transparent, conductive film using a simple spin-coating process

High power TiO2 and high capacity Sn-doped TiO2 nanomaterial anodes for lithium-ion batteries

A range of phase-pure anatase TiO2 (∼5 nm) and Sn-doped TiO2 nanoparticles with the formula Ti1-xSnxO2 (where x = 0, 0.06, 0.11 and 0.15) were synthesized using a continuous hydrothermal flow synthesis (CHFS) reactor. Charge/discharge cycling tests were carried out in two different potential ranges of 3 to 1 V and also a wider range of 3 to 0.05 V vs Li/Li+. In the narrower potential range, the undoped TiO2 nanoparticles display superior electrochemical performance to all the Sn-doped titania crystallites. In the wider potential range, the Sn-doped samples perform better than undoped TiO2. The sample with composition Ti0.85Sn0.15O2, shows a capacity of ca. 350 mAh g−1 at an applied constant current of 100 mA g−1 and a capacity of 192.3 mAh g−1 at a current rate of 1500 mA g−1. After 500 charge/discharge cycles (at a high constant current rate of 382 mA g−1), the same nanomaterial anode retains a relatively high specific capacity of 240 mAh g−1. The performance of these nanomaterials is notable, particularly as they are processed into electrodes, directly from the CHFS process (after drying) without any post-synthesis heat-treatment, and they are made without any conductive surface coating