Flame Spray Pyrolysis Synthesis of Vo-Rich Nano-SrTiO3-x.

Engineering of oxygen vacancies (Vo) in nanomaterials allows diligent control of their physicochemical properties. SrTiO3 possesses the typical ABO3 structure and has attracted considerable attention among the titanates due to its chemical stability and its high conduction band energy. This has resulted in its extensive use in photocatalytic energy-related processes, among others. Herein, we introduce the use of Flame Spray Pyrolysis (FSP); an industrial and scalable process to produce Vo-rich SrTiO3 perovskites. We present two types of Anoxic Flame Spray Pyrolysis (A-FSP) technologies using CH4 gas as a reducing source: Radial A-FSP (RA-FSP); and Axial A-FSP (AA-FSP). These are used for the control engineering of oxygen vacancies in the SrTiO3-x nanolattice. Based on X-ray photoelectron spectroscopy, Raman and thermogravimetry-differential thermal analysis, we discuss the role and the amount of the Vos in the so-produced nano-SrTiO3-x, correlating the properties of the nanolattice and energy-band structure of the SrTiO3-x. The present work further corroborates the versatility of FSP as a synthetic process and the potential future application of this process to engineer photocatalysts with oxygen vacancies in quantities that can be measured in kilograms.

Non-graphitized carbon/Cu2O/Cu0 nanohybrids with improved stability and enhanced photocatalytic H2 production.

Cu2O is a highly potent photocatalyst, however photocorrosion stands as a key obstacle for its stability in photocatalytic technologies. Herein, we show that nanohybrids of Cu2O/Cu0 nanoparticles interfaced with non-graphitized carbon (nGC) constitute a novel synthesis route towards stable Cu-photocatalysts with minimized photocorrosion. Using a Flame Spray Pyrolysis (FSP) process that allows synthesis of anoxic-Cu phases, we have developed in one-step a library of Cu2O/Cu0 nanocatalysts interfaced with nGC, optimized for enhanced photocatalytic H2 production from H2O. Co-optimization of the nGC and the Cu2O/Cu0 ratio is shown to be a key strategy for high H2 production, > 4700 µmoles g-1 h-1 plus enhanced stability against photocorrosion, and onset potential of 0.234 V vs. RHE. After 4 repetitive reuses the catalyst is shown to lose less than 5% of its photocatalytic efficiency, while photocorrosion was < 6%. In contrast, interfacing of Cu2O/Cu0 with graphitized-C is not as efficient. Raman, FT-IR and TGA data are analyzed to explain the undelaying structural functional mechanisms where the tight interfacing of nGC with the Cu2O/Cu0 nanophases is the preferred configuration. The present findings can be useful for wider technological goals that demand low-cost engineering, high stability Cu-nanodevices, prepared with industrially scalable process.

Quantitative In Situ Monitoring of Cu-Atom Release by Cu2O Nanocatalysts under Photocatalytic CO2 Reduction Conditions: New Insights into the Photocorrosion Mechanism.

Cu2O is among the most promising photocatalysts for CO2 reduction, however its photocorrosion remains a standalone challenge. Herein, we present an in situ study of the release of Cu ions from Cu2O nanocatalysts under photocatalytic conditions in the presence of HCO3 as a catalytic substrate in H2O. The Cu-oxide nanomaterials were produced by Flame Spray Pyrolysis (FSP) technology. Using Electron Paramagnetic Resonance (EPR) spectroscopy in tandem with analytical Anodic Stripping Voltammetry (ASV), we monitored in situ the Cu2+ atom release from the Cu2O nanoparticles in comparison with CuO nanoparticles under photocatalytic conditions. Our quantitative, kinetic data show that light has detrimental effect on the photocorrosion of Cu2O and ensuing Cu2+ ion release in the H2O solution, up to 15.7% of its mass. EPR reveals that HCO3 acts as a ligand of the Cu2+ ions, promoting the liberation of {HCO3-Cu} complexes in solution from Cu2O, up to 27% of its mass. HCO3 alone exerted a marginal effect. XRD data show that under prolonged irradiation, part of Cu2+ ions can reprecipitate on the Cu2O surface, creating a passivating CuO layer that stabilizes the Cu2O from further photocorrosion. Including isopropanol as a hole scavenger has a drastic effect on the photocorrosion of Cu2O nanoparticles and suppresses the release of Cu2+ ions to the solution. Methodwise, the present data exemplify that EPR and ASV can be useful tools to help quantitatively understand the solid-solution interface photocorrosion phenomena for Cu2O.

In Tandem Control of La-Doping and CuO-Heterojunction on SrTiO3 Perovskite by Double-Nozzle Flame Spray Pyrolysis: Selective H2 vs. CH4 Photocatalytic Production from H2O/CH3OH.

ABO3 perovskites offer versatile photoactive nano-templates that can be optimized towards specific technologies, either by means of doping or via heterojunction engineering. SrTiO3 is a well-studied perovskite photocatalyst, with a highly reducing conduction-band edge. Herein we present a Double-Nozzle Flame Spray Pyrolysis (DN-FSP) technology for the synthesis of high crystallinity SrTiO3 nanoparticles with controlled La-doping in tandem with SrTiO3/CuO-heterojunction formation. So-produced La:SrTiO3/CuO nanocatalysts were optimized for photocatalysis of H2O/CH3OH mixtures by varying the La-doping level in the range from 0.25 to 0.9%. We find that, in absence of CuO, the 0.9La:SrTiO3 material achieved maximal efficient photocatalytic H2 production, i.e., 12 mmol g-1 h-1. Introduction of CuO on La:SrTiO3 enhanced selective production of methane CH4. The optimized 0.25La:SrTiO3/0.5%CuO catalyst achieved photocatalytic CH4 production of 1.5 mmol g-1 h-1. Based on XRD, XRF, XPS, BET, and UV-Vis/DRS data, we discuss the photophysical basis of these trends and attribute them to the effect of La atoms in the SrTiO3 lattice regarding the H2-production, plus the effect of interfacial CuO on the promotion of CH4 production. Technology-wise this work is among the first to exemplify the potential of DN-FSP for scalable production of complex nanomaterials such as La:SrTiO3/CuO with a diligent control of doping and heterojunction in a single-step synthesis.

MOF-Derived Defective Co3O4 Nanosheets in Carbon Nitride Nanocomposites for CO2 Photoreduction and H2 Production.

In photocatalysis, especially in CO2 reduction and H2 production, the development of multicomponent nanomaterials provides great opportunities to tune many critical parameters toward increased activity. This work reports the development of tunable organic/inorganic heterojunctions comprised of cobalt oxides (Co3O4) of varying morphology and modified carbon nitride (CN), targeting on optimizing their response under UV-visible irradiation. MOF structures were used as precursors for the synthesis of Co3O4. A facile solvothermal approach allowed the development of ultrathin two-dimensional (2D) Co3O4 nanosheets (Co3O4-NS). The optimized CN and Co3O4 structures were coupled forming heterojunctions, and the content of each part was optimized. Activity was significantly improved in the nanocomposites bearing Co3O4-NS compared with the corresponding bulk Co3O4/CN composites. Transient absorption spectroscopy revealed a 100-fold increase in charge carrier lifetime on Co3O4-NS sites in the composite compared with the bare Co3O4-NS. The improved photocatalytic activity in H2 production and CO2 reduction is linked with (a) the larger interface imposed from the matching 2D structure of Co3O4-NS and the planar surface of CN, (b) improvements in charge carrier lifetime, and (c) the enhanced CO2 adsorption. The study highlights the importance of MOF structures used as precursors in forming advanced materials and the stepwise functionalization of the individual parts in nanocomposites for the development of materials with superior activity.

Control of monomeric Vo's versus Vo clusters in ZrO2-x for solar-light H2 production from H2O at high-yield (millimoles gr-1 h-1).

Pristine zirconia, ZrO2, possesses high premise as photocatalyst due to its conduction band energy edge. However, its high energy-gap is prohibitive for photoactivation by solar-light. Currently, it is unclear how solar-active zirconia can be designed to meet the requirements for high photocatalytic performance. Moreover, transferring this design to an industrial-scale process is a forward-looking route. Herein, we have developed a novel Flame Spray Pyrolysis process for generating solar-light active nano-ZrO2-x via engineering of lattice vacancies, Vo. Using solar photons, our optimal nano-ZrO2-x can achieve milestone H2-production yield, > 2400 µmolg-1 h-1 (closest thus, so far, to high photocatalytic water splitting performance benchmarks). Visible light can be also exploited by nano-ZrO2-x at a high yield via a two-photon process. Control of monomeric Vo versus clusters of Vo's is the key parameter toward Highly-Performing-Photocatalytic ZrO2-x. Thus, the reusable and sustainable ZrO2-x catalyst achieves so far unattainable solar activated photocatalysis, under large scale production.