The application of a novel fluidised photo reactor under UV-Visible and natural solar irradiation in the photocatalytic generation of hydrogen

With advancements in the development of visible light responsive catalysts for H2 production frequently being reported, photocatalytic water splitting has become an attractive method as a potential ‘solar fuel generator’. The development of novel photo reactors which can enhance the potential of such catalyst, however, is rarely reported. This is particularly important as many reactor configurations are mass transport limited, which in term limits the efficiency of more effective photocatalysts in larger scale applications. This paper describes the performance of a novel fluidised photo reactor for the production of H2 over two catalysts under UV-Visible light and natural solar illumination. Catalysts Pt-C3N4 and NaTaO3.La were dispersed in the reactor and the rate of H2 was determined by GC-TCD analysis of the gas headspace. The unit was an annular reactor constructed from stainless steel 316 and quartz glass with a propeller located in the base to control fluidisation of powder catalysts. Reactor properties such as propeller rotational speed were found to enhance the photo activity of the system through the elimination of mass transport limitations and increasing light penetration. The optimum conditions for H2 evolution were found to be a propeller rotational speed of 1035 rpm and 144 W of UV-Visible irradiation, which produced a rate of 89 µmol h-1 g-1 over Pt-C3N4. Solar irradiation was provided by the George Ellery Hale Solar Telescope, located at the California Institute of Technology.

Unidirectional suppression of hydrogen oxidation on oxidized platinum clusters

Solar-driven water splitting to produce hydrogen may be an ideal solution for global energy and environment issues. Among the various photocatalytic systems, platinum has been widely used to co-catalyse the reduction of protons in water for hydrogen evolution. However, the undesirable hydrogen oxidation reaction can also be readily catalysed by metallic platinum, which limits the solar energy conversion efficiency in artificial photosynthesis. Here we report that the unidirectional suppression of hydrogen oxidation in photocatalytic water splitting can be fulfilled by controlling the valence state of platinum; this platinum-based cocatalyst in a higher oxidation state can act as an efficient hydrogen evolution site while suppressing the undesirable hydrogen back-oxidation. The findings in this work may pave the way for developing other high-efficientcy platinum-based catalysts for photocatalysis, photoelectrochemistry, fuel cells and water-gas shift reactions.

Atmospheric pressure chemical vapour deposition of boron doped titanium dioxide for photocatalytic water reduction and oxidation

Boron-doped titanium dioxide (B-TiO) films were deposited by atmospheric pressure chemical vapour deposition of titanium(iv) chloride, ethyl acetate and tri-isopropyl borate on steel and fluorine-doped-tin oxide substrates at 500, 550 and 600 °C, respectively. The films were characterised using powder X-ray diffraction (PXRD), which showed anatase phase TiO at lower deposition temperatures (500 and 550 °C) and rutile at higher deposition temperatures (600 °C). X-ray photoelectron spectroscopy (XPS) showed a dopant level of 0.9 at% B in an O-substitutional position. The ability of the films to reduce water was tested in a sacrificial system using 365 nm UV light with an irradiance of 2 mW cm. Hydrogen production rates of B-TiO at 24 μL cm h far exceeded undoped TiO at 2.6 μL cm h. The B-TiO samples were also shown to be active for water oxidation in a sacrificial solution. Photocurrent density tests also revealed that B-doped samples performed better, with an earlier onset of photocurrent. © 2013 The Owner Societies.

An Investigation into the Optimum Thickness of Titanium Dioxide Thin Films Synthesized by Using Atmospheric Pressure Chemical Vapour Deposition for Use in Photocatalytic Water Oxidation

Twenty eight films of titanium dioxide of varying thickness were synthesised by using atmospheric pressure chemical vapour deposition (CVD) of titanium(IV) chloride and ethyl acetate onto glass and titanium substrates. Fixed reaction conditions at a substrate temperature of 660 degrees C were used for all depositions, with varying deposition times of 5-60 seconds used to control the thickness of the samples. A sacrificial electron acceptor system composed of alkaline sodium persulfate was used to determine the rate at which these films could photo-oxidise water in the presence of 365 nm light. The results of this work showed that the optimum thickness for CVD films on titanium substrates for the purposes of water oxidation was approximate to 200 nm, and that a platinum coating on the reverse of such samples leads to a five-fold increase in the observed rate of water oxidation.

Orange Zinc Germanate with Metallic Ge-Ge Bonds as a Chromophore-Like Center for Visible-Light-Driven Water Splitting

The efficiency of solar-energy-conversion devices depends on the absorption region and intensity of the photon collectors. Organic chromophores, which have been widely stabilized on inorganic semiconductors for light trapping, are limited by the interface between the chromophore and semiconductor. Herein we report a novel orange zinc germanate (Zn-Ge-O) with a chromophore-like structure, by which the absorption region can be dramatically expanded. Structural characterizations and theoretical calculations together reveal that the origin of visible-light response can be attributed to the unusual metallic Ge-Ge bonds which act in a similar way to organic chromophores. Benefiting from the enhanced light harvest, the orange Zn-Ge-O demonstrates superior capacity for solar-driven hydrogen production.

Irradiation of oxygen and water ices at by 4 keV singly and doubly charged ions; sputtering and molecular synthesis

The icy surfaces of dust grains in the Interstellar Medium and those of comets, satellites and Kuiper Belt Objects are continuously exposed tophoton and charged particle irradiation. These energetic particles maysputter and induce chemical changes in the ices and the underlyingsurfaces.In the present work 258 nm thick O2 and H2O ices were deposited at 10 K with the thickness measured by a laser interferometer method. Asimple model fit to the reflected laser intensity as measured by aphotodiode detector enabled the refractive index of the ices to bedetermined. The ices were then irradiated with various singly and doublycharged ions such as He+, 13C+, N+, O+ , Ar+, 13C2+, N2+ and O2+ at 4keV. The decrease in ice thickness as a function of ion dose wasmonitored by a laser interferometer and the model used to determine thesputtering yield as shown in Figure 1.In the case of O2 ice thesputtering yields increased with increasing ion mass in good agreementwith a model calculation [Fama, J, Shi, R.A Baragiola, Surface Sci.,602, 156 (2007)]. In the case of O2 ice, O2+ has a significant lowersputtering yield when compared to O+. The sputtering yields for O2 icewere found to be at least 9 times larger compared to those for H2O ice.For H2O ice the sputter yields for C, N and O ions were found todecrease with increasing mass. Doubly charged C, N and O ions which werefound to have the same sputtering yield as the singly charged ionswithin the experimental errors. A preliminary TPD study was carried outusing a QMS to detect the desorbed species from water ice afterirradiation by 6 × 10^15 ions of 13C+ and 13C2+. The formation of13CO and 13CO2 was observed with the yield of 13CO almost of a factor of100 larger than of 13CO2. This is in contrast to our earlier work whereonly CO¬2 was observed.

Stable Isolated Metal Atoms as Active Sites for Photocatalytic Hydrogen Evolution

The process of using solar energy to split water to produce hydrogen assisted by an inorganic semiconductor is crucial for solving our energy crisis and environmental problems in the future. However, most semiconductor photocatalysts would not exhibit excellent photocatalytic activity without loading suitable co-catalysts. Generally, the noble metals have been widely applied as co-catalysts, but always agglomerate during the loading process or photocatalytic reaction. Therefore, the utilization efficiency of the noble co-catalysts is still very low on a per metal atom basis if no obvious size effect exists, because heterogeneous catalytic reactions occur on the surface active atoms. Here, for the first time, we have synthesized isolated metal atoms (Pt, Pd, Rh, or Ru) stably by anchoring on TiO2, a model photocatalystic system, by a facile one-step method. The isolated metal atom based photocatalysts show excellent stability for H-2 evolution and can lead to a 6-13-fold increase in photocatalytic activity over the metal clusters loaded on TiO2 by the traditional method. Furthermore, the configurations of isolated atoms as well as the originality of their unusual stability were analyzed by a collaborative work from both experiments and theoretical calculations.

Simultaneous cellulose conversion and hydrogen production assisted by cellulose decomposition under UV-light photocatalysis

Photocatalytic conversion of cellulose to sugars and carbon dioxide with simultaneous production of hydrogen assisted by cellulose decomposition under UV or solar light irradiation was achieved upon immobilization of cellulose onto a TiO2 photocatalyst. This approach enables production of hydrogen from water without using valuable sacrificial agents, and provides the possibility for recovering sugars as liquid fuels.

Active sites on hydrogen evolution photocatalyst

Solar hydrogen production assisted with semiconductor materials is a promising way to provide alternative energy sources in the future. Such a photocatalytic reaction normally takes place on the active sites of the catalysts surface, and the identification of the active sites is crucial for understanding the photocatalytic reaction mechanism and further improving the photocatalytic efficiency. However, the active sites of model catalysts are still largely disputed because of their structural complexity. Conventionally, H-2 evolution from solar water splitting over Pt/TiO2 is widely deemed to take place on metallic Pt nanoparticles. Oppositely, we report through a combined experimental and theoretical approach, that metallic Pt nanoparticles have little contribution to the activity of photocatalytic H-2 evolution; the oxidized Pt species embedded on the TiO2 surface are the key active sites and primarily responsible for the activity of the hydrogen evolution Pt/TiO2 photocatalyst.

Suspension plasma sprayed coatings using dilute hydrothermally produced titania feedstocks for photocatalytic applications

Titanium dioxide coatings have potential applications including photocatalysts for solar assisted hydrogen production, solar water disinfection and self-cleaning windows. Herein, we report the use of suspension plasma spraying (SPS) for the deposition of conformal titanium dioxide coatings. The process utilises a nanoparticle slurry of TiO2 (ca. 6 and 12 nm respectively) in water, which is fed into a high temperature plasma jet (ca. 7000-20 000 K). This facilitated the deposition of adherent coatings of nanostructured titanium dioxide with predominantly anatase crystal structure. In this study, suspensions of nano-titanium dioxide, made via continuous hydrothermal flow synthesis (CHFS), were used directly as a feedstock for the SPS process. Coatings were produced by varying the feedstock crystallite size, spray distance and plasma conditions. The coatings produced exhibited ca. 90-100% anatase phase content with the remainder being rutile (demonstrated by XRD). Phase distribution was homogenous throughout the coatings as determined by micro-Raman spectroscopy. The coatings had a granular surface, with a high specific surface area and consisted of densely packed agglomerates interspersed with some melted material. All of the coatings were shown to be photoactive by means of a sacrificial hydrogen evolution test under UV radiation and compared favourably with reported values for CVD coatings and compressed discs of P25.

Interaction of water, hydrogen and their mixtures with SnO2 based materials: the role of surface hydroxyl groups in detection mechanisms

DRIFTS, TGA and resistance measurements have been used to study the mechanism of water and hydrogen interaction accompanied by a resistance change (sensor signal) of blank and Pd doped SnO2. It was found that a highly hydroxylated surface of blank SnO2 reacts with gases through bridging hydroxyl groups, whereas the Pd doped materials interact with hydrogen and water through bridging oxygen. In the case of blank SnO2 the sensor signal maximum towards H-2 in dry air (R-0/R-g) is observed at similar to 345 degrees C, and towards water, at similar to 180 degrees C, which results in high selectivity to hydrogen in the presence of water vapors (minor humidity effect). In contrast, on doping with Pd the response to hydrogen in dry air and to water occurred in the same temperature region (ca. 140 degrees C) leading to low selectivity with a high effect of humidity. An increase in water concentration in the gas phase changes the hydrogen interaction mechanism of Pd doped materials, while that of blank SnO2 is unchanged. The interaction of hydrogen with the catalyst doped SnO2 occurs predominantly through hydroxyl groups when the volumetric concentration of water in the gas phase is higher than that of H-2 by a factor of 1000.

Net energy analysis of a solar combi system with Seasonal Thermal Energy Store

EU targets require nearly zero energy buildings (NZEB) by 2020. However few monitored examples exist of how NZEB has been achieved in practise in individual residential buildings. This paper provides an example of how a low-energy building (built in 2006), has achieved nearly zero energy heating through the addition of a solar domestic hot water and space heating system (“combi system”) with a Seasonal Thermal Energy Store (STES). The paper also presents a cumulative life cycle energy and cumulative life cycle carbon analysis for the installation based on the recorded DHW and space heating demand in addition to energy payback periods and net energy ratios. In addition, the carbon and energy analysis is carried out for four other heating system scenarios including hybrid solar thermal/PV systems in order to obtain the optimal system from a carbon efficiency perspective.

Low energy C-13(+) and C-13(2+) ion irradiation of water ice

In this paper we report the results of the first experimental study of the irradiation of low temperature water ice (30 and 90 k) using low energy (4keV) C-13(+) and C-(2+) ions. (CO2)-C-13 and H2o2 were readily formed within the H2O ice with the product ion yield and grwoth rate observed to be highly dependent on both the sample temperature and the ion charge state.