Preparation of transparent silica as potential carrier for photocatalysts and photosynthetic bacteria is presented. SiO2 was obtained by sol-gel techniques using tetraethyl orthosilicate as precursor. Glycol and glycerol were used as solvents. The increase of porosity of the studied materials was reached by application of soluble and commercial potato starch as a filler. Calcinations at 825 K for 6 hours removed all organic compounds. The rate of gelation was enhanced applying hydrochloric acid. Different materials were obtained in a series of syntheses with different concentrations of individual components. Transparency of the obtained materials varied between 50 and 97% (in range of λ 350 - 800 nm). Surface area varied between 300 and 400 m2/g and pore diameter was 5 – 18 nm. Samples were studied with SEM, nitrogen sorption at 77 K and UV-Vis spectroscopy. The obtained transparent materials with occluded TiO2 or CaTiO3 were tested in photocatalytic splitting of water.

We examined LEDs as a cheap and test lamp source to simulate monochromatic laser radiation to help us cost out optics while evaluating materials for renewable fuels. The light source spectrum was recorded using a fiber optic spectrophotometer and a calibrated silicon photodiode was used to determine the intensity. Photon flux from the LEDs was recorded using actinometry. We chose CdS and Fe3O4 as photocatalysts. The as-prepared and annealed samples were characterised using X-Ray Diffraction, UV-Visible spectroscopy, UV-Visible Diffuse reflectance spectroscopy, Fourier Transform Infra-red spectroscopy, Attenuated Total Reluctance -FTIR spectroscopy, Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). CdS and Fe3O4 were evaluated for hydrogen evolution using DI water, sacrificial agents and an electron donor (methyl viologen) using three light sources (LEDs, sunlight and mercury vapour lamp). Products were collected by an inverted burette (Generation1), balloons with a B-14 adapter (Generation2) and septum cells (Generation3). Developing an analytical technique to quantify products continues to remain a challenge.

The combination of dwindling oil reserves and growing concerns over carbon dioxide emissions and associated climate change is driving the urgent development of routes to utilize renewable feedstocks as sustainable sources of fuels. Catalysis has a rich history of facilitating energy efficient selective molecular transformations and contributes to 90% of chemical manufacturing processes and to more than 20% of all industrial products. In a post-petroleum era catalysis will be central to overcoming the engineering and scientific barriers to economically feasible routes to bio-fuels. This article will highlight some of the recent developments in the development of solid acid and base catalysts for the transesterification of oils to biodiesel. Particular attention will be paid to the challenges faced when developing new catalysts and importance of considering the design of pore architectures to improve in-pore diffusion of bulky substrates.

Structural colors were obtained by the deposition of plant cell walls biopolymers films on reflective support. Multilayered xyloglucan(XG)/cellulose nanocrystals(CN) thin films were obtained by spin-assisted layer-by-layer assembly while arabinoxylan (AX) thin films were elaborated via the spin-coating of AX/melamine formaldehyde resin followed by a cross-linking step. The effects of aqueous solutions on the stability of the structural colors were evaluated. The films were subsequently used to detect cellulase and xylanase activities by the change in the colors due to the film degradation. This enzymatic assay method appeared to be about 150 more sensitive that a standard method. Moreover due its simplicity, the method could be used to detect other biomass-hydrolyzing enzymes and more generally for other heterocatalytic degradations of solid polymer layers.

The Ni-doped (CuIn)0.2Zn1.6S2 photocatalysts were prepared via a two-step ultrasonic-hydrothermal method under an environmental-friendly condition. XRD pattern profiles suggested that Ni2+ successfully doped into (CuIn)0.2Zn1.6S2 lattice. UV-Vis spectra indicated that the optical properties of the photocatalysts greatly depended on the amount of Ni doped. SEM images show that the samples were microspheres. The microsphere structures were gradually damaged with the increment of Ni doping amount. The photoactivity of (CuIn)0.2Zn1.6S2 was enhanced when Ni2+ was doped into the crystal structure. The H2 evolution performance over the prepared samples from inorganic/organic sacrificial solution was systematic investigated.

Progress in achieving improved performance in the generation and utilization of hydrogen depends on our ability to identify materials with optimized electrical and (photo)- electrochemical performance. Given their high volume fraction of interfaces, high chemical stability and versatility (ionic, electronic, optical property control), nanocrystalline electroceramic materials are of growing interest for advanced energy conversion and storage technologies. As grain size decreases towards the Debye length and grain boundaries come in closer proximity, space charge properties begin to dominate, resulting in modified charge transport. Through systematic variation of grain boundary properties by heterogeneous indiffusion of cations, the electronic and ionic carrier profiles in the space charge region may be altered. The relationships between space charge potential and defect profiles in the space charge regions are quantitatively analyzed, and implications for nano-ionic materials in thin film solid oxide fuel cells are discussed. From the standpoint of photoelectrochemical water splitting for hydrogen generation, optimizing the band gap, band alignments, and transport properties while retaining stability has remained a challenging objective. Novel nanocrystalline composite structures are discussed which exhibit features amenable to optimization of required properties and electrical measurements to determine key transport properties of titanium dioxide nanopowder, a photoanode material are introduced.

The goal in this study was to synthesize a lanthanum - nickel phase (Ruddlesden-Popper phases) La4Ni3O10. This material was prepared using a polymeric route. An easy synthesis method is presented in order to obtain an economical cathode material, which can be used in Solid Oxide Fuel Cells (SOFC). The polymeric precursors were prepared following the Castillo method. The originality of this work was to optimize the ratio HMTA/ metallic salts from 1 to 6. The obtained powders were characterized by thermal analysis; Differential Scanning Calorimetry (DSC Q10 Instrument TA), Thermogravimetric Analysis (TGA - Q50 Instrument TA-) and X-ray diffractometer (Bruker, D8 Advance diffractometer), in order to determine the crystallized phase. Experiments 5 and 6 did not present coagulation but after few days, solution 5 was transformed into a gel. Gels 2 to 5 were heated in order to obtain a solid material. These powders are characterized by thermogravimetric and thermo-differential methods. The powders obtained at 800, 900 and 1000°C were analyzed by X-ray diffraction and it was found that the temperature to get to the La4Ni3O10 phase was 1000ºC.

In this work, NiSx was deposited on FTO by chemical bath and worked as the inner layer in order to enhance the photocurrent of CdS film. It is found the unannealed CdS/NiSx had a higher photocurrent than unannealed CdS, but after annealing, the photocurrent of CdS/NiSx showed dramatical decrease. The mechanism was discussed in detail by UPS and current-potential curves.

Oxidation catalysis is a reaction necessary for the production of plastics and other materials that seem now essential to our everyday lives. Unfortunately, most oxidation processes suffer from poor selectivity or yields, creating unwanted byproducts and waste. In nature, oxidative enzymes like methane monooxygenase and the family of cytochromes provide a more selective method for oxidation of organic compounds. Of particular interest is the low temperature, selective oxidation of cellulosic biomass for the production of biofuels or other useful replacements for materials currently derived from petroleum feedstocks. An enzymatic approach could replace the high temperature pyrolysis technology in use today. A series of inorganic mimics of some oxidative enzymes, using transition metal – amino acid complexes encapsulated in large pore zeolites have been synthesized and examined as oxidation catalysts under benign conditions. Several of these demonstrate turnovers comparable to native enzymes in the reaction of model compounds for the oxidation of lignin and cellulose.

Rhenium-oxide-modified supported iridium nanoparticles on silica catalyzes direct hydrogenolysis of glycerol to 1,3-propanediol in an aqueous media. The selectivity to 1,3-propanediol at an initial stage reaches 67%. The yield of 1,3-propanediol reaches 38% at 81% conversion of glycerol. The characterization of catalyst shows that oxidized Re clusters are formed on Ir metal particles. The synergy between Ir metal and ReOx clusters enables the catalytic activity.

Hydrogen production from renewables such as bio-ethanol is one of the most promising processes for energy carriers in a sustainable way. In this work we review and compare two catalytic systems: one based on thermal activation over bimetallic catalysts (Rh-Pd/CeO2) and the other over photo-excited semiconductor catalysts (Au/TiO2 anatine, rutile and anatase/rutile). It is found that the hydrogen yield is far higher on the thermally activated catalysts (at 773K) when compared to that of the photo-exited catalysts (at room temperature); about 60 times. However, the photo-excited catalysts are a promising way to create a fully sustainable system for future applications if the complete removal of hydrogen atoms from water and ethanol are obtained at room temperature.

The US Department of Energy (DOE) hydrogen production research and development portfolio focuses on low-cost, highly efficient and environmentally friendly production technologies based on diverse, domestic resources. Within the DOE, work on hydrogen production technologies integrates basic and applied research, as well as technology development and demonstration. The integration of basic and applied research is of particular importance in “transformational” production technologies, such as photoelectrochemical (PEC) hydrogen production, where scientific advances are needed for achieving the long-term DOE performance and cost targets. In the case of renewable hydrogen production via PEC solar water splitting, high solar-to-hydrogen conversion efficiency has been demonstrated to date on the laboratory scale, but only with high-cost, low-durability material systems. In order to identify and develop the appropriate high-efficiency, low-cost, durable and scalable PEC material systems, research and development efforts in the DOE EERE (Energy Efficiency and Renewable Energy) Office have keyed in on specific focus areas, including: 1) the engineering of solar energy absorption properties in PEC semiconductor materials, such as the bandgap lowering in stable metal oxides as well as bandgap raising in nanostructured sulfide catalysts; 2) the engineering of PEC solid-liquid interfaces for optimal reaction rates and stability, such as surface nitrogenation in III-V semiconductor systems; 3) the standardization of PEC measurement and reporting methodologies, using national and international peer-review process, for facilitating research progress; and 4) the design and analysis of integrated PEC device and system configurations for scalable hydrogen production. As described in this presentation, all of these research and development areas rely heavily on collaborative efforts among academia, industry and national laboratory partners, utilizing state of the art resources in materials theory, synthesis, characterization and analysis. The collaboration extends nationally among research programs supported by the DOE EERE as well as Office of Science; and internationally via networking through the International Energy Agency’s Hydrogen Implementation Agreement Annex-26. Key and encouraging accomplishments resulting from the collaborative work are highlighted in this presentation.

The present work reports the renewable hydrogen production by an anaerobic photocatalytic reforming of formic acid over CdS sensitized Na2Ti2O4(OH)2 nanotubes. the Na2Ti2O4(OH)2 nanotube was prepared and charactered by X-ray diffraction, UV-visible absorption, transmission electron microscopy, etc. The activity of the catalyst in formic acid was investigated. The greatest photocatalytic reforming activity of formic acid occurs as the formic acid initial concentration is 20 v.%. A probable mechanism for the photocatalytic reforming process was proposed and discussed.

The direct methanol fuel cell (DMFC) is a promising power source for electronic applications due to its high efficiency and compactness. To improve the efficiency, many support materials have been developed. We investigated uniform graphene nanoflake films as a support for catalytic Pt nanoparticles in direct carbon monooxide and formic acid electro-oxidation. Pt nanoparticles were deposited on the surface of graphene films with chemical reduction method. Chemical functionalization of graphene with ethylenediamine enables Pt nanoparticles mobilize on graphene uniformly. By simply changing the loading amount of Pt precursor, various particle sizes were achieved. The particle size of Pt plays prominent role in fuel cell test. The electrochemically active surface area of different sample are 6.3 (5 wt% Pt/G), 4.1 (20 wt% Pt/G), and 3.0 (50 wt% Pt/G) cm2mg-1 corresponding to the particle size 3±1nm, 10±2nm, 20±2nm respectively. The results obtained are ascribed to a uniform network made of 2-4 nm Pt monolayer nanopaticles on the surface of graphene flakes. Graphene will play significant role in developing next-generation advanced Pt based fuel cells and their relevant electrodes in the field of energy.

Titanate nanotube (TNT) was prepared by alkaline hydrothermal method starting from TiO2 (P25), and then CdS-TNT was prepared for visible light harvesting by immersing TNT in Cd(CH3COO)2 and then (NH2)2CS aqueous solutions subsequently and heat treated at specialtemperature. After loading with Pt, photocatalytic reduction of gas phase CO2 with water vapor was carried out under UV-VIS and visible light irradiation. The results showed that the main reaction products were CH4, C2H4, C2H6 and H2, which were online characterized by gaschromatography when the flow rate of 5000 ppm CO2 is 0.35 ml/min. The hydrogenation process also realized under visible light illumination for Pt-CdS/TNT and producted 0.44 μmol/min CH4. The maximum yield of methane reached about 130 μmol/min when Pt-CdS/TNTwas irradiated with UV-Vis light. The time profile for production yield increased steadily with time up to about 6–7 h, then a decrease of the reaction rate occurred. It is suggested that thadsorption of intermediate products CO, O2 etc. on Pt and the oxidation of Pt might be the reasons for the photocatalytic reaction deterioration.

Concerns about the availability and long-term supply of petroleum-derived fuels have caused the search for alternative sources of energy. Liquid fuels will for some applications be necessary for an indefinite period of time. Therefore, defining relevant feedstocks, producing fuels from these feedstocks and the properties of these fuels are critical issues. Fuels powering compression-ignition (diesel) and turbine (jet) engines are among these liquid energy sources. Biodiesel, defined as the mono-alkyl esters of vegetable oils, animal fats or other triacylglycerol-based feedstocks plays a prominent role in this connection as alternative to petrodiesel fuels. Important issues facing biodiesel are feedstock supply as not enough vegetable oil is available to replace the whole petrodiesel market and the issue of fuel properties, especially cold flow and oxidative stability. The search for additional feedstocks coupled with the food vs fuel issue has increased interest in inedible oils derived from sources such as used cooking oils, jatropha and algae. However, biodiesel from these sources, as biodiesel derived from classical sources such as commodity vegetable oils, must meet performance criteria and this is not necessarily the case. Therefore, modifying the composition of biodiesel, i.e., its fatty ester profile, is a critical issue to enhance its use in the marketplace. Esters of specific fatty acids impart improved properties to biodiesel with esters of decanoic and palmitoleic acid displaying favorable properties for enrichment in biodiesel feedstocks. Renewable diesel is another fuel that can be obtained from triacylglycerol-based feedstocks. In its composition, i.e. alkane-type hydrocarbons, it more closely resembles petrodiesel fuel. While biodiesel is obtained from triacylglycerol-based feedstocks via a transesterification reaction using an alcohol in presence of a catalyst under mild conditions, renewable diesel can be obtained from such feedstocks via a hydrodeoxygenation reaction using hydrogen in presence of a catalyst under more severe conditions. Biodiesel and renewable diesel are compared regarding their production and properties and it is suggested that each fuel has a role to play in an alternative energy mix based on its properties.

The addition of Fe addition with suitable amount to Ni /Al2O3 catalyst showed higher catalytic performance than corresponding monometallic Ni and Fe catalysts in the steam reforming of tar from the pyrolysis of cedar wood. Characterization of the catalysts indicates the formation of the Ni-Fe alloys and the surface segregation of Fe atoms on the alloys, and it was also suggested that the structure was almost maintained during the reaction. The surface Fe atoms accept oxygen atom from steam and subsequently supply oxygen species to adsorbed carbonaceous species on neighboring surface Ni atoms, which is connected to the promotion of the steam reforming reaction of tar and the suppression of the coke formation.

Catalytic monoliths loaded with ZnO-supported Co-Fe catalysts were prepared in one step by the in situ urea method and tested in the ethanol steam reforming reaction to produce hydrogen. The most active and selective formulation was attained with a Fe/Co molar ratio between 0.05 and 0.1, which showed negligible amounts of methane among the reaction products, thus offering an active and selective material for the low-temperature steam reforming of ethanol for small-scale energy applications.

α-Fe2O3 nanorod arrays were fabricated by a low-temperature aqueous chemical growth (ACG) technique and followed by an annealing process. For the surface doping of α-Fe2O3 nanorods, β-FeOOH nanorods obtained via ACG were coated with a thin layer of Cr3+ precursor solution by spin coating, and then underwent the annealing treatment in air. Conducting polymer polypyrrole (PPy) decorated α-Fe2O3 nanorods were prepared by electrodeposition method using malic acid contained pyrrole aqueous solution. Primary results showed that the photocurrents of α-Fe2O3 nanorod array photoanodes were greatly enhanced by surface doping of Cr3+, as well as PPy decoration. This might be due to the retarded charge recombination and promoted surface reaction rate of photogenerated holes with water. Further investigation on surface modification of α-Fe2O3 nanorod array photoanodes is currently conducted in our group.

In this work a series of Eosin Y-ZnO(x%)/TiO2 were prepared. ZnO well dispersed on the surface of TiO2, which improves the adsorption of Eosin Y and the excited electron to transfer to the conduction band of TiO2. Therefore the visible light activity of 0.2%Pt-Eosin Y-ZnO(x%)/TiO2 is much higher than that of the 0.2%Pt-Eosin Y-TiO2 and 0.2%Pt-Eosin Y-ZnO. The 0.2%Pt-Eosin Y- ZnO(1.5%)/TiO2 has the highest visible light activity among the catalysts coupled with various ZnO amount, whose activity is increased by a factor of 3.5 compared to that of 0.2%Pt-Eosin Y-TiO2. It is proposed that, 0.2%Pt-Eosin Y-ZnO(1.5%)/TiO2 has the optimal trapping sites of carriers and thickness of the space-charge layer on the TiO2 particle surface, so these factors result a more efficient charge separation, an increased lifetime of the charge carriers, and the enhanced of hydrogen production .