2.3. Evaluation of Photocatalytic Water Splitting 6507 2.3.1. Photocatalytic Activity 6507 2.3.2. Photocatalytic Stability 6507 3. UV-Active Photocatalysts for Water Splitting 6507 3.1. d0 Metal Oxide Photocatalyts 6507 3.1.1. Ti-, Zr-Based Oxides 6507 3.1.2. Nb-, Ta-Based Oxides 6514 3.1.3. W-, Mo-Based Oxides 6517 3.1.4. Other d0 Metal Oxides 6518 3.2. d10 Metal Oxide Photocatalyts 6518 3.3. f0 Metal Oxide Photocatalysts 6518 3.4. Nonoxide Photocatalysts 6518 4. Approaches to Modifying the Electronic Band Structure for Visible-Light Harvesting 6519

Semiconductor-based Photocatalytic Hydrogen Generation

Rod Borup is a Team Leader in the fuel cell program at Los Alamos National Lab in Los Alamos, New Mexico. He received his B.S.E. in Chemical Engineering from the University of Iowa in 1988 and his Ph.D. from the University of Washington in 1993. He has worked on fuel cell technology since 1994, working in the areas of hydrogen production and PEM fuel cell stack components. He has been awarded 12 U.S. patents, authored over 40 papers related to fuel cell technology, and presented over 50 oral papers at national meetings. His current main research area is related to water transport in PEM fuel cells and PEM fuel cell durability. Recently, he was awarded the 2005 DOE Hydrogen Program R&D Award for the most significant R&D contribution of the year for his team's work in fuel cell durability and was the Principal Investigator for the 2004 Fuel Cell Seminar (San Antonio, TX, USA) Best Poster Award. Jeremy Meyers is an Assistant Professor of materials science and engineering and mechanical engineering at the University of Texas at Austin, where his research focuses on the development of electrochemical energy systems and materials. Prior to joining the faculty at Texas, Jeremy workedmore » as manager of the advanced transportation technology group at UTC Power, where he was responsible for developing new system designs and components for automotive PEM fuel cell power plants. While at UTC Power, Jeremy led several customer development projects and a DOE-sponsored investigation into novel catalysts and membranes for PEM fuel cells. Jeremy has coauthored several papers on key mechanisms of fuel cell degradation and is a co-inventor of several patents. In 2006, Jeremy and several colleagues received the George Mead Medal, UTC's highest award for engineering achievement, and he served as the co-chair of the Gordon Research Conference on fuel cells. Jeremy received his Ph.D. in Chemical Engineering from the University of California at Berkeley and holds a Bachelor's Degree in Chemical Engineering from Stanford University. Bryan Pivovar received his B.S. in Chemical Engineering from the University of Wisconsin in 1994. He completed his Ph.D. in Chemical Engineering at the University of Minnesota in 2000 under the direction of Profs. Ed Cussler and Bill Smyrl, studying transport properties in fuel cell electrolytes. He continued working in the area of polymer electrolyte fuel cells at Los Alamos National Laboratory as a post-doc (2000-2001), as a technical staff member (2001-2005), and in his current position as a team leader (2005-present). In this time, Bryan's research has expanded to include further aspects of fuel cell operation, including electrodes, subfreezing effects, alternative polymers, hydroxide conductors, fuel cell interfaces, impurities, water transport, and high-temperature membranes. Bryan has served at various levels in national and international conferences and workshops, including organizing a DOE sponsored workshop on freezing effects in fuel cells and an ARO sponsored workshop on alkaline membrane fuel cells, and he was co-chair of the 2007 Gordon Research Conference on Fuel Cells. Minoru Inaba is a Professor at the Department of Molecular Science and Technology, Faculty of Engineering, Doshisha University, Japan. He received his B.Sc. from the Faculty of Engineering, Kyoto University, in 1984 and his M.Sc. in 1986 and his Dr. Eng. in 1995 from the Graduate School of Engineering, Kyoto University. He has worked on electrochemical energy conversion systems including fuel cells and lithium-ion batteries at Kyoto University (1992-2002) and at Doshisha University (2002-present). His primary research interest is the durability of polymer electrolyte fuel cells (PEFCs), in particular, membrane degradation, and he has been involved in NEDO R&D research projects on PEFC durability since 2001. He has authored over 140 technical papers and 30 review articles. Kenichiro Ota is a Professor of the Chemical Energy Laboratory at the Graduate School of Engineering, Yokohama National University, Japan. He received his B.S.E. in Applied Chemistry from the University of Tokyo in 1968 and his Ph.D. from the University of Tokyo in 1973. He has worked on hydrogen energy and fuel cells since 1974, working on materials science for fuel cells and water electrolysis. He has published more than 150 original papers, 70 review papers, and 50 scientific books. He is now the president of the Hydrogen Energy Systems Society of Japan, the chairman of the Fuel Cell Research Group of the Electrochemical Society of Japan, and the chairman of the National Committee for the Standardization of the Stationary Fuel Cells. ABSTRACT TRUNCATED« less

Scientific aspects of polymer electrolyte fuel cell durability and degradation.

Graphene, emerging as a true 2-dimensional material, has received increasing attention due to its unique physicochemical properties (high surface area, excellent conductivity, high mechanical strength, and ease of functionalization and mass production). This article selectively reviews recent advances in graphene-based electrochemical sensors and biosensors. In particular, graphene for direct electrochemistry of enzyme, its electrocatalytic activity toward small biomolecules (hydrogen peroxide, NADH, dopamine, etc.), and graphenebased enzyme biosensors have been summarized in more detail; Graphene-based DNA sensing and environmental analysis have been discussed. Future perspectives in this rapidly developing field are also discussed.

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Graphene Based Electrochemical Sensors and Biosensors: A Review

Because of the remarkably high theoretical energy output, metal–air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal–air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal–air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic–organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal–air batteries (219 references).

Metal–air batteries: from oxygen reduction electrochemistry to cathode catalysts

Advances in the development of novel cobalt Fischer-Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels.

Gold-Modified Mo2C Nanoparticles Supported on Nitrogen-Doped Carbon Nanotubes for Electrochemical Nitrogen Fixation

A new method of producing fuel from biological oils and fats is provided, which comprises the following steps: (a) proceeding with a catalytic cracking-deoxygenation reaction for the biological oils and fats under heating in the presence of a cracking-deoxygenation catalyst; (b) mixing the product of step (a) with hydrogen gas; and (c) proceeding with a catalytic hydrodeoxygenation reaction for the mixture from step (b) under heating in the presence of a hydrodeoxygenation catalyst. By means of the method of the present invention, clean fuel produced by using biological oils and fats as raw materials is compatible with the fuel composition produced from crude oil refining.

Method for preparing fuel by using biological oils and fats

The well-dispersed Ni-LTA-derived catalysts with high-density Ni sites were fabricated by the ion-exchanged method, where the degraded LTA structure as a sacrificial component promoted the dispersion of Ni sites. As Ni content reached 11.6 wt%, an excellent catalyst efficiency (0.075 molC3/(gcat·h)) and an outstanding propylene consumption rate on a per Ni basis (38.3 molC3/(molNi·h)) with ~100% selectivity to oligomers containing 75.1% of C6 were obtained for propylene dimerization under mild conditions (70 °C, 2.5 MPa and WHSV = 3.6 h−1). Moreover, it has been proposed that the three-coordinated Ni2+ ion in a trigonal structure is the active site. The uniform coordinatively unsaturated Ni2+ ion in the ion-exchanged Ni-LTA catalysts, presenting a strong Lewis acid concentration, boosts the catalytic activity for the propylene dimerization, whereas NiO nanoparticles are confirmed to be spectators for the reaction. The understanding of Ni active sites promotes the rational design of improved catalysts for the dimerization of light olefins. 

Identification of uniform high-density isolated Ni active sites on LTA zeolite for propylene dimerization

In this study, the conceptual process flowsheet was developed and the economic feasibility of woody biomass conversion to biofuel as feedstock was analysed by considering several promising experimental processes for lignin depolymerization, such as hydrodeoxygenation and hydrogenolysis, along with lignocellulosic biomass fractionation processes. The engineering simulation process toward the commercial production of bio-gasoline from lignocellulosic biomass using SuperPro Designer® was modeled. The compatibility of the end products with the current gasoline specifications was evaluated and various blending options were investigated to meet the octane number and Reid vapor pressure requirement of the product. The economic potential of the simulated engineering process was then evaluated from an economic perspective. The operating costs and capital investment of three scenario using three different catalytic systems were estimated and discussed to assess of the potential of commercializing of woody biomass valorization process. The main potential market segments were identified, including the process by-products such as xylose and cellulose pulp. From the economic evaluation study, it was found that selling the biomass fractionation products alone does have a greater profit than valorization of lignin to produce bio-gasoline, with net present value of RMB 22,653,000 and RMB 177,000, respectively at the same return on investment if the plant is set up in Hong Kong. It was also found that catalysts play a pivotal role in determination of the profitability in the valorization process, not only because of the price of the catalyst, but also the product distributions obtained with various types of it. To obtain the same gross profit, the sale price of bio-gasoline has to be set higher with platinum catalysts than with ruthenium catalysts (nearly 10 folds). Thus, catalyst development and process improvement are crucial in the establishment of bio-based circular economy.

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Economic feasibility of gasoline production from lignocellulosic wastes in Hong Kong

A computational examination of the phosphine-catalyzed domino reaction of α-benzyl allenoate with 5-phenylmethylene thiazolone has been carried out at the SMD(toluene)M06-2X/6-311+G(d,p)//M06-2X/6-31G(d) level. Various possible reaction pathways have been located and compared. Computations show that the preferred mechanism consists of four reaction steps: (I) the nucleophilic attack of phosphine catalyst to α-benzyl allenoate and generation of dienolate intermediate; (II) the nucleophilic conjugate addition to 5-phenylmethylene thiazolone; (III) the intramolecular cyclization, and (IV) the liberation of catalyst. The first step is the rate-determining step with an overall free energy barrier of 29.4 kcal/mol, and the second step is found to be the stereoselectivity-determining step. The predicted high enantioselectivities are in good agreement with the experimental observations. The present study should be useful for understanding this kind of reaction in the future.

Mechanisms and stereoselectivities of phosphine-catalyzed domino reaction of α-benzyl allenoate with 5-phenylmethylene thiazolone: a computational investigation

Changhai Liang

Papers

Gold-Modified Mo2C Nanoparticles Supported on Nitrogen-Doped Carbon Nanotubes for Electrochemical Nitrogen Fixation

Method for preparing fuel by using biological oils and fats

Identification of uniform high-density isolated Ni active sites on LTA zeolite for propylene dimerization

Economic feasibility of gasoline production from lignocellulosic wastes in Hong Kong

Mechanisms and stereoselectivities of phosphine-catalyzed domino reaction of α-benzyl allenoate with 5-phenylmethylene thiazolone: a computational investigation