This critical review shows the basis of photocatalytic water splitting and experimental points, and surveys heterogeneous photocatalyst materials for water splitting into H2 and O2, and H2 or O2 evolution from an aqueous solution containing a sacrificial reagent Many oxides consisting of metal cations with d0 and d10 configurations, metal (oxy)sulfide and metal (oxy)nitride photocatalysts have been reported, especially during the latest decade The fruitful photocatalyst library gives important information on factors affecting photocatalytic performances and design of new materials Photocatalytic water splitting and H2 evolution using abundant compounds as electron donors are expected to contribute to construction of a clean and simple system for solar hydrogen production, and a solution of global energy and environmental issues in the future (361 references)

Heterogeneous photocatalyst materials for water splitting

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

In the previous paper Ralph Brodd and Martin Winter described the different kinds of batteries and fuel cells. In this paper I will describe lithium batteries in more detail, building an overall foundation for the papers that follow which describe specific components in some depth and usually with an emphasis on the materials behavior. The lithium battery industry is undergoing rapid expansion, now representing the largest segment of the portable battery industry and dominating the computer, cell phone, and camera power source industry. However, the present secondary batteries use expensive components, which are not in sufficient supply to allow the industry to grow at the same rate in the next decade. Moreover, the safety of the system is questionable for the large-scale batteries needed for hybrid electric vehicles (HEV). Another battery need is for a high-power system that can be used for power tools, where only the environmentally hazardous Ni/ Cd battery presently meets the requirements. A battery is a transducer that converts chemical energy into electrical energy and vice versa. It contains an anode, a cathode, and an electrolyte. The anode, in the case of a lithium battery, is the source of lithium ions. The cathode is the sink for the lithium ions and is chosen to optimize a number of parameters, discussed below. The electrolyte provides for the separation of ionic transport and electronic transport, and in a perfect battery the lithium ion transport number will be unity in the electrolyte. The cell potential is determined by the difference between the chemical potential of the lithium in the anode and cathode, ∆G ) -EF. As noted above, the lithium ions flow through the electrolyte whereas the electrons generated from the reaction, Li ) Li+ + e-, go through the external circuit to do work. Thus, the electrode system must allow for the flow of both lithium ions and electrons. That is, it must be both a good ionic conductor and an electronic conductor. As discussed below, many electrochemically active materials are not good electronic conductors, so it is necessary to add an electronically conductive material such as carbon * To whom correspondence should be addressed. Phone and fax: (607) 777-4623. E-mail: stanwhit@binghamton.edu. 4271 Chem. Rev. 2004, 104, 4271−4301

http://www.chemie.uni-regensburg.de/Anorganische_Chemie/Vortrag/StudentenWS06-07/Vortrag_Amereller.pdf

Lithium Batteries and Cathode Materials

Since the discovery of mechanically exfoliated graphene in 2004, research on ultrathin two-dimensional (2D) nanomaterials has grown exponentially in the fields of condensed matter physics, material science, chemistry, and nanotechnology. Highlighting their compelling physical, chemical, electronic, and optical properties, as well as their various potential applications, in this Review, we summarize the state-of-art progress on the ultrathin 2D nanomaterials with a particular emphasis on their recent advances. First, we introduce the unique advances on ultrathin 2D nanomaterials, followed by the description of their composition and crystal structures. The assortments of their synthetic methods are then summarized, including insights on their advantages and limitations, alongside some recommendations on suitable characterization techniques. We also discuss in detail the utilization of these ultrathin 2D nanomaterials for wide ranges of potential applications among the electronics/optoelectronics, electrocat...

Recent Advances in Ultrathin Two-Dimensional Nanomaterials

The lithium storage properties of graphene nanosheet (GNS) materials as high capacity anode materials for rechargeable lithium secondary batteries (LIB) were investigated. Graphite is a practical anode material used for LIB, because of its capability for reversible lithium ion intercalation in the layered crystals, and the structural similarities of GNS to graphite may provide another type of intercalation anode compound. While the accommodation of lithium in these layered compounds is influenced by the layer spacing between the graphene nanosheets, control of the intergraphene sheet distance through interacting molecules such as carbon nanotubes (CNT) or fullerenes (C60) might be crucial for enhancement of the storage capacity. The specific capacity of GNS was found to be 540 mAh/g, which is much larger than that of graphite, and this was increased up to 730 mAh/g and 784 mAh/g, respectively, by the incorporation of macromolecules of CNT and C60 to the GNS.

Large reversible Li storage of graphene nanosheet families for use in rechargeable lithium ion batteries.

‐based perovskite oxides doped with Sr and Mg exhibit high ionic conductivity over a wide range of oxygen partial pressure. In this study, the stability of ‐based oxide was investigated. The ‐based oxide was found to be very stable in reducing, oxidizing, and atmospheres. Solid oxide fuel cells (SOFCs) using ‐based perovskite‐type oxide as the electrolyte were studied for use in intermediate‐temperature SOFCs. The power‐generation characteristics of cells were strongly affected by the electrodes. Both Ni and (Ln:rare earth) were suitable for use as anode and cathode, respectively. Rare‐earth cations in the Ln site of the Co‐based perovskite cathode also had a significant effect on the power‐generation characteristics. In particular, a high power density could be attained in the temperature range 973–1273 K by using a doped for the cathode. Among the examined alkaline earth cations, Sr‐doped exhibits the smallest cathodic overpotential resulting in the highest power density. The electrical conductivity of increased with increasing Sr doped into the Sm site and attained a maximum at . The cathodic overpotential and internal resistance of the cell exhibited almost the opposite dependence on the amount of doped Sr. Consequently, the power density of the cell was a maximum when was used as the cathode. For this cell, the maximum power density was as high as 0.58 W/cm2 at 1073 K, even though a 0.5 mm thick electrolyte was used. This study revealed that a ‐based oxide for electrolyte and a ‐based oxide for the cathode are promising components for SOFCs operating at intermediate temperature.

https://iopscience.iop.org/article/10.1149/1.1838783/pdf

Intermediate Temperature Solid Oxide Fuel Cells Using a New LaGaO3 Based Oxide Ion Conductor I. Doped as a New Cathode Material

It was found for the first time that controlling the charge density in oxide semiconductors with an acceptor was effective for improving the activity to photolysis of H2O. Although the photodecomposition activity of NiO supported on nondoped KTaO3 was negligibly small, doping small amount of acceptors such as tri- or tetravalent cations to KTaO3 increased the formation rate of H2 and O2. In particular, it was found that NiO supported on KTaO3 doped with 8 mol % Zr4+ exhibits higher activity to the photocatalytic decomposition of H2O than that of a well-known photocatalyst of Pt/TiO2 .

Effects of Acceptor Doping to KTaO3 on Photocatalytic Decomposition of Pure H2O

Oxide ion conductivity in Sr-doped La10Ge6O27 apatite oxide

Mixed electronic–oxide ionic conductivity and oxygen permeating property of Fe-, Co- or Ni-doped LaGaO3 perovskite oxide

Photoinduced reduction of CO2 by H2O to produce CH4 and CH3OH has been investigated on wellcharacterized standard TiO2 catalysts and on a Cu2+ loaded TiO2 catalyst. The efficiency of this photoreaction depends strongly on the kind of catalyst and the ratio of H2O to CO2. Anatase TiO2, which has a large band gap and numerous surface OH groups, shows high efficiency for photocatalytic CH4 formation. Photogenerated Ti3+ ions, H and CH3 radicals are observed as reactive intermediates, by ESR at 77 K. Cu-loading of the small, powdered TiO2 catalyst (Cu/TiO2) brings about additional formation of CH3OH. XPS studies suggest that Cu+ plays a significant role in CH3OH formation.

Hiroyasu Nishiguchi

Papers

Intermediate Temperature Solid Oxide Fuel Cells Using a New LaGaO3 Based Oxide Ion Conductor I. Doped as a New Cathode Material

Effects of Acceptor Doping to KTaO3 on Photocatalytic Decomposition of Pure H2O

Oxide ion conductivity in Sr-doped La10Ge6O27 apatite oxide

Mixed electronic–oxide ionic conductivity and oxygen permeating property of Fe-, Co- or Ni-doped LaGaO3 perovskite oxide

Photocatalytic reduction of CO2 with H2O on TiO2 and Cu/TiO2 catalysts