Scientific studies on photocatalysis started about two and a half decades ago. Titanium dioxide (TiO 2 ), which is one of the most basic materials in our daily life, has emerged as an excellent photocatalyst material for environmental purification. In this review, current progress in the area of TiO 2 photocatalysis, mainly photocatalytic air purification, sterilization and cancer therapy are discussed together with some fundamental aspects. A novel photoinduced superhydrophilic phenomenon involving TiO 2 and its applications are presented.

/pdf/titanium-dioxide-photocatalysis-4yiwrh1scn.pdf

Titanium dioxide photocatalysis

Abstract Scientific studies on photocatalysis started about two and a half decades ago. Titanium dioxide (TiO 2 ), which is one of the most basic materials in our daily life, has emerged as an excellent photocatalyst material for environmental purification. In this review, current progress in the area of TiO 2 photocatalysis, mainly photocatalytic air purification, sterilization and cancer therapy are discussed together with some fundamental aspects. A novel photoinduced superhydrophilic phenomenon involving TiO 2 and its applications are presented.

Titanium dioxide as photocatalysis

ion. The oxidative addition mechanism was originally proposed22i because of the lack of a strong rate dependence on polar factors and on the acidity of the medium. Later, however, the electrophilic substitution mechanism also was proposed. Recently, the oxidative addition mechanism was confirmed by investigations into the decomposition and protonolysis of alkylplatinum complexes, which are the reverse of alkane activation. There are two routes which operate in the decomposition of the dimethylplatinum(IV) complex Cs2Pt(CH3)2Cl4. The first route leads to chloride-induced reductive elimination and produces methyl chloride and methane. The second route leads to the formation of ethane. There is strong kinetic evidence that the ethane is produced by the decomposition of an ethylhydridoplatinum(IV) complex formed from the initial dimethylplatinum(IV) complex. In D2O-DCl, the ethane which is formed contains several D atoms and has practically the same multiple exchange parameter and distribution as does an ethane which has undergone platinum(II)-catalyzed H-D exchange with D2O. Moreover, ethyl chloride is formed competitively with H-D exchange in the presence of platinum(IV). From the principle of microscopic reversibility it follows that the same ethylhydridoplatinum(IV) complex is the intermediate in the reaction of ethane with platinum(II). Important results were obtained by Labinger and Bercaw62c in the investigation of the protonolysis mechanism of several alkylplatinum(II) complexes at low temperatures. These reactions are important because they could model the microscopic reverse of C-H activation by platinum(II) complexes. Alkylhydridoplatinum(IV) complexes were observed as intermediates in certain cases, such as when the complex (tmeda)Pt(CH2Ph)Cl or (tmeda)PtMe2 (tmeda ) N,N,N′,N′-tetramethylenediamine) was treated with HCl in CD2Cl2 or CD3OD, respectively. In some cases H-D exchange took place between the methyl groups on platinum and the, CD3OD prior to methane loss. On the basis of the kinetic results, a common mechanism was proposed to operate in all the reactions: (1) protonation of Pt(II) to generate an alkylhydridoplatinum(IV) intermediate, (2) dissociation of solvent or chloride to generate a cationic, fivecoordinate platinum(IV) species, (3) reductive C-H bond formation, producing a platinum(II) alkane σ-complex, and (4) loss of the alkane either through an associative or dissociative substitution pathway. These results implicate the presence of both alkane σ-complexes and alkylhydridoplatinum(IV) complexes as intermediates in the Pt(II)-induced C-H activation reactions. Thus, the first step in the alkane activation reaction is formation of a σ-complex with the alkane, which then undergoes oxidative addition to produce an alkylhydrido complex. Reversible interconversion of these intermediates, together with reversible deprotonation of the alkylhydridoplatinum(IV) complexes, leads to multiple H-D exchange

Activation of c-h bonds by metal complexes

Photophysics, photochemistry and solar energy conversion with tris(bipyridyl)ruthenium(II) and its analogues

The chemistry of copper is extremely rich because it can easily access Cu0, CuI, CuII, and CuIII oxidation states allowing it to act through one-electron or two-electron processes. As a result, both radical pathways and powerful two-electron bond forming pathways via organmetallic intermediates, similar to those of palladium, can occur. In addition, the different oxidation states of copper associate well with a large number of different functional groups via Lewis acid interactions or π-coordination. In total, these feature confer a remarkably broad range of activities allowing copper to catalyze the oxidation and oxidative union of many substrates.

Oxygen is a highly atom economical, environmentally benign, and abundant oxidant, which makes it ideal in many ways.1 The high activation energies in the reactions of oxygen require that catalysts be employed.2 In combination with molecular oxygen, the chemistry of copper catalysis increases exponentially since oxygen can act as either a sink for electrons (oxidase activity) and/or as a source of oxygen atoms that are incorporated into the product (oxygenase activity). The oxidation of copper with oxygen is a facile process allowing catalytic turnover in net oxidative processes and ready access to the higher CuIII oxidation state, which enables a range of powerful transformations including two-electron reductive elimination to CuI. Molecular oxygen is also not hampered by toxic byproducts, being either reduced to water, occasionally via H2O2 (oxidase activity) or incorporated into the target structure with high atom economy (oxygenase activity). Such oxidations using oxygen or air (21% oxygen) have been employed safely in numerous commodity chemical continuous and batch processes.3

However, batch reactors employing volatile hydrocarbon solvents require that oxygen concentrations be kept low in the head space (typically <5–11%) to avoid flammable mixtures, which can limit the oxygen concentration in the reaction mixture.4,5,6 A number of alternate approaches have been developed allowing oxidation chemistry to be used safely across a broader array of conditions. For example, use of carbon dioxide instead of nitrogen as a diluent leads to reduced flammability.5 Alternately, water can be added to moderate the flammability allowing even pure oxygen to be employed.6 New reactor designs also allow pure oxygen to be used instead of diluted oxygen by maintaining gas bubbles in the solvent, which greatly improves reaction rates and prevents the build up of higher concentrations of oxygen in the head space.4a,7 Supercritical carbon dioxide has been found to be advantageous as a solvent due its chemical inertness towards oxidizing agents and its complete miscibility with oxygen or air over a wide range of temperatures.8 An number of flow technologies9 including flow reactors,10 capillary flow reactors,11 microchannel/microstructure structure reactors,12 and membrane reactors13 limit the amount of or afford separation of hydrocarbon/oxygen vapor phase thereby reducing the potential for explosions.

Enzymatic oxidizing systems based upon copper that exploit the many advantages and unique aspects of copper as a catalyst and oxygen as an oxidant as described in the preceding paragraphs are well known. They represent a powerful set of catalysts able to direct beautiful redox chemistry in a highly site-selective and stereoselective manner on simple as well as highly functionalized molecules. This ability has inspired organic chemists to discover small molecule catalysts that can emulate such processes. In addition, copper has been recognized as a powerful catalyst in several industrial processes (e.g. phenol polymerization, Glaser-Hay alkyne coupling) stimulating the study of the fundamental reaction steps and the organometallic copper intermediates. These studies have inspiried the development of nonenzymatic copper catalysts. For these reasons, the study of copper catalysis using molecular oxygen has undergone explosive growth, from 30 citations per year in the 1980s to over 300 citations per year in the 2000s.

A number of elegant reviews on the subject of catalytic copper oxidation chemistry have appeared. Most recently, reviews provide selected coverage of copper catalysts14 or a discussion of their use in the aerobic functionalization of C–H bonds.15 Other recent reviews cover copper and other metal catalysts with a range of oxidants, including oxygen, but several reaction types are not covered.16 Several other works provide a valuable overview of earlier efforts in the field.17 This review comprehensively covers copper catalyzed oxidation chemistry using oxygen as the oxidant up through 2011. Stoichiometric reactions with copper are discussed, as necessary, to put the development of the catalytic processes in context. Mixed metal systems utilizing copper, such as palladium catalyzed Wacker processes, are not included here. Decomposition reactions involving copper/oxygen and model systems of copper enzymes are not discussed exhaustively. To facilitate analysis of the reactions under discussion, the current mechanistic hypothesis is provided for each reaction. As our understanding of the basic chemical steps involving copper improve, it is expected that many of these mechanisms will evolve accordingly.

/pdf/aerobic-copper-catalyzed-organic-reactions-3ctljpvivz.pdf

Aerobic Copper-Catalyzed Organic Reactions

Existing methods of solar energy conversion are classified into 4 types: (1) thermal; (2) photophysical; (3) photochemical (including photoelectrolysis); and (4) photobiological (based on natural photosynthesis). Thermal conversion under direct conditions is an attractive method of conversion, but further conversion of heat into mechanical or electrical energy make thermal conversion seem unsuitable for large-scale use. Methods based on direct conversion into electrical or chemical energy of fossil fuels make them much more attractive for large scale use. For high efficiency of solar energy conversion, the development of moleuclar photocatalytic systems for solar energy conversion - a kind of simplified analog to natural photosynthesizing systems seem very attractive. For obtaining the highest possible efficiency, systems which do not involve free radicals and free atom intermediates appear to be the most advantageous. 345 references. (BLM)

Potential Methods and Perspectives of Solar Energy Conversion via Photocatalytic Processes

Complexes of Co, Cu and Fe with bipyridyl, and cobalt complexes with ammonia, ethylenediamine and oxyacids are shown to be efficient catalysts for water oxidation by Ru(bpy)
 3
 3+
 in both alkaline and weakly acidic media. Partially hydrolyzed forms of these complexes are assumed to be active.

Homogeneous catalysts for dioxygen evolution from water. Water oxidation by trisbipyridylruthenium(III) in the presence of cobalt, iron and copper complexes

The processes of vibrational relaxation, i.e., of the vibrational excitation and deexcitation of molecules, are known to play the key role in providing them with the energy needed to participate in chemical reactions. At present numerous experimental data are known concerning vibrational relaxation in gases, liquids, and solids. In contrast, vibrational relaxation on surfaces is much less studied. Fairly detailed experimental data have been obtained for vibrational relaxation processes with physically adsorbed small molecules [1–10]. At the same time, theoretical works in this field are rather numerous. However, most of these works cover only some specific aspects of the vibrational relaxation on surfaces rather than this phenomenon as a whole.

Vibrational Relaxation of Adsorbed Molecules. Mechanisms and Manifestations in Chemical Reactions on Solid Surfaces

Photochemistry is recognized to be important for various physicochemical processes in the atmosphere, such as formation of the ozone layer and smogs, degradation of waste substances, etc. [1]. However, up to the present the emphasis in atmospheric photochemistry has been mainly on the study of photochemical reactions that occur with molecules directly excited by absorption of light quanta. However, the major components and impurities of the earth's atmosphere (such as nitrogen, oxygen, water, carbon dioxide, methane, methane halides, etc.) are totally transparent to most solar radiation. Electronically excited states of these molecules are formed only upon absorption of vacuum ultraviolet light quanta with energy hv ≥ 5 eV (i.e., with wavelength λ ≤ 200 nm). Only a small portion of the energy of solar light is found in this spectral region. In other words, most of the energy of the solar flux cannot participate in such direct photochemical reactions.

Possible Impact of Heterogeneous Photocatalysis on the Global Chemistry of the Earth's Atmosphere

Role of vanadium alkylperoxo complexes in epoxidation of cyclohexene and oxidation of cyclohexane by organic hydroperoxides in the presence of bis (acetylacetonato)vanadyl

Kirill I Zamaraev

Papers

Potential Methods and Perspectives of Solar Energy Conversion via Photocatalytic Processes

Homogeneous catalysts for dioxygen evolution from water. Water oxidation by trisbipyridylruthenium(III) in the presence of cobalt, iron and copper complexes

Vibrational Relaxation of Adsorbed Molecules. Mechanisms and Manifestations in Chemical Reactions on Solid Surfaces

Possible Impact of Heterogeneous Photocatalysis on the Global Chemistry of the Earth's Atmosphere

Role of vanadium alkylperoxo complexes in epoxidation of cyclohexene and oxidation of cyclohexane by organic hydroperoxides in the presence of bis (acetylacetonato)vanadyl