Novel photocatalyst-based colourimetric indicator for oxygen

The preparation and characterisation of a novel, UV-activated solvent-based, colourimetric indicator for O-2 is described, comprising a redox dye (methylene blue, MB), semiconductor photocatalyst (TiO2), and a sacrificial electron donor (SED), all dispersed/dissolved in a polymer medium (sulfonated polystyrene, SPS). Upon exposure, the indicator is readily photobleached as the MB is converted into its oxygen-sensitive, leuco form, LMB. Unlike its water-based counterpart, the recovery of the original colour is very slow (ca. 5 days cf. 6 min), probably due to the largely hydrophobic nature of the polymer encapsulation medium. The kinetics of film photobleaching appear to fit very well, in terms of: irradiance, [TiO2] and [MB], to the usual Langmuir-Hinshelwood type equation associated with a photocatalytic process. The glycerol appears not only to function as a SED, but also a plasticizer and medium for dye dissolution. The kinetics of colour recovery of the photobleached film appear directly dependent upon the ambient level of O-2 but shows a more complex dependence upon the relative humidity, RH. The photobleached film does not recover any of its colour over a 24 h period if the RH

Photochemical reduction of oxygen adsorbed to nanocrystalline TiO2 films: A transient absorption and oxygen scavenging study of different TiO2 preparations

Transient absorption spectroscopy (TAS) has been used to study the interfacial electron-transfer reaction between photogenerated electrons in nanocrystalline titanium dioxide (TiO2) films and molecular oxygen. TiO2 films from three different starting materials (TiO2 anatase colloidal paste and commercial anatase/rutile powders Degussa TiO2 P25 and VP TiO2 P90) have been investigated in the presence of ethanol as a hole scavenger. Separate investigations on the photocatalytic oxygen consumption by the films have also been performed with an oxygen membrane polarographic detector. Results show that a correlation exists between the electron dynamics of oxygen consumption observed by TAS and the rate of oxygen consumption through the photocatalytic process. The highest activity and the fastest oxygen reduction dynamics were observed with films fabricated from anatase TiO2 colloidal paste. The use of TAS as a tool for the prediction of the photocatalytic activities of the materials is discussed. TAS studies indicate that the rate of reduction of molecular oxygen is limited by interfacial electron-transfer kinetics rather than by the electron trapping/detrapping dynamics within the TiO2 particles.

Kinetics and mechanism of a macrocyclic chromium(III) complex oxidation to chromium(IV) by hexacyanoferrate(III) in strongly alkaline media

Oxidation of the macrocyclic Cr(III) complex cis-[Cr(cycb)(OH)(2)](+), where cycb = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, by an excess of the hexacyanoferrate( III) in basic solution, slowly produces Cr(V) species. These species, detected using e.p.r. spectroscopy, are stable under ambient conditions for many hours, and the hyperfine structure of the e.p.r. spectrum is consistent with the interaction of the d-electron with four equivalent nitrogen nuclei. Electro-spray ionization mass spectrometry suggests a concomitant oxidation of the macrocyclic ligand, in which double bonds and double bonded oxygen atoms have been introduced. By comparison basic chromate(III) solutions are oxidized rapidly to chromate(VI) by hexacyanoferrate(III) without any detectable generation of stable Cr(V) intermediates.

Light-driven oxygen scavenging by titania/polymer nanocomposite films

We demonstrate that UV illumination of nanocrystalline TiO2 films in the presence of excess organic hole scavengers can result in the deoxygenation of a closed environment. The kinetics of deoxygenation are investigated under continuous UV illumination as a function of film preparation and hole scavenger employed. Optimum deoxygenation is observed using methanol as a hole scavenger, although efficient deoxygenation is also observed for a range of different polymer/TiO2 nanocomposite films deposited on glass and plastic substrates. Transient absorption spectroscopy is used to probe the kinetics of the deoxygenation reaction, focusing on the kinetics of the reduction of oxygen by photogenerated TiO2 electrons. Under aerobic conditions, this oxygen reduction reaction is observed to exhibit first order kinetics with a rate constant of 70 s(-1), more than one order of magnitude faster than alternative reaction pathways for the photogenerated electrons. These observations are discussed in terms of the Langmuir-Hinshelwood equation for photocatalytic action. (C) 2004 Elsevier B.V. All rights reserved.

Kinetics and mechanism of a fast leuco-Methylene Blue oxidation by copper(II)-halide species in acidic aqueous media

The kinetics of a fast leuco-Methylene Blue (LMB) re-oxidation to Methylene Blue (MB) by copper(II)-halide (Cl-, Br-) complexes in acidic aqueous media has been studied spectrophotometrically using a stopped-flow technique. The reaction follows a simple first order rate expression under an excess of the copper(II) species (and H+(aq)), and the pseudo-first order rate constant (k'(obs)) is largely independent of the atmosphere used (air, oxygen, argon). The rate law, at constant Cl- (Br-) anion concentration, is given by the expression: (d[MB+])/dt = ((k(a)K[H+] + k(b))/(1 + K[H+])).[Cu-II][LMB] = k'(obs)[LMB], where K is the protonation constant, and k(a) and k(b) are the pseudo-second order rate constants for protonated and deprotonated forms of LMB, respectively The rate law was determined based on the observed k'(obs) vs. [Cu-II] and [H+] dependences. The rate dramatically increases with [Cl-] over the range: 0.1-1.5 M, reflecting the following reactivity order: Cu2+(aq)

The kinetics of semiconductor photocatalysis: Light intensity effects

The kinetics of the photomineralisation of 4-chlorophenol, 4-CP, by oxygen, sensitized by TiO2 as a function of incident light intensity are described. Degussa P25 TiO2 in the form of either a thin film or a dispersion is used as the photocatalyst. With a TiO2 dispersion the initial rate of photomineralisation, R-i, depends upon I-0.64, implying that electron-hole recombination is the dominant process with respect to photogenerated holes (where R-i is expected proportional to I-0.5), but that the light intensities used spanned both the high (R-i expected proportional to I-0.5) and low (R-i expected proportional to I) intensity regimes. With a TiO2 film R-i is proportional to I indicating that the photocatalytically active particles of the TiO2 film are shielded in some way and so operate under low intensity conditions. Most significantly, it was also found that the apparent value of the Langmuir adsorption coefficient, K4-CP, as determined from the kinetic data, was not independent of I for either a TiO2, film or dispersion photocatalyst. Rather K4-CP increased with decreasing light intensity. A possible mechanism is suggested as a rationale for the observed light intensity effects reported.

Response characteristics of optical sensors for oxygen: models based on a distribution in tau(o) or kappa(q)

The features of two popular models used to describe the observed response characteristics of typical oxygen optical sensors based on luminescence quenching are examined critically. The models are the 'two-site' and 'Gaussian distribution in natural lifetime, tau(o),' models. These models are used to characterise the response features of typical optical oxygen sensors; features which include: downward curving Stern-Volmer plots and increasingly non-first order luminescence decay kinetics with increasing partial pressures of oxygen, pO(2). Neither model appears able to unite these latter features, let alone the observed disparate array of response features exhibited by the myriad optical oxygen sensors reported in the literature, and still maintain any level of physical plausibility. A model based on a Gaussian distribution in quenching rate constant, k(q), is developed and, although flawed by a limited breadth in distribution, rho, does produce Stern-Volmer plots which would cover the range in curvature seen with real optical oxygen sensors. A new 'log-Gaussian distribution in tau(o) or k(q)' model is introduced which has the advantage over a Gaussian distribution model of placing no limitation on the value of rho. Work on a 'log-Gaussian distribution in tau(o)' model reveals that the Stern-Volmer quenching plots would show little degree in curvature, even at large rho values and the luminescence decays would become increasingly first order with increasing pO(2). In fact, with real optical oxygen sensors, the opposite is observed and thus the model appears of little value. In contrast, a 'log-Gaussian distribution in k(o)' model does produce the trends observed with real optical oxygen sensors; although it is technically restricted in use to those in which the kinetics of luminescence decay are good first order in the absence of oxygen. The latter model gives a good fit to the major response features of sensors which show the latter feature, most notably the [Ru(dpp)(3)(2+)(Ph4B-)(2)] in cellulose optical oxygen sensors. The scope of a log-Gaussian model for further expansion and, therefore, application to optical oxygen sensors, by combining both a log-Gaussian distribution in k(o) with one in tau(o) is briefly discussed.

OXYGEN CATALYSIS BY ANHYDROUS RUTHENIUM(IV) OXIDE

The results of a kinetic study of the oxidation of water to oxygen by Ce(IV) ions in different acid media, mediated by anhydrous ruthenium(IV) oxide are described. In an acid medium which is predominantly HClO4 the kinetics are diffusion controlled and first order with respect to both [Ce(IV)] and [RuO2] and exhibit an activation energy of 19 kJ mol-1. In 0.5 mol dm-3 H2SO4 the kinetics are much slower and complex, the rate decreasing with increasing [Ce(III)]. The kinetics of catalysis observed in all the different acid media studied are readily interpreted using an electrochemical model in which the catalyst particles are considered as acting as microelectrodes which mediate electron transfer between a Nernstian reduction reaction (Ce(IV) --> Ce(III)) and an irreversible oxidation reaction (H2O --> 2H+ + 1/2O2). This electrochemical model is used to analyse the complex kinetics observed in 0.5 mol dm-3 H2SO4 and extract mechanistic information concerning the nature of the rate determining step.

COMPARATIVE-STUDY OF NEW AND ESTABLISHED HETEROGENEOUS OXYGEN CATALYSTS

The kinetics of catalysis of a number of new and established heterogeneous O2 catalysts have been studied using Ce(IV) as the oxidant via both the disappearance of the Ce(IV) ions and concomitant appearance of O2. The most active of the catalysts tested utilised a PGM(IV) oxide, usually Ru or Ir, prepared by the Adams method, which appears to generate microcrystalline powders with high surface areas and optimum activities per unit area.

Further evidence for double-strand breaks originating from a paired radical precursor from studies of oxygen fixation processes

By using a fast reaction technique which employs H2S gas as a fast-reacting chemical repair agent, it is possible to measure the competition kinetics between chemical repair reactions and oxygen fixation reactions in model DNA and cellular systems. In plasmid pBR322 DNA irradiated with electrons, we have compared the oxygen fixation reactions of the free radical precursors that lead to the production of single-strand (SSBs) and double-strand breaks (DSBs). For the oxygen-dependent fixation of radical damage leading to SSBs, a second-order rate constant of 2.3 x 10(8) dm(3) mol(-1) s(-1) was obtained compared to 8.9 x 10(7) dm(3) mol(-1) s(-1) for DSBs. The difference is in general agreement with predictions from a multiple-radical model where the precursor of a DSB originates from two radicals. The fixation of this precursor by oxygen will require both radicals to be fixed for the DSB to be formed, which will have slower kinetics than that of single free-radical precursors of SSBs. (C) 1999 by Radiation Research Society.

Cell type-dependent uptake, localization, and cytotoxicity of 1.9 nm gold nanoparticles

Background: This follow-up study aims to determine the physical parameters which govern the differential radiosensitization capacity of two tumor cell lines and one immortalized normal cell line to 1.9 nm gold nanoparticles. In addition to comparing the uptake potential, localization, and cytotoxicity of 1.9 nm gold nanoparticles, the current study also draws on comparisons between nanoparticle size and total nanoparticle uptake based on previously published data.

Methods: We quantified gold nanoparticle uptake using atomic emission spectroscopy and imaged intracellular localization by transmission electron microscopy. Cell growth delay and clonogenic assays were used to determine cytotoxicity and radiosensitization potential, respectively. Mechanistic data were obtained by Western blot, flow cytometry, and assays for reactive oxygen species.

Results: Gold nanoparticle uptake was preferentially observed in tumor cells, resulting in an increased expression of cleaved caspase proteins and an accumulation of cells in sub G1 phase. Despite this, gold nanoparticle cytotoxicity remained low, with immortalized normal cells exhibiting an LD50 concentration approximately 14 times higher than tumor cells. The surviving fraction for gold nanoparticle-treated cells at 3 Gy compared with that of untreated control cells indicated a strong dependence on cell type in respect to radiosensitization potential.

Conclusion: Gold nanoparticles were most avidly endocytosed and localized within cytoplasmic vesicles during the first 6 hours of exposure. The lack of significant cytotoxicity in the absence of radiation, and the generation of gold nanoparticle-induced reactive oxygen species provide a potential mechanism for previously reported radiosensitization at megavoltage energies.

The role of Na surface species on oxygen charge transfer in the Pt/YSZ system

The role of sodium surface species in the modification of a platinum (Pt) catalyst film supported on 8 mol% yttria-stabilised-zirconia (YSZ) was investigated under a flow of 20 kPa oxygen at 400 °C. Cyclic and linear sweep voltammetry were used to investigate the kinetics of the oxygen charge transfer reaction. The Pt/YSZ systems of both ‘clean’ and variable-coverage sodium-modified catalyst surfaces were also characterised using SEM, XPS and work function measurements using the Kelvin probe technique.

Samples with sodium coverage from 0.5 to 100% were used. It was found that sodium addition modifies the binding energy of oxygen onto the catalyst surface. Cyclic voltammetry experiments showed that higher overpotentials were required for oxygen reduction with increasing sodium coverage. In addition, sodium was found to modify oxygen storage and/or adsorption and diffusion increasing current densities at higher cathodic overpotential. Ex situ XPS measurements showed the presence of sodium hydroxide, carbonate and/or oxide species on the catalyst surface, while the Kelvin probe technique showed a decrease of approximately 250 meV in the work function of samples with more than 50% sodium coverage (compared to a nominally ‘clean’ sample).

TAP studies on 2% Ag/gamma-Al2O3 catalyst for selective reduction of oxygen in a H-2-rich ethylene feed

Catalysts currently employed for the polymerization of ethylene have previously been found to deactivate in the presence of oxygen. It is, therefore, important that oxygen is removed from the ethylene feedstock prior to the polymerization. The Ag/gamma-Al2O3 catalyst exhibits excellent activity and selectivity toward oxygen reduction with hydrogen in the presence of ethylene. TAP vacuum pulse experiments have been utilised to understand the catalytic behaviour of the Ag/gamma-Al2O3 catalyst. TAP multi-pulse experiments have determined the types of active sites that are found on the Ag/gamma-Al2O3 catalyst, and the intrinsic activity of these sites. The lifetime of the reactive adsorbed oxygen intermediate has also been determined through TAP consecutive pulse experiments. Multi-pulse and consecutive pulse data have been combined with ethylene adsorption/desorption rate constants to provide an overview of the Ag/gamma-Al2O3 catalyst system.

Integrating intrinsic and global kinetics as a dual kinetic model for automotive catalysis

The majority of the kinetic models employed in catalytic after-treatment of exhaust emissions use a global kinetic approach owing to the simplicity because one expression can account for all the steps in a reaction. The major drawback of this approach is the limited predictive capabilities of the models. The intrinsic kinetic approach offers much more information about the processes occurring within the catalytic converter; however, it is significantly more complex and time consuming to develop. In the present work, a methodology which allows accessing a model that combines the simplicity of the global kinetic approach and the accuracy of the intrinsic kinetic approach is reported. To assess the performance of this new approach, the oxidation of carbon monoxide in the presence of nitric oxide as well as a driving cycle was investigated. The modelling of carbon monoxide oxidation with oxygen which utilised the intrinsic kinetic approach with the global kinetic approach was used for the carbon monoxide + nitric oxide reaction (and all remaining reactions for the driving cycle). The comparison of the model results for the dual intrinsic + global kinetic approach with the experimental data obtained for both the reactor and the driving cycle indicate that the dual approach is promising with results significantly better than those obtained with only the global kinetics approach.

Hydroprocessing of waste cooking oil over a dispersed nano catalyst: Kinetics study and temperature effect

The kinetics of hydrodeoxygenation of waste cooking oil (WCO) is investigated with unsupported CoMoS catalysts. A kinetic model is established and a comprehensive analysis of each reaction pathway is carried out. The results show that hydrodecarbonylation/decarboxylation (HDC) routes are the predominant reaction pathways in the elimination of oxygen, with the rate constant three times as high as that of hydrodeoxygenation (HDO). However, the HDC activity of the CoMoS catalyst deactivates due to gradual loss of sulfur from the catalyst. HDO process is insensitive to the sulfur deficiency. The kinetic modeling shows that direct hydrodecarbonylation of fatty acids dominates the HDC routes and, in the HDO route, fatty acids are transferred to aldehydes/alcohols and then to C-18 hydrocarbons, a final product, and the reduction of acids is the rate limiting step. The HDO route via alcohols is dominant over aldehydes due to a significantly higher reaction rate constant. The difference of C-18/C-17 ratio in unsupported and supported catalysts show that a support with Lewis acid sites may play an important role in the selectivity for the hydrodeoxygenation pathways and promoting the final product quality