Wojciech Macyk

Visible light inactivation of bacteria and fungi by modified titanium dioxide.

Visible light induced photocatalytic inactivation of bacteria (Escherichia coli, Staphylococcus aureus, Enterococcus faecalis) and fungi (Candida albicans, Aspergillus niger) was tested. Carbon-doped titanium dioxide and TiO2 modified with platinum(IV) chloride complexes were used as suspension or immobilised at the surface of plastic plates. A biocidal effect was observed under visible light irradiation in the case of E. coli in the presence of both photocatalysts. The platinum(IV) modified titania exhibited a higher inactivation effect, also in the absence of light. The mechanism of visible light induced photoinactivation is briefly discussed. The observed detrimental effect of photocatalysts on various microorganism groups decreases in the order: E. coli > S. aureus approximately E. faecalis>>C. albicans approximately A. niger. This sequence results most probably from differences in cell wall or cell membrane structures in these microorganisms and is not related to the ability of catalase production.

Visible‐Light Detoxification and Charge Generation by Transition Metal Chloride Modified Titania

Amorphous microporous metal oxides of titanium (AMM-Ti) modified with chlorides of PtIV, IrIV, RhIII, AuIII, PdII, CoII, and NiII have been prepared by the sol-gel method and characterized by various surface analytical methods. These hybrid AMM-Ti powders are catalysts for the photodegradation of 4-chlorophenol (4-CP) in aqueous solution when illuminated with visible (lambda > or = 400 or 455 nm) or UV (lambda > or = 335 nm) light. The initial rate depends on the dopant level and is highest at 3.0% Pt in the case of PtIV/AMM-Ti. When employed in a photoelectrochemical cell, the activity spectrum of the photocurrent extends downward to about 600 nm, as does the photodegradation of 4-CP. It is suggested that the metal salt acts as a redox-active chromophore, transmitting the photogenerated charges to the amorphous matrix.

Photosensitization of Crystalline and Amorphous Titanium Dioxide by Platinum(IV) Chloride Surface Complexes

Anatase, rutile, and amorphous titania powders were surface-modified by grinding with PtCl4 and H2[PtCl6]. Only the anatase modification afforded hybrid photocatalysts capable of degradation of 4-chlorophenol (4-CP) with visible light, with sufficient stability towards decomplexation. Grinding with K2[PtCl4] produced materials of only low photocatalytic activity. Most efficient photocatalysts contained up to 2 wt% of PtIV. At higher surface loading the excess fraction of the complex is desorbed into the aqueous solution. Scavenging experiments with benzoic acid and tetranitromethane revealed that hydroxyl radicals are produced by the primary reduction of oxygen by conduction band electrons generated through electron injection from a postulated surface platinum(III) complex. It is proposed that the latter is formed from a charge-transfer ligand-to-metal (CTLM) excited state through homolysis of the Pt-Cl bond. Accordingly. the primary oxidation of 4-CP may occur by adsorbed chlorine atoms, the intermediary existence of which was demonstrated by scavenging experiments with phenol.

Nanoscale optoelectronic switches and logic devices

The photoelectrochemical photocurrent switching (PEPS) effect, in the beginning regarded as a scientific curiosity, has become a field of extensive study for numerous research groups all over the world. This unique effect can be utilized for nanoscale switching and information processing, furthermore, is can serve as an interface between molecular information processing and macroscopic electronics. This review summarizes recent efforts in understanding photocurrent switching effects and their application for the construction of nanoscale switches and logic devices. Furthermore, some future prospects concerning the development of electronic/optoelectronic devices based on photoactive semiconducting hybrid materials are presented.

Ligand and medium controlled photochemistry of iron and ruthenium mixed-ligand complexes: prospecting for versatile systems

Abstract Selected Fe and Ru systems, whose photochemical behaviour is sensitive to numerous parameters, are presented. These systems, containing multiple species in equilibrium, are versatile enough to be adapted to special tasks and may also be used to model the phenomena and mechanisms occurring in nature. The role of various parameters is analysed and principal emphasis is given to the ligand sphere influence on the nature of the excited state and thereby on the photochemical mode. This is crucial in the case of Fe(II) complexes of the type [Fe(CN) 5 L] n − , whereas in the carbolyl–cyclopentadienyl complexes, represented by [cpRu(CO) 2 ] 2 , the nature of the excited state is of less importance than for pentacyanoferrates(II). The photochemistry of the carbonyl–cyclopentadienyl complexes is more susceptible to the impact of the medium and the role of the secondary processes is more significant.

VISIBLE LIGHT PHOTOCATALYSIS BY A TITANIA TRANSITION METAL COMPLEX

Publisher Summary This chapter discusses visible light photocatalysis by a titania transition metal complex. Hexachloroplatinic acid in solution only induces a stoichiometric visible light photooxidation of the ubiquitous water pollutant 4-chlorophenol (4-CP), whereas, the reaction becomes photocatalytic when the complex is supported onto titania. It was found that the most active catalyst was obtained when the complex was covalently attached to titania. Different from a single crystal electrode, it is more difficult to measure the flatband potential of a semiconductor powder, which is necessary to estimate the absolute positions of the valence and conduction band edges. The degradation of atrazine in general affords cyanuric acid as the final product when the photocatalyst is an unmodified titania material. In the photodegradation with sunlight, a significant difference between the photocatalysts prepared by adsorption from solution and by grinding becomes apparent.

Photodynamic activity of platinum(IV) chloride surface-modified TiO2 irradiated with visible light.

The visible light-induced phototoxicity of titanium dioxide modified with platinum(IV) chloride complexes, [TiO2/PtCl4], was tested. In vitro experiments with the mouse melanoma cells (S-91) have demonstrated phototoxicity of the [TiO2/PtCl4] material. Detection of efficiently generated various reactive oxygen species (.OH, O2. -, H2O2, 1O2) and also reactive chlorine species has proven the photodynamic activity of the tested material, induced by visible light (lambda>455 nm). The cellular death (recognized as a necrosis) is a result of the cell membrane peroxidation.

Synthesis, structure and photoelectrochemical properties of the TiO2–Prussian blue nanocomposite

The nanocomposite comprising of two simple components – titanium dioxide and Prussian blue – have been synthesized and used for photoelectrode construction. Switching of the photocurrent direction in semiconducting systems upon changes of the electrode potential has been observed. The nanocomposite was characterized by optical spectroscopy and electrochemistry. The structure of the surface complex was modeled using simple quantum chemical models. The behaviour of the photoelectrode was simulated by an adequate electronic circuit. Possible applications of the composite material have been presented.

Highly efficient rutile TiO2 photocatalysts with single Cu(II) and Fe(III) surface catalytic sites

Highly active photocatalysts were obtained by impregnation of nanocrystalline rutile TiO2 powders with small amounts of Cu(II) and Fe(III) ions, resulting in the enhancement of initial rates of photocatalytic degradation of 4-chlorophenol in water by factors of 7 and 4, compared to pristine rutile, respectively. Detailed structural analysis by EPR and X-ray absorption spectroscopy (EXAFS) revealed that Cu(II) and Fe(III) are present as single species on the rutile surface. The mechanism of the photoactivity enhancement was elucidated by a combination of DFT calculations and detailed experimental mechanistic studies including photoluminescence measurements, photocatalytic experiments using scavengers, OH radical detection, and photopotential transient measurements. The results demonstrate that the single Cu(II) and Fe(III) ions act as effective cocatalytic sites, enhancing the charge separation, catalyzing “dark” redox reactions at the interface, thus improving the normally very low quantum yields of UV light-activated TiO2 photocatalysts. The exact mechanism of the photoactivity enhancement differs depending on the nature of the cocatalyst. Cu(II)-decorated samples exhibit fast transfer of photogenerated electrons to Cu(II/I) sites, followed by enhanced catalysis of dioxygen reduction, resulting in improved charge separation and higher photocatalytic degradation rates. At Fe(III)-modified rutile the rate of dioxygen reduction is not improved and the photocatalytic enhancement is attributed to higher production of highly oxidizing hydroxyl radicals produced by alternative oxygen reduction pathways opened by the presence of catalytic Fe(III/II) sites. Importantly, it was demonstrated that excessive heat treatment (at 450 °C) of photocatalysts leads to loss of activity due to migration of Cu(II) and Fe(III) ions from TiO2 surface to the bulk, accompanied by formation of oxygen vacancies. The demonstrated variety of mechanisms of photoactivity enhancement at single site catalyst-modified photocatalysts holds promise for developing further tailored photocatalysts for various applications.

An integrated photocatalytic/enzymatic system for the reduction of CO2 to methanol in bioglycerol–water

Summary A hybrid enzymatic/photocatalytic approach for the conversion of CO2 into methanol is described. For the approach discussed here, the production of one mol of CH3OH from CO2 requires three enzymes and the consumption of three mol of NADH. Regeneration of the cofactor NADH from NAD+ was achieved by using visible-light-active, heterogeneous, TiO2-based photocatalysts. The efficiency of the regeneration process is enhanced by using a Rh(III)-complex for facilitating the electron and hydride transfer from the H-donor (water or a water–glycerol solution) to NAD+. This resulted in the production of 100 to 1000 mol of CH3OH from one mol of NADH, providing the possibility for practical application.