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Wojciech Macyk

Publications and source records attributed to Wojciech Macyk.

8 recordsLinked to original sources
PubMed2006

Singlet oxygen photogeneration at surface modified titanium dioxide.

Substitution of surface -OH groups of TiO2 may influence competition between photoinduced energy and electron-transfer processes and lead to improved singlet oxygen generation. In contrast to neat TiO2, surface modified titanium dioxide can photocatalyze degradation of a very stable substance, cyanuric acid. Presented results are in contradiction to usually accepted hypothesis of the mechanism of cyanuric acid photodegradation in the presence of fluorinated TiO2 (F-TiO2) in which "bulk" hydroxyl radicals play a key role. It seems plausible that the difference of activity observed for TiO2 and F-TiO2 is not related to various types of generated hydroxyl radicals, but rather to competition between electron-transfer processes (formation of radicals) and energy-transfer processes (formation of singlet oxygen).

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PubMed2006

Redox-controlled photosensitization of nanocrystalline titanium dioxide.

Photosensitization of nanocrystalline titanium dioxide materials has been achieved by chemisorption of the pentacyanothiamineferrate(II) complex, which offers a relatively high redox potential that determines the photoelectrochemical properties of the photosensitized TiO(2). The adsorbed pentacyanoferrate complex binds to TiO(2) through the cyanide bridge and forms a new surface complex characterized by a metal-to-metal charge-transfer transition (MMCT) (Fe(II)-->Ti(IV)). The photosensitization can be observed only at low potentials at which Fe(II) moieties are present. Photocurrent switching between anodic and cathodic can be induced by varying either the photoelectrode potential or the wavelength of the incident light. Simple molecular modeling-together with spectroscopic and electrochemical measurements-allows the elucidation of the mechanism of the observed photoelectrochemical behavior.

Journal Article↗
PubMed2006

Optoelectronic switches based on wide band gap semiconductors.

Switching of photocurrent direction in semiconducting systems upon changes of the electrode potential or incident light wavelength was realized by a series of photoelectrodes covered with titania modified with pentacyanoferrate complexes, [Fe(CN)(5)L](n)(-) (L = NH(3), thiodiethanol, thiodipropanol). These materials were characterized by optical spectroscopy and electrochemistry. The structure of the surface complexes was modeled using simple quantum-chemical models. The electrodes described in this paper enable control of the photocurrent direction by two stimuli: Changing the wavelength or the photoelectrode potential easily switches the direction of photocurrent. The materials are different from those of similar characteristics studied by other authors: They are not composites comprising of two types of semiconductors but rather engineered uniform materials. The photocurrent switching phenomenon is an intrinsic feature resulting from a specific electronic structure of the surface-modified semiconductor.

Ammonia↗
PubMed2006

Light-driven OR and XOR programmable chemical logic gates.

Photoelectrodes made of nanocrystalline titanium dioxide modified with various pentacyanoferrates exhibit unique photoelectrochemical properties; photocurrent direction can be switched from anodic to cathodic and vice versa upon changes in photoelectrode potential and incident light wavelength (PhotoElectrochemical Photocurrent Switching, PEPS effect). At certain potentials, anodic photocurrent generated upon UV irradiation has the same intensity as the cathodic photocurrent generated upon visible irradiation. Under these conditions, simultaneous irradiation with UV and visible light results in compensation of anodic and cathodic photocurrents, and zero net photocurrent is observed. This process can be used for construction of unique light-driven chemical logic gates.

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PubMed2005

Photoelectrochemical properties of a dinitrogen-fixing iron titanate thin film.

The band edge positions of a nitrogen-fixing nanostructured semiconductor thin film are determined both in the dark through spectroelectrochemistry and under irradiation by photovoltage measurements. Both methods afford the same result indicating that the film in addition to the dinitrogen-fixing phase Fe2Ti2O7 also contains titanium dioxide. Thus, both methods enable the analysis of a mixture of semiconducting thin films. For pH 7, values of -0.4 and +1.6 V were estimated for the conduction and valence band edge of the iron titanate film, respectively. A 3-fold photocurrent increase by methanol was observed only when the film was calcined at 600 degrees C but not below or above this temperature; the films calcined at temperatures other than 600 degrees C were also inactive in the photoreduction of dinitrogen. For a matter of comparison, an iron(III) oxide film was characterized analogously.

Journal Article↗
PubMed2003

Photoelectrochemical properties of platinum(IV) chloride surface modified TiO2.

Anatase (TH), rutile (TiO2-R), and a mixture of anatase and rutile (P25) were surface modified by chemisorbed chloroplatinate(IV) complexes. All materials gave rise to anodic photocurrents when deposited on conducting glass and irradiated in the wavelength range of 330-650 nm. In the presence of formate "current-doubling" factors of 5-7 were measured. Flatband potentials were obtained by the suspension method through recording the photovoltage as function of the pH value. The value of -0.54 V as found for TH is shifted to -0.49, -0.45, and -0.28 V (vs. NHE, pH = 7) when the surface is covered by 1, 2, and 4 wt% of H2[PtCl6], respectively. The flatband potential shifts by 50 and 60 mV per pH unit for P25 and 4% H2[PtCl6]/TH, respectively, as found by a novel method based on the use of different pH-independent redox systems of the bipyridinium type. Whereas the rutile based material was inactive, the TH and P25 samples photocatalyzed the mineralization of 4-CP with visible light. Moreover, the capability of H2[PtCl6]/TH to mineralize also cyanuric acid, the end-product of atrazine decomposition in photocatalytic processes with unmodified TiO2, was observed upon UV and also visible light irradiation. From these experimental results an energy diagram is proposed to rationalize the reactions observed.

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