Facile Synthesis of Potassium Poly(heptazine imide) (PHIK)/Ti-Based Metal-Organic Framework (MIL-125-NH2) Composites for Photocatalytic Applications.

Photocatalytically active composites comprising potassium poly(heptazine imide) (PHIK) and a Ti-based metal-organic framework (MOF, MIL-125-NH2) are prepared in situ by simply dispersing both materials in water. The driving forces of composite formation are the electrostatic interactions between the solids and the diffusion of potassium ions from PHIK to MIL-125-NH2. This mechanism implies that other composites of poly(heptazine imide) salts and different MOFs bearing positive surface charge can potentially be obtained in a similar fashion. The suggested strategy thus opens a new avenue for the facile synthesis of such materials. The composites are shown to have a superior photocatalytic activity in Rhodamine B degradation under blue light irradiation. The reaction rate is doubled compared to that of pure MOF compound and is 7 times higher than the activity of the pristine PHIK. The results of the electron paramagnetic resonance (EPR) investigations and the analysis of the electronic structures of the solids suggest the electron transfer from MIL-125-NH2 to PHIK in the composite. The possible pathways for the dye degradation and the rationalization of the increased activity of the composites are elaborated.

Evidence on dye clustering in the sensitization of TiO2 by aluminum phthalocyanine.

As previous studies have shown, the photocatalytic reduction of Cr(VI) to Cr(III) in the presence of 4-chlorophenol can be carried out efficiently under visible irradiation using TiO2 modified with hydroxoaluminum-tricarboxymonoamide phthalocyanine (AlTCPc) in spite of the high aggregation tendency of the dye. In the present work, photocurrent and absorption spectra of AlTCPc modified TiO2 films are studied together with absorption and fluorescence of the dye in solution as a function of the concentration of the dye to clarify (a) the role of aggregates and the nature of the species responsible for electron injection into the semiconductor and (b) the reasons why, as reported earlier, the photocatalytic activity is nearly independent of dye loading at constant TiO2 mass. Results are consistent with the presence of AlTCPc clusters with similar properties both on the TiO2 surface and in H2O-DMSO solution. The actual photoactive species is the monomeric dye electronically coupled to the semiconductor. Monomer concentration depends only slightly on AlTCPc analytical concentration, in a way similar to surfactant monomers in micellar equilibrium, thus explaining the independence of photocatalytic activity on dye concentration.

Exploiting electron storage in TiO2 nanoparticles for dark reduction of As(V) by accumulated electrons.

UV irradiation of an ethanolic sol of TiO2 nanoparticles produces a trapped Ti(III) centre and a noticeable Burstein shift. Direct evidence that the accumulated charges can drive the otherwise forbidden reduction of As(V) by conduction band electrons is presented.

Photoreduction of Cr(VI) using hydroxoaluminiumtricarboxymonoamide phthalocyanine adsorbed on TiO2.

Hydroxoaluminiumtricarboxymonoamide phthalocyanine (AlTCPc) adsorbed at different loadings on TiO(2) Degussa P-25 was tested for Cr(vi) photocatalytic reduction under visible irradiation in the presence of 4-chlorophenol (4-CP) as sacrificial donor. A rapid reaction takes place in spite of the presumable aggregation of the dye on the TiO(2) surface. The removal of Cr(vi) is fairly negligible under visible-light irradiation, either without photocatalyst or in the presence of bare TiO(2). The fast capture of conduction band electrons by Cr(vi), which forms a surface complex with TiO(2), inhibits the formation of reactive oxygen species in the reductive pathway. This fact and the easier oxidation of 4-CP as compared to AlTCPc hinder the photobleaching of the dye and make feasible Cr(vi) reduction under visible irradiation. The consumption of Cr(vi) follows a pseudo-first order kinetics; the decay constant depends, in the studied range, on the photocatalyst mass, but it is barely affected by dye loading. The presence of 4-CP is essential, but its concentration has no effect on the Cr(vi) decay rate. Oxidation products of 4-CP, such as hydroquinone, catechol or benzoquinone, are not observed. Direct evidence of the one-electron reduction of Cr(vi) to Cr(v) was obtained by EPR spectroscopy using citric acid as Cr(v) trapping agent. In this case, disappearance of Cr(v) also follows a first order decay, but conduction band electrons do not seem to be involved. The fact that oxidation products of 4-CP are not observed is consistent with the fast dark removal of reaction intermediates by Cr(v), proved by EPR.

Electron transfer from photoexcited TiO2 to chelating alizarin molecules: reversible photochromic effect in alizarin@TiO2 under UV irradiation.

Reduction of alizarin molecules coupled to TiO(2) nanoparticles (A@TiO(2)) occurs on UV irradiation in the presence of a sacrificial electron donor. Evidence is presented that reduction is mediated by conduction-band electrons and yields a 1,2,9,10-tetrahydroxyanthracene species which remains coupled to the TiO(2) nanoparticles. The spectrum of the reduced complex displays two overlapping broad bands centred at 480 and 650 nm which can harvest visible photons besides 900 nm, in agreement with theoretical predictions by TDDFT. The potential relevance of the dual-redox behaviour of strongly TiO(2) coupled anthraquinone dyes in the field of photocatalysis and in connection with their utilization in the development of dye-sensitized TiO(2) solar cells is briefly discussed.

Photon flux and wavelength effects on the selectivity and product yields of the photocatalytic air oxidation of neat cyclohexane on TiO(2) particles.

Product selectivity and yields of cyclohexanol and cyclohexanone formation in the photocatalytic air oxidation of cyclohexane on TiO(2) particles were determined as a function of the irradiation wavelength (254 < or = lambda/nm < or = 366) and the photon flux (0.3 < or = I(0)/neinstein cm(-2) s(-1) < or = 5.0). Photonic efficiencies for total monooxygenated products (cyclohexanol + cyclohexanone) ranged from 10 to 25% depending on photon energy and fluency. The cyclohexanol-to-cyclohexanone ratio linearly increases with the incident photon flux at each wavelength and varies more than a magnitude order -- from 3 to 32%-at the same incident photon fluency -- 5 neinstein cm(-2) s(-1) -- by changing the irradiation wavelength from 366 to 303 nm. Experimental evidence indicates that both spectral and intensity effects emerge as a consequence of the change in the frequency of photon absorption per particle. A mechanism is proposed which accounts for the origin of the selectivity changes.

Heterogeneous photocatalytic reduction of chromium(VI) over TiO2 particles in the presence of oxalate: involvement of Cr(V) species.

Cr(VI) photocatalytic reduction experiments over TiO2 particles under near UV irradiation in the presence of excess oxalate were performed at acid pH (2 and 3) and under air and N2 bubbling. Initial photonic efficiencies for Cr(VI) reduction are nearly the same under aerobic and anaerobic conditions, but show a significant increase at the lowest pH. At pH 2, the addition of oxalate facilitates Cr(VI) reduction, hindering the electron-shuttle mechanism taking place in pure water. The oxalate synergistic effect at pH 2 is lower than that previously found for EDTA and negligible at pH 3. Chromium(V) oxalate concentration profiles were obtained by EPR spectroscopy in the presence of excess oxalate at pH 1.5. Coordinated Cr(V) complexes [Cr(V)(O)(Ox)2]-, [Cr(V)(OH2)(Ox)2]-, and [Cr(V)(O)(OH)2(Ox)]- were identified, on the basis of the comparison of their corresponding g values with recent literature data. The kinetic analysis of the temporal evolution of the paramagnetic Cr(V) species indicates also an effective photocatalytic degradation of chromium(V) oxalate complexes. This new evidence reinforces previous findings regarding sequential one-electron-transfer processes in Cr(VI) photocatalytic reduction, suggesting that this route may represent a general behavior for the Cr(VI) reduction over UV-irradiated TiO2 particles.

Application of photoacoustic calorimetry to the determination of volume changes in reactions involving radical anions in aqueous solutions.

The particular features of the application of photoacoustic calorimetry to the determination of volume changes in reactions involving radical anions in aqueous solutions are addressed. Analysis of recent literature data on volume changes of redox pairs, including our previous results on the couples NO2(-)/NO2 and SO4(2-)/(SO4)*-, together with known values of molal volume changes for ionization reactions, allow us to derive an empirical correlation for these categories of reactions. Finally, the pertinence of describing the volume changes of complex processes as a simple sum of separable terms is critically examined.