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The enzymatic reduction of carbon dioxide presents limited applicability due to denaturation and the impossibility of biocatalyst recovery; disadvantages that can be minimized by its immobilization. Here, a recyclable bio‐composed system was constructed by in‐situ encapsulation under mild conditions using formate dehydrogenase in a ZIF‐8 metalorganic framework (MOF) in the presence of magnetite. The partial dissolution of ZIF‐8 in the enzyme's operation medium can be relatively inhibited if the concentration of magnetic support used exceeds 10 mg mL−1. The bio‐friendly environment for immobilization does not harm the integrity of the biocatalyst, and the production of formic acid is improved 3.4‐fold compared to the free enzyme because the MOFs act as concentrators of the enzymatic cofactor. Furthermore, the bio‐composed system retains 86 % of its activity after a long time of five cycles, thus indicating an excellent magnetic recovery and a good reusability. [ABSTRACT FROM AUTHOR]

The dynamics of carrier recombination and transport of two CuInS2 superstrate solar cells was studied by intensity modulated photovoltage and photocurrent spectroscopy (IMVS and IMPS respectively). For the analysis of the resulting data two different approaches were implemented. In the first approach, the typically used analysis in Dye Sensitized Solar Cells (DSSC) was adapted to obtain the characteristic times of the processes involved. The second approach was based on the fittings of both the IMVS and IMPS data to the solution of the continuity equation. These fittings allow the calculation of different dynamic parameters of the cells. Moreover, consistency between the obtained parameters was observed, in good agreement with the typical analysis for DSSC. The resulting dynamics was associated with the presence and distribution of defect states among the samples. Moreover, from the performed analysis, a relation between the results and the post-treatment applied to the solar cells could be established. The difference in the dynamics of the cells is mainly observed in the difference between the electron lifetimes of both solar cells. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Herein we report the characterization and photoelectrochemical behavior of nanocrystalline TiO2 films modified with some alizarin derivatives. Particularly, alizarin complexone (3-[N,N-bis(carboxymethyl)-aminomethyl]-1,2-dihydroxyanthraquinone) and its Fe(ii) and Fe(iii) metal complexes have been examined. Based on UV-Visible and Raman spectroscopic studies we proposed that AC forms a tridentate complex with titanium dioxide involving the 2-OH and (methylimino) diacetate groups, while Fe(ii) and Fe(iii) AC-complexes bind to titanium dioxide through the carbonyl (C=O) and hydroxyl (OH) groups at the 1,9 positions of the alizarin framework. These findings allow the design of different nanostructures with diverse photoelectrochemical behavior. Analysis of the j–V curves reveals a sign reversal at −90 mV and −100 mV upon the excitation of AC@TiO2 and [FeIIIAC]@TiO2 photoelectrodes, respectively, whereas [FeIIAC]@TiO2 displays only anodic photocurrents. A description involving both electronic and geometric factors to account for these differences is proposed. [ABSTRACT FROM AUTHOR]

The enzymatic reduction of carbon dioxide presents limited applicability due to denaturation and the impossibility of biocatalyst recovery; disadvantages that can be minimized by its immobilization. Here, a recyclable bio-composed system was constructed by in-situ encapsulation under mild conditions using formate dehydrogenase in a ZIF-8 metalorganic framework (MOF) in the presence of magnetite. The partial dissolution of ZIF-8 in the enzyme's operation medium can be relatively inhibited if the concentration of magnetic support used exceeds 10 mg mL -1 . The bio-friendly environment for immobilization does not harm the integrity of the biocatalyst, and the production of formic acid is improved 3.4-fold compared to the free enzyme because the MOFs act as concentrators of the enzymatic cofactor. Furthermore, the bio-composed system retains 86 % of its activity after a long time of five cycles, thus indicating an excellent magnetic recovery and a good reusability., (© 2023 Wiley-VCH GmbH.)

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.