Ceria-supported vanadia is catalytically active in oxidative dehydrogenation (ODH) reactions. Here, we provide direct spectroscopic evidence for the participation of the ceria support in the redox catalysis. To unravel the structural dynamics of vanadia/ceria (VO x /CeO2) catalysts during ethanol ODH, we have applied a combination of operando multiwavelength Raman and operando UV–vis spectroscopy. Our approach consists of the targeted use of different Raman excitation wavelengths, enabling the selective enhancement of ceria (at 385 nm) and vanadia (at 515 nm) vibrational features. As part of the support dynamics, ceria lattice oxygen is shown to directly participate in the ODH reaction, while V–O–Ce interface bonds are broken during substrate adsorption, resulting in ethoxide formation. The presence of V–O–Ce bonds is considered to be crucial for the observed synergy effect in catalytic performance, allowing ceria to act as an oxygen buffer stabilizing the vanadium center. By providing an experimental basis for a detailed understanding of working VO x /CeO2 catalysts, our results highlight the importance of active support participation in oxide catalysis.

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BackgroundMelanins comprise a chemically-diverse group of polymeric pigments whose function is related to protection against physical and chemical stress factors. These polymers have current and potential applications in the chemical, medical, electronics and materials industries. The biotechnological production of melanins offers the possibility of obtaining these pigments in pure form and relatively low cost. In this study, Escherichia coli strains were engineered to evaluate the production of melanin from supplemented catechol or from glycerol-derived catechol produced by an Escherichia coli strain generated by metabolic engineering.ResultsIt was determined that an improved mutant version of the tyrosinase from Rhizobium etli (MutmelA), could employ catechol as a substrate to generate melanin. Strain E. coli W3110 expressing MutmelA was grown in bioreactor batch cultures with catechol supplemented in the medium. Under these conditions, 0.29 g/L of catechol melanin were produced. A strain with the capacity to synthesize catechol melanin from a simple carbon source was generated by integrating the gene MutmelA into the chromosome of E. coli W3110 trpD9923, that has been modified to produce catechol by the expression of genes encoding a feedback inhibition resistant version of 3-deoxy-d-arabino-heptulosonate 7-phosphate synthase, transketolase and anthranilate 1,2-dioxygenase from Pseudomonas aeruginosa PAO1. In batch cultures with this strain employing complex medium with 40 g/L glycerol as a carbon source, 1.21 g/L of catechol melanin were produced. The melanin was analysed by employing Fourier transform infrared spectroscopy, revealing the expected characteristics for a catechol-derived polymer.ConclusionsThis constitutes the first report of an engineered E. coli strain and a fermentation process for producing a catechol melanin from a simple carbon source (glycerol) at gram level, opening the possibility of generating a large quantity of this polymer for its detailed characterization and the development of novel applications.

Novel mesoporous, high specific surface area (up to 562 m2 g−1) 0D-nanocarbon-based silicon-containing ceramic composites were produced by a straightforward sol–gel method followed by polymer-to-ceramic transformation.

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