Institute of Fundamental Technological Research

The present paper reports on an innovative and simple route for the preparation of new hybrid materials based on TiO2 and carbonaceous supports with relatively high biochar content prepared via controlled laboratory batch pyrolysis system. Pine tar was used as a precursor for secondary char (confirmed by TGA) serving as a coating and “connecting material” between commercially available Degussa P25 TiO2 and biomass derived porous carbon support (biochar) produced from softwood or Lignin. The prepared hybrid materials were characterized by a series of physico-chemical characterization techniques such as XRD, XPS, TGA, UV–vis, XRF, SEM, COD and BET analysis. The results confirmed that the method used is viable and can be used to embed TiO2 in the structure of biochar. In aqueous phase phenol degradation, the TiO2/(secondary char-coated biochar) hybrid materials proved photocatalitically active, and especially the TiO2/secondary char-coated SWP700) showed better photocatalytic performance than the commercial TiO2 counterpart.

Biochar,Lignin,Pyrolysis,Secondary char,Water detoxification

We present a facile and green approach to produce crystalline TiO2 nanoparticles on a surface of different carbonaceous materials derived from lignocellulosic biomass such as STARBON-800® obtained by carbonization at 800 °C and biochar-SWP700 (Soft Wood Pellets (SWP) obtained by pyrolysis at 700 °C) via novel low-temperature ultrasound-promoted green methodology coupled with citric acid as a cross-linking agent. In comparison to other methods, the developed method has several significant benefits such as simplicity, great ability to get crystalline TiO2 particles (elimination of high-temperature treatment (material calcination at >300 °C) needed in the conventional sol-gel method, which is extremely important in transforming amorphous TiO2 into a photoactive crystalline phase) elimination of risky chemicals and oxidizing agent, and also ability to change some parameters (e. g. ultrasound intensity). Prepared materials were characterized by XRD, DR UV−vis, N2 physisorption, HR-XPS, XRF, HR-TEM, FT-IR and subsequently tested for their photocatalytic activities both in photocatalytic phenol degradation (in water) and oxidation of methanol (in air) under UV and visible light irradiation.

Molybdenum trioxide-supported palladium catalyst Pd/MoO3(SPD) is prepared by the sonophotodeposition procedure (SPD). This method combining sonication with ultraviolet irradiation is used at room temperature and atmospheric pressure and does not require the use of chemical reducing agent. For comparison, the Pd/MoO3 catalysts are also prepared by the ultrasound irradiation and traditional impregnation - H2 reduction methods. The Pd/MoO3 catalysts are characterized by X-ray diffraction (XRD), electron microscopy (SEM, TEM, HRTEM), energy dispersive (EDS, STEM) analysis and X-ray photoelectron spectroscopy (XPS). The SPD treatment improves the platelets-like morphology of the MoO3 oxide grains making more difficult formation of hydrogen bronzes HXMoO3 (x > 0.9) studied by microcalorimetric method. The “in situ” reduction of precursor ions during the SPD treatment generates much better dispersed Pd-nanoclusters than other preparation methods. It results in much higher activity of Pd/MoO3(SPD) catalyst for the cinnamaldehyde hydrogenation than its MoO3-supported counterparts and Pd/SiO2, a reference catalyst.

Palladium,Molybdenum trioxide,Sonophotodeposition,Cinnamaldehyde,Hydrogen bronze

A series of new inorganic-organic hybrid materials based on TiO2 and new biochar-based supports (biochar obtained by pyrolysis of Miscanthus Straw Pellets (MSP) and Soft Wood Pellets (SWP) at 550 and 700 oC) were successfully prepared using ultrasound-assisted
methodology. The resulting composites were characterized by a wide range physicochemical techniques and investigated in water and gas phase photocatalytic test reaction. Our best composite (TiO2/SWP700) achieved phenol degradation of 64.1% (under UV light) and 33.6% (under visible light). In addition, it also showed an extraordinarily high activity (~90%) in selective oxidation of methanol to methyl formate in flow gas phase, high selectivity to
methyl formate (~80 %) and high yield of methyl formate (~88 %) after 240 minutes of illumination. It can be noticed that when TiO2 is supported on biochar, presented a superior photocatalytic ability and could be recycled at least 5 times in both photocatalytic runs tests with reproducible high photocatalytic efficiency.

Biochar,TiO2,Synthesis of composite photocatalysts,Sonication for composite preparation,Phenol degradation,Methanol oxidation

This review comprises the preparation, properties and heterogeneous photocatalytic applications of TiO2 immobilized on carbon materials derived from earth-abundant, renewable and biodegradable agricultural residues and sea food waste resources. The overview provides key scientific insights into widely used TiO2 supported on carbonaceous materials emanating from biopolymeric materials such as lignin, cellulose, cellulose acetate, bacterial cellulose, bamboo, wood, starch, chitosan and agricultural residues (biochar, charcoal, activated carbon and their magnetic forms, coal fly ash) or seafood wastes namely eggshell, clamshell and fish scales; materials that serve as a support/template for TiO2. Heightened awareness and future inspirational developments for the valorisation of various forms of carbonaceous functional materials is the main objective. This appraisal abridges various strategies available to upgrade renewable carbon-based feedstock via the generation of sustainable TiO2/carbon functional materials and provides remarks on their future prospects. Hopefully, this will stimulate the development of efficient and novel composite photocatalysts and engender the necessary knowledge base for further advancements in greener photocatalytic technologies.

It has been demonstrated that sonophotodeposition can be one choice as a green method to synthesize bimetallic supported photocatalysts with enhanced performance for selective oxidations. A series of Pd–Cu supported on Titania-P90 photocatalysts were successfully prepared using this innovative method of effective synergistic combination of sonication and light. In addition, our method does not require the use of strong chemical reduction agent and it is executed in a short time, room temperature and atmospheric pressure. The prepared materials were characterized by a number of techniques such as High-Resolution Transmission Electron Microscopy (HRTEM), DR UV–vis spectroscopy, X-ray Photoelectron Spectroscopy (XPS) and powder X-ray diffraction (XRD). Additionally, better bimetallic systems were obtained (methanol conversion >50% and selectivity to methyl formate >80%) by SonoPhotoDeposition (SPD) than in the case of the conventional photodeposition methodology. It has been discussed the possible reasons of the observed slight deactivation (8% after 2 h reaction test) of the best performing material in gas phase methanol selective photo-oxidation.

Sonophotodeposition,Bimetallic,TiO2,Sonication,Methanol photo-oxidation

In recent years, a good number of methods have become available for the preparation of an important group of photoactive materials for applications in photocatalysis and solar cells. Nevertheless, the benefits derived from preparing those materials through unconventional approaches are very attractive from the green chemistry point of view. This critical review work is focused on sonication as one of these promising new synthetic procedures that allow control over size, morphology, nanostructure and tuning of catalytic properties. Ultrasound-based procedures offer a facile, versatile synthetic tool for the preparation of light-activated materials often inaccessible through conventional methods.

Photoactive materials by sonication,Photocatalysis,Ultrasounds,Solar cells,Perovskites,Quantum dots

The aim of this work is to develop bimetallic Pd–Au/TiO2 P90 systems, which are highly active and selective for the photocatalytic oxidation of methanol to form methyl formate. Modification of commercial TiO2 P90 with Pd–Au nanoparticles was successfully achieved for the first time by means of a sonophotodeposition (SPD) method. The prepared materials were characterized by TEM, UV/Vis spectroscopy, X-ray photoelectron spectroscopy, and powder XRD. The Pd–Au bimetallic nanoparticles supported on titania exhibited remarkably enhanced catalytic activity in selective methanol oxidation to form methyl formate due to the synergism of Au and Pd particles, as well as the strong interaction between TiO2 and Pd–Au. SPD is a green methodology that can be used to prepare well-defined bimetallic surfaces on semiconductor supports with great promise for catalytic applications, in which selectivity can be tuned through adjustment of the surface composition.

Carbonaceous N-containing materials derived from leather skin residues have been found to have unprecedented photocatalytic properties as compared to P25 Evonik, with an interesting degradation potential for contaminants in water (e.g. phenol). The carbonaceous materials were prepared by carbonization of the leather skin residues at different temperatures (180–600 °C). Different crystalline species of Cr2O3 and TiO2 were found in the materials obtained. In spite of a low surface area and phase crystallinity, a thermally treated material at 180 °C containing doped chromium oxides (eskolaite phase) provided remarkably improved activities with respect to classical titania derived materials.

Leather skin residues,Photocatalysis,Chromium oxide,Phenol degradation

The average size of the TiO2 nanoparticles was controlled at around 30 nm on Starbon 800 without using any surfactant, which is attributed to the hydrolysis and condensation (it is also proposed to be a plausible condensation with the carboxylate groups on the carbon surface) of the dissolved titanium(IV) isopropoxide into TiO2 by ultrasonic waves. As the Starbon in the composites has very good contact with the TiO2 nanoparticles (there is no Ti leaching after 240 min of photocatalysis, XRF analysis) it enhances the photo-electron conversion (better than Norit and graphene oxide carbons) of TiO2 by reducing the recombination of photo-generated electron–hole pairs. We have prepared an excellent new hybrid photocatalyst for aqueous phase phenol total mineralization.