The total annual production of synthetic dye is more than 7 × 105 tons. Annually, through only textile waste effluents, around one thousand tons of non-biodegradable textile dyes are discharged into natural streams and water bodies. Therefore, with growing environmental concerns and environmental awareness there is a need for the removal of dyes from local and industrial water effluents with a cost effective technology. In general, these dyes have been found to be resistant to biological as well as physical treatment technologies. In this regard, heterogeneous advanced oxidation processes (AOPs), involving photo-catalyzed degradation of dyes using semiconductor nanoparticles is considered as an efficient cure for dye pollution. In the last two decades TiO2 has received considerable interest because of its high potential as a photocatalyst to degrade a wide range of organic material including dyes. This review starts with (i) a brief overview on dye pollution, dye classification and dye decolourization/degradation strategies; (ii) focuses on the mechanisms involved in comparatively well understood TiO2 photocatalysts and (iii) discusses recent advancements to enhance TiO2 photocatalytic efficiency by (a) doping with metals, non-metals, transition metals, noble metals and lanthanide ions, (b) structural modifications of TiO2 and (c) immobilization of TiO2 by using various supports to make it a flexible and cost-effective commercial dye treatment technology.
A systematic study on the photocatalytic activity of well-defined, macroscopic bulk single-crystal TiO2 anatase and rutile samples has been carried out, which allows us to link photoreactions at surfaces of well-defined oxide semiconductors to an important bulk property with regard to photochemistry, the life time of e-h pairs generated in the bulk of the oxides by photon absorption. The anatase (101) surface shows a substantially higher activity, by an order of magnitude, for CO photo-oxidation to CO2 than the rutile (110) surface. This surprisingly large difference in activity tracks the bulk e-h pair lifetime difference for the two TiO2 modifications as determined by contactless transient photoconductance measurements on the corresponding bulk materials.
Most oxygen evolution reaction (OER) electrocatalysts are not stable in corrosive acids. Even the expensive RuO2 or IrO2, the most acid-resistant oxides, can be dissolved at an oxidative potential. Herein, we realize that the failures of OER catalysts are mostly caused by the weak interface between catalysts and the substrates. Hence, the study of the interface structure between catalysts and substrates is critical. In this work, we observe that the cheap OER catalysts Co3O4 can be more durable than the state-of-the-art RuO2 if the interface quality is good enough. The Co3O4 nanosheets deposited on carbon paper (Co3O4/CP) is prepared by electroplating of Co-species and followed by a two-step calcination process. The 1st step occurs in vacuum in order to maintain the surface integrity of the carbon paper and converts Co-species to Co(II)O. The 2nd step is a calcination in ambient conditions which enables the complete transformation of Co(II)O to Co3O4 without degrading the mechanical strength of the Co3O4-CP interface. Equally important, an in situ formation of a layer of amorphous carbon on top of Co3O4 further enhances the OER catalyst stability. Therefore, these key advances make the Co3O4 catalyst highly active toward the OER in 0.5 M H2SO4 with a small overpotential (370 mV), to reach 10 mA/cm2. The observed long lifetime for 86.8 h at a constant current density of 100 mA/cm2, is among the best of the reported in literature so far, even longer than the state-of-art RuO2 on CP. Overall, our study provides a new insight and methodology for the construction of a high-performance and high stability OER electrocatalysts in corrosive acidic environments