• Energy Research
• 2016-2025close

The present chain of five papers considers the concept of solar-to-chemical energy conversion using TiO2-based semiconductors. The series reports the effect of chromium on the key performance-related properties of polycrystalline TiO2 (rutile), including electronic structure, photocatalytic activity, intrinsic defect disorder, electrochemical coupling and surface versus bulk properties. In this work, we show that the effect of chromium on photocatalytic performance of TiO2 depends on its elemental content and the related defect disorder that is determined by oxygen activity in the oxide lattice. At high oxygen activity, chromium leads to enhanced photocatalytic performance only for dilute solid solutions (up to 0.04–0.043 at.% Cr). Higher chromium content results in a decrease of photocatalytic activity below that for pure TiO2, despite the observed substantial decrease of the band gap. The photocatalytic performance of Cr-doped TiO2 annealed in reducing conditions is low within the entire studied range of compositions. The obtained results led to derivation of a theoretical model representing the mechanism of the light-induced reactivity of TiO2 with water and the related charge transfer. The photocatalytic performance is considered in terms of a competitive effect of several key performance-related properties. The performance is predominantly influenced by the concentration of titanium vacancies acting as reactive surface sites related to anodic charge transfer.

Abstract The recent climate change agreement in Paris highlights the imperative to aggressively decarbonize the energy economy and develop new technologies, especially for the generation of electrical energy that are environmentally clean. This challenge can only be addressed by a multi-pronged approach to research and education of the next generation of scientists and engineers as well as informed public discourse. Consequently this requires the introduction of new and comprehensive education programs on sustainable energy technologies for universities and, possibly, high schools. Among others, the new programs should provide in-depth knowledge in the development of new materials for more efficient energy conversion systems and devices. The enhanced level of education is also needed for properly assessing the competing technologies in terms of their economic and social benefits. The increasing recognition of the significance of clean and efficient energy conversion indicates the need for a comprehensive education program to be developed. The purpose of the present work is to consider the structure of both an education program and the related textbook where the energy-related fundamental and applied subjects are presented in a concentrated and uniform manner. Such a textbook could be an education aid for students of energy-related courses as well as the teachers involved in the formulation of the education programs. The textbook, which should be dedicated mainly for students at the undergraduate levels at universities, and possibly high schools, should include in-depth interdisciplinary sections dedicated to energy experts and graduate students. This paper considers the present international efforts in reducing the impact of climate change and the need to develop new technologies for clean energy generation. It is argued that progress in this area requires recognition of hydrogen as the main energy carrier of the future. This work also delineates the goals of the Sustainable Energy Network, SEN, involved in the UN program of Future Earth.

The present chain of five papers considers the concept of solar-to-chemical energy conversion using TiO2-based semiconductors. The series reports the effect of chromium on the key performance-related properties of polycrystalline TiO2 (rutile), including electronic structure, photocatalytic activity, intrinsic defect disorder, electrochemical coupling and surface versus bulk properties. This work considers the effect of oxygen activity on segregation-induced surface versus bulk composition for both polycrystalline and single-crystal specimens of Cr-doped TiO2. It has been documented that annealing of Cr-doped TiO2 at 1273 K in oxidising conditions results in an enrichment and depletion of the surface layer with chromium. It is shown that the segregation-induced enrichment factor for single crystal is substantially larger than that for polycrystalline specimen. The effect is considered in terms of a theoretical model showing that surface segregation of solute in polycrystalline specimen is encumbered by its segregation to grain boundaries. It is also shown that the segregation-induced enrichment is profoundly influenced by oxygen activity. The new insight of this work involves (i) the determination of well-defined chromium segregation in Cr-doped TiO2, including single-crystal and polycrystalline specimens, after annealing in the gas phase of controlled oxygen activity, and (ii) identification of the predominant driving force of segregation of chromium in Cr-doped TiO2 that is based on electrostatic interactions between the low-dimensional surface structure (LDSS) and electrically charge segregating species.