Lead oxide-modified TiO2 photocatalyst: tuning light absorption and charge carrier separation by lead oxidation state

Modification of TiO2 with metal oxide nanoclusters such as FeOx, NiOx has been shown to be a promising approach to the design of new photocatalysts with visible light absorption and improved electron–hole separation. To study further the factors that determine the photocatalytic properties of structures of this type, we present in this paper a first principles density functional theory (DFT) investigation of TiO2 rutile(110) and anatase(001) modified with PbO and PbO2 nanoclusters, with Pb2+ and Pb4+ oxidation states. This allows us to unravel the effect of the Pb oxidation state on the photocatalytic properties of PbOx-modified TiO2. The nanoclusters adsorb strongly at all TiO2 surfaces, creating new Pb–O and Ti–O interfacial bonds. Modification with PbO and PbO2 nanoclusters introduces new states in the original band gap of rutile and anatase. However the oxidation state of Pb has a dramatic impact on the nature of the modifications of the band edges of TiO2 and on the electron–hole separation mechanism. PbO nanocluster modification leads to an upwards shift of the valence band which reduces the band gap and upon photoexcitation results in hole localisation on the PbO nanocluster and electron localisation on the surface. By contrast, for PbO2 nanocluster modification the hole will be localised on the TiO2 surface and the electron on the nanocluster, thus giving rise to two different band gap reduction and electron–hole separation mechanisms. We find no crystal structure sensitivity, with both rutile and anatase surfaces showing similar properties upon modification with PbOx. In summary the photocatalytic properties of heterostructures of TiO2 with oxide nanoclusters can be tuned by oxidation state of the modifying metal oxide, with the possibility of a reduced band gap causing visible light activation and a reduction in charge carrier recombination.

Eco-innovation – does additional engagement lead to additional rewards?

Purpose: Eco-innovation is any form of product, process or organisational innovation that contributes towards sustainable development. Firms can eco-innovate in a variety of ways. The purpose of this paper is to identify nine different eco-innovation activities – including such items as reducing material use per unit of output, reducing energy use per unit of output, reducing carbon dioxide (CO2) “footprint” – and the authors ask whether these act as substitutes or complements to one another. Design/methodology/approach: Eco-innovation is any form of product, process or organisational innovation that contributes towards sustainable development. Firms can eco-innovate in a variety of ways. In this paper the authors identify nine different eco-innovation activities – including such items as reducing material use per unit of output, reducing energy use per unit of output, reducing CO2 “footprint” – and the authors ask whether these act as substitutes or complements to one another. Findings: Introducing only one eco-innovation activity has little payoff (in terms of turnover per worker) with only those firms who reduce their CO2 “footprint” having higher levels of turnover per worker. When introducing more than one eco-innovation activity the authors find that certain eco-innovation activities complement one another (e.g. reducing material use within the firm at the same time as improving the ability to recycle the product after use) others act as substitutes (e.g. reducing material use within the firm at the same time as recycling waste, water or materials within the firm). Practical implications: The results suggest that firms can maximise their productive capacity by considering specific combinations of eco-innovation. This suggests that firms should plan to introduce eco-innovation which act as complements, thereby, boosting productivity. It also suggests that eco-innovation stimuli, introduced by policy makers, should be targeted at complementary eco-innovations. Originality/value: The paper analyses whether eco-innovations act as complements or substitutes. While a number of studies have analysed the importance of eco-innovation for firm performance, few have assessed the extent to which diverse types of eco-innovation interact with each other to complement or substitute for one another.