This tutorial review considers defect chemistry of TiO2 and its solid solutions as well as defect-related properties associated with solar-to-chemical energy conversion, such as Fermi level, bandgap, charge transport and surface active sites. Defect disorder is discussed in terms of defect reactions and the related charge compensation. Defect equilibria are used in derivation of defect diagrams showing the effect of oxygen activity and temperature on the concentration of both ionic and electronic defects. These defect diagrams may be used for imposition of desired semiconducting properties that are needed to maximize the performance of TiO2-based photoelectrodes for the generation of solar hydrogen fuel using photo electrochemical cells (PECs) and photocatalysts for water purification. The performance of the TiO2-based semiconductors is considered in terms of the key performance-related properties (KPPs) that are defect related. It is shown that defect engineering may be applied for optimization of the KPPs in order to achieve optimum performance.

This study aims to develop a novel approach for the production of analytically robust and miniaturized polymeric ion sensors that are vitally important in modern analytical chemistry (e.g., clinical chemistry using single blood droplets, modern biosensors measuring clouds of ions released from nanoparticle tagged biomolecules, lab-on-a-chip applications, etc.). This research has shown that the use of a water repellent polymethyl methacrylate/polydecyl methacrylate (PMMA/PDMA) copolymer as the ion sensing membrane, along with a hydrophobic poly(3-octylthiophene 2,5-diyl) (POT) solid-contact as the ion-to-electron transducer, is an excellent strategy for avoiding the detrimental water layer formed at the buried interface of solid-contact ISEs. Accordingly, it has been necessary to implement a rigorous surface analysis scheme employing electrochemical impedance spectroscopy (EIS), in-situ neutron reflectometry/EIS (NR/EIS), secondary ion mass spectrometry (SIMS) and small angle neutron scattering (SANS) to probe structurally the solid-contact/membrane interface, so as to identify the conditions that eliminate the undesirable water layer in all solid-state polymeric ion sensors. In this work, we provide the first experimental evidence that the PMMA/PDMA copolymer system is susceptible to water “pooling” at the interface in areas surrounding physical imperfections in the solid-contact, with the exposure time for such an event in a PMMA/PDMA copolymer ISE taking nearly twenty times longer than that for a plasticized polyvinyl chloride (PVC) ISE, and the simultaneous use of a hydrophobic POT solid-contact with a PMMA/PDMA membrane can eliminate totally this water layer problem.

This paper presents the very first direct structural evidence for the formation of a 100 +/- 10 A water layer in coated-wire polymeric-membrane ion-selective electrodes (ISEs).