Alagappan Annamalai

Bifunctional TiO2 underlayer for α-Fe2O3 nanorod based photoelectrochemical cells: enhanced interface and Ti4+ doping

A thin, compact TiO2 underlayer for hematite-based photoelectrochemical cells was prepared by simple spin coating and showed a dramatic increase in device performance and photocurrent density. The introduction of TiO2 underlayers induced a noticeable change in the nanostructure. In contrast to the conventional strategies based on underlayers, the compact TiO2 underlayers can act as both a charge recombination barrier and also as a source for titanium dopants. One could simply take advantage of fortuitous doping of Sn from FTO into hematite lattice during the activation step, and is converted into intentional doping of Ti4+ from the TiO2 underlayer into the hematite lattice. Ti4+ doping in hematite lattice is highly probable during the sintering of FTO/TiO2/α-Fe2O3 photoanodes at 800 °C, which has been confirmed by XPS measurements. Based on electrochemical studies, it is evident that the TiO2 underlayer effectively suppresses charge recombination at the FTO/α-Fe2O3 interface and provides possible Ti4+ doping apart from Sn diffusion from FTO substrates when sintered at high temperature (800 °C). In contrast, only charge recombination was suppressed at lower sintering temperature (550 °C). This is the first report on the elemental doping of Ti4+ from the TiO2 underlayer when sintered at high temperature.

Sn/Be Sequentially co-doped Hematite Photoanodes for Enhanced Photoelectrochemical Water Oxidation : Effect of Be2+ as co-dopant

For ex-situ co-doping methods, sintering at high temperatures enables rapid diffusion of Sn4+ and Be2+ dopants into hematite (α–Fe2O3) lattices, without altering the nanorod morphology or damaging their crystallinity. Sn/Be co-doping results in a remarkable enhancement in photocurrent (1.7 mA/cm2) compared to pristine α–Fe2O3 (0.7 mA/cm2), and Sn4+ mono-doped α-Fe2O3 photoanodes (1.0 mA/cm2). From first-principles calculations, we found that Sn4+ doping induced a shallow donor level below the conduction band minimum, which does not contribute to increase electrical conductivity and photocurrent because of its localized nature. Additionally, Sn4+-doping induce local micro-strain and a decreased Fe-O bond ordering. When Be2+ was co-doped with Sn4+-doped α–Fe2O3 photoanodes, the conduction band recovered its original state, without localized impurities peaks, also a reduction in micro-strain and increased Fe-O bond ordering is observed. Also the sequence in which the ex-situ co-doping is carried out is very crucial, as Be/Sn co-doping sequence induces many under-coordinated O atoms resulting in a higher micro-strain and lower charge separation efficiency resulting undesired electron recombination. Here, we perform a detailed systematic characterization using XRD, FESEM, XPS and comprehensive electrochemical and photoelectrochemical studies, along with sophisticated synchrotron diffraction studies and extended X-ray absorption fine structure.

Trade-off between Zr Passivation and Sn Doping on Hematite Nanorod Photoanodes for Efficient Solar Water Oxidation : Effects of a ZrO2 Underlayer and FTO Deformation

Herein we report the influence of a ZrO2 underlayer on the PEC (photoelectrochemical) behavior of hematite nanorod photoanodes for efficient solar water splitting. Particular attention was given to the cathodic shift in onset potential and photocurrent enhancement. Akaganite (β-FeOOH) nanorods were grown on ZrO2-coated FTO (fluorine-doped tin oxide) substrates. Sintering at 800 °C transformed akaganite to the hematite (α-Fe2O3) phase and induced Sn diffusion into the crystal structure of hematite nanorods from the FTO substrates and surface migration, shallow doping of Zr atoms from the ZrO2 underlayer. The ZrO2 underlayer-treated photoanode showed better water oxidation performance compared to the pristine (α-Fe2O3) photoanode. A cathodic shift in the onset potential and photocurrent enhancement was achieved by surface passivation and shallow doping of Zr from the ZrO2 underlayer, along with Sn doping from the FTO substrate to the crystal lattice of hematite nanorods. The Zr based hematite nanorod photoanode achieved 1 mA/cm(2) at 1.23 VRHE with a low turn-on voltage of 0.80 VRHE. Sn doping and Zr passivation, as well as shallow doping, were confirmed by XPS, Iph, and M-S plot analyses. Electrochemical impedance spectroscopy revealed that the presence of a ZrO2 underlayer decreased the deformation of FTO substrate, improved electron transfer at the hematite/FTO interface and increased charge-transfer resistance at the electrolyte/hematite interface. This is the first systematic investigation of the effects of Zr passivation, shallow doping, and Sn doping on hematite nanorod photoanodes through application of a ZrO2 underlayer on the FTO substrate.

Photoelectrochemical, impedance and optical data for self Sn-diffusion doped Fe2O3 photoanodes fabricated at high temperature by one and two-step annealing methods.

The optical, morphological and photoelectrochemical (PEC) properties of transition metal oxide semiconductors are important to understand their influence on water oxidation performance. Herein, we provide experimental evidences for a better understanding of the factors that dictate the interactions of Sn-diffusion doping on the PEC properties of Fe2O3 photoanodes fabricated at high temperature by one- and two-step annealing methods. The synthesis, characterization methods and other experimental details are provided. Limited previous information on the PEC and electrochemical impedance spectroscopic studies has been published. This data article contains Supplementary data, figures and methods related to the research article by Shinde et al. (2015) [1]. Here, we provide a further set of the obtained experimental data results.

Influence of Sb5+ as a Double Donor on Hematite (Fe3+) Photoanodes for Surface-Enhanced Photoelectrochemical Water Oxidation

To exploit the full potential of hematite (α-Fe2O3) as an efficient photoanode for water oxidation, the redox processes occurring at the Fe2O3/electrolyte interface need to be studied in greater detail. Ex situ doping is an excellent technique to introduce dopants onto the photoanode surface and to modify the photoanode/electrolyte interface. In this context, we selected antimony (Sb5+) as the ex situ dopant because it is an effective electron donor and reduces recombination effects and concurrently utilize the possibility to tuning the surface charge and wettability. In the presence of Sb5+ states in Sb-doped Fe2O3 photoanodes, as confirmed by X-ray photoelectron spectroscopy, we observed a 10-fold increase in carrier concentration (1.1 × 1020 vs 1.3 × 1019 cm-3) and decreased photoanode/electrolyte charge transfer resistance (∼990 vs ∼3700 Ω). Furthermore, a broad range of surface characterization techniques such as Fourier-transform infrared spectroscopy, ζ-potential, and contact angle measurements reveal that changes in the surface hydroxyl groups following the ex situ doping also have an effect on the water splitting capability. Theoretical calculations suggest that Sb5+ can activate multiple Fe3+ ions simultaneously, in addition to increasing the surface charge and enhancing the electron/hole transport properties. To a greater extent, the Sb5+- surface-doped determines the interfacial properties of electrochemical charge transfer, leading to an efficient water oxidation mechanism.