Hen Dotan

Probing the photoelectrochemical properties of hematite (α-Fe2O3) electrodes using hydrogen peroxide as a hole scavenger

We study hematite (α-Fe2O3) photoelectrodes for water splitting by examining the fate of photogenerated holes. Using H2O2 as an efficient hole scavenger, we collect all holes that arrive at the electrode/electrolyte interface. This provides the ability to distinguish between and quantify bulk and surface recombination processes involved in the photoelectrochemical oxidation of water. Below 1.0 VRHE, electrolyte oxidation kinetics limits the performance but above 1.2 VRHE bulk recombination becomes the limiting factor.

Identifying champion nanostructures for solar water-splitting

Charge transport in nanoparticle-based materials underlies many emerging energy-conversion technologies, yet assessing the impact of nanometre-scale structure on charge transport across micrometre-scale distances remains a challenge. Here we develop an approach for correlating the spatial distribution of crystalline and current-carrying domains in entire nanoparticle aggregates. We apply this approach to nanoparticle-based α-Fe₂O₃ electrodes that are of interest in solar-to-hydrogen energy conversion. In correlating structure and charge transport with nanometre resolution across micrometre-scale distances, we have identified the existence of champion nanoparticle aggregates that are most responsible for the high photoelectrochemical activity of the present electrodes. Indeed, when electrodes are fabricated with a high proportion of these champion nanostructures, the electrodes achieve the highest photocurrent of any metal oxide photoanode for photoelectrochemical water-splitting under 100 mW cm(-2) air mass 1.5 global sunlight.

Resonant light trapping in ultrathin films for water splitting

Semiconductor photoelectrodes for solar hydrogen production by water photoelectrolysis must employ stable, non-toxic, abundant and inexpensive visible-light absorbers. Iron oxide (α-Fe(2)O(3)) is one of few materials meeting these requirements, but its poor transport properties present challenges for efficient charge-carrier generation, separation, collection and injection. Here we show that these challenges can be addressed by means of resonant light trapping in ultrathin films designed as optical cavities. Interference between forward- and backward-propagating waves enhances the light absorption in quarter-wave or, in some cases, deeper subwavelength films, amplifying the intensity close to the surface wherein photogenerated minority charge carriers (holes) can reach the surface and oxidize water before recombination takes place. Combining this effect with photon retrapping schemes, such as using V-shaped cells, provides efficient light harvesting in ultrathin films of high internal quantum efficiency, overcoming the trade-off between light absorption and charge collection. A water photo-oxidation current density of 4 mA cm(-2) was achieved using a V-shaped cell comprising ~26-nm-thick Ti-doped α-Fe(2)O(3) films on back-reflector substrates coated with silver-gold alloy.

Enhancement in the Performance of Ultrathin Hematite Photoanode for Water Splitting by an Oxide Underlayer

A 2-nm thick Nb(2)O(5) underlayer deposited by atomic layer deposition increases the charge separation efficiency and the photovoltage of ultrathin hematite films by suppressing electron back injection. Absorbed photon-to-current efficiencies (APCE) as high as 40%, which are one of the highest ever reported with hematite photoanodes, are obtained at 400 nm at +1.43 V vs. RHE.

On the Solar to Hydrogen Conversion Efficiency of Photoelectrodes for Water Splitting

Reference EPFL-ARTICLE-203195doi:10.1021/jz501716gView record in Web of Science Record created on 2014-11-13, modified on 2017-05-12

Photoelectrochemical water splitting in separate oxygen and hydrogen cells

Solar water splitting provides a promising path for sustainable hydrogen production and solar energy storage. One of the greatest challenges towards large-scale utilization of this technology is reducing the hydrogen production cost. The conventional electrolyser architecture, where hydrogen and oxygen are co-produced in the same cell, gives rise to critical challenges in photoelectrochemical water splitting cells that directly convert solar energy and water to hydrogen. Here we overcome these challenges by separating the hydrogen and oxygen cells. The ion exchange in our cells is mediated by auxiliary electrodes, and the cells are connected to each other only by metal wires, enabling centralized hydrogen production. We demonstrate hydrogen generation in separate cells with solar-to-hydrogen conversion efficiency of 7.5%, which can readily surpass 10% using standard commercial components. A basic cost comparison shows that our approach is competitive with conventional photoelectrochemical systems, enabling safe and potentially affordable solar hydrogen production.

Systematic comparison of different dopants in thin film hematite (α-Fe2O3) photoanodes for solar water splitting

Numerous studies have shown that the addition of different impurities as dopants in hematite (α-Fe2O3) photoanodes improves water photo-oxidation. The improvements observed may have resulted from electronic and/or catalytic effects, but also from changes in the layer morphology and microstructure induced by different precursors. The latter could be quite substantial, especially in mesoporous layers produced by chemical routes, making it difficult to make a systematic comparison between different dopants. This work attempts to overcome this difficulty by comparing different dopants in thin films produced by pulsed laser deposition (PLD), a physical deposition method that produces highly reproducible films with no significant variations in the microstructure and morphology. This enables systematic comparison of the effect of different dopants without spurious side effects due to variations in the microstructure and morphology. Thus, we examine the effect of Sn, Nb, Si, Pt, Zr, Ti, Zn, Ni and Mn dopants on the photoelectrochemical properties of thin (∼50 nm) film hematite photoanodes deposited by PLD from Fe2O3 targets doped with ∼1 cation% of the respective dopants onto FTO coated glass substrates. The morphology and microstructure of the films were nearly the same, independent of the different dopants in the films. The Sn-doped hematite photoanode outperformed all the other photoanodes that were examined in this work in both the photocurrent and photovoltage, achieving the highest photocurrent (∼1 mA cm−2) and the lowest onset potential (∼1.1 VRHE). Based on a figure of merit that accounts for the maximum photocurrent × photovoltage product (i.e., power) as well as the potential at which the maximum power is achieved, our photoanodes ranked in the following order: Sn > Nb > Si > Pt > Zr > Ti > Zn > Ni > Mn. These observations are not always consistent with other reports on doped hematite photoanodes, suggesting that the photoelectrochemical properties and performance depend not only on the identity of the dopant but also on the dopant concentration, distribution and the morphology and microstructure of the photoanode in which the dopant is incorporated.

Hybrid bio-photo-electro-chemical cells for solar water splitting

Photoelectrochemical water splitting uses solar power to decompose water to hydrogen and oxygen. Here we show how the photocatalytic activity of thylakoid membranes leads to overall water splitting in a bio-photo-electro-chemical (BPEC) cell via a simple process. Thylakoids extracted from spinach are introduced into a BPEC cell containing buffer solution with ferricyanide. Upon solar-simulated illumination, water oxidation takes place and electrons are shuttled by the ferri/ferrocyanide redox couple from the thylakoids to a transparent electrode serving as the anode, yielding a photocurrent density of 0.5 mA cm−2. Hydrogen evolution occurs at the cathode at a bias as low as 0.8 V. A tandem cell comprising the BPEC cell and a Si photovoltaic module achieves overall water splitting with solar to hydrogen efficiency of 0.3%. These results demonstrate the promise of combining natural photosynthetic membranes and man-made photovoltaic cells in order to convert solar power into hydrogen fuel.

The Photosystem II D1-K238E mutation enhances electrical current production using cyanobacterial thylakoid membranes in a bio-photoelectrochemical cell

The conversion of solar energy (SEC) to storable chemical energy by photosynthesis has been performed by photosynthetic organisms, including oxygenic cyanobacteria for over 3 billion years. We have previously shown that crude thylakoid membranes from the cyanobacterium Synechocytis sp. PCC 6803 can reduce the electron transfer (ET) protein cytochrome c even in the presence of the PSII inhibitor DCMU. Mutation of lysine 238 of the Photosystem II D1 protein to glutamic acid increased the cytochrome reduction rates, indicating the possible position of this unknown ET pathway. In this contribution, we show that D1-K238E is rather unique, as other mutations to K238, or to other residues in the same vicinity, are not as successful in cytochrome c reduction. This observation indicates the sensitivity of ET reactions to minor changes. As the next step in obtaining useful SEC from biological material, we describe the use of crude Synechocystis membranes in a bio-photovoltaic cell containing an N-acetyl cysteine-modified gold electrode. We show the production of significant current for prolonged time durations, in the presence of DCMU. Surprisingly, the presence of cytochrome c was not found to be necessary for ET to the bio-voltaic cell.

Heteroepitaxial hematite photoanodes as a model system for solar water splitting

Heteroepitaxial multilayer Pt(111)/Fe2O3(0001) films were deposited on sapphire c-plane (0001) substrates by RF magnetron sputtering and pulsed laser deposition, respectively. The films were highly crystalline, displaying an in-plane mosaic spread of less than 1° and a homogenous surface morphology with roughness of ∼3 A. Ellipsometry and UV-vis spectroscopy measurements were shown to be in excellent agreement with modelling, demonstrating that the optics of the system including absorption in the hematite layer are well described. For polycrystalline hematite photoanodes deposited on platinum, full characterization of the system is hampered by the inability to make measurements in alkaline electrolyte containing hydrogen peroxide (H2O2) due to spontaneous decomposition of H2O2 by the exposed platinum. The pin-hole free high quality of the heteroepitaxial films is demonstrated by the ability to make stable and reproducible measurements in H2O2 containing electrolyte allowing for accurate extraction of charge separation and injection efficiency. The combination of excellent crystalline quality in addition to the well characterized optics and electrochemical properties of the heteroepitaxial hematite photoanodes demonstrate that Al2O3(0001)/Pt(111)/Fe2O3(0001) is a powerful model system for systematic investigation into solar water splitting photoanodes.