Extraction of mobile charge carrier photogeneration yield spectrum of ultrathin-film metal oxide photoanodes for solar water splitting.

Light absorption in strongly correlated electron materials can excite electrons and holes into a variety of different states. Some of these excitations yield mobile charge carriers, whereas others result in localized states that cannot contribute to photocurrent. The photogeneration yield spectrum, ξ(λ), represents the wavelength-dependent ratio between the contributing absorption that ultimately generates mobile charge carriers and the overall absorption. Despite being a vital material property, it is not trivial to characterize. Here, we present an empirical method to extract ξ(λ) through optical and external quantum efficiency measurements of ultrathin films. We applied this method to haematite photoanodes for water photo-oxidation, and observed that it is self-consistent for different illumination conditions and applied potentials. We found agreement between the extracted ξ(λ) spectrum and the photoconductivity spectrum measured by time-resolved microwave conductivity. These measurements revealed that mobile charge carrier generation increases with increasing energy across haematite's absorption spectrum. Low-energy non-contributing absorption fundamentally limits the photoconversion efficiency of haematite photoanodes and provides an upper limit to the achievable photocurrent that is substantially lower than that predicted based solely on absorption above the bandgap. We extended our analysis to TiO2 and BiVO4 photoanodes, demonstrating the broader utility of the method for determining ξ(λ).

Two-site H2O2 photo-oxidation on haematite photoanodes.

H2O2 is a sacrificial reductant that is often used as a hole scavenger to gain insight into photoanode properties. Here we show a distinct mechanism of H2O2 photo-oxidation on haematite (α-Fe2O3) photoanodes. We found that the photocurrent voltammograms display non-monotonous behaviour upon varying the H2O2 concentration, which is not in accord with a linear surface reaction mechanism that involves a single reaction site as in Eley-Rideal reactions. We postulate a nonlinear kinetic mechanism that involves concerted interaction between adions induced by H2O2 deprotonation in the alkaline solution with adjacent intermediate species of the water photo-oxidation reaction, thereby involving two reaction sites as in Langmuir-Hinshelwood reactions. The devised kinetic model reproduces our main observations and predicts coexistence of two surface reaction paths (bi-stability) in a certain range of potentials and H2O2 concentrations. This prediction is confirmed experimentally by observing a hysteresis loop in the photocurrent voltammogram measured in the predicted coexistence range.

Film Flip and Transfer Process to Enhance Light Harvesting in Ultrathin Absorber Films on Specular Back-Reflectors.

Optical interference is used to enhance light-matter interaction and harvest broadband light in ultrathin semiconductor absorber films on specular back-reflectors. However, the high-temperature processing in oxygen atmosphere required for oxide absorbers often degrades metallic back-reflectors and their specular reflectance. In order to overcome this problem, a newly developed film flip and transfer process is presented that enables high-temperature processing without degradation of the metallic back-reflector and without the need of passivation interlayers. The film flip and transfer process improves the performance of photoanodes for photoelectrochemical water splitting comprising ultrathin (<20 nm) hematite (α-Fe2 O3 ) films on silver-gold alloy (90 at% Ag-10 at% Au) back-reflectors. Specular back-reflectors are obtained with high reflectance below hematite films, which is necessary for maximizing the productive light absorption in the hematite film and minimizing nonproductive absorption in the back-reflector. Furthermore, the film flip and transfer process opens up a new route to attach thin film stacks onto a wide range of substrates including flexible or temperature sensitive materials.

Empirical Analysis of the Photoelectrochemical Impedance Response of Hematite Photoanodes for Water Photo-oxidation.

Photoelectrochemical impedance spectroscopy (PEIS) is a useful tool for the characterization of photoelectrodes for solar water splitting. However, the analysis of PEIS spectra often involves a priori assumptions that might bias the results. This work puts forward an empirical method that analyzes the distribution of relaxation times (DRT), obtained directly from the measured PEIS spectra of a model hematite photoanode. By following how the DRT evolves as a function of control parameters such as the applied potential and composition of the electrolyte solution, we obtain unbiased insights into the underlying mechanisms that shape the photocurrent. In a subsequent step, we fit the data to a process-oriented equivalent circuit model (ECM) whose makeup is derived from the DRT analysis in the first step. This yields consistent quantitative trends of the dominant polarization processes observed. Our observations reveal a common step for the photo-oxidation reactions of water and H2O2 in alkaline solution.

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.

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.

Empirical in operando analysis of the charge carrier dynamics in hematite photoanodes by PEIS, IMPS and IMVS.

In this Perspective, we introduce intensity modulated photocurrent/voltage spectroscopy (IMPS and IMVS) as powerful tools for the analysis of charge carrier dynamics in photoelectrochemical (PEC) cells for solar water splitting, taking hematite (α-Fe2O3) photoanodes as a case study. We complete the picture by including photoelectrochemical impedance spectroscopy (PEIS) and linking the trio of PEIS, IMPS and IMVS, introduced here as photoelectrochemical immittance triplets (PIT), both mathematically and phenomenologically, demonstrating what conclusions can be extracted from these measurements. A novel way of analyzing the results by an empirical approach with minimal presumptions is introduced, using the distribution of relaxation times (DRT) function. The DRT approach is compared to conventional analysis approaches that are based on physical models and therefore come with model presumptions. This work uses a thin film hematite photoanode as a model system, but the approach can be applied to other PEC systems as well.

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.

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.