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Photoelectrochemical (PEC) water splitting is a means to store solar energy in the form of hydrogen. Knowledge of practical limits for this process can help researchers assess their technology and guide future directions. We develop a model to quantify loss mechanisms in PEC water splitting based on the current state of materials research and calculate maximum solar-to-hydrogen (STH) conversion efficiencies along with associated optimal absorber band gaps. Various absorber configurations are modeled considering the major loss mechanisms in PEC devices. Quantitative sensitivity analyses for each loss mechanism and each absorber configuration show a profound impact of both on the resulting STH efficiencies, which can reach upwards of 25 % for the highest performance materials in a dual stacked configuration. Higher efficiencies could be reached as improved materials are developed. The results of the modeling also identify and quantify approaches that can improve system performance when working with imperfect materials.

Herein, we report the development of optically transparent high surface area electrodes (HSEs) made of indium tin oxide (ITO) using a facile, template-free, scalable wet chemical synthetic approach. The transparent HSEs are electronically conductive and physically robust, with tunable electrochemically accessible roughness factors from 1 through ∼100. These transparent HSEs can serve as a broadly functionalizable scaffold ideally suited to bridge the gap between the need to minimize ionic and electronic transport lengths within a device and the need to achieve high loadings of active material per surface area (e.g. for high capacity as needed for batteries or high optical density as required for electrochromics or photovoltaics). This gap currently stands as a major hurdle for the utilization of many nanomaterials in electronic and optoelectronic devices. The synthetic approach described here for ITO is transferable to other transparent conducting oxide (TCO) materials. This is the first report of a large...

We report a hierarchically branched TiO2 nanorod structure that serves as a model architecture for efficient photoelectrochemical devices as it simultaneously offers a large contact area with the electrolyte, excellent light-trapping characteristics, and a highly conductive pathway for charge carrier collection. Under Xenon lamp illumination (UV spectrum matched to AM 1.5G, 88 mW/cm2 total power density), the branched TiO2 nanorod array produces a photocurrent density of 0.83 mA/cm2 at 0.8 V versus reversible hydrogen electrode (RHE). The incident photon-to-current conversion efficiency reaches 67% at 380 nm with an applied bias of 0.6 V versus RHE, nearly two times higher than the bare nanorods without branches. The branches improve efficiency by means of (i) improved charge separation and transport within the branches due to their small diameters, and (ii) a 4-fold increase in surface area which facilitates the hole transfer at the TiO2/electrolyte interface.

Photoelectrochemical (PEC) water splitting for hydrogen production is a promising technology that uses sunlight and water to produce renewable hydrogen with oxygen as a by-product. In the expanding field of PEC hydrogen production, the use of standardized screening methods and reporting has emerged as a necessity. This article is intended to provide guidance on key practices in characterization of PEC materials and proper reporting of efficiencies. Presented here are the definitions of various efficiency values that pertain to PEC, with an emphasis on the importance of solar-to-hydrogen efficiency, as well as a flow chart with standard procedures for PEC characterization techniques for planar photoelectrode materials (i.e., not suspensions of particles) with a focus on single band gap absorbers. These guidelines serve as a foundation and prelude to a much more complete and in-depth discussion of PEC techniques and procedures presented elsewhere.

Solar-to-hydrogen (STH) conversion efficiency is the most important figure of merit to gage the potential of a semiconductor material to photoelectrochemically split water (see Chapter “ Efficiency Definitions in the Field of PEC”). It is projected that STH conversion efficiencies in excess of 10 % will be needed for practical hydrogen production systems [1]. Taken in conjunction with gas detection measurements (see Chapter “ Stability Testing”), the photocurrent density (j SC) under short-circuited conditions (i.e., zero applied bias) in a 2-electrode measurement is critical in determining the STH conversion efficiency. Moreover, applied bias experiments using the 2-electrode configuration can shed important light on the water splitting capabilities and limits of a PEC material system.

It is important to determine the conductivity and flat-band potential (Efb) of a photoelectrode before carrying out any photoelectrochemical experiments. These properties help to elucidate the band structure of a semiconductor which ultimately determines its ability to drive efficient water splitting. The three different techniques that can estimate the Efb are: Illuminated OCP, Mott–Schottky and Photocurrent Onset. The Efb should be independent of the technique used to determine it. Due to the inherent shortcomings of each technique, there is often a lack of agreement of the values determined by the various analyses. Researchers should be aware of these limitations in interpreting results.

In a UV-Vis (ultraviolet-visible light) spectroscopic measurement, light absorption as a function of wavelength provides information about electronic transitions occurring in the material. For semiconductors, UV-Vis spectroscopy offers a convenient method of estimating the optical band gap, since it probes electronic transitions between the valence band and the conduction band. Transmission UV-Vis, Diffuse Reflectance UV-Vis, and Absorption UV-Vis configurations are discussed.

The goal of PEC materials development is to design a material system that has the potential to satisfy most, if not all, of the requirements for cost-effective PEC hydrogen production. Figure 1 presents a recommended flowchart for the characterization of candidate PEC materials. The key knowledge gained as well as limitations of the different characterization techniques, highlighted in Table 1, are described in detail in following sections of this document. A material that can survive the rigorous testing set forth in this flowchart will be a particularly promising candidate for incorporation into an industrially deployable device for PEC hydrogen production. This organized approach to PEC characterization is intended to streamline the process for material screening so that discovery of promising candidates occurs at a faster and more orderly pace.

The incident photon-to-current efficiency (IPCE) is a measure of the ratio of the photocurrent (converted to an electron transfer rate) versus the rate of incident photons (converted from the calibrated power of a light source) as a function of wavelength. Measuring the IPCE is also useful to determine the band gap. The band gap derived from IPCE may be higher than that obtained by optical spectroscopy techniques. Applied bias IPCE and white light bias IPCE experiments are discussed. Photocurrent spectroscopy examines the photocurrent produced by an electrochemical cell as a function of wavelength of the incident light. The optical bulk band gap of the semiconductor electrode can be determined along with information about whether it is a direct or indirect transition.

Herein, a high surface area electrode (HSE) consisting of indium tin oxide (ITO) as a scaffold and ultrathin Ti-doped hematite (α-Fe2O3) as the absorber material is developed. The HSE exhibits sixfold improvement in photoactivity over an analogous photoelectrode with a flat morphology. Interfacial recombination due to dopant impurities and shunting resulting from a high pinhole density in the hematite layer limit the device performance. These limitations are mitigated by introducing a tin oxide barrier layer, which reduces recombination at the solid–solid interface and mitigates shunting. Employing the HSE with an appropriate barrier layer improves charge separation efficiency and catalytic activity compared to conventional planar devices. This strategy can potentially be extended to other light absorber materials whose performance is affected by charge transport limitations.

Photoelectrochemical water splitting is a promising route for the renewable production of hydrogen fuel. This work presents the results of a technical and economic feasibility analysis conducted for four hypothetical, centralized, large-scale hydrogen production plants based on this technology. The four reactor types considered were a single bed particle suspension system, a dual bed particle suspension system, a fixed panel array, and a tracking concentrator array. The current performance of semiconductor absorbers and electrocatalysts were considered to compute reasonable solar-to-hydrogen conversion efficiencies for each of the four systems. The U.S. Department of Energy H2A model was employed to calculate the levelized cost of hydrogen output at the plant gate at 300 psi for a 10 tonne per day production scale. All capital expenditures and operating costs for the reactors and auxiliaries (compressors, control systems, etc.) were considered. The final cost varied from $1.60–$10.40 per kg H2 with the particle bed systems having lower costs than the panel-based systems. However, safety concerns due to the cogeneration of O_2 and H_2 in a single bed system and long molecular transport lengths in the dual bed system lead to greater uncertainty in their operation. A sensitivity analysis revealed that improvement in the solar-to-hydrogen efficiency of the panel-based systems could substantially drive down their costs. A key finding is that the production costs are consistent with the Department of Energy's targeted threshold cost of $2.00–$4.00 per kg H_2 for dispensed hydrogen, demonstrating that photoelectrochemical water splitting could be a viable route for hydrogen production in the future if material performance targets can be met.

We report the molecular beam epitaxy growth of Al0.3Ga0.7As∕GaAs multijunction solar cells with epitaxial, semimetallic ErAs nanoparticles at the interface of the tunnel junction. The states provided by these nanoparticles reduce the bias required to pass current through the tunnel junction by three orders of magnitude, and therefore drastically reduce the voltage losses in the tunnel junction. We have measured open-circuit voltages which are 97% of the sum of the constituent cells, which result in nearly double the efficiency of our multijunction cell with a conventional tunnel junction.