Light-absorbing semiconductor electrodes coated with electrocatalysts are key components of photoelectrochemical energy conversion and storage systems. Efforts to optimize these systems have been slowed by an inadequate understanding of the semiconductor-electrocatalyst (sem|cat) interface. The sem|cat interface is important because it separates and collects photoexcited charge carriers from the semiconductor. The photovoltage generated by the interface drives "uphill" photochemical reactions, such as water splitting to form hydrogen fuel. Here we describe efforts to understand the microscopic processes and materials parameters governing interfacial electron transfer between light-absorbing semiconductors, electrocatalysts, and solution. We highlight the properties of transition-metal oxyhydroxide electrocatalysts, such as Ni(Fe)OOH, because they are the fastest oxygen-evolution catalysts known in alkaline media and are (typically) permeable to electrolyte. We describe the physics that govern the charge-transfer kinetics for different interface types, and show how numerical simulations can explain the response of composite systems. Emphasis is placed on "limiting" behavior. Electrocatalysts that are permeable to electrolyte form "adaptive" junctions where the interface energetics change during operation as charge accumulates in the catalyst, but is screened locally by electrolyte ions. Electrocatalysts that are dense, and thus impermeable to electrolyte, form buried junctions where the interface physics are unchanged during operation. Experiments to directly measure the interface behavior and test the theory/simulations are challenging because conventional photoelectrochemical techniques do not measure the electrocatalyst potential during operation. We developed dual-working-electrode (DWE) photoelectrochemistry to address this limitation. A second electrode is attached to the catalyst layer to sense or control current/voltage independent from that of the semiconductor back ohmic contact. Consistent with simulations, electrolyte-permeable, redox-active catalysts such as Ni(Fe)OOH form "adaptive" junctions where the effective barrier height for electron exchange depends on the potential of the catalyst. This is in contrast to sem|cat interfaces with dense electrolyte-impermeable catalysts, such as nanocrystalline IrOx, that behave like solid-state buried (Schottky-like) junctions. These results elucidate a design principle for catalyzed photoelectrodes. The buried heterojunctions formed by dense catalysts are often limited by Fermi-level pinning and low photovoltages. Catalysts deposited by "soft" methods, such as electrodeposition, form adaptive junctions that tend to provide larger photovoltages and efficiencies. We also preview efforts to improve theory/simulations to account for the presence of surface states and discuss the prospect of carrier-selective catalyst contacts.

The optical properties of electrocatalysts are important for photoelectrochemical water splitting because colored catalysts on the surface of semiconductor photoelectrodes parasitically absorb photons and lower the system efficiency. We present a model that describes the coupling of colored oxygen evolution reaction (OER) electrocatalyst thin films with semiconductor photoelectrodes. We use this model to define an "optocatalytic" efficiency (Φo-c) based on experimental optical and electrokinetic data collected in basic solution. Because transition-metal oxides, hydroxides, and oxyhydroxides often exhibit electrochromism, in situ spectroelectrochemistry is used to quantify the optical absorption of active NiOx, CoOx, NiCoOx, Ni0.9Fe0.1Ox, and IrOx catalyst films at OER potentials. For the highest-activity Ni0.9Fe0.1Ox catalyst, Φo-c is maximized (0.64) for a thickness of ∼0.4 nm (∼2 monolayers). This work quantitatively shows that ultrathin catalyst films are appropriate to optimize the performance of water-splitting photoelectrodes and thus assists in the design and study of efficient photoelectrochemical water-splitting devices.

We develop a theory of charge transfer at semiconductor-catalyst interfaces to elucidate the current-potential behavior of semiconductor-catalyst-solution systems used for solar water splitting and compare simulations based on this theory to experimental data. Ion-permeable catalysts are found to form semiconductor-catalyst interfaces where the effective barrier height changes under operation yielding higher photovoltages and efficiencies relative to dense catalysts with the same catalytic activity. Such behavior is not captured by current equivalent circuit models, but is central to the study and design of efficient water-splitting systems.

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A comprehensive analysis of a model describing charge carrier injection and transport in lightemitting electrochemical cells (LECs) and related mixed ionic electronic conductors (MIECs) is given. Ions are treated using a modified drift-diffusion transport equation that accounts for volume exclusion effects, and electronic injection is treated using a spatially dependent tunneling mechanism that explicitly accounts for both forward and backward fluxes. Systems containing both one and two mobile ionic species are treated and compared. The unique physics of LECs stem from ionic polarization processes that can lead to field screening and narrowed injection barriers, producing increased electrode exchange currents via tunneling. The latter process promotes the establishment of electronic quasi-equilibrium throughout the double-layer regions and hence promotes bulk-limited conduction. Explicit expressions are given describing the conditions necessary to assume field screening and bulk-limited conduction, which determine the applicability of either traditional semiconductor device models such as Fowler-Nordheim or electrochemical models such as the Nernst equation. Having established these conditions, several distinct regimes of bulk-limited LEC behavior are described. Explicit formulae for the biases delineating these regimes are given as well as formulae for the current in each regime. At low biases, the current generally increases exponentially with bias; the bulk remains field-free, and the transport is predominantly unipolar and diffusive. At high biases the current rises much less rapidly, and bulk transport is bipolar, occurring through a combination of drift and diffusion. The nature of the bulk region in the high-bias regime is markedly different in systems with one and two mobile ionic species. At intermediate biases, space charge effects preferentially drive injection of the minority carrier causing a transition from unipolar to bipolar injection. It is demonstrated that many of the models proposed to describe LECs exist upon a common continuum, and that the major factor separating them is simply the magnitude of the applied bias. This work allows one to estimate at what biases an idealized LEC with particular equilibrium concentrations of ionic and electronic carriers will transition from one mechanism to another. It also aids in conceptually mapping mechanisms and internal details of the system onto each regime of behavior.