Interpretation of photocurrent transients at semiconductor electrodes:Effects of band-edge unpinning

The transient photocurrent response of semiconductor electrodes to chopped illumination often shows spikes and overshoots that are usually interpreted as evidence that surface recombination is occurring. In the case of the high intensities used for light-driven water splitting, the interpretation is less straightforward since the electron transfer reactions are so slow that the minority carrier concentration at or near the surface increases to high values that modify the potential drop across the Helmholtz layer in the electrolyte, leading to ‘band edge unpinning’. In addition, changes in chemical composition of the surface or local changes in pH may also alter the potential distribution across the semiconductor/electrolyte junction. A quantitative theory of band edge unpinning due to minority carrier build up is presented, and numerical calculations of transient photocurrent responses are compared with experimental examples for n-type Fe2O3 and p-type lithium-doped CuO electrodes. It is shown that the apparently high reaction orders (up to third order) with respect to hole concentration reported for hematite photoanodes can be explained as arising from an acceleration of hole transfer by the increased voltage drop across the Helmholtz layer associated with band edge unpinning. The limitations of the band edge unpinning model are discussed considering additional effects associated with modification of the potential distribution brought about by light-induced changes in surface composition, surface dipoles and surface ionic charge.</p

Nanostructured Ternary FeCrAl Oxide Photocathodes for Water Photoelectrolysis

A sol–gel method for the synthesis of semiconducting FeCrAl oxide photocathodes for solar-driven hydrogen production was developed and applied for the production of meso- and macroporous layers with the overall stoichiometry Fe_0.84Cr_1.0Al_0.16O₃. Using transmission electron microscopy and energy-dispersive X-ray spectroscopy, phase separation into Fe- and Cr-rich phases was observed for both morphologies. Compared to prior work and to the mesoporous layer, the macroporous FeCrAl oxide photocathode had a significantly enhanced photoelectrolysis performance, even at a very early onset potential of 1.1 V vs RHE. By optimizing the macroporous electrodes, the device reached current densities of up to 0.68 mA cm^–2 at 0.5 V vs RHE under AM 1.5 with an incident photon-to-current efficiency (IPCE) of 28% at 400 nm without the use of catalysts. Based on transient measurements, this performance increase could be attributed to an improved collection efficiency. At a potential of 0.75 V vs RHE, an electron transfer efficiency of 48.5% was determined

Oriented Films of Conjugated 2D Covalent Organic Frameworks as Photocathodes for Water Splitting

Light-driven water electrolysis at a semiconductor surface is a promising way to generate hydrogen from sustainable energy sources, but its efficiency is limited by the performance of available photoabsorbers. Here we report the first time investigation of covalent organic frameworks (COFs) as a new class of photoelectrodes. The presented 2D-COF structure is assembled from aromatic amine-functionalized tetraphenylethylene and thiophene dialdehyde building blocks to form conjugated polyimine sheets, which π-stack in the third dimension to create photoactive porous frameworks. Highly oriented COF films absorb light in the visible range to generate photo-excited electrons that diffuse to the surface and are transferred to the electrolyte resulting in proton reduction and hydrogen evolution. The observed photoelectrochemical activity of the 2D-COF films and their photocorrosion stability in water pave the way for a novel class of photoabsorber materials with versatile optical and electronic properties that are tunable through the selection of appropriate building blocks and their three-dimensional stacking

Electron Collection in Host–Guest Nanostructured Hematite Photoanodes for Water Splitting: The Influence of Scaffold Doping Density

Nanostructuring has proven to be a successful strategy in overcoming the trade-off between light absorption and hole transport to the solid/electrolyte interface in hematite photoanodes for water splitting. The suggestion that poor electron (majority carrier) collection hinders the performance of nanostructured hematite electrodes has led to the emergence of host–guest architectures in which the absorber layer is deposited onto a transparent high-surface-area electron collector. To date, however, state of the art nanostructured hematite electrodes still outperform their host–guest counterparts, and a quantitative evaluation of the benefits of the host–guest architecture is still lacking. In this paper, we examine the impact of host–guest architectures by comparing nanostructured tin-doped hematite electrodes with hematite nanoparticle layers coated onto two types of conducting macroporous SnO₂ scaffolds. Analysis of the external quantum efficiency spectra for substrate (SI) and electrolyte side (EI) illumination reveals that the electron diffusion length in the host–guest electrodes based on an undoped SnO₂ scaffold is increased substantially relative to the nanostructured hematite electrode without a supporting scaffold. Nevertheless, electron collection is still incomplete for EI illumination. By contrast, an electron collection efficiency of 100% is achieved by fabricating the scaffold using antimony-doped SnO₂, showing that the scaffold conductivity is crucial for the device performance

Oriented Films of Conjugated 2D Covalent Organic Frameworks as Photocathodes for Water Splitting

Light-driven water electrolysis at a semiconductor surface is a promising way to generate hydrogen from sustainable energy sources, but its efficiency is limited by the performance of available photoabsorbers. Here we report the first time investigation of covalent organic frameworks (COFs) as a new class of photoelectrodes. The presented 2D-COF structure is assembled from aromatic amine-functionalized tetraphenylethylene and thiophene dialdehyde building blocks to form conjugated polyimine sheets, which π-stack in the third dimension to create photoactive porous frameworks. Highly oriented COF films absorb light in the visible range to generate photo-excited electrons that diffuse to the surface and are transferred to the electrolyte resulting in proton reduction and hydrogen evolution. The observed photoelectrochemical activity of the 2D-COF films and their photocorrosion stability in water pave the way for a novel class of photoabsorber materials with versatile optical and electronic properties that are tunable through the selection of appropriate building blocks and their three-dimensional stacking