Hematite Photoelectrodes Research Articles

Water Oxidation at Hematite Photoelectrodes: The Role of Surface States

Hematite (α-Fe(2)O(3)) constitutes one of the most promising semiconductor materials for the conversion of sunlight into chemical fuels by water splitting. Its inherent drawbacks related to the long penetration depth of light and poor charge carrier conductivity are being progressively overcome by employing nanostructuring strategies and improved catalysts. However, the physical-chemical mechanisms responsible for the photoelectrochemical performance of this material (J(V) response) are still poorly understood. In the present study we prepared thin film hematite electrodes by atomic layer deposition to study the photoelectrochemical properties of this material under water-splitting conditions. We employed impedance spectroscopy to determine the main steps involved in photocurrent production at different conditions of voltage, light intensity, and electrolyte pH. A general physical model is proposed, which includes the existence of a surface state at the semiconductor/liquid interface where holes accumulate. The strong correlation between the charging of this state with the charge transfer resistance and the photocurrent onset provides new evidence of the accumulation of holes in surface states at the semiconductor/electrolyte interface, which are responsible for water oxidation. The charging of this surface state under illumination is also related to the shift of the measured flat-band potential. These findings demonstrate the utility of impedance spectroscopy in investigations of hematite electrodes to provide key parameters of photoelectrodes with a relatively simple measurement.

Facile fabrication of tin-doped hematite photoelectrodes – effect of doping on magnetic properties and performance for light-induced water splitting

We present a new, easily scalable method for the deposition of nanocrystalline hematite photoelectrodes based on the spin-coating of a mixed solution containing tin(II) and iron(III) chlorides followed by thermal treatment. Our facile approach does not require any additional film-forming organic species and allows simple control of the photoelectrochemical performance of the electrode by adjusting the degree of tin doping. When annealed at 650 °C a strong increase in the water oxidation photocurrent is observed with increasing tin concentration. The maximum performance (0.45 mA cm−2 at 1.43 V vs. RHE) was found at the highest possible tin loading (20 : 100, Sn : Fe). The contrasting performance of electrodes annealed at 650 °C and 800 °C suggests different activation processes for dopant diffusion and activation. The doping of tin into the crystal structure of hematite thin films is directly evidenced by X-ray photoelectron spectroscopy and indirectly by changes in the intrinsic magnetic parameters (Morin temperature, Néel temperature) of the hematite films. The magnetization measurements thus represent a potential technique to quantify doping amounts in hematite.

Voltage dependent photocurrent of thin film hematite electrodes

The current density (J) vs. applied voltage (V) curves of thin-film hematite electrodes under illumination exhibit non-ideal behavior; as a result, very poor fill factors and photocurrent densities are generally observed. A simple model is presented to describe the photocurrent density behavior of hematite photoelectrodes, which assumes only drift collection of holes in a uniform electric field. Excellent agreement is found between the model and experimental results. Use of this model provides important insight into the limitations of hematite electrodes as well as strategies to achieve improved efficiency.

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.

Impedance characterization of dye-sensitized solar cells in a tandem arrangement for hydrogen production by water splitting

The present work reports the photoelectrochemical characterization of a dye-sensitized solar cell (DSC) to assist water split in a photoelectrochemical (PEC) cell. Performance parameters were extracted from standard current–voltage characteristic ( I–V) and the charge transfer phenomena occurring at different interfaces of the DSC were evaluated by electrochemical impedance spectroscopy (EIS). The DSC comprised the N719 dye and a robust electrolyte (1-propyl-3-methylimidazolium iodide in guanidinium thiocyanate additive). At 1 sun illumination the DSC yielded a short-circuit photocurrent density of 14.9 mA cm −2, an open-circuit voltage of 0.797 V, a fill factor of 0.712 and an overall efficiency of 8.5%. Different PEC systems based on silicon-doped and undoped hematite photoelectrodes were considered. The required additional anodic bias necessary for actual water cleavage was supplied by two DSCs in series operating just under open-circuit voltage (1.56 V), allowing a conversion efficiency of about 1.12% for the silicon-doped hematite deposited by APCVD, 0.51% for the silicon-doped prepared by USP and 0.12% for the undoped hematite sample.

Controlling Photoactivity in Ultrathin Hematite Films for Solar Water‐Splitting

AbstractA promising route to increase the performance of hematite (α‐Fe2O3) photoelectrodes for solar hydrogen production through water‐splitting is to use an extremely thin layer of this visible light absorber on a nanostructured scaffold. However, the typically poor performance of ultrathin (ca. 20 nm) films of hematite has been the limiting factor in implementing this approach. Here, the surprising effect of a substrate pretreatment using tetraethoxysilicate (TEOS) is reported; it results in drastic improvements in the photoperformance of 12.5 nm thick films of hematite. These films exhibit a water oxidation photocurrent onset potential at 1.1 V versus the reversible hydrogen electrode (vs. RHE) and a plateau current of 0.63 mA cm−2 at 1.5 V vs. RHE under standard illumination conditions, representing the highest reported performance for ultrathin hematite films. In contrast, almost no photoactivity is observed for the photoanode with the same amount of hematite on an untreated substrate. A detailed study of the effects of the TEOS treatment shows that a monolayer of SiOx is formed, which acts to change the hematite nucleation and growth mechanism, increases its crystallinity, reduces the concentration of carrier trapping states of the ultrathin films, and suggests its further application to quantum‐dot and extremely‐thin‐absorber (ETA)‐type solar cells.

NiFe-oxide electrocatalysts for the oxygen evolution reaction on Ti doped hematite photoelectrodes

Nickel iron binary oxide electrocatalysts prepared from different precursors were evaluated to facilitate the oxygen evolution reaction (OER) on semiconducting metal-oxide photoelectrodes. The electrocatalysts deposited from Ni(II) and Ni(II)Fe(II) precursors had the highest activity for OER, however, their presence on the surface of the Ti doped hematite photoelectrode decreased the incident photon-to-current efficiency (IPCE) of the photoelectrode for water splitting in an alkaline electrolyte. In contrast, the NiFe-oxide deposited from the Ni(II)–Fe(III) precursor which had a lower OER activity was found to increase the IPCE of the photoelectrode by as much as a factor of 5.

Fabrication of nanostructured α-Fe 2O 3 electrodes using ferrocene for solar hydrogen generation

Nanostructured thin films of α-Fe 2O 3 were prepared through atmospheric chemical vapour deposition (APCVD) using ferrocene and iron pentacarbonyl as precursors. Higher optical absorption was observed for hematite films prepared using ferrocene, which was attributed to the higher packing density. Photoelectrochemical (PEC) studies of the films prepared using ferrocene showed superior performance to that of iron pentacarbonyl. Photocurrent density of 540 µA/cm 2 and 1.5 µA/cm 2 at 1.23 V RHE was achieved for hematite films prepared using ferrocene and iron pentacarbonyl, respectively. Our findings suggest that ferrocene can be used as a promising alternative to iron pentacarbonyl to prepare hematite photoelectrodes using APCVD.