Photoanode For Photoelectrochemical Water Oxidation Research Articles

Low-Temperature Atomic Layer Deposition of Crystalline and Photoactive Ultrathin Hematite Films for Solar Water Splitting.

We developed a low-temperature atomic layer deposition route to deposit phase pure and crystalline hematite (α-Fe2O3) films at 230 °C without the need for postannealing. Homogenous and conformal deposition with good aspect ratio coverage was demonstrated on a nanostructured substrate and analyzed by transmission electron microscopy. These as-deposited α-Fe2O3 films were investigated as photoanodes for photoelectrochemical water oxidation and found to be highly photoactive. Combined with a TiO2 underlayer and a low-cost Ni(OH)2 catalyst, hematite films of less than 10 nm in thickness reached photocurrent densities of 0.3 mA cm(-2) at 1.23 V vs RHE and a photocurrent onset potential of less than 0.9 V vs RHE, previously unseen for films this thin and without high temperature annealing. In a thickness-dependent photoelectrochemical analysis, we identified a hematite thickness of only 10 nm to yield the highest internal quantum efficiency when using a suitable underlayer such as TiO2 that induces doping of the hematite film and reduces electron/hole recombination at the back contact. We find that, at high bias potentials, photocurrent density and quantum efficiency proportionally increase with light absorption in films thinner than 10 nm and are limited by the space charge layer width in thicker films. Thus, we propose to apply hematite films of 10 nm in thickness for future developments on suitable nanostructured conductive scaffolds that can now be extended to organic scaffolds due to our low-temperature process.

N-Fe₂O₃ to N⁺-TiO₂Heterojunction Photoanode for Photoelectrochemical Water Oxidation.

To improve the performance of the thin hematite photoanode for photoelectrochemical water oxidation, in this work, an nN(+) α-Fe2O3 (hematite)-TiO2 heterojunction photoanode is constructed on fluorine-doped tin oxide substrate to establish a built-in field in the space charge region for facilitating the charge separation in the hematite layer. Charge distribution in the hematite-TiO2 heterostructure is investigated using Kelvin probe force microscopy, which confirms the improvement of charge separation in hematite layer by the formation of energy-matched nN(+) α-Fe2O3-TiO2 heterojunction. Compared to the hematite photoanode, an eightfold enhancement of the photocurrent density at 1.23 V versus reversible hydrogen electrode is measured in the hematite-TiO2 heterojunction photoanode. By using hydrogen peroxide as a hole scavenger, it demonstrates that both charge separation and charge injection efficiencies in the hematite-TiO2 heterojunction photoanode are superior to those in the hematite photoanode. It results from the significant suppressions of the charge recombinations occurring within the hematite layer as well as at the interface of photoelectrode and electrolyte by the formation of the nN(+) α-Fe2O3-TiO2 heterojunction.

Efficient photoelectrochemical water splitting using three dimensional urchin-like hematite nanostructure modified with reduced graphene oxide

Herein, we present a highly photoactive photoanode for solar water oxidation using three dimensional (3D) urchin-like hematite (α-Fe2O3) nanostructures modified with ultra-thin reduced graphene oxide (rGO). rGO acts as both electron conducting scaffold and surface passivation layer. By virtue of these combined effects, the composite photoanode exhibits 1.47 times higher photocurrent density (1.06 mA cm−2, at 1.23 V vs. reversible hydrogen electrode (RHE)) and two-fold enhancement in the photoconversion efficiency than that of pristine α-Fe2O3. The dual effect of rGO as both electron conducting scaffold and surface passivation layer is further evidenced from the 1.82 and 1.67 fold enhancements in charge separation and charge injection efficiencies at 1.23 and 1 V vs. RHE respectively. To get further evidence about the origin of the improved photoactivity of the rGO modified photoanode, a series of electrochemical, photoelectrochemical and impedance spectroscopy measurements were carried out. Our results demonstrate the benefits of a noble metal free highly promising photoanode for photoelectrochemical water oxidation.

A morphology effect of hematite photoanode for photoelectrochemical water oxidation

Hematite has been a popular photoanode for photoelectrochemical water splitting; however, its performance varies widely in the literature. In-depth understanding of the structure–performance relationship of hematite photoanode is still lacking. Here, we report a finding that without the use of co-catalysts or any alteration in crystal structure, the performance of hematite photoanode can be markedly improved by properly enlarging the space among α-Fe2O3 nanocrystalline, i.e., by increasing the pore size in the electrode. Such a finding indicates that in addition to the known catalytic and crystal effects, the internal structure of the hematite electrode is also a very sensitive factor to PEC efficiency.

ChemInform Abstract: High‐Performance Silicon Photoanodes Passivated with Ultrathin Nickel Films for Water Oxidation.

AbstractDeposition of a thin nickel film (approximately 2 nm thick) on n‐type silicon with its native oxide yields a high‐performance metal‐insulator‐semiconductor photoanode for photoelectrochemical water oxidation in both aqueous KOH (pH 14) and aqueous borate buffer (pH 9.5) solutions.

Photo-electrochemical water splitting system with three-layer n-type organic semiconductor film as photoanode under visible irradiation

A three-layer structure of n-type organic semiconductors (PTCDA/PTCDA:PCBM/PCBM) is successfully identified as photoanode for photoelectrochemical water oxidation during the overall splitting of water into hydrogen/oxygen in a nearly stoichiometric ratio (H2:O2 = 2:1) under visible irradiation (λ > 420 nm). A possible charge separation mechanism under visible light illumination was also proposed.

Photo-assisted electrodeposition of cobalt–phosphate (Co–Pi) catalyst on hematite photoanodes for solar water oxidation

A photo-assisted electrodeposition approach was used to deposit a cobalt–phosphate water oxidation catalyst (“Co–Pi”) onto recently improved dendritic mesostructures of α-Fe2O3. A comparison between this approach, electrodeposition of Co–Pi, and Co2+ wet impregnation showed that photo-assisted electrodeposition of Co–Pi yields superior α-Fe2O3 photoanodes for photoelectrochemical water oxidation. Stable photocurrent densities of 1.0 mA cm−2 at 1.0 V and 2.8 mA cm−2 at 1.23 V vs. RHE measured under standard illumination and basic conditions were achieved. By allowing deposition only where visible light generates oxidizing equivalents, photo-assisted electrodeposition provides a more uniform distribution of Co–Pi onto α-Fe2O3 than obtained by electrodeposition. This approach of fabricating catalyst-modified metal-oxide photoelectrodes may be attractive for optimization in conjunction with tandem or hybrid photoelectrochemical cells.

Gold-colloid-modified AgCl photocatalyst for water oxidation to O2.

Better with gold! Gold nanoparticles have a deep red color and an absorption maximum at about 530 nm. They have been used to remarkably improve the performance of silver chloride photoanodes for photoelectrochemical water oxidation to dioxygen. The Figure shows O2 production versus time for an AgCl electrode modified with Au colloids.