Surface Self-Transforming FeTi-LDH Overlayer in Fe(2) O(3) /Fe(2) TiO(5) Photoanode for Improved Water Oxidation.

Integrating hematite nanostructures with efficient layer double hydroxides (LDHs) is highly desirable to improve the photoelectrochemical (PEC) water oxidation performance. Here, an innovative and facile strategy is developed to fabricate the FeTi-LDH overlayer decorated Fe2 O3 /Fe2 TiO5 photoanode via a surface self-transformation induced by the co-treatment of hydrazine and NaOH at room temperature. Electrochemical measurements find that this favorable structure can not only facilitate the charge transfer/separation at the electrode/electrolyte interface but also accelerate the surface water oxidation kinetics. Consequently, the as-obtained Fe2 O3 /Fe2 TiO5 /LDH photoanode exhibits a remarkably increased photocurrent density of 3.54 mA cm-2 at 1.23 V versus reversible hydrogen electrode (RHE) accompanied by an obvious cathodic shift (≈140 mV) in the onset potential. This work opens up a new and effective pathway for the design of high-performance hematite photoanodes toward efficient PEC water oxidation.

Fouemina JCN ，Li G ，She X ，Yan D ，Lv X ，Nie K ，Deng J ，Xu H ... -  《-》

Enhanced Charge Separation through ALD-Modified Fe2 O3 /Fe2 TiO5 Nanorod Heterojunction for Photoelectrochemical Water Oxidation.

Hematite suffers from poor charge transport and separation properties for solar water splitting. This paper describes the design and fabrication of a 3D Fe2 O3 /Fe2 TiO5 heterojunction photoanode with improved charge separation, via a facile hydrothermal method followed by atomic layer deposition and air annealing. A highly crystallized Fe2 TiO5 phase forms with a distinct interface with the underlying Fe2 O3 core, where a 4 nm Fe2 TiO5 overlayer leads to the best photoelectrochemical performance. The favorable band offset between Fe2 O3 and Fe2 TiO5 establishes a type-II heterojunction at the Fe2 O3 /Fe2 TiO5 interface, which drives electron-hole separation effectively. The Fe2 O3 /Fe2 TiO5 composite electrode exhibits a dramatically improved photocurrent of 1.63 mA cm(-2) at 1.23 V versus reversible hydrogen electrode (RHE) under simulated 1 sun illumination (100 mW cm(-2) ), which is 3.5 times that of the bare Fe2 O3 electrode. Decorating the Fe2 O3 /Fe2 TiO5 heterojunction photoanode with earth-abundant FeNiOx cocatalyst further expedites surface reaction kinetics, leading to an onset potential of 0.8 V versus RHE with a photocurrent of 2.7 mA cm(-2) at 1.23 V and 4.6 mA cm(-2) at 1.6 V versus RHE. This sandwich photoanode shows an excellent stability for 5 h and achieves an overall Faradaic efficiency of 95% for O2 generation. This is the best performance ever reported for Fe2 O3 /Fe2 TiO5 photoanodes.

Li C ，Wang T ，Luo Z ，Liu S ，Gong J ... -  《-》

A Facile Surface Passivation of Hematite Photoanodes with Iron Titanate Cocatalyst for Enhanced Water Splitting.

The surface modification of semiconductor photoelectrodes with passivation overlayers has attracted great attention as an effective strategy to improve the charge separation and charge transfer processes across the semiconductor-electrolyte interface. In this work, a thin Fe2 TiO5 layer was decorated on nanostructured hematite nanoflake and nanocoral photoanodes (by thermal oxidation of iron foils) by a facile water-based solution method. Photoelectrochemical measurements show that the Fe2 O3 /Fe2 TiO5 heterostructure exhibits an obvious enhancement in photoelectrochemical water oxidation performance compared to the pristine hematite. For example, at 1.23 V versus the reversible hydrogen electrode (VRHE ) in 1 m KOH under AM 1.5 G (100 mW cm(-2) ) illumination, a 4-8× increase in the water oxidation photocurrent is achieved for Fe2 O3 /Fe2 TiO5 , and a considerable cathodic shift of the onset potential up to 0.53-0.62 VRHE is obtained. Moreover, the performance of the Fe2 O3 /Fe2 TiO5 heterostructure can be further improved by decoration with a SnOx layer. The enhancement in photocurrent can be attributed to the synergistic effect of Fe2 TiO5 /SnOx overlayers passivating surface states, and thus reducing surface electron-hole recombination.

Wang L ，Nguyen NT ，Schmuki P 《-》

NiO Nanoparticles Anchored on Phosphorus-Doped α-Fe(2) O(3) Nanoarrays: An Efficient Hole Extraction p-n Heterojunction Photoanode for Water Oxidation.

The photoelectrochemical (PEC) water-splitting efficiency of a hematite-based photoanode is still far from the theoretical value due to its poor surface reaction kinetics and high density of surface trapping states. To solve these drawbacks, a photoanode consisting of NiO nanoparticles anchored on a gradient phosphorus-doped α-Fe2 O3 nanorod (NR) array (NiO/P-α-Fe2 O3 ) was fabricated to achieve optimal light absorption and charge separation, as well as rapid surface reaction kinetics. Specifically, a photoanode with the NR array structure allowed a high mass-transport rate to be achieved, while phosphorus doping effectively decreased the number of surface trapping sites and improved the electrical conductivity of α-Fe2 O3 . Furthermore, the p-n junction that forms between NiO and P-α-Fe2 O3 can further improve the PEC performance due to efficient hole extraction and the water oxidization catalytic activity of NiO. Consequently, the NiO/P-α-Fe2 O3 NR photoanode produced a high photocurrent density of 2.08 mA cm-2 at 1.23 V versus a reversible hydrogen electrode and a 110 mV cathodic shift of the onset potential. This rational design of structure offers a new perspective in exploring high-performance PEC photoanodes.

Li F ，Li J ，Zhang J ，Gao L ，Long X ，Hu Y ，Li S ，Jin J ，Ma J ... -  《-》

Surviving High-Temperature Calcination: ZrO(2) -Induced Hematite Nanotubes for Photoelectrochemical Water Oxidation.

Nanotubular Fe2 O3 is a promising photoanode material, and producing morphologies that withstand high-temperature calcination (HTC) is urgently needed to enhance the photoelectrochemical (PEC) performance. This work describes the design and fabrication of Fe2 O3 nanotube arrays that survive HTC for the first time. By introducing a ZrO2 shell on hydrothermal FeOOH nanorods by atomic layer deposition, subsequent high-temperature solid-state reaction converts FeOOH-ZrO2 nanorods to ZrO2 -induced Fe2 O3 nanotubes (Zr-Fe2 O3 NTs). The structural evolution of the hematite nanotubes is systematically explored. As a result of the nanostructuring and shortened charge collection distance, the nanotube photoanode shows a greatly improved PEC water oxidation activity, exhibiting a photocurrent density of 1.5 mA cm-2 at 1.23 V (vs. reversible hydrogen electrode, RHE), which is the highest among hematite nanotube photoanodes without co-catalysts. Furthermore, a Co-Pi decorated Zr-Fe2 O3 NT photoanode reveals an enhanced onset potential of 0.65 V (vs. RHE) and a photocurrent of 1.87 mA cm-2 (at 1.23 V vs. RHE).

Li C ，Li A ，Luo Z ，Zhang J ，Chang X ，Huang Z ，Wang T ，Gong J ... -  《-》