Synthesis of mesoporous functional hematite nanofibrous photoanodes by electrospinning

Iron(III) oxide (hematite, Fe₂O₃) nanofibers, as visible light‐induced photoanode for water oxidation reaction of a water splitting process, were fabricated through electrospinning method followed by calcination treatment. The prepared samples were characterized with scanning electron microscopy, and three‐electrode galvanostat/potentiostat for evaluating their photoelectrochemical (PEC) properties. The diameter of the as‐spun fibers is about 300 nm, and calcinated fibers have diameter less than 110 nm with mesoporous structure. Optimized multilayered electrospun α‐Fe₂O₃ nanostructure mats showed photocurrent density of 0.53 mA/cm² under dark and visible illumination conditions at voltage 1.23 V and constant intensity (900 mW/cm²). This photovoltaic performance of nanostructure mats makes it suitable choice for using in the PEC water splitting application as an efficient photoanode. This method, if combined with appropriate flexible conductive substrate, has the potential for producing flexible hematite solar fuel generators. Copyright © 2015 John Wiley & Sons, Ltd.     

提高氧化铁光电催化分解水效率的策略进展

为了解决能源危机与环境污染问题,发展一种可再生的清洁能源至关重要.太阳能是一种取之不尽用之不竭的清洁能源,而氢气是一种良好的能源载体.利用太阳能光电催化水分解制氢,是一项有望能够解决能源与环境问题的技术,具有很大的应用前景.其中,氧化铁因为具有合适的能带位置与带隙、良好的稳定性与廉价无毒等优点,成为一种理想的光阳极材料.但是,在实际的测试中,氧化铁仅仅只能得到一个较低的光电转换效率,这可能是因为其较短的空穴扩散距离、较低的电导率以及极度缓慢的水氧化反应动力学所致.整个光电催化水氧化可分为三个过程,即光吸收过程、电荷分离过程以及表面空穴注入过程.这三个过程的效率共同决定了器件的太阳能转化效率.鉴于此,本文将从如何提高这三个效率的角度出发,总结近期研究报道中提高氧化铁光电催化分解水效率的一些策略.光吸收过程是指半导体中价带的电子在吸收具有一定能量的光子后发生跃迁,产生空穴-电子对的过程.其光子的损失主要来源于光的反射、透射以及半导体吸收边的限制.提高光吸收效率的主要策略包括制备具有特定纳米结构的氧化铁电极、利用表面等离子体共振效应以及组成双光吸收系统和掺杂等.电荷分离过程指的是受光激发产生的空穴电子对,在内建电场的作用下发生电荷分离,即光生空穴流向电极表面,光生电子流向半导体内部并从外电路导出.电荷分离效率的损失主要来源于光生载流子在迁移过程中的复合.因此,为了提高电荷分离效率,常见的策略是提高载流子在电荷分离过程中的复合时间τ₁和减少电荷迁移到表面(空穴)或者基底(电子)的时间τ₂.具体的策略包括制备特定的纳米结构(缩短体表相距离,减少τ₂)、构建异质结(增强能带弯曲,提高τ₁和减少τ₂)、掺杂(减少τ₂)和钝化复合中心(提高τ₁)等.表面空穴注入是指到达表面的光生空穴发生水氧化反应生成氧气的过程.除了空穴注入外,表面还可能存在复合与逆反应过程.因此,为了提高表面空穴注入效率,我们既可以提高水氧化反应动力学,具体的手段包括引入水氧化催化剂、F掺杂和碱处理等;也可以采用减少复合反应的策略,具体的方法包括引入钝化层、酸处理和高温热处理等;还可以采用减少逆反应的方法,最常见的手段就是在基底与氧化铁层之间引入电子阻挡层.上述三种途径都能提高表面空穴注入效率.最后,通过结合上述的一些策略,目前得到的最高性能的氧化铁电极在1.23 V(相对于可逆氢电极)能够达到6 mA cm^?2的光电催化分解水电流,但这个值依然明显低于氧化铁的理论值(12.6 mA cm^?2).这可能是由于体相复合所致.除此之外,氧化铁表面的水氧化机理现在依然不清晰,这些都是需要我们在未来解决的问题.     

Prospects of electrochemically synthesized hematite photoanodes for photoelectrochemical water splitting: A review

Hematite (α-Fe₂O₃) is found to be one of the most promising photoanode materials used for the application in photoelectrochemical (PEC) water splitting due to its narrow band gap energy of 2.1 eV, which is capable to harness approximately 40% of the incident solar light. This paper reviews the state-of-the-art progress of the electrochemically synthesized pristine hematite photoanodes for PEC water splitting. The fundamental principles and mechanisms of anodic electrodeposition, metal anodization, cathodic electrodeposition and potential cycling/pulsed electrodeposition are elucidated in detail. Besides, the influence of electrodeposition and annealing treatment conditions are systematically reviewed; for examples, electrolyte precursor composition, temperature and pH, electrode substrate, applied potential, deposition time as well as annealing temperature, duration and atmosphere. Furthermore, the surface and interfacial modifications of hematite-based nanostructured photoanodes, including elemental doping, surface treatment and heterojunctions are elaborated and appraised. This review paper is concluded with a summary and some future prospects on the challenges and research direction in this cutting-edge research hotspot. It is anticipated that the present review can act as a guiding blueprint and providing design principles to the scientists and engineers on the advancement of hematite photoanodes in PEC water splitting to resolve the current energy- and environmental-related concerns.     

Unraveling the role of Ti_3C_2 MXene underlayer for enhanced photoelectrochemical water oxidation of hematite photoanodes

Hematite is regarded as a promising photoanode for photoelectrochemical(PEC) water splitting.However,the charge recombination occurred at the interface of FTO/hematite strictly limits the PEC performance of hematite.Herein,we reported a Ti3C2 MXene underlayer modified hematite(Ti-Fe2O3) photoanode via a simple drop-casting followed by hydrothermal and annealing processes.Owing to the bifunctional role of Ti3C2 MXene underlayer in improving the interfacial properties of FTO/hematite and providing Ti source for the construction of Fe2 TiO5/Fe2O3 heterostructure in hematite nanostructure,the bulk and interfacial charge transfer dynamics of hematite are significantly enhanced,and consequently enhancing the PEC performance.Compared with the pristine hematite,the as-prepared Ti-Fe2O3 photoanode shows an increased photocurrent density from 0.80 mA/cm² to 1.30 mA/cm² at 1.23 V vs.RHE.Moreover,a further promoted PEC performance including a dramatically increased photocurrent density of 2.49 mA/cm² at1.23 V vs.RHE and an obviously lowered onset potential is achieved for the Ti-Fe2O3 sample after the subsequent surface F-treatment and the loading of FeNiOOH cocatalyst.Such results suggest that the introduction of Ti3C2 MXene underlayer is a facile but effective approach to improve the PEC water splitting activity of hematite.     

Growth of p-type hematite by atomic layer deposition and its utilization for improved solar water splitting

Mg-doped hematite (α-Fe(2)O(3)) was synthesized by atomic layer deposition (ALD). The resulting material was identified as p-type with a hole concentration of ca. 1.7 × 10(15) cm(-3). When grown on n-type hematite, the p-type layer was found to create a built-in field that could be used to assist photoelectrochemical water splitting reactions. A nominal 200 mV turn-on voltage shift toward the cathodic direction was measured, which is comparable to what has been measured using water oxidation catalysts. This result suggests that it is possible to achieve desired energetics for solar water splitting directly on metal oxides through advanced material preparations. Similar approaches may be used to mitigate problems caused by energy mismatch between water redox potentials and the band edges of hematite and many other low-cost metal oxides, enabling practical solar water splitting as a means for solar energy storage.     

The Role of Surface States in the Oxygen Evolution Reaction on Hematite

Hematite (α‐Fe₂O₃) is an extensively investigated semiconductor for photoelectrochemical (PEC) water splitting. The nature and role of surface states on the oxygen evolution reaction (OER) remain however elusive. First‐principles calculations were used to investigate surface states on hematite under photoelectrochemical conditions. The density of states for two relevant hematite terminations was calculated, and in both cases the presence and the role of surface states was rationalized. Calculations also predicted a Nerstian dependence on the OER onset potential on pH, which was to a very good extent confirmed by PEC measurements on hematite model photoanodes. Impedance spectroscopy characterization confirmed that the OER takes place via the same surface states irrespective of pH. These results provide a framework for a deeper understanding of the OER when it takes place via surface states.     

Simple method for synthesis of silicon nanowire: Pulsed laser deposition in furnace from p-Si wafer target

Si nanowires (NWs) were fabricated in a vacuum furnace using a Nd:YAG pulsed laser with the wavelength of 325 nm. Commercial p-type Si wafer is used for the target, and no catalytic materials are used. Scanning electron microscopy (SEM) images indicate that the diameters of Si NWs ranged from 10 to 150 nm. Si NWs have various sizes and shapes with a substrate position inside the furnace, and their morphologic construction is reproducible. The formation mechanism of the NWs is discussed.     

Si衬底上生长的铁硅化合物结构和取向分析

采用分子束外延法分别在650-920 ℃的Si（110）和920 ℃的Si（111）衬底表面生长出铁的硅化物纳米结构,并主要分析了920 ℃高温下纳米结构的形貌、组成相及其与Si 衬底的取向关系. 扫描隧道显微镜（STM）研究表明,920 ℃高温下,Si（110）衬底上生长的铁硅化合物完全以纳米线的形式存在,且其尺寸远大于650 ℃低温下外延生长的纳米线尺寸;Si（111）衬底上生长出三维岛和薄膜两种形貌的铁硅化合物,其中三维岛具有金属特性且直径约300 nm、高约155 nm,薄膜厚度约2 nm. 电子背散射衍射研究表明920 ℃高温下Si（110）衬底上生长的纳米线仅以β-FeSi₂的形式存在,且β-FeSi₂相与衬底之间存在唯一的取向关系：β-FeSi₂（101）//Si（111）;β-FeSi₂ [010]//Si[110];Si（111）衬底上生长的三维岛由六方晶系的Fe₂Si 相组成,Fe₂Si 属于164 空间群,晶胞常数为a=0.405 nm,c=0.509 nm;与衬底之间的取向关系为Fe₂Si（001）∥Si（111）和Fe₂Si[120]//Si[112].     

Cobalt oxide and carbon modified hematite nanorod arrays for improved photoelectrochemical water splitting

Given the proper band gap, low cost and good stability, hematite(α-Fe_2O_3) has been considered as a promising candidate for photoelectrochemical(PEC) water splitting, however suffers from the sluggish surface water oxidation reaction kinetics. In this study, a simple dip-coating process was used to modify the surface of α-Fe_2O_3 nanorod arrays with cobalt oxide(CoO_x) and carbon(C) for the improved PEC performance, with a photocurrent density at 1.6 V(vs. reversible hydrogen electrode, RHE) increased from 0.10 mA/cm~2 for the pristine α-Fe_2O_3 to 0.37 mA/cm~2 for the CoO_x/C modified α-Fe_2O_3 nanorods. As revealed by electrochemical analysis, thanks to the synergistic effect of CoO_x and C, the PEC enhancement could be attributed to the enhanced charge transfer ability, decreased surface charge recombination, and accelerated water oxidation reaction kinetics. This study serves as a good example for improving PEC water splitting performance via a simple method.     

Photoelectrochemical Behavior of Sn‐Doped α‐Fe2O3 Photoanode with Different Reducer

Hematite has been considered as one of the most promising photoanode candidates for solar water‐splitting. However, its photoelectrochemical (PEC) efficiency is largely constrained by its sluggish oxygen evolution reaction. In this work, the photoelectrochemical performance of hematite was investigated in electrolytes containing different sacrificial agent. The photocurrent densities, onset potential, charge transfer resistance, Helmholtz capacitance at semiconductor liquid junctions (SCLJs), and their correlations were systematically studied. It was found that the onset potential is around the C_H peak potential and is related to the photovoltage. The surface states pinning the Fermi levels of the hematite photoanode are related to the adsorbed water molecules regardless of the sacrificial agents in the electrolyte.     

Iron Oxide Photoelectrode with Multidimensional Architecture for Highly Efficient Photoelectrochemical Water Splitting

Nanostructured metal oxide semiconductors have shown outstanding performances in photoelectrochemical (PEC) water splitting, but limitations in light harvesting and charge collection have necessitated further advances in photoelectrode design. Herein, we propose anodized Fe foams (AFFs) with multidimensional nano/micro-architectures as a highly efficient photoelectrode for PEC water splitting. Fe foams fabricated by freeze-casting and sintering were electrochemically anodized and directly used as photoanodes. We verified the superiority of our design concept by achieving an unprecedented photocurrent density in PEC water splitting over 5 mA cm⁻² before the dark current onset, which originated from the large surface area and low electrical resistance of the AFFs. A photocurrent of over 6.8 mA cm⁻² and an accordingly high incident photon-to-current efficiency of over 50 % at 400 nm were achieved with incorporation of Co oxygen evolution catalysts. In addition, research opportunities for further advances by structual and compositional modifications are discussed, which can resolve the low fill factoring behavior and improve the overall performance.     

New insight into the effect of interface supercapacitance on the performance of titanium dioxide/carbon nanowire array for photoelectrochemical water oxidation

The electrode/electrlyte interface is of great signifance to photoelectrochemical (PEC) water oxidation as the reaction mainly occur here. Herein, we focus on the effect of supercapactance of the electrode/electrlyte interface on the performance of PEC. It is discovered that the supercapacitor on the interface is crucial because it links the charge transport and solution ion adsorption on its two sides. In this study, we demonstrate an approach to promote the performance of TiO₂ nanowire array (TiO₂ NWs) photoanode in photoelectrochemical cells (PECs) by increasing its supercapacitance. A 2−5 nm carbon layer was coated and the interface supercapacitance increases by about 150 times. This enhances the separation rate of electron-hole pairs by collecting more holes. Meanwhile, it also promotes the water oxidation rate by adsorbing more OH⁻ on its surface. As a result, the photocurrent density of C-TiO₂ NWs was about 8 times higher than that of its carbon-free counterpart. This approach of increasing the supercapacitance of photoanodes would be attractive for enhancement of the efficiency of PECs and this work demonstrate the importance of supercapacitance of the interface for PECs.     

Si衬底上生长的铁硅化合物结构和取向分析

采用分子束外延法分别在650-920℃的Si(110)和920℃的Si(111)衬底表面生长出铁的硅化物纳米结构,并主要分析了920℃高温下纳米结构的形貌、组成相及其与Si衬底的取向关系.扫描隧道显微镜(STM)研究表明,920℃高温下,Si(110)衬底上生长的铁硅化合物完全以纳米线的形式存在,且其尺寸远大于650℃低温下外延生长的纳米线尺寸;Si(111)衬底上生长出三维岛和薄膜两种形貌的铁硅化合物,其中三维岛具有金属特性且直径约300 nm、高约155 nm,薄膜厚度约2 nm.电子背散射衍射研究表明920℃高温下Si(110)衬底上生长的纳米线仅以β-FeSi2的形式存在,且β-FeSi2相与衬底之间存在唯一的取向关系:β-FeSi2(101)//Si(11 1);β-FeSi2[010]//Si[110];Si(111)衬底上生长的三维岛由六方晶系的Fe2Si相组成,Fe2Si属于164空间群,晶胞常数为a=0.405 nm,c=0.509 nm;与衬底之间的取向关系为Fe2Si(001)∥Si(111)和Fe2Si[1 20]//Si[112].     

A co-activation strategy for enhancing the performance of hematite in photoelectrochemical water oxidation

Hematite(α-Fe_2O_3) is a promising photoanode for photoelectrochemical(PEC) water splitting.However,the severe charge recombination and sluggish water oxidation kinetics extremely limit its use in photohydrogen conversion.Herein,a co-activation strategy is proposed,namely through phosphorus(P)doping and the loading of CoAl-layered double hydroxides(CoAl-LDHs) cocatalysts.Unexpectedly,the integrated system,CoAl-LDHs/P-Fe_2O_3 photoanode,exhibits an outstanding photocurrent density of 1.56 mA/cm~2 at 1.23 V(vs.reversible hydrogen electrode,RHE),under AM 1.5 G,which is 2.6 times of pureα-Fe_2O_3.Systematic studies reveal that the remarkable PEC performance is attributed to accelerated surface OER kinetics and enhanced carrier separation efficiency.This work provides a feasible strategy to enhance the PEC performance of hematite photoanodes.     

Activation of α-Fe2O3 for Photoelectrochemical Water Splitting Strongly Enhanced by Low Temperature Annealing in Low Oxygen Containing Ambient

Photoelectrochemical (PEC) water splitting is a promising method for the conversion of solar energy into chemical energy stored in the form of hydrogen. Nanostructured hematite (α-Fe₂O₃) is one of the most attractive materials for a highly efficient charge carrier generation and collection due to its large specific surface area and the short minority carrier diffusion length. In the present work, the PEC water splitting performance of nanostructured α-Fe₂O₃ is investigated which was prepared by anodization followed by annealing in a low oxygen ambient (0.03 % O₂ in Ar). It was found that low oxygen annealing can activate a significant PEC response of α-Fe₂O₃ even at a low temperature of 400 °C and provide an excellent PEC performance compared with classic air annealing. The photocurrent of the α-Fe₂O₃ annealed in the low oxygen at 1.5 V vs. RHE results as 0.5 mA cm⁻², being 20 times higher than that of annealing in air. The obtained results show that the α-Fe₂O₃ annealed in low oxygen contains beneficial defects and promotes the transport of holes; it can be attributed to the improvement of conductivity due to the introduction of suitable oxygen vacancies in the α-Fe₂O₃. Additionally, we demonstrate the photocurrent of α-Fe₂O₃ annealed in low oxygen ambient can be further enhanced by Zn-Co LDH, which is a co-catalyst of oxygen evolution reaction. This indicates low oxygen annealing generates a promising method to obtain an excellent PEC water splitting performance from α-Fe₂O₃ photoanodes.     

Enhanced growth of crystalline-amorphous core-shell silicon nanowires by catalytic thermal CVD using in situ generated tin catalyst

In this work,we prepared silicon nanowires(Si NWs) on both fluorine-doped SnO 2(FTO) coated glass substrate and common glass substrate by catalytic thermal chemical vapor deposition(CVD) using indium film as the catalyst.It is confirmed that indium can catalyze the growth of Si NWs.More importantly,we found that tin generated in situ from the reduction of SnO 2 by indium can act as catalyst,which greatly enhances the growth of Si NWs on FTO substrate.The obtained Si NWs have a uniform crystalline-amorphous core-shell structure that is formed via vapor-liquid-solid and vapor-solid growth of silicon sequentially.This work provides a strategy to prepare Si NWs in high yield by catalytic thermal CVD using the low melting point metal catalysts.     

Near infrared-driven photoelectrochemical water splitting: Review and future prospects

Photoelectrochemical (PEC) water splitting supplies an environmentally friendly, sustainable approach to generating renewable hydrogen fuels. Oxides semiconductors, e.g. TiO₂, BiVO₄, and Fe₂O₃, have been widely developed as photoelectrodes to demonstrate the utility in PEC systems. Even though significant effort has been made to increase the PEC efficiency, these materials are still far from practical applications. The main issue of metal oxides is the wide bandgap energy that hinders effective photons harvesting from sunlight. In solar spectrum, over 40% of the energy is located in the near-infrared (NIR) region. Developing sophisticated PEC systems that can be driven by NIR illumination is therefore essential. This review gives a concise overview on PEC systems based on the use of NIR-driven photoelectrodes. Promising candidates as efficient yet practical NIR-responsive photoelectrodes are suggested and discussed. Future outlooks on the advancement of PEC water splitting are also proposed.     

Solar Water Splitting with a Hydrogenase Integrated in Photoelectrochemical Tandem Cells

Hydrogenases (H₂ases) are benchmark electrocatalysts for H₂ production, both in biology and (photo)catalysis in vitro. We report the tailoring of a p‐type Si photocathode for optimal loading and wiring of H₂ase through the introduction of a hierarchical inverse opal (IO) TiO₂ interlayer. This proton‐reducing Si|IO‐TiO₂|H₂ase photocathode is capable of driving overall water splitting in combination with a photoanode. We demonstrate unassisted (bias‐free) water splitting by wiring Si|IO‐TiO₂|H₂ase to a modified BiVO₄ photoanode in a photoelectrochemical (PEC) cell during several hours of irradiation. Connecting the Si|IO‐TiO₂|H₂ase to a photosystem II (PSII) photoanode provides proof of concept for an engineered Z‐scheme that replaces the non‐complementary, natural light absorber photosystem I with a complementary abiotic silicon photocathode.     

Ultra‐Narrow Depletion Layers in a Hematite Mesocrystal‐Based Photoanode for Boosting Multihole Water Oxidation

Significant charge recombination that is difficult to suppress limits the practical applications of hematite (α‐Fe₂O₃) for photoelectrochemical water splitting. In this study, Ti‐modified hematite mesocrystal superstructures assembled from highly oriented tiny nanoparticle (NP) subunits with sizes of ca. 5 nm were developed to achieve the highest photocurrent density (4.3 mA cm^?2 at 1.23 V vs. RHE) ever reported for hematite‐based photoanodes under back illumination. Owing to rich interfacial oxygen vacancies yielding an exceedingly high carrier density of 4.1×10²¹ cm^?3 for super bulk conductivity in the electrode and a large proportion of ultra‐narrow depletion layers (<1 nm) inside the mesoporous film for significantly improved hole collection efficiency, a boosting of multihole water oxidation with very low activation energy (E_a=44 meV) was realized.     

Perovskite Oxide Based Electrodes for High‐Performance Photoelectrochemical Water Splitting

Photoelectrochemical (PEC) water splitting is an attractive strategy for the large‐scale production of renewable hydrogen from water. Developing cost‐effective, active and stable semiconducting photoelectrodes is extremely important for achieving PEC water splitting with high solar‐to‐hydrogen efficiency. Perovskite oxides as a large family of semiconducting metal oxides are extensively investigated as electrodes in PEC water splitting owing to their abundance, high (photo)electrochemical stability, compositional and structural flexibility allowing the achievement of high electrocatalytic activity, superior sunlight absorption capability and precise control and tuning of band gaps and band edges. In this review, the research progress in the design, development, and application of perovskite oxides in PEC water splitting is summarized, with a special emphasis placed on understanding the relationship between the composition/structure and (photo)electrochemical activity.