Dual Effects of Nanostructuring and Oxygen Vacancy on Photoelectrochemical Water Oxidation Activity of Superstructured and Defective Hematite Nanorods

An Ar atmospheric treatment is rationally used to etch and activate hematite nanoflakes (NFs) as photoanodes toward enhanced photoelectrochemical water oxidation. The formation of a highly ordered hematite nanorods (NRs) array containing a high density of oxygen vacancy is successfully prepared through in situ reduction of NFs in Ar atmosphere. Furthermore, a hematite (104) plane and an iron suboxide layer at the absorber/back‐contact interface are formed. The material defects produced by a thermal oxidation method can be critical for the morphology transformation from 2D NFs to 1D NRs. The resulting hematite NR photoanodes show high efficiency toward solar water splitting with improved light harvesting capabilities, leading to an enhanced photoresponse due to the artificially formed oxygen vacancies.     

Effects of TiO2 nanorod length and post-annealing on the electrical properties of TiO2 nanobarbed fiber structures

TiO2 nanobarbed fiber (NBF) structures consisting of TiO2 nanorods (NRs) on TiO2 nanofibers (NFs) were fabricated. The mean length and diameter of the TiO2 NRs grown for 6 h was 1.38 microm and 71 nm, respectively. One NR was connected to other NRs and the junction points between the TiO2 NRs increased with increasing TiO2 NR length. The crystal structure of the TiO2 NFs and NRs was rutile and anatase, respectively. After post-annealing, only the intensity of the TiO2 NBF peaks increased without any significant structural changes. Raman spectroscopy showed that the TiO2 NBF structure consisted of anatase (TiO2 NFs) and rutile (TiO2 NRs). The bandgap of the TiO2 NBF structure prepared during a TiO2 NR growth time from 0 to 6 h decreased from 3.23 eV to 3.10 eV. The conductivity of the TiO2 NBFs with longer NRs was enhanced by post-annealing.     

Design and roles of RGO-wrapping in charge transfer and surface passivation in photoelectrochemical enhancement of cascade-band photoanode

Fast charge transfer and anti-photocorrosion are two crucial factors for developing efficient,durable photoanodes for photoelectrochemical (PEC) cells.Reduced graphene oxide (RGO) is a promising photoanode element that can provide both of these.In this study,we elucidated the roles of RGO in the charge transfer and surface passivation of photoanodes by the precise design of a RGO-wrapped photoanode and examination of its PEC properties.Arrays of hetero-nanorods (HNRs) with three different designs were fabricated as photoanodes using RGO,CdSe nanopartides (NPs),and ZnO nanorods (NRs) as building blocks.CdSe@ZnO HNRs were prepared by decorating ZnO NRs with CdSe NPs.Finite-element analysis and experimental studies demonstrated that in the CdSe@ZnO HNRs,if only the ZnO NRs were wrapped by RGO,the conductivity between CdSe and ZnO was enhanced by RGO to shuttle charges.If RGO only surrounded the outside of the CdSe@ZnO HNRs,the corrosion was slowed owing to the passivation effect of RGO,which increased the electron lifetime of the photoanode.If both CdSe and ZnO were fully wrapped by RGO,the advantages of the two aforementioned cases were both obtained.RGO-wrapped CdSe@ZnO HNRs with position-controlled designs are promising photoanode materials with a high PEC efficiency,and the developed synthesis process can be applied to explore the design and fabrication of next-generation photoanodes using RGO as a building block.     

Film Flip and Transfer Process to Enhance Light Harvesting in Ultrathin Absorber Films on Specular Back‐Reflectors

Optical interference is used to enhance light–matter interaction and harvest broadband light in ultrathin semiconductor absorber films on specular back‐reflectors. However, the high‐temperature processing in oxygen atmosphere required for oxide absorbers often degrades metallic back‐reflectors and their specular reflectance. In order to overcome this problem, a newly developed film flip and transfer process is presented that enables high‐temperature processing without degradation of the metallic back‐reflector and without the need of passivation interlayers. The film flip and transfer process improves the performance of photoanodes for photoelectrochemical water splitting comprising ultrathin (<20 nm) hematite (α‐Fe₂O₃) films on silver–gold alloy (90 at% Ag–10 at% Au) back‐reflectors. Specular back‐reflectors are obtained with high reflectance below hematite films, which is necessary for maximizing the productive light absorption in the hematite film and minimizing nonproductive absorption in the back‐reflector. Furthermore, the film flip and transfer process opens up a new route to attach thin film stacks onto a wide range of substrates including flexible or temperature sensitive materials.     

Sn-doped hematite nanostructures for photoelectrochemical water splitting

We report on the synthesis and characterization of Sn-doped hematite nanowires and nanocorals as well as their implementation as photoanodes for photoelectrochemical water splitting. The hematite nanowires were prepared on a fluorine-doped tin oxide (FTO) substrate by a hydrothermal method, followed by high temperature sintering in air to incorporate Sn, diffused from the FTO substrate, as a dopant. Sn-doped hematite nanocorals were prepared by the same method, by adding tin(IV) chloride as the Sn precursor. X-ray photoelectron spectroscopy analysis confirms Sn(4+) substitution at Fe(3+) sites in hematite, and Sn-dopant levels increase with sintering temperature. Sn dopant serves as an electron donor and increases the carrier density of hematite nanostructures. The hematite nanowires sintered at 800 °C yielded a pronounced photocurrent density of 1.24 mA/cm(2) at 1.23 V vs RHE, which is the highest value observed for hematite nanowires. In comparison to nanowires, Sn-doped hematite nanocorals exhibit smaller feature sizes and increased surface areas. Significantly, they showed a remarkable photocurrent density of 1.86 mA/cm(2) at 1.23 V vs RHE, which is approximately 1.5 times higher than that of the nanowires. Ultrafast spectroscopy studies revealed that there is significant electron-hole recombination within the first few picoseconds, while Sn doping and the change of surface morphology have no major effect on the ultrafast dynamics of the charge carriers on the picosecond time scales. The enhanced photoactivity in Sn-doped hematite nanostructures should be due to the improved electrical conductivity and increased surface area.     

Dye sensitized solar cell of TiO2 nanoparticle/nanorod composites prepared via low-temperature synthesis in oleic acid

Titania (TiO₂) nanorods (NRs) and nanoparticles (NPs) were synthesized using oleic acid as a surfactant and employed as photoanodes for dye sensitized solar cell (DSSC) fabrication. The synthesized NRs and NPs were characterized using transmission electron microscopy and X-ray diffraction. The photovoltaic performances were compared between NRs, NPs, and their composites. The results showed that the power conversion efficiencies (η) of the composites depend on the relative compositions of NRs and NPs in photoanodes, reaching the greatest at 10% NR content. η of the pure NRs DSSC was lower than that of the NPs DSSC. Electrochemical impedance spectroscopy revealed that the highest η at 10% NRs is mainly due to reduced charge transport resistance at the TiO₂/dye/electrolyte interface and electrolyte diffusion resistance, overcoming the reduction of the number of adsorbed dye molecules.     

Ternary non-noble metal zinc-nickel-cobalt carbonate hydroxide cocatalysts toward highly efficient photoelectrochemical water splitting

TiO₂ photoanodes have aroused intensive research interest in photoelectrochemical (PEC) water splitting. However, they still suffer from poor electron-hole separation and sluggish oxygen evolution dynamics, leading to the low photoconversion efficiency and limiting commercial application. Here, we designed and fabricated novel ternary non-noble metal carbonate hydroxide (ZNC-CH) nanosheet cocatalysts and integrated them with TiO₂ nanorod arrays as highly efficient photoanodes of PEC cells. Compared with the pristine TiO₂, the photocurrent of photoanode with the optimal amount of ZNC-CH represents 3.2 times enhancement, and the onset potential is shifted toward the negative potential direction of 62 mV. The remarkable enhancement is attributed to the suppressed carrier recombination and enhanced charge transfer efficiency at the interface of TiO₂, ZNC-CH and electrolyte, which is closely related to the zinc elements modulated intrinsic activity of catalysts. Our results demonstrate that the introduction of multimetallic ZNC-CH cocatalysts onto photoanodes is a promising strategy to improve the PEC efficiency.     

Surface,Bulk, and Interface: Rational Design of Hematite Architecture toward Efficient Photo‐Electrochemical Water Splitting

Collecting and storing solar energy to hydrogen fuel through a photo‐electrochemical (PEC) cell provides a clean and renewable pathway for future energy demands. Having earth‐abundance, low biotoxicity, robustness, and an ideal n‐type band position, hematite (α‐Fe₂O₃), the most common natural form of iron oxide, has occupied the research hotspot for decades. Here, a close look into recent progress of hematite photoanodes for PEC water splitting is provided. Effective approaches are introduced, such as cocatalysts loading and surface passivation layer deposition, to improve the hematite surface reaction in thermodynamics and kinetics. Second, typical methods for enhancing light absorption and accelerating charge transport in hematite bulk are reviewed, concentrating upon doping and nanostructuring. Third, the back contact between hematite and substrate, which affects interface states and electron transfer, is deliberated. In addition, perspectives on the key challenges and future prospects for the development of hematite photoelectrodes for PEC water splitting are given.     

具有高度有序氧空位的α-Fe2O3纳米带的制备及光电催化水氧化性能研究

本研究针对α-Fe₂O₃中空穴迁移距离短(2~4 nm)和水氧化动力学缓慢的问题, 通过钯催化氧化法构筑了有序氧空位掺杂的一维α-Fe₂O₃纳米带(α-Fe₂O₃ NBs)阵列, 以提高光电催化分解水产氢性能。采用不同表征方法对光阳极进行形貌、结构分析。结果表明：一维α-Fe₂O₃ NBs表面形成了有序氧空位, 周期为1.48 nm, 对应于10倍的(11¯2)晶面间距。光电化学及产氢性能表明：α-Fe₂O₃ NBs起始电位为0.587 V (vs. RHE), 在1.6 V (vs. RHE)时光电流密度为3.3 mA·cm^-2, 产氢速率达29.46 μmol·cm^-2·h^-1。这归因于引入有序氧空位提高了载流子密度, 促进了空穴的分离传输, 并作为表面活性位点, 促使表面水氧化反应加速进行。     

Periodic FTO IOs/CdS NRs/CdSe Clusters with Superior Light Scattering Ability for Improved Photoelectrochemical Performance

Periodic fluorine‐doped tin oxide inverse opals (FTO IOs) grafted with CdS nanorods (NRs) and CdSe clusters are reported for improved photoelectrochemical (PEC) performance. This hierarchical photoanode is fabricated by a combination of dip‐coating, hydrothermal reaction, and chemical bath deposition. The growth of 1D CdS NRs on the periodic walls of 3D FTO IOs forms a unique 3D/1D hierarchical structure, providing a sizeable specific surface area for the loading of CdSe clusters. Significantly, the periodic FTO IOs enable uniform light scattering while the abundant surrounded CdS NRs induce additional random light scattering, combining to give multiple light scattering within the complete hierarchical structure, significantly improving light‐harvesting of CdS NRs and CdSe clusters. The high electron collection ability of FTO IOs and the CdS/CdSe heterojunction formation also contribute to the enhanced charge transport and separation. Due to the incorporation of these enhancement strategies in one hierarchical structure, FTO IOs/CdS NRs/CdSe clusters present an improved PEC performance. The photocurrent density of FTO IOs/CdS NRs/CdSe clusters at 1.23 V versus reversible hydrogen electrode reaches 9.2 mA cm^?2, which is 1.43 times greater than that of CdS NRs/CdSe clusters and 3.83 times of CdS NRs.     

具有自组装纳米结构的AIE光敏剂用于增强光动力治疗（英文）

基于具有聚集诱导发光(AIE)性质的2,3-双(4’-(二苯基)-[1,1’-联苯]-4-基]富甲腈(BDBF)分子,制备了三种纳米结构并用于图像引导光动力学治疗(PDT).普兰尼克F127可包封BDBF形成常见的球形纳米粒子(F127@BDBF NPs),该纳米粒子可发射红色荧光,荧光量子效率(FQY)为9.8%.此外, BDBF也可在水中自组装成纳米棒(BDBF NRs).与F127@BDBF NPs相比, BDBF NRs呈现出较强的橙色荧光,具有较高的荧光量子产率(23.3%),以及基本相同的单线态氧(1O2)产生能力.利用F127对BDBF NRs进行进一步修饰可得到BDBF@F127 NRs,该纳米粒子仍然保持了棒状形貌和较好的1O2产生能力.同时,与溶解态的BDBF相比,三种纳米结构的单线态氧产生效率增强.这些纳米结构在水溶液和生理条件下具有良好的稳定性.细胞的光毒性实验表明,三种纳米结构均能有效抑制肿瘤细胞增殖.因此,通过简单的自组装方法制备高荧光量子效率和较强单线态氧产生能力的纳米结构可作为一种有效的途径来增强光动力.     

Surface Self-Transforming FeTi-LDH Overlayer in Fe2O3/Fe2TiO5 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 Fe₂O₃/Fe₂TiO₅ 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 Fe₂O₃/Fe₂TiO₅/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.     

Solar water oxidation in sputter-deposited nanocrystalline WO3 photoanodes via tuning of Ar:O2 flow rate combinations

Thin film WO₃ photoanodes were prepared by reactive sputtering in Ar and O₂ gas mixtures of various flow rate combinations. Furnace annealed films were nanocrystalline monoclinic WO₃ with (002), (020) and (200) plane orientations. Water oxidation in 0.33 M H₂SO₄ electrolyte under simulated solar illumination showed that photoanodes deposited in highest Ar and O₂ flow rate combinations exhibited highest photocurrent of 4.1 mA cm⁻² (at 1.3 V vs Ag/AgCl) compared to 3–3.8 mA cm⁻² for photoanodes deposited in lower flow rate combinations. The higher photocurrents were ascribed to lower bulk resistivity and charge transfer resistance at the WO₃/electrolyte interface. These photoanodes consisted of randomly oriented (002), (020) and (200) planes in contrast to the preferentially orientated (002) and (200) planes of photoanodes which were highly resistive with poorer photocurrent responses. These results were interpreted in terms of the effects of Ar:O₂ flow rate combinations on the distribution of oxygen vacancies and formation of crystallographic shear planes in the sputtered films.     

Robust green synthetic approach for the production of iron oxide nanorods and its potential environmental and cytotoxicity applications

A facile and eco-friendly green method has been developed for the synthesis of hematite nanorod-like architecture (G-Fe₂O₃ NRs) using the resin obtained from the stem of the banana flower (Musa Paradisiaca Linn). In this green hydrothermal synthesis, the resin played dual roles as oxygen source and as structure directing stabilizing agents, which followed the facile one-step process, and it is suitable for scaling up to large-scale synthesis. Various techniques were used to investigate the physicochemical properties such as structural, morphological, surface area, thermal, magnetic, band gap and lifetime properties of the green synthesised G-Fe₂O₃ NRs. Investigations of G-Fe₂O₃ NRs by electron microscopes showed the average length and girth of the NRs were ranging from 528 ± 173 nm and 72 ± 21 nm. Significant impact on the physicochemical properties by this green synthetic approach yielded concrete results in their catalytic activities overcoming major environmental concerns. Especially, our green catalyst showed better redox kinetics with the lesser over potential than the commercially available bulk counterparts upon evaluating the photoelectrochemical water splitting ability such as oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Moreover, the photocatalytic efficiency of G-Fe₂O₃ NRs was evaluated by solar induced photoreduction of dichromate [toxic hexavalent chromium Cr(VI) to sustainable harmless trivalent chromium Cr(III)] and degradation of malachite green (MG). Both the processes involve the photocatalytic conversion by sequential adsorption of analytes on mineral surface and the overall efficiency was achieved mainly due to the high surface area (59.87 m²/g) of the catalyst. The cytotoxicity studies indicate that G-Fe₂O₃ NRs possesses much potential to work against A-549 (lung cancer) cell line.     

Multi-Layered PtAu Nanoframes and Their Light-Enhanced Electrocatalytic Activity via Plasmonic Hot Spots (Small 17/2023)

Here, the rational design of complex PtAu double nanoframes (DNFs) for plasmon-enhanced electrocatalytic activity toward the methanol oxidation reaction (MOR) is reported. The synthetic strategy for the DNFs consists of on-demand multiple synthetic chemical toolkits, including well-faceted Au growth, rim-on selective Pt deposition, and selective Au etching steps. DNFs are synthesized by utilizing Au truncated octahedrons (TOh) as a starting template. The outer octahedral (Oh) nanoframes (NFs) nest the inner TOh NFs, eventually forming DNFs with a tunable intra-nanogap distance. Residual Au adatoms on Pt skeletons act as light entrappers and produce plasmonic hot spots between inner and outer frames through localized surface plasmon resonance (LSPR) coupling, which promotes enhanced electrocatalytic activity for the MOR. Importantly, the correlation between the gap-induced hot carriers and electrocatalytic activity is evaluated. The highest catalytic activity is achieved when the gap is the narrowest. To further harness their light-trapping capability, hierarchically structured triple NFs (TNFs) are synthesized, wherein three NFs are entangled in a single entity with a high density of hot regions, exhibiting superior electrocatalytic activity toward the MOR with a sixfold larger current density under light irradiation compared to the dark conditions.     

Fe2O3–TiO2 Nano‐heterostructure Photoanodes for Highly Efficient Solar Water Oxidation

Harnessing solar energy for the production of clean hydrogen by photo­electrochemical water splitting represents a very attractive, but challenging approach for sustainable energy generation. In this regard, the fabrication of Fe₂O₃–TiO₂ photoanodes is reported, showing attractive performances [≈2.0 mA cm⁻² at 1.23 V vs. the reversible hydrogen electrode in 1 M NaOH] under simulated one‐sun illumination. This goal, corresponding to a tenfold photoactivity enhancement with respect to bare Fe₂O₃, is achieved by atomic layer deposition of TiO₂ over hematite (α‐Fe₂O₃) nanostructures fabricated by plasma enhanced‐chemical vapor deposition and final annealing at 650 °C. The adopted approach enables an intimate Fe₂O₃–TiO₂ coupling, resulting in an electronic interplay at the Fe₂O₃/TiO₂ interface. The reasons for the photocurrent enhancement determined by TiO₂ overlayers with increasing thickness are unraveled by a detailed chemico‐physical investigation, as well as by the study of photo­generated charge carrier dynamics. Transient absorption spectroscopy shows that the increased photoelectrochemical response of heterostructured photoanodes compared to bare hematite is due to an enhanced separation of photogenerated charge carriers and more favorable hole dynamics for water oxidation. The stable responses obtained even in simulated seawater provides a feasible route in view of the eventual large‐scale generation of renewable energy.     

Nonepitaxial Gold‐Tipped ZnSe Hybrid Nanorods for Efficient Photocatalytic Hydrogen Production

For the first time, colloidal gold (Au)–ZnSe hybrid nanorods (NRs) with controlled size and location of Au domains are synthesized and used for hydrogen production by photocatalytic water splitting. Au tips are found to grow on the apices of ZnSe NRs nonepitaxially to form an interface with no preference of orientation between Au(111) and ZnSe(001). Density functional theory calculations reveal that the Au tips on ZnSe hybrid NRs gain enhanced adsorption of H compared to pristine Au, which favors the hydrogen evolution reaction. Photocatalytic tests reveal that the Au tips on ZnSe NRs effectively enhance the photocatalytic performance in hydrogen generation, in which the single Au‐tipped ZnSe hybrid NRs show the highest photocatalytic hydrogen production rate of 437.8 µmol h^?1 g^?1 in comparison with a rate of 51.5 µmol h^?1 g^?1 for pristine ZnSe NRs. An apparent quantum efficiency of 1.3% for hydrogen evolution reaction for single Au‐tipped ZnSe hybrid NRs is obtained, showing the potential application of this type of cadmium (Cd)‐free metal–semiconductor hybrid nanoparticles (NPs) in solar hydrogen production. This work opens an avenue toward Cd‐free hybrid NP‐based photocatalysis for clean fuel production.     

光电催化分解水用可见光响应型氧化物光阳极的改性研究进展

光电催化分解水是绿色制氢的重要途径之一。由于水氧化反应在热力学和动力学上极难发生, 因而制备高效光阳极成为光电催化分解水的瓶颈问题。为满足未来商业化应用需求(太阳能制氢转换效率>10%), 研制高效光阳极成为亟待解决的关键难题。研究表明, 具有价格低廉、吸光性良好、毒性小且光电化学稳定性高等突出优点的可见光响应型氧化物: WO₃、α-Fe₂O₃和BiVO₄,是目前光电催化分解水用光阳极的理想材料。在过去几十年里, 围绕该类氧化物光阳极的研究已取得显著成果。本文重点论述了高效光电催化分解水制氢用WO₃、α-Fe₂O₃和BiVO₄光阳极改性的研究进展。另外, 文中简述了此类可见光响应型氧化物光阳极在无偏压光电催化分解水中的研究现状, 并提出其存在的问题及未来发展方向。     

In Situ Formation of Oxygen Vacancies Achieving Near-Complete Charge Separation in Planar BiVO4 Photoanodes

Despite a suitable bandgap of bismuth vanadate (BiVO₄) for visible light absorption, most of the photogenerated holes in BiVO₄ photoanodes are vanished before reaching the surfaces for oxygen evolution reaction due to the poor charge separation efficiency in the bulk. Herein, a new sulfur oxidation strategy is developed to prepare planar BiVO₄ photoanodes with in situ formed oxygen vacancies, which increases the majority charge carrier density and photovoltage, leading to a record charge separation efficiency of 98.2% among the reported BiVO₄ photoanodes. Upon loading NiFeO_x as an oxygen evolution cocatalyst, a stable photocurrent density of 5.54 mA cm⁻² is achieved at 1.23 V versus the reversible hydrogen electrode (RHE) under AM 1.5 G illumination. Remarkably, a dual-photoanode configuration further enhances the photocurrent density up to 6.24 mA cm⁻², achieving an excellent applied bias photon-to-current efficiency of 2.76%. This work demonstrates a simple thermal treatment approach to generate oxygen vacancies for the design of efficient planar photoanodes for solar hydrogen production.     

Effects of pre-annealing conditions on the characteristics of ZnO nanorods and ZnO/p-Si heterojunction diodes grown through hydrothermal method

Pre-annealing of seed layers before the growth of ZnO nanorods (NRs), at various temperatures (non-annealing ~ 800 °C) and in various atmospheres (vacuum, N₂, or O₂), was systematically studied to investigate the effects of pre-annealing on the material properties of ZnO NRs as well as the rectifying behaviour of ZnO NRs/p-Si heterojunction diodes (HJDs). A seed layer was initially prepared on the Si substrate through hydrothermal (HT) method and subsequently pre-annealed; finally, the ZnO NRs were grown through the same HT method. We found that without the annealed seed layer, the ZnO NRs cannot be grown on the Si template and increase in the pre-annealing temperature led to better crystallization and fewer defect-centres in ZnO NRs. However, at a high pre-annealing temperature, the characteristics of ZnO NRs degraded due to the evaporation of oxygen atoms, resulting in more oxygen-vacancy-related defects. The smallest diameter and shortest length of ZnO NRs were observed on the samples pre-annealed at 450 °C. The short length of ZnO NRs implies a slow growth rate, because of which the NRs have sufficient time to align normal to the surface of the substrate. When the seed layer is pre-annealed in an O₂ atmosphere, the oxygen atoms fill the oxygen-vacancy-related defects, which lead to a higher nucleation density and improved characteristics of ZnO NRs. This leads to an extremely high rectification ratio of 1.8 × 10⁵ in ZnO NR/p-Si HJDs. The related mechanisms were explored in this study.