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.     

Nanostructure-based WO3 photoanodes for photoelectrochemical water splitting

Nanostructured WO(3) has been developed as a promising water-splitting material due to its ability of capturing parts of the visible light and high stability in aqueous solutions under acidic conditions. In this review, the fabrication, photocatalytic performance and operating principles of photoelectrochemical cells (PECs) for water splitting based on WO(3) photoanodes, with an emphasis on the last decade, are discussed. The morphology, dimension, crystallinity, grain boundaries, defect and separation, transport of photogenerated charges will also be mentioned as the impact factors on photocatalytic performance.     

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...     

Nanostructured Ni/Ti_3C_2T_x MXene hybrid as cathode for lithium-oxygen battery

Ti_3C_2 belongs to MXenes family,which is a new two-dimensional material and has been applied in many fields.With simple method of hydrothermal and high temperature calcination,nano structured Ni/Ti_3C_2T_x hybrid was synthesized.The stable layer structure of Ti_3C_2 MXene providing high surface area as well as excellent electronic conductivity are beneficial for deposition and decomposition of discharge product Li_2O_2.Furthermore,possessing special catalytic activity,Ni nanoparticles with size of about 20 nm could accelerate Li_2O_2 breaking down.Taking advantage of two kinds of materials,Ni/Ti_3C_2T_x hybrid as cathode of Li-O_2 battery can achieve a maximal specific capacity of 20,264 mAh/g in 100 mA/g and 10,699 mAh/g in 500 mA/g at the first cycle.This work confirms that the prepared Ni/Ti_3C_2T_x hybrid exhibiting better cycling stability points out a new guideline to improve the electrochemical performance of lithium-oxygen batteries.     

Sm-doped g-C_3N_4/Ti_3C_2 MXene heterojunction for visible-light photocatalytic degradation of ciprofloxacin

A heterojunction of Sm-doped g-C_3N_4/Ti_3C_2 MXene(SCN/MX) was constructed via prepolymerization and solid mixture-calcination method.The modified g-C_3N_4 presented a hollow porous seaweed-like shape which can increase its specific area and active sites.In SCN/MX composite,the optical properties,no matter optical absorption ability or separation performance of photo-induced electrons and holes,were enhanced.Among them,Sm-doping may play an important role on transferring the photogenerated electrons to suppress their recombination,and Ti_3C_2 MXene would broaden light absorption and further improve the carrier migration efficiency.The SCN/MX presented higher photocatalytic degradation efficiency( 99%) of cipro floxacin under visible light irradiation.The quenching experiments and electron spin-resonance spectroscopy confirmed that the dominated active materials were superoxide radical and holes.The degradation mechanisms of ciprofloxacin(CIP) over the SCN/MX were attacking of the active materials on the piperazine ring and quinolone ring,and the final products were CO_2,H_2O and F~-.     

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.     

Mechanical properties and frictional resistance of Al composites reinforced with Ti_3C_2T_x MXene

Two-dimensional(2D) Ti_3C_2T_x MXene is an attractive additive not only used in base oil due to its low friction coefficient,but also used in composites due to its high aspect ratio and rich surface functional groups.So far there has been intense research into polymer matrix composites reinforced with Ti_3C_2T_x,Here we report on the use of 2D Ti_3C_2T_x to enhance the mechanical and frictional properties of Al matrix composites.Ti_3C_2T_x/Al composites were designed and prepared by pre s sureless sintering followed by hot extrusion technique.The prepared composites exhibit a homogeneous distribution of Ti_3C_2T_x.The Vickers hardness and the tensile strength continuously increase with increasing Ti_3C_2T_x content.A hardness of 0.52 GPa and a tensile strength of 148 MPa were achieved in the 3 wt% Ti_3C_2T_x/Al composite.The frictional properties of pure Al and the Ti_3C_2T_x/Al composite were comparably studied under dry sliding.A low friction coefficient of 0.2,twice lower than that of pure Al,was achieved in the 3 wt%Ti_3C_2T_x/Al composite.Ti_3C_2T_x acting as a solid lubricant reduces the abrasive wear in the composite,improving the frictional properties of Al matrix composites.     

Chelation-mediated in-situ formation of ultrathin cobalt (oxy) hydroxides on hematite photoanode towards enhanced photoelectrochemical water oxidation

In this work,a facile chelation-mediated route was developed to fabricate ultrathin cobalt(oxy)hydroxides(CoOOH)nanosheets on hematite photoanode(Fe₂O₃).The route contains two steps of the adsorption of[Co-EDTA]^2-species on Fe₂O₃ nanorod array followed by the hydrolysis in alkaline solution.The resulting CoOOH/Fe₂O₃ exhibits a remarkably improved photocurrent density of 2.10 mA cm^-2 at 1.23 V vs.RHE,which is ca.2.8 times that of bare Fe₂O₃.In addition,a negative shift of onset potential ca.200 mV is achieved.The structural characterizations reveal the chelate EDTA plays important roles that enhance the adsorption of Co species and the formation of contact between CoOOH and Fe₂O₃.(Photo)electrochemical analysis suggests,besides providing active sites for water oxidation,CoOOH at large extent promotes the charge separation and the charge transfer via passivating surface states and suppressing charge recombination.It also found CoOOH possesses some oxygen vacancies,which could act as trapping centers for photogenerated holes and facilitate the charge separation.Intensity modulated photocurrent spectroscopy(IMPS)shows that,under low applied potential the water oxidation mainly occurs on CoOOH,while under high applied potential the water oxidation could occur on both CoOOH and Fe₂O₃.The findings not only provide an efficient strategy for designing ultrathin(oxy)hydroxides on semiconductors for PEC applications but also put forward a new insight on the role of CoOOH during water oxidation.     

Designing N-doped graphene/ReSe_2/Ti_3C_2 MXene heterostructure frameworks as promising anodes for high-rate potassium-ion batteries

Developing high-performance anodes for potassium ion batteries(KIBs) is of paramount significance but remains challenging.In the normal sense,electrode materials are prepared by ubiquitous wet chemical routes,which otherwise might not be versatile enough to create desired heterostructures and/or form clean interfacial areas for fast transport of K-ions and electrons.Along this line,rate capability/cycling stability of resulting KIBs are greatly handicapped.Herein we present an all-chemical vapor deposition approach to harness the direct synthesis of nitrogen-doped graphene(NG)/rhenium diselenide(ReSe_2)hybrids over three-dimensional MXene supports as superior heterostructure anode material for KIBs.In such an innovative design,1 T'-ReSe2 nanoparticles are sandwiched in between the NG coatings and MXene frameworks via strong interfacial interactions,thereby affording facile K~+ diffusion,enhancing overall conductivity,boosting high-power performance and reinforcing structural stability of electrodes.Thus-constructed anode delivers an excellent rate performance of 138 mAh g^-1 at 10.0 A g^-1 and a high reversible capacity of 90 mAh g^-1 at 5 A g^-1 after 300 cycles.Furthermore,the potassium storage mechanism has been systematically probed by advanced in situlex situ characterization techniques in combination with first principles computations.     

Preparation and characterization of γ-In2Se3 thin-film photoanodes for photoelectrochemical water splitting

Journal of Solid State Electrochemistry - Indium selenide (γ-In2Se3) films were prepared using RF magnetron sputtering. Influence of deposition time on structural, optical, morphological, and...     

A comparative study on photoelectrochemical performance of TiO2 photoanodes enhanced by different polyoxometalates

Based on the incorporation of polyoxometalates (POMs) into TiO₂ film, the photoelectrochemical performance of POMs/TiO₂ anode was elucidated by comparative investigation on the electron transport and electron–hole recombination in POMs/TiO₂ anode. The photoelectrochemical performance of the POMs/TiO₂ anode was clearly dependent on the type and content of POMs. Compared to the TiO₂ anode, the POMs/TiO₂ anode with low POMs loadings (0.75%) displayed the enhanced photoelectrochemical performance, while the excessive content (7.5%) of POMs could almost cause a negative effect. Thus, POMs could act as either “shallow electron trap” or “deep electron trap” depending on the different types and contents of POMs. This study reveals that the introduction of POMs into TiO₂ anode could facilitate photogenerated electron transfer and reduce electron–hole recombination, which is urgently desired to develop advanced composite materials of POMs/TiO₂ for application in photoelectrochemical catalysis and solar cells.     

Electromagnetic interference shielding Ti_3C_2T_x-bonded carbon black films with enhanced absorption performance

The demand for flexible and freestanding electromagnetic interference(EMI) shielding materials are more and more urgent to combat with serious electromagnetic(EM) radiation pollution.Twodimensional Ti_3C_2T_x is considered as promising EMI shielding material to graphenes because of the low cost and high electrical conductivity.However,the shielding performance still needs to be optimized to decrease the reflection effectiveness(SE_R) and increase absorption effectiveness(SEA).Herein,we prepared Ti_3C_2T_x-bonded carbon black films with a porous structure.The SE_R decreased from 20 dB to12 dB and the SEA increased from 31 dB to 47 dB.The best EMI shielding effectiveness can be as high as60 dB with SE_A of 15 dB and SE_R of45 dB.Their calculated specific shielding effectiveness can be as high as8718 dB cm~2/g.These results indicate that the porous structure can enhance the absorption of the EMI shielding films,resulting from the enhanced scattering and reflectio n.Conseque ntly,this work provides a promising MXene-based EMI shielding film with lightweight and flexibility.     

Preparation and optimization of TiO2 photoanodes fabricated by pulsed laser deposition for photoelectrochemical water splitting

Journal of Solid State Electrochemistry - Quasi-1D TiO2 nanostructures prepared by pulsed laser deposition (PLD) are tested as photoanodes for photoelectrochemical water splitting application and...     

Si-doped Fe2O3 nanotubular/nanoporous layers for enhanced photoelectrochemical water splitting

The present work reports the enhancement of the photoelectrochemical water splitting performance of in-situ silicon (Si)-doped nanotubular/nanoporous (NT/NP) layers. These layers were grown by self-organizing anodization on Fe-Si alloys of various Si content. The incorporation of Si is found to retard the layer growth rates, leads to a more pronounced nanotubular morphology, and most importantly, an improved photoelectrochemical behavior. By increasing Si content from 1, 2 to 5 at.% in the iron oxide NT/NP photoanodes, the photocurrent onset potential shifts favorably to lower values. At 1.3 V vs. RHE, hematite layer with 5 at.% Si shows a 5-fold increase of the photocurrent, i.e. 0.5 mA cm^− 2 in comparison to 0.1 mA cm^− 2 for the undoped samples. The study also reveals that a suitable layer thickness is essential to achieve a beneficial effect of the Si doping.     

Sulfide@hydroxide core-shell nanostructure via a facile heating-electrodeposition method for enhanced electrochemical and photoelectrochemical water oxidation

Designing low-cost,easy-fabricated,highly stable and active electrocatalysts for oxygen evolution reaction (OER) is crucial for electrochemical (EC) and solar-d...     

New semiconducting oxide photoanodes for water splitting in a photoelectrochemical cell Electrochemistry of n-type NiTiO3

The electrochemical behaviour of NiTiO₃ has been studied. The interest in this mixed-metal oxide lays in its possible use for solar-energy conversion. Anodic oxidation of NiTi0₃ was very irreversible. The electrode became aged, probably due to formation of a porous film of an irreducible higher oxide. The stirring-independent Cottrell behaviour of the anodic oxidation of NiTiO₃ should be due to current limitation by diffusion of a reaction product away from the NiTi0₃ surface through this irreducible higher oxide, which should be of a porous nature. The diffusion-limiting species could not be OH^?, as the Cottrell slopes only increased by about five times for a pH increase from 3 to 14. Five and two processes were involved in the anodic oxidation of NiTiO₃ at pH 14 and 3 respectively, as determined by chronopotentiometry. The same number of processes appeared upon inversion of the current.     

Additive-free porous assemblies of Ti_3C_2T_x by freeze-drying for high performance supercapacitors

Ti_3C_2T_x has shown great potential in energy storage filed,but the restacking between Ti_3C_2T_x nanosheets seriously hampers the maximization of its capacitance.In this study,we rationally designed and synthesized porous Ti_3C_2T_x assemblies without any additive by introducing ice as spacers using a facile freeze-drying method.The porous Ti_3C_2T_x assemblies have a three-dimensional network structure,which consists of ultra large Ti_3C_2T_x lamellar walls and lots of macro-and mesopores.It has been proven that there are more-O groups on the surface of the porous Ti_3C_2T_x assemblies than the Ti_3C_2T_x film.The porous Ti_3C_2T_x assemblies deliver a maximum areal capacitance of 1668 mF/cm2 when the mass loading is 8.4 mg/cm2,an optimized specific capacitance of 247.2 F/g when the mass loading is 5.3 mg/cm2,and87% capacitance retention over 10000 cycles.The symmetric solid-state supercapacitors based on the porous Ti_3C_2T_x assemblies show an areal capacitance of 355.8 mF/cm2,the maximum power density of50 mW/cm2 and an outstanding flexibility under different deformation.     

Ti_3C_2T_x/PEDOT:PSS hybrid materials for room-temperature methanol sensor

It is essential to develop a methanol gas sensor with high selectivity and low working temperature for human health and environmental monitoring.In this work,a blend of PEDOT:PSS and Ti_3C_2T_x with the mass ratio of 4:1 is used to fabricate a methanol gas sensor.It possesses a high response ratio of the largest response and the second largest response(5.54) and an enhanced response compared to pure PEDOT:PSS and pure Ti_3C_2T_x tested at room temperature.These findings may pave the way towards design of the MXenes based high-performance gas-sensing materials in the future.     

Porous and free-standing Ti_3C_2T_x-RGO film with ultrahigh gravimetric capacitance for supercapacitors

MXene-based electrode materials exhibit favorable supercapacitor performance in sulfuric acid due to praised pseudocapacitance charge storage mechanism.However,self-stacking of conventional MXene electrodes severely restricts their electrochemical performance,especially at high loading.Herein,a flexible cross-linked porous Ti₃C₂T_x-MXene-reduced graphene oxide(Ti₃C₂T_x-RGO) film is skillfully designed and synthesized by microscopic ...