Graphene Quantum Dots as Hole Extraction and Transfer Layer Empowering Solar Water Splitting of Catalyst-Coupled Zinc Ferrite Nanorods.

Despite the narrow band gap energy, the performance of zinc ferrite (ZnFe2O4) as a photoharvester for solar-driven water splitting is significantly hindered due to its sluggish charge transfer and severe charge recombination. This work reports the fabrication of a hybrid nanostructured hydrogenated ZnFe2O4 (ZFO) photoanode with enhanced photoelectrochemical water-oxidation activity through coupling N-doped graphene quantum dots (GQDs) as a hole transfer layer and Co-Pi as a catalyst. The GQDs not only reduce the surface-mediated nonradiative electron-hole pair recombination but also induce a built-in interfacial electric field leading to a favorable band alignment at the ZFO/GQDs interface, helping rapid photogenerated hole separation and serving as a conducting hole transfer highway, improve the hole transportation into the Co-Pi catalyst for enhanced water oxidation reaction kinetics. The optimized ZFO/GQD/Co-Pi hybrid photoanode delivers a 23-fold photocurrent enhancement at 1.23 V versus the reversible hydrogen electrode (RHE) and a significant 360 mV reduction in the onset potential, reaching 0.65 VRHE compared with the ZFO photoanode under 1 sun illumination in a neutral electrolytic environment. This investigation underscores the mechanism of synergistic interplay between the hole transport layer and cocatalyst in boosting the solar-illuminated water-splitting activity of the ZFO photoanode.

Effect of defect-rich Co-CeOx OER cocatalyst on the photocarrier dynamics and electronic structure of Sb-doped TiO2 nanorods photoanode.

This work demonstrates the in-depth mechanism of enhanced photoelectrochemical (PEC) water oxidation of Sb-doped rutile TiO2 nanorods (NRs) photoanode coupled with oxygen vacancy defect-rich Co-doped CeOx (Co-CeOx) oxygen evolution reaction (OER) cocatalyst. The defect-rich Co-CeOx cocatalyst modification improves the conductivity, light absorption, charge transfer efficiency, and surface photovoltage generation of the Co-CeOx/Sb-TiO2 hybrid NRs photoanode. The Co-CeOx cocatalyst also serves as the surface passivating overlayer for the Sb-TiO2 photoanode, which suppresses the surface states mediated recombination of electron-hole pairs in the NRs. The PEC studies further indicate that Co-CeOx cocatalyst induces remarkably large band bending at the semiconductor/electrolyte interface and shortens the carrier diffusion length and depletion layer width, facilitating the rapid separation and transportation of the photocarriers for the surface PEC reactions. The experimental and theoretical studies confirm that the Co-doping in CeOx cocatalyst enhances the surface oxygen vacancy defects, which provides active catalytic sites for OH- adsorption and charge transportation for enhanced OER kinetics. The density functional theory (DFT) calculations demonstrate a higher conductivity of the Co-CeOx cocatalyst, advantageous for rapid charge transfer capability during PEC reactions. The synergy between all these merits helps the optimized Co-CeOx/Sb-TiO2 photoanode to deliver a maximum photocurrent density of 1.41 mA cm-2 at 1.23 V vs. reversible hydrogen electrode (VRHE) and an ultra-low turn on potential (Von) of 0.1 VRHE under AM 1.5G solar illumination compared to the Sb-TiO2 NRs (0.96 mA cm-2 at 1.23 VRHE and Von = 0.42 VRHE). This work demonstrates the design of an efficient defect-rich cocatalyst modified photoanode for solar energy harvesting.

Dual co-catalysts activated hematite nanorods with low turn-on potential and enhanced charge collection for efficient solar water oxidation.

Hematite (α-Fe2O3) photoanode suffers from significant photocarrier recombination and sluggish water oxidation kinetics for photoelectrochemical water splitting. To address these challenges, this work demonstrates the construction of dual co-catalysts modified Fe2O3nanorods photoanode by strategically incorporating CoPi and Co(OH)xfor photoelectrochemical water oxidation. The Fe2O3/CoPi/Co(OH)xnanorods photoanode exhibits the lowest ever turn-on potential of 0.4VRHE(versus reversible hydrogen electrode) and a photocurrent density of 0.55 mA cm-2at 1.23VRHE, 358% higher than that of pristine Fe2O3nanorods. The dual co-catalysts modification enhances the light-harvesting efficiency, surface photovoltage and hole transfer kinetics of the hybrid photoanode. The dual co-catalyst coupling also increases the carrier density and significantly reduces the depletion width (1.9 nm), resulting in improved conductivity and favorable band bending, boosting photogenerated hole transfer efficiency for water oxidation.

Earth abundant transition metal ferrite nanoparticles anchored ZnO nanorods as efficient and stable photoanodes for solar water splitting.

Poor light absorption, severe surface charge recombination and fast degradation are the key challenges with ZnO nanostructures based electrodes for photoelectrochemical (PEC) water splitting. Here, this study attempts to design an efficient and durable nano-heterojunction photoelectrode by integrating earth abundant chemically stable transition metal spinel ferrites MFe2O4 (M = Co and Ni) nano-particles on ZnO Nanorod arrays. The low band gap magnetic ferrites improve the solar energy harvesting ability of the nano-heterojunction electrodes in ultraviolet-visible light region resulting in a maximum increase of 105% and 190% in photocurrent density and applied bias photon-to-current efficiency, respectively, compared to pristine ZnO nanorods. The favourable type-II band alignment at the ferrites/ZnO nano-heterojunction provides significantly enhanced photo-generated carrier separation and transfer, endowing the excellent solar H2 evolution ability (743 and 891 µmol cm-2 h-1for ZnO/CoFe2O4 and ZnO/NiFe2O4, respectively) of the photoanodes by using sacrificial agent. The hybrid nanostructures deliver long term stability of the electrode against photocorrosion. This work demonstrates an easy but effective strategy to develop low-cost earth abundant ferrites-based heterojunction electrodes, which offers excellent PEC activity and stability.

The formation and detection techniques of oxygen vacancies in titanium oxide-based nanostructures.

TiO2 and other titanium oxide-based nanomaterials have drawn immense attention from researchers in different scientific domains due to their fascinating multifunctional properties, relative abundance, environmental friendliness, and bio-compatibility. However, the physical and chemical properties of titanium oxide-based nanomaterials are found to be explicitly dependent on the presence of various crystal defects. Oxygen vacancies are the most common among them and have always been the subject of both theoretical and experimental research as they play a crucial role in tuning the inherent properties of titanium oxides. This review highlights different strategies for effectively introducing oxygen vacancies in titanium oxide-based nanomaterials, as well as a discussion on the positions of oxygen vacancies inside the TiO2 band gap based on theoretical calculations. Additionally, a detailed review of different experimental techniques that are extensively used for identifying oxygen vacancies in TiO2 nanostructures is also presented.

Nano-engineering of p-n CuFeO2-ZnO heterojunction photoanode with improved light absorption and charge collection for photoelectrochemical water oxidation.

The effective utilization of abundant visible solar light for photoelectrochemical water splitting is a green approach for energy harvesting, to reduce the enormous rise of carbon content in the atmosphere. Here, a novel efficient design strategy for p-n type nano-heterojunction photoanodes is demonstrated, with the goal of improving water splitting efficiency by growing low band gap p-CuFeO2 nanolayers on n-ZnO nanorods by an easy and scalable electrochemical route. The photoconversion efficiency of p-n CuFeO2/ZnO photoanodes is found to be ∼450% higher than that of pristine ZnO nanorod electrodes under visible solar light illumination (λ > 420 nm, intensity 10 mW cm-2). The p-n CuFeO2/ZnO nano-engineering not only boosts the visible light absorption but also resolves limitations regarding effective charge carrier separation and transportation due to interfacial band alignment. This photoanode also shows remarkably enhanced stability, where the formation of p-n nano-heterojunction enhances the easy migration of holes to the electrode/electrolyte interface, and of electrons to the counter electrode (Pt) for hydrogen generation. Therefore, this work demonstrates that p-n nano-engineering is a potential strategy to design light-harvesting electrodes for water splitting and clean energy generation.

Surface functionalized H2Ti3O7 nanowires engineered for visible-light photoswitching, electrochemical water splitting, and photocatalysis.

This article demonstrates comprehensive studies on different visible-light driven photoelectrochemical and photocatalytic aspects of a hydrothermally synthesized n-type H2Ti3O7 (HTO) nanowire mesh and its carbon and nitrogen functionalized counterparts, namely C-HTO and N-HTO. It was found that the presence of various defect states within the band gap of HTO, C-HTO and N-HTO nanowires, make them photoactive under visible-light. The photo-conversion efficiencies of HTO, C-HTO, and N-HTO nanowire electrodes are about 0.066, 0.129, and 0.076%, respectively, at around 1 V vs. Ag/AgCl. Carbon functionalization of HTO nanowires has been found to be most beneficial in increasing the charge carrier density, resulting in the highest current density, high photo conversion efficiency, remarkable photoelectrochemical water splitting performance and enhanced photocatalytic activity. The photocurrent density of the C-HTO NWs was found to be 0.0562 mA cm-2 at 1 V vs. Ag/AgCl, which is almost two times that of the pristine HTO NWs (0.029 mA cm-2). Although nitrogen functionalization increases the charge carrier density of the HTO nanowires, nitrogen incorporation produces lots of recombination centres in the nanowires, which are found to play a detrimental role in the photoelectrochemical and photocatalytic performance of N-HTO nanowires, limiting the expected performance. Therefore, the present study demonstrates a suitable surface engineering technique for nanostructures to maximize the utilization of green solar light.

High-Performance Supercapacitor Electrode Based on Cobalt Oxide-Manganese Dioxide-Nickel Oxide Ternary 1D Hybrid Nanotubes.

We report a facile method to design Co3O4-MnO2-NiO ternary hybrid 1D nanotube arrays for their application as active material for high-performance supercapacitor electrodes. This as-prepared novel supercapacitor electrode can store charge as high as ∼2020 C/g (equivalent specific capacitance ∼2525 F/g) for a potential window of 0.8 V and has long cycle stability (nearly 80% specific capacitance retains after successive 5700 charge/discharge cycles), significantly high Coulombic efficiency, and fast response time (∼0.17s). The remarkable electrochemical performance of this unique electrode material is the outcome of its enormous reaction platform provided by its special nanostructure morphology and conglomeration of the electrochemical properties of three highly redox active materials in a single unit.

Hydrogenated NiO nanoblock architecture for high performance pseudocapacitor.

Supercapacitor electrodes are fabricated with the self-organized 3D architecture of NiO and hydrogenated NiO (H-NiO) nano-blocks (NBs) grown by the facile electrodeposition and high temperature annealing of the Ni foil on Cu substrate. The unique architecture of H-NiO NBs electrode exhibits excellent cycling stability (only 5.3% loss of its initial specific capacitance after 3000 cycles at current density of 1.1 A g(-1)) along with the high specific and areal capacitance of ∼1272 F g(-1) and 371.8 mF cm(-2), respectively at scan rate of 5 mV s(-1) compared with the pure NiO NBs electrode (∼ 865 F g(-1) and 208.2 mF cm(-2), respectively at scan rate of 5 mV s(-1)). H-NiO NBs electrode also exhibits excellent rate capability; nearly 61% specific capacity retention has been observed when the current density increases from 1.11 to 111.11 A g(-1). This electrode offers excellent energy density of 13.51 Wh kg(-1) and power density of 19.44 kW kg(-1) even at a high current density of 111.11 A g(-1). The superior pseudocapacitive performance of the H-NiO NBs electrode is because of the high electron and ion conductivity of the active material because of the incorporation of hydroxyl groups on the surface of NiO NBs.

Influence of film thickness and oxygen partial pressure on cation-defect-induced intrinsic ferromagnetic behavior in luminescent p-type Na-doped ZnO thin films.

In this article, we have investigated the effect of oxygen partial pressure (PO2) and film thickness on defect-induced room-temperature (RT) ferromagnetism (FM) of highly c-axis orientated p-type Na-doped ZnO thin films fabricated by pulse laser deposition (PLD) technique. We have found that the substitution of Na at Zn site (NaZn) can be effective to stabilize intrinsic ferromagnetic (FM) ordering in ZnO thin films with Curie temperature (TC) as high as 509 K. The saturation magnetization (MS) is found to decrease gradually with the increase in thickness of the films, whereas an increase in "MS" is observed with the increase in PO2 of the PLD chamber. The enhancement of ferromagnetic signature with increasing PO2 excludes the possibility of oxygen vacancy (VO) defects for the magnetic origin in Na-doped ZnO films. On the other hand, remarkable enhancement in the green emission (IG) are observed in the photoluminescence (PL) spectroscopic measurements due to Na-doping and that indicates the stabilization of considerable amount of Zn vacancy (VZn)-type defects in Na-doped ZnO films. Correlating the results of PL and X-ray photoelectron spectroscopy (XPS) studies with magnetic measurements we have found that VZn and Na substitutional (NaZn) defects are responsible for the hole-mediated FM in Na-doped ZnO films, which might be an effective candidate for modern spintronic technology.

Defect-driven magnetism in luminescent n/p-type pristine and Gd-substituted SnO2 nanocrystalline thin films.

The effects of rare-earth-element Gd doping on the intrinsic magnetic ordering, photoluminescence, and electrical-conducting properties of the pristine SnO(2) nanocrystalline thin films fabricated by radio-frequency (RF) sputtering are investigated. The pristine SnO(2) thin film exhibits significant ferromagnetism while Gd doping results in an absence of intrinsic ferromagnetism. The presence of large amounts of singly ionized oxygen vacancies (V(O)(+)) is traced by photoluminescence spectroscopic analysis and they are found to be responsible for the observed ferromagnetism in pristine SnO(2) thin films. A significant reduction of oxygen vacancies is observed after Gd doping, and that might be insufficient to mediate long-range ferromagnetic ordering between V(O)(+) defects in a Gd-doped SnO(2) system. Although the associated magnetic moment is increased by 1 order of magnitude, because of the insertion of Gd(3+) ions, which have localized f-shell paramagnetic moment, there is no intrinsic FM ordering. Hall measurement reveals that the pure SnO(2) exhibits n-type behavior whereas Gd-doped SnO(2) films show the p-type conductivity with higher resistivity. The studies demonstrate that only structural defects such as V(O)(+) defects, not magnetic ions such as Gd(3+), are responsible for inducing ferromagnetism in SnO(2) thin films.

The microscopic origin of self-organized nanostripe pattern formation on an electropolished aluminium surface.

By correlating the experimental evidence obtained from atomic force microscopy, conventional x-ray diffraction, and a surface sensitive modified x-ray diffraction technique with the results of density functional theory based computations, we demonstrate that self-organized nanostripe patterns formed on the electropolished surface of aluminium originate as a consequence of relaxation and reconstruction of the new surfaces exposed and textural changes at the surface caused by the dissolution during polishing.