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Conventional heterojunction photodetectors rely on planar junction architecture which suffer from low interfacial contact area, inferior light absorption characteristics and complex fabrication schemes. Heterojunctions based on mixed dimensional nanostructures such as 0D-1D, 1D-2D, 1D-3D etc have recently garnered exceptional research interest owing to their atomically sharp interfaces, tunable junction properties such as enhanced light absorption cross-section. In this work, a flexible broadband UV-vis photodetector employing mixed dimensional heterostructure of 1D NiO nanofibers and 3D Fe 2 O 3 nanoparticles is fabricated. NiO nanofibers were synthesized via economical and scalable electro-spinning technique and made composite with Fe 2 O 3 nanoclusters for hetero-structure fabrication. The optical absorption spectra of NiO nanofibers and Fe 2 O 3 nanoparticles exhibit peak absorption in UV and visible spectra, respectively. The as-fabricated photodetector displays quick response times of 0.09 s and 0.18 s and responsivities of 5.7 mA W -1 (0.03 mW cm -2 ) and 5.2 mA W -1 (0.01 mW cm -2 ) for UV and visible spectra, respectively. The fabricated NiO-Fe 2 O 3 device also exhibits excellent detectivity in the order of 10 12 jones. The superior performance of the device is ascribed to the type-II heterojunction between NiO-Fe 2 O 3 nanostructures, which results in the localized built-in potential at their interface, that aids in the effective carrier separation and transportation. Further, the flexible photodetector displays excellent robustness when bent over ∼1000 cycles thereby proving its potential towards developing reliable, diverse functional opto-electronic devices., (© 2022 IOP Publishing Ltd.)

A highly efficient, nanostructured, solar-responsive zinc-oxide (SRZO) photoanode has been achieved by utilization of a versatile solution precursor plasma spray (SPPS) deposition technique. For the first time, it is demonstrated that a front-illumination type SRZO photo-anode fabricated with a ZnO/stainless steel (SS-304) configuration can generate an enhanced photo-electrochemical (PEC) current of 390 μA cm -2 , under solar radiation from a solar simulator with an AM1.5 global filter (∼1 sun). The SRZO electrode displayed a solar-to-hydrogen (STH) conversion efficiency of 2.32% when investigated for H 2 evolution in a PEC cell. These electrodes exhibited a maximum peak efficiency of 86% using 320 nm photons during incident photon-to-current conversion efficiency measurement. Interestingly, the film lattice of SRZO showed a significant red-shift of 0.37 eV in the ZnO band gap thereby providing solar photon absorptivity to SRZO. Further, an enhanced charge transport property by virtue of increased donor density (∼4.11 × 10 17 cm -3 ) has been observed, which is higher by an order of magnitude than that of its bulk counterpart. Efficient optical absorption of solar photons and higher donor-density of SRZO have been thus attributed to its superior PEC performance., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

To improve the limited efficiency and stability of CdS photoanodes in a photoelectrochemical (PEC) cell, the nanostructured CdS photoanode was modified with Ni(OH)2, NiO, Co(OH)2, and Co3O4 water-oxidation-nano co-catalysts (WOC). Co(OH)2 nanorice and Ni(OH)2 nanosheet co-catalysts were obtained by a simple chemical precipitation method. Modification by the co-catalysts gives longer stability (>8 h) to CdS electrodes, and facilitates impulsive H2 evolution in PEC cells. Nano-NiO modification yields a two-fold increase in photocurrent density and the highest H2 evolution of 2.5 mmol h(-1). A dual role for Ni related co-catalysts over CdS surface, that is forming a p-n junction and acting as an effective co-catalyst, improves the photocurrent and hydrogen evolution rate, respectively. Improvement in stability was measured using X-ray photoelectron spectroscopy and prolong chronoamperometry measurements. The present report focuses on exploration of chemically synthesized earth-abundant and cost-effective co-catalysts for PEC H2 generation.

Highly aligned, vertically oriented, TiO2 nanotube arrays fabricated by electrochemical anodization were functionalised by carbon quantum dots (CQD) synthesized by an electrochemical reduction technique. Here, we report the photo-electrochemical properties of such TiO2 nanotubes array-CQD composite material and it has been found that the properties are significantly enhanced compared to that in pristine (bare) nanotubes. The TiO2 nanotubes were characterized by X-ray diffraction and scanning electron microscopy, whereas the CQD samples were characterized by transmission electron microscopy, optical absorption spectroscopy. CQDs synthesized under two different conditions showed a distinct size difference and corresponding absorption spectra revealed concominant shift in the absorption edges. Furthermore, the photo-electrochemical measurements were carried out with the help of photo-current, incident photon to current conversion efficiency (IPCE), Mott-Schottky plots and the impedance analysis. The photo-current data revealed 30% improvement in TiO2-CQD samples compared to bare TiO2 nanotubes samples. A higher photo-conversion efficiency was observed along with the shifting of the peak value towards visible wavelengths. The Mott-Schottky plots revealed shift in the flat-band potential in the CQD-TiO2 samples and corresponding lowering of the charge transfer resistance was observed through the impedance spectroscopy.

Herein we report the surface modification of a CdS film by niobia nanoparticles via thioglycerol as an organic linker and thus fabricate an efficient and a stable photoanode for a photoelectrochemical (PEC) cell. We have synthesized three differenly sized (∼3, ∼6 ,and ∼9 nm) niobia nanoparticles by a hydrothermal synthesis approach and have further investigated the particle-size-dependent PEC performance of the nanoparticle-modified CdS photoanode. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) confirm the formation of Nb2O5 nanoparticles that are prepared via decomposition of the niobium peroxo complex during the hydrothermal reaction and reveal the presence of surface OH(-) groups over niobia nanoparticles that impart a high catalytic property to a material. The nano-Nb2O5-modified photoanode displayed a 23-fold higher power conversion efficiency compared to that of CdS. This modified structure increases the open circuit voltage (OCV) from 0.65 to 0.77 V, which is attributed to the nano-Nb2O5-induced surface passivation effect over bare CdS. Linking of nanoparticles on the CdS surface improves the photocorrosion stability of the CdS photoanode for even longer than 4 h in contrast to the tens of minutes for the base CdS surface. The uniform coverage of the CdS photoanode surface by niobia nanoparticles is thus found to be the controlling parameter for achieving a higher PEC performance and stability of the photoanode. This finding directed us to design an improved CdS photoanode for efficient and prolonged PEC hydrogen generation from a PEC cell.

Nanocrystalline Bi5Ti3FeO15 layered perovskite exhibiting Aurivillius phase was synthesized by polymerized complex (PC) method and investigated for its physico-chemical as well as optical properties. The crystallization of Bi5Ti3FeO15 synthesized by PC method was found to occur in the temperature range of 800-1050 degress C, whereas the single crystalline Bi5Ti3FeO15 formed at 1030 degrees C by solid state reaction (SSR) method. The observation of highly pure phase and such lower crystallization temperature in Bi5Ti3FeO15 prepared by PC method, is in total contrast to that observed in Bi5Ti3FeO15 prepared by the conventional solid-state reaction (SSR) method. The band gap of nanocrystalline Bi5Ti3FeO15 determined from UV-Vis diffusion reflectance spectrometer was 2.38 eV (525 nm). The photocatalytic activity of Pt/Bi5Ti3FeO15 prepared by PC method was investigated with the photodecomposition of isopropyl alcohol (IPA) and hydrogen production from water-methanol mixed solution under visible light (lambda > or = 420 nm). The respective activities for PC sample were higher than that of Pt/Bi5Ti3FeO15 prepared by SSR as well as Pt/TiO(2-x)N(x).

A bulk heterojunction photocatalyst of interfacing CaFe(2)O(4) and MgFe(2)O(4) nanoparticles is highly active for oxidative degradation of isopropyl alcohol and hydrogen production from water under visible light, because the exciton easily reaches the interface and dissociates to minimize recombination.

Nanocrystalline CaFe2O4 oxide semiconductor with spinel structure was synthesized by polymerized complex (PC) method and investigated for its physical and optical properties. The crystallization of CaFe2O4 made by PC method was found to occur in the temperature range of 700-1100 degrees C. The observation of highly pure phase and such lower crystallization tempearture in CaFe2O4 made by PC method, is in total contrast to that observed in CaFe2O4 prepared by the conventional solid-state reaction (SSR) method. The activation energy required for the growth of nanocrystalline CaFe2O4 in PC sample was found to be 8.4 kJ/mol. The band gap of nanocrystalline CaFe2O4 determined by UV-DRS was 1.91 eV (647 nm). The photocatalytic activity of PC materials for iso-propyl alcohol photodegradation under visible light (> or =420 nm) was much higher than that of SSR materials.

Indium was substituted at gallium site in chalcopyrite AgGaS(2) structure by using a simple solid solution method. The spectroscopic analysis using extended x-ray absorption fine structure and x-ray photoelectron spectroscopy confirmed the indium substitution in AgGaS(2) lattice. The band gap energy of AgGa(1-x)In(x)S(2) (x=0-1) estimated from the onset of absorption edge was found to be reduced from 2.67 eV (x=0) to 1.9 eV (x=1) by indium substitution. The theoretical and experimental studies showed that the indium s orbitals in AgGa(1-x)In(x)S(2) tailored the band gap energy, thereby modified the photocatalytic activity of the AgGa(1-x)In(x)S(2).

Narrowly dispersed Pb-doped zinc sulfide nanoparticles were synthesized at room temperature using a chemical method in which the nanoparticle surfaces were passivated using mercaptoethanol. The maximum intensity of the broad green luminescence (approximately 530 nm) from these nanoparticles was observed at an optimum dopant concentration of 0.104 Pb wt%. The emission intensity was found to depend on the synthesis pH conditions, thus yielding maximum intensity at 5.0 pH. Comparatively lower emission intensities were observed for the other pH values (2.5-9.0 pH range). This may be due to the pH-dependent Cl- (as well as Na+) incorporation into the ZnS matrix, which possibly helps in inducing required density of impurity (donor/co-activator) states in the energy gap of ZnS nanoparticles. X-ray diffraction analysis using Debye functional analysis showed that the particle size is 2.8+/-0.3 nm.

Nitrogen-doped perovskite type materials, Sr2Nb2O7-xNx (0, 1.5 < x < 2.8), have been studied as visible light-active photocatalysts for hydrogen production from methanol-water mixtures. Nitrogen doping in Sr2Nb2O7 red-shifted the light absorption edge into the visible light range and induced visible light photocatalytic activity. There existed an optimum amount of nitrogen doping that showed the maximum rate of hydrogen production. Among the potential variables that might cause this activity variation, the crystal structure appeared to be the most important. Thus, as the extent of N-doping increased, the original orthorhombic structure of the layered perovskite was transformed into an unlayered cubic oxynitride structure. The most active catalytic phase was an intermediate phase still maintaining the original layered perovskite structure, but with a part of its oxygen replaced by nitrogen and oxygen vacancy to adjust the charge difference between oxygen and doped nitrogen. These experimental observations were explained by density functional theory calculations. Thus, in Sr2Nb2O7-xNx, N2p orbital was the main contributor to the top of the valence band, causing band gap narrowing while the bottom of conduction band due to Nb 4d orbital remained almost unchanged.

The energetics of the TiO(2) polymorphs (rutile, anatase, and brookite) were studied by high temperature oxide melt drop solution calorimetry. Relative to bulk rutile, bulk brookite is 0.71 +/- 0.38 kJ/mol (6) and bulk anatase is 2.61 +/- 0.41 kJ/mol higher in enthalpy. The surface enthalpies of rutile, brookite, and anatase are 2.2 +/- 0.2 J/m(2), 1.0 +/- 0.2 J/m(2), and 0.4 +/- 0.1 J/m(2), respectively. The closely balanced energetics directly confirm the crossover in stability of nanophase polymorphs inferred by Zhang and Banfield (7). An amorphous sample with surface area of 34,600 m(2)/mol is 24.25 +/- 0.88 kJ/mol higher in enthalpy than bulk rutile.