Valence Band Edge Positions Research Articles

Composition-dependent band structure parameters and band-gap bowing effect in a caesium lead mixed halide system: a cyclic voltammetry investigation.

Cyclic voltammetry techniques have been employed to study the effect of halide substitution on the band edge parameters and band gap bowing effect in the case of CsPbX3 [X = I, Br, Cl] perovskite nanocrystals (PNCs). A series of compositions, viz. CsPbI3, CsPb(I-Br)3, CsPbBr3, CsPb(Br-Cl)3 and CsPbCl3, have been prepared by a hot injection method. From powder XRD and HR-TEM analysis, the formation of a highly crystalline, cubic phase of the perovskite having size in the range from 7-20 nm has been confirmed. Sharp peaks in the photoluminescence spectra suggest the formation of quantum dots with narrow-size distribution. The composition-dependent optical band gap (εopgap) for CsPbX3 displays a systematic shift towards shorter wavelengths from I to Br to Cl substitutions. The cyclic voltammetry investigation on the dispersion of PNCs in nonaqueous solvents yielded prominent cathodic and anodic peaks. These are correlated to conduction (e1) and valence band edge (h1) positions, respectively. The h1 has been decreased substantially with I to Br to Cl in CsPbX3. Meanwhile, e1 shows a marginal increase. The values derived from CV data demonstrated an excellent match with UVPS results, reported for a similar system. From these results, the quasi-particle gap (εqpgap) and exciton binding energy have been estimated for all the compositions. The negative band gap bowing effect noted in these PNCs is attributed to the size quantization effect. The band-edge parameters reported in this work will be valuable in matching these heterojunctions with suitable electron/hole transport materials for optimum device-performance.

One-Pot Facile Synthesis of ZrO2-CdWO4: A Novel Nanocomposite for Hydrogen Production via Photocatalytic Water Splitting

ZrO2-based nanocomposites are highly versatile materials with huge potential for photocatalysis. In this study, ZrO2-CdWO4 nanocomposites (NC) were prepared via the green route using aqueous Brassica rapa leaf extract, and its photocatalytic water-splitting application was evaluated. Brassica rapa leaf extract acts as a reducing agent and abundant phytochemicals are adsorbed onto the nanoparticle surfaces, improving the properties of ZrO2-CdWO4 nanocomposites. As-prepared samples were characterized by using various spectroscopic and microscopic techniques. The energy of the direct band gap (Eg) of ZrO2-CdWO4 was determined as 2.66 eV. FTIR analysis revealed the various functional groups present in the prepared material. XRD analysis showed that the average crystallite size of ZrO2 and CdWO4 in ZrO2-CdWO4 was approximately 8 nm and 26 nm, respectively. SEM and TEM images suggested ZrO2 deposition over CdWO4 nanorods, which increases the roughness of the surface. The prepared sample was also suggested to be porous. BET surface area, pore volume, and half pore width of ZrO2-CdWO4 were estimated to be 19.6 m2/g. 0.0254 cc/g, and 9.457 Å, respectively. PL analysis suggested the conjugation between the ZrO2 and CdWO4 by lowering the PL graph on ZrO2 deposition over CdWO4. The valence and conduction band edge positions were also determined for ZrO2-CdWO4. These band positions suggested the formation of a type I heterojunction between ZrO2 and CdWO4. ZrO2-CdWO4 was used as a photocatalyst for hydrogen production via water splitting. Water-splitting results confirmed the ability of the ZrO2-CdWO4 system for enhanced hydrogen production. The effect of various parameters such as photocatalyst amount, reaction time, temperature, water pH, and concentration of sacrificial agent was also optimized. The results suggested that 250 mg of ZrO2-CdWO4 could produce 1574 µmol/g after 5 h at 27 °C, pH 7, using 30 vol. % of methanol. ZrO2-CdWO4 was reused for up to seven cycles with a high hydrogen production efficiency. This may prove to be useful research on the use of heterojunction materials for photocatalytic hydrogen production.

Exploring the electronic structure of BiVO4 thin films using energy-resolved electrochemical impedance spectroscopy

Bismuth vanadate (BiVO4) is a promising photoelectrochemical water-splitting semiconductor. This study focuses on elucidating the electronic structure of BiVO4 by analyzing energy-resolved electrochemical impedance spectroscopy (ER-EIS) data. The primary objective is to demonstrate the effectiveness of the ER-EIS, which is typically applied to organic semiconductors, in estimating the band edge positions of BiVO4 films deposited on FTO substrates.The impedance spectra analysis as a function of an applied overpotential permits an estimation of the density of states, where the limits correspond to the valence (VB) and conduction band (CB) edge positions that determine the redox reactions the semiconductor can promote. The energy difference between the CB and VB corresponds to the material's band gap (Eg). The calculated Eg using ER-EIS closely matches the reported optical properties of the material, and the energy positions of the VB and CB align with the reported values for BiVO4.

Anisotropic properties of two-dimensional (2D) tin dihalide (SnX2, X = Cl, Br, I) monolayer binary materials

This paper investigated the electronic properties and photoresponse of two-dimensional SnX2 (X = Cl, Br, I) monolayer binary materials using computational techniques. The calculated band structure and density of states indicate that these are large band gap semiconducting materials with an indirect band gap. The studied chemical bonding mechanism shows the existence of the hybrid bonding of ionic and covalent bonds in these dihalide materials. The valence band (VB) and conduction band (CB) edge positions are also estimated, using the concept of electronegativity and band gap, to investigate the photocatalytic activity of SnX2. Next, we investigated the polarization and energy-dependent dielectric and optical functions along the crystallographic axes of these materials in the linear response approach of the perturbing incident oscillating light field. These materials exhibit an anisotropic behavior of these functions, especially in the high-energy visible and low-energy ultraviolet (UV) regions. The absorption of incident light photons is very fast in SnI2 than SnBr2 and SnCl2 in the low-energy UV region. It demonstrates the higher absorption coefficient and optical conductivity in Snl2. The obtained average static refractive index of SnCl2 is comparable to that of glass (1.5), showing its application as transparent material. The low reflection coefficient, less than 20%, makes them superior for antireflection coating materials in the infrared and visible regions. The prominent energy loss peaks show the existence of plasmon resonances in these materials. The most of losses occur in the UV region. The investigated electronic and photoresponse properties indicate that these Sn-based dihalide materials are excellent for electronic devices and optoelectronic applications. Also, the calculated VB and CB edge positions with respect to the normal hydrogen electrode show the favorable water-splitting capability of these materials.

Lattice distortion-driven band gap engineering and enhanced electrocatalytic activity of Mn-substituted nanostructured SrTiO3 materials: A comprehensive investigation

The lattice distortion and electrocatalytic activity are investigated by the mono-substituent of Mn with different concentrations to generate localized states in the electronic structure of SrTiO3. The sol-gel approach has been employed to fabricate SrTiO3 and SrTi1-xMnxO3 nanostructures (NSs). The structural analysis indicates Mn incorporation into Ti sites of SrTiO3, which shifts the lattice towards a higher diffraction angle with a single-phase cubic structure. The optical absorption spectra exhibit a decrease in band gap from 3.27 to 1.89 eV and reveal the shift in band edge positions towards the visible region. XPS analysis is carried out to confirm the formation of oxygen vacancies and valence band edge position. For SrTi0.88Mn0.12O3, OER and HER have the overpotential of 445 and 157 mV at a current density of 100 and 10 mA cm−2. Hence, the substitution of Mn (x = 0.12) into SrTiO3 lattice results in lattice distortion that enhances the electrochemical performance compared to SrTiO3. The current work manifestly established the optimal Mn composition (x = 0.12) in SrTiO3 lattice as desirable materials with defective valence states for required electrocatalytic redox potential as well as the acceleration of charge transfer kinetics towards water splitting applications.

S-doped copper selenide thin films synthesized by chemical bath deposition for photoelectrochemical water splitting

The utilization of fossil fuels to meet ever-increasing energy demands is causing a significant threat to the Earth's climate and its inhabitants. To address this issue, photoelectrochemical (PEC) water splitting has emerged as a promising solution to produce oxygen (O2) and hydrogen (H2) in a cost-effective, environmentally friendly, clean, and renewable manner. In this study, we present the development of cost-effective Cu3Se2 and S-doped Cu3Se2 thin films on Fluorine-doped Tin Oxide (FTO) substrates using a chemical bath deposition (CBD) process to enhance the efficiency of PEC water oxidation to produce oxygen. The X-Ray Diffraction (XRD) pattern confirms the presence of a single-phase tetragonal Cu3Se2 crystal structure with a noticeable shift in the characteristic (211) reflection towards a higher 2θ value, from 38.1° to 38.4°, indicating the successful doping of S in the Cu3Se2 thin films. To further validate successful S doping in the Cu3Se2 crystal lattice, X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray (EDX), Fourier transform infrared (FTIR), and Raman Spectroscopy were employed. TEM reveals a granular structure with an average particle size of 7–8 nm, which is consistent with the crystallite size determined by XRD. Furthermore, the valence band and conduction band edge positions are found to be 1.56 and −0.57 eV, respectively. The presence of S increased the band gap of Cu3Se2, from 1.97 to 2.15 eV, thus confirming the bending of the band edge upon doping. The specific surface areas (SSA) of pristine and S-doped Cu3Se2 were determined to be 5.03 and 111.48 m2g−1, respectively, showing a twenty-two-fold increase upon doping. The PEC performance of the materials was evaluated through chopped chronoamperometry (CA), linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), and Mott-Schottky (M-S) analysis. The S-doped Cu3Se2, prepared under optimum conditions, exhibited a photocurrent density difference of 880 µA cm−2, which was 6 times greater than for the pristine Cu3Se2 thin film. The results of S-doped Cu3Se2 indicate a negative slope, implying p-type conductivity, and a lower flat band potential value of 0.33 V vs. RHE. Our approach provides a green and cost-effective solution to fabricate S-doped Cu3Se2 thin films for producing hydrogen and oxygen using CBD.

Density functional analysis of oxide dipole layer voltage shifts in high κ/metal gate stacks

The mechanism of gate threshold voltage (VT) shifts observed in high κ/metal gate stacks is investigated by a density functional theory. This finds that VT depends on the band alignments and the chemical trends between the component oxide layers, such as HfO2, SrO, La2O3, Al2O3, and SiO2. Based on the electron counting rule, we have built three insulating SiO2/SrO, SiO2/La2O3, and SiO2/Al2O3 interfaces, all of which feature a clean bandgap. Two methods have been adopted to derive the band alignments between these four oxides, which are consistent with each other. The results show staggered, “staircase” band alignments and enable La2O3 and Al2O3 layers to shift the metal electrode Fermi level in opposite directions and to approach the Si conduction band and valence band edge positions, respectively. This analysis updates previous empirical models of this effect based on metal oxide ion densities or electronegativity scales and confirms that the oxide layer scheme is suitable for controlling the effective metal work functions in metal–oxide–semiconductor field-effect transistors.

Sub‐Stochiometric Nickel Oxide Hole‐Selective Contacts in Solar Cells: Comparison of Simulations and Experiments with Sputtered Films

Sub‐stochiometric nickel oxide (NiOx) films were investigated as a hole selective contact option in silicon (Si) heterojunction solar cells. Numerical simulations were carried out to evaluate the impacts of the NiOx electronic properties variations and the NiOx/Si interface defect density (Dit) on device performance. Simulation data suggest that the best performance is achievable for wide bandgaps (Eg) and corresponding high valence band edge (EVB) positions in the NiOx films. Overall, in simulations, the performance remains practically unchanged for the nickel vacancy concentrations [VNi] = 1017–1021 cm−3, assuming high EVB and low Dit. The experimental data measured using NiOx films prepared by radio‐frequency magnetron sputtering reveal that the increase in [VNi] lifts the conductivity, concurrently decreasing Eg and EVB. As a result, we concluded that the performance of the fabricated sputtered NiOx/Si heterojunction solar cell is limited by high Dit as well as narrow Eg and low EVB.

(Invited) High Efficiency, Ultras-table Solar Hydrogen Production Utilizing Industry Standard Materials

Solar water splitting and green hydrogen fuel production has been extensively studied but is confronted with fundamental challenges of simultaneously achieving both high efficiency and long-term stability. The commonly utilized approaches include photovoltaic-electrolysis (PV-E), photoelectrochemical, and photocatalytic processes, and numerous materials have been studied. In this presentation, I will report on our recent developments of gallium nitride (GaN) based photoelectrochemical and photocatalytic water splitting studies. GaN is one of the most produced semiconductors. By alloying with indium, the energy bandgap of InGaN can be continuously varied across nearly the entire solar spectrum. Recent studies have further shown that the conduction and valence band edge positions of InGaN can staddle water redox potentials for indium compositions up to 40-50%, corresponding to an energy bandgap ~1.7 eV. This is a unique property not commonly seen in other materials. Significantly, by growing GaN nanostructures under N-rich conditions, the surfaces can be transformed to be N-rich, which can protect against photocorrosion and oxidation during harsh photocatalysis reaction conditions. Studies have further shown that, during the initial solar water splitting reaction, the N-rich surfaces are transformed to be gallium oxynitride, which not only further protects the surfaces of the light absorber but exhibits significantly enhanced photocatalytic and photoelectrochemical performance with continued reaction, which is in direct contrast to the rapid performance degradation of other known light absorbers. We have demonstrated double-junction InGaN/Si photoelectrode that can exhibit solar-to-hydrogen efficiency of 10% with stability over 100 hrs under practical two-electrode measurement conditions. Moreover, we have developed unique photocatalytic process wherein high efficiency solar hydrogen can be produced utilizing tap water, or seawater, without any wire connection, or electricity input. The demonstration of large-scale solar water splitting systems and the performance will be discussed and reported. Moreover, the use of GaN-based photocatalytic nanostructures for converting carbon dioxide and methane to liquid fuels under sunlight will be presented.

Strain dependences of electronic properties, band alignments and thermal properties of bilayer WX2 (X = Se, Te)

ABSTRACT We presented a comprehensive study of electronic properties and phonon thermal transport properties in layered WX2 (X = Se, Te) using first-principles calculations combined with density functional perturbation theory (DFPT). Our results indicated that the spin–orbit coupling (SOC) and biaxial strains have significant effects on the band gaps and band alignments of the bilayer WX2 (X = Se, Te), and the d-orbital of the W atom played a dominant role at the valence and conduction band edge positions. We found that the band gaps decreased with the increase of strain and WTe2 have the transition from indirect band gap to direct band gap at 2% strain. We also calculated their lattice thermal conductivities , group velocities, cumulative thermal conductivities along the x and y directions, and scattering rates at room temperature. The calculated along x and y directions of WSe2 are 70.81 and 78.38 W/m K, respectively, whereas those of WTe2 were relatively low (55.05 W/m K along x-direction and 59.97 W/m K along y-direction), which mainly originated from their relatively smaller phonon group velocities and atomic weights. Two materials exhibited that , and group velocities in the y-direction were higher than those in the x-direction. We also investigated the size dependence of the and contributions of different acoustic and optical branches to the total . It was found that the nanostructure may be efficient to reduce .

Highly anisotropic mechanical and optical properties of 2D NbOX2 (X = Cl, Br, I) revealed by first-principle

In the latest experimental success, NbOI2 two-dimensional (2D) crystals with anisotropic electronic and optical properties have been fabricated (Adv. Mater. 33 (2021), 2101505). In this work inspired by the aforementioned accomplishment, we conduct first-principles calculations to explore the mechanical, electronic, and optical properties of NbOX2 (X = Cl, Br, I) nanosheets. We show that individual layers in these systems are weakly bonded, with exfoliation energies of 0.22, 0.23, and 0.24 J m−2, for the isolation of the NbOCl2, NbOBr2, and NbOI2 monolayers, respectively, distinctly lower than those of the graphene. The optoelectronic properties of the single-layer, bilayer, and bulk NbOCl2, NbOBr2, and NbOI2 crystals are investigated via density functional theory calculations with the HSE06 approach. Our results indicate that the layered bulk NbOCl2, NbOBr2, and NbOI2 crystals are indirect gap semiconductors, with band gaps of 1.79, 1.69, and 1.60 eV, respectively. We found a slight increase in the electronic gap for the monolayer and bilayer systems due to electron confinement at the nanoscale. Our results show that the monolayer and bilayer of these novel 2D compounds show suitable valence and conduction band edge positions for visible-light-driven water splitting reactions. The first absorption peaks of these novel monolayers along the in-plane polarization are located in the visible range of light which can be a promising feature to design advanced nanoelectronics. We found that the studied 2D systems exhibit highly anisotropic mechanical and optical properties. The presented first-principles results provide a comprehensive vision about direction-dependent mechanical and optical properties of NbOX2 (X = Cl, Br, I) nanosheets.

Photocatalytic Recovery of Gold from a Non-Cyanide Gold Plating Solution as Au Nanoparticle-Decorated Semiconductors.

In this work, a photocatalytic process was carried out to recover gold (Au) from the simulated non-cyanide plating bath solution. Effects of semiconductor types (TiO2, WO3, Nb2O3, CeO2, and Bi2O3), initial pH of the solution (3–10), and type of complexing agents (Na2S2O3 and Na2SO3) and their concentrations (1–4 mM each) on Au recovery were explored. Among all employed semiconductors, TiO2 exhibited the highest photocatalytic activity to recover Au from the simulated spent plating bath solution both in the absence and presence of complexing agents, in which Au was completely recovered within 15 min at a pH of 6.5. The presence of complexing agents remarkably affected the size of deposited Au on the TiO2 surface, the localized surface plasmon effect (LSPR) behavior, and the valence band (VB) edge position of the obtained Au/TiO2, without a significant change in the textural properties or the band gap energy. The photocatalytic activity of the obtained Au/TiO2 tested via two photocatalytic processes depended on the common reduction mechanism rather than the textural or optical properties. As a result, the Au/TiO2 NPs obtained from the proposed recovery process are recommended for use as a photocatalyst for the reactions occurring at the conduction band rather than at the valence band. Notably, they exhibited good stability after the fifth photocatalytic cycle for Au recovery from the actual cyanide plating bath solution.

Unfolding the Role of B Site-Selective Doping of Aliovalent Cations on Enhancing Sacrificial Visible Light-Induced Photocatalytic H2 and O2 Evolution over BaTaO2N

The doping of foreign cations and anions is one of the effective strategies for engineering defects and modulating the optical, electronic, and surface properties that directly govern the photocatalytic O2 and H2 evolution reactions. BaTaO2N (BTON) is a promising 600 nm-class photocatalyst because of its absorption of visible light up to 660 nm, small band gap (Eg = 1.9 eV), appropriate valence band-edge position for oxygen evolution, good stability under light irradiation in concentrated alkaline solutions, and nontoxicity. Although the photocatalytic and photoelectrochemical water-splitting efficiencies of BaTaO2N have been progressively improved, it is still far from the requirements set for practical applications. Here, we employ a 5% B site-selective doping of aliovalent metal cations (Al3+, Ga3+, Mg2+, Sc3+, and Zr4+) to enhance sacrificial visible light-induced photocatalytic H2 and O2 evolution over BaTaO2N. The results of physicochemical characterizations reveal that no significant change in crystal structure, crystal morphology, and optical absorption edge is observed upon cation doping. Therefore, the difference observed in O2 and H2 evolution during the photocatalytic reactions over pristine and doped BaTaO2N photocatalysts is explained by examining optical, electronic, and surface properties. Also, molecular dynamics (MD) is used to gain insights into the respective effect of cation doping on adsorption energy of water molecules and formed intermediates (H* for H2 evolution and HO*, O*, and HOO* for O2 evolution) on the BaTaO2N surfaces terminated with TaO6, TaN6, and TaO4N2 octahedra. Finally, the experimental reaction rates for H2 and O2 evolution are correlated well using a linear energy–performance relationship, elucidating the doping and surface-termination trends observed in the BaTaO2N photocatalysts.

The impact of chemical composition of halide surface ligands on the electronic structure and stability of lead sulfide quantum dot materials.

There is a high fundamental interest in the surface and bulk chemistry of quantum dot (QD) solids, as they have proven to be very promising materials in optoelectronic devices. The choice of surface ligands for quantum dots in solid devices determines many of the film properties, as the ligands influence for example the doping density, chemical stability and charge transport. Lead halide ligands have developed as the main ligand of choice for lead sulfide quantum dots, as they have been shown to passivate quantum dot surfaces and enhance the chemical stability. In this study, we successfully varied the ligand composition on the surface of PbS quantum dot films from pure lead iodide to pure lead bromide and investigated its influence on the chemical and electronic structure of the QD solids using hard X-ray photoelectron spectroscopy (HAXPES). Furthermore, we developed a surface treatment to prevent the surface oxidation of a bulk PbS reference sample. Through measurements of this sample and of lead halide reference samples, we were able to assign the contributions of different chemical bonding to the Pb 4f core level and of different atomic orbitals to the valence band spectral shape of the QD materials. Overall, we found that the valence band edge position was very similar for all different iodide:bromide ratios and that all investigated compositions were able to protect the quantum dot surfaces within solid films from oxidation. However, the ligand composition significantly influences the sample stability under X-rays. The iodide rich QD solids showed the highest stability with very little to no chemical changes over several hours of X-ray exposure, while the bromide rich QD solids changed already within the first hour of exposure.

Theoretical Prediction of a Bi-Doped β-Antimonene Monolayer as a Highly Efficient Photocatalyst for Oxygen Reduction and Overall Water Splitting.

The photo-/electrocatalysts with high activities for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and the oxygen reduction reaction (ORR) are of significance for the advancement of photo-/electrochemical energy systems such as solar energy to resolve the global energy crisis, reversible water electrolyzers, metal–air batteries, and fuel cells. In the present work, we have systematically investigated the photochemical performance of the 2D β-antimonene (β-Sb) monolayer. From density functional theory investigations, β-Sb with single-atom doping possesses a trifunctional photocatalyst with high energetics and thermal stabilities. In particular, it is predicted that the performance of the HER activity of β-Sb will be superior to most of the 2D materials. Specifically, β-Sb with single atom replacement has even superior that the reference catalysts IrO2(110) and Pt(111) with relatively low overpotential values for ORR and OER mechanisms. The superior catalytic performance of β-Sb has been described by its electronic structures, charge transfer mechanism, and suitable valence and conduction band edge positions versus normal hydrogen electrode. Meanwhile, the low overpotential of multifunctional photocatalysts of the Bi@β-Sb monolayer makes them show a remarkable performance in overall water splitting (0.06 V for HER, 0.25 V for OER, and 0.31 V for ORR). In general, the Bi@β-Sb monolayer may be an excellent trifunctional catalyst that exhibits high activity toward all electrode reactions of hydrogen and oxygen.

Tuning the Band Alignment and Electronic Properties of GaSe/Sn X 2 ( X = S , Se ) Two-Dimensional van der Waals Heterojunctions via an Electric Field

Two-dimensional (2D) material-based van der Waals heterostructures (vdWHs) have been identified as an excellent platform from which to expand various device applications for light-emitting, photovoltaic, and field-effect transistors because of their different band alignments, including type-I, type-II, and type-III. However, it is difficult to achieve transformations between types of band alignment in a single heterostructure for diverse applications. In this study, the effects of a vertical electric field on the band alignment transition and electronic properties of 2D ${\rm{GaSe}}/{\rm{SnS}}_{2}$ (${\rm{SnSe}}_{2}$) vdWHs are investigated systematically using density functional theory calculations. The study shows that the electric field can modulate not only the band gap but also the band alignment to produce multifunctional device applications. A positive electric field can control the band alignment transformation from type-II to type-I for electric field values of approximately 0.39 V/\AA{} (0.12 V/\AA{}), while a negative electric field can transform the type-II to type-III band alignments for electric field values of about \ensuremath{-}0.2 V/\AA{} (\ensuremath{-}0.16 V/\AA{}) in ${\rm{GaSe}}/{\rm{SnS}}_{2}$ (${\rm{SnSe}}_{2}$) vdWHs. We trace these surprising results to the conduction band and valence band edge position movements for the linear decrease of ${\rm{GaSe}}$, while the linear increase of ${\rm{SnS}}_{2}$ (${\rm{SnSe}}_{2}$) occurs with the applied electric field. The present work may provide a direction for tunable multiple-band alignments in 2D vdWHs and help achieve multifunctional device applications.

Photoelectrochemical water oxidation in anodic TiO2 nanotubes array: Importance of mass transfer

In this study, 1-μm-thick TiO2 nanotubes array was prepared through anodization in aqueous or organic electrolytes, and their photoelectrochemical properties were compared. TiO2 nanotubes array prepared in an aqueous electrolyte exhibited better intrinsic characteristics for water oxidation, including larger naked surface area, higher oxygen vacancies leading to improved electrical conductivity, higher donor density, and lower valence band edge position, compared to those prepared in an organic electrolyte. However, a higher photocurrent density was observed in the TiO2 nanotubes array prepared in an organic electrolyte because of facile mass transfer, resulting in effective interaction between the generated holes and reactant.

Time-Retrenched Synthesis of BaTaO2N by Localizing an NH3 Delivery System for Visible-Light-Driven Photoelectrochemical Water Oxidation at Neutral pH: Solid-State Reaction or Flux Method?

Among 600 nm class transition-metal oxynitrides, BaTaO2N with a cubic Pm3̅m perovskite-type structure is promising for solar water oxidation due to its absorption of visible light up to 660 nm, narrower band gap (Eg = 1.9 eV), appropriate valence band edge position for oxygen evolution, good stability in concentrated alkaline solutions, and nontoxicity. However, high defect density stemmed from long high-temperature ammonolysis limits the separation and transfer efficiency of photogenerated charge carriers in BaTaO2N. Here, a NH3 delivery system is specifically localized just above the synthesis mixture to reduce the synthesis time and defect density of BaTaO2N by a fresh supply of more active nitriding species and minimizing the generation of N2 and H2. Particularly, the effects of synthesis temperature (700–950 °C), synthesis time (1–8 h), and gas composition are systematically investigated to gain insights into the formation of single-phase BaTaO2N by solid-state reaction and flux method. Time-dependent experiments conducted at 950 °C show that single-phase BaTaO2N can be synthesized ≥6 and ≥4 h by solid-state reaction and flux method, respectively, revealing the advantage of the flux method over solid-state reaction in a localized NH3 delivery system. Subsequently, the separation and transfer efficiency and kinetics of photogenerated charge carriers are studied in BaTaO2N samples. Photoelectrochemical studies made it possible to resolve trends during visible-light-induced water oxidation, evidencing the inverse relationship between recombination and charge transfer phenomena. Transient absorption spectroscopy reveals that the dynamics of the photogenerated charge carriers in both types of BaTaO2N samples are different: (i) BaTaO2N synthesized by flux method has a greater number of holes despite the similar number of deeply trapped charge carriers and (ii) solid-state reaction led to the formation of a higher number of free electrons in BaTaO2N. The findings demonstrate the advantage of reducing the transfer distance of active nitriding species to the surface of the synthesis mixture for enhancing the photoelectrochemical water oxidation of BaTaO2N at neutral pH.

Effect of a Cocatalyst on a Photoanode in Water Splitting: A Study of Scanning Electrochemical Microscopy.

With a proper band gap of ∼2.4 eV for solar light absorption and suitable valence band edge position for oxygen evolution, scheelite-monoclinic bismuth vanadate (BiVO4) has become one of the most attractive photocatalysts for efficient visible-light-driven photoelectrochemical (PEC) water splitting. Several studies have indicated that surface modification of BiVO4 with a cocatalyst such as NiFe layered double hydroxide (LDH) can significantly increase the PEC water splitting performance of the catalyst. Herein, we experimentally investigated the charge transfer dynamics and charge carrier recombination processes by scanning electrochemical microscopy (SECM) with the feedback mode on the surface of BiVO4 and BiVO4/NiFe-LDH as model samples. The ratio of rate constants for photogenerated hole (kh+0) to electron (ke-0) via the photocatalyst of BiVO4/NiFe-LDH reacting with the redox couple is found to be five times larger than that of BiVO4 under illumination. In this case, the ratio of the rate constants kh+0/ke-0 stands for the interfacial charge recombination process. This implies the cocatalyst NiFe-LDH suppresses the electron back transfer greatly and finally reduces the surface recombination. Control experiments with cocatalysts CoPi and RuOx onto BiVO4 further verify this conclusion. Therefore, the SECM characterization allows us to make an overall analysis on the function of cocatalysts in the PEC water splitting system.

Nitrogen-Ion Implantation Induced Bandgap Tailoring in Multifunctional Brownmillerite KBiFe2O5

In the present work, KBiFe2O5 (KBFO) films were implanted with 1 MeV N+-ions at different fluencies i.e., 1015, 1016 and 1017 ions cm−2 and their structural, optical and electronic properties were analyzed. From the X-ray diffraction studies, it is evident that the crystal structure of these films belong to that of brownmillerite. Effective bandgaps of these implanted films, as observed from the UV–visible absorption spectroscopy, are tuned from 1.72 eV to 1.60 eV with increasing the ion fluences. X-ray photoelectron spectroscopy reveals that the valence states of Bi and Fe ions in both pristine and implanted films are in trivalent states and also confirm the presence of nitrogen in the implanted films. A clear shift in valence band (VB) edge position towards lower binding energy in N+-ion implanted films is observed due to the occupation of N 2p states above O 2p states in the VB.