Recombination Rate Research Articles

Titanium-coated high-density Fe2O3 single crystal nanowire array for solar water splitting

Fe2O3 holds promising n-type semiconductor material in the field of solar water splitting due to its excellent photocatalytic properties. However, the photoelectrochemical performance of Fe2O3 is limited by its inherent properties such as poor conductivity, and charge separation efficiency owing to its recombination rate. Therefore, researchers are more focused on nanostructuring, doping, and surface coating to overcome these issues of Fe2O3. In this study, we have investigated a low-cost way to fabricate a Ti coating layer on a high-density Fe2O3 single-crystal nanowire array for solar water splitting. Firstly, we have prepared a high-density single-crystal Fe2O3 nanowire array at lower temperatures by a new approach stress-induced atomic diffusion method. Thereafter, the prepared nanowire array was coated by Ti film using RF sputtering. The optimal film thickness of 13 nm titanium coatings layer into Fe2O3 single crystal nanowire array exhibited a high photocurrent density of 1.36 mA/cm2 at 1.23 V versus RHE and solar to hydrogen conversion efficiency (STH) of 1.67%, which could be resulting from adjusted optoelectronic properties of the nanowires.

Pattern‐Matched Polymer Ligpands Toward Near‐Perfect Synergistic Passivation for High‐Performance and Stable Br/Cl Mixed Perovskite Light‐Emitting Diodes

Mixed Br/Cl perovskite nanocrystals (PeNCs) exhibit bright pure‐blue emission benefiting for fulfilling the Rec. 2100 standard. However, phase segregation remains a significant challenge that severely affects the stability and emission spectrum of perovskite light‐emitting diodes (PeLEDs). Here, we demonstrate the optimization of the spacing between polydentate functional groups of polymer ligands to match the surface pattern of CsPbBr1.8Cl1.2 PeNCs, resulting in effective synergistic passivation effect and significant improvements in PeLED performances. The block and alternating copolymers with different inter‐functional group spacing are facilely synthesized as ligands for PeNCs. Surprisingly, block copolymers with a higher functional group density do not match PeNCs, while alternating copolymers enable efficient PeNCs with the high photoluminescence intensity, low non‐radiative recombination rate and high exciton binding energy. Density functional theory calculations clearly confirm the almost perfect match between alternating copolymers and PeNCs. Finally, pure‐blue PeLEDs are achieved with the emission at 467 nm and Commission Internationale de l'Eclairage (CIE) coordinates of (0.131, 0.071), high external quantum efficiency (9.1%) and record spectral and operational stabilities (~ 80 mins) in mixed‐halide PeLEDs. Overall, this study contributes to designing the polymer ligands and promoting the development of high‐performance and stable pure‐color PeLEDs towards display applications.

Pattern-Matched Polymer Ligpands Toward Near-Perfect Synergistic Passivation for High-Performance and Stable Br/Cl Mixed Perovskite Light-Emitting Diodes.

Mixed Br/Cl perovskite nanocrystals (PeNCs) exhibit bright pure-blue emission benefiting for fulfilling the Rec. 2100 standard. However, phase segregation remains a significant challenge that severely affects the stability and emission spectrum of perovskite light-emitting diodes (PeLEDs). Here, we demonstrate the optimization of the spacing between polydentate functional groups of polymer ligands to match the surface pattern of CsPbBr1.8Cl1.2 PeNCs, resulting in effective synergistic passivation effect and significant improvements in PeLED performances. The block and alternating copolymers with different inter-functional group spacing are facilely synthesized as ligands for PeNCs. Surprisingly, block copolymers with a higher functional group density do not match PeNCs, while alternating copolymers enable efficient PeNCs with the high photoluminescence intensity, low non-radiative recombination rate and high exciton binding energy. Density functional theory calculations clearly confirm the almost perfect match between alternating copolymers and PeNCs. Finally, pure-blue PeLEDs are achieved with the emission at 467 nm and Commission Internationale de l'Eclairage (CIE) coordinates of (0.131, 0.071), high external quantum efficiency (9.1%) and record spectral and operational stabilities (~ 80 mins) in mixed-halide PeLEDs. Overall, this study contributes to designing the polymer ligands and promoting the development of high-performance and stable pure-color PeLEDs towards display applications.

Tearing-mediated Reconnection in Magnetohydrodynamic Poorly Ionized Plasmas. I. Onset and Linear Evolution

In high-Lundquist-number plasmas, reconnection proceeds via the onset of tearing, followed by a nonlinear phase during which plasmoids continuously form, merge, and are ejected from the current sheet (CS). This process is understood in fully ionized, magnetohydrodynamic plasmas. However, many plasma environments, such as star-forming molecular clouds and the solar chromosphere, are poorly ionized. We use theory and computation to study tearing-mediated reconnection in such poorly ionized systems. In this paper, we focus on the onset and linear evolution of this process. In poorly ionized plasmas, magnetic nulls on scales below v A,n0/ν ni0, with v A,n0 the neutral Alfvén speed and ν ni0 the neutral–ion collision frequency, will self-sharpen via ambipolar diffusion. This sharpening occurs at an increasing rate, inhibiting the onset of reconnection. Once the CS becomes thin enough, however, ions decouple from neutrals and the thinning of the CS slows, allowing the onset of tearing in a time of order νni0−1 . We find that the wavelength and growth rate of the mode that first disrupts the forming sheet can be predicted from a poorly ionized tearing dispersion relation; as the plasma recombination rate increases and ionization fraction decreases, the growth rate becomes an increasing multiple of ν ni0 and the wavelength becomes a decreasing fraction of v A,n0/ν ni0.

Drivers of genomic differentiation landscapes in populations of disparate ecological and geographical settings within mainland Apis cerana.

Elucidating the evolutionary processes that drive population divergence can enhance our understanding of the early stages of speciation and inform conservation management decisions. The honeybee Apis cerana displays extensive population divergence, providing an informative natural system for exploring these processes. The mainland lineage A. cerana includes several peripheral subspecies with disparate ecological and geographical settings radiated from a central ancestor. Under this evolutionary framework, we can explore the patterns of genome differentiation and the evolutionary models that explain them. We can also elucidate the contribution of non-genomic spatiotemporal mechanisms (extrinsic features) and genomic mechanisms (intrinsic features) that influence these genomic differentiation landscapes. Based on 293 whole genomes, a small part of the genome is highly differentiated between central-peripheral subspecies pairs, while low and partial parallelism partly reflects idiosyncratic responses to environmental differences. Combined elements of recurrent selection and speciation-with-gene-flow models generate the heterogeneous genome landscapes. These elements weight differently between central-island and other central-peripheral subspecies pairs, influenced by glacial cycles superimposed on different geomorphologies. Although local recombination rates exert a significant influence on patterns of genomic differentiation, it is unlikely that low-recombination rates regions were generated by structural variation. In conclusion, complex factors including geographical isolation, divergent ecological selection and non-uniform genome features have acted concertedly in the evolution of reproductive barriers that could reduce gene flow in part of the genome and facilitate the persistence of distinct populations within mainland lineage of A. cerana.

Comprehensive analysis of the complete mitochondrial genome of Lilium tsingtauense reveals a novel multichromosome structure.

Lilium tsingtauense mitogenome comprises 27 independent chromosome molecules, it undergoes frequent genomic recombination, and the rate of recombination and mutation between different repetitive sequences affects the formation of multichromosomal structures. Given the extremely large genome of Lily, which likely harbors additional genetic resources, it serves as an ideal material for studying the phylogenetic evolution of organisms. Although the Lilium chloroplast genome has been documented, the sequence of its mitochondrial genome (mitogenome) remains uncharted. Using BGI short reads and Nanopore long reads, we sequenced, assembled, and annotated the mitogenome of Lilium tsingtauense. This effort culminated in the characterization of Lilium's first complete mitogenome. Comparative analysis with other angiosperms revealed the unique multichromosomal structure of the L. tsingtauense mitogenome, spanning 1,125,108 bp and comprising 27 independent circular chromosomes. It contains 36 protein-coding genes, 12 tRNA genes, and 3 rRNA genes, with a GC content of 44.90%. Notably, three chromosomes in the L. tsingtauense mitogenome lack identifiable genes, hinting at the potential existence of novel genes and noncoding elements. The high degree of observed genome fragmentation implies frequent reorganization, with recombination and mutation rates among diverse repetitive sequences likely driving the formation of multichromosomal structures. Our comprehensive analysis, covering genome size, coding genes, structure, RNA editing, repetitive sequences, and sequence migration, sheds light on the evolutionary and molecular biology of multichromosomal mitochondria in Lilium. This high-quality mitogenome of L. tsingtauense not only enriches our understanding of multichromosomal mitogenomes but also establishes a solid foundation for future genome breeding and germplasm innovation in Lilium.

Rational Bi[sbnd]Mo[sbnd]O nanospheres decorated g-C3N4 for photocatalytic performance of dye degradation

Developing a superior heterostructured composite, optimizing performance through synergies from complementary advantages in diverse materials, remains an ongoing challenge. The rise in organic contaminants in freshwater bodies possesses a major threat to human health. Various dyes such as Rhodamine B, Eosin Y and Methylene Blue are found in excess concentration due to industrial usage and their removal is important for environmental remediation and contaminant-free water. In this study, we report synthesis and fabrication of Bi2MoO6/g-C3N4 (BM/CN) composite photocatalyst and Rhodamine B photodegradation studies. The composite photocatalysts have been characterized using XRD, TGA, FT-IR, UV–Vis, TRPL, SEM, TEM, XPS, electrochemical, and BET studies over g-C3N4, Bi2MoO6, and Bi2MoO6 (10–40 wt%) supported on g-C3N4 photocatalysts. The photocatalytic studies are performed using various composite photocatalysts of BM/CN show 30%-Bi2MoO6 supported on g-C3N4 (30BM/CN) exhibits maximum visible light activation for dye degradation with 3.6 and 2.4-fold higher rate of degradation than bare g-C3N4 and Bi2MoO6, respectively. Higher surface area, broad light absorption, enhanced lifetime, lower charge transfer and higher transient photocurrents of the composite photocatalysts compared to g-C3N4 and Bi2MoO6. Moreover, study is aided with scavenger tests to support the proposed mechanism.The increased photoactivity of 30BM/CN is due to the synergistic interplay of improved charge generation and a reduction in the electron-hole (e−/h+) recombination rate.

Epitaxial analysis of GaInP/AlGaInP red light-emitting diodes with ternary AlGaP quantum barriers for quantum efficiency enhancement

We have numerically analyzed Gallium Indium Phosphide (GaInP)/Aluminum Gallium Indium Phosphide (AlGaInP) red light-emitting diodes (LEDs) by utilizing ternary Aluminum Gallium Phosphide (AlGaP) quantum barriers instead of the conventional quaternary AlGaInP quantum barriers. The simulation findings show that the use of AlGaP quantum barriers in AlGaInP red light-emitting diodes leads to a significant increase in both electron and hole concentration in the quantum wells which in turn enhances the rate of radiative recombination compared to conventional (reference) red light-emitting diodes. Furthermore, the proposed LEDs have a substantial decline in efficiency droop from 38% to 32%.

Enhanced Photocatalytic Activity of V2C MXene-Coupled ZnO Porous Nanosheets with Increased Surface Area and Effective Charge Transfer

Photocatalysis performs excellently when degrading organic pollutants, but the photocatalytic degradation rate is not high for most photocatalysts due to their narrow sunlight adsorption range and high recombination rate of electron hole pairs. Herein, we use V2C-MXene with a wide sunlight adsorption range to couple ZnO porous nanosheets and form ZnO/MXene hybrids using a facile electrostatic self-assembly method. The ZnO/MXene hybrids acquired demonstrated improved photochemical efficiency in breaking down methylene blue (MB) when contrasted with porous ZnO nanosheets. The degradation rate of MB reached 99.8% under UV irradiation for 120 min after the ZnO/MXene hybrid formation, while 38.6% was attained by the ZnO porous nanosheets. Moreover, photodegradation rate constants (k) were calculated as 3.05 × 10−3 and 5.42 × 10−2 min−1 for ZnO porous nanosheets and ZnO/MXene hybrids, respectively, indicating that the photodegradation performance was enhanced by 17.8 times after the modification of V2C. This was probably because the modification of V2C can increase the specific surface area to provide more sites for MB adsorption, widen the sunlight adsorption range to produce good photothermal effect, and facilitate the transfer of photogenerated carriers in ZnO to promote the reaction of more photogenerated carriers with MB. Hence, this work offers a simple approach to creating effective photocatalysts for breaking down organic contaminants.

Effects of demographic history on recombination hotspots in soybean.

Recombination is the primary mechanism underlying genetic improvement in populations and allows plant breeders to create new allelic combinations for agronomic improvement. Soybean [Glycine max (L.) Merr.] has gone through multiple genetic bottlenecks that have significantly affected its genetic diversity, linkage disequilibrium, and altered allele frequencies. To investigate the impact of genetic bottlenecks on recombination hotspots in soybeans, historical recombination was studied in three soybean populations. The populations were wild soybean [Glycine soja (Sieb. and Zucc.)], landraces, and North American elite soybean cultivars that have been genotyped with the SoySNP50K BeadChip. While each population after a genetic bottleneck had an increased average haplotype block size, they did not have a significant difference in the number of hotspots between each population. Instead, the increase in observed haplotype block size is likely due to an elimination of individuals that contained historical recombination at hotspots which decreased the observed rate of recombination for the hotspot after each genetic bottleneck. Conversely, heterochromatic DNA which has an increased haplotype block size compared to euchromatic DNA had a significantly different number of hotspots but not a significant difference in the average hotspot recombination rate. Previously identified genomic motifs associated with hotspots were also associated with hotspots found in the historical populations suggesting a common mechanism. This characterization of historical recombination hotspots in soybeans provides further insights into the effect genetic bottlenecks and selection have on recombination hotspots.

Preparation of a Nanosheeted Uranyl-Organic Framework for Enhanced Photocatalytic Oxidation of Toluene.

Preparation of ultrathin metal-organic framework (MOF) nanosheets is an effective way to improve the catalytic efficiency of MOF photocatalysts owing to their superiority in reducing the recombination rate of photogenerated electrons and holes and enhancing charge transfer. Herein, a light-sensitive two-dimensional uranyl-organic framework named HNU-68 was synthesized. Due to its interlayer stacking structure, the corresponding ultrathin nanosheets with a thickness of 4.4 nm (HNU-68-N) can be obtained through ultrasonic exfoliation. HNU-68-N exhibited an enhanced ability to selectively oxidize toluene to benzaldehyde, with the value of turnover frequency being approximately three times higher than that of the bulk HNU-68. This enhancement is attributed to the smaller size and interface resistance of the layered HNU-68-N nanosheets, which facilitate more thorough substrate contact and faster charge transfer, leading to an improvement in the photocatalytic efficiency. This work provides a potential candidate for the application of ultrathin uranyl-based nanosheets.

Two-Dimensional Electron-Hole Plasma in Colloidal Quantum Shells Enables Integrated Lasing Continuously Tunable in the Red Spectrum.

Combining integrated optical platforms with solution-processable materials offers a clear path toward miniaturized and robust light sources, including lasers. A limiting aspect for red-emitting materials remains the drop in efficiency at high excitation density due to non-radiative quenching pathways, such as Auger recombination. Next to this, lasers based on such materials remain ill characterized, leaving questions about their ultimate performance. Here, we show that colloidal quantum shells (QSs) offer a viable solution for a processable material platform to circumvent these issues. We first show that optical gain in QSs is mediated by a 2D plasma state of unbound electron-hole pairs, opposed to bound excitons, which gives rise to broad-band and sizable gain across the full red spectrum with record gain lifetimes and a low threshold. Moreover, at high excitation density, the emission efficiency of the plasma state does not quench, a feat we can attribute to an increased radiative recombination rate. Finally, QSs are integrated on a silicon nitride platform, enabling high spectral contrast, surface emitting, and TE-polarized lasers with ultranarrow beam divergence across the entire red spectrum from a small surface area. Our results indicate QS materials are an excellent materials platform to realize highly performant and compact on-chip light sources.

Fine Purification Engineering Enables Efficient Perovskite QLEDs with Efficiency Exceeding 23.

Perovskite quantum dots (PeQDs) have great application prospects in fields such as displays and solar cells due to their adjustable band gap, high absorption coefficient, high carrier mobility, and solution processability. However, the ionic crystal characteristic of PeQDs and their surface ligands have led to problems such as solvent sensitivity, poor crystal stability, and difficulty in adjusting the photoelectric properties, which are challenges in high-quality PeQDs. Here, to solve the problem of fluorescence degradation caused by phase change and loss of surface ligands during the purification process of CsPbI3 QDs, this work develops a purification strategy that finely regulates the polarity of the purification solvent, to obtain high-purity perovskite. This strategy can tune the surface ligand concentration and optoelectronic properties while maintaining the crystal stability. The optimized purification process enables the quantum dots to maintain the same level of luminescence performance as the original solution (PLQY is ∼90%). Meanwhile, the electrical properties are improved to significantly increase the exciton recombination rate under an electrical drive. Finally, a highly efficient QLED with an external quantum efficiency of exceeding 23% can be achieved. This scheme for fine purification of CsPbI3 QDs will provide some inspiration for the development of efficient PeQDs and the realization of high-performance optoelectronic devices.

Fine‐Tuning Crystal Structures of Lead Bromide Perovskite Nanocrystals through Trace Cadmium(II) Doping for Efficient Color‐Saturated Green LEDs

AbstractDecreasing perovskite nanocrystal size increases radiative recombination due to the quantum confinement effect, but also increases the Auger recombination rate which leads to carrier imbalance in the emitting layers of electroluminescent devices. Here, we overcome this trade‐off by increasing the exciton effective mass without affecting the size, which is realized through the trace Cd2+ doping of formamidinium lead bromide perovskite nanocrystals. We observe an ~2.7 times increase in the exciton binding energy benefiting from a slight distortion of the [BX6]4− octahedra caused by doping in the case of that the Auger recombination rate is almost unchanged. As a result, bright color‐saturated green emitting perovskite nanocrystals with a photoluminescence quantum yield of 96 % are obtained. Cd2+ doping also shifts up the energy levels of the nanocrystals, relative to the Fermi level so that heavily n‐doped emitters convert into only slightly n‐doped ones; this boosts the charge injection efficiency of the corresponding light‐emitting diodes. The light‐emitting devices based on those nanocrystals reached a high external quantum efficiency of 29.4 % corresponding to a current efficiency of 123 cd A−1, and showed dramatically improved device lifetime, with a narrow bandwidth of 22 nm and Commission Internationale de I'Eclairage coordinates of (0.20, 0.76) for color‐saturated green emission for the electroluminescence peak centered at 534 nm, thus being fully compliant with the latest standard for wide color gamut displays.

RECENT PROGRESS IN THE SYNTHESIS AND PHOTOCATALYTIC DEGRADATION OF ORGANIC POLLUTANTS BY GRAPHENE-BASED TiO2 NANOCOMPOSITE: A REVIEW

Numerous sustainable water processing techniques have been widely investigated and are capable of boosting the quality of water. Among these techniques, photonanocatalysis has stood tall with great promises in the last few decades. Nonetheless, a major challenge in the environmental remediation of photocatalyst technology is to develop an ideal photocatalyst that must have excellent photocatalytic efficiency, large specific surface area, maximum harvesting of solar energy, high durability and recyclability. Due to their stability, low toxicity, low cost and superhydrophilicity TiO2 has been used by researchers as an efficient photocatalyst for the degradation of organic pollutants. Unfortunately, it suffers greatly due to its high band gap with 3.2[Formula: see text]eV, insufficient visible light response, fast photogenerated electrons and holes recombination rate and serious agglomeration. Keeping these views, the present review highlights the principal results of studies on current practical synthesis and photocatalytic activity of graphene-based TiO2 nanocomposite materials for the treatment of water. The amalgamation of graphene oxide (GO) and reduced graphene oxide (rGO) with nanoscale TiO2 particles results in synergistic properties thereby tuning and increasing the functionality of the composite. In this regard, the review also addressed the progress and insight into graphene-based TiO2 nanocomposite in photocatalytic removal of organic pollutants including basis mechanism, possible key strategies of the composite, and an overview of how to elevate efficacy. Finally, brief challenges and future perspectives in this field are also presented. Indeed, this work illustrated that graphene-based TiO2 composite nanomaterials can be a green signal in the future of photocatalysis targeting water pollution remediation.

Fabrication and characterization of C–doped TiO2 nanoparticles for the photodegradation of organic dyes

A low-cost sol-gel method is used to synthesize C-doped TiO2 (C–TiO2) nanoparticles. Nanoparticles of undoped TiO2 and varying C weight percentages (4%, 6%, and 8%) of C–TiO2 are generated. XRD, FTIR, FESEM-EDS, UV–Vis DRS, PL, BET, and XPS are used to analyze the characteristics of all the nanoparticles. The EDS data indicate that the TiO2 lattice has been successfully doped with carbon. The band-gap energy of 6% C–TiO2 is shifted to 2.94 eV, as confirmed by UV–Vis DRS, resulting in improved visible-light absorption and, hence, increased photocatalytic activity by lowering the electron-hole recombination rate. Under natural sunlight irradiation, 6% C–TiO2 achieves a 91% removal efficiency of Rhodamine B (RhB) dye in 90 min and 84% removal efficiency of Congo Red (CR) dye in 30 min. A probable photodegradation pathway was estimated using the scavenger test, and the •O2 − and •OH radicals are recognized as potentially active species for RhB degradation.

Outstanding photocatalytic activity of a mechano-thermally synthesized Z-scheme BiFeO3- Fe2O3 heterostructure

In this study, α-Bi2O3 and α-Fe2O3 powder mixtures experienced a novel mechano-thermal procedure, which includes high-energy ball milling followed by heat treatment, resulting in the successful synthesis of a BiFeO3-Fe2O3 nanocomposite. Simultaneous thermal analysis (STA) and X-ray diffraction (XRD) showed that the formation and characteristics of BiFeO3-Fe2O3 nanocomposite are greatly influenced by the milling process, heat-treatment temperature, and the α-Bi2O3:α-Fe2O3 molar ratio. X-ray photoelectron spectroscopy (XPS) spectra confirmed the presence of Bi, Fe, and O, indicating the formation of the BiFeO3 phase. Field emission scanning electron microscopy (FESEM) analysis showed the development of plate-like microstructures in the BiFeO3 phase with an average thickness of 88 nm. Diffuse reflectance spectroscopy (DRS) indicated that the 20 h-milled nanocomposite with a molar ratio of α-Bi2O3:α-Fe2O3 (1:3) exhibited the lowest band gap of 2.38 eV after heat treatment at 750 °C. The reduction in photoluminescence (PL) peaks and increase in photocurrent in the above sample suggested a decrease in charge carrier recombination rate, leading to high photocatalytic activity of 85 and 42% for methylene blue (MB) and methyl orange (MO) degradation, respectively. The effect of various pH levels on the photocatalytic activity of both dyes was examined, with MO degrading by 94% in an acidic environment after 300 min of visible light exposure, while MB experienced similar degradation in an alkaline setting. The kinetics and mechanism of photocatalytic degradation were extensively studied using the Langmuir-Hinshelwood (L-H) model, revealing the significant role of hydroxyl radicals in photodegradation. A Z-scheme mechanism for charge transfer in the nanocomposite was postulated, drawing upon radical scavenging and Mott-Schottky experiments. The prepared photocatalyst showed excellent stability and reusability following a cyclic experiment.

High-output ∼3 μ m MIR pulsed laser enabled by surface state regulation in PtTe2 optical switch

Mid-infrared (MIR) pulsed lasers operating in the ∼3 μm region play a crucial role in various applications, including molecular spectroscopy, ultrafast molecular imaging, and laser-assisted surgery. Despite recent advancements in MIR gain platforms, a notable technological challenge remains in the absence of an effective optical Q-switch. Here, a remarkable optical Q-switch in the 3 μm region based on a Dirac semimetal PtTe2 saturable absorber is realized. By modulating the surface state of PtTe2, the pulsed laser exhibited an increase in average power, escalating from 521 to 588 mW, accompanied by a significant decrease in pulse width from 368 to 187 ns. Nondegenerate pump–probe measurements showed that the recombination rate of the photocarrier in thinner PtTe2 nanoplates was effectively accelerated, primarily attributed to the substantial increase in surface state density, leading to better saturable absorption performance. As the thickness of the PtTe2 nanoplates decreases, the nonsaturable loss decreases from 12% to 3%, while the modulation depth increases from 6% to 12%. The enhanced ultrafast nonlinear absorption enables flexible modulation of saturation absorption parameters, which endows high-performance MIR pulsed laser generation.

Integration of TiO2/ZnIn2S4 p‐n Heterojunction with Titanium Defects to Boost PEC Oxygen Production

TiO2 is a widely used photoelectric conversion semiconductor material. However, due to its selective absorption of ultraviolet light and high recombination rate of photogenerated carriers, it exhibits poor photoelectrochemical water splitting performance. In this study, intrinsic defect titanium vacancy and semiconductor recombination agents ZnIn2S4 were introduced into an anodization‐annealed TiO2 film (TiO2 NT) to enhance the photoanode activity. The activity‐enhanced TiO2 photoanode (ZIS@TiO2 NT‐EA) was characterized by surface analyses and photoelectrochemical measurements. The results indicated that the introduction of titanium vacancies into the TiO2 NT‐EA changed its semiconductor type from n to p. After the ZnIn2S4 nanoparticles were loaded on the TiO2 NT‐EA film, the carrier concentration of the ZIS@TiO2 NT‐EA increased nearly 12 times than the pristine TiO2 NT. Due to the higher carrier separation efficiency resulting from the formation of p‐n heterojunction, the photocurrent density of the ZIS@TiO2 NT‐EA reached 3.89 mA cm‐2 at 1.23 V vs. RHE, nearly 3 times higher than that of the original TiO2 NT. The maximum applied bias photon‐to‐current efficiency (ABPE) value of the ZIS@TiO2 NT EA reached 2.15% at 0.496 V vs. RHE, which is very competitive if compared with all the reported TiO2 film electrodes in the PEC water splitting application.

Schottky junction-mediated carrier separation in BiOBr/Ti3C2Tx van der Waals heterojunction photocatalyst for increased removal of Cr(VI) under visible-light

The photocatalytic removal of pollutants can integrate efficient solar energy utilization with wastewater treatment. Herein, we report a simple strategy to construct BiOBr/Ti3C2Tx composite photocatalysts consisting of self-assembled van der Waals (vdw) heterojunction structures containing Schottky junctions. The vdW interaction between BiOBr and Ti3C2Tx and the structural stability of the catalysts were validated by density functional theory (DFT) calculations and an ab initio molecular dynamic simulation (AIMD). Compared to BiOBr, the BiOBr/Ti3C2Tx composites exhibited an enhanced light absorption capability and photocurrent response, along with a lower carrier recombination rate and charge-transfer resistance. The BiOBr/Ti3C2Tx activity for the photoreduction of hexavalent chromium (Cr(VI)) under visible-light irradiation considerably surpassed that of the original BiOBr (53.9%). Using the BTC-0.8 catalyst (with a Ti3C2Tx: BiOBr mass ratio of 0.8%) optimal reduction efficiency (94.0%) for Cr(VI) with a reaction rate approximately 3.5 times that of pure BiOBr. The BTC-0.8 catalyst was viable over a wide pH range and maintained an 83.9% photoreduction rate after four cycling experiments. The exceptional photocatalytic ability of BiOBr/Ti3C2Tx was achieved because Ti3C2Tx served as an electron injection layer that separated photogenerated carriers. The Schottky junction constructed within the BiOBr/Ti3C2Tx vdW heterojunctions suppressed electron backflow, promoting carrier separation. The excellent photocatalytic performance and strong cyclic stability of BiOBr/Ti3C2Tx demonstrated the considerable application potential of this photocatalyst.