Recombination Phenomena Research Articles

In-situ preparation of BiOBr/Bi-doped CsPbBr3 S-scheme heterojunction for efficient photocatalytic CO2 reduction

Metal halide perovskite nanocrystals have garnered significant attention in the realm of photocatalytic CO2 reduction in recent years owing to their remarkable reducing properties and high selectivity. However, the issue of low photocatalytic activity due to severe carrier recombination phenomena in perovskite has posed a significant challenge. To address this, a one-pot in-situ preparation strategy was employed to create a BiOBr/Bi-doped perovskite nanocrystal S-scheme heterojunction, resulting in a significant improvement in the CO2 photoreduction performance. The heterojunction material exhibited a CO yield of 151.56 μmolg-1h−1, with a selectivity for CO of 93.6 %. The molar ratio of the components was modulated using an in-situ water aging strategy, yielding a photocatalyst performance that exceeded that of pure BiOBr. The synthesis strategy of one-step in-situ preparation of heterojunctions overcomes the problem of insufficient bonding caused by two-step methods. And various characterizations and DFT calculations strongly support the S-scheme mechanism of the photocatalyst. The active site effectively reduces the energy barrier for the transition from *COOH to *CO intermediate, thereby significantly improving photocatalytic activity.

Real-time dynamics of the Schwinger model as an open quantum system with Neural Density Operators

Ab-initio simulations of multiple heavy quarks propagating in a Quark-Gluon Plasma are computationally difficult to perform due to the large dimension of the space of density matrices. This work develops machine learning algorithms to overcome this difficulty by approximating exact quantum states with neural network parametrisations, specifically Neural Density Operators. As a proof of principle demonstration in a QCD-like theory, the approach is applied to solve the Lindblad master equation in the 1 + 1d lattice Schwinger Model as an open quantum system. Neural Density Operators enable the study of in-medium dynamics on large lattice volumes, where multiple-string interactions and their effects on string-breaking and recombination phenomena can be studied. Thermal properties of the system at equilibrium can also be probed with these methods by variationally constructing the steady state of the Lindblad master equation. Scaling of this approach with system size is studied, and numerical demonstrations on up to 32 spatial lattice sites and with up to 3 interacting strings are performed.

Elucidating Interfacial Hole Extraction and Recombination Kinetics in Perovskite Thin Films

Hybrid organic–inorganic perovskite solar cells (PSCs) are receiving huge attention owing to their marvelous advantages, such as low cost, high efficiency, and superior optoelectronics characteristics. Despite their promising potential, charge-carrier dynamics at the interfaces are still ambiguous, causing carrier recombination and hindering carrier transport, thus lowering the open-circuit voltages (Voc) of PSCs. To unveil this ambiguous phenomenon, we intensively performed various optoelectronic measurements to investigate the impact of interfacial charge-carrier dynamics of PSCs under various light intensities. This is because the charge density can exhibit different mobility and charge transport properties depending on the characteristics of the charge transport layers. We explored the influence of the hole transport layer (HTL) by investigating charge transport properties using photoluminescence (PL) and time-resolved (TRPL) to unveil interfacial recombination phenomena and optoelectronic characteristics. We specifically investigated the impact of various thicknesses of HTLs, such as 2,2′,7,7′-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene (spiro-OMeTAD), and poly(triaryl)amine (PTAA), on FA0.83MA0.17Pb(Br0.05I0.95)3 perovskite films. The HTLs are coated on perovskite film by altering the HTL’s concentration and using F4-TCNQ and 4-tert-butylpyridine (tBP) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSi) as dopants both for spiro-OMeTAD and PTAA. These HTLs diversified the charge concentration gradients in the absorption layer, thus leading to different recombination rates based on the employed laser intensities. At the same time, the generated charge carriers are rapidly transferred to the interface of the HTL/absorption layer and accumulate holes at the interface because of inefficient capacitance and mobility differences caused by differently doped HTL thicknesses. Notably, the charge concentration gradient is low at lower light intensities and did not accumulate holes at the HTL/absorption layer interface, even though they have high charge mobility. Therefore, this study highlights the importance of interfacial charge recombination and charge transport phenomena to achieve highly efficient and stable PSCs.

Investigation of the Performance of a Sb2S3-Based Solar Cell with a Hybrid Electron Transport Layer (h-ETL): A Simulation Approach Using SCAPS-1D Software

In order to reduce current leakage and improve electron transfer in solar cells, charge transport layers (CTL), mainly hybrid electron transport layers (h-ETL), are considered as a solution. In this research contribution, computational analysis using SCAPS-1D software is performed to explore the output photovoltaic parameters of a Sb2S3-based solar cell with h-ETL. No theoretical works on this configuration have been previously reported. The main objectives of the present work are to propose a h-ETL with good band alignment with the Sb2S3 absorber, high transparency, and Cd free; to mitigate the instability and cost issues associated with using Spiro-OMeTAD HTL; and to optimize the solar cell. Thus, we calibrated the J-V characteristics and electrical parameters of the FTO/(ZnO/TiO2)/Sb2S3/Spiro-OMeTAD/Au solar cell by numerical simulation and compared them with those of the experiment. Subsequently, our simulations show that to replace the TiO2 ETL used in the experiment and to form the h-ETL with ZnO, IGZO is found to be a good candidate. It has better band alignment with the Sb2S3 absorber than TiO2 ETL, which reduces the trap states at the ETL/Sb2S3 interface; it has high transparency due to its wide bandgap; and an intense electric field is generated at the IGZO/Sb2S3 interface, which reduces the recombination phenomenon at this interface. MoO3, MASnBr3, Cu2O, CuI, and CuSCN HTL were also tested to replace the Spiro-OMeTAD HTL. Simulation results show that the cell with MoO3 HTL achieves higher performance due to its high hole mobility and high quantum efficiency in the visible region; it also allows the solar cell to have better thermal stability (TC=−0.32%/K) than the cell with Spiro-OMeTAD HTL (TC=−0.53%/K). The parameters that could improve the solar cell efficiency (η) obtained after these substitutions were also optimized. In particular, the parameters of the Sb2S3 absorber layer (thickness, defect density, and doping), ETL and HTL layer thicknesses, h-ETL/Sb2S3 interface defect density, and series and shunt resistances have been optimized. Finally, by combining high performance and thermal stability, the results show that the thermal stability of the solar cell depends on the back contact type; thus, nickel (Ni) was found to combine high performance and better thermal stability among the back contacts investigated. After these improvements, the efficiency of the Sb2S3-based solar cell increased from 5.08% (JSC=16.19 mA/cm2, VOC=0.56 V, and FF=55.40%) to 15.43% (JSC=18.51 mA/cm2, VOC=1.11 V, and FF=74.76%). This study proposes an approach to optimize the Sb2S3 upper subcell for tandem solar cells.

Hierarchical Hollow TiO2@Bi2WO6 with Light-Driven Excited Bi(3-x)+ Sites for Efficient Photothermal Catalytic CO2 Reduction.

Converting CO2 into valuable chemicals via sustainable energy sources is indispensable for human development. Photothermal catalysis combines the high selectivity of photocatalysis and the high yield of thermal catalysis, which is promising for CO2 reduction. However, the present photothermal catalysts suffer from low activity due to their poor light absorption ability and fast recombination of photogenerated electrons and holes. Here, a TiO2@Bi2WO6 heterojunction photocatalyst featuring a hierarchical hollow structure was prepared by an in situ growth method. The visible light absorption and photothermal effect of the TiO2@Bi2WO6 photocatalyst is promoted by a hierarchical hollow structure, while the recombination phenomenon is significantly mitigated due to the construction of the heterojunction interface and the existence of excited Bi(3-x)+ sites. Such a catalyst exhibits excellent photothermal performance with a CO yield of 43.7 μmol h-1 g-1, which is 15 and 4.7 times higher than that of pure Bi2WO6 and that of physically mixed TiO2/Bi2WO6, respectively. An in situ study shows that the pathway for the transformation of CO2 into CO over our TiO2@Bi2WO6 proceeds via two important intermediates, including COO- and COOH-. Our work provides a new idea of excited states for the design and synthesis of highly efficient photothermal catalysts for CO2 conversion.

Carbon nitride coupled with carbon nanohorns for improved photocatalytic hydrogen production and dyes degradation

In the present study we attempted to develop photoactive nanocomposites via the facile coupling of carbon nitride (CN) with single walled carbon nanohorns (CNHs). Photocatalytic activity was evaluated for the degradation of Rhodamine B (RhB) and the production of H2. The CNHs content noticeably affected the photoactivity of the nanocomposites and the best performing material exhibited a 3-fold increase in photocatalytic H2 production compared to pristine CN using 1 wt% Pt as co-catalyst. A systematic study was undertaken to explain the mechanistic aspects of the photo-reaction process. The active species responsible for the photodegradation of RhB were identified using reference reactions. Such species were further studied using in-situ spin-trap EPR experiments. Photoluminescence and time-resolved fluorescence decay kinetics suggested faster transfer of photogenerated electron/hole pairs resulting in reduced charge recombination phenomena in the nanocomposites. The combined photocatalytic application and characterization of the prepared materials revealed that the promotion of the redox reactions in based on improvements on the charge separation efficiency.

Preparation of copper porphyrin photosensitized iron-based MOFs composite photocatalyst and study on CO2 reduction performance

Fe-based MIL-101(Fe) MOFshavea high potential to capture CO2 due to their high porosity, porous structure,and significant interaction with CO2, but the photogenerated electron and hole recombination phenomenon is relatively obvious. Copper tetracarboxyphenyl porphyrin (Cu-TCPP) was incorporated into MIL-101(Fe) as a photosensitive material to forma heterostructure. This enhanced the light absorption capability and the photogenerated electron-hole pairs separation in the composite catalyst. Based on the above factors, the current study reported the synthesis of MIL-101(Fe) by hydrothermal method, and a new composite photocatalyst Cu-TCPP@MIL-101(Fe) was prepared by using Cu-TCPP as a copper source with different mass ratios. Themorphologicaland structural characterizationof the composite catalyst was carried out by XRD, SEM, TEM, BET, and FT-IR, and the CO2 reduction performance of the composite catalyst Cu-TCPP@MIL-101(Fe) was determined by a vacuum CO2 reduction system under simulated sunlight irradiation. The results revealed that MIL-101(Fe) was loaded with Cu-TCPP with the formation of type II heterojunctions that are capable of inhibitingthe electron-hole recombination with improved light absorption capacity, and accelerated reduction rate of CO2. The reduction rateof CO2 into CO was found to be 29 μmol·g−1·h−1.

SYNTHESIS OF NICKEL-DOPED BIVO4 MATERIALS BY HYDROTHERMAL METHOD AND EVALUATE THE PHOTOCATALYTIC ABILITY TO DECOMPOSE METHYLENE BLUE UNDER VISIBLE LIGHT

Ni-doped BiVO4 photocatalysts were successfully synthesized by hydrothermal method. The catalytic samples were characterized by scanning electron microscopy (SEM), UV-vis diffuse reflection spectroscopy (DRS), photoluminescence spectroscopy (PL) and X-ray diffraction (XRD). Based on the results of PL spectrum analysis, the electron-hole recombination phenomenon is limited by the presence of the second metal Ni in the structure at Bi3+ positions. The catalyst materials at the Ni doping ratios all have the monoclinic-scheelite BiVO4 structure as shown by the XRD and Raman methods. The photocatalytic ability of methyl blue (MB) on the Ni/BiVO4 catalyst was studied under visible light irradiation in order to contribute to reducing the current environmental pollution problem. The removal efficiency of MB varies with the doping ratio of Ni/BiVO4, reaching the highest decomposition efficiency of 84.77% in the 5% mol Ni sample, which is 30% higher than that of the BiVO4 sample. The BiVO4 material modified with Ni gives a high photocatalytic efficiency of organic pigment decomposition under visible light indicates the potential improvement in the efficiency of a material for existing applications and exploit many new applications in the future.

Observation of Long-Lived Plasma Formations in a Toroidal air Vortex under Normal Conditions

Purpose. Experimentally investigate the difference between the characteristic lifetime of plasma formations in a stationary and rotating toroidal air volume under normal ambient conditions.Methods. Experimental study of plasmoids was carried out by videotaping with a high-speed camera with subsequent frame-by-frame processing of the recording. Generation of plasmoids was performed by mechanical rupture of the plasma cord of the welding arc in the field of permanent magnets. The creation of toroidal rotation of the plasma formation in air occurs when it passes through a hole in a solid screen. Numerical estimation of mechanical forces acting on ions in the air vortex is performed by order of magnitude using experimental data.Results. Two different in design laboratory installations for observation of plasma formations in air under normal external conditions have been created. The lifetime of such "long-lived" plasmoids in air is equal to about two milliseconds, which significantly exceeds the lifetime of a plasma-forming welding arc in the free state under the same conditions. The increase in plasmoid lifetime is considered and explained within the framework of mechanical ideas about spatial separation of heavy and light ions inside the plasma under the action of inertia forces as a result of rotational motion of air. The proposed mechanical model of the phenomenon is obviously simplified and does not take into account diffusion, recombination and other related phenomena, since the main and only difference between the observed "longlived" and "ordinary" plasmoids lies in the nature of the mechanical motion of the medium.Conclusion: Two experimental setups allowing to generate and observe the behavior of plasma formations with a characteristic lifetime of the order of two milliseconds are created and described. The results of observations indirectly confirm a simple mechanical hypothesis about the connection between the lifetime of a free plasma formation and the rotational motion of the gas inside it.

Unraveling the genetic evolution of SARS-CoV-2 Recombinants using mutational dynamics across the different lineages.

Recombination serves as a common strategy employed by RNA viruses for their genetic evolution. Extensive genomic surveillance during the COVID-19 pandemic has reported SARS-CoV-2 Recombinant strains indicating recombination events during the viral evolution. This study introspects the phenomenon of genome recombination by tracing the footprint of prominent lineages of SARS-CoV-2 at different time points in the context of on-going evolution and emergence of Recombinants. Whole genome sequencing was carried out for 2,516 SARS-CoV-2 (discovery cohort) and 1,126 (validation cohort) using nasopharyngeal samples collected between the time period of March 2020 to August 2022, as part of the genomic surveillance program. The sequences were classified according to the different lineages of SARS-CoV-2 prevailing in India at respective time points. Mutational diversity and abundance evaluation across the 12 lineages identified 58 Recombinant sequences as harboring the least number of mutations (n = 111), with 14 low-frequency unique mutations with major chunk of mutations coming from the BA.2. The spontaneously/dynamically increasing and decreasing trends of mutations highlight the loss of mutations in the Recombinants that were associated with the SARS-CoV-2 replication efficiency, infectivity, and disease severity, rendering them functionally with low infectivity and pathogenicity. Linkage disequilibrium (LD) analysis revealed that mutations comprising the LD blocks of BA.1, BA.2, and Recombinants were found as minor alleles or as low-frequency alleles in the LD blocks from the previous SARS-CoV-2 variant samples, especially Pre-VOC. Moreover, a dissipation in the size of LD blocks as well as LD decay along with a high negative regression coefficient (R squared) value was demonstrated in the Omicron and BA.1 and BA.2 lineages, which corroborated with the breakpoint analysis. Together, the findings help to understand the evolution and emergence of Recombinants after the Omicron lineages, for sustenance and adaptability, to maintain the epidemic spread of SARS-CoV-2 in the host population already high in immunity levels.

Effect of hydrogen concentration on the friction evolution mechanism of few-layer graphene: A molecular dynamics study in nanoscratch processes

This article explored the friction evolution mechanism of graphene under different hydrogen concentrations and scratch depths based on molecular dynamics. In a vacuum, graphene exhibits excellent frictional properties when the scratch depth is less than the layer distance of graphene. However, as the depth increases, the diamond tip contacts more CC bonds, and the phenomenon of fracture and recombination of CC bonds in the graphene layer intensifies, increasing surface friction. In a low concentration of hydrogen environment, compared with the friction in a vacuum, it increases due to the interlocking effect of the protruding hydrogen atoms on the diamond tip and the scratch path. As the concentration of the hydrogen environment increases, the friction force does not increase monotonically. In addition, in a hydrogen environment, the stability of the planar structure of graphene will be weakened, thereby affecting the wrinkling effect and wear path.

Characterization of Recombination Phenomena in Perovskites from Logarithmic and Power-Law Spectroscopy Transients

Characterization of Recombination Phenomena in Perovskites from Logarithmic and Power-Law Spectroscopy Transients

Multifunctional flexible perovskites with carbon nanotube/PC71BM stack for effective charge extraction and slow recombination phenomena

Multifunctional flexible perovskites with carbon nanotube/PC71BM stack for effective charge extraction and slow recombination phenomena

Design and Performance Enhancement of a GaAs-Based Homojunction Solar Cell Using Ga0.5In0.5P as a Back Surface Field (BSF): A Simulation Approach

The GaAs semiconductor is a solar energy promising material for photovoltaic applications due to its good optical and electronic properties. In this work, a homojunction GaAs solar cell with AlxGa1-xAs and GayIn1-yP solar energy materials as window and back surface field (BSF) layers, respectively, was simulated and investigated using SCAPS-1D software. The performance of the GaAs-based solar cell is evaluated for different proportions ofxandy, which allowed us to obtain the values of 0.8 and 0.5 forxandy, respectively, as the best values for high performance. We then continued the optimization by taking into account some parameters of the solar cell, such as thickness, doping, and bulk defect density of the p-GaAs base, n-GaAs emitter, and Ga0.5In0.5P BSF layer. Solar cell efficiency increases with emitter thickness, but the recombination phenomenon is more pronounced than that of electron-hole pair generation in the case of a thicker base. The effect of variation in the work function of the back contact has also been studied, and the best performance is for a platinum (Pt) electrode. The optimized GaAs-based solar cell achieves a power conversion efficiency of 35.44% (JSC=31.52 mA/cm2,VOC=1.26 V,FF=89.14%) and a temperature coefficient of -0.036%/°C. These simulation results provide insight into the various ways to improve the efficiency of GaAs-based solar cells.

Role of excess-carrier generation and recombination in memristivity

We incorporate the role of excess carrier generation and recombination phenomena in nanostructured material and develop an approach to obtain V-I characteristic for a memristor. The V-I characteristic curve for the memristor is pinched hysteresis loop which is an important signature of memristor. This analysis suggests that our approach may be an alternate viable in realising the underlying theory behind memristivity as an inherent property of nanostructured materials.

Combined DFT-D3 Computational and Experimental Studies on g-C3N4: New Insight into Structure, Optical, and Vibrational Properties.

Graphitic carbon nitride (g-C3N4) has emerged as one of the most promising solar-light-activated polymeric metal-free semiconductor photocatalysts due to its thermal physicochemical stability but also its characteristics of environmentally friendly and sustainable material. Despite the challenging properties of g-C3N4, its photocatalytic performance is still limited by the low surface area, together with the fast charge recombination phenomena. Hence, many efforts have been focused on overcoming these drawbacks by controlling and improving the synthesis methods. With regard to this, many structures including strands of linearly condensed melamine monomers, which are interconnected by hydrogen bonds, or highly condensed systems, have been proposed. Nevertheless, complete and consistent knowledge of the pristine material has not yet been achieved. Thus, to shed light on the nature of polymerised carbon nitride structures, which are obtained from the well-known direct heating of melamine under mild conditions, we combined the results obtained from XRD analysis, SEM and AFM microscopies, and UV-visible and FTIR spectroscopies with the data from the Density Functional Theory method (DFT). An indirect band gap and the vibrational peaks have been calculated without uncertainty, thus highlighting a mixture of highly condensed g-C3N4 domains embedded in a less condensed "melon-like" framework.

Construction of 3D/3D heterojunction between new noble metal free ZnIn2S4 and non-inert metal NiMoO4 for enhanced hydrogen evolution performance under visible light

Promoting the separation of electron and hole plays an important role in photocatalytic hydrogen production. However, single semiconductor materials cannot fully realize their potential due to the rapid recombination of photogenerated carriers. Therefore, in this experiment, a new photocatalyst ZnIn2S4/NiMoO4 was prepared by using an electrostatic self-assembly method, which greatly improved the electron-hole recombination phenomenon. After 5 h reaction under visible light irradiation, ZIS/NMO-3 composite catalyst prepared in ethanol showed the best photocatalytic activity, and the hydrogen evolution capacity reached 173.09 μmol. The hydrogen evolution capacity of ZIS/NMO-3 was 2.47 and 25.83 times that of short rod-like NiMoO4 and microflower-like spherical ZnIn2S4, respectively. Through some physical characterization and electrochemical experiments, it can be seen that NiMoO4 and ZnIn2S4 have good composability. Meanwhile, the composite catalyst ZnIn2S4/NiMoO4-3 has high current response characteristics. It can be seen from the fluorescence emission spectra that the composite catalyst presents the lowest peak value, which indicates that ZIS/NMO-3 can effectively inhibit the recombination of photogenerated electrons and holes. When ZnIn2S4 is loaded on NiMoO4, the separation of photogenerated carrier will be accelerated due to the formation of heterojunction, thus improving the photocatalytic activity. At the same time, the large specific surface area will also provide more abundant active sites for the composite catalyst, which provides a good condition for photocatalytic hydrogen production. This work provides an efficient, uncomplicated and feasible method for the synthesis of ZIS/NMO-3 composite catalyst with excellent properties.

Photosystem II as a chemiluminescence-induced photosensitizer for photoelectrochemical biofuel cell-type biosensing system

Herein, photosystem II (PSII), extracted from spinach, is used for the first time as an efficient and green sensitizer for a photobioanode in a photoelectrochemical glucose biofuel cell (PBFC) setup. The concept is based on the formation of hemin-catalyzed luminol chemiluminescence (CL) after the enzymatic oxidation of glucose and the simultaneous production of hydrogen peroxide by glucose oxidase. The photosynthetic enzyme PSII, combined with an osmium polymer serving as mediator and photosensitizer, is immobilized and wired on microporous carbonaceous material (MC) for the chemiluminescence-induced oxidation of water to O2 at the photobioanode (GCE|MC|Os polymer|PSII). Also, bilirubin oxidase immobilized on multiwalled carbon nanotubes (MWCNTs) coated electrode (GCE|MWCNT|BOx) serves as a biocathode. The photoelectrochemical biofuel cell (PBFC) is applied to a biosensor model system to validate the appropriateness of such a bioanode operating in a self-powered mode. Os redox polymer attached to MCs provides abundant PSII immobilization and a reliable electron transfer pathway. The well-matching energy levels of photosensitive entities reduce recombination phenomena while MC enhances the charge collection. Substantial photocatalytic water oxidation was observed under CL due to the well-matched CL emission and PSII absorption. The electrode is rationally designed to gain the maximum luminol CL power for the photobioanode. The open circuit potential of PBFC linearly increased with the CL power intensity and, in turn, glucose concentrations in the range of 0–6 mmol L−1. The PBFC yielded an OCP of 0.531 V in 30 mmolL−1 glucose. The study may open a new horizon to the green and pioneering PEC biosensing realm.

Boosting photocatalytic oxidation of organic pollutants on Z-scheme carbon nitride / Ag3PO4 / Ag composites by coupling with carbon nanotubes

ABSTRACT The present study reports the development of ternary and quaternary carbon nitride (CN) based nanocomposites through the coupling of CN with single-walled carbon nanotubes (SWCNTs), Ag3PO4 (AP) and Ag nanoparticles (NP). A facile wet-chemistry process was developed for the synthesis of the composites. The prepared materials were characterised using XRD, ATR, DR-UV-Vis, photoluminescence (PL) spectroscopy and EPR. Photocatalytic dye degradation (rhodamine b, RhB) is greatly improved in composite materials. The most active photocatalyst was the quaternary composite bearing SWCNTs, Ag3PO4 and Ag NP, that presented a 2- and a 3-fold increase in photoactivity compared with the CN functionalised only with SWCNTs and the pure CN, respectively. The enhanced activity is associated with improvements in several important materials properties. Adsorption in the visible light is improved by the presence of Ag3PO4 and Ag NP. The latter provided plasmon resonance effects, absorbing light up to 700 nm. The presence of SWCNTs reduced charge recombination phenomena reducing by half the PL intensity. In addition, charge availability was further increased due to the formation of heterojunctions through the coupling of CN with Ag3PO4 and Ag NP. The PL intensity of the ternary composite was reduced to 1% of the pure CN PL intensity. In-situ EPR spectroscopy using spin-traps revealed the formation of superoxide anion radicals () that provide evidence for charge transfer via a Z-scheme mechanism. production was enhanced 8.5 times in the ternary composite compared with the pure CN. The importance of the stepwise functionalization of CN through the formation of ternary and quaternary composites towards the development of advanced photoactive materials is highlighted herein.

Probing size-dependent defects in zinc oxide using synchrotron techniques: impact on photocatalytic efficiency.

In the present study, synchrotron-based X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS) and X-ray excited optical luminescence (XEOL) have been used to investigate the induced defect states in metal oxide nanomaterials. Specifically, two synthesis approaches have been followed to develop unique nano-sized peanut-shaped (N-ZnO) nanostructures and micron-sized hexagonal rods (M-ZnO). XANES analysis at the Zn K-edge revealed the presence of defect states with a divalent oxidation state of zinc (Zn2+) in a tetrahedral structure. Furthermore, XAS measurements performed at the Zn L3,2-edge and O K-edge confirm higher oxygen-related defects in M-ZnO, while N-ZnO appeared to have a higher concentration of surface defects due to size confinement. Moreover, the in-line XEOL and time dependent-XEOL measurements exposed the radiative excitonic recombination phenomena occurring in the band-tailing region as a function of absorption length, X-ray energy excitation, and time. Based on the chronology developed in the defect state improvement, a possible energy band diagram is proposed to accurately locate the defect states in the two systems. Furthermore, the increased absorption intensity at the Zn L3,2-edge and the O K-edge under the UV lamp suggests delayed recombination of electrons and holes, highlighting their potential use as photo catalysts. The photocatalytic activity degrading the rhodamine B dye established M-ZnO as a superior catalyst with a rapid degradation rate and significant mineralization. Overall, this work provides valuable insights into ZnO defect states and provides a foundation for efficient advanced materials for environmental or other optoelectronic applications.