Time-resolved Photoluminescence Spectra Research Articles

Construction of a CoNiHHTP MOF/PHI Z-Scheme Heterojunction for ppb Level NO2 Photoelectric Sensing with 405 nm Irradiation at RT.

Ultrasensitive photoelectric detection of nitrogen dioxide (NO2) with PHI under visible light irradiation at room temperature (RT) remains an ongoing challenge due to the low charge separation and scarce adsorption sites. In this work, a dimensionally matched ultrathin CoNiHHTP MOF/PHI Z-scheme heterojunction is successfully constructed by taking advantage of the π-π interactions existing between the CoNiHHTP MOF and PHI. The amount-optimized heterojunction possesses a record detection limit of 1 ppb (response = 15.6%) for NO2 under 405 nm irradiation at RT, with reduced responsive (3.6 min) and recovery (2.7 min) times, good selectivity and reversibility, and long-time stability (150 days) compared with PHI, even superior to others reported at RT. Based on the time-resolved photoluminescence spectra, in situ X-ray photoelectron spectra, and diffuse reflectance infrared Fourier transform spectroscopy results, the resulting sensing performance is attributed to the favorable Z-scheme charge transfer and separation. Moreover, the Ni nodes favorably present in adjacent metal sites between the lamellae contribute to charge transfer and redistribution, whereas Co nodes could act as selective centers for promoted adsorption of NO2. Interestingly, it is confirmed that the CoNiHHTP MOF/PHI heterojunction could effectively reduce the influence of O2 in the gas-sensitive reaction due to their unique bimetallic (Co and Ni) nodes, which is also favorable for the improved sensing performances for NO2. This work provides a feasible strategy to develop promising PHI-based optoelectronic gas sensors at RT.

Structural and photophysical properties of two-dimensional lead bromide hybrid perovskite (C8H17NH3)2PbBr4

The structural versatility of organic compounds imparts manifold properties to hybrid organic−inorganic perovskites, where two-dimensional (2D) halide perovskites are potential future platforms for light-emitting devices because of their unique quantum well configuration and dielectric confinement. Notwithstanding the numerous studies on the organic−inorganic perovskites carried out to date, precisely charactering the structure and photoluminescence mechanism remain considerable challenges. Herein, by applying Rietveld refinement, we have obtained crystal structure and atomic sites of 2D layered OA2PbBr4 perovskite, which undergoes a phase transition at 190 K with activation energies of 29.6 and 3.8 meV for the two phases, respectively. The theoretical analysis based on the crystal structure were performed to understand the nature of vibrations and band structure. Steady-state PL shows a narrow emission and a broad emission located at 409 and 487 nm, respectively. With temperature cooling down to 118 K, narrow emission gradually narrowed and enhanced. Meanwhile, intensity of broad emission first weakens and then increases. The turning point occurs near 198 K. By applying time-resolved PL (TRPL) and transient absorption (TA) spectra experiment, we observed a rapid carrier transfer from the FE to the STE state, and demonstrated the narrow and broad bands originate from free exciton and self-trapped exciton emission, respectively. And the self-trapping depth is proved to be 26.3 meV by low-temperature PL. Our findings indicate the synthesized 2D perovskite has potential applications in optoelectronic and display devices.

Growth of β-Ga2O3 nanostructures by thermal oxidation of GaN-on-sapphire for optoelectronic devices applications

Heterostructures of wide-bandgap semiconductors, like β-Ga2O3/ GaN, are being used in many high-power, high-frequency electronic and optoelectronic devices. This paper presents the growth of β-Ga2O3 thin film and nanostructures by thermally oxidizing (at 1000 °C) the planar and nano-structured GaN surfaces respectively. The nano-structures of GaN (having 300–500 nm long vertical nano-kinks) are fabricated by metal-assisted chemical etching of GaN surface for 1–2 hours. The thermally grown β-Ga2O3 samples are polycrystalline. The chemical analysis of the samples using X-ray photoelectron spectroscopy (XPS) showed enhancement of Ga-O peak intensity (at 20.21–20.3 eV) at the expense of the Ga-N peak intensity (at 19.2–19.7 eV) in the thermal oxidation process. The O1s XPS spectra of the oxidized samples exhibited prominent signature of O2- ions (530.7–530.9 eV) representing the formation of Ga2O3 with presence of adsorbed hydroxyl group at the surface (532.2 – 532.4 eV). The valance band XPS spectra disclosed the formation of an additional Ga(4 s)–O(2p) hybridization energy state, and the valence band maxima increased from 2.3 eV to 3.25 eV. The Raman spectra of the oxidized samples exhibited multiple Ag and Bg vibrational modes of β-Ga2O3 along with intense E2(high), A1(LO) modes of GaN. The time-resolved photoluminescence spectra of the samples demonstrated fast transition of charge carriers from excited state to ground state with 460–820 pico-seconds average career lifetime.

Two-Site Occupation for Constructing Double Perovskite BaLaMgNbO6:Cr3+ Ultrabroadband NIR Phosphors.

Given the escalating significance of near-infrared (NIR) spectroscopy across industries, agriculture, and various domains, there is an imminent need to address the development of a novel generation of intelligent NIR light sources. Here, a series of Cr3+-doped BaLaMgNbO6 (BLMN) ultrabroadband NIR phosphor with a coverage range of 650-1300 nm were developed. The emission peak locates at 830 nm with a full width at half maximum of 210 nm. This ultrabroadband emission originates from the 4T2→4A2 transition of Cr3+ and the simultaneous occupation of [MgO6] and [NbO6] octahedral sites confirmed by low photoluminescence spectra (77-250 K), time-resolved photoluminescence spectra, and electron paramagnetic resonance spectra. The fluxing strategy improves the luminescence intensity and thermal stability of BLMN:0.02Cr3+ phosphors. The internal quantum efficiency (IQE) is 51%, external quantum efficiency (EQE) can reach 33%, and thermal stability can be maintained at 60%@100 °C. Finally, we successfully demonstrated the application of BLMN:Cr3+ ultrabroadband in the qualitative analysis of organic matter and food freshness detection.

Uncovering the Effect of A-Site Cations on Localized Excitons Photoluminescence of Manganese-Doped Zinc Chloride Nanocrystals.

Elucidating the key factors that affect the localized excitons (LEs) photoluminescence (PL) in lead-free metal halide nanocrystals (NCs) is important for their optoelectronic applications. However, the effect of A-site cations on LEs based PL is not well understood. Herein, we varied the A-site cation ratio (Rb/Cs) to investigate the influence on LEs based PL in manganese-doped zinc chloride NCs. Through time-resolved photoluminescence (TR-PL) spectra and density functional theory (DFT) calculations, we discovered that Cl vacancy is energetically more favorable in Mn2+-doped Rb3ZnCl5 NCs compared to Mn2+-doped Cs3ZnCl5 NCs. The higher concentration of Cl vacancy increases the nonradiative recombination process in Rb3ZnCl5:Mn2+ NCs, ultimately determining the PL efficiency. This research enhances the understanding of the A-site cation effect on LEs-based PL in lead-free metal halide NCs.

Construction of an all-organic S-scheme heterostructure based on PEDOT immobilized g-C3N4 nanosheets by electrostatic self-assembly with enhanced visible-light photocatalytic hydrogen production

Inspired by photosynthesis in nature, exploring all-organic S-scheme heterojunction photocatalysts for efficient H2 production is of great significance in addressing energy shortage issues. In this paper, poly(3,4-ethylenedioxythiophene) (PEDOT) immobilized g-C3N4(CN) nanosheets were constructed by an electrostatic self-assembly strategy to obtain an all-organic S-scheme heterojunction, significantly enhancing the visible-light photocatalytic H2 production performance of g-C3N4. The optimized 5PEDOT/CN exhibits the highest H2 production rate of 3.15 mmol g−1h−1, a 31.5-fold enhancement over pristine CN. According to the staggered energy band positions of two components and the results of electron spin resonance tests, the S-scheme heterojunction electron-transfer mechanism is confirmed, which greatly facilitates the spatial charge separation and retains the strong reducing ability of high-energy potential electrons for efficient photocatalytic H2 production. Based on the results of FT-IR spectra, XPS spectra, fluorescence spectra, hydroxyl radical tests and time-resolved photoluminescence spectra, it is confirmed that the significantly improved photocatalytic activity is mainly attributed to the enhanced charge separation by the S-scheme heterojunction and the tightly contacted interface dependent on N···S interactions in PEDOT immobilized CN nanosheet heterojunctions, along with the enhanced visible-light absorption ability. This work presents a novel approach to the design and fabrication of all-organic S-scheme heterojunction photocatalysts for solar-light-driven energy production.

Highly efficient broadband near-infrared luminescence phosphors Ca3MgSn0.5Zr0.5Ge3O12:Pr3+,Cr3+ for multifunctional applications in pc-LEDs field

Exploring high-performance broadband near-infrared (NIR) emitting materials is crucial for the development of NIR devices. In this study, Ca3MgSn0.5Zr0.5Ge3O12:Cr3+ and rare earth ion Pr3+ co-doped Ca3MgSn0.5Zr0.5Ge3O12:Pr3+,Cr3+ phosphors were successfully synthesized. By utilizing time-resolved emission spectroscopy (TRES), photoluminescence (PL) spectra, and fluorescence decay curve, the Ca3MgSn0.5Zr0.5Ge3O12:Cr3+ phosphor is determined to exhibit a broadband emission (650–1150 nm) with a peak at 795 nm due to Cr3+ occupying multiple cationic sites. Ca3MgSn0.5Zr0.5Ge3O12:0.1Cr3+ has excellent thermal stability (86%@425 K), and co-doping Pr3+ ions into Ca3MgSn0.5Zr0.5Ge3O12:0.1Cr3+ obtains highly efficient NIR emission. The Ca3MgSn0.5Zr0.5Ge3O12:0.01Pr3+,0.1Cr3+ phosphor has quantum yield of 89.4% thanks to the energy transfer effect from Pr3+ to Cr3+. The fabricated NIR phosphor-converted light emitting diodes (pc-LEDs) by integrating the blue chip with Ca3MgSn0.5Zr0.5Ge3O12:0.01Pr3+,0.1Cr3+ has diverse applications including night vision, non-destructive testing, and medical imaging.

Optical regulation by localized states of Cu2+ ions with highly sensitive to trap density and thermalization in manganese-doped perovskite nanocrystals

Mn2+-doped perovskites nanocrystals (NCs) have already been extensively studied in fascinating optical, electronic, and magnetic properties. Such interesting traits make them paid considerable attention in light emitting diodes, solar cells, etc. However, the underlying thermal and photophysical processes governing the overall charge carrier dynamics in Mn-doped NCs are far from clear. Herein, trap concentration and thermalization-dependent optical properties of Mn–Cu co-doped CsPbCl3 NCs were investigated via using steady-state, time-resolved PL spectra, variable-temperature PL spectra, and ultrafast transient absorption spectra. The combined experimental and theoretical studies reveal that Cu2+, as an effective hole trap, can trap the holes from Mn2+ and emit the holes to Mn2+ level at lighter and higher doping, respectively. Moreover, this hole trap is highly thermally sensitive, which is responsible for the abnormal thermal effect of Mn2+ emission with increasing temperature. These findings demonstrate an approach of charge regulation through ion doping, which is meaningful for fabricating efficient photoelectric materials and devices.

Molten salt synthesis of 1T/2H mixed phase MoS2 for boosting photocatalytic H2 evolution via Schottky junction under EY-sensitized system

Clean H2 fuel obtained from the photocatalytic water splitting to hydrogen reaction could efficiently alleviate current energy crisis and the concomitant environmental pollution problems. Therefore, it is desirable to search for a highly efficient photocatalytic system to decrease the energy barrier of water splitting reaction. Herein, the 1T/2H mixed phase MoS2 sample with Schottky junction between contact interfaces is developed through molten salt synthesis for photocatalytic hydrogen production under a dye-sensitized system (Eosin Y-TEOA-MoS2) driven by the visible light. In mixed phase MoS2 sample, the photogenerated electrons of 2H-phase MoS2 migrated to the 1T-phase MoS2 are difficult to jump back because of the existence of Schottky barrier, which greatly suppresses the quenching of EY and therefore results in an enhanced hydrogen evolution performance. Therefore, the optimized MoS2 sample (MoS2-350) has an initial hydrogen evolution rate of 213 μmol h−1 and corresponding apparent quantum yield of 36.1 % at 420 nm, far higher than those of pure Eosin Y. It is strongly confirmed by the steady‐state/time-resolved photoluminescence (PL) spectra and transient photocurrent response experiments. With the assistance of Density functional theory (DFT) calculation, the function of Schottky junction in photocatalytic hydrogen evolution reaction is well explained. In addition, a new and universal method (SVM curve) of judging oxidation or reduction quenching for photosensitizers is proposed.

Carrier recombination in highly Al doped 4H-SiC: dependence on the injection conditions

We investigate carrier recombination mechanisms in heavily aluminum (Al) doped p-type 4H-SiC, a material crucial for power devices. The recombination mechanisms in Al-doped p-type 4H-SiC have remained unclear, with reports suggesting various possibilities. To gain insights, we employ photoluminescence (PL) measurements, particularly time-resolved PL (TR-PL), as they are well-suited for studying carrier lifetimes in heavily Al-doped p-type 4H-SiC. We examine the temperature and excitation intensity dependencies of TR-PL and PL spectra and discuss the underlying recombination mechanisms. We observe that the dominant recombination mechanism varies with injection conditions for the samples with Al concentration less than 1019 cm−3. Under low injection conditions, recombination via the Al acceptor level appears dominant, exhibiting weak temperature dependence. However, under high injection conditions, Shockley–Read–Hall recombination takes precedence, leading to shorter carrier lifetimes with increasing temperature. This temperature dependence implies that presences of the deep recombination centers with the small capture barrier for holes.

Highly stable CsPbBr3/ PMA perovskite nanocrystals for improved optical performance

In this study, to address the stability issues, we synthesized a CsPbBr3-coated poly (maleic anhydride-alt-1-octadecene) (CsPbBr3/PMA) using a modified hot-injection method. The CsPbBr3/PMA perovskite nanocrystals (PNCs) exhibited effective green emission at 522 nm with an improved photoluminescence quantum yield (86.8 %) compared to traditional CsPbBr3 PNCs (54.2 %). The ligands in the polymer coating can bond with the uncoordinated Pb and Br ions on the surface of PNCs to minimize surface defects and avoid exposure to the external environment, enhancing the stability of the perovskites. Time-resolved photoluminescence spectra showed longer lifetimes for CsPbBr3/PMA PNCs, while transient absorption measurements provided valuable insights into the intraband hot-exciton relaxation and recombination. We demonstrate the potential application of CSPbBr3/PMA in a down-conversion white-light-emitting diode (LED) by coupling green CsPbBr3/PMA and red K2SiF6:Mn4+ phosphor-coated glass slides onto a 455-nm blue GaN LED. The white LED produced a white light with the International Commission on Illumination color coordinates of (0.323, 0.345), luminous efficiency of 58.4 lm/W, and color rendering index of 83.2. The fabricated, white-LED system obtained a wide color gamut of 125.3 % of the National Television Standards Committee and 98.9 % of Rec. 2020. The findings demonstrate that CsPbBr3/PMA can be an efficient down-conversion material for white LEDs and backlighting.

Surface‐enhanced Raman scattering of carbazole‐based covalent triazine framework

AbstractA kind of carbazole‐based covalent triazine framework (CTF‐Cz) has been synthesized from a carbazole derivative. The porous polymer can efficiently adsorb probe molecules due to the strong intermolecular interactions caused by the polar triazine moiety. CTF‐Cz directly serves as the surface‐enhanced Raman scattering substrate without any post proceeding techniques. The enhancement factor of CTF‐Cz is ~105 for detecting rhodamine 6G (R6G). The lowest unoccupied molecular orbital energy level of CTF‐Cz (−3.93 eV) is much lower than that of R6G, which is in favor of the charge transfer from R6G to CTF‐Cz for illumination under a 532 nm laser, which is proved by time resolved photoluminescence spectra. The efficient charge transfer induced by the strong intermolecular π–π interactions and large molecular‐orbital delocalization contribute to the enhanced Raman signals of R6G on CTF‐Cz.

Novel cathode buffer layer enabling over 21.6%/20.9% efficiency in wide bandgap/inorganic perovskite solar cells

Different types of hybrid organic/inorganic halide perovskite solar cells (PSCs) have attracted extensive research attention and showed extremely considerable practical application potential in current energy field, for instance, wide bandgap (WBG) PSCs are widely used in fabricating high-efficiency tandem devices, while inorganic perovskite solar cells (IPSCs) had been sought after by researchers due to its excellent thermal stability. However, either WBG PSCs or IPSCs were severely influenced by the carrier extraction and transport between the electron transfer layer and anode/cathode. On this basis, an in-situ oxygen plasma treated Ti doped ZnO film named TZO (O) was used as cathode buffer layer to regulate the energy-level alignment between the SnO2 layer and ITO electrode, optimize the crystal quality of perovskite and passivate perovskite defects through providing superior SnO2 film. It is found that the more suitable energy levels for the interlamination availably polished up carrier transport effect to a great extent, which could be seen in steady-state and time-resolved photoluminescence spectra, in addition to this, the perovskite film covered on TZO (O)/ SnO2 demonstrated larger perovskite crystals and less surface defects. As a consequence, the power conversion efficiency (PCE) of the optimized device with a bandgap of ≈ 1.66 eV up to 21.62%, and the efficiency of CsPbI2.85Br0.15 IPSCs is enhanced from 19.21% to 20.92%. Moreover, the unencapsulated TZO (O)-treated wide bandgap PSCs shows enhanced stability, retaining 89.47% of its initial efficiency after 1000 h in a N2 filled environment, while the unencapsulated IPSCs-based TZO (O) still remains 83.77% of its initial efficiency under continuous illumination in air for 325 h. This work exhibited that the buffer layer TZO (O) is a promising interfacial modification material for both n-i-p type wide bandgap PSCs and IPSCs.

Anthracene and tetraphenylsilane based conjugated porous polymer nanoparticles for sensitive detection of nitroaromatics in water

Conjugated porous polymers (CPPs) are a kind of promising sensing materials for the detection of nitroaromatic compounds, but their sensing applications in aqueous media are limited because of their poor dispersity or solubility in water. In this study, we prepared anthracene and tetraphenylsilane based CPPs named PSiAn by conventional Suzuki coupling and Suzuki-miniemulsion polymerization, respectively. The structure, morphology and porosity of the CPPs were characterized by Fourier Transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance (1H NMR), transmission electron microscope (TEM) and N2 sorption isotherm, respectively. Both of the CPPs have porous structure which is beneficial for the adsorption and diffusion of the analytes within them. The particle size of PSiAn nanoparticles prepared by Suzuki-miniemulsion polymerization is 10–40 nm from the TEM image, which facilitates the dispersion in the aqueous phase. Combined with the porosity and nanoparticle morphology, PSiAn nanoparticles realized the efficient photoluminescence (PL) sensing of nitroaromatic explosives in aqueous phase. The limit of detection (LOD) and limit of quantitation (LOQ) of PSiAn nanoparticles for 2,4,6-trinitrophenol (TNP) detection in the pure aqueous phase are 0.33 μM and 1.11 μM, respectively. Meanwhile, the good selectivity and anti-interference in presence of other nitro-compounds were observed. Furthermore, the spike/recovery test for the TNP detection in real water samples by PL sensing based on PSiAn nanoparticles indicates the quantitative recovery of TNP from 100.74 % to 101.00 %. The electrochemical test, ultraviolet–visible absorption spectra, excitation and emission spectra, and time-resolved PL spectra were investigated to explore the PL sensing mechanism. As a result, it is found that the fluorescence inner filter effect might be the predominant quenching mechanism during the detection of nitrophenolic compounds such as TNP and 4-nitrophenol (4-NP).

Study of Indium Phosphide Quantum Dots/Carbon Quantum Dots System for Enhanced Photocatalytic Hydrogen Production from Hydrogen Sulfide

Quantum dots (QDs) are promising semiconductor nanocrystals in photocatalysis due to their unique properties and in contrast to bulk semiconductors. Different from the traditional modification methods of indium phosphide (InP) QDs such as metal doping, shell design, and surface ligand modification, we firstly constructed the indium phosphide quantum dot and carbon quantum dot (InP QDs/CQDs) system and used it for the study of photocatalytic hydrogen production from hydrogen sulfide (H2S) in this work. The photocatalytic performance tests show that the average rate of photocatalytic decomposition of hydrogen sulfide to produce hydrogen of the InP QDs/CQDs system increases by 2.1 times in contrast to InP QDs alone. The steady-state and time-resolved photoluminescence spectra demonstrated that the introduction of CQDs can effectively improve the separation efficiency of photo-generated carriers. In addition, the surface electronegativity of the InP QDs/CQDs system is weaker than that of InP QDs, which may reduce the repulsion between the photocatalyst and reaction substrate, promoting the surface oxidation reaction in the photocatalytic process. This work indicates that the construction of the QDs hybrid system can improve their photocatalytic performance, providing a way to optimize QDs in photocatalysis.

Tm3+-doped Cs2Ag0.6Na0.4In0.9Bi0.1Cl6 microcrystals for thermometry

Lead-free double perovskites have superb luminescence properties for broad applications. However, increasing or improving near-infrared (NIR) photoluminescence (PL) is still a challenge. In this paper, a high-performance microcrystal is designed based on Tm3+ heavily doped Cs2Ag0.6Na0.4In0.9Bi0.1Cl6 (CANIBC), which realize both the self-trapped excitons (STEs) and Tm3+ NIR emission. The emission mechanism and energy transfer (ET) process are studied by steady-state and time-resolved PL spectra. The ET efficiency from STEs to Tm3+ can reach 38.3 %, and the NIR PL quantum yield of Tm3+ can reach 22.7 %. Meanwhile, the PL spectra of Tm3+-doped CANIBC microcrystals (MCs) with different concentrations are used to investigate their temperature sensing properties based on both fluorescence intensity ratio (FIR) and lifetime. Based on the FIR, relative sensitivity (Sr) can reach 2.93 % K−1 at 303 K. Moreover, based on lifetimes, Sr can maintain more than 1.55 % K−1 from 303 to 453 K, and maximum Sr can also achieve 2.38 % K−1 at 360 K. These excellent luminescence and sensing properties offer greater development potential in the field of NIR phosphor and thermometry.

Enhanced quantum yield at high exciton density in monolayer transition metal dichalcogenides

Monolayer transition metal dichalcogenides are a class of atomically thin semiconductors that have a direct bandgap, making them promising candidates for optoelectronic and photonic devices. However, the low quantum yield at high charge injection levels significantly limits their applicability in optoelectronic devices that function under high current densities, such as light-emitting diodes and lasers. To address this issue, we demonstrate the use of hexagonal boron nitride encapsulation as a means of tuning the photoluminescence properties in monolayer transition metal dichalcogenides. Our results show a several-fold enhancement in the photoluminescence quantum yield at high exciton densities. This improvement is attributed to the suppressed exciton–exciton annihilation, which is supported by experimental time-resolved photoluminescence spectra and theoretical analysis. Our findings provide a simple and effective method for achieving highly efficient optoelectronic devices based on monolayer transition metal dichalcogenides.

Electron spin dynamics in multi-energy level systems under the excitation of circular polarization modulated continuous-wave laser

Time-resolved photoluminescence spectroscopy under the excitation of circular polarization modulated continuous-wave laser can quantitatively extract the electron spin polarization degrees and electron spin relaxation time, providing an important tool to detect electron spin dynamics. We theoretically analyze the electron spin dynamics in four-, six- and eight-energy level systems under the excitation of circular polarization modulated continuous-wave laser by solving the rate equations of electron population. The relationship between the time-resolved photoluminescence spectra and the spin information of the spin system is provided. The electron spin polarization degrees of the ground and excited states, the establishment time of the steady-state spin polarization and the electron spin relaxation time can be directly derived from the time-resolved photoluminescence spectra. And the theoretical model is verified experimentally by the measurement of electron spin dynamics in Ce3+: YAG crystal.

Fabrication and Characterization of 2D Layered Perovskites with a Gradient Band Gap.

Vertical gradient band-gap heterostructures of two-dimensional (2D) layered perovskites have attracted considerable research interest due to their superior optoelectronic properties and demonstrated potential for use in optical devices. However, its fabrication has been challenging. In this investigation, 2D Ruddlesden-Popper mixed halide perovskite single crystals with a vertical gradient band gap were synthesized by using a solid-state halide diffusion process. X-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements after diffusion confirm that the crystalline and morphology remain intact. The transmittance and photoluminescence (PL) spectra show the formation of a vertical gradient band gap that is ascribed to gradient halide distribution through halide intermixing. The mixed halide crystal exhibits high stability with completely suppressed phase segregation in the time-dependent PL measurement. The time-resolved photoluminescence (TRPL) spectra prove that the mixed halide sample has an enhanced carrier transport due to the Förster resonance energy transfer (FRET) effect. Besides, the halide diffusion behavior is found to be different from the previously proposed "layer-by-layer" diffusion model in exfoliated crystals. The gradient band-gap structure is critical for various applications in which vertical carrier transport is demanded.

Simplified synthesis of direct Z-scheme Bi2WO6/PhC2Cu heterojunction that shows enhanced photocatalytic degradation of 2,4,6-TCP: Kinetic study and mechanistic insights

For this work, we employed n-type Bi2WO6 and p-type PhC2Cu to formulate a direct Z-scheme Bi2WO6/PhC2Cu (PCBW) photocatalyst via simplified ultrasonic stirring technique. An optimal 0.6PCBW composite exhibited the capacity to rapidly photodegrade 2,4,6-TCP (98.6% in 120 min) under low-power blue LED light, which was 8.53 times and 12.53 times faster than for pristine PhC2Cu and Bi2WO6, respectively. Moreover, electron spin resonance (ESR), time-resolved PL spectra, and quantitative ROS tests indicated that the PCBW enhanced the separation capacity of photocarriers. It also more readily associated with dissolved oxygen in water to generate reactive oxygen species (ROS). Among them, the ability of PCBW to produce ·O2- in one hour was 12.07 times faster than for pure PhC2Cu. In addition, the H2O2 formation rate and apparent quantum efficiency of PCBW are 10.73 times that of PhC2Cu, which indicates that PCBW not only has excellent photocatalytic performance, but also has outstanding ROS production ability. Furthermore, Ag photodeposition, in situ X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations were utilized to determine the photogenerated electron migration paths in the PCBW, which systematically confirmed that Z-scheme heterojunction were successfully formed. Finally, based on the intermediate products, three potential 2,4,6-TCP degradation pathways were proposed.