ZnO Clusters Research Articles

Effect of Acetylene Properties on its Gas Sensing by NiO Doped ZnO Clusters: A Transition State Theory Model

The sensitivity of nickel oxide doped zinc oxide to industrial gas acetylene was calculated and compared to available experimental data. The adsorption of C2H2 on the NiO-doped ZnO surface and the activation transition states formed afterward were studied computationally. B3LYP version of density functional theory with 6-311G** basis set, including dispersion correction (GD3BJ) was performed for the calculations with the help of Gaussian 09 software. Thermodynamic quantities of the reaction of C2H2 with NiO-doped ZnO surfaces, such as Gibbs free energy, enthalpy, and entropy, were used to interpret the reaction at the temperature range 25–325 °C. Response and response time variation with different NiO doping percentages were calculated. The calculations took into account the combustion of acetylene as it approached its autoignition temperature, which was not considered in previous works. The results show that the optimum response operating temperature of the C2H2 gas sensor is below the autoignition temperature of acetylene at 300 °C. A good agreement of theoretical response and response time with variation of temperature and acetylene concentration was obtained with the experiment. This study was the first to take into account the autoignition of C2H2 in gas sensor calculations and noted that gases can be easily distinguished by their autoignition temperature.

Highly Dispersed ZnO Sites in a ZnO/ZrO2 Catalyst Promote Carbon Dioxide‐to‐Methanol Conversion

AbstractZnO/ZrO2 catalysts have shown better activity in the CO2 hydrogenation to methanol compared with single component counterparts, but the interaction between ZnO and ZrO2 is still poorly understood. In particular, the effect of the ZrO2 support phase (tetragonal vs. monoclinic) was not systematically explored. Here, we have synthesized ZnO/ZrO2 catalysts supported on tetragonal ZrO2 (ZnO/ZrO2‐t) and monoclinic ZrO2 (ZnO/ZrO2‐m), which resulted in the formation of different ZnOx species, consisting of sub‐nanometer ZnO moieties and large‐sized ZnO particles, respectively. ZnO/ZrO2‐t exhibited a higher methanol selectivity (81 vs. 39 %) and methanol yield (1.25 vs. 0.67 mmol g−1 h−1) compared with ZnO/ZrO2‐m. The difference in performance was attributed to the redox state and degree of dispersion of Zn, based on spectroscopy and microscopy results. ZnO/ZrO2‐t had a high density of ZnOx‐ZrOy sites, which favored the formation of active HCOO* species and enhanced the yield and selectivity of methanol along the formate pathway. Such ZnO clusters were further dispersed on ZrO2‐t during catalysis, while larger ZnO particles on ZnO/ZrO2‐m remained stable throughout the reaction. This study shows that the phase of ZrO2 supports can be used to control the dispersion of ZnO and the catalyst surface chemistry, and lead to enhanced catalytic performance.

Highly Dispersed ZnO Sites in a ZnO/ZrO2 Catalyst Promote Carbon Dioxide-to-Methanol Conversion.

ZnO/ZrO2 catalysts have shown better activity in the CO2 hydrogenation to methanol compared with single component counterparts, but the interaction between ZnO and ZrO2 is still poorly understood. In particular, the effect of the ZrO2 support phase (tetragonal vs. monoclinic) was not systematically explored. Here, we have synthesized ZnO/ZrO2 catalysts supported on tetragonal ZrO2 (ZnO/ZrO2-t) and monoclinic ZrO2 (ZnO/ZrO2-m), which resulted in the formation of different ZnOx species, consisting of sub-nanometer ZnO moieties and large-sized ZnO particles, respectively. ZnO/ZrO2-t exhibited a higher methanol selectivity (81 vs. 39 %) and methanol yield (1.25 vs. 0.67 mmol g-1 h-1) compared with ZnO/ZrO2-m. The difference in performance was attributed to the redox state and degree of dispersion of Zn, based on spectroscopy and microscopy results. ZnO/ZrO2-t had a high density of ZnOx-ZrOy sites, which favored the formation of active HCOO* species and enhanced the yield and selectivity of methanol along the formate pathway. Such ZnO clusters were further dispersed on ZrO2-t during catalysis, while larger ZnO particles on ZnO/ZrO2-m remained stable throughout the reaction. This study shows that the phase of ZrO2 supports can be used to control the dispersion of ZnO and the catalyst surface chemistry, and lead to enhanced catalytic performance.

A comprehensive study of cytosine-ZnO interactions: Theoretical and experimental insights

This paper presents a comprehensive investigation of the adsorption of cytosine, a DNA base, on ZnO model clusters, specifically Zn2O2, Zn3O3, Zn4O4, Zn6O6, Zn8O8 ring (R) and cubic rocksalt. A density functional theory (DFT) method was used to simulate the adsorption of cytosine on ZnO (C/ZnO) clusters. The B3LYP/LanL2DZ method, which includes a correction for the dispersion contribution, was used. The calculated energy gap (Eg) for cytosine showed a strong dependence on the cluster size, highlighting variations corresponding to the dimensions of the clusters. The proposed physisorption mechanism involves the formation of an N...Zn bond between cytosine and the active Zn site on ZnO. In addition, experimental data, including microscopic and spectroscopic evidence, were integrated to further elucidate the interactions between cytosine and ZnO. A composite of C and ZnO was prepared by the wet chemical method and characterised by SEM, XRD and FT-IR analyses. The interaction of cytosine with ZnO nanoparticles was observed by UV–vis spectroscopy. The experimental results were then compared with those obtained from DFT calculations, taking into account the new insights into the cytosine-ZnO interactions. This comparison provided a holistic understanding of the system.

Discharge fault detection of dry air switchgear based on ZnO-MoS2 gas sensor

Abstract When discharge faults occur in dry air switchgear, the air decomposes to produce diverse gases, with NO2 reaching the highest levels. Detecting the NO2 level can reflect the operation status of the equipment. This paper proposes to combine ZnO cluster with MoS2 to improve the gas-sensitive properties of the monolayer. Based on the Density Functional Theory (DFT), the effect of (ZnO)n size on the behavior of MoS2 is considered. Key parameters such as adsorption energy and band gap of (ZnO)n-MoS2/NO2 system were calculated. The ZnO-MoS2 heterojunction was successfully synthesized by a hydrothermal method. The gas sensor exhibits a remarkable response and a fast response-recovery time to 100 ppm NO2. In addition, it demonstrates excellent selectivity, long-term stability and a low detection limit. This work confirms the potential of the ZnO-MoS2 composite structure as a highly effective gas sensor for NO2 detection, which provides valuable theoretical and experimental insights for fault detection in dry air switchgear.

Low-temperature oxidation of methane mediated by Al-doped ZnO cluster and nanowire: a first-principles investigation.

First-principles calculations are performed to investigate the catalytic oxidation of methane by using N2O as an oxidizing agent over aluminum (Al)-doped Zn12O12 cluster and (Zn12O12)2 nanowire. The impact of Al impurity on the geometry, electronic structure, and surface reactivity of Zn12O12 and (Zn12O12)2 is thoroughly studied. Our study demonstrates that Al-doped ZnO systems have a better adsorption ability than the corresponding pristine counterparts. It is found that N2O molecule is initially decomposed on the Al site to provide the N2 molecule, and an Al-O intermediate which is an active species for the CH4 oxidation. The conversion of CH4 into CH3OH over AlZn11O12 and (AlZn11O12)2 requires an activation energy of 0.45 and 0.29eV, respectively, indicating it can be easily performed at normal temperatures. Besides, the overoxidation of methanol into formaldehyde cannot take place over the AlZn11O12 and (AlZn11O12)2, due to the high energy barrier needed to dissociate C-H bond of the CH3O intermediate. Dispersion-corrected density functional theory calculations were performed through GGA-PBE exchange-correlation functional combined with a numerical double-ζ plus polarization (DNP) basis set as implemented in DMol3. To include the relativistic effects of core electrons of Zn atoms, DFT-semicore pseudopotentials were adopted. The DFT + D scheme proposed by Grimme was used to involve weak dispersion interactions within the DFT calculations. The reaction energy paths were generated by the minimum energy path calculations using the NEB method.

Can ZnO/Cu catalyst provide promising activity for glycerol direct dehydrogenation? A combined density functional theory and coverage-dependent microkinetics study

Non-oxidative dehydrogenation (NODH) reaction of glycerol is a perfect atom economical technical route to produce higher-value 1,3-dihydroxyacetone (DHA). Cu-based catalyst (especially ZnO/Cu system), is known as active species for alcohol dehydrogenation, which may be also promising one for glycerol NODH. In this study, we combine coverage-dependent free energy profile using first-principle calculation, and microkinetic model, to investigate the NODH of glycerol on the ZnO/Cu(111) surface, and a detailed comparison is made with Cu (111) surface. The coverage-dependent microkinetic model takes into account the lateral adsorbate–adsorbate self-interactions and cross-interactions, and their effect on binding energy of both intermediate and transition state. Besides, it guarantees the reaction kinetics is based on the coverage self-consistent between surface model and microkinetic result under practically reaction conditions. Compared with coverage-dependent kinetics simulation (20 %–30 %), coverage-independent model overestimates the DHA selectivity on Cu (111) (over 90 %). Our coverage-dependent kinetics simulation illustrates that both glycerol conversion and DHA selectivity are most determined by the first dehydrogenation step (OH bond scission) of glycerol on Cu (111). However, when ZnO cluster adsorbed on the Cu (111) surface, ZnO cluster promotes the electron transferring between glycerol and Cu sites, which accelerates OH bond scission process of glycerol. Under coverage-dependent microkinetic model, the turnover frequency and selectivity of DHA on ZnO/Cu(111) get much improvement compared with Cu (111). Finally, the superior of ZnO/Cu(111) is further proved by continuous stirred tank reactor simulation, where NODH of glycerol need shorter residence times or lower temperature to reach 100 % conversion, as well as keep higher DHA selectivity.

The Development and Atomic Structure of Zinc Oxide Crystals Grown within Polymers from Vapor Phase Precursors.

Sequential infiltration synthesis (SIS), also known as vapor phase infiltration (VPI), is a quickly expanding technique that allows growth of inorganic materials within polymers from vapor phase precursors. With an increasing materials library, which encompasses numerous organometallic precursors and polymer chemistries, and an expanding application space, the importance of understanding the mechanisms that govern SIS growth is ever increasing. In this work, we studied the growth of polycrystalline ZnO clusters and particles in three representative polymers: poly(methyl methacrylate), SU-8, and polymethacrolein using vapor phase diethyl zinc and water. Utilizing two atomic resolution methods, high-resolution scanning transmission electron microscopy and synchrotron X-ray absorption spectroscopy, we probed the evolution of ZnO nanocrystals size and crystallinity level inside the polymers with advancing cycles─from early nucleation and growth after a single cycle, through the formation of nanometric particles within the films, and to the coalescence of the particles upon polymer removal and thermal treatment. Through in situ Fourier transform infrared spectroscopy and microgravimetry, we highlight the important role of water molecules throughout the process and the polymers' hygroscopic level that leads to the observed differences in growth patterns between the polymers, in terms of particle size, dispersity, and the evolution of crystalline order. These insights expand our understanding of crystalline materials growth within polymers and enable rational design of hybrid materials and polymer-templated inorganic nanostructures.

Fabrication of antibacterial drug (furazolidone) sensor using zeolitic imidazolate framework-8 (ZIF-8)–derived ZnO clusters as sensing material

Fabrication of antibacterial drug (furazolidone) sensor using zeolitic imidazolate framework-8 (ZIF-8)–derived ZnO clusters as sensing material

Formation of High Hardness ZnO/Cu Nanocomposite by Thermal Oxidation from Cu-Zn Alloy Strips

Due to their superior thermal, electrical, and mechanical properties, brass and Cu-Zn alloys are widely used in a broad range of applications. In applications requiring greater durability, corrosion resistance, and wear resistance, however, the ZnO/Cu composite is preferable. Typically, ZnO/Cu composites are manufactured through powder metallurgy. In this article, brass strips are thermally oxidized in an oxygen atmosphere to produce ZnO/Cu composite strips. The optimal temperature and oxygen pressure are 600–650 °C and less than one atmosphere, respectively. The homogeneous distribution of nanoscale ZnO clusters in the Cu matrix can be attributed to the diffusion of both Zn and O in the matrix. In addition, the composite is substantially harder than brass, increasing from 70–90 HV to 200–240 HV. Therefore, thermal oxidation has been shown to be a simple and cost-effective process for producing ZnO/Cu composites with high hardness.

Aviation fuel hydrocarbons from camphorwood and low-density polyethylene: Cascade catalytic approach with CaO and Zn/HBeta

In this study, the co-pyrolysis of camphorwood and low-density polyethylene employing a cascade catalyst system consisting of CaO and Zn-modified HBeta in a fixed-bed reactor was investigated for the production of aviation fuel hydrocarbons (C8–C16). The effect of Zn loading on HBeta, CaO to Zn/HBeta mass ratio, and the feedstock to catalyst mass ratio on both oil yield and composition was investigated. Results revealed that loading Zn onto HBeta led to ZnO cluster and oxygen-bridged Zn dimers ([ZnOZn]2+) formation, which affects HBeta's acid properties and aromatization capacity. The 10 wt%Zn/HBeta catalyst with more ZnO content exhibited weak acid sites, and moderate aromatization capacity, increasing oil yield from 32.06 to 44.25 wt% compared to 3 wt%Zn/HBeta and favoring presence of straight-chain components in oil products. CaO also enhanced straight-chain alkane formation. The highest oil yield, reaching 48.44 wt%, was obtained when CaO and 10 wt%Zn/HBeta cascade by a 1:1 mass ratio was adopted, producing oil with aviation fuel with a maximum yield of 18.45 wt%, and selectivity of 38.09 area%, of which 26.54 area% being aromatics and 11.55 area% being alkanes. Furthermore, the feedstock-to-catalyst ratio influenced the products significantly, with lower feedstock-to-catalyst ratio enhanced aromatization and the ratio of 2:1 recommended. Therefore, this cascade catalytic approach, which combines cost-effective CaO and 10 wt%Zn/HBeta catalysts shows significant potential for enhancing bio-aviation fuel production from solid wastes. Moreover, it provides a viable and promising solution for addressing concerns related to low oil yield and excessive aromatization.

High performance near ultraviolet ray detector by cluster-wrapped surface structure in ferroelectrics

High-sensitivity detectors for near-ultraviolet rays are of great importance in civil and military fields. Recently, great efforts have been made to enhance the sensitivity, but mainly at the cost of increasing energy consumption or bulk volume. High-performance near-ultraviolet ray detector was fabricated using ZnO clusters compounded in ferroelectric Bi4.5Na0.5Ti4O15 composites, which exhibit ultrahigh sensitivity detectivity (D*), linear dynamic response (LDR) and photoconductance σ(λ) of up to 3.9 × 1011 Jones, 52.04 dB, and 3.9 × 10-10 S/m, respectively. The three-parameter criterions are over a wide wavelength range larger than that of a semiconductor. High external quantum efficiency 4.6 % is to ensure the self-powered device. Such a brilliant virtue is attributed to the artificial transport layer by the superior ZnO cluster surface-wrapped structure, which effectively transports the electrons or holes induced by photons. These pioneering findings indicate that the ZnO cluster surface-wrapped structure may be useful for the assembly of ferroelectric high-performance UV photoelectronic devices in the near future.

Nanostructured ZnO with Tunable Morphology from Double-Salt Ionic Liquids as Soft Template.

ZnO nanostructures with tunable morphology were synthesized by the hydrothermal method from two ionic liquids (ILs), 1-ethyl-3-methylimidazolium acetate [C2mim]CH3CO2 and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C2mim](CF3SO2)2N and their corresponding double-salt ILs (DSILs). ILs served as soft templates. DSILs were noted for the production of smaller particle size along with uniformity compared to their pure IL counterparts. A changeover of the shape of ZnO from nano-prism to a hexagonal disk-like structure was observed with the addition of [C2mim]CH3CO2 in the medium during synthesis while nano-dice- and rod-shaped particles were obtained from [C2mim](CF3SO2)2N. The effect of concentration of both ILs was explored for the variations of size and shape, and at high concentrations, the morphology was distinct and sharp with uniform size in each case. The synthesized products exhibited excellent phase (wurtzite) purity and polycrystalline nature. The smallest crystallite size was acquired from DSILs, indicating the advantageous effect of the dual anions. The selective adsorption effect of [C2mim]CH3CO2 on certain facets promoted the growth of ZnO clusters along the [1010] direction, while [C2mim](CF3SO2)2N favored the growth along the [0001] direction. Consequently, DSILs rendered interpenetrating hexagonal disks due to the combined action of the anions for controlling the shape. The band gap energies of the nanoparticles (NPs) were consistent with the distribution of size. Extremely strong red emission and negligible UV emission for the synthesized ZnO NPs demonstrate their potential in the advancement of optoelectronic devices.

Zn Redistribution and Volatility in ZnZrOx Catalysts for CO2 Hydrogenation.

ZnO-ZrO2 mixed oxide (ZnZrOx) catalysts are widely studied as selective catalysts for CO2 hydrogenation into methanol at high-temperature conditions (300-350 °C) that are preferred for the subsequent in situ zeolite-catalyzed conversion of methanol into hydrocarbons in a tandem process. Zn, a key ingredient of these mixed oxide catalysts, is known to volatilize from ZnO under high-temperature conditions, but little is known about Zn mobility and volatility in mixed oxides. Here, an array of ex situ and in situ characterization techniques (scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), Infrared (IR)) was used to reveal that Zn2+ species are mobile between the solid solution phase with ZrO2 and segregated and/or embedded ZnO clusters. Upon reductive heat treatments, partially reversible ZnO cluster growth was observed above 250 °C and eventual Zn evaporation above 550 °C. Extensive Zn evaporation leads to catalyst deactivation and methanol selectivity decline in CO2 hydrogenation. These findings extend the fundamental knowledge of Zn-containing mixed oxide catalysts and are highly relevant for the CO2-to-hydrocarbon process optimization.

Microstructure, Mechanical, and <i>In-Vitro</i> Characterization of a Novel Biodegradable Zinc-Based Composite Fabricated at Room Temperature

A novel Zn biodegradable composite was produced by direct extrusion of Zn powders at room temperature. The powders were efficiently consolidated to a high relative density, and the composite reached a UTS higher than 120 MPa and elongation of almost 70%. Microstructural observations showed ultra-fine Zn grains decorated by well-dispersed ZnO clusters at the grain boundaries. The degradation behavior of the composite and an as-cast Zn reference accessed by immersion tests in HBSS for both materials were similar and gave an equivalent corrosion rate. Additional static immersion tests in DMEM + 5% FSB showed a similar corrosion rate (0.015 mm/y), but SEM analysis of the corroded surface suggested that the degradation process of each as-cast or DE consolidated composite differs. MTT assays with extracts of both as-cast and extruded composites showed similar cytotoxicity, which was dependent on the dilution of the extracts. It was concluded that the proposed methodology brings the potential for an interesting solution to produce a sound Zn-ZnO composite with good biocompatibility, satisfactory corrosion rate, and high yield strength.

Study on the Properties and Morphology of Nano-ZnO Modified Asphalt Based on Molecular Dynamics and Experiments

Plenty of research has verified that nano-ZnO particles could improve the properties of asphalt, but studies on nano-ZnO-modified asphalt haven’t been conducted at the molecular level. Therefore, to investigate the effect of ZnO particles on the properties, structure and morphology of asphalt, the molecular dynamics (MD) methods were carried out. In this study, the models of asphalt, ZnO cluster and ZnO/asphalt blending systems with different particle sizes were built using Materials Studio software. Then, the interaction energies of ZnO/asphalt blending systems under different temperatures were calculated, and the effect of ZnO particles on the modulus and glass transition temperature of matrix asphalt was simulated. The results indicated that the bulk modulus of asphalt increased by ZnO with particle size at 4 Å, 6 Å, 8 Å and 10 Å increased by 15.09%, 12.46%, 10.06% and 8.51%, respectively, which can illustrate that the shear resistance ability and low-temperature properties of asphalt were enhanced. Compared with matrix asphalt, the glass transition temperature of the ZnO/asphalt system decreased by less than 0.1 K, indicating that ZnO’s effect on the low temperature of asphalt was not apparent. With the increase of ZnO particle size, the diffusion coefficient decreased sharply. Compared to matrix asphalt, when the particle size increased to 8 Å and 10 Å, the diffusion coefficient decreased by 13% and 22%, respectively. So, in practice projects, to achieve better dispersion of particle materials in base bitumen, a smaller particle size would be recommended. The results of the radial distribution function (RDF) and AFM simulation indicated that ZnO particles changed the micro-structure of asphalt and increased the roughness of the asphalt surface. As a result, ZnO particles bring matrix asphalt better physical properties.

UV Photoluminescence Microscopy of Individual ZnO Nanostructured Clusters

Ultraviolet (UV) photoluminescence (PL) spectra were acquired from individual nanostructured ZnO clusters less than 1 μm in size. The nanostructured clusters were formed by aggregation of a small number of nanoparticles. This analysis employed a microscopy apparatus specially designed for PL assessments of nanostructures at UV wavelengths with a spatial resolution of 0.395 μm. Atomic force microscopy was also employed to ascertain the sizes and morphologies of the nanostructured clusters. The ZnO samples were prepared by laser ablation in liquid (LAL) and comprised spherical, rhomboid, or gel-coated particles. PL emissions originating from free excitons (FX), FX phonon replicas, and defects were observed. The FX peak widths and positions were found to vary (with positions from 3.30 to 3.36 eV), suggesting that a range of particle sizes and morphologies was obtained from the LAL process. FX peaks at higher energies exhibited greater widths as a consequence of a quantum size effect originating from the crystallites comprising the nanostructured clusters. The rhomboid particles showed less-intense emissions related to defects compared with the other two types while also exhibiting the least intense emissions related to FX phonon replicas. This work also examined the mechanism by which nanoparticles were produced by LAL on the basis of the spectroscopic data. The information presented herein is expected to assist in the design and fabrication of semiconductor nanoparticles for future nanotechnology applications.

Does Water Play a Crucial Role in the Growth of ZnO Nanoclusters in ZnO/Cu Catalyst?

The catalytically active configuration of ZnO/Cu in the commercial ZnO/Cu/Al2O3 catalyst for methanol synthesis from CO2 is still not clear. In this study, we employ density functional theory based methods to shed light on the structure and stoichiometry of ZnO clusters both free in the gas phase and also deposited on the Cu(111) surface under methanol synthesis conditions. Specifically, we investigate the structural evolution of ZnO clusters in the presence of hydrogen and water. We find that the stability of ZnO clusters increases with the concentration of water until the ratio of Zn and OH in the clusters reaches 1:2, with a morphological transition from planar to 3D configurations for clusters containing more than 4 Zn atoms. These clusters exhibit weak interaction with CO2, and water is predicted to block the active center. The Cu(111) surface plays an important role in enhancing the adsorption of CO2 on the ZnO/Cu(111) systems. We infer that ZnO nanostructures covered with OH species may be the morphology of the ZnO during the methanol synthesis from the hydrogenation of CO2 on the industrial catalyst.

One-step cladding metal oxide nanowires with a carbon-dots-embedded ZnO amorphous layer toward boosted photoelectrochemical water oxidation

An effective method was proposed for constructing carbon dots (CDs)-sensitized multijunction composite photoelectrodes via one-step cladding a CDs-embedded ZnO amorphous overlayer on vertically aligned metal oxide nanowires. This strategy involved the double role of hexamethylenetetramine (HMTA) in the ethylene glycol (EG) solvent mixed with a controllable trace amount of water. In the water-deficient synthetic system, a limited portion of HMTA served as the pH buffer and hydroxyl source to force the hydrolytic process of zinc ions for the production of ZnO. The precipitated ZnO clusters were instantly capped by EG molecules through the activated alkoxidation reaction, and further crosslinked into an amorphous network surrounding the individual nanowires. Meanwhile, the excess HMTA was simultaneously depleted as the precursor for producing CDs in the EG solution through thermal condensation, which were packed in the gradually formed aggregates. We revealed that a CDs-embedded amorphous ZnO overlayer with an appropriate proportion of ingredient could be tailored through an optimal tradeoff between hydrolysis and condensation of HMTA. Benefiting from the synergy of the amorphous ZnO layer and the embedded CDs, the multijunction composite photoanodes exhibited significantly improved PEC performance and stability for water oxidation.

MOF derived ZnO clusters on ultrathin Bi2MoO6 yolk@shell reactor: Establishing carrier transfer channel via PANI tandem S–scheme heterojunction

Solar driven semiconductor photocatalytic oxidation is a sustainable environmental remediation method. However, how to design an ideal interface for efficient photogenerated carrier transfer/separation is still the key to improve the photocatalytic performance. To solve this problem, we established a yolk@shell reactor by loading MOF derived ZnO clusters on ultrathin Bi2MoO6. The ZnO clusters can enhance the internal electric field and promote the directional migration of charge carriers to limit its recombination. More importantly, the high conductivity polymer PANI is coated to establish a high–speed electron transfer channel in tandem reactor, so that a large amount of carrier is accelerated to surface to participate in the oxidation reaction. The constructed heterojunction has great ability to degrade doxycycline under visible–light with a small amount of catalyst through the S–scheme transfer path. This work provides an important strategy for S–scheme heterojunction efficient carrier transfer and its application in environmental remediation.