Fabrication of an S-Scheme Heterojunction Photocatalyst MoS2/PANI with Greatly Enhanced Photocatalytic Performance.

As a promising catalyst, MoS2 has been widely studied owing to its high chemical reactivity, excellent electrical carrier mobility, good optical properties, and narrow band gap. However, the high recombination rate of photoinduced charge carriers limits its practical application in photocatalysis. In this study, MoS2 was coupled with PANI to fabricate an S-scheme heterojunction MoS2/PANI. The synthesized products were characterized systematically, and their photocatalytic properties were evaluated by photocatalytic degradation of norfloxacin (NOR) and rhodamine B (RhB). The obtained results indicated that the fabricated MoS2/PANI inorganic-organic heterojunction displayed tremendously enhanced photocatalytic activity. The degradation efficiencies for 60 mg L-1 of NOR and RhB are 86 and 100% under the simulated sunlight irradiation for 1 h with 10 mg of catalyst, which are 13 and 47 times higher than those of pure MoS2, respectively. Interestingly, it is superior to the previously reported related materials. The remarkably enhanced photocatalytic activity of MoS2 is assigned to the high charge conductivity feature of PANI and the formed S-scheme heterojunction that result in a steric separation of holes and electrons and conserve the initial powerful redox ability of the parent catalysts. This study provides a facile method to greatly improve the photocatalytic activity of MoS2 and facilitates its application for highly efficient removal of organic pollutants, such as antibiotic drugs and organic dyes, utilizing solar energy.

Fabrication of a Heterojunction by Coupling a Metal-Organic Framework and N-Doped Carbon for the Photocatalytic Removal of Antibiotic Drugs with High Efficiency.

Norfloxacin (NOR) and tetracycline (TC), two widely used antibiotic drugs released to the aquatic environment, induce harm to ecosystems. In this study, an effective method was developed successfully to remove NOR and TC by photocatalysis with a novel heterojunction NC/NH2-MIL-53(Fe), which was fabricated by combining a metal-organic framework (MOF) material (NH2-MIL-53(Fe)) and N-doped carbon (NC) nanoparticles via a facile solvent thermal method. The prepared product exhibits outstanding photocatalytic efficiencies toward degradation of NOR and TC that are 15 and 6 times higher than those of pure NH2-MIL-53(Fe), respectively. Moreover, it is higher than those of the related materials reported previously. The greatly enhanced photocatalytic performance is assigned to the fabricated heterojunction with well-matched energy band gaps, where the NC acts as an efficient electron transfer/reservoir material to effectively promote the migration and transfer and restrain the recombination of charge carriers. In addition, the formed heterojunction increases specific surface area and light absorbance. The photocatalytic activity enhanced mechanism, degradation products, and pathway were investigated. The present study offers a novel strategy to significantly improve the photocatalytic performances of MOFs for highly efficient photocatalytic removal of antibiotic drugs in wastewater.

Fabrication of a Covalent Organic Framework-Based Heterojunction via Coupling with ZnAgInS Nanosphere with High Photocatalytic Activity.

Covalent organic frameworks (COFs) exhibit visible-light activity for the degradation of organic pollutants. However, the recombination rates of their photoinduced electron-hole pairs are relatively high, limiting their practical application. In this work, we fabricated a 1,3,5-triformylphloroglucinol (Tp) and p-phenylenediamine (Pa-1) (TpPa-1) COF-based heterojunction through coupling the TpPa-1 COF with a ZnAgInS nanosphere via a facile oil bath heating method. The results show that the prepared heterojunction exhibits outstanding catalytic activity for the degradation of high concentrations the antibiotic tetracycline (TC) and the dye rhodamine B (RhB), which is driven by simulated sunlight. Its degradation rates for RhB and TC were 30× and 18× higher than that of the pure TpPa-1 COF, respectively. The greatly enhanced photocatalytic performances can be ascribed to the formed heterojunction with good band-gap match, which promotes the migration and separation of light-induced electrons and holes and increases both light absorbance and the specific surface area. This study introduces an effective and feasible strategy for improving the photocatalytic performances of COFs via subtly integrating TpPa-1 COFs with a ZnAgInS nanosphere into an organic-inorganic hybrid. The results of the photocatalytic experiments indicate that the fabricated hybrid has a potential application in the highly efficient removal of organic pollutants.

Construction of MOF/COF Hybrids for Boosting Sunlight-Induced Fenton-like Photocatalytic Removal of Organic Pollutants.

In this work, a metal-organic framework (MOF) material of NH2-MIL88B was hybridized with TpPa-1-COF through covalent bonding, and the hybrid was subsequently employed for the degradation of Rhodamine B (RhB) and tetracycline (TC) by simulated sunlight-induced Fenton-like exciting H2O2. The obtained results show that its photocatalytic activity is much better than those of its parent MOF and covalent organic framework (COF). Moreover, it is much higher than that of bare photocatalysis without Fenton-like excitation of H2O2. The high degradation efficiency is ascribed to two factors. One is the formation of hybrid, which promotes charge separation and light absorbance. Another is the Fenton-like excitation of H2O2, which produces more hydroxyl radicals (•OH). This report presents a facile approach to greatly improve the photocatalytic property of MOF materials by the formation of hybrid with COFs and Fenton-like excitation of H2O2.

Fabrication of 2D-2D Heterojunction Catalyst with Covalent Organic Framework (COF) and MoS2 for Highly Efficient Photocatalytic Degradation of Organic Pollutants.

In this work, for the first time, we fabricated a novel covalent organic framework (COF)-based 2D-2D heterojunction composite MoS2/COF by a facile hydrothermal method. The results of photocatalytic degradation of TC and RhB under simulated solar light irradiation showed that the as-prepared composite exhibited outstanding catalytic efficiency compared with pristine COFs and MoS2. The significantly enhanced catalytic efficiency can be ascribed to the formation of 2D-2D heterojunction with a well-matched band position between COF and MoS2, which can effectively restrain the recombination of charge carriers and increase the light absorption as well as the specific surface area. Moreover, the fabricated 2D-2D layered structure can effectively increase the contact area with an intimate interface contact, which greatly facilitates the charge mobility and transfer in the interfaces. This study reveals that artful integration of organic (COFs) and inorganic materials into a single hybrid with a 2D-2D interface is an effective strategy to fabricate highly efficient photocatalysts.

Fabrication of Hierarchical Co9S8@ZnAgInS Heterostructured Cages for Highly Efficient Photocatalytic Hydrogen Generation and Pollutants Degradation.

In the present study, a hierarchical Co9S8@ZnAgInS heterostructural cage was developed for the first time which can photocatalytically produce hydrogen and degrade organic pollutants with high efficiency. First, the Co9S8 dodecahedron was synthesized using a metal-organic framework (MOFs) material, ZIF-67, as a precursor, then two kinds of metal sulfide semiconductors were elaborately integrated into a hierarchical hollow heterostructural cage with coupled heterogeneous shells and 2D nanosheet subunits. The artfully designed hollow heterostructural composite exhibited remarkable photocatalytic activity without using any cocatalysts, with a 9395.3 µmol g-1 h-1 H2 evolution rate and high degradation efficiency for RhB. The significantly enhanced photocatalytic activity can be attributed to the unique architecture and intimate-contact interface between Co9S8 and ZnAgInS, which promote the transfer and separation of the photogenerated charges, increase light absorption, and offer large surface area and active sites. This work presents a new strategy to design highly active semiconductor photocatalysts by using MOF materials as precursors and coupling of metal sulfide semiconductors to form hollow architecture dodecahedron cages with an intimate interface.

Improvement Photocatalytic Activity of P25 by Modification with a Rare Earth-Free Upconversion Nanocrystal.

It has been reported that coupling TiO2 with rare earth upconversion nanocrystals (UCNCs) is an efficient strategy to significantly improve photocatalytic activity of TiO2. However, the rare earth materials are scarcity and cost, and the synthesis process of UCNCs using the rare earth materials is complicated. In the present study, we have designed a new approach using a rare earth-free upconversion nanocrystal (REF-UCNCs) as upconversion luminescent material to replace the rare earth UCNCs. A novel nanocomposite photocatalyst of REF-UCNCs@P25: Mo/GN was developed for the first time. Based on the designed structure, the REF-UCNCs, Mo-doping, and GN (graphene) have a synergistic effect that can improve catalytic activity of P25 significantly. The results of photocatalytic experiments using RhB as a model pollutant under simulated solar light irradiation show that the photocatalytic efficiency of the as-prepared catalyst is 3-folds higher than that of benchmark substance P25. This work provides a new strategy for efficiently improving catalytic activity of semiconductor photocatalysts by coupling with REF-UCNCs. This approach is facile and low-cost which can be widely applied for modification of semiconductor photocatalysts and facilitates their applications in environmental protection issues using solar light.

Improving Upconversion Luminescence by Coating Active Shell: A Case Study on NaYF4:Gd, Yb, Er@NaYF4:Yb, Pr.

Upconversion nanocrystals (UCNCs) have a lot of advantages over other fluorescent materials. However, their applications are still limited due to the relatively low upconversion luminescence (UCL). In the present study, a novel core/shell structural upconversion nanocrystal NaYF4:Gd, Yb, Er@NaYF4:Yb, Pr was prepared successfully with a facilely solvothermal method and the properties of the nanocrystal were investigated. It was interesting to find that the as-prepared nano-crystal showed excellent UCL. Its UCL intensity was 65, 44, and 20 times higher than those of core nanocrystal NaYF4:Gd, Yb, Er, core/inert-shell nanocrystal NaYF4:Gd, Yb, Er@NaYF4, and core/active-shell nanocrystal NaYF4:Gd, Yb, Er@NaYF4:Yb, respectively. Moreover, the measured UCL lifetime of the as-prepared nanocrystal was longer than those of the controls. The mechanism of the UCL enhancement of the product was discussed in detail. The high UCL of the as-prepared product could be ascribed to the function of the shell, energy transfer from the active shell to the core, and Pr³âº-doping in the shell. This study provided a new insight into the fabrication of core­ shell structural upconversion nanocrystals with high UCL. The high UCL potentially increases the overall upconversion nanocrystal detectability for highly sensitive biological, medical, and optical detections.

Facile synthesis of hierarchical Mn3O4 superstructures and efficient catalytic performance.

The development of novel materials with excellent performance depends not only on the constituents but also on their remarkable micro/nanostructures. In this work, manganese oxide (Mn3O4) hausmannite structures with a uniform three-dimensional (3D) flower-like hierarchical architecture have been successfully synthesized by a novel chemical route using surfactants as structure-directing agents. Microstructure analysis indicates that the obtained 3D flower-like Mn3O4 superstructure consists of a large number of two-dimensional (2D) Mn3O4 nanosheets, which is different from the reported 3D Mn3O4 hierarchical structures based on zero-dimensional nanoparticles or one-dimensional nanowires and nanorods. This 3D Mn3O4 hierarchical architecture provides us with another type of manganese oxide with different superstructural characteristics, which may have potential practical applications in the catalytic degradation of organic pollutants. The catalytic performance of this hierarchical Mn3O4 superstructure, which was prepared by three different types of structure-directing agents, including cetyltrimethylammonium bromide (CTAB), poly(vinylpyrrolidone) (PVP), and poly(ethylene oxide)-poly(propylene oxide) (P123), was evaluated for the catalytic degradation of organic pollutants, e.g. methylene blue. Interestingly, the hierarchical Mn3O4 superstructure prepared using CTAB as a template showed efficient catalytic degradation. The formation processes and possible growth mechanism of this novel 3D Mn3O4 hierarchical superstructure assembled by 2D Mn3O4 nanosheets are discussed in detail.

Preparation of Novel Europium Complex Doped Ag@SiO2 Nanoparticles with Intense Fluorescence.

In this study, a new europium complex of 4,4'-bis (1",1",1",2",2",3",3"-heptafluoro-4",6"- hexanedion-6"-yl)-o-terpheny-Eu(3+)-4,7-diphenyl-1,10-phenanthroline-2,9-dicarboxylic acid-(3-aminopropyl) trimethoxysilane (BHHT-Eu(3+)-DPPDA-APTMS) was prepared first. Then novel core-shell Ag@SiO2 nanoparticles with BHHT-Eu(3+)-DPPDA-APTMS doped in shell were synthesized by a facile water-in-oil microemulsion method. The properties of the prepared complex and nanoparticles, and the effect of metal enhanced fluorescence for the nanoparticles were investigated. The prepared nanopartilces exhibited intense fluorescence, uniform morphology and good water-solubility. The fluorescent intensities of silver core-present nanopartciles were significant higher than that of silver core-absent nanoparticles owing to the metal enhanced fluorescence of silver core. It is expectable that the as-prepared nanoparticles can serve as a potential fluorescent nanoprobe, applying in high sensitive biological and medical detections.

Synthesis of NaYF4 and NaLuF4 Based Upconversion Nanocrystals and Comparison of Their Properties.

In this study, four kinds of upconversion nanocrystals (UCNs) have been successfully synthesized by a facile solvothermal method. The morphology, crystalline phase, composition, grain size, upconversion luminescence and cell image of the UCNs were investigated. The properties of the NaLuF4-based UCNs were compared with the counterparts of NaYF4-based UCNs. It is found that the NaLuF4-based UCNs are apt to form hexagonal phase structures, while NaYF4-based UCNs of NaYF4:Yb, Er and NaYF4:Gd, Yb, Er are cubic and hexagonal phases respectively. The upconversion emission intensities of the NaLuF4-based UCNs are higher than that of NaYF4-based UCNs, and Gd3+ presented UCNs are higher than that of Gd3+ absented UCNs. The bioimaging application of NaLuF4:Gd, Yb, Er shows that bright upconversion luminescence can be observed when UCNs-labeled HeLa cells are excited with 980 nm light.

Synthesis of fluorescent and magnetic bi-functional NaLuF4-based upconversion nanocrystals.

Fluorescent and magnetic bi-functional NaLuF4-based upconversion nanocrystals have been developed by a facile thermal decomposition method. The influences of Mn2+ and Gd3+ doping on the upconversion luminescent and magnetic properties of the nanocrystals were investigated. The results show that Mn2+ doping can promote the transition of green to red and increase the red emission significantly. When the Mn2+ and Gd3+ are co-doped in the nanocrystals, it has a synergistic effect which can further improve the transition and red emission. Moreover, the nanocrystals co-doped with Mn2+ and Gd3+ exhibit excellent superparamagnetic properties. These results suggest that the developed nanocrystals, which have strong pure red upconversion emission and superparamagnetic properties, can serve as a potential upconversion luminescence and magnetic resonance probe for dual-modality bioimaging. This work presents a facile and effective method for modulating the transition of short-wavelength emission to red emission of upconversion nanocrystals, leading the naocrystals exhibiting excellent upconversion luminescence and magnetic properties.

ZnO nanoparticles co-doped with Fe3+ and Eu3+ ions for solar assisted photocatalysis.

In this study, ZnO nanoparticles co-doped with Fe3+ and Eu3+ were prepared by a facile co-precipitation method. The structure and morphology of the as-prepared nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and diffuse reflectance absorption spectra, respectively. The photocatalytic activities of the prepared catalysts were evaluated by photocatalytic degradation of methyl orange in aqueous solution with solar light irradiation. The co-doped Fe3+ and Eu3+ showed a synergistic effect, which significantly increased the photocatalytic activity of ZnO. The influences of calcination time, photocatalytic reaction temperature and catalyst loading on the photocatalytic activity of the catalyst were also investigated. It was found that there were an optimum photocatalytic reaction temperature and an optimum catalyst loading for high photocatalytic efficiency, and the photocatalytic efficiency decreased with increase in calcination time. The results of this study demonstrate that the as-prepared product of Eu3+/Fe3+/ZnO is a promising photocatalyst for solar assisted degradation of organic pollutions.

Synthesis of NaYF4, NaLuF4 and NaGdF4-based upconversion nanocrystals with hydro (solvo) thermal methods.

Serials of NaYF4, NaLuF4 and NaGdF4-based nanocrystals have been synthesized successfully by solvothermal and hydrothermal, respectively. The properties of the products were characterized and compared. The nanocrystals prepared by hydrothermal method exhibited uniform hexagonal phase and large size, while the nanocrystals prepared by solvothermal method displayed high upconversion luminescence (UCL) and small size. The UCL intensities of the nanocrystals prepared by solvothermal method were higher than that of nanocrystals from hydrothermal method. Whether using solvothermal or hydrothermal method, the UCL intensities of the nanocrystals were in the sequence (from strong to weak) of NaLuF4:Gd/Yb/Tm, NaLuF4:Yb/Tm, NaGdF4:Yb/Tm, NaYF4:Gd/Yb/Tm and NaYF4:Yb/Tm, respectively. This is the first time to systematically compare three kinds of host-based nanocrystals, which are prepared by two different approaches with various lanthanide ions doped. This work could provide new insight into fabrication of upconversion nanocrystals with intense UCL and controllable morphology and size via using suitable doping ions, host materials and efficient approaches.

Preparation and characterization of ZnO-graphene composite photocatalyst.

ZnO is one of potential semiconductor materials in photocatalytic field, and appears to be a suitable alternative to TiO2, due to its photochemical properties and photodegradation mechanism similar to TiO2. Graphene is a single 2D carbon sheet with large specific surface and excellent electric conductivity. The combination of ZnO and graphene could extremely improve the photocatalytic activity of ZnO. Herein we prepared ZnO-graphene nanocomposite photocatalyst using graphite and ZnO by a facile one-step hydrothermal method. During the hydrothermal reactions, both of the reduction of graphene oxide and loading of ZnO were occurred simultaneously and the desired product was obtained. The as-prepared ZnO-graphene photocatalyst exhibited extraordinaire photocatalytic properties. Results of photocatalytic degradation of methyl orange show that the photocatalysis efficiency of the composite was significant enhanced, compared to pure ZnO. This work could provide new avenue for the fabrication of ZnO-carbon based composites, facilitating their application in pollutions degradation issues.

Ag/ZnO-C nanocomposite-preparation and photocatalytic properties.

In this present study, Ag-hybridized ZnO was prepared through a powder-sol method first, then Ag/ZnO-AC (activated carbon) composite was synthesized by a adsorption method using Ag/ZnO and AC as precursors. The structure and morphology of as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectrum (FT-IR), Raman spectra, and diffuse reflectance absorption spectra, respectively. The photocatalytic performances of the prepared catalysts were investigated by photocatalystic degradation of methyl orange. The influences of initial pH value, initial dye concentration and the calcination temperature on the photocatalytic activity of the catalysts were investigated and the results were discussed. Comparing with pure ZnO and ZnO-AC, Ag/ZnO-AC composite showed greatly enhanced photocatalytic activity. The results demonstrate that the hybridization of silver, activated carbon and ZnO can significantly improve the photocatalytic activity of ZnO. This work could provide new insights into the fabrication of noble metal/ZnO-carbon based composites and facilitate their application in environmental protection issues.

Dehydration-Reaction-Based Low-Temperature Synthesis of Amorphous SnOx for High-Performance Perovskite Solar Cells.

The development of methodologies for synthesizing carrier-transporting materials is critical for optoelectronic device fabrication. Amorphous metal oxides have emerged as potential carrier transport materials for perovskite tandem solar cells and flexible electronics due to their ease of fabrication and excellent electronic properties. However, perovskite solar cells employing amorphous metal oxides as the electron-transporting layers (ETLs) remain inefficient. This research describes a moderate dehydration reaction for the low-temperature synthesis of amorphous SnOx. We investigated this amorphous SnOx as the ETL for perovskite solar cells and demonstrated a maximum power conversion efficiency (PCE) of 20.4%, the greatest efficiency ever attained with an amorphous metal oxide ETL produced below 100 °C. Remarkably, the device maintained 85% of its initial efficiency for more than 4800 h. Furthermore, flexible perovskite solar cells based on this amorphous SnOx have a maximum PCE of 11.7%. Finally, this amorphous SnOx was used to fabricate LEDs and exhibited a maximum external quantum efficiency of over 3%.

Highly Reversible Conversion Anodes Composed of Ultralarge Monolithic Grains with Seamless Intragranular Binder and Wiring Network.

Conversion anodes enable a high capacity for lithium-ion batteries due to more than one electron transfer. However, the collapse of the host structure during cycling would cause huge volume expansion and phase separation, leading to the degradation and disconnection of the mixed conductive network of the electrode. The initial nanostructuring and loose spatial distribution of active species are often resorted to in order to alleviate the evolution of the electrode morphology, but at the cost of the decrease of grain packing density. The utilization of ultralarge microsized grains of high density as the conversion anode is still highly challenging. Here, a proof-of-concept grain architecture characterized by endogenetic binder matrix and wiring network is proposed to guarantee the structural integrity of monolithic grains as large as 50-100 µm during deep conversion reaction. Such big grains were fabricated by self-assembly and pyrolysis of a Keggin-type polyoxometalate-based complex with protonated tris[2-(2-methoxyethoxy)-ethyl]amine (TDA-1-H+). The metal-organic precursor can guarantee the firm adherence of numerous Mo-O clusters and nuclei into a highly elastic monolithic structure without evident grain boundaries and intergranular voids. The pyrolyzed TDA-1-H+ not only serves as in situ binder and conductive wire to glue adjacent Mo-O moieties but also acts as a Li-ion pathway to promote sufficient lithiation on surrounding Mo-O. Such a monolithic electrode design leads to an unusual high-conversion-capacity performance (1000 mAh/g) with satisfactory reversibility (reaching at least 750 cycles at 1 A/g). These cycled grains are not disassembled even after undergoing long-term cycling. The conception of the intragranular binder is further confirmed by consolidating the MoO2 porous network after in situ stuffing of MoS2 nanobinders.

Stacking of Tailored Chalcogenide Nanosheets around MoO2-C Conductive Stakes Modulated by a Hybrid POM⊂MOF Precursor Template: Composite Conversion-Insertion Cathodes for Rechargeable Mg-Li Dual-Salt Batteries.

Mg anode has pronounced advantages in terms of high volumetric capacity, resource abundance, and dendrite-free electrochemical plating, which make rechargeable Mg-based batteries stand out as a representative next-generation energy storage system utilized in the field of large-scale stationary electric grid. However, sluggish Mg2+ diffusion in cathode lattices and facile passivation on the Mg anode hinder the commercialization of Mg batteries. Exploring a highly electroactive cathode prototype with hierarchical nanostructure and compatible electrolyte system with the capability of activating both an anode and a cathode is still a challenge. Here, we propose a POM⊂MOF (NENU-5) core-shell architecture as a hybrid precursor template to achieve the stacking of tailored chalcogenide nanosheets around MoO2-C conductive stakes, which can be employed as conversion-insertion cathodes (Cu1.96S-MoS2-MoO2 and Cu2Se-MoO2) for Mg-Li dual-salt batteries. Li-salt modulation further activates the capacity and rate performance at the cathode side by preferential Li-driven displacement reaction in Cu+ extrusible lattices. The heterogeneous conductive network and conformal dual-doped carbon coating enable a reversible capacity as high as 200 mAh/g with a coulombic efficiency close to 100%. The composite cathode can endure a long-term cycling up to 400 cycles and a high current density up to 2 A/g. The diversity of MOF-based materials infused by functional molecules or clusters would enrich the nanoengineering of electrodes to meet the performance demand for future multivalent batteries.

Development of a novel capillary electrophoresis chemiluminescence system for amino acid analysis.

In the present study, a novel peroxyoxalate CE-CL system was developed to achieve high signal stability and sensitivity based on a design of a new interface including a new mixing mode and a new grounding electrode mode. Amino acids fluorescently tagged with dansyl chloride and naphthalene-2,3-dicarboxaldehyde(NDA) were used for the study. Experiment results show this new system is quite effective to separate and detect amine acid with high stability and resolute. The detection limits were 1.1 nmol/L for dansyl-leucine (Leu) and 2.0 nmol/L for dansyl-aspartic acid (Asp). The relative standard deviations of peak height and migration time were in the ranges of 2.3-3.8% and 1.2-1.5%, respectively.