Appropriate oxygen vacancies and Mo-N bond synergistically modulate charge transfer dynamics of MoO3-x/S-CN for superior photocatalytic disinfection: Unveiling synergistic effects and disinfection mechanism.

Highly efficient charge transfer is a critical factor to modulate the photocatalytic activity. However, the conscious modulation of charge transfer efficiency is still a great challenge. Herein, a novel interfacial Mo-N bond and appropriate oxygen vacancies (OVs) modulated S-scheme MoO3-x/S-CN heterojunction was rationally fabricated for efficient photocatalytic disinfection. The results of characterizations and density functional theory (DFT) calculations suggested that the enhanced charge transfer dynamics is ascribed to the optimizing oxygen vacancies density and forming interfacial Mo-N bond. It can improve charge transfer efficiency from 36.4% (MoO3-x) to 52.5% (MoO3-x/S-CN) and produce more reactive oxygen species (ROS), achieving entirely inactivate of 7.60-log E. coli and S. aureus within 50 min and 75 min. Besides, MoO3-x/S-CN can well resist the disturbance from the coexisting substances, and can be applied in a wide pH range, and even authentic water bodies. Monitoring of bacterial antioxidant systems and membrane integrity revealed that bacterial inactivation begins with the oxidation of cell membrane and dies from leakage of intracellular substances and destruction of cell structure. This work provides an inspiration on consciously modulating S-scheme charge transfer efficiency by optimizing oxygen vacancies density and atomic-level interface control for promoting the photocatalytic antibacterial activity.

Insights into the role of reactive oxygen species in photocatalytic H2O2 generation and OTC removal over a novel BN/Zn3In2S6 heterojunction.

Developing photocatalysts with superior performance to generate hydrogen peroxide (H2O2) and degrade oxytetracycline (OTC) is an effective strategy for the treatment of energy crisis and water purification. Herein, BN nanosheets were anchored onto the Zn3In2S6 microspheres for the research. Experimental and density functional theory (DFT) results demonstrate that due to different work functions and unique 2D/2D contact, the electron is spatially separated in BN/Zn3In2S6 nanocomposite, which increases the electron transfer efficiency from 43.7% (Zn3In2S6) to 55.6% (BN/ZIS-4). As a result, BN/ZIS-4 with optimal ratio of BN and Zn3In2S6 exhibits the highest OTC degradation efficiency (84.5%) and H2O2 generation rate (115.5 µmol L-1) under visible light illumination, which is 2.2 and 2.9 times than that of pristine Zn3In2S6. H2O2 generation is dominated by two pathways: two-step single-electron process (O2 → ∙O2- → H2O2) and another way (O2 → ∙O2- → 1O2 → H2O2). In the process of degrading OTC, ∙O2-, 1O2 and ∙OH are regarded as the main active species. This work offers a new insight for designing efficient, stable and reusable photocatalysts to solve current environmental conundrums.

Influence of Electronic Modulation of Phenanthroline-Derived Ligands on Separation of Lanthanides and Actinides.

The solvent extraction, complexing ability, and basicity of tetradentate N-donor 2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-1,10-phenanthroline (CyMe4-BT- Phen) and its derivatives functionalized by Br, hydroxyphenyl, nitryl were discussed and compared. It was demonstrated that four BTPhen ligands are able to selectively extract Am(lll) over Eu(lll). It was notable that the distribution ratio of 5-nitryl-CyMe4-BTPhen for Eu(lll) was suppressed under 0.02, which was much lower compared to DEu(lll) = 1 by CyMe4-BTPhen. The analysis of the effect of the substituent on the affinity to lanthanides was conducted by UV/vis and fluorescence spectroscopic titration. The stability constants of various ligands with Eu(lll) were obtained by fitting titration curve. Additionally, the basicity of various ligands was determined to be 3.1 ± 0.1, 2.3 ± 0.2, 0.9 ± 0.2, 0.5 ± 0.1 by NMR in the media of CD3OD with the addition of DClO4. The basicity of ligands follows the order of L1 > L2 > L3 > L4, indicating the tendency of protonation decreases with the electron-withdrawing ability increase.

Metal-organic framework-derived CuCo/carbon as an efficient magnetic heterogeneous catalyst for persulfate activation and ciprofloxacin degradation.

Herein, the authors synthesis an efficient and easily recycled CuCo/C catalyst through one-step carbonization of Cu@Co-MOF-71 (Abbreviated as Cu@Co-MOF in this work) precursor. The prepared CuCo/C has a high degradation efficiency of 90% for ciprofloxacin (CIP) by activating PMS in a wide value of pH 3-9 within 30 min. After pyrolysis, the carbon matrix as a dispersant can promote the highly uniform distribution of active metals. Additionally, the CIP removal efficiency was 85% after four cycles and the catalyst was easily separated from the solution by using magnets, showing the good stability and reusability. To further study the superiority of CuCo/C activated PMS in degrading CIP, the factors such as pH, the dosage of PMS and catalyst, temperature, inorganic ions and pollutant (CIP) concentration were investigated. Furthermore, the Liquid chromatography-mass spectrometry (LC-MS) was utilized to analyze the intermediate products and possible degradation pathways of CIP. Typically, the quenching experiments and electron paramagnetic resonance (EPR) technology were investigated to confirm the main reaction species including SO4▪-, OH▪ and O2▪- radicals as well as nonradical (1O2). This work put forward a simple method for synthesis of metal-organic framework (MOF) derived catalysts and its application in treatment of organic pollutants.

Integrating the Z-scheme heterojunction and hot electrons injection into a plasmonic-based Zn2In2S5/W18O49 composite induced improved molecular oxygen activation for photocatalytic degradation and antibacterial performance.

The semiconductor-based photocatalysts with local surface plasmon resonance (LSPR) effect can extend light response to near-infrared region (NIR), as well as promote charge-carriers transfer, which provide a novel insight into designing light-driven photocatalyst with excellent photocatalytic performance. Here, we designed cost-effective wide-spectrum Zn2In2S5/W18O49 composite with enhanced photocatalytic performance based on a dual-channel charge transfer pathway. Benefiting from the synergistic effect of Z-scheme heterostructure and unique LSPR effect, the interfacial charge-carriers transfer rate and light-absorbing ability of Zn2In2S5/W18O49 were enhanced significantly under visible and NIR (vis-NIR) light irradiation. More reactive oxygen species (ROS) were formed by efficient molecular oxygen activation, which were the critical factors for both Escherichia coli (E. coli) photoinactivation and tetracycline (TC) photodegradation. The enhancement of molecular oxygen activation (MOA) ability was verified via quantitative analyses, which evaluated the amount of ROS through degrading nitrotetrazolium blue chloride (NBT) and p-phthalic acid (TA). By combining theoretical calculations with diverse experimental results, we proposed a credible photocatalytic reaction mechanism for antibiotic degradation and bacteria inactivation. This study develops a new insight into constructing promising photocatalysts with efficient photocatalytic activity in practical wastewater treatment.

2D/2D Heterojunction systems for the removal of organic pollutants: A review.

Photocatalysis is considered to be an effective way to remove organic pollutants, but the key to photocatalysis is finding a high-efficiency and stable photocatalyst. 2D materials-based heterojunction has aroused widespread concerns in photocatalysis because of its merits in more active sites, adjustable band gaps and shorter charge transfer distance. Among various 2D heterojunction systems, 2D/2D heterojunction with a face-to-face contact interface is regarded as a highly promising photocatalyst. Due to the strong coupling interface in 2D/2D heterojunction, the separation and migration of photoexcited electron-hole pairs are facilitated, which enhances the photocatalytic performance. Thus, the design of 2D/2D heterojunction can become a potential model for expanding the application of photocatalysis in the removal of organic pollutants. Herein, in this review, we first summarize the fundamental principles, classification, and strategies for elevating photocatalytic performance. Then, the synthesis and application of the 2D/2D heterojunction system for the removal of organic pollutants are discussed. Finally, the challenges and perspectives in 2D/2D heterojunction photocatalysts and their application for removing organic pollutants are presented.

In suit constructing 2D/1D MgIn2S4/CdS heterojunction system with enhanced photocatalytic activity towards treatment of wastewater and H2 production.

A novel visible-light-driven 2D/1D MgIn2S4/CdS catalyst with heterostructure was fabricated for sewage treatment and energy conversion. In this study, MIS/CdS-0.3 heterostructure catalyst displayed the remarkable photocatalytic performance, which could reduce about 100% of Cr(VI) within 30 min and decompose approximately 95.98% of oxytetracycline (OTC) after 60 min. Meanwhile, the degradation details and possible decomposition pathways for OTC solution were further verified by 3D EEM and LC-MS. Moreover, the as-obtained 2D/1D MgIn2S4/CdS hybrid composites signally promoted the hydrogen evolved in the light illumination at 420 nm. Meanwhile, some consequences based on various characterization technologies confirmed that the significant photo-induced charge separation rate is a crucial factor in the enhancement of photocatalytic capacity. The intimate contact and the formation of heterostructure between 2D MgIn2S4 nanosheets and 1D CdS nanorods with matched band gaps were beneficial for charge migration. Moreover, the band structures and the density of states (DOS) of MgIn2S4 and CdS were obtained based on density functional theory (DFT). In addition, the results of cycling experiments, XRD spectra and PL showed that the composition and performance of the composite are well-maintained, suggesting the great recyclability and stability. This work indicated that developing a 2D/1D heterostructure photocatalyst offers a cracking approach to enhance the photocatalytic property of semiconductor-based catalysts for pollutant removal and the generation of clean energy.

Fabrication of visible-light-driven silver iodide modified iodine-deficient bismuth oxyiodides Z-scheme heterojunctions with enhanced photocatalytic activity for Escherichia coli inactivation and tetracycline degradation.

At present, various organic pollutants and pathogenic microorganisms presented in wastewater have severely threatened aquatic ecosystem and human health. Meanwhile, semiconductor photocatalysis technology for water purification has attracted increasingly significant attention. Herein, we successfully constructed a series of novel visible-light-driven (VLD) Bi4O5I2/AgI hybrid photocatalysts with different AgI amounts. Compared with pristine AgI and Bi4O5I2, Bi4O5I2/AgI with the optimal AgI contents exhibited remarkably enhanced photocatalytic performance in probe experiment for Escherichia coli (E. coli) disinfection and tetracycline (TC) degradation. The efficiency for TC degradation and E. coli inactivation reached 82% and 100% in 30 min, respectively. The enhanced electron-hole separation efficiency was responsible for improved photocatalytic activity. In addition, the destruction process of the chemical structure of TC molecules was further investigated by three-dimensional excitation-emission matrix fluorescence spectra (3D EEMs). The activity and crystal phase of the catalysts did not change significantly after four cycles, demonstrating their excellent recyclability and stability of catalysts. The Ag+ ion leaking experiments, radical trapping experiments and ESR tests demonstrated that OH, O2- and h+ were the main active species in photocatalytic disinfection processes. Furthermore, the photocatalytic mechanism of Bi4O5I2/AgI nanomaterials was discussed in detail in conjunction with the energy band structure, and a reasonable Z-scheme interfacial charge transfer mechanism was proposed. This work is expected to provide an efficient water disinfection method.

Comparative Proteomic Analysis of Three Gelatinous Chinese Medicines and Their Authentications by Tryptic-digested Peptides Profiling using Matrix-assisted Laser Desorption/Ionization-time of Flight/Time of Flight Mass Spectrometry.

BACKGROUND: Gelatinous Chinese medicines (GCMs) including Asini Corii Colla, Testudinis Carapacis ET Plastri Colla, and Cervi Cornus Colla, were made from reptile shell or mammalian skin or deer horn, and consumed as a popular tonic, as well as hemopoietic and hemostatic agents. Misuse of them would not exert their functions, and fake or adulterate products have caused drug market disorder and affected food and drug safety. GCMs are rich in denatured proteins, but insufficient in available DNA fragments, hence commonly used cytochrome c oxidase I barcoding was not successful for their authentication. OBJECTIVE: In this study, we performed comparative proteomic analysis of them and their animal origins to identify the composition of intrinsic proteins for the first time. MATERIALS AND METHODS: A reliable and convenient approach was proposed for their authentication, by the incorporation of sodium dodecyl sulfate-polyacrylamide gel electrophoresis, two-dimensional electrophoresis, and matrix-assisted laser desorption/ionization-time of flight/time of flight mass spectrometry (MALDI-TOF/TOF-MS). RESULTS: A total of 26 proteins were identified from medicinal parts of original animals, and GCMs proteins presented in a dispersive manner in electrophoresis analyses due to complicated changes in the structure of original proteins caused by long-term decoction and the addition of ingredients during their manufacturing. In addition, by comparison of MALDI-TOF/TOF-MS profiling, 19 signature peptide fragments originated from the protein of GCM products were selected according to criteria. CONCLUSION: These could assist in the discrimination and identification of adulterates of GCMs and other ACMs for their form of raw medicinal material, the pulverized, and even the complex. SUMMARY: Comparative proteomic analysis of three gelatinous Chinese medicines was conducted, and their authentications were based on tryptic-digested peptides profiling using matrix-assisted laser desorption/ionization-time of flight/time of flight mass spectrometry. Abbreviations used: GCMs: Gelatinous Chinese medicines, COI: Cytochrome c oxidase I, SDS-PAGE: Sodium dodecyl sulfate polyacrylamide gel electrophoresis, 2-DE: Two-dimensional electrophoresis, MALDI-TOF/TOF-MS: Matrix-assisted laser desorption/ionization-time of flight/time of flight mass spectrometry, LC: Liquid chromatography, ChP: Chinese Pharmacopoeia, HPLC: High performance liquid chromatography, LC-ESI+-MS: Liquid chromatography-electro spray ionization-mass spectrometry, IEF: isoelectric focusing, HCCA: α-Cyano-4-hydroxycinnamic acid.

Effects of comprehensive function of factors on retention behavior of microparticles in gravitational field-flow fractionation.

Gravitational field-flow fractionation (GrFFF) is a useful technique for separation and characterization for micrometer-sized particles. Elution behavior of micrometer-sized particles in GrFFF was researched in this study. Particles in GrFFF channel are subject to hydrodynamic lift forces (HLF), fluid inertial forces and gravity, which drive them to different velocities by carrier flow, resulting in a size-based separation. Effects of ionic strength, flow rate and viscosity as well as methanol were investigated using polystyrene latex beads as model particles. This study is devoted to experimental verification of the effect of every factor and their comprehensive function. All experiments were performed to show isolated influence of every variable factor. The orthogonal design test was used to evaluate various factors comprehensively. Results suggested that retention ratio of particles increases with increasing flow rate or the viscosity of carrier liquid by adjusting external forces acting on particles. In addition, retention ratio increases as ionic strength decreases because of decreased electrostatic repulsion between particles and channel accumulation wall. As far as methanol, there is no general trend due to the change of both density and viscosity. On the basis of orthogonal design test it was found that viscosity of carrier liquid plays a significant role in determining resolution of micrometer-sized particles in GrFFF.