Bi2Te3 nanosheets promoted Pd for ethylene glycol electrooxidation both in the dark and under visible light irradiation.

Ethylene glycol electrooxidation catalyzed by Pd nanoparticles was found to be largely improved by Bi2Te3 nanosheets both in the dark and under visible light irradiation.

[Adsorption Performance and Mechanism of Oxytetracycline in Water by KOH Modified Biochar Derived from Corn Straw].

The pollution control of tetracycline antibiotics in the environment has become a hot topic, and biochar adsorption has become an important technology to remove organic pollutants. Pyrolytic biochars (BC400, BC500, and BC600) were prepared from corn straw and then were modified by KOH to obtain KBC400, KBC500, and KBC600. Among them, KBC400 was selected for secondary pyrolysis activation at 400-600℃ to obtain AKBC400, AKBC500, and AKBC600. The structure characteristics and surface properties of AKBC were also characterized. The adsorption kinetics and thermodynamic characteristics of oxytetracycline hydrochloride (OTC) in the solution by AKBC were investigated using batch experiments. Compared to that of BC400, the specific surface area and pore structure of AKBC were significantly improved, and the aromaticity was also enhanced, resulting in the notable enhancement of the adsorption capacities for OTC. The pseudo-second-order kinetics model could better fit the adsorption process, and AKBC500 had the largest adsorption rate constant and capacity. Both the intraparticle diffusion and film diffusion were the rate-limiting steps. The Langmuir, Freundlich, and Temkin models could fit the adsorption isotherms perfectly. The adsorption of OTC on AKBC was a spontaneous, endothermic, and entropy-increasing process by both physisorption and chemisorption. The pH values in the range of 3.0-7.0 were favorable for the adsorption of OTC by AKBC. The adsorption capacity decreased with the humic acid concentration over 10 mg·L-1. The adsorption mechanism of OTC by AKBC involved pore filling, hydrogen bonding, π-π conjugation, cation-π bond, and strong electrostatic effect. AKBC still had good reusability for OTC removal after five times of regeneration. The obtained AKBC is a potential adsorbent for OTC removal from water due to the good pore structure, high adsorption capacity, and stable adsorption effect.

Recent progress of Ni-based nanomaterials for the electrocatalytic oxygen evolution reaction at large current density.

The precise design and development of high-performing oxygen evolution reaction (OER) for the production of industrial hydrogen gas through water electrolysis has been a widely studied topic. A profound understanding of the nature of electrocatalytic processes reveals that Ni-based catalysts are highly active toward OER that can stably operate at a high current density for a long period of time. Given the current gap between research and applications in industrial water electrolysis, we have completed a systematic review by constructively discussing the recent progress of Ni-based catalysts for electrocatalytic OER at a large current density, with special focus on the morphology and composition regulation of Ni-based electrocatalysts for achieving extraordinary OER performance. This review will facilitate future research toward rationally designing next-generation OER electrocatalysts that can meet industrial demands, thereby promoting new sustainable solutions for energy shortage and environment issues.

A Ni(II) Coordination Polymer as a Multifunctional Luminescent Sensor for Detection of UO22+, Cr2O72-, CrO42- and Nitrofurantoin.

A new Ni coordination polymer [Ni(MIP)(BMIOPE)]n (1) was constructed (BMIOPE = 4,4'-bis(2-methylimidazol-1-yl)diphenyl ether, and H2MIP = 5-methylisophthalic acid), possessing two-dimensional (2D) twofold parallel interwoven net structure with a 44∙62 point symbol. Complex 1 has been successfully obtained based on mixed-ligand strategy. The fluorescence titration experiments revealed that complex 1 could act as multifunctional luminescent sensor to simultaneously detect UO22+, Cr2O72- and CrO42-, and NFT (nitrofurantoin). The limit of detection (LOD) values for complex 1 are 2.86 × 10-5, 4.09 × 10-5, 3.79 × 10-5 and 9.32 × 10-5 M for UO22+, Cr2O72-, CrO42- and NFT. The Ksv values are 6.18 × 103, 1.44 × 104, 1.27 × 104 and 1.51 × 104 M-1 for NFT, CrO42-, Cr2O72- and UO22+. Finally, the mechanism of its luminescence sensing is studied in detail. These results manifest that complex 1 is a multifunctional sensor for sensitive fluorescent UO22+, Cr2O72-, CrO42- and NFT detection.

Sulfadiazine inhibits hydrogen production during sludge anaerobic fermentation by affecting pyruvate decarboxylation.

The overuse and random discharge of antibiotics can cause serious environmental pollution. Sludge acts as a repository for antibiotics, its anaerobic fermentation process will inevitably be affected. This study investigated the effects of a typical antibiotic contaminant, sulfadiazine (SDZ), on the anaerobic fermentation of sludge for hydrogen production. Results demonstrated that the production of hydrogen was significantly inhibited by SDZ, and the inhibition was enhanced with increasing SDZ content. Within 5 days, the cumulative amount of hydrogen with 500 mg SDZ/kg dry sludge was 8.5 mL, which was only 32.2% of that in the control (26.4 mL). Mechanistic investigation showed that the reduced hydrogen production when SDZ existed was mainly attributed to the suppression of pyruvate decarboxylation during the hydrogen production stage, and the diversity of microorganisms, especially the abundance of microorganisms and the activities of key enzymes closely related to hydrogen production were inhibited with SDZ, resulting in less hydrogen accumulation.

Enhanced reductive debromination of decabromodiphenyl ether by organic-attapulgite supported Fe/Pd nanoparticles: Synergetic effect and mechanism.

Effective removal of polybrominated diphenyl ethers (PBDEs) from the environment is essential for the ecosystem and human health. Reductive debromination of PBDEs by nanoscale zerovalent iron (nZVI) has become an important technology. However, the agglomeration and low persistence catalytic activity of nZVI particles have become urgent problems to be improved. Herein, we report the first application of a new organo-attapulgite (OA) supported Fe/Pd nanoparticles (OA-Fe/Pd) composite for decabromodiphenyl ether (BDE209) removal. BDE209 was efficiently removed using OA-Fe/Pd with a reaction rate that was 9.97 times greater than that of the nZVI due to the synergetic effect of support material OA and Pd loading. OA could prevent nZVI particles from agglomeration and adsorb BDE209 molecules to its surface. Pd could supply atomic hydrogen and also prevent the oxidation of nZVI particles. The degradation of BDE209 by OA-Fe/Pd was affected by many factors and followed pseudo first-order kinetics. The degradation of BDE209 by OA-Fe/Pd underwent a stepwise debromination manner with the H-transfer dominant mechanism. BDE209 (25 mg∙L-1) could be degraded to penta-BDEs to diphenyl ether (DE) by 3.0 g∙L-1 OA-Fe/Pd within 240 min under neutral condition. This study provides some inspiration for improving the removal efficiency of PBDEs with nZVI-based materials.

Highly efficient debromination of 4,4'-dibrominated diphenyl ether by organic palygorskite-supported Pd/Fe nanoparticles.

Organic palygorskite (OP)-supported Pd/Fe nanoparticles composite (OP-Pd/Fe) was prepared by stepwise reduction method. The removal capacity of 4,4'-dibrominated diphenyl ether (BDE15) by OP-Pd/Fe was compared with other various materials. For better understanding the possible mechanism, the synthesized and reacted OP-Pd/Fe materials were characterized by TEM, SEM, XRD, and XPS, respectively. The effects of major influencing parameters on the degradation of BDE15 were also studied. Benefit from the synergistic effect of the carrier and bimetallic nanoparticles, BDE15 could be completely debrominated into diphenyl ether (DE) under suitable conditions. A two-stage adsorption/debromination removal mechanism was proposed. The degradation of BDE15 with OP-Pd/Fe was mainly stepwise debromination reaction, and hydrogen transfer mode was assumed as the dominated debromination mechanism. The removal process fitted well to the pseudo first-order kinetic equation. The observed rate constants increased with increasing Pd loading and OP-Pd/Fe dosage while decreased with increasing initial BDE15 concentration, the tetrahydrofuran/water ratio, and the initial pH of the solution. The work provides a new approach for the treatment of PBDEs pollution.

In2S3 nanoparticles coupled to In-MOF nanorods: The structural and electronic modulation for synergetic photocatalytic degradation of Rhodamine B.

Enhancing photocatalytic performance via electronic modulation have attracted much attention for synergetic photocatalytic degradation of antibiotic pollutant. In this study, a new hetero-structured system is raised, which comprises In2S3 coupled to In-MOF and operates as an efficient photocatalyst for RhB degradation. The formation of hetero-structure and occurred electron modulation of In2S3/In-MOF hybrid was confirmed by relevant characterizations. Surprisingly, the In2S3/In-MOF hybrid represented enhanced photocatalytic ability over In-MOF. The photocatalysis of Rhodamine B in presence of In2S3/In-MOF hybrid has achieved 92.2 % degradation.

Synthesis of PtRu alloy nanofireworks as effective catalysts toward glycerol electro-oxidation in alkaline media.

Electro-oxidation of glycerol is a key anodic reaction in direct alcohol fuel cell (DAFCs). Exploring the cost-effective nanocatalysts for glycerol oxidation reaction (GOR) is very important for the development of DAFC, but it is still challenging. In this paper, nanofirework-like PtRu alloy catalyst was successfully synthesized and used for GOR in alkaline medium. Thanks to the unique nanofirework-like structure and synergetic effects, the activity and stability of the as-prepared PtRu alloy nanofireworks (NFs) toward GOR were significantly improved relative to Pt NFs. In particular, the peak current density of GOR catalyzed by the optimized Pt1Ru3 NFs catalyst reached 2412.0 mA mg-1, surpassing that of commercial Pt/C catalyst. This work has important guidance for the design of advanced anode electrocatalysts for fuel cells.

Efficient photocatalytic H2 evolution and Cr(VI) reduction under visible light using a novel Z-scheme SnIn4S8/CeO2 heterojunction photocatalysts.

Semiconductor photocatalysis technology is a promising method for hydrogen production and water pollution treatment. Here, the SnIn4S8/CeO2 (SISC) composites were fabricated by a stirring and calcination method, and the mass ratio of SnIn4S8 to CeO2 was optimized. The 50 wt% SISC heterojunction photocatalyst has the highest visible light catalytic activity. The degradation rate of hexavalent chromium (Cr (VI)) is 98.8% in 75 min of light irradiation, which is 2.48 times that of pure CeO2. Besides, the 50 wt% SISC composite photocatalyst also has the highest photocatalytic hydrogen production efficiency (0.6193 mmol g-1 h-1), which exhibits a higher photocatalytic activity than pure CeO2 and SnIn4S8. The enhanced photocatalytic performance can be attributed to the Z-scheme heterojunction structure between CeO2 and SnIn4S8, which can effectively separate and transfer photo-generated charges, thereby reducing the recombination of photo-generated carriers. We hope this work can provide ideas for constructing Z-scheme heterojunction structures and improving photocatalytic activity under visible light.

Highly efficient activation of peroxymonosulfate by Co3O4/Bi2WO6 p-n heterojunction composites for the degradation of ciprofloxacin under visible light irradiation.

Photocatalytic technology assisted via peroxymonosulfate (PMS) has good potential in water treatment. In this study, the Co3O4/Bi2WO6 composite was constructed via an in-situ calcination process and used to activate PMS for the degradation of ciprofloxacin (CIP) under visible light irradiation. The obtained 5 wt% Co3O4/Bi2WO6(CBWO-2) can highly effectively remove 86.2% CIP within 5 min visible light irradiation in presence of PMS. The excellent degradation performance of Co3O4/Bi2WO6/PMS system can be attributed to the synergistic effect between p-n heterojunction and PMS activation. The conduction band and valence band deviation between Co3O4 and Bi2WO6 were calculated by XPS techniques. Besides, DFT calculations were performed to further confirm the internal structure between Co3O4 and Bi2WO6. This work not only provides an approach to fabricate heterostructures but also indicated that Co3O4/Bi2WO6/PMS/Vis system is a potential environment remediation alternative for the efficient removal of recalcitrant organic compounds from wastewaters.

Novel Z-scheme W18O49/CeO2 heterojunction for improved photocatalytic hydrogen evolution.

The novel Z-scheme heterojunction photocatalyst W18O49/CeO2 was prepared by hydrothermal synthesis. The photocatalytic properties of W18O49/CeO2 were evaluated by photocatalytic hydrogen evolution under visible light. The result shows that the 15 wt% W18O49/CeO2 composite has the best hydrogen production efficiency of about 0.2061 mmol g-1h-1, which was 1.93 times higher than that the obtained pure CeO2. The characterization results demonstrated that the existence of Z-scheme heterojunction structure at the contact interface of W18O49 and CeO2 was the origin of the enhanced photocatalytic performance for hydrogen evolution, which could greatly increase the accumulation of photo-generated electrons and the separation efficiency of charge carrier. In accordance with density functional theory (DFT) calculation, we further confirmed the formation of Z-scheme heterojunction structures. This work is anticipated to expand the ideas for modifying CeO2 semiconductor materials to improve the rate of photocatalytic hydrogen production.

Redox response, antibacterial and drug package capacities of chitosan-α-lipoic acid conjugates.

Chitosan-α-lipoic acid (CS-LA) conjugates were prepared by amino reaction. The methotrexate (MTX) was successfully loaded within CS-LA copolymer by the ring-opening polymerizations of disulfide bond under the action of reducing agent. The obtained copolymer was investigated by fourier transform infrared spectrometer (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and nuclear magnetic resonance (1H NMR) analysis. The ring-opening polymerization process effected on rheological properties were studied. The graft of LA increased the apparent viscosity of CS-LA, and the loaded of MTX by redox reduced its apparent viscosity enormously. The load of MTX under the action of DTT decreased the apparent viscosity and moduli of CS-LA-MTX hydrogel. In dynamic oscillatory experiment, the package of MTX reduced the rigidity of CS-LA and damaged the gel structure of CS-LA. The antimicrobial ability of CS-LA against E. coli was processed by the inhibition zone and growth curves. The modification of LA raised the antibacterial activity of CS-LA. The cytotoxicity assay of CS-LA-MTX to prostate cancer cells (RM-1) was examined. The load of MTX within CS-LA-MTX greatly enhanced the cytotoxicity to RM-1 cells. In summary, CS-LA hydrogel may provide a new copolymer carrier for drug package in food and biomedical application.

Photocatalytic degradation of sulfamethazine using a direct Z-Scheme AgI/Bi4V2O11 photocatalyst: Mineralization activity, degradation pathways and promoted charge separation mechanism.

Z-scheme heterojunction can not only promote the separation of photogenerated carriers, but also retain the strong redox potential of the system, which would greatly improve the photocatalytic performance of catalyst. Herein, a Z-scheme AgI/Bi4V2O11 heterojunction photocatalyst was prepared by a hydrothermal process combined with in situ coprecipitation process. Multiple techniques were employed to investigate the morphology, composition, chemical and electronic properties of the as-prepared samples. The obtained Z-scheme AgI/Bi4V2O11 heterojunction photocatalyst exhibited remarkably enhanced photocatalytic performance towards sulfamethazine (SMZ) degradation under visible light irradiation. Especially, the 20 wt% AgI/Bi4V2O11 composites exhibited the highest photocatalytic activity for sulfamethazine (SMZ) degradation and 91.47% SMZ would be eliminated within 60 min. In comparison with NO3- and SO42-, the presence of Cl- and HCO3- presented more obviously inhibition effects on SMZ degradation. The possible degradation pathways of SMZ were speculated by identifying degradation intermediates. O2-, h+ and OH all involved in the photocatalytic degradation SMZ. The highly enhanced photocatalytic performance might be attributed to form Z-scheme junction between AgI and BVO, which are conducive to the efficient charges separation and maintain high redox potential. This work enriches Bi4V2O11-based Z-scheme heterojunction photocatalytic system and provides a reference for the preparation of effective Z-scheme junction photocatalysts.

The thiolated chitosan: Synthesis, gelling and antibacterial capability.

Chitosan-1-(mercaptomethyl)-cyclopropane acetic acid (CS-MCA) copolymer was synthesized by amino linkage. The obtained copolymer was characterized by FTIR, 1H NMR, XRD, TGA and SEM. Porous and reticulate morphologies were found on the CS-MCA surface. The effects of pH on the rheological properties of CS-MCA were investigated. On the one hand, the apparent viscosity of CS-MCA indicated a shear-thinning behavior. The graft of MCA enhanced the moduli and the maximum elastic properties were observed at pH = 7.00. The addition of dithiothreitol reduced the viscosity and modulus of CS-MCA hydrogel, and the gelation time, temperature and frequency were obtained in dynamic oscillatory tests. The antibacterial effect of CS-MCA against E. coli was investigated for the inhibition zone and bacterial growth curve. These results showed that CS-MCA had better antibacterial ability than chitosan without modification. Therefore, the rheological behavior and functional activities can be applied for the hydrocolloid gels in food and pharmaceutical applications.

Comparison of the physicochemical, rheological, and morphologic properties of chitosan from four insects.

The present work aimed to compare the physicochemical, rheological, and morphologic properties of chitosan extracted from cicada slough, silkworm chrysalis, mealworm, grasshopper and shrimp shells. The physicochemical properties including solubility, fat binding capacity, water binding capacity, ash, viscosity average molecular weight and moisture content of them were determined. The characterization results showed that insect chitosan was quite different from shrimp shell chitosan including thermal stability, rheological characteristics and surface morphology. Crystallinity index values of chitosan from cicada slough, silkworm chrysalis, mealworm, grasshopper and shrimp shells were observed to be 64.8%, 32.9%, 51.9%, 50.1% and 49.1%, respectively. The crystallinity indices of shrimp shell, mealworm and grasshopper chitosan were very close to each other. Flow behavior revealed that chitosan from four insects exhibited the lower viscosity than shrimp shell chitosan. According to dynamic oscillatory analysis, insect chitosan revealed lower modulus values than shrimp shell chitosan. Each of them had a novel structure and different morphologic properties. These results will contribute to increasing potential application of insect chitosan in food and pharmaceutical industries.

Synergistic effect and degradation mechanism on Fe-Ni/CNTs for removal of 2,4-dichlorophenol in aqueous solution.

Fe-Ni bimetallic nanoparticles supported on CNTs (Fe-Ni/CNTs) were synthesized, characterized, and applied for removal of 2,4-dichlorophenol (2,4-DCP) in aqueous solution. The removal performance was enhanced drastically on Fe-Ni/CNTs with respect to monometallic Fe/CNTs. The synergistic effect between Fe-Ni nanoparticles and CNTs has been studied in detail. The research results indicated that the doping of Ni played an important role in promoting the catalytic degradation of 2,4-DCP. And the presence of CNTs not only could effectively reduce the aggregation of nanoparticles but also facilitate the mass transfer of 2,4-DCP and the formation of active atomic hydrogen during the catalytic process. In addition, the removal kinetics of 2,4-DCP by Fe-Ni/CNTs were in agreement with a pseudo-first-order model, and the rate constants were dependent on a number of factors including the initial concentration of 2,4-DCP, the dosage of Fe-Ni/CNTs, pH value of the solution, and doping amount of Ni. The degradation mechanism involved the adsorption by CNTs and catalytic reduction by Fe under the stimulating of Ni, and the preferred dechlorination followed the order of para-Cl > ortho-Cl. The study confirmed that Fe-Ni/CNTs had a potential to be a promising catalytic material for removal of chlorophenol and had a great prospect for practical application.

Screening of antimicrobials in animal-derived foods with desorption corona beam ionization (DCBI) mass spectrometry.

The relatively new technique, desorption corona beam ionization (DCBI), was coupled with an ion-trap mass spectrometer for the rapid detection of 10 antimicrobials in animal-derived food. Under positive ion mode, 10 common antimicrobials were identified without prior sample preparation. With simple pre-treatment, semi-quantification based on peak area was achieved. There was a good correlation (R2 > 0.99) in the rational linear ranges (1-3 orders of magnitude) for all 10 target analytes. Compared with a conventional liquid chromatographic method, the DCBI-MS method was highly sensitive; e.g., roxithromycin was detected at 0.02 µg/g, whereas the value was 0.2 mg/kg in the European Union Commission Regulation (No 37/2010) and 0.3 µg/mL in a recently reported LC method. The proposed method allowed for the simple, rapid, sensitive and specific detection of antimicrobials in animal-derived foods. Our approach could be used for other atmospheric pressure chemical ionization (APCI) related ambient mass spectrometry methods to detect other compounds.

Binding mechanism of five typical sweeteners with bovine serum albumin.

In this work, the interactions between bovine serum albumin (BSA) and five sweeteners including aspartame (APM), acesulfame (AK), sucralose (TGS), sodium cyclamate (SC), and rebaudioside-A (REB-A) have been studied by multispectroscopic techniques, and molecular simulation in order to provide much useful information for the application of new and safer artificial sweeteners. Fluorescence quenching assays indicated that the formation of complexes between sweeteners and BSA mainly induced the fluorescence quenching of protein and the binding site number were about 1 indicting that there is one mainly binding site of APM, AK, TGS, SC, or REB-A in domain of BSA with relatively weak interactions. Molecular modeling results indicated that hydrogen bonding interactions were the mainly binding forces of sweeteners with BSA. Circular dichroism spectra indicated that APM and REB-A obviously induced the secondary structure changes of BSA. The presence of APM increased the fraction of α-Helix of BSA from 65.4% to 73.8%, while the presence of REB-A resulted in decreasing the fraction of α-helix of BSA from 65.4% to 51.2%. The melting temperature studies showed that these five sweeteners except REB-A act as stabilizers to increase the thermal stability of BSA during the thermal denaturation process. In addition, AK, TGS, and SC obviously increased the esterase-like activity of BSA, and such loss of activity of BSA induced by APM and REB-A.

Adsorption behavior of Ni(II) onto activated carbons from hide waste and high-pressure steaming hide waste.

This work reports the preparation and adsorption of Ni(II) via activated carbons which produced from hide waste (HWAC) and high-pressure steaming hide waste (HWSAC) with potassium silicate as the activating agent. The best preparation condition for HWAC and HWSAC was the activation temperature of 700 °C using an impregnation ratio of 2:1. Both of them were characterized by N2 adsorption/desorption isotherms, SEM and FT-IR spectra. The surface area of HWAC and HWSAC was 1804.37 and 1361.26 m2/g, respectively. Despite the surface area of HWAC being larger than that of HWSAC, but the adsorption capacity of Ni(II) for HWAC was lower than that for HWSAC. Furthermore, the adsorption capacity of Ni(II) for both HWAC and HWSAC showed pH-dependent behavior and increased with the increase in pH value, which can be attributed to the functional groups of HWAC and HWSAC materials through the electrostatic attraction. The adsorption data for HWAC and HWSAC were fitted with four isotherm models (Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich) and four kinetic models (pseudo-first order model, pseudo-second order model, intra-particle diffusion and Elovich equation), indicating that Langmuir isotherm and Pseudo-second order model fitted well with high coefficient of determination (R2 > 0.99) for both the two adsorbents. The positive enthalpy of adsorption (ΔH) and free energy of adsorption (ΔG) indicate a spontaneous and endothermic nature of the process. These results demonstrated that activated carbon can be prepared from hide waste which could remove heavy metal such as Ni(II) effectively.