Highly efficient activation of peroxymonosulfate by ZIF-67 anchored cotton derived for ciprofloxacin degradation.

Metal-organic framework (MOF) and MOF-derived materials have attracted extensive research interest as environmental catalysts. In this study, a composite material (ZIF-67/CCot-8) was successfully prepared using cotton fiber as a substrate and growing ZIF-67 in situ. This material exhibited excellent catalytic performance and significantly improved the efficiency of antibiotics degradation. ZIF-67/CCot-8 at a concentration of 0.05 g/L, combined with 0.2 mM peroxymonosulfate (PMS), removed approximately 97% of ciprofloxacin (CIP) and 99% of tetracycline and sulfamethoxazole within 15 min. The high catalytic efficiency of this catalyst is mainly attributed to the uniform distribution of ZIF-67-derived nanoparticles on the surface of the cotton fibers, providing abundant active sites and thereby significantly enhancing the efficiency of antibiotics degradation. Radical quenching experiments and electron paramagnetic resonance (EPR) analyses revealed that sulfate radicals (SO4•-) and singlet oxygen (1O2) were the main active species. Mass spectrometry (MS) was used to elucidate the CIP degradation pathway. The growth of the roots and stems of soybean sprouts in different water environments (tap water, treated water, and untreated water) was also observed. The results demonstrated a significant improvement in the inhibition of plant growth in the post-degradation CIP solution, indicating a substantial reduction in the toxicity of the degraded aqueous solution. To validate the practicality of the ZIF-67/CCot-8/PMS system, a continuous-flow water-treatment device was designed. This system removed 98% of the CIP solution within 180 min, demonstrating its excellent durability. This study presents a potential pathway for effective antibiotics removal using MOF-derived materials.

Enhanced hydrogen production via urea electrolysis over Ni-NiO electrodeposited on Ti mesh.

The sluggish kinetics of anodic oxygen evolution reaction (OER) is regarded as the main bottleneck for ineffective hydrogen production efficiency, limiting the industrial application of electrochemical water splitting. Substituting the OER by urea electrooxidation reaction (UOR) and simultaneously developing highly active and economical bifunctional electrocatalyst for UOR and hydrogen evolution reaction (HER) is a promising method to realize energy-saving hydrogen production and urea-rich wastewater abatement. Herein, self-supporting Ni-NiO film grown on Ti mesh (Ni-NiO/TM) was successfully prepared by a facile cathodic electrodeposition method with using nickel acetate as the only raw material. Electrodeposition process was optimized by modulating the electrodeposition time and potential. x-ray diffraction, scanning electron microscopy, transmission electron microscopy, x-ray photoelectron spectroscopy and Raman characterization revealed the optimized Ni-NiO/TM was comprised of crystalline Ni and amorphous NiO and its morphology exhibited nanosphere structure, assembled by nanosheets. Ni-NiO/TM sample prepared under the potential of -1.5 V and deposition time of 10 min illustrated the lowest UOR potential of 1.34 V at 50 mA cm-2and robust stability, superior to the recently reported literatures. Furthermore, the HER potential was only -0.235 V to drive the current density of 50 mA cm-2. The cell voltage of urea-assisted electrolysis for hydrogen production in Ni-NiO/TM||Ni-NiO/TM two-electrode system only required 1.56 V to deliver 50 mA cm-2, obviously lower than that (>1.72 V) for overall water splitting. This work demonstrated the potential of Ni-based material as bifunctional electrocatalyst for energy-saving H2production by urea-rich wastewater electrolysis.

Effects and mechanism on cadmium adsorption removal by CaCl2-modified biochar from selenium-rich straw.

As every-one knows, cadmium contamination poses a significant and permanent threat to people and aquatic life. Therefore, research on how to remove cadmium from wastewater is essential to protect the natural environment. In this study, agricultural and forestry waste straw sprayed with selenium-enriched foliar fertilizer was prepared as biochar, which was altered by calcium chloride (CaCl2) to remove Cd2+ from water. The outcomes demonstrated that biochar generated by pyrolysis at 700 °C (BC700) had the best adsorption effect. Secondly, pseudo-second-order kinetics and Langmuir adsorption models were used to predict the Cd2+ adsorption. Finally, electrostatic adsorption, ion exchange, and complexation of oxygen functional groups (OFGs) were demonstratedto be the main adsorption mechanisms. These conclusions indicate that selenium-rich straw biochar is a novel adsorbent for agroforestry waste recovery. Meanwhile, this work will offer a promising strategy for the overall utilization of rice straw.

Performance and mechanism of FeS2/FeSxOy as highly effective Fenton-like catalyst for phenol degradation.

Developing a highly efficient Fenton-like catalyst working in a wide pH range is imperative to accomplish its practical wastewater treatment. Herein, FeS2/FeSxOy catalyst was synthesized by hydrothermal-solvothermal vulcanization with thioacetamide as a sulfur source. Characterization results confirmed FeS2/FeSxOy consisted of pyrite, kornelite, and szomolnokite. FeS2/FeSxOy exhibited superior catalytic activity toward H2O2 activation with more than 96% phenol removal within 5 min in pH 3.0 ∼ 8.0 at 30°C. Radical scavenging experiment and EPR analysis revealed both hydroxyl radicals (·OH) and superoxide anion radicals (O2·-) anticipated in phenol elimination, but ·OH played a dominant role. The detailed degradation experiments and density functional theory (DFT) calculation confirmed the vital role of FeS2 in enhancing phenol abatement. This study not only developed a highly active catalyst for H2O2 activation but also theoretically analyzed the FeS2 function in depth, which provided a guide for designing a highly efficient Fenton-like catalyst.

Boosting visible light photocatalysis in BiOI/BaFe12O19 magnetic heterojunction.

Many previous studies have underestimated the role of magnetic components in improving photocatalytic performance. It is significance to explore the migration mechanism of photoinduced carriers in magnetic heterojunction. Here, a magnetic heterojunction, BiOI/BaFe12O19, was synthesized by a simple preparation method. The optimal synthesis conditions and photocatalytic reaction conditions were explored. The growth mechanism of bismuth iodide oxide (BiOI) was elaborated by introducing a micromagnetic field stemming from barium ferrite (BaFe12O19). The electrochemical impedance spectroscopy (EIS), Mott-Schottky curve (MS), transient fluorescence spectrometer (PL), and photocurrent response plot (i ~ t) tests indicated that the BiOI/BaFe12O19 possessed a higher transfer capacity of electrons, higher separation efficiency of photoinduced carriers, stronger photocurrent response, and higher carriers density, compared with pure BiOI. The ultraviolet-visible diffuse reflectance spectrophotometer (UV-vis DRS), electron paramagnetic resonance spectrometer (EPR), MS, and quenching experiments revealed band structure configuration and migration mechanism of photoinduced carriers. The enhancement mechanism of photocatalysis and photocatalytic reaction mechanism was clearly proclaimed in BiOI/BaFe12O19 catalytic system.

Boosting catalytic activity of SrCoO2.52 perovskite by Mn atom implantation for advanced peroxymonosulfate activation.

Material-enhanced heterogeneous peroxymonosulfate (PMS) activation for degradation of antibiotic in water has attracted intensive attention. However, one challenge is the electron transfer efficiency from the material to PMS for reactive oxygen species (ROS) production. Considering that the B-sites of perovskite oxides are closely associated with the catalytic performance, partial substitution of the B-sites of perovskite oxides can enhance the redox cycle of metals. Consequently, adjusting the ratio of each element at the B site can introduce oxygen vacancies on the surface of perovskite. Herein, a method was developed in which manganese (Mn) partially substitutes B-sites to modify surface properties of SrCoO2.52 perovskite oxides, resulting in the enhancement of catalytic activity. In degradation kinetics studies using SrCoMnO3-δ-0.5/PMS (SrCoMnO3-δ-0.5 denotes that the molar substitution of Mn at the B site of SrCoO2.52 perovskite oxide is 0.5) reaction system and sulfamethoxazole (SMX) as the target pollutant, it was found that the reaction rate constant (kobs) is 0.287 min-1 which is 2.4 times that of SrCoO2.52/PMS system. Experimental and theoretical analyses revealed that Mn-O covalent bonding governs the intrinsic catalytic activity of SrCoMnO3-δ-0.5 perovskite oxides. The Mn sites exhibits stronger adsorption energy with PMS than the Co sites, facilitating the breaking of O-O bond. Simultaneously, oxygen vacancies and surface adsorbed oxygen species have a synergistic effect for PMS adsorption. This work can provide a potential route in developing advanced catalysts based on manipulation of the B-sites of perovskite oxides for PMS activation.

Peroxymonosulfate activation using a composite of copper and nickel oxide coated on SBA-15 for the removal of sulfonamide antibiotics.

The sluggish Ni(II)/Ni(III) redox cycle does not benefit perxymonosulfate (PMS) activation for recalcitrant pollutant degradation. To solve this problem, a heterogeneous catalyst, Cu0.2Ni0.8O/SBA-15 (CNS), was constructed to activate PMS for decomposing two sulfonamide antibiotics, sulfachlorpyridazine (SACP) and sulfapyridine (SAP). SACP and SAP were completely degraded over Cu0.2Ni0.8O/SBA-15/PMS (CNSP) after 90 min. O2.- was the dominant active species involved in the degradation of SACP and SAP. Structural analysis and elemental valence state observations indicated that Cu(Ⅰ) provided electrons through Cu-O-Ni bonds to realize the charge compensation for Ni(Ⅲ) in the CNSP system. Thus, the in situ Cu(I)/Cu(II) promoting the Ni(II)/Ni(III) cycle could accelerate the PMS activation. This work provides new insights into the electron transfer between transition metals and the charge compensation mechanism for PMS activation. The degradation mechanism was proposed based on the XPS results before and after the reaction, a radical quenching test, and an EPR test. Combined with the SACP and SAP degradation intermediates identified by LC-MS, we suggest that the choice of treatment process depends on the occurrence of a steric hindrance effect between the molecular structure of the degradation target and free radicals.

Enhanced peroxymonosulfate activation over heterogeneous catalyst Cu0.76Co2.24O4/SBA-15 for efficient degradation of sulfapyridine antibiotic.

The largest source of resistant bacteria or viruses is the overuse and misuse of antibiotics in humans and animals. These resistant bacteria or viruses may evolve into superbacteria or superviruses, which causes global plague. Therefore, it is significant to find a highly efficiency and low-cost method to eliminate antibiotics in water environment from inappropriate discharge. Here, a highly active and highly stable heterogeneous catalyst, Cu0.76Co2.24O4/SBA-15 (CCS) was prepared for peroxymonosulfate (PMS) activation in aim of decomposing persistent sulfapyridine (SPD). The reaction mechanism was thoroughly investigated via in situ quenching test and in situ electron paramagnetic resonance. Four reactive species, SO4·-, O2·-, 1O2 and ·OH were generated in Cu0.76Co2.24O4/SBA-15/PMS (CCSP) system. The SO4·- and O2·- were dominant active species responsible for SPD degradation. Co(Ⅱ)↔Co(Ⅲ)↔Co(Ⅱ) redox reaction cycle was constructed due to the different redox potential of Co(Ⅱ)/Co(Ⅲ), HSO5-/SO4∙-, and HSO5-/SO5∙-. Interestingly, Cu(Ⅰ) could urge the redox reaction cycle for PMS activation to be more thermodynamically feasible. Therefore, CCS possessed a highly catalytic activity and excellent stability. Meanwhile, the anions interference test indicated Cl-, NO3-, HCO3-, and H2PO4- had almost no inhibitory effect on SPD degradation over this catalytic system. We sincerely expected that this catalyst system would be applied extensively into antibiotics degradation in real water bodies.

Three-dimensional Nanoporous Cu-Doped Ni Coating as Bifunctional Electrocatalyst for Hydrazine Sensing and Hydrogen Evolution Reaction.

Developing a cost-effective and efficient bifunctional electrocatalyst with simple synthesis strategy for hydrazine sensing and H evolution reaction (HER) is of utmost importance. Herein, a three-dimensional porous Cu-doped metallic Ni coating on Ti mesh (Ni(Cu) coating/TM) was successfully electrodeposited by a facile electrochemical method. Electrochemical etching of the electrodeposited Ni(Cu) coating with metallic Ni and Cu mixed phase on a Ti mesh contributed to the formation of a three-dimensional porous Cu-doped metallic Ni coating. Owing to the large specific surface area and enhanced electroconductivity caused by the porous structure and Cu doping, respectively, the developed Ni(Cu) coating/TM exhibited superior hydrazine sensing performance and electrocatalytic activity toward hydrogen evolution reaction (HER). The Ni(Cu) coating/TM electrode presented a good sensitivity of 3909µA mM-1cm-2and two relatively broad linear ranges from 0.004 mM to 2.915 mM and from 2.915 mM to 5.691 mM as well as a low detection limit of 1.90µM. In addition, the Ni(Cu) coating/TM required a relatively low HER overpotential of 140 mV to reach -10 mA cm-2and exhibited robust durability in alkaline solution. The excellent hydrazine electrooxidation and HER performance guarantee its promising application in hydrazine detection and energy conversion.

Effect of Radiation-Induced Cross-Linking on Thermal Aging Properties of Ethylene-Tetrafluoroethylene for Aircraft Cable Materials.

The effects of electron beam irradiation on ethylene-tetrafluoroethylene copolymer (ETFE) were studied. Samples were irradiated in air at room temperature by a universal electron beam accelerator for various doses. The effect of irradiation on samples and the cross-linked ETFE after aging were investigated with respect to thermal characteristics, crystallinity, mechanical properties, and volume resistivity using thermo-gravimetric analysis (TGA), differential scanning calorimeter (DSC), universal mechanical tester, and high resistance meter. TGA showed that thermal stability of irradiated ETFE is considerably lower than that of unirradiated ETFE. DSC indicates that crystallinity is altered greatly by cross-link. The analysis of mechanical properties, fracture surface morphology, visco-elastic properties and volume resistivity certify radiation-induced cross-linking is vital to aging properties.

Visible-Light-Driven Photocatalytic Activity of Magnetic BiOBr/SrFe12O19 Nanosheets.

Magnetic BiOBr/SrFe12O19 nanosheets were successfully synthesized using the hydrothermal method. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), and UV-visible diffused reflectance spectra (UV-DRS), and the magnetic properties were tested using a vibration sample magnetometer (VSM). The as-produced composite with an irregular flaky-shaped aggregate possesses a good anti-demagnetization ability (Hc = 861.04 G) and a high photocatalytic efficiency. Under visible light (λ > 420 nm) and UV light-emitting diode (LED) irradiation, the photodegradation rates of Rhodamine B (RhB) using BiOBr/SrFe12O19 (5 wt %) (BOB/SFO-5) after 30 min of reaction were 97% and 98%, respectively, which were higher than that using BiOBr (87%). The degradation rate of RhB using the recovered BiOBr/5 wt % SrFe12O19 (marked as BOB/SFO-5) was still more than 85% in the fifth cycle, indicating the high stability of the composite catalyst. Meanwhile, after five cycles, the magnetic properties were still as stable as before. The radical-capture experiments proved that superoxide radicals and holes were main active species in the photocatalytic degradation of RhB.

Synthesis of α-Fe2O3/Bi2WO6 layered heterojunctions by in situ growth strategy with enhanced visible-light photocatalytic activity.

Layered heterojunction structure with larger interface region for electron migration has attracted much attention in recent years. In this work, layered α-Fe2O3/Bi2WO6 heterojunctions with strong interlayer interaction were successfully synthesized through a facile in situ growth method. The strong interaction between α-Fe2O3 and Bi2WO6 had resulted in excellent photoelectrochemical performance. It was found that such structure promoted the interfacial photogenerated charges separation according to EIS and Tafel analysis, except for the expansion of visible-light absorption range. PL and TRPL characterizations further demonstrated that the recombination ratio of photoexcited electron-hole pairs was greatly reduced. The toluene photocatalytic degradation tests had showed that α-Fe2O3/Bi2WO6 composites exhibited much well activity under visible-light irradiation. Especially, 4%-Fe2O3/Bi2WO6 sample displayed the highest photocatalytic activity, which was around 3 and 4 times higher than that of pure Bi2WO6 and α-Fe2O3. Based on ESR results and free radical trapping experiments, hydroxyl radicals (·OH) and holes (h+) were regarded as the main active species. The establishment of Fe2O3/Bi2WO6 with layered heterojunctions could provide new insights into the construction of novel photocatalysts.

Dy(III) Doped BiOCl Powder with Superior Highly Visible-Light-Driven Photocatalytic Activity for Rhodamine B Photodegradation.

Dy-doped BiOCl powder photocatalyst was synthesized A one⁻step coprecipitation method. The incorporation of Dy3+ replaced partial Bi3+ in BiOCl crystal lattice system. For Rhodamine B (RhB) under visible light irradiation, 2% Dy doped BiOCl possessed highly efficient photocatalytic activity and photodegradation efficiency. The photodegradation ratio of RhB could reach 97.3% after only 30 min of photocatalytic reaction; this was more than relative investigations have reported in the last two years. The main reason was that the 4f electron shell of Dy in the BiOCl crystal lattice system can generate a special electronic shell structure that facilitated the transfer of electron from valance band to conduction band and separation of the photoinduced charge carrier. Apart from material preparation, this research is expected to provide important references for RhB photodegradation in practical applications.

Facile Fabrication of Dumbbell-Like ß-Bi2O3/Graphene Nanocomposites and Their Highly Efficient Photocatalytic Activity.

ß-Bi2O3 decorated graphene nanosheets (ß-Bi2O3/GN) were prepared by a facile solution mixing method. The crystal structure, surface morphology, and photo absorbance properties of the products were characterized by XRD, SEM, and UV-VIS diffuse reflection, respectively. Moreover, the effect of graphene content on photocatalytic activity was systematically investigated, and the results indicated that these composites possessed a high degradation rate of Rhodamine B (RhB), which was three times higher than that of bare ß-Bi2O3 when graphene content was 1 wt %. This high photocatalytic activity was attributed predominantly to the presence of graphene, which served as an electron collector and transporter to efficiently lengthen the lifetime of the photogenerated charge carriers from ß-Bi2O3.

Magnetic Photocatalyst BiVO4/Mn-Zn ferrite/Reduced Graphene Oxide: Synthesis Strategy and Its Highly Photocatalytic Activity.

Magnetic photocatalyst BiVO4/Mn-Zn ferrite (Mn1-xZnxFe2O4)/reduced graphene oxide (RGO) was synthesized by a simple calcination and reduction method. The magnetic photocatalyst held high visible light-absorption ability with low band gap energy and wide absorption wavelength range. Electrochemical impedance spectroscopies illustrated good electrical conductivity which indicated low charge-transfer resistance due to incorporation of Mn1-xZnxFe2O4 and RGO. The test of photocatalytic activity showed that the degradation ratio of rhodamine B (RhB) reached 96.0% under visible light irradiation after only 1.5 h reaction. The photocatalytic mechanism for the prepared photocatalyst was explained in detail. Here, the incorporation of RGO enhanced the specific surface area compared with BiVO4/Mn1-xZnxFe2O4.The larger specific surface area provided more active surface sites, more free space to improve the mobility of photo-induced electrons, and further facilitated the effective migration of charge carriers, leading to the remarkable improvement of photocatalytic performance. Meanwhile, RGO was the effective acceptor as well as transporter of photo-generated electron hole pairs. •O2- was the most active species in the photocatalytic reaction. BiVO4/Mn1-xZnxFe2O4/RGO had quite a wide application in organic contaminants removal or environmental pollution control.

Facile Synthesis of Magnetic Photocatalyst Ag/BiVO4/Mn1-xZnxFe2O4 and Its Highly Visible-Light-Driven Photocatalytic Activity.

Ag/BiVO4/Mn1-xZnxFe2O4 was synthesized with a dip-calcination in situ synthesis method. This work was hoped to provide a simple method to synthesis three-phase composite. The phase structure, optical properties and magnetic feature were confirmed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectrometer (XPS), transmission electron microscopy (TEM), ultraviolet-visible diffuse reflectance spectrophotometer (UV-vis DRS), and vibrating sample magnetometer (VSM). The photocatalytic activity was investigated by Rhodamine B (RhB) photo-degradation under visible light irradiation. The photo-degradation rate of RhB was 94.0~96.0% after only 60 min photocatalytic reaction under visible light irradiation, revealing that it had an excellent visible-light-induced photocatalytic activity. In the fifth recycle, the degradation rate of Ag/BiVO4/Mn1-xZnxFe2O4 still reached to 94.0%. Free radical tunnel experiments confirmed the dominant role of •O2- in the photocatalytic process for Ag/BiVO4/Mn1-xZnxFe2O4. Most importantly, the mechanism that multifunction Ag could enhance photocatalytic activity was explained in detail.

New Insights into Sensitization Mechanism of the Doped Ce (IV) into Strontium Titanate.

SrTiO3 and Ce4+ doped SrTiO3 were synthesized by a modified sol⁻gel process. The optimization synthesis parameters were obtained by a series of single factor experiments. Interesting phenomena are observable in Ce4+ doped SrTiO3 systems. Sr2+ in SrTiO3 system was replaced by Ce4+, which reduced the surface segregation of Ti4+, ameliorated agglomeration, increased specific surface area more than four times compared with pure SrTiO3, and enhanced quantum efficiency for SrTiO3. Results showed that Ce4+ doping increased the physical adsorption of H2O and adsorbed oxygen on the surface of SrTiO3, which produced additional catalytic active centers. Electrons on the 4f energy level for Ce4+ produced new energy states in the band gap of SrTiO3, which not only realized the use of visible light but also led to an easier separation between the photogenerated electrons and holes. Ce4+ repeatedly captured photoelectrons to produce Ce3+, which inhibited the recombination between photogenerated electrons and holes as well as prolonged their lifetime; it also enhanced quantum efficiency for SrTiO3. The methylene blue (MB) degradation efficiency reached 98.7% using 3 mol % Ce4+ doped SrTiO3 as a photocatalyst, indicating highly photocatalytic activity.

New Insights into Mn1-xZnxFe2O4 via Fabricating Magnetic Photocatalyst Material BiVO4/Mn1-xZnxFe2O4.

BiVO4/Mn1-xZnxFe2O4 was prepared by the impregnation roasting method. XRD (X-ray Diffractometer) tests showed that the prepared BiVO4 is monoclinic crystal, and the introduction of Mn1-xZnxFe2O4 does not change the crystal structure of BiVO4. The introduction of a soft-magnetic material, Mn1-xZnxFe2O4, was beneficial to the composite photocatalyst's separation from the liquid solution using an extra magnet after use. UV-vis spectra analysis indicated that Mn1-xZnxFe2O4 enhanced the absorption intensity of visible light for BiVO4. EIS (electrochemical impedance spectroscopy) investigation revealed that the introduction of Mn1-xZnxFe2O4 enhanced the conductivity of BiVO4, further decreasing its electron transfer impedance. The photocatalytic efficiency of BiVO4/Mn1-xZnxFe2O4 was higher than that of pure BiVO4. In other words, Mn1-xZnxFe2O4 could enhance the photocatalytic reaction rate.

Magnetic composite BiOCl-SrFe12O19: a novel p-n type heterojunction with enhanced photocatalytic activity.

The magnetic composite BiOCl-SrFe12O19, a novel p-n type heterojunction was synthesized by hydrolysis with a medium temperature sintering method. The microstructure and magnetic properties of the prepared material were characterized by FTIR, XRD, SEM, TEM, HRTEM, SAED, and VSM. The results showed the [001] facet of BiOCl with high photocatalytic activity was exposed in the BiOCl-SrFe12O19. The heterostructured BiOCl-SrFe12O19 had better magnetic properties, contributing to its reuse and improvement in photocatalysis. Moreover, the composite was blessed with excellent photocatalytic activity and stability. In the BiOCl-SrFe12O19 system, SrFe12O19 not only inhibited the growth of BiOCl along the [001] direction to enhance the exposure of the [001] wafer, but also acted as a sensitizer absorbing light irradiation. The magnetic field generated from SrFe12O19 made BiOCl, under light irradiation, produce more photo-induced electrons and holes and simultaneously hampered their recombination. For the first time we propose the possible mechanism of how to enhance photocatalytic activity by a magnetic field effect originating from the magnetic photocatalyst itself.