Preparation and photocatalytic performance study of dual Z-scheme Bi2Zr2O7/g-C3N4/Ag3PO4 for removal of antibiotics by visible-light

At present, the high re-combination rate of photogenerated carriers and the low redox capability of the photocatalyst are two factors that severely limit the improvement of photocatalytic performance. Herein, a dual Z-scheme photocatalyst bismuthzirconate/graphitic carbon nitride/silver phosphate (Bi₂Zr₂O₇/g-C₃N₄/Ag₃PO₄ (BCA)) was synthesized using a co-precipitation method, and a dual Z-scheme heterojunction photocatalytic system was established to decrease the high re-combination rate of photogenerated carriers and consequently improve the photocatalytic performance. The re-combination of electron-hole pairs (e⁻ and h⁺) in the valence band (VB) of g-C₃N₄ increases the redox potential of e⁻ and h⁺, leading to significant improvements in the redox capability of the photocatalyst and the efficiency of e⁻-h⁺ separation. As a photosensitizer, Ag₃PO₄ can enhance the visible light absorption capacity of the photocatalyst. The prepared photocatalyst showed strong stability, which was attributed to the efficient suppression of photo-corrosion of Ag₃PO₄ by transferring the e⁻ to the VB of g-C₃N₄. Tetracycline was degraded efficiently by BCA-10% (the BCA with 10 wt.% of AgPO₄) under visible light, and the degradation efficiency was up to 86.2%. This study experimentally suggested that the BCA photocatalyst has broad application prospects in removing antibiotic pollution.     

Preparation of floating BiOCl0.6I0.4/ZnO photocatalyst and its inactivation of Microcystis aeruginosa under visible light

Frequent occurrence of harmful algal blooms has already threatened aquatic life and human health. In the present study, floating BiOCl_0.6I_0.4/ZnO photocatalyst was synthesized in situ by water bath method, and and applied in inactivation of Microcystis aeruginosa under visible light. The composition, morphology, chemical states, optical properties of the photocatalyst were also characterized. The results showed that BiOCl_0.6I_0.4 exhibited laminated nanosheet structure with regular shape, and the light response range of the composite BZ/EP-3 (BiOCl_0.6I_0.4/ZnO/EP-3) was tuned from 582 to 638 nm. The results of photocatalytic experiments indicated that BZ/EP-3 composite had stronger photocatalytic activity than a single BiOCl_0.6I_0.4 and ZnO, and the removal rate of chlorophyll a was 89.28% after 6 hr of photocatalytic reaction. The photosynthetic system was destroyed and cell membrane of algae ruptured under photocatalysis, resulting in the decrease of phycobiliprotein components and the release of a large number of ions (K⁺, Ca²⁺ and Mg²⁺). Furthermore, active species trapping experiment determined that holes (h⁺) and superoxide radicals (·O₂⁻) were the main active substance for the inactivation of algae, and the p-n mechanism of photocatalyst was proposed. Overall, BZ/EP-3 showed excellent algal removal ability under visible light, providing fundamental theories for practical algae pollution control.     

In situ construction of Z-scheme FeS2/Fe2O3 photocatalyst via structural transformation of pyrite for photocatalytic degradation of carbamazepine and the synergistic reduction of Cr(VI)

Pyrite is the most abundant sulfide semiconductor mineral with excellent optical properties. However, few reports have investigated its photocatalytic activity because of the low photogenerated carrier separation efficiency. In this work, a Z-scheme FeS₂/Fe₂O₃ composite photocatalyst was fabricated in situ via structural transformation of pyrite through heat treatment. A remarkably enhanced photocatalytic performance was observed over the FeS₂/Fe₂O₃ composite photocatalyst. Compared with the pristine pyrite, the degradation efficiency of carbamazepine (CBZ) reached 65% at the added hexavalent chromium (Cr(Ⅵ)) concentration of 20 mg/L and the Cr(Ⅵ) was nearly completely reduced in the mixed system using FeS₂/Fe₂O₃ within 30 min under simulated solar light irradiation. The enhanced photocatalytic activity can be attributed to the efficient separation and transfer of photogenerated carriers in the FeS₂/Fe₂O₃ composite photocatalyst. This facilitated the generation of ?OH, hole (h⁺) and ?O₂^? species, which participated in the photocatalytic reaction with CBZ. Based on the measurement of the active species and electric properties, a Z-scheme electron transfer pathway was proposed for the FeS₂/Fe₂O₃ composite photocatalyst. This work broadens the application potential of pyrite in environmental remediation.     

Synergistic effects of structural, crystalline, and chemical defects on the photocatalytic performance of Y-doped ZnO for carbaryl degradation

In this study, a photocatalytic material consisting of ZnO and yttrium-doped ZnO (YZO) nanoparticles was obtained via a facile precipitation conducted under ambient pressure whereby crystalline ZnO was successfully doped with yttrium. YZO had a hexagonal wurtzite polycrystalline structure with smaller crystal and grain sizes than ZnO, which in turn meant larger specific surface area and pore volume. Chemical defects were also produced, which facilitated photocatalytic activity, because such defects can act as reaction centers. The optical band gap magnitude and the diamagnetic nature of YZO were also determined. The structural, crystalline, and chemical defects of YZO synergistically enhanced the photocatalytic degradation of carbaryl; indeed, the kinetic rate constant of this reaction catalyzed by YZO was 11.17 × 10⁻² min⁻¹ under natural sunlight irradiation, higher than the value measured for ZnO (8.68 × 10⁻² min⁻¹). Evidence thus indicates that yttrium-doping effectively modified some properties of ZnO nanoparticles so that YZO nanoparticles proved a suitable photocatalytic material for carbaryl degradation.     

Decomplexation of Cu-1-hydroxyethylidene-1,1-diphosphonic acid by a three-dimensional electrolysis system with activated biochar as particle electrodes

The feasibility of decomplexation removal of typical contaminants in electroplating wastewater, complexed Cu(II) with 1-hydroxyethylidene-1,1-diphosphonic acid (Cu-HEDP), was first performed by a three-dimensional electric reactor with activated biochar as particle electrodes. For the case of 50 mg/L Cu-HEDP, Cu(II) removal (90.7%) and PO initial pH 7, acid-treated almond shell biochar (AASB) addition 20 g/L, and reaction time 180 min, with second-order rate constants of 1.10 × 10⁻³ and 1.94 × 10⁻⁵ min⁻¹respectively. The growing chelating effect between Cu(II) and HEDP and the comprehensive actions of adsorptive accumulation, direct and indirect oxidation given by particle electrodes accounted for the enhanced removal of Cu-HEDP, even though the mineralization of HEDP was mainly dependent on anode oxidation. The performance attenuation of AASB particle electrodes was ascribed to the excessive consumption of oxygen-containing functionalities during the reaction, especially acidic carboxylic groups and quinones on particle electrodes, which decreased from 446.74 to 291.48 µmol/g, and 377.55 to 247.71 µmol/g, respectively. Based on the determination of adsorption behavior and indirect electrochemical oxidation mediated by in situ electrogenerated H₂O₂ and reactive oxygen species (e.g., •OH), a possible removal mechanism of Cu-HEDP by three-dimensional electrolysis was further proposed.     

Fabrication of Bi-Bi3O4Cl plasmon photocatalysts for removal of aqueous emerging contaminants under visible light

Photocatalytic oxidation of emerging contaminants (ECs) in water has recently gained extensive attentions. In this study, bismuth oxychloride-based plasmon photocatalysts (Bi-Bi₃O₄Cl) exhibiting high performance were successfully developed by reducing Bi³⁺ on the surface of Bi₃O₄Cl. Consequently, the photocatalysts were used to remove ECs from water. The effects of developmental process and Bi metal plasmon resonance on the photoelectric performances of Bi-Bi₃O₄Cl were investigated through a series of characterizations. The UV-vis diffuse reflection and photoluminescence spectra revealed that the light absorption range of the photocatalyst gradually increased and the electron recombination rate gradually decreased with the introduction of Bi metals. The optimal removal rates of ciprofloxacin and tetrabromobisphenol A by Bi-Bi₃O₄Cl were 93.8% and 96.4%; the respective reaction rate constants were 5.48 and 4.93 times higher than that of Bi₃O₄Cl. The mechanism study indicated that main reactants in the photocatalytic system were •O₂⁻ radicals and photogenerated holes, and the existence of oxygen vacancies and Bi metals promoted electron transfer in photocatalyst. In conclusion, this research produces a novel, green, highly efficient, and stable visible light photocatalyst for the removal of ECs from water.     

Rural vehicle emission as an important driver for the variations of summertime tropospheric ozone in the Beijing-Tianjin-Hebei region during 2014–2019

Tropospheric ozone (O₃) pollution is increasing in the Beijing-Tianjin-Hebei (BTH) region despite a significant decline in atmospheric fine aerosol particles (PM_2.5) in recent years. However, the intrinsic reason for the elevation of the regional O₃ is still unclear. In this study, we analyzed the spatio-temporal variations of tropospheric O₃ and relevant pollutants (PM_2.5, NO₂, and CO) in the BTH region based on monitoring data from the China Ministry of Ecology and Environment during the period of 2014–2019. The results showed that summertime O₃ concentrations were constant in Beijing (BJ, 0.06 µg/(m³•year)) but increased significantly in Tianjin (TJ, 9.09 µg/(m³•year)) and Hebei (HB, 6.06 µg/(m³•year)). Distinct O₃ trends between Beijing and other cities in BTH could not be attributed to the significant decrease in PM_2.5 (from -5.08 to -6.32 µg/(m³•year)) and CO (from -0.053 to -0.090 mg/(m³•year)) because their decreasing rates were approximately the same in all the cities. The relatively stable O₃ concentrations during the investigating period in BJ may be attributed to a faster decreasing rate of NO₂ (BJ: -2.55 µg/(m³•year); TJ: -1.16 µg/(m³•year); HB: -1.34 µg/(m³•year)), indicating that the continued reduction of NO_x will be an effective mitigation strategy for reducing regional O₃ pollution. Significant positive correlations were found between daily maximum 8 hr average (MDA8) O₃ concentrations and vehicle population and highway freight transportation in HB. Therefore, we speculate that the increase in rural NO_x emissions due to the increase in vehicle emissions in the vast rural areas around HB greatly accelerates regional O₃ formation, accounting for the significant increasing trends of O₃ in HB.     

Photocatalytic degradation of organochlorine compounds using TiO2 supported on fiberglass cloth

The feasibility of photocatalytic degradation of organochlorine compounds using TiO₂ supported on fiberglass cloth as a photocatalyst was studied. The results showed that 2.0×10^-4 mol/dm³ of dichloroethylene, trichloroethylene and tetrachloroethylene can be completely photocatalytically degraded within a short time under illumination with a 375W medium pressure mercury lamp. The effects of parameters such as illumination time, initial concentration of organochlorine compounds, amount of air flow and concentration of H₂O₂ on the photocatalytic degradation were investigated. The TiO₂ supported on the fiberglass was not easily detached and after 500h illumination there was no significant loss of photocatalytic activity of TiO₂. The passible mechanisms of photocatalytic degradation were discussed.     

Hydrothermal-treated Pt/Al2O3 as an excellent catalyst for toluene total oxidation

The preparation of highly active supported noble metal catalysts with a low noble metal loading has always been the ultimate goal of researchers working on catalysis. Hydrothermally treated Pt/Al₂O₃ (Pt/Al₂O₃-H) exhibits better catalytic activity than that (Pt/Al₂O₃-C) treated via the conventional calcination approach. At the high space velocity of 100,000 mL/(g∙hr), the temperature that correspond to 50% toluene conversion (T₅₀) of Pt/Al₂O₃-H is 115°C lower than that of Pt/Al₂O₃-C, and the turnover frequency (TOF) value can reach 0.0756 sec⁻¹. The mechanism by which the hydrothermal approach enhances Pt/Al₂O₃ activity has been investigated. The structure associated with the high catalytic activity of Pt nanoparticles (NPs) can be retained via hydrothermal treatment. Furthermore, the support is transformed to AlO(OH) with numerous surface hydroxyl groups, which in turn can facilitate the adsorption of toluene. And the synergistic effects of Pt NPs and AlO(OH) increases the contents of Pt in oxidation state and active oxygen, which are beneficial for toluene oxidation.     

Photocatalytic degradation of 4-chlorophenol under P-modified TiO2/UV system:Kinetics, intermediates, phytotoxicity and acute toxicity

A series of phosphorus-modified titanium dioxide samples with varying P/Ti atomic ratio were conveniently prepared via a conventional solgel route. The effects of phosphorus content and calcination temperature on the crystalline structure, grain growth, surface area, and the photocatalytic activity of P-modified TiO₂ were investigated. The XRD results showed that P species slow down the particle growth of anatase and increase the anatase-to-rutile phase transformation temperature to more than 900℃. Kinetic studies on the P-modified TiO₂ to degraded 4-chlorophenol had found that the TP5₅₀₀ prepared by adopting a P/Ti atomic ratio equal to 0.05 and calcined at 500℃ had an apparent rate constant equal to 0.0075 min^-1, which is superior to the performance of a commercial photocatalyst Degussa P25 K_app = 0.0045 min^-1 and of unmodified TiO₂ (TP0₅₀₀) K_app = 0.0022 min^-1. From HPLC analyses, various hydroxylated intermediates formed during oxidation had been identified, including hydroquinone (HQ), benzoquinone (BQ) and (4CC) 4-chlorocatechol as main products. Phytotoxicity was assessed before and after irradiation against seed germination of tomato (Lycopersicon esculentum) whereas acute toxicity was assessed by using Folsomia candida as the test organism. Intermediates products were all less toxic than 4-chlorophenol and a significant removal of the overall toxicity was accomplished     

D301树脂对水中氟虫腈的吸附去除研究

文章研究D301树脂对水溶液中氟虫腈的吸附行为,考察了吸附剂投加量和溶液pH值对吸附效果的影响,对吸附等温线和吸附动力学进行了探讨,并选择不同模型对吸附曲线进行拟合。结果表明,当氟虫腈溶液初始浓度为2 mg/L,吸附剂投加量为0.5 g/L时,氟虫腈的去除率达到100%;溶液pH值在3⁹范围内变化时,对吸附的影响较小,相对而言pH=7的吸附效果最好;D301树脂对氟虫腈的吸附等温线满足Langmuir吸附等温式和Freundlich吸附等温式,相关系数R2分别为0.994和0.991;吸附动力学符合Lagergren一级反应方程。总体来说,D301树脂对氟虫腈的吸附效果较好。     

UNITANK工艺特性及其基于ASM2D的模拟分析

UNITANK采用A/O工艺的空间结构,利用SBR工艺的控制策略,但也有其独特的性质。混掺现象对于UNITANK运行产生明显影响,建立UNITANK工艺模型必须考虑混掺,并将各个反应池建立不同的模型以反映这种现象;ASM2D与UNITANK工艺模型结合较好模拟了UNITANK运行的动态变化,对于控制和改造UNITANK工艺具有很好的指导意义。     

基于D优化方法的CSADT设计

考虑到试验设计人员更关注模型参数的估计精度,而传统试验优化方法以产品可靠性与寿命相关参数的预测精度为目标,提出将D优化方法引入恒定应力加速退化试验(CSADT)设计中。首先,用随机过程描述CSADT中产品性能退化的过程,通过对数似然函数,推导Fisher信息矩阵,基于D优化方法建立优化目标,以试验费用为约束条件,明确优化问题,给出最优试验变量:各应力水平、各应力下样本分配和试验时间分配。然后,应用该方法给出仿真实例。最后,通过模型参数偏差的敏感性分析,说明在一定偏差范围内,优化结果具有良好的稳健性。     

D301R树脂对铬(Ⅵ)的吸附性能研究

在pH=2.63的HAc-NaAc体系中,D301R树脂对Cr(Ⅵ)有较好的吸附性。树脂的静态饱和吸附容量为206mg/g。用 5％NH4CI和10％NH3·H2O的混合液能定量洗脱,测得吸附速率常数k298=2.52×10~(-4)/s。吸附过程遵守Freundlich等温式。298K 时测得吸附热力学参数△H=3.33kJ/mol、△G=-6.96kJ/mol、△S=34.5J/(mol·K)。树脂功能基与Cr(Ⅵ)的配位比为1:1。     

D墨铸铁玻璃模具的组织与性能研究

研究对玻璃模具用D型石墨铸铁的化学成分进行了合理设计和优选。结果表明,显微组织、抗氧化、抗生长和热疲劳抗力等性能,均有显著的改善和提高。经工业性试验,模具的寿命成倍提高。     

城市突发环境事件的三维矩阵管理模式研究

针对我国环境事件频繁发生和应急管理法制建设缺位、体制不健全之间的矛盾,结合矩阵管理与应急管理理念,创建了基于事件分级、事件生命周期和事件运行管理为三维的矩阵管理模式,并以此模式分析结果为基础,提出城市应急管理能力建设的阶段性建议。     

浅层岩溶二维地电影像勘探技术与效果

在吸收传统的电阻率法勘探技术精华和方法理论的基础上,应用二维的观点和数字模拟重构技术,论述了二维地电影像系统的理论、方法、技术,并通过实测案例展示了该技术在研究工程与环境地质调查问题的优势及可行性。     

《立体构成》课程建设中教学方法的改革与实践

本文通过对《立体构成》课程教学对象的分析，探讨了该课程在理论与实践教学环节教学方法的改进。实践证明，这些改进对于充分发掘学生潜力，激发学生的求知欲望，提高教师业务水平，促进《立体构成》课程教学改革具有重要意义。