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.     

Efficient photocatalysis of tetracycline hydrochloride (TC-HCl) from pharmaceutical wastewater using AgCl/ZnO/g-C3N4 composite under visible light: Process and mechanisms

AgCl/ZnO/g-C₃N₄, a visible light activated ternary composite catalyst, was prepared by combining calcination, hydrothermal reaction and in-situ deposition processes to treat/photocatalyse tetracycline hydrochloride (TC-HCl) from pharmaceutical wastewater under visible light. The morphological, structural, electrical, and optical features of the novel photocatalyst were characterized using scanning electron microscopy (SEM), UV-visible light absorption spectrum (UV–Vis DRS), X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and transient photocurrent techniques. All analyses confirmed that the formation of heterojunctions between AgCl/ZnO and g-C₃N₄ significantly increase electron-hole transfer and separation compared to pure ZnO and g-C₃N₄. Thus, AgCl/ZnO/g-C₃N₄ could exhibit superior photocatalytic activity during TC-HCl assays (over 90% removal) under visible light irradiation. The composite could maintain its photocatalytic stability even after four consecutive reaction cycles. Hydrogen peroxide (H₂O₂) and superoxide radical (^·O₂) contributed more than holes (h⁺) and hydroxyl radicals (^·OH) to the degradation process as showed by trapping experiments. Liquid chromatograph-mass spectrometer (LC-MS) was used for the representation of the TC-HCl potential degradation pathway. The applicability and the treatment potential of AgCl/ZnO/g-C₃N₄ against actual pharmaceutical wastewater showed that the composite can achieve removal efficiencies of 81.7%, 71.4% and 69.0% for TC-HCl, chemical oxygen demand (COD) and total organic carbon (TOC) respectively. AgCl/ZnO/g-C₃N₄ can be a prospective key photocatalyst in the field of degradation of persistent, hardly-degradable pollutants, from industrial wastewater and not only.     

Construction of Ag2CO3/BiOBr/CdS ternary composite photocatalyst with improved visible-light photocatalytic activity on tetracycline molecule degradation

Photocatalytic degradation was considered as a best strategy for the removal of antibiotic drug pollutants from wastewater. The photocatalyst of ABC (Ag₂CO₃/BiOBr/CdS) composite synthesized by hydrothermal and precipitation method. The ABC composite used to investigate the degradation activity of tetracycline (TC) under visible light irradiation. The physicochemical characterization methods (e.g. scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), ultraviolet visible spectroscopy (UV), photoluminescence (PL) and time resolved photoluminescence (TRPL) clearly indicate that the composite has been construct successfully that enhances the widened visible light absorption, induces charge transfer and separation efficiency of electron – hole pairs. The photocatalytic activity of all samples was examined through photodegradation of tetracycline in aqueous medium. The photocatalytic degradation rate of ABC catalyst could eliminate 98.79% of TC in 70 min, which is about 1.5 times that of Ag₂CO_3, 1.28 times that of BiOBr and 1.1 times that of BC catalyst, respectively. The role of operation parameters like, TC concentration, catalyst dosage and initial pH on TC degradation activity were studied. Quenching experiment was demonstrated that ·OH and O₂^·− were played a key role during the photocatalysis process that was evidently proved in electron paramagnetic resonance (EPR) experiment. In addition, the catalyst showed good activity perceived in reusability and stability test due to the synergistic effect between its components. The mechanism of degradation of TC in ABC composite was proposed based on the detailed analysis. The current study will give an efficient and recyclable photocatalyst for antibiotic aqueous pollutant removal.     

Synthesis, crystal structure, photodegradation kinetics and photocatalytic activity of novel photocatalyst ZnBiYO4

ZnBiYO₄ was synthesized by a solid-state reaction method for the first time. The structural and photocatalytic properties of ZnBiYO₄ were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV-Vis diffuse reflectance. ZnBiYO₄ crystallized with a tetragonal spinel structure with space group I41/A. The lattice parameters for ZnBiYO₄ were a = b = 11.176479 Å and c= 10.014323 Å. The band gap of ZnBiYO₄ was estimated to be 1.58 eV. The photocatalytic activity of ZnBiYO₄ was assessed by photodegradation of methyl orange under visible light irradiation. The results showed that ZnBiYO₄ had higher catalytic activity compared with N-doped TiO₂ under the same experimental conditions using visible light irradiation. The photocatalytic degradation of methyl orange with ZnBiYO₄ or N-doped TiO₂ as catalyst followed first-order reaction kinetics, and the first-order rate constant was 0.01575 and 0.00416 min^-1 for ZnBiYO₄ and N-doped TiO₂, respectively. After visible light irradiation for 220 min with ZnBiYO₄ as catalyst, complete removal and mineralization of methyl orange were observed. The reduction of total organic carbon, formation of inorganic products, SO₄^2- and NO₃^-, and evolution of CO₂ revealed the continuous mineralization of methyl orange during the photocatalytic process. The intermediate products were identified using liquid chromatography- mass spectrometry. The ZnBiYO₄/(visible light) photocatalysis system was found to be suitable for textile industry wastewater treatment and could be used to solve other environmental chemical pollution problems.     

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.     

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.     

Synergistic effect of N- and F-codoping on the structure and photocatalytic performance of TiO2

Three types of TiO₂ nanostructures were synthesized via a facile hydrolysis method at 195 ℃. Effects of the preparation method and doping with N and F on the crystal structure and photocatalytic performance of TiO₂ were investigated. The nanomaterials were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller porosimetry, ultraviolet-visible diffuse reflectance spectroscopy and fluorescent emission spectra. Their photo-catalytic activity was examined by the photodegradation of methylene blue in aqueous solution under both ultra-violet and visible light irradiation. The results show that nitrogen and fluorine co-doped anatase TiO₂ had the characteristics of a smaller crystalline size, broader light absorption spectrum and lower charge recombination than pure TiO₂. Most importantly, more efficient photocatalytic activity under both ultra-violet and visible light was observed. The obtained N-F-TiO₂ nanomaterial shows considerable potential for water treatment under sunlight irradiation.     

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.     

Visible light driven mineralization of spiramycin over photostructured N-doped TiO2 on up conversion phosphors

A novel visible light-active photocatalyst formulation(NdT/OP) was obtained by supporting N-doped TiO_2(NdT) particles on up-conversion luminescent organic phosphors(OP). The photocatalytic activity of such catalysts was evaluated for the mineralization process of spiramycin in aqueous solution. The effect of NdT loading in the range 15–60 wt.% on bulk and surface characteristics of NdT/OP catalysts was investigated by several chemicophysical characterization techniques. The photocatalytic performance of NdT/OP catalysts in the removal of spyramicin from aqueous solution was assessed through photocatalytic tests under visible light irradiation. Total organic carbon(TOC) of aqueous solution,and CO and CO_2 gas concentrations evolved during the photodegradation were analyzed. A dramatic enhancement of photocatalytic activity of the photostructured visible active NdT/OP catalysts,compared to NdT catalyst,was observed. Only CO_2 was detected in gas-phase during visible light irradiation,proving that the photocatalytic process is effective in the mineralization of spiramycin,reaching very high values of TOC removal. The photocatalyst NdT/OP at 30 wt.% of NdT loading showed the highest photocatalytic activity(58%of TOC removed after 180 min irradiation against only 31% removal after 300 min of irradiation of NdT). We attribute this enhanced activity to the high effectiveness in the utilization of visible light through improved light harvesting and exploiting. OP particles act as "photoactive support",able to be excited by the external visible light irradiation,and reissue luminescence of wavelength suitable to promote NdT photomineralization activity.     

Photocatalytic degradation of paraquat using nano-sized Cu-TiO2/SBA-15 under UV and visible light

Photocatalytic degradation of paraquat using mesoporous-assembled Cu-TiO₂/SBA15 under UV and visible light was investigated. The catalyst was synthesized by impregnation of Cu-TiO₂ colloids onto SBA-15. The colloids of Cu-TiO₂ were prepared via sol-gel method while the mesoporous support was prepared using hydrothermal technique. The catalyst was characterized using X-ray diffraction, nitrogen adsorption-desorption, transmission electron microscopy, UV diffuse reflectance spectroscopy, Zeta potential and X-ray adsorption spectroscopy. Results from characterizations showed that Cu doped TiO₂ had a small crystalline size and was well-dispersed on SBA-15. The inclusion of SBA-15 significantly enhanced the photocatalytic activity of the catalyst. Among the three types of undoped catalyst in this study (P25, TiO₂, TiO₂/SBA-15), TiO₂/SBA-15 yielded the highest degradation of paraquat for all pH under UV illumination. Meanwhile 2 wt.% Cu-TiO₂/SBA-15 yielded the highest activity under visible light.     

国际化学危险品分类体系简介

介绍了当前国际化学危险品的各种分类体系,对比了GHS与TDG、EU_CLP、DOT、WHMIS等对化学危险品的具体分类。有助于GHS的理解与掌握,全面推进GHS在我国的实施。     

土壤整体质量的生态毒性评价

土壤样品采自沈阳西部污灌区 .进行了污染物 (重金属和矿物油 )含量分析和生态毒性试验 .重金属采用原子吸收分光光度仪测定 ,矿物油采用紫外分光光度计测定 .生态毒性试验分别参照国际标准组织 (ISO)和OECD指南 ,进行了植物毒性试验、蚯蚓毒性试验和蚕豆根尖微核试验 .植物试验以小麦种子发芽根伸长抑制率为试验终点 ,试验周期50h ,蚯蚓毒性试验以蚯蚓死亡率、体重增长抑制率为试验终点 ,试验周期28d .土壤中矿物油含量在145mg/kg～1121mg/kg ,重金属Cd为0.34mg/kg～1.81mg/kg .土壤对植物和蚯蚓显示不同程度的毒性效应 ,土壤的蚕豆根尖微核率明显高于对照 .种子发芽根伸长抑制率为2.0%至-35.1% ,蚯蚓死亡率为0%～40%.体重增长抑制率由14d的-2.3%～-19.4%在28d增加到-2.1%～10.7% ,蚕豆根尖微核率最高达6.62/100.研究表明 ,土壤中的污染物积累较低 ,但具有明显的生态毒性 .     

多目标规划在预测区域总产值-排污-水质协调解中的应用研究

以某区域水环境－经济系统为研究实例，寻求值－排污－水质综合协调解方法，寻求净收益最大时的总体规划方案。建立目标参数规划模型，寻求不同生产规模条件下的产值－排污－水质协调解，又探讨了水环境标准约束下的某化工区废水治理费用的计算方法，提出了以供决策者选择的方案。     

滇池富营养化特性评价

介绍了滇池水质状况,对滇池富营养化特性进行了分析和评价,并提出了对策.     

生态保护地协同管控成效评估

分区分类管理是我国生态保护的重要管控制度,生态保护地是事关国家生态安全的关键区域,开展生态保护地保护成效评估及不同类型生态保护地之间的协同管控成效评估具有重要意义。以吉林省自然保护地和重点生态功能区等生态保护地（即禁止开发区和限制开发区）为研究对象,以重要生态空间、植被生态、水源涵养功能为主要内容,基于“禁止开发区—限制开发区—省域”的管控梯度差异,评估分析了生态保护地的协同管控成效。结果表明：（1）从重要生态空间协同管控成效来看,自然保护地的重要生态空间面积比例最高、人类活动干扰指数最低,这与生态保护管控严格程度呈现很好地正相关。但是1980—2015年间重要生态空间面积比例均有所减少,减少幅度与管控严格程度没有表现出正相关。（2）从植被生态协同管控成效来看,植被覆盖总体呈现出自东向西逐步降低的特点,与东部分布有重点生态功能区和森林类自然保护区、西部分布较多的湿地类自然保护地的空间特征一致。但是,由于湿地及水域类型自然保护地面积占比较高,且分布在吉林西部草原和平原区的面积比例较高,自然保护地的年际变化较大、且植被覆盖稳定度低于重点生态功能区。（3）从水源涵养功能协同管控成效来看,水源涵养能力呈现出东部和西部高、中部低的特点,与这两个区域主要分布有森林、草地和湿地等重要生态空间密切相关,也与分布着大面积的重点生态功能区和各类自然保护地密切相关。自然保护区的水源涵养能力最高,且年际变化最小、稳定性最高。     

乌海市城区环境噪声现状分析

对乌海市《城市区域环境噪声标准》适用区域进行了划分,以乌海市2011年城区环境噪声监测统计数据为基础,分析了乌海市暴露在不同等效声级下的城区面积分布状况和达标情况。     

后勤装备防腐涂层加速试验环境谱研究

结合后勤装备服役特点,综合考虑亚热带沿海地区湿热、紫外光照、盐雾等主要腐蚀因素的影响,建立了适用于后勤装备表面涂层的加速试验环境谱,给出了各环境块的具体确定方法,并且提出了建立加速谱与装备实际使用环境的当量加速关系的方法。为后勤装备外露关键部位涂层使用寿命评定、涂层有效性检验和腐蚀修理方案制定提供了重要的依据。     

烟气脱硫副产物的综合利用

通过分析烟气脱硫石膏的性能 ,介绍了脱硫石膏的利用情况和研究进展 ,利用脱硫石膏生产建筑材料 ,如 β石膏和α石膏的工艺日臻成熟 ,利用脱硫石膏生产水泥辅料已进入工业化 ,而利用脱硫石膏生产充填尾砂胶结剂已经完成试验阶段 ,脱硫石膏在农业上也有很广泛的用途。     

氯苯类化合物的生物降解

经过2个月的驯化,从某染料厂和某毛纺厂活性污泥中分离出能够生长于1,4-二氯苯、1,2,4-三氯苯和六氯苯的4种微生物.通过测定该混合菌降解氯苯类化合物过程中的累积好氧量、微生物生长曲线及降解产物Cl^-的释放,证明在好氧条件下该混合菌能够以1,4二氯苯和1,2,4-三氯苯为唯一碳源和能源,降解产物Cl^-浓度的变化与微生物生长周期有关.通过好氧振荡瓶培养法测得3种氯苯的生物降解顺序为:1,4-二氯苯[356.7μg/(L·d)]>1,2,4-三氯苯[110.4μg/(L·d)]>六氯苯[～6μg/(L·d)],说明氯取代数越多,氯苯类化合物越难被好氧降解.     

哈尔滨松北区城市湿地的生态安全分析

以哈尔滨松北区城市湿地为研究对象,选择10个指标,采用因子分析法和聚类分析法,研究了松花江发生污染事故前后城市湿地的生态安全状况.结果表明:发生污染前哈尔滨松北区城市湿地东区的生态安全程度最高,发生污染后中区的生态安全程度最低;西区的抗干扰能力较差.各主因子中以水因子的下降幅度最大,说明水污染直接影响了哈尔滨松北区城市湿地的生态安全.最后有针对性地提出了哈尔滨松北区城市湿地的生态安全对策.