A novel and stretchable carbon-nanotube/Ni@TiO2:W photocatalytic composite for the complete removal of diclofenac drug from the drinking water

We present the structural, morphological and photocatalytic properties of stretchable composites made with carbon nanotubes (CNTs), silicon rubber and Ni@TiO₂:W nanoparticles (TiWNi NPs) with average size of 37 ± 2 nm. Microscopy images showed that the TiWNi NPs decorated the surface of the CNT fibers, which are oriented in a preferential direction. TiWNi NPs presented a mixture of anatase/rutile phases with cubic structure. The performance of the TiWNi powders and stretchable composites was evaluated for the photocatalytic degradation of diclofenac (DCF) anti-inflammatory drug under ultraviolet-visible light. The results revealed that the maximum DCF degradation percentages were 34.6%, 91.9%, 97.1%, 98.5% and 100% for the CNT composite (stretched at 0%), TiWNi powders, CNT + TiWNi (stretched at 0%), CNT + TiWNi (stretched at 50%) and CNT + TiWNi (stretched at 100%), respectively. Thus, stretching the CNT + TiWNi composites was a good strategy to enhance the DCF degradation percentage from 97.1% to 100%, since stretching created additional defects (oxygen vacancies) that acted as electron sink, delaying the electron-hole recombination, and favors the DCF degradation. Raman/absorbance measurements confirmed the presence of such defects. Moreover, the reactive oxygen species (ROS) were determined by the scavenger's experiments and found that the main ROS were the ·OH and O₂⁻ radicals, which attacked the DCF molecules, causing their degradation. The results of this investigation confirmed that the stretchable CNT/TiWNi-based composites are a viable alternative to remove pharmaceutical contaminants from water and can be manually separated from the decontaminated water, which is unviable using photocatalytic powders.     

Carbonate-induced enhancement of phenols degradation in CuS/peroxymonosulfate system: A clear correlation between this enhancement and electronic effects of phenols substituents

This study investigated the enhancement effects of dissolved carbonates on the peroxymonosulfate-based advanced oxidation process with CuS as a catalyst. It was found that the added CO₃²⁻ increased both the catalytic activity and the stability of the catalyst. Under optimized reaction conditions in the presence of CO₃²⁻, the degradation removal of 4-methylphenol (4-MP) within 2 min reached 100%, and this was maintained in consecutive multi-cycle experiments. The degradation rate constant of 4-MP was 2.159 min⁻¹, being 685% greater than that in the absence of CO₃²⁻ (0.315 min⁻¹). The comparison of dominated active species and 4-MP degradation pathways in both CO₃²⁻-free and CO₃²⁻-containing systems suggested that more CO₃•⁻/¹O₂ was produced in the case of CO₃²⁻deducing an electron transfer medium, which tending to react with electron-rich moieties. Meanwhile, Characterization by X-ray photoelectron spectroscopic and cyclic voltammetry measurement verified CO₃²⁻ enabled the effective reduction of Cu²⁺ to Cu⁺. By investigating the degradation of 11 phenolics with different substituents, the dependence of degradation kinetic rate constant of the phenolics on their chemical structures indicated that there was a good linear relationship between the Hammett constants σ_p of the aromatic phenolics and the logarithm of k in the CO₃²⁻-containing system. This work provides a new strategy for efficient removal of electron-rich moieties under the driving of carbonate being widely present in actual water bodies.     

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.     

Comparison of UV and UV-LED activated sodium percarbonate for the degradation of O-desmethylvenlafaxine

As an active metabolite of venlafaxine and emerging antidepressant, O-desmethylvenlafaxine (ODVEN) was widely detected in different water bodies, which caused potential harm to human health and environmental safety. In this study, the comparative work on the ODVEN degradation by UV (254 nm) and UV-LED (275 nm) activated sodium percarbonate (SPC) systems was systematically performed. The higher removal rate of ODVEN can be achieved under UV-LED direct photolysis (14.99%) than UV direct photolysis (4.57%) due to the higher values of photolysis coefficient at the wavelength 275 nm. Significant synergistic effects were observed in the UV/SPC (80.38%) and UV-LED/SPC (53.57%) systems and the former exhibited better performance for the elimination of ODVEN. The degradation of ODVEN all followed the pseudo-first-order kinetics well in these processes, and the pseudo-first-order rate constant (k_obs) increased with increasing SPC concentration. Radicals quenching experiments demonstrated that both ·OH and CO₃·⁻ were involved in the degradation of ODVEN and the second-order rate constant of ODVEN with CO₃·⁻ (1.58 × 10⁸ (mol/L)⁻¹ sec⁻¹) was reported for the first time based on competitive kinetic method. The introduction of HA, Cl⁻, NO₃⁻ and HCO₃⁻ inhibited the ODVEN degradation to varying degrees in the both processes. According to quantum chemical calculation, radical addition at the ortho-position of the phenolic hydroxyl group was confirmed to be the main reaction pathways for the oxidation of ODVEN by ·OH. In addition, the oxidation of ODVEN may involve the demethylation, H-abstraction, OH-addition and C-N bond cleavage. Eventually, the UV-LED/SPC process was considered to be more cost-effective compared to the UV/SPC process, although the UV/SPC process possessed a higher removal rate of ODVEN.     

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.     

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.     

Impact factors of the degradation of bisphenol A by nitrocellulose membrane under illumination

Nitrocellulose membrane (NCM) can produce hydroxyl radicals under illumination, which promotes the oxidative degradation of organic pollutants. In this paper, NCM was used to oxidize bisphenol A (BPA) under simulated sunlight. The effects of pH, temperature, light intensity, anion and cation on the degradation of BPA were analyzed. The photodegradation process of BPA was discussed. The optimal photolysis rate was 0.031 min^?1 when the temperature was 30°C, the light intensity was 2.67 × 10⁴ Lux, and the pH value was 9.0. The alkaline environment, temperature and light intensity can promote the photodegradation of BPA. Except for nitrate ions, anions and cations can inhibit the photodegradation of BPA. Compared with cations, anions have a greater inhibitory effect on BPA degradation. The degradation products of BPA by NCM were analyzed by gas chromatographic/mass. This study may provide useful information for the BPA degradation by NCM in complex water samples.     

Photocatalytic degradation of dichlorvos using TiO2 supported on hollow glass microbeads

In this paper, a method for TiO₂ supported on hollow glass microbeads was described and the feasibility of photocatalytic degradation of dichlorvos using supported TiO₂(TiO₂/beads) was studied. The results showed that 1.0×10^-4 mol.dm^-3 of dichlovos could be completely photocatalytically degraded into PO₄^3- after 120 min illumination with a 375 W medium pressure mercury lamp. The effects of the amount of TiO₂/beads and concentration of Cu²⁺ on the photocatalytic degradation were also investigated. Some intemediate products of photocatalytic degradation of dichlorvos were detected.     

0D/3D direct Z-scheme heterojunctions hybridizing by MoS2 quantum dots and honeycomb conjugated triazine polymers (CTPs) for enhanced photocatalytic performance

Herein, a novel direct Z-scheme photocatalyst was accomplished by hybridization of 0D MoS₂ quantum dots (MSQDs) and 3D honeycomb-like conjugated triazine polymers (CTP) (namely, CTP-MSQD). The unique 0D/3D hierarchical structure significantly enhanced the exposure of active sites and light harvesting property, while the formed p-n junction enabled the direct strong interface coupling without the necessity of any mediators. The optimized CTP-MSQD3 exhibited continuously increased visible-light-driven photocatalytic activity and strong durability both in Cr(VI) reduction and H₂ evolution, featured a rate of 0.069 min⁻¹ and 1070 µmol/(hr∙g), respectively, which were 8 times than those of pure 3D-CTP (0.009 min⁻¹ and 129 µmol/(hr∙g)). We believe that this work provides a promising photocatalyst system that combines a 0D/3D hierarchical structure and a Z-scheme charge flow for efficient and stable photocatalytic conversion.     

Photocatalytic performance and dispersion stability of nanodispersed TiO2 hydrosol in electrolyte solutions with different cations

The existence of electrolytes in aquatic environment on the photocatalytic performance and coagulation of nanodispersed TiO₂ hydrosol and the corresponding photocatalytic alteration were investigated by studying cations (Na⁺, K⁺, Ca ²⁺, Mg²⁺, and Al³⁺). The photocatalysis reactions of nano TiO₂ with different dosages of electrolytes were measured by monitoring the degradation of Rhodamine B (RhB) under ultraviolet A (UV-A) irradiation over time. The results showed that the photocatalytic performance of TiO₂ was improved by the presence of Al³⁺, while the performance was impaired by the other tested cations. The negative influences of divalent ions on the photocatalytic performance of TiO₂ were more significant than monovalent ions. The TiO₂ sol dispersed stable at nano scale at low concentration of electrolyte (< 0.01?mol/L) with slight change of pH, and coagulated into micro sizes at high concentration of electrolytes (> 0.1?mol/L) with larger increase or decrease of pH. The positive effects of Al³⁺ on the photodegradation rate of RhB might relate to the strong hydrolytic action of Al³⁺ in aquatic solutions. The photocatalytic processes of TiO₂ in the presence of all ions followed the Langmuir-Hinshelwood model, and the reaction kinetic constant was increased with the decrease of pH caused by different cations. These work suggested a new perspective about the relationship between coagulation and photocatalytic performance of TiO₂ hydrosols in electrolyte with hydrolysable cations, which demonstrated that TiO₂ hydrosols may be suitable as photocatalysts in aquatic environments.     

Effect of CaO on retention of S, Cl, Br, As, Mn, V, Cr, Ni, Cu, Zn, W and Pb in bottom ashes from fluidized-bed coal combustion power station

This work was conducted to evaluate whether Ca-bearing additives used during coal combustion can also help with the retention of some other elements. This work was focused on the evaluation of bottom ashes collected during four full-scale combustion tests at an operating thermal fluidized-bed power station. Bottom ashes were preferred to fly ashes for the study to avoid interference from condensation processes usually occurring in the post-combustion zone. This work focused on the behaviors of S, Cl, Br, As, Mn, V, Cr, Ni, Cu,Zn, W, and Pb. Strong positive correlations with CaO content in bottom ashes were observed（for all four combustion tests） for S, As, Cl and Br（R = 0.917-0.999）. Strong inverse proportionality was calculated between the contents of Pb, Zn, Ni, Cr and Mn and CaO, so these elements showed association to materials other than Ca-bearing compounds（e.g., to aluminosilicates, organic matter, etc.）. Somewhat unclear behaviors were observed for W, Cu, and V. Their correlation coefficients were evaluated as statistically ＂not significant＂, i.e., these elements were not thought to be significantly associated with CaO. It was also discovered that major enrichment of CaO in the finest bottom ash fractions could be advantageously used for simple separation of elements strongly associated with these fractions, mainly S and As, but also Cl or Br. Removal of5% of the finest ash particles brings about a decrease in As concentration down to 77%-80% of its original bulk ash content, which can be conveniently used e.g., when high As content complicates further ash utilization.     

The monitoring,Evaluation, reporting,verification, and certification of energy-efficiency projects

In this paper, we present an overview of guidelinesdeveloped for the monitoring, evaluation, reporting,verification, and certification (MERVC) ofenergy-efficiency projects for climate changemitigation. The monitoring and evaluation ofenergy-efficiency projects is needed to determine moreaccurately their impact on greenhouse gas (GHG)emissions and other attributes, and to ensure that theglobal climate is protected and that countryobligations are met. Reporting, verification andcertification will be needed for addressing therequirements of the Kyoto Protocol. While the cost ofmonitoring and evaluation of energy-efficiencyprojects is expected to be about 5–10% of a project'sbudget, the actual cost of monitoring and evaluationwill vary depending on many factors, including thelevel of precision required for measuring energy andGHG reductions, type of project, and amount of fundingavailable.     

珊瑚钨锡矿硅质尾矿中Cd、As、Zn、F富集迁移及环境污染

硅质尾矿在释放中性矿山废水(NMD)时所伴生的多元素复合污染问题值得重视。本文以桂东北珊瑚矿尾矿作为研究对象,通过分析该尾矿的组构、元素富集及迁移特性,筛选出主要污染元素,并探讨尾矿胶结层对元素富集迁移的影响。结果表明:(1)该尾矿中Cd、As、Zn及F富集程度较高、可交换态含量(易迁移释放量)较大,是主要的污染元素,而Cu、Pb、Tl产生污染的可能性较小;(2)胶结层对重金属具有再富集作用,但其对可交换态Cd、As(Tl)再富集明显,而对可交换态Cu、Pb、Zn再富集则不明显。胶结层中次生伊利石、石膏等胶结物趋向于吸附富集活性可交换态Cd、As。这表明该尾矿可能迁移释放出含Cd、As浓度较高的NMD。研究表明,硅质尾矿风化释出NMD的同时,可能伴生Cd、As、Zn等重金属以及F的复合污染。     

不同粒径降尘中痕量金属元素Cu、Pb、Zn、Cr的形态分析

运用Ｔｅｓｓｌｅｒ形态分类法和石墨炉原子吸收分光光度法研究了不同粒径降尘样品中痕量金属元素Ｃｕ、Ｐｂ、Ｚｎ、Ｃｒ的存在形态，讨论了不同存在形态的分布规律。结果表明，Ｃｕ、Ｐｂ、Ｚｎ、Ｃｒ在降尘中的主要形态按顺序分别为有机结合态、铁锰氧化物结合态、铁锰氧化物结合态、残渣晶格态，其活性顺序为Ｚｎ＞Ｐｂ＞Ｃｕ＞Ｃｒ；４种元素的可交换态、碳酸盐结合态、铁锰氧化物结合态在小颗粒中的分布均比在大颗粒中占优势，说明小颗粒中金属元素较为活泼，其环境危害性更大。     

共沉淀-离心-X射线荧光法快速测定表层海水中的Fe,Ni,Mn,Cu,Zn,Pb

基于共沉淀的富集作用,采用自制的离心管离心沉淀,以手持式X-射线荧光仪(XRF)测定,由此建立了表层海水中Fe,Ni,Mn,Cu,Zn,Pb的共沉淀-离心-XRF快速分析方法。测定时间为5 min/样;线性范围125μg/L～1 000μg/L,可以满足近岸表层海水中铁和锰的分析要求;基底加标200μg/L回收率为94.5%～116%;连续7次测定6种金属浓度均为500μg/L的海水加标样品,相对标准偏差(RSD)为2.86%～5.85%。与ICP-MS法比较,测定结果无显著性差异。本方法具有化学试剂污染小、方便快捷、可现场快速测定方法等优点。该方法已成功应用于厦门西港和福建九龙江河口表层海水中可溶态铁锰的现场测定,并在现场以手持式XRF对颗粒物中铁锰进行了测定,获得了该海域颗粒物中和海水中铁锰的分布。     

水体富营养化的形成、危害和防治

对水体富营养化的形成过程、富营养化给水质造成的影响和危害及富营养化问题的防治对策进行了简要的概括和总结。认为富营养化问题应该引起我们足够的重视     

山水林田湖草生命共同体的科学认知、路径及制度体系保障

山水林田湖草生命共同体是对人与自然和谐统一关系的新认知,是生态文明理论的重要组成部分。以建立一个山水林田湖草生命共同体的研究范式为目的,系统剖析了山水林田湖草生命共同体理论与应用在基础探索、快速发展和多元繁荣三个阶段的研究重点与特征;再次审视了山水林田湖草生命共同体的内涵、阐明了概念新认知、基本特征、人与生命共同体关系;最后提出面向山水林田湖草生命共同体的“问题—目标—时空策略—目的”的实施路径,及构建以自然资源监测监管体系、自然资源资产产权体系、国土空间规划体系、国土空间用途管制体系、国土空间生态修复体系、法律法规体系等为主的制度体系,进而提升其科学性和实用性,为构建国土空间治理体系及治理能力现代化提供决策支撑。     

中国资源的进出口与产出率：演化、挑战及对策

资源可持续利用是实现中国可持续发展和生态文明的重要保障,然而过去30多年经济的快速发展带来了严重的资源短缺和环境污染。为了揭示1949年以来尤其是改革开放以来中国资源利用与经济发展之间的关系,论文系统梳理中国资源供给状况,总结中国资源进出口及资源产出率演化特点、面临的挑战及相应的对策。研究发现：中国近年来进口以金属矿产、石油、部分固体废弃产品构成的自然矿产和城市矿产资源为主,主要出口以工业产品、水海产品等为代表的资源类型,进出口的结构类型随年份变化不大,但进口量呈现快速增长的态势;中国资源产出率逐步增长,达到1.6元/kg,但仍与发达国家有较大差距。为了应对面临的挑战,未来中国应着力提升在全球价值链的地位,同时国内应大力发展循环经济,提高资源产出率。