类芬顿反应的催化剂、原理与机制研究进展

芬顿氧化法是高级氧化技术的一种,通过产生高活性的自由基降解水中有机污染物,在水处理领域受到广泛关注.近年来,针对芬顿反应的研究主要集中在开发高活性、高稳定性的非均相类芬顿催化剂.本文综述了近年来非均相芬顿催化领域的研究进展,分析了铁基、锰基、铜基、钴基等过渡金属及其氧化物,以及负载型催化剂的构造特点、催化机理和作用机制,探讨了过氧化氢和过硫酸盐的催化活化路径与方式,总结了非均相类芬顿催化体系实现高效降解有机污染物的机理与途径,以期为高效类芬顿催化剂的设计和应用提供科学依据.     

高级催化氧化法去除水中邻苯二甲酸酯的研究进展

普遍认为,邻苯二甲酸酯类物质（Phthalic Acid Esters,PAEs）是内分泌干扰物质（Endocrine Disrupting Chemicals,EDCs）,被广泛应用于增塑剂、化妆品中,具有致畸性,致癌性,致突变性以及拟/抗雌激素活性、拟/抗甲状腺激素活性等内分泌干扰特性。邻苯二甲酸酯类物质很容易扩散到环境中,在土壤、大气、水环境中均有检出,是环境中常见污染物,严重威胁人体健康和生态环境,已经引起国内外的广泛关注。在综述邻苯二甲酸酯类物质的物理化学性质、毒性影响、国内外天然水体、地下水和生活污水中的污染现状的基础上,讨论消除水环境中PAEs污染的强化混凝、吸附、膜处理、生物处理和高级氧化技术。高级氧化技术因其能够快速有效地去除饮用水和污水中不同种类的有机污染物而备受关注,且发展迅速。重点介绍了高级催化氧化法对水环境中PAEs的去除,包括催化湿式过氧化物氧化过程,催化臭氧氧化过程,光催化氧化过程,超声波、微波辅助催化氧化过程以及高级纳米催化氧化过程。其中,Fenton催化氧化技术在氧化过程中通过使用催化剂或协同紫外光等方式产生高度反应性羟基自由基,可无选择性地将PAEs完全降解为无毒无害的小分子物质,对PAEs的氧化去除效果最好。虽然在高级氧化过程中应用催化剂可大大提高氧化效率和降解程度,但催化氧化法耗能较大、催化剂消耗量大、受水体pH值的影响,且研究大多限于实验室阶段,未能大量投入工业应用,需要进一步发展创新。因此,开发新型高效催化剂、提高催化剂选择性、优化催化氧化反应条件、优化设计催化反应器、与其他技术耦合是水体中PAEs类环境激素污染控制技术的发展方向。     

纳米零价铁及其在环境介质中氧化后性质演变研究进展

纳米零价铁(nZVI)尺寸小、比表面积大、表面能高、还原性强,对环境污染物具有良好的去除效果,常用于土壤及水体修复领域.而nZVI的上述特性使其在含氧环境介质中易发生氧化现象,导致物理化学性质发生变化并影响污染物的去除.本文综述了nZVI在不同环境介质中氧化后物理化学性质演变研究进展,包括nZVI制备方法及特性综述、nZVI氧化导致的结构组成和性质的演变、氧化后对重金属去除机理探讨和对环境的毒性变化,并对nZVI氧化研究与其环境领域中的应用关系进行了展望,期待为深入研究提供理论借鉴.     

污染物环境界面行为的多尺度计算模拟

污染物的环境界面行为研究一直是环境科学领域的核心和热点内容之一.借助于计算方法能够突破实验方法分析水平的限制,提供从微观到介观的多尺度上的污染物界面行为的化学机制与结构特征.量子力学方法、全原子分子动力学模拟和基于粗粒化体系模型的分子动力学模拟及耗散粒子动力学模拟等不同分子间作用计算方法可依次从原子尺度、分子尺度到介观尺度实现污染物环境界面行为的模拟分析,提供丰富多样的污染物与环境表面相互作用信息.本文综述了典型分子间作用计算模拟方法在污染物的环境界面生成、吸附乃至催化转化等方面的应用进展,分析了现有研究存在的问题和不足,并对未来的研究重点提出了展望.     

电化学模拟-质谱技术在环境领域的发展与应用

有机污染物的环境转化及生态风险是环境领域的研究热点,然而常规的研究手段程序繁琐、成本较高,且信息量有限,因此当前迫切地需要发展一项可以快速评估有机污染物的环境转化行为与风险的技术手段。在线电化学模拟-质谱技术是由注射泵、电化学反应池、联机的高效液相色谱仪及质谱检测仪组成的可用于快速评估有机污染物环境转化行为及风险的技术。本文对电化学模拟-质谱技术在环境领域中的发展与应用情况进行了详细的阐述。采用该技术可以使有机污染物在电化学反应池内发生氧化或还原反应,经联机的质谱仪检测得到活性中间产物及最终产物的结构信息,以模拟有机污染物在环境中的氧化或还原的转化过程以及研究污染物的环境结合残留机制;通过在电极表面产生电芬顿反应,可模拟研究难降解有机污染物在敏化光解或高级氧化处理工艺中的转化路径;根据有机化合物在电化学反应池内的起始反应电压可以判断有机污染物在环境中的持久稳定性。此外,电化学模拟-质谱技术可用于模拟研究有机污染物在生物体内经代谢后形成的活性中间产物与酶、蛋白质及DNA等生物大分子的结合致毒机制。与传统研究手段相比,电化学模拟-质谱技术具有快速、简便及产物信息全面等显著优越性,将在有机污染物的环境行为、水处理技术、环境监测、环境健康风险等研究领域有更广泛的应用。由于该技术刚刚起步,今后在电极材料的多样化、系统的自动化等方面有待进一步发展。     

卷首语

持久性有机污染物(POPs)由于在环境中难降解,可沿食物链累积放大,可以长距离迁移至世界各地且具有很高的毒性,是一类对环境和人类生存威胁最大的化学污染物.POPs的甄别、环境过程、健康影响与污染控制是二十一世纪环境科学领域的重大科学问题.为避免环境和人类健康受到POPs危害,国际社会于2001年5月共同通过了《关于持久性有机污     

细菌芳烃外二醇双加氧酶研究进展

外二醇双加氧酶(EDOs)是一种多功能细菌芳烃开环氧化酶,在环境保护、化工合成及生物技术等领域中有着巨大的应用潜力.本文综述了EDOs自开发以来的研究成果,包括分类学研究,酶的催化机制,在生物降解、生物合成、生物技术中的应用及其开发改造新技术.EDOs属于3个进化关系相互独立的酶家族,它们利用活性位点金属离子Fe/Mn(II)与底物和氧气结合,通过形成一种烷基过氧化中间产物,使芳香化合物开环断裂.利用这一催化机制,EDOs可以广泛地降解多种环境污染物,同时,某些EDOs还能够参与生物活性物质的合成,并且在生物传感器等生物技术中也有着广泛的应用.近年来,结合宏基因组、杂交酶等技术手段,研究人员开发改造出更多的EDOs资源,旨在为EDOs的深入研究提供更全面的信息.     

纳米金属氧化物模拟天然酶催化水体中酚类污染物转化的研究进展

天然酶作为一种绿色催化剂,能够介导水体中酚类污染物形成酚氧自由基中间体,随后这些活性中间体通过共价偶联机制生成大分子聚合产物.纳米金属氧化物(N-MOs)兼具纳米材料和天然酶"双重身份",有望克服天然酶稳定性差、难回收、易失活和价格昂贵等缺点,高效地催化氧化水体中酚类污染物的转化.本文概述了两种天然酶(过氧化物酶和酚氧化酶)的基本性能及其催化偶联酚类污染物转化的作用机理,系统地探讨了N-MOs的纳米特性及其模拟天然酶催化氧化底物的显色反应、作用效能和影响因素,并阐释了N-MOs作为纳米酶催化氧化酚类污染物转化的最新研究进展及其潜在的应用价值,旨在为拓展和开发新型、有效地纳米酶在环境中的应用提供新的理论基础和技术指导.     

挥发性有机污染物甲硫醇治理方法及反应过程研究进展

甲硫醇(CH3SH)作为一种典型的挥发性含硫有机污染物(SVOCs),具有很强的毒性,其存在会对环境和人体健康以及生产生活造成严重的危害.随着我国环保工作的深入开展,加强甲硫醇治理研究工作刻不容缓.本文介绍了甲硫醇治理的常见方法,主要包括物理法、化学法和生物法,并对催化法反应过程以及反应机理进行了探究.通过对比分析各治理方法的优缺点,指出催化分解法在甲硫醇治理方面具有显著的优势和重要的研究前景.合理调控催化剂的酸碱性能、有效提高催化剂的氧化还原性能、构建高性能催化剂将是催化分解法处理甲硫醇研究方向的重点.     

金属卟啉衍生物催化降解污染物研究进展

由于工业化和城市化的快速发展而带来的环境问题已经引起了人们的广泛关注.土壤和地下水中不断排放的持久性污染物,对人们的健康造成了极大的威胁,因此需要更加有效的策略来解决.卟啉类物质由于具有特殊的氧化还原性质和光敏性,已经被广泛用于有机污染物的去除.本文总结了金属卟啉的最新研究进展,对其在类芬顿和光催化领域的应用进行了详细的介绍,并且讨论了高价铁氧卟啉物种,单重态氧和超氧自由基的产生机理.最后,指出了现有研究的不足以及未来的发展方向.     

The abatement of major pollutants in air and water by environmental catalysis

This review reports the research progress in the abatement of major pollutants in air and water by environmental catalysis. For air pollution control, the selective catalytic reduction of NO _x (SCR) by ammonia and hydrocarbons on metal oxide and zeolite catalysts are reviewed and discussed, as is the removal of Hg from flue gas by catalysis. The oxidation of Volatile organic compounds (VOCs) by photo- and thermal-catalysis for indoor air quality improvement is reviewed. For wastewater treatment, the catalytic elimination of inorganic and organic pollutants in wastewater is presented. In addition, the mechanism for the procedure of abatement of air and water pollutants by catalysis is discussed in this review. Finally, a research orientation on environment catalysis for the treatment of air pollutants and wastewater is proposed.     

Biofuel production,hydrogen production and water remediation by photocatalysis,biocatalysis and electrocatalysis

The energy crisis and environmental pollution have recently fostered research on efficient methods such as environmental catalysis to produce biofuel and to clean water. Environmental catalysis refers to green catalysts used to breakdown pollutants or produce chemicals without generating undesirable by-products. For example, catalysts derived from waste or inexpensive materials are promising for the circular economy. Here we review environmental photocatalysis, biocatalysis, and electrocatalysis, with focus on catalyst synthesis, structure, and applications. Common catalysts include biomass-derived materials, metal–organic frameworks, non-noble metals nanoparticles, nanocomposites and enzymes. Structure characterization is done by Brunauer–Emmett–Teller isotherm, thermogravimetry, X-ray diffraction and photoelectron spectroscopy. We found that water pollutants can be degraded with an efficiency ranging from 71.7 to 100%, notably by heterogeneous Fenton catalysis. Photocatalysis produced dihydrogen (H₂) with generation rate higher than 100 μmol h⁻¹. Dihydrogen yields ranged from 27 to 88% by methane cracking. Biodiesel production reached 48.6 to 99%.

     

Treatment of organic pollutants by homogeneous and heterogeneous Fenton reaction processes

Nowadays, the water ecosystem is being polluted due to the rapid industrialization and massive use of antibiotics, fertilizers, cosmetics, paints, and other chemicals. Chemical oxidation is one of the most applied processes to degrade contaminants in water. However, chemicals are often unable to completely mineralize the pollutants. Enhanced pollutant degradation can be achieved by Fenton reaction and related processes. As a consequence, Fenton reactions have received great attention in the treatment of domestic and industrial wastewater effluents. Currently, homogeneous and heterogeneous Fenton processes are being investigated intensively and optimized for applications, either alone or in a combination of other processes. This review presents fundamental chemistry involved in various kinds of homogeneous Fenton reactions, which include classical Fenton, electro-Fenton, photo-Fenton, electro-Fenton, sono-electro-Fenton, and solar photoelectron-Fenton. In the homogeneous Fenton reaction process, the molar ratio of iron(II) and hydrogen peroxide, and the pH usually determine the effectiveness of removing target pollutants and subsequently their mineralization, monitored by a decrease in levels of total organic carbon or chemical oxygen demand. We present catalysts used in heterogeneous Fenton or Fenton-like reactions, such as H₂O₂–Fe³⁺(solid)/nano-zero-valent iron/immobilized iron and electro-Fenton-pyrite. Surface properties of heterogeneous catalysts generally control the efficiency to degrade pollutants. Examples of Fenton reactions are demonstrated to degrade and mineralize a wide range of water pollutants in real industrial wastewaters, such as dyes and phenols. Removal of various antibiotics by homogeneous and heterogeneous Fenton reactions is exemplified.     

苯胺的超临界水氧化研究1

苯胺的超临界水氧化表明,氧化剂Ｈ２Ｏ２、试验温度、压力和停留时间以及水样的起始ＴＯＣ值对ＴＯＣ的去除率有显著影响．在本试验中,选取了硫酸铜、硫酸铁、硫酸锰等金属盐进行苯胺的均相催化氧化试验研究,结果表明,这些金属盐对苯胺的氧化有不同的催化活性,筛选出硫酸锰和和硫酸亚铁进行了进一步的研究．以硫酸锰作催化剂为例,在４５０℃,２８ＭＰａ,Ｋ＝１．１,ｐＨ＝４．０的条件下,当停留时间为４６ｓ时,ＴＯＣ去除率达到１００%．     

Energy and environmental applications of carbon nanotubes

Energy and environment are major global issues inducing environmental pollution problems. Energy generation from conventional fossil fuels has been identified as the main culprit of environmental quality degradation and environmental pollution. In order to address these issues, nanotechnology plays an essential role in revolutionizing the device applications for energy conversion and storage, environmental monitoring, as well as green engineering of environmental friendly materials. Carbon nanotubes and their hybrid nanocomposites have received immense research attention for their potential applications in various fields due to their unique structural, electronic and mechanical properties. Here, we review the applications of carbon nanotubes (1) in energy conversion and storage such as in solar cells, fuel cells, hydrogen storage, lithium ion batteries and electrochemical supercapacitors, (2) in environmental monitoring and wastewater treatment for the detection and removal of gas pollutants, pathogens, dyes, heavy metals and pesticides and (3) in green nanocomposite design. Integration of carbon nanotubes in solar and fuel cells has increased the energy conversion efficiency of these energy conversion applications, which serve as the future sustainable energy sources. Carbon nanotubes doped with metal hydrides show high hydrogen storage capacity of around 6?wt% as a potential hydrogen storage medium. Carbon nanotubes nanocomposites have exhibited high energy capacity in lithium ion batteries and high specific capacitance in electrochemical supercapacitors, in addition to excellent cycle stability. High sensitivity and selectivity towards the detection of environmental pollutants are demonstrated by carbon nanotubes based sensors, as well as the anticipated potentials of carbon nanotubes as adsorbent to remove environmental pollutants, which show high adsorption capacity and good regeneration capability. Carbon nanotubes are employed as reinforcement material in green nanocomposites, which is advantageous in supplying the desired properties, in addition to the biodegradability. This article presents an overview of the advantages imparted by carbon nanotubes in electrochemical devices of energy applications and green nanocomposites, as well as nanosensor and adsorbent for environmental protection.     

中国环境基准理论与方法学研究进展及主要科学问题

环境基准是指环境介质中的环境要素对特定保护对象不产生不良或有害效应的最大限值,是环境标准制修订的科学依据。环境基准理论与方法学一直是国际环境科学和环境保护科学研究领域的前沿,也是国家环境管理的重大科技需求。本文在总结国际和我国环境基准研究成果的基础上,较为系统地阐述了环境基准的基本概况、理论方法学及重要进展。同时,结合学科特点和环境基准科技需求,综合分析了与环境基准理论方法学密切相关的系列关键科学问题。     

Supported single-atom catalysts: synthesis,characterization, properties,and applications

In recent years, there has been a wide research in supported single-atom catalysts (SACs), which contain only isolated individual metal atoms dispersed on an appropriate support or coordinated with the surface atoms of the support. The SACs exhibit many fascinating characteristics including high activity, selectivity, and maximum atomic utilization. These characteristics arise from the low coordination status, quantum size effect, and the strong metal–support interaction, which have proved to be very powerful in many typical heterogeneous catalysis field including oxidation, hydrogenation, the water–gas shift reaction, methanol steam reforming, electrocatalysis, and photocatalysis. In this review, we summarized the recent progress in synthesis, characterizations, properties, and applications of SACs.     

Crystalline mesoporous transition metal oxides: hard-templating synthesis and application in environmental catalysis

Mesoporous silicas such as MCM-41 and SBA-15 possess high surface areas, ordered nanopores, and excellent thermal stability, and have been often used as catalyst supports. Although mesoporous metal oxides have lower surface areas compared to mesoporous silicas, they generally have more diversified functionalities. Mesoporous metal oxides can be synthesized via a soft-templating or hard-templating approach, and these materials have recently found some applications in environmental catalysis, such as CO oxidation, N₂O decomposition, and elimination of organic pollutants. In this review, we summarize the synthesis of mesoporous transition metal oxides using mesoporous silicas as hard templates, highlight the application of these materials in environmental catalysis, and furnish some prospects for future development.     

氯/溴稳定同位素分析技术及其在环境科学研究中的应用

稳定同位素分析被认为是环境污染物溯源和转化途径探究的有效工具.针对氯/溴稳定同位素研究已经开发了一些较为可靠的分析技术,被广泛应用于氯乙烯、氯苯、溴酚、多溴二苯醚和有机氯农药等有机污染物的研究.本文综述了近年来氯/溴同位素分析技术的最新进展,介绍了稳定同位素分析技术在含氯/溴有机污染物的溯源分析和降解途径识别等方面的应用实例,分析了现有分析技术在仪器测定、分析策略、理论知识等方面的不足,展望了该技术的发展方向及其在环境科学领域内的应用前景.     

氟喹诺酮类抗生素环境行为及其生态毒理研究进展

氟喹诺酮类抗生素(FQs)是治疗人和动物细菌性感染的高效广谱抗菌药,随着氟喹诺酮类抗生素在禽畜养殖业的广泛使用,由此引起的环境污染受到人们的关注。本文综述了氟喹诺酮类抗生素在水体、土壤/沉积物中的污染现状、吸附降解环境行为及其生态毒理研究进展。FQs抗生素的环境行为和风险应从环境多介质层面进行评估,同时应加强对生态毒性机理以及与其他环境污染物的联合毒性效应的研究。