微波诱导催化技术在环境治理中的应用研究

微波诱导催化技术以其快速、高效和无二次污染等特点,日益受到环保研究者的重视。目前,微波诱导催化技术已在大气污染控制、水污染控制及固体废弃物处理与处置等环境治理领域取得了显著效果。阐述了微波诱导催化技术的基本原理、催化反应的催化剂和载体及催化反应的机制,归纳了微波诱导催化技术在环境治理中的应用现况及实例,分析了微波诱导催化技术在实际应用中存在的问题,并提出相应的解决措施,最后对微波诱导催化技术在环境治理领域中的进一步应用进行了展望。     

The chemical exploitation of nickel phytoextraction: An environmental, ecologic and economic opportunity for New Caledonia

Herein, we explore the outlines of an innovative method based on the chemical recovery of metal-rich biomass produced in phytoextraction technologies. Taking advantage of the adaptive capacity of some New Caledonian plants to hyperaccumulate Ni²⁺ cations in their aerial parts, this technique is based on the direct use of metals derived from plants as “Lewis acid” catalysts in organic chemistry. Metallic cations contained in New Caledonian nickel hyperaccumulators are recovered through a simple cost-effective process and serve the preparation of heterogeneous catalysts used in synthetic transformations allowing access to molecules with high added-value. The design of all processes is in line with the principles of green chemistry; it is adapted to the new economic constraints; it offers a new relevant outlet for metal-rich biomass; and it represents an alternative to non-renewable mineral materials.     

负载TiO2/Fe3+的玻璃纤维反应器光催化苯酚

以玻璃纤维为载体,将TiO2负载到其表面形成了空间玻璃纤维反应器,引入Fe3+作为掺杂改性离子,形成了负载TiO2/Fe3+的空间玻璃纤维光催化反应器,并以高压汞灯为光源进行了光催化降解水中苯酚的实验研究,考察了影响苯酚光催化降解的因素,确定了在UV365～250 W光源照射下,pH为3～5,O2通入量1.0 L/(min.L),反应器内上升流速为0.7 m/min等实验条件下,初始浓度为30 mg/L的苯酚废水经120 min光催化反应后,降解率可达到85%,矿化率可达80%。     

Non-Fickian dispersion in a single fracture

Solute transport in fractured rocks is of major interest in many applications, from the petroleum industry to ground water management. This work focuses on the dispersion process in a transparent replica of a real single fracture. The fracture exhibits strong changes in heterogeneity, with the first half very heterogeneous and the second half fairly homogeneous. Three models have been used to interpret the tracer experiments: the classical advection-dispersion equation (ADE), the continuous time random walk (CTRW), and the stratified model. The main goals were to test these models and to study possible correlations between fitting parameters and heterogeneities. As expected, the solution derived from the ADE equation appears to be unable to model long-time tailing behavior. On the other hand, the results confirm the CTRW robustness and the coefficient beta seems well correlated to heterogeneities. Finally, the stratified model is also able to describe non-Fickian dispersion. The parameters defined by this model are correlated to the heterogeneities of the fracture.     

大气中有机胺类物质反应机理和消除过程研究

综述大气中有机胺可能的来源、健康危害及其在大气中的均相和非均相化学转化机制,阐述有机胺的反应产物对二次有机气溶胶及其对大气气溶胶的物理和化学性质的改变,此类改变增强大气气溶胶间接气候效应(如成云结核能力等)。大气中的有机胺主要通过与大气氧化剂的反应和非均相反应过程的溶解或置换进入颗粒相,而后随着湿沉降(如云滴、雾滴、雨滴等)到达地面或海面。     

Heterogeneous oxidation of SO2 by O3-aged black carbon and its dithiothreitol oxidative potential

Ozone (O₃) is an important atmospheric oxidant. Black carbon (BC) particles released into the atmosphere undergo an aging process via O₃ oxidation. O₃-aged BC particles may change their uptake ability toward trace reducing gases such as SO₂ in the atmosphere, leading to different environmental and health effects. In this paper, the heterogeneous reaction process between O₃-aged BC and SO₂ was explored via in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Combined with ion chromatography (IC), DRIFTS was used to qualitatively and quantitatively analyze the sulfate product. The results showed that O₃-aged BC had stronger SO₂ oxidation ability than fresh BC, and the reactive species/sites generated on the surface had an important role in the oxidation of SO₂. Relative humidity or 254 nm UV (ultraviolet) light illumination enhanced the oxidation uptake of SO₂ on O₃-aged BC. The oxidation potentials of the BC particles were detected via dithiothreitol (DTT) assay. The DTT activity over BC was decreased in the process of SO₂ reduction, with the consumption of oxidative active sites.     

光助芬顿反应催化降解气体中甲苯

以甲苯作为挥发性有机污染物(VOCs)的代表,利用连续进气动态实验装置,研究光助芬顿反应降解气体中甲苯的作用.考察了芬顿试剂溶液初始p H、H2O2浓度、Fe2+浓度以及甲苯初始浓度对降解甲苯的影响,并利用在线质谱和色谱对产物进行了定性、定量分析.结果表明,紫外光照加快了羟基自由基的生成,显著提高了气体中甲苯的去除率;p H=3.0、H2O2浓度为20 mmol·L-1、Fe2+浓度为0.3 mmol·L-1的条件下,甲苯去除率最高;当甲苯初始浓度为260 mg·m-3时,去除率能够达到98%;光助芬顿反应催化降解气体中甲苯实验未检测到CO2之外的中间产物,CO2产率分析表明去除的甲苯全部转化为CO2.     

Polymer hydrogels with enhanced stability and heterogeneous Fenton activity in organic pollutant removal

Polymer hydrogel-based materials have been shown to act as novel Fenton catalysts for water treatment, but the rational design of hydrogel-based catalysts with good stability has been a great challenge. To increase the stability and activity of polymer-based Fenton catalysts, uniform urchin-like α-Fe_2O_3 was grown in situ in a PVA carrier matrix here. PVA molecules promoted the growth of urchin-like α-Fe_2O_3, and then the PVA hydrogel acted as a barrier and carrier to reduce agglomeration. Through coordination by hydroxyl groups,PVA had good combination with Fe ions and α-Fe_2O_3. The formation of Fe–O–C bonds between iron oxides and polymers was reported for the first time, enhancing the material stability during catalysis. Under higher PVA concentrations, the resulting composite hydrogel could generate more ˙OH due to the increase in the number of active sites because of the hairy urchin-like structure. In tetracycline degradation through a heterogeneous Fenton reaction, the resulting material had good catalytic activity from pH 2 to pH 10 with low iron leaching, good reusability and remained at a level of nearly 90%after five consecutive cycles. Density functional theory calculations were used to further prove the mechanism of structural change of the iron oxides. The HOMO and LUMO energies of the iron oxides changed from 5.428 and 4.899 eV to 5.926 and 5.310 eV,indicating that the presence of PVA could influence the charge of the iron atom. The results provide new insights into the preparation of polymer hydrogel-based heterogeneous Fenton catalysts with enhanced stability for water treatment.     

阻挡放电联合金属氧化物催化降解H2S的研究

采用介质阻挡放电联合金属氧化物催化降解气态H2S,考察了单组分及复合金属氧化物催化剂、催化剂与低温等离子体结合方式对H2S及副产物O3去除性能的影响,分析了等离子体联合Mn复合金属氧化物催化降解H2S机理。结果表明,金属负载量相同条件下,电压低于22kV时,Mn复合金属氧化物对H2S的催化活性高于单组分Mn金属氧化物,催化活性及对O3的分解能力从大到小依次为:Ag+Mn、Cu+Mn、Fe+Mn、Mn。当电压为18 kV时,Ag+Mn、Cu+Mn、Fe+Mn复合催化剂分别比单组分Mn催化剂对H2S的去除效率提高了近10%、6%、4%。等离子体后催化区域中Mn催化剂催化氧化H2S的效率明显低于等离子体催化区域。Mn催化剂在等离子体后催化区域中能有效催化分解O3。随着电压的升高,Mn金属氧化物在等离子体后催化区域对H2S催化作用逐渐增强。在电压22 kV时,等离子体联合后催化比单独等离子体作用时,H2S去除效率提高了近11%。     

Carbon nanotubes-incorporated MIL-88B-Fe as highly efficient Fenton-like catalyst for degradation of organic pollutants

CNTs were incorporated into MIL-88B-Fe to get a new Fenton-like catalyst (C@M). Fe(II) was introduced in C@M to get a fast initiation of Fenton-like reaction. Fe(II) content in C@M was related with oxygen-containing functional groups on CNTs. C@M shows efficient catalytic degradation of pollutants over a wide pH range. Iron-based metal organic frameworks have been verified to be efficient heterogeneous Fenton catalysts due to their open pore channels and highly uniform distribution of metallic centers. In these catalysts, however, the iron element is mainly in the form of Fe(III), which results in a process required to reduce Fe(III) to Fe(II) to initiate Fenton reaction. To address this problem, carbon nanotubes (CNTs) with electron-rich oxygen-functional groups on the surface were incorporated into the metal organic frameworks (MIL-88B-Fe) to improve Fe(II) content for an enhanced Fenton-like performance. The prepared CNT@MIL-88B-Fe (C@M) showed much stronger catalytic ability toward H₂O₂ than MIL-88B-Fe. The pseudo-first-order kinetic constant for phenol degradation by C@M (0.32 min^–1) was about 7 times that of MIL-88B-Fe, and even higher than or comparable to the values of reported heterogeneous Fenton-like catalysts. Moreover, the Fenton-like system could effectively degrade various kinds of refractory organic pollutants and exhibited excellent catalytic activity over a wide pH range (4–9). XPS analysis confirmed that Fe(II) content of the catalyst gradually increased with CNT loadings. Electron spin resonance analysis showed that the signal intensity (•OH) of C@M was much higher than MIL-88B-Fe, which was consistent with the degradation efficiency of pollutants. Furthermore, the Fe(II) content of the catalyst gradually increased along with the oxygen-functional group content of CNTs. The result demonstrated that oxygen-containing functional groups of CNTs have a significant impact on the enhanced catalytic performance of C@M. This study provides a new insight to enhance Fenton reaction by using nanocarbon materials.