钴负载MCM-41分子筛催化臭氧氧化水中氯代苯甲酸

通过水热法合成介孔分子筛MCM-41,采用等体积浸渍法制备了Co负载MCM-41分子筛催化剂(Co/MCM-41).小角X-射线粉末衍射(XRD)、紫外-可见漫反射光谱(UV-vis DRS)、N2吸附-脱附等温线及透射电镜(TEM)等对催化剂的成分、结构的表征结果显示,Co/MCM-41保持了纯硅MCM-41有序的介孔结构,钴元素以钴氧化物形式存在,比表面达到772 m.2g-1.将Co/MCM-41分子筛用于催化臭氧氧化水中对氯苯甲酸(p-CBA)的研究,结果表明,在优化条件下(2%负载量和25℃反应温度),催化剂的加入显著改善了TOC去除率,达到84.6%,是单独臭氧氧化的1.6倍.     

Ce-MCM-41分子筛用于臭氧氧化对氯苯甲酸的活性评价

通过水热法合成了铈掺杂MCM-41(Ce-MCM-41)介孔分子筛,并将其用于臭氧氧化水中对氯苯甲酸(p-CBA).小角X射线衍射(XRD)、氮气吸附-脱附(BET)、紫外可见漫反射光谱(UV-Vis DRS)、透射电镜(TEM)表征结果表明,铈成功进入MCM-41分子筛骨架,以正四面体形式存在,且Ce-MCM-41保持了纯硅MCM-41有序的介孔结构,具有较高的比表面积;铈的掺杂显著提高MCM-41催化臭氧氧化对氯苯甲酸的活性,反应60 min后,TOC去除率由MCM-41的63%提高到86%(Si/Ce=60),而单独臭氧氧化仅为52%;铈的溶出仅为0.085 mg.L-1,较同样负载量的铈负载Ce/MCM-41的溶出(0.44 mg.L-1)有较大减少.催化剂重复使用3次后仍保持较高的活性,这表明Ce-MCM-41具有较好的活性和稳定性,是一种有前景的臭氧氧化催化剂.     

Pd/MCM-41催化水溶液中碘苯Ullmann反应的研究

以水溶剂中Ullmann反应为目标反应,设计具有纳米介孔结构的Pd/MCM-41作为其高效催化剂.与传统SiO2载体负载的Pd催化剂比较,该催化剂在以水为介质的碘苯偶合（Ullmann反应）中显示出优良的催化活性和对联苯的选择性.     

石墨烯改性Al-MCM-41介孔分子筛负载铁芬顿催化剂降解苯酚

采用高温回流法将石墨烯(gh)掺杂于Al-MCM-41介孔分子筛中,通过浸渍法制备了石墨烯改性Al-MCM-41介孔分子筛负载铁芬顿催化剂(gh-Al-MCM-41-Fe),利用比表面仪、扫描电子显微镜-X射线能谱(SEM-EDX)对催化剂进行了表征,考察了不同p H条件下该催化剂对苯酚的催化降解效能.结果表明,gh-Al-MCM-41-Fe催化剂具有介孔结构,表明颗粒分布均匀,石墨烯的掺杂减小了颗粒粒径,与多种催化剂(非介孔Al2O3-Cu Al2O4、介孔Al2O3-Cu、介孔Al2O3-Fe、介孔Al-MCM-41-Fe)相比,gh-Al-MCM-41-Fe具有最高的苯酚催化降解效能,反应符合一级反应特征,石墨烯的掺杂能明显提高苯酚降解率和COD去除率,减少铁的溶出,拓宽p H范围,当p H值为3—5,反应90 min,COD去除率达到60%以上.     

温度对等离子体与催化剂结合脱除Nox的影响

考察了温度对介质阻挡放电和CuZSM-5催化剂"一段法"结合脱除氮氧化物(NOx)的影响.实验表明,在250℃和300℃时,对于NO/N2,NO/O2/N2和 NO/C2H4/N2三个体系,"一段法"脱除NOx的活性都相对较低.在NO/O2/C2H4/N2体系中,250℃介质阻挡放电和CuZSM-5结合脱除NOx产生了明显的协同效应.在300℃,等离子体对脱除NOx起负作用.相对低温(150℃)时,等离子体的促进作用很小.电学实验表明,当反应温度由25℃升至450℃,"一段法"体系的李萨如(Lissajous)图形由平行四边形(25℃)逐渐变为椭圆形(450℃),表明较高温度时催化剂的介电性质发生了变化.原位发射光谱证明在不同温度下,"一段法"体系中等离子体气相产生的活性物种数量明显不同.     

酞菁锌改性介孔分子筛催化降解孔雀石绿

以介孔分子筛MCM-41为载体,采用浸渍法将1,4,8,11,15,18,22,25-八环戊氧基酞菁锌(α-CyOPcZn)负载到分子筛上得到了一种新型的催化剂CyOPcZn/MCM-41.并通过氮气吸附、红外光谱扫描及电镜扫描对催化剂的结构进行表征.考察了该催化剂的用量、H2O2浓度对孔雀石绿降解作用的影响.实验结果表明,在模拟可见光照射下,当催化剂用量0.6 g.L-1、H2O2浓度为0.1 mmol.L-1时,60 min后使0.1 mmol.L-1的孔雀石绿水溶液的脱色率达到98.6%,并呈现出一级反应的动力学特征,速率常数k为0.0891 min-1.催化剂重复使用3次后,脱色率可达96%以上.     

单双介质阻挡放电降解苯的对比研究

在相同实验条件下,研究了单、双介质阻挡放电反应器的等离子体发射光谱,对苯的降解效率,以及CO和CO2的生成,检测了NO和NO2的浓度.结果表明,与单介质阻挡放电反应器相比,双介质阻挡放电反应器的发射光谱具有红移现象;单、双介质阻挡放电反应器对苯的降解效率、CO2的生成浓度及选择性几乎一致;采用双介质阻挡放电明显降低了CO的生成浓度,CO的生成选择性也有所下降.更为重要的是,双介质阻挡放电反应器极大地降低了NO2的生成,在本文的实验条件下,没有检测到NO.     

负载型分子筛催化剂对甲苯的催化性能

采用不同类型分子筛浸渍负载活性组分Ru制备Ru/M(M=β、MCM-41、Y、ZSM-5)催化剂，考察其对甲苯的催化性能，并通过XRD、BET、SEM、XPS、H₂-TPR、NH₃-TPD等表征，分析催化剂的孔道结构、酸性位等物化结构对催化活性的影响.结果发现以贵金属Ru为活性组分，Y为载体的催化剂催化性能最优，在300℃左右，甲苯基本完全降解，CO2选择性接近99%，几乎无副产物生成.由此说明，适宜的孔径尺寸、丰富的酸性位、较好的氧化还原性能和较大的比表面积能有效促进分子筛催化剂对甲苯的催化氧化.     

铈负载SBA-15分子筛催化臭氧氧化水中环丙沙星

通过水热法合成纯硅介孔分子筛SBA-15,并采用等体积浸渍法制备Ce负载SBA-15分子筛催化剂(Ce/SBA-15),将其应用于催化臭氧氧化环丙沙星(CIP).小角X射线衍射(XRD)、透射电镜(TEM)表征结果表明,Ce/SBA-15保持了纯硅SBA-15有序的介孔结构.Ce/SBA-15催化臭氧氧化环丙沙星(CIP)结果显示,催化剂有良好的活性,对环丙沙星的矿化率为63.3%,比单独臭氧氧化高出22.9%;随着铈负载量增加,催化剂活性呈现先增大后减小趋势,负载量为2%时催化效果最佳;TOC去除率随着反应温度增加而提高;溶液初始pH对反应有显著的影响,pH=5.01时TOC去除率最大.以水杨酸作为羟基自由基(·OH)捕获剂,用比色法测定·OH产量为0.0072 mmol·L~(-1).溶液中投加1 mmol·L~(-1)磷酸根时,催化臭氧氧化中TOC去除率降低了25.8%,催化效果受到明显抑制,表明·OH的生成发生在Ce/SBA-15表面.     

高硅分子筛的合成及其在VOCs吸附去除领域的应用

挥发性有机物(VOCs)是导致大气污染的主要成分之一.VOCs的处理方法有很多种,其中吸附法操作简单、经济合理,是富集和分离VOCs的有效方法之一.近年来,结合沸石转轮与蓄热式燃烧(RTO)或催化燃烧(RCO)的VOCs处理技术日益引起人们的关注.分子筛是沸石转轮技术的核心材料,其通常具有均匀的孔道结构,比表面积大,在气体吸附分离领域具有广阔的应用前景.不同类型的分子筛因具有不同的结构特性,应用的领域也有较大差异.高硅分子筛疏水性好、稳定性高,是吸附VOCs的理想吸附剂.目前,国内外对高硅分子筛的合成方法总结归纳相对较少,本文系统地评述了常用提高分子筛硅铝比的方法,并探讨了高硅分子筛在VOCs吸附领域的应用.     

Synthesis and characterization of Fe-MCM-41 from rice husk silica by hydrothermal technique for arsenate adsorption

Rice husk (RH) agro-waste was used as a raw material for synthesizing mesoporous molecular sieves, MCM-41. The Fe-MCM-41 was prepared by the hydrothermal technique (HT), resulting in a higher surface area and crystallinity than when prepared under ambient conditions. In addition, a hexagonal structure was clearly seen with hydrothermal technique (HT) preparation. The adsorption of arsenate by HT-Fe-MCM-41 was investigated. The factors studied affecting arsenate adsorption capacity were ferric content in MCM-41, contact time, pH of solution, and initial arsenate concentration. It was found that HT-Fe-MCM-41 at the Si/Fe mole ratio of 10 gave the highest adsorption capacity. Arsenate adsorption reached equilibrium within 4 h. The adsorption capacity of HT-Fe-MCM-41 (Si/Fe = 10) was affected by the initial pH value and the initial arsenate concentration. The adsorption capacity was highest at pH 3 and decreased thereafter with increases in the pH of solution value. The Langmuir model fit the arsenate adsorption isotherm well. The maximum adsorption capacity for arsenate was 1,111 μg g⁻¹.     

Amelioration of free copper by hydrothermal vent microbes as a response to high copper concentrations

We examined the effect of increased copper concentrations (0–10 μM) on hydrothermal vent micro- organisms and the production of copper (Cu)-binding ligands as a response. Hydrothermal vent microbes originated from diffuse fluids at the Lilliput mussel field and the Irina II site in the Logatchev hydrothermal vent field, both on the Mid-Atlantic Ridge. Parallel studies were also conducted with amino acids supplemented to the incubations in order to verify whether dissolved amino acids, present in hydrothermal fluids, can buffer the bioavailable copper and reduce the active production of Cu-binding ligands. In all incubations, ligand concentrations increased with rising copper concentrations, but microbial cell numbers remained constant. This study shows that microbes were able to cope with as much as 10 μM dissolved copper by buffering the free copper concentration. The presence of amino acids had no significant influence on the active ligand production. Our results imply that mediation of chemical speciation by vent microbes may have an important impact on hydrothermal trace metal fluxes into the ocean.     

Scientists as Stakeholders in Conservation of Hydrothermal Vents

Abstract: Hydrothermal vents are deep‐sea ecosystems that are almost exclusively known and explored by scientists rather than the general public. Continuing scientific discoveries arising from study of hydrothermal vents are concommitant with the increased number of scientific cruises visiting and sampling vent ecosystems. Through a bibliometric analysis, we assessed the scientific value of hydrothermal vents relative to two of the most well‐studied marine ecosystems, coral reefs and seagrass beds. Scientific literature on hydrothermal vents is abundant, of high impact, international, and interdisciplinary and is comparable in these regards with literature on coral reefs and seagrass beds. Scientists may affect hydrothermal vents because their activities are intense and spatially and temporally concentrated in these small systems. The potential for undesirable effects from scientific enterprise motivated the creation of a code of conduct for environmentally and scientifically benign use of hydrothermal vents for research. We surveyed scientists worldwide engaged in deep‐sea research and found that scientists were aware of the code of conduct and thought it was relevant to conservation, but they did not feel informed or confident about the respect other researchers have for the code. Although this code may serve as a reminder of scientists’ environmental responsibilities, conservation of particular vents (e.g., closures to human activity, specific human management) may effectively ensure sustainable use of vent ecosystems for all stakeholders.     

Hydrothermal treatment of MSWI fly ash for simultaneous dioxins decomposition and heavy metal stabilization

Researches on the hydrothermal treatment of municipal solid waste incineration (MSWI) fly ash were conducted to eliminate dioxins and stabilize heavy metals. In order to enhance decomposing polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzo-furans (PCDFs) during hydrothermal process, a strong reductant carbohydrazide (CHZ) is introduced. A hydrothermal reactor was set up by mixing raw MSWI fly ash or the pre-treated fly ash with water and then heated to a pre-set temperature; CHZ was spiked into solution according to specially defined dosage. Experimental results showed that under the temperatures of 518 K and 533 K, the decomposition rates of PCDDs/PCDFs were over 80% and 90%, respectively, by total concentration. However, their toxic equivalent (TEQ) decreased only slightly or even increased due to the rising in concentration of congeners 2, 3, 7, 8-TCDD/TCDF, which might be resulted from the highly chlorinated congeners losing their chlorine atoms and being degraded during the hydrothermal process. Better results of TEQ reduction were also obtained under the higher tested temperature of 533 K and reactor with addition of 0.1%wt CHZ was corresponded to the best results. Good stabilization of heavy metals was also obtained in the same hydrothermal process especially when ferrous sulphate was added as auxiliary agent.     

DNA damage in oral epithelial cells of individuals chronically exposed to indoor radon (<Superscript>222</Superscript>Rn) in a hydrothermal area

Hydrothermal areas are potentially hazardous to humans as volcanic gases such as radon (²²²Rn) are continuously released from soil diffuse degassing. Exposure to radon is estimated to be the second leading cause of lung cancer, but little is known about radon health-associated risks in hydrothermal regions. This cross-sectional study was designed to evaluate the DNA damage in the buccal epithelial cells of individuals chronically exposed to indoor radon in a volcanic area (Furnas volcano, Azores, Portugal) with a hydrothermal system. Buccal epithelial cells were collected from 33 individuals inhabiting the hydrothermal area (Ribeira Quente village) and from 49 individuals inhabiting a non-hydrothermal area (Ponta Delgada city). Indoor radon was measured with Ramon 2.2 detectors. Chromosome damage was measured by micronucleus cytome assay, and RAPD-PCR was used as a complementary tool to evaluate DNA damage, using three 10-mer primers (D11, F1 and F12). Indoor radon concentration correlated positively with the frequency of micronucleated cells (r _s = 0.325, p = 0.003). Exposure to radon is a risk factor for the occurrence micronucleated cells in the inhabitants of the hydrothermal area (RR = 1.71; 95% CI, 1.2–2.4; p = 0.003). One RAPD-PCR primer (F12) produced differences in the banding pattern, a fact that can indicate its potential for detecting radon-induced specific genomic alterations. The observed association between chronic exposure to indoor radon and the occurrence of chromosome damage in human oral epithelial cells evidences the usefulness of biological surveillance to assess mutations involved in pre-carcinogenesis in hydrothermal areas, reinforcing the need for further studies with human populations living in these areas.     

CuO/zeolite catalyzed oxidation of gaseous toluene under microwave heating

The development of a combined process of catalytic oxidation and microwave heating for treatment of toluene waste gas was described in this work. Toluene, a typical toxic volatile organic compound, was oxidized through a fixed bed reaction chamber containing zeolite-supported copper oxide (CuO/zeolite) catalyst mixed with silicon carbide (SiC), an excellent microwave-absorbing material. The target compound was efficiently degraded on the surface of the catalyst at high reaction temperature achieved by microwave-heated SiC. A set of experimental parameters, such as microwave power, air flow and the loading size of CuO etc., were investigated, respectively. The study demonstrated these parameters had critical impact on toluene degradation. Under optimal condition, 92% toluene was removed by this combined process, corresponding to an 80%–90% TOC removal rate. Furthermore, the catalyst was highly stable even after eight consecutive 6-h runs. At last, a hypothetical degradation pathway of toluene was proposed based on the experimental data obtained from gas chromatography-mass spectrum and Fourier transform infrared spectroscopy analyses.