Characterizing the optimal operation of photocatalytic degradation of BDE-209 by nano-sized TiO2

Brominated flame retardants have been widely used in industry. There is a rapid growing public concern for their availabilities in the environment. Advanced oxidation process (AOP) is a promising and efficient technology which may be used to remove emerging chemicals such as brominated flame retardants. This project aims at investigating optimal operational conditions for the removal of BDE-209 using nano-scaled titanium(IV) oxide. The residual PBDE congeners after photocatalytical degradation of BDE-209 by TiO₂ were analysed by gas chromatography-mass spectrometry (GC-MS). It was found that the degradability of BDE-209 by TiO₂ was attributed to its photocatalytic activity but not the small size of the particles. The half-life of removing BDE-209 by TiO₂ was 3.05 days under visible light. Tetra- and penta-BDEs were the major degraded products of BDE-209. Optimum conditions for photocatalytical degradation of BDE-209 was found to be at pH 12 (93% ± 1%), 5, 10, 20 mg/L (93.0% ± 1.70%, 91.6% ± 3.21%, 91.9% ± 0.952%, respectively), respectively of humic acid and in the form of anatase/rutile TiO₂ (82% ± 3%). Hence, the efficiency of removing BDE-209 can be maximized while being cost effective at the said operating conditions.     

Effects of WOx modification on the activity, adsorption and redox properties of CeO2 catalyst for NOx reduction with ammonia

A series of WO₃/CeO₂ (WOx/CeO₂) catalysts were synthesized by wet impregnation of ammonium metatungstate on a CeO₂ support. The resulting solid acid catalysts were characterized by X-ray diffraction (XRD), UV-Vis spectroscopy (UV-Vis), Raman spectroscopy (Raman), in-situ Fourier transform infrared spectroscopy (in-situ FT-IR) of ammonia adsorption, NH₃-TPD, H₂ temperature-programmed reduction (H₂-TPR), NH₃/NO oxidation and activity measurements for NOx reduction by NH₃ (NH₃-SCR). The results show that polytungstate (WOx) species are the main species of tungsten oxide on the surface of ceria. The addition of tungsten oxide enhances the Brönsted acidity of ceria catalysts remarkably and decreases the amount of surface oxygen on ceria, with strong interaction between CeO₂ and WOx. As a result, the N₂ selectivity of NH₃ oxidation and NH₃-SCR at high temperatures (> 300℃) is enhanced. Therefore, a wide working temperature window in which NOx conversion exceeds 80% (NOx conversion > 80%) from 200 to 450℃, is achieved over 10 wt.% WOx/CeO₂ catalyst. A tentative model of the NH₃-SCR reaction route on WOx/CeO₂ catalysts is presented.     

Effect of CeO2 and Al2O3 on the activity of Pd/Co_3O_4/cordierite catalyst in the three-way catalysis reactions (CO/NO/CnHm)

The present article studies the effect of CeO₂ and Al₂O₃ on the activity of Pd/Co₃O₄/cordierite catalyst in conversion of NO, CO, C_nH_m. The catalysts were characterized by temperature programmed reduction with hydrogen, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. It is shown that the effect of CeO₂ on the properties of Pd/Co₃O₄/cordierite catalyst depends on preparation method. The catalyst obtained by co-deposition of cerium and cobalt oxides has higher activity in CO oxidation (CO + O₂ and CO + NO) and total hexane oxidation (C₆H₁₄ + O₂). Such phenomenon is probably caused by more than stoichiometric amount of formed oxygen vacancies, an increase in both mobility of surface oxygen and dispersity of components in the catalytic composition. It is demonstrated that CeO₂ addition promotes the SO₂ resistance of Pd/Co₃O₄/cordierite. The second support decreases the activity of Pd/Co₃O₄/cordierite catalyst in the reactions of CO and C₆H₁₄ with oxygen because of CoAl₂O₄ formation.     

Aminobenzenesulfonamide functionalized SBA-15 nanoporous molecular sieve: A new and promising adsorbent for preconcentration of lead and copper ions

A rapid method for the extraction and monitoring of nanogram level of Pb²⁺ and Cu²⁺ ions using uniform silanized mesopor (SBA-15) functionalized with aminobenzenesulfonamide groups and flame atomic absorption spectrometry (FAAS) is presented. Aminobenzenesulfonamide functionalized SBA-15 was synthesized according to procedure in the literature and the presence of organic groups in the silica framework was demonstrated by FT-IR spectra. The functionalized product showed the BET surface area 110 m²/g and pore diameter 5.1 nm, based on adsorption-desorption of N₂ at 77 K. The effect of several variables such as (amount of adsorbent, stirring time, pH and presence of other ions in the medium) has been studied. Lead and copper were completely extracted at pH greater than 3 after stirring for 10 min. The maximum capacity of the adsorbent was found to be 191.3 ± 1.4 and 155.0 ± 1.0 μg of lead and copper ions/mg functionalized SBA-15, respectively. The preconcentration factor of the method was found to be 200. The detection limit of the technique was 3.4 and 0.4 ng/mL for Pb²⁺ and Cu²⁺, respectively. The applications of this methodology for real samples were examined by various water type, black tea and pepper samples.     

Measurement of air exchange rates in different indoor environments using continuous CO2 sensors

A new air exchange rate (AER) monitoring method using continuous CO₂ sensors was developed and validated through both laboratory experiments and field studies. Controlled laboratory simulation tests were conducted in a 1-m³ environmental chamber at different AERs (0.1-10.0 hr^-1). AERs were determined using the decay method based on box model assumptions. Field tests were conducted in classrooms, dormitories, meeting rooms and apartments during 2-5 weekdays using CO₂ sensors coupled with data loggers. Indoor temperature, relative humidity (RH), and CO₂ concentrations were continuously monitored while outdoor parameters combined with on-site climate conditions were recorded. Statistical results indicated that good laboratory performance was achieved: duplicate precision was within 10%, and the measured AERs were 90%-120% of the real AERs. Average AERs were 1.22, 1.37, 1.10, 1.91 and 0.73 hr^-1 in dormitories, air-conditioned classrooms, classrooms with an air circulation cooling system, reading rooms, and meeting rooms, respectively. In an elderly particulate matter exposure study, all the homes had AER values ranging from 0.29 to 3.46 hr??1 in fall, and 0.12 to 1.39 hr^-1 in winter with a median AER of 1.15.     

Synthesis of TiO2 nanoparticles in different thermal conditions and modeling its photocatalytic activity with artificial neural network

Titanium dioxide (TiO₂) nanoparticles were prepared by sol gel route. The preparation parameters were optimized in the removal of 4-nitrophenol (4-NP). All catalysts were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). An artificial neural network model (ANN) was developed to predict the photocatalytic removal of 4-NP in the presence of TiO₂ nanoparticles prepared under desired conditions. The comparison between the predicted results by designed ANN model and the experimental data proved that modeling of the removal process of 4-NP using artificial neural network was a precise method to predict the extent of 4-NP removal under different conditions.     

镍掺杂二氧化钛光催化剂的制备与光催化性能研究

利用溶胶-凝胶法制备了镍掺杂的二氧化钛,采用紫外可见分光光度计、傅里叶红外分光光度计、X衍射仪(XRD)、扫描电镜(SEM)等测试手段对结果进行了表征。表征结果表明在550℃下煅烧的产物主要是锐钛型二氧化钛,镍的掺杂使得二氧化钛的紫外可见反射光谱明显红移,且镍掺杂二氧化钛的粒度减小,团聚程度下降。以活性艳蓝KN-R为模型降解目标物,通过比较镍掺杂二氧化钛、纯二氧化钛以及标准P25二氧化钛的光催化性能发现镍掺杂二氧化钛的光催化活性最好。当钛酸正丁酯/乙醇比为1:25;钛酸正丁酯/冰乙酸比为1:1;钛酸正丁酯/硝酸镍比为1 000:3;煅烧温度为550℃,煅烧时间为2 h时,镍掺杂二氧化钛的光催化效率最高,达到73.3%。     

沸石负载介孔TiO_2的制备及其可见光催化性能研究

以人工沸石为载体,采用溶胶-凝胶法,制备出了沸石负载介孔改性TiO2光催化剂。以亚甲基蓝为目标污染物,研究了不同掺杂金属及介孔薄膜制备方法对纳米TiO2可见光催化性能的影响。用扫描电镜(SEM)、紫外-可见吸收光谱(UV-vis)等手段研究了掺杂改性前后TiO2的变化。研究发现,N-Fe掺杂可使催化剂的光吸收谱带红移。当掺杂Fe的比为0.2%,焙烧温度为500℃时制备的TiO2效果最好,在可见光照射2 h后,亚甲基蓝的去除率可达90%。研究表明经十六烷基三甲基溴化铵(CTAB)作为模板剂修饰后的TiO2催化效果有明显提高,通过将经过萃取去除模板剂的共掺TiO2和直接高温焙烧的TiO2对比后发现,前者比后者降解亚甲基蓝的效果要好,原因在于,高温直接焙烧去除模板剂很容易使模板剂形成的骨架塌陷,减小了比表面积,从而影响了其光催化性能。     

改性甘蔗渣对Pb~(2+)、Cd~(2+)的吸附行为研究

为提高废弃甘蔗渣对重金属离子Cd2+和Pb2+的吸附能力,文章采用简单的方法制备了乙二胺四乙酸二酐(EDTAD)修饰的甘蔗渣。经FTIR分析,有大量的羰基修饰在了甘蔗渣的表面,为其吸附重金属离子提供了更多的活性位点。实验结果表明:经过修饰后的甘蔗渣对Cd2+和Pb2+的吸附量分别为46.46 mg/g、119.36 mg/g,是未修饰的3.69和12.31倍,且均能在20 min内达到最大吸附量并保持平衡,其吸附符合Langmuir等温吸附模型,且吸附过程遵循二级动力学模型。在pH 4~7范围内,修饰SCB对Cd2+和Pb2+具有较高的吸附能力。除此之外,在Cd2+、Pb2+、Cu2+和Zn2+共存的情况下,修饰SCB对Pb2+仍能保持较高的吸附量。修饰后的甘蔗渣对Cd2+和Pb2+的吸附能力有了显著提高,且具有一定的抗干扰能力,有望应用于实际工业废水处理。     

铝钛改性MCM-41材料对污水中铅镉的吸附研究

研究了改性MCM-41材料对污水中重金属铅、镉离子的吸附行为。在MCM-41材料中加入Al、Ti两种诱因金属离子来合成新的Al-Ti-MCM-41及Ti-Al-MCM-41改性材料,通过氮气吸附-脱附等温线对Al-Ti-MCM-41(Al/Ti=1∶1)及Al-Ti-MCM-41(Al/Ti=2∶1)样品进行了表征,并采用改性后的MCM-41材料为吸附剂对含有二价铅、镉离子的溶液进行吸附实验,考察了吸附剂投加量,Pb2+、Cd2+初始质量浓度和吸附温度对吸附的影响。结果表明:改性Al-Ti-MCM-41(Al/Ti=1∶1)材料的最可几孔径和比孔容分别为16.68 nm和0.046 cm3/g,由BJH计算得到的平均孔径为17.02 nm;Al-Ti-MCM-41(Al/Ti=2∶1)的最可几孔径和比孔容分别为16.88 nm和0.083 cm3/g,由BJH计算得到的平均孔径为17.08 nm。Al-Ti-MCM-41(Al/Ti=1∶1)对Cd2+的吸附率为99.8%;Al-Ti-MCM-41(Al/Ti=2∶1)对Pb2+的吸附率为99.96%;Pb2+和Cd2+的吸附容量随吸附剂投加量的增加而降低,随离子初始浓度的增大而增加;温度越高越有利于吸附。该研究重点考察改性MCM-41材料在重金属铅镉离子污染治理中的性能,从而为解决重金属铅镉的污染,加强环境保护提供理论支撑和技术支持,具有明确的现实意义。