Hydrothermal-treated Pt/Al2O3 as an excellent catalyst for toluene total oxidation

The preparation of highly active supported noble metal catalysts with a low noble metal loading has always been the ultimate goal of researchers working on catalysis. Hydrothermally treated Pt/Al₂O₃ (Pt/Al₂O₃-H) exhibits better catalytic activity than that (Pt/Al₂O₃-C) treated via the conventional calcination approach. At the high space velocity of 100,000 mL/(g∙hr), the temperature that correspond to 50% toluene conversion (T₅₀) of Pt/Al₂O₃-H is 115°C lower than that of Pt/Al₂O₃-C, and the turnover frequency (TOF) value can reach 0.0756 sec⁻¹. The mechanism by which the hydrothermal approach enhances Pt/Al₂O₃ activity has been investigated. The structure associated with the high catalytic activity of Pt nanoparticles (NPs) can be retained via hydrothermal treatment. Furthermore, the support is transformed to AlO(OH) with numerous surface hydroxyl groups, which in turn can facilitate the adsorption of toluene. And the synergistic effects of Pt NPs and AlO(OH) increases the contents of Pt in oxidation state and active oxygen, which are beneficial for toluene oxidation.     

Theoretical insights into the degradation mechanisms, kinetics and eco-toxicity of oxcarbazepine initiated by OH radicals in aqueous environments

As an anticonvulsant, oxcarbazepine (OXC) has attracted considerable attention for its potential threat to aquatic organisms. Density functional theory has been used to study the mechanisms and kinetics of OXC degradation initiated by OH radicals in aqueous environment. A total of fourteen OH-addition pathways were investigated, and the addition to the C8 position of the right benzene ring was the most vulnerable pathway, resulting in the intermediate IM8. The H-abstraction reactions initiated by OH radicals were also explored, where the extraction site of the methylene group (C14) on the seven-member carbon heterocyclic ring was found to be the optimal path. The calculations show that the total rate constant of OXC with OH radicals is 9.47 × 10⁹ (mol/L)⁻¹sec⁻¹, and the half-life time is 7.32 s at 298 K with the [·OH] of 10⁻¹¹ mol/L. Moreover, the branch ratio values revealed that OH-addition (89.58%) shows more advantageous than H-abstraction (10.42%). To further understand the potential eco-toxicity of OXC and its transformation products to aquatic organisms, acute toxicity and chronic toxicity were evaluated using ECOSAR software. The toxicity assessment revealed that most degradation products such as OXC-2OH, OXC-4OH, OXC-1O-1OOH, and OXC-1OH' are innoxious to fish and daphnia. Conversely, green algae are more sensitive to these compounds. This study can provide an extensive investigation into the degradation of OXC by OH radicals and enrich the understanding of the aquatic oxidation processes of pharmaceuticals and personal care products (PPCPs).     

Fractionation of residual Al in natural water treatment from reservoir with poly-aluminum-silicate-chloride (PASiC): Effect of OH/Al, Si/Al molar ratios and initial pH

An aluminum fractionation study was conducted for a surface reservoir water treatment to understand the performance of poly-aluminum-silicate-chloride (PASiC) in terms of the residual Al fractions as a function of initial pH. The coagulation performance expressed as turbidity and organic matter removal was established as supporting data. Some extra data were evaluated in terms of the residual Al ratio of the composite PASiC coagulant. The main residual Al sources were the Al fractions derived from the use of PASiC. The turbidity and organic matter removal ability was optimal at initial pH 6.00-7.00, while the concentrations of various residual Al species and the residual Al ratio of PASiC were minimal at an initial pH range of 7.00-8.00. Under the conditions of OH/Al molar ratio = 2.00 and Si/Al molar ratio = 0.05, PASiC had superior coagulation performance and comparatively low residual Al concentrations. The Al fraction in the composite PASiC coagulant seldom remained under such conditions. Experimental data also indicated that the suspended (filterable) Al fraction was the dominant species, and organic-bound or organo-Al complex Al was considered to be the major species of dissolved Al in water treated by PASiC coagulation. Additionally, the dissolved inorganic monomeric Al species dominated the dissolved monomeric Al fraction.     

Adsorption characteristics and mechanism of Cr （Ⅵ） on chitoan-yttrium porous microsphere

以壳聚糖和Y2（OH）5NO3为原料通过乳液交联法制备了壳聚糖-钇（Ch—Y）复合微球,通过扫描电镜、透射电镜、X射线衍射、红外光谱等方法对其表面形貌、结构进行了表征.探讨了溶液的pH值、反应时间、投加量、离子初始浓度对其吸附性能的影响.研究结果表明,壳聚糖-钇（Ch—Y）复合微球在pH值为3的酸性环境中对Cr（Ⅵ）保持了较高的吸附能力,吸附容量为52.39mg·g-1,其吸附行为符合Langmuir吸附等温模型;通过吸附机理的研究,发现壳聚糖-钇（Ch—Y）对Cr（Ⅵ）吸附是化学吸附静电吸附协同氧化Cr（Ⅵ）离子作用来实现的.     

珠江三角洲轻型汽油车匀速状态挥发性有机物排放特征研究

以18辆轻型汽油车(LDGVs)为研究对象,利用底盘测功机搭建挥发性有机物(VOCs)采样系统.利用气相色谱-质谱仪(GC-MS)和高效液相色谱(HPLC)识别了匀速25 km·h~(-1)时尾气VOCs化学成分谱和排放因子,并在分析时考虑了排放标准、行驶工况和车辆属性等因素的影响.结果表明,轻型汽油车低速匀速工况下尾气组成以烷烃(40.8%,C_5～C_7烷烃较多)为主,其次是芳香烃(29.5%)和含氧VOCs(26.0%),烯炔烃(3.6%)和卤代烃(0.1%)较少.其中,甲醛、异戊烷、甲苯、苯、间/对二甲苯、丙酮、2-甲基戊烷、正戊烷、1,2,4-三甲基苯和壬醛是比例最高的物质(52.01%).低速匀速行驶中生成了比例更低的烯烃和比例更高的C_5～C_7烷烃和OVOCs.排放标准为国III、IV和V的轻型汽油车在低速匀速工况下,VOCs排放因子分别为(50.12±46.83)、(40.26±31.15)和(3.25±0.65) mg·km~(-1).国IV到国V车的烷烃、烯炔烃、芳香烃、卤代烃和总VOCs降幅均超过88%,而OVOCs降幅只有约55%,说明OVOCs在国V车的排放富集程度更高.总体来讲,国V车排放的VOCs反应活性约为国IV车排放的VOCs反应活性的11%.车辆属性对VOCs排放的影响表现为:年份、里程和排量的增加会促进VOCs排放的整体增加,而基准质量对VOCs排放的影响相对较小.     

Fenton反应及其参与的光催化体系的机理研究进展

综述了光催化降解有机污染物和杀菌的机理,其中降解有机物机理的主要内容为空穴和羟基自由基(·OH)氧化分解有机污染物,杀菌机理与降解有机物类似,即电子和空穴或含氧自由基攻击细菌的细胞壁、细胞膜和胞内成分,使细菌失活。分别从Fe~(2+)和Cu~(2+)两种离子介导的Fenton反应总结了Fenton反应的机理,得出两种离子介导的Fenton反应具有类似机理的结论。最后阐述了目前在光催化体系中引入Fenton反应的研究现状及作用机理,发现将Fenton反应引入光催化体系是促进光催化活性的有效途径。     

某工业园区VOCs臭氧生成潜势及优控物种

臭氧(O3)污染日趋严重,控制光化学反应前体物之一的挥发性有机污染物(volatile organic compounds,VOCs)对减少臭氧生成有重要意义.为研究天津某工业园区VOCs臭氧生成潜势,采集了园区6个代表企业厂界气体样品,使用质子转移反应飞行时间质谱仪(PTR-TOF-MS)对VOCs进行了定量分析,估算了各企业臭氧生成潜势,运用VOCs/NO_x研究了臭氧生成控制敏感性因素,并在熵值法基础上筛选出了减少臭氧生成优先控制VOCs物种.结果表明,通过PEC法估算臭氧生成F企业最高为0.423 3 mg·m~(-3),MIR法估算结果 C企业最高为1.573 3 mg·m~(-3);PEC法估算结果与臭氧浓度更接近,适用于园区对臭氧生成的估算;VOCs和NOx均为工业园区臭氧生成敏感性因素,需同时控制;园区内VOCs物种臭氧生成贡献大小为烷烃烯炔烃醇类芳香烃,优先控制物种为正庚烷及其同分异构体、正壬烷、正辛烷及其同分异构体、正十一烷、戊烷、正癸烷、甲醇.     

某石油化工园区秋季VOCs污染特征及来源解析

利用快速连续在线自动监测系统对某典型石油化工园区2014年秋季(9、10、11月)大气中VOCs进行监测,并对其组成、光化学反应活性、时间变化特征和来源进行解析.结果表明:秋季大气中VOCs的混合体积分数明显高于国内外其他城市和工业地区,且烷烃是大气中VOCs的最主要成分.研究区秋季3个月份大气中VOCs的混合体积分数之间差异不显著,但各种烃类的日夜变化特征明显:烷烃、烯烃和芳香烃呈现"单峰单谷"变化趋势,乙炔的变化趋势呈"W"型.PMF受体模型解析结果表明主要来源于天然气交通及溶剂、炼油厂的泄漏或挥发等过程,其次为其他交通来源,沥青对于研究区VOCs来源也有一定的贡献.等效丙烯体积和最大臭氧生成潜势对VOCs的光化学反应活性计算结果表明,烯烃和烷烃分别是各自混合体积分数的最主要的贡献者.     

2021年夏季新乡市城区臭氧超标日污染特征及敏感性

基于2021年6～8月新乡市市委党校站点观测的挥发性有机物(VOCs)、常规空气污染物和气象参数,采用基于观测的模型(OBM)对臭氧(O₃)超标日的O₃敏感性和前体物的管控策略进行了研究.结果发现,O₃超标日呈现高温、低湿和低压的气象特征.在臭氧超标日,O₃及其前体物的浓度均有上升.臭氧超标日的VOCs最高浓度组分为含氧挥发性有机物(OVOCs)和烷烃,臭氧生成潜势(OFP)和·OH反应性最大的VOCs组分为OVOCs.通过相对增量反应性(RIR)分析,新乡6月O₃超标日臭氧生成处于VOCs控制区,7月和8月处于VOCs和氮氧化物(NO_x)协同控制区,臭氧生成对烯烃和OVOCs最为敏感.6月各前体物的RIR值在一天中会发生变化,但始终保持为VOCs控制区;7月和8月在上午为VOCs控制区,中午为协同控制区,下午分别为协同控制区和NO_x控制区.通过模拟不同前体物削减情景,结果表明削减VOCs始终有利于管控臭氧,而削减NO_x     

Al2O3为载体的催化剂净化贫燃汽车尾气研究

在富氧条件下,考察了C₃H₆和C₂H₅OH在Ag/Al₂O₃、In/Al₂O₃、Sn/Al₂O₃、Co/Al₂O₃、Pt/Al₂O₃和Ag/Al₂O₃+Pt/Al₂O₃组合催化剂上选择性还原NO的性能.结果表明,Ag/Al₂O₃具有最高的NO还原活性.在负载型过渡金属氧化物催化剂上,会生成显著量的CO,其HC和CO氧化转化温度也远远高于Pt/Al₂O₃催化剂.串联组合Ag/Al₂O₃+Pt/Al₂O₃催化剂可显著拓宽活性温度范围,促进HC和CO氧化,降低N₂O和CH₃CHO生成量.