Density functional theory (DFT) studies of vanadium-titanium based selective catalytic reduction (SCR) catalysts

Based on density functional theory (DFT) and basic structure models, the chemical reactions on the surface of vanadium-titanium based selective catalytic reduction (SCR) denitrification catalysts were summarized. Reasonable structural models (non-periodic and periodic structural models) are the basis of density functional calculations. A periodic structure model was more appropriate to represent the catalyst surface, and its theoretical calculation results were more comparable with the experimental results than a non-periodic model. It is generally believed that the SCR mechanism where NH₃ and NO react to produce N₂ and H₂O follows an Eley-Rideal type mechanism. NH₂NO was found to be an important intermediate in the SCR reaction, with multiple production routes. Simultaneously, the effects of H₂O, SO₂ and metal on SCR catalysts were also summarized.     

Mechanism and catalytic performance for direct dimethyl ether synthesis by CO2 hydrogenation over CuZnZr/ferrierite hybrid catalyst

Direct synthesis of dimethyl ether(DME) by CO_2 hydrogenation has been investigated over three hybrid catalysts prepared by different methods:co-precipitation,sol-gel,and solid grinding to produce mixed Cu,ZnO,ZrO_2 catalysts that were physically mixed with a commercial ferrierite(FER) zeolite.The catalysts were characterized by N_2 physisorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),temperature programmed desorption of CO_2(CO_2-TPD),temperature programmed desorption of NH_3(NH_3-TPD),and temperature programmed H2 reduction(H_2-TPR).The results demonstrate that smaller CuO and Cu crystallite sizes resulting in better dispersion of the active phases,higher surface area,and lower reduction temperature are all favorable for catalytic activity.The reaction mechanism has been studied using in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).Methanol appears to be formed via the bidentate-formate(b-HCOO) species undergoing stepwise hydrogenation,while DME formation occurs from methanol dehydration and reaction of two surface methoxy groups.     

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl^? and PO₄^3? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min^?1 (R²=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H₂O and the oxidation reaction with H₂O₂ were found during the degradation pathway of 5 mg/L TCEP in the UV/H₂O₂ system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H₂O₂ system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.     

杭州湾北岸36种挥发性有机物污染特征及来源解析

为研究杭州湾北岸VOCs（挥发性有机物）的浓度水平、组成特征、反应活性和潜在来源,采用GC-FID在线监测系统对杭州湾北岸环境大气中的36种VOCs开展了为期1 a（2017年12月-2018年11月）的连续观测,采用LOH（VOCs的·OH消耗速率）和OFP（O₃生成潜势）2种方法估算了大气VOCs的反应活性,并利用PMF（正定矩阵因子分解）和CPF（条件概率函数）模型分析其来源.结果表明:①φ（VOCs）小时平均值在冬季（26.47×10-9）最高,夏季（9.76×10-9）最低;全年φ（VOCs）小时平均值为21.24×10-9,其中烷烃、烯烃+炔烃、芳香烃、卤代烃的贡献率分别为33.24%、34.13%、15.63%、17.00%;φ（烷烃）、φ（芳香烃）和φ（卤代烃）呈较明显的昼夜变化特征,φ（烯烃）和φ（炔烃）无明显昼夜变化趋势.②大气VOCs的总LOH和OFP分别为9.39 s-1和220.57 μg/m3,KOH（·OH反应速率常数）和MIR（最大增量反应活性）系数的平均值分别为17.34×10-12 cm3/（molecule·s）和3.31;KOH和MIR系数的平均值分别与间/对-二甲苯的KOH和乙苯的MIR系数接近,表明大气VOCs的化学反应活性较强;VOCs关键活性物种为异戊二烯、乙烯、丙烯、甲苯、二甲苯和顺-2-丁烯.③特征物种相关性分析表明,杭州湾北岸大气存在老化现象,异戊烷和正戊烷受煤燃烧源影响较大,二甲苯和乙苯受溶剂排放源影响较大,甲苯和苯除受机动车尾气影响外,还受其他排放源影响.④PMF和CPF模型来源分析表明,大气VOCs主要来自石化工业源、燃料挥发源、生物质燃烧和煤燃烧源、机动车排放源和溶剂使用源,其中,机动车排放源主要来自西北方向,其他源主要来自西北、西和西南方向.研究显示,杭州湾北岸大气VOCs来源复杂,受周边工业区的影响较大.      

Chemical characteristics of road dust PM2.5 fraction in oasis cities at the margin of Tarim Basin

In order to understand the compositions characteristics of particulate matter with aerodynamic diameter less than 2.5 μm (PM_2.5) fraction in road dust (RD_2.5) of oasis cities on the edge of Tarim Basin, 30 road dust (RD) samples were collected in Kashi, Cele, and Yutian in the spring, 2018, and RD_2.5 was collected using the resuspension approach. Eight water-soluble ions, 39 trace elements and 8 fractions of carbon-containing species in PM_2.5 were analyzed. Ca²⁺ and Ca were the most abundant ions and elements in RD_2.5 (7.1% and 9.5%). Cl^- in RD_2.5 was affected not only by attributed to saline-alkali soils in oasis cities of the Tarim Basin and dust from Taklimakan Desert but also by human activities. Moreover, the organic carbon/elemental carbon (OC/EC) ratio indicated that carbon components in RD_2.5 in Cele town mainly come from fossil fuel combustion, while those in Yutian and Kashi mainly come from biomass combustion. It is noteworthy that high Ca in RD_2.5 was seriously affected by anthropogenic emissions, and high Na and K contents in RD_2.5 could be derived from soil and desert dust. It was estimated that Cd, Tl, Sn and Cr were emitted from anthropogenic emissions using the enrichment factor. The coefficients of divergence (COD) result indicated that the influence of local emission on road dust emission is greater than that of long-distance transmission. This study is the first time to comprehensively analyze the chemical characteristics of road dust in oasis cities, and the results provides the sources of road dust at the margin of Tarim Basin.     

乡村文化记忆资源的“文—旅”协同评价模型与应用——以苏州金庭镇为例

乡村文化记忆资源是乡村“文—旅”协同的链接点。基于文化记忆理论从文化信息层、物质载体层与社会行为层解析其内涵和协同框架,构建“文—旅”空间协调度、文化记忆连续性和旅游市场认同度的协同评价模型,以苏州金庭镇为例进行实证分析。结果表明:（1）时间格局上,旅游景点与生活生产类空间关联性不断提升,与功能象征类空间依赖减弱,与社会表征类和精神意识类空间关系有所降低但维持高度耦合水平。（2）空间格局上,与生活生产类空间呈极核带状格局,与其余三类空间呈现一核多极格局。（3）旅游景点与生活生产类空间协同关系从“文—旅”空间协调度、文化记忆连续性转向旅游市场认同度为主导,其余空间以“文—旅”空间协调度为主导。（4）影响协同关系的机制包括记忆延续与文化交融、空间优化与旅游融合和社会支持与政策保障等。研究结论可为乡村旅游地的文化振兴和文旅融合提供理论指导和应用模式。     

区域产业结构转型升级水平与旅游扶贫效率耦合关系——以武陵山片区为例

以武陵山片区42个国家级贫困县（市、区）为案例地,综合运用SBM模型、改进的熵值法与耦合协调模型,揭示产业结构转型升级水平与旅游扶贫效率耦合协调关系的时空演化特征。结果表明:（1）武陵山片区整体及各分片区产业结构转型升级指数均呈波浪式变化,湖北片区、重庆片区以及武陵山片区整体的旅游扶贫效率呈上升态势,而湖南片区和贵州片区略有下降;（2）产业结构转型升级水平与旅游扶贫效率不耦合、不协调的县域单元主要集中在武陵山片区中部,数量逐年减少,实现耦合和协调的县域数量显著增加并向边缘地带形成集聚态势;（3）不耦合失调（类型1）向耦合协调（类型2）转变是核心转变路径,促使类型2的地区数量显著增多,并逐渐在研究区域边缘形成带状分布。研究可为集中连片特困地区产业结构优化升级和跨越贫困陷阱提供参考借鉴。     

基于SVR的长江经济带水环境承载力评价

基于DPSIRM模型构建区域水环境承载力评价指标体系,并基于SVR模型构建了区域水环境承载力评价模型,利用交叉验证法对SVR模型参数进行优化选择,进一步提高模型预测精度.运用该模型研究了长江经济带2009~2018年的水环境承载力演变趋势及空间差异,结果表明：长江经济带水环境承载力等级整体呈现升高趋势,其中上游城市群承载等级由II级（超载）提升到了IV级（弱可承载）;中游城市群承载等级由II级（超载）提升到了IV级（弱可承载）;下游长三角区域承载等级由I级（重超载）提升到了IV级（弱可承载）.将评价结果与熵权-TOPSIS法的评价结果相比较,相同率达到91.7%,说明SVR模型评价区域水环境承载力可行,评价结果可靠.以下游区域为例,分别对其6个子系统的承载力进行剖析,并运用单因素轮换OAT法对各子系统内的评价指标进行敏感性分析,便于决策者识别指标敏感性.     

我国能源资源税改革对城乡居民的收入分配效应——基于CGE模型的分析

通过构建包含7个城镇居民组和5个农村居民组的多收入阶层CGE模型,并将劳动力要素分为农业劳动力、技术工人和生产工人3类,在低税率、实际税率和高税率三种情景下模拟了煤炭、石油和天然气资源税改革单独实施和同时实施对城镇和农村居民的收入分配效应,并对税收补偿措施的效果进行分析.结果表明：单独实施煤炭资源税或天然气资源税改革对城镇居民组收入差距有正向的缩小作用,有利于收入分配公平,但对农村居民组收入差距起到负向的扩大作用,不利于收入分配公平;单独实施石油资源税改革则同时缩小了城镇和居民组的收入差距,有利于收入分配公平;同时实施三类能源资源税改革的收入分配效应与税率组合方式有关;将能源资源税收入以补贴的方式返还给农村居民可以缩小其收入差距,有利于收入分配公平.     

含菌气溶胶扩散对人群的潜在影响风险

为分析生物气溶胶释放对人群潜在影响风险的情况,利用CALPUFF模型定量模拟了2019年7月24~8月20日中牧兰州生物药厂含菌气溶胶扩散、浓度空间分布、对人群潜在健康风险,并结合公开报道的检测数据开展验证.结果显示：生物药厂的含菌气溶胶排放源附近高值区主要集中于厂区四周,影响范围主要以厂区为中心,并向四周逐渐扩散;检测结果中兰州兽研所1#,兰州大学2#地区健康风险比例41.49：1,在模拟的相对风险大小的误差区间（36.15±8.48）范围内,说明本研究含菌气溶胶对人群潜在影响风险的模拟结果可信.