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.     

Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO^?)-initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO^? attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σ_p constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established.     

随机振动响应峰值因子的预计理论研究

简要介绍了超越概率理论、超越频次理论、损伤等效理论和功率谱密度(PSD)的时域拟合理论等4种常见的峰值因子预计理论,并基于三角级数提出了一种新的预计理论。结合试飞加速度数据样本,对比分析超越频次理论、PSD时域拟合理论和三角级数理论的预估精度。研究表明,上述4种常见的预计理论本质上属于统计学理论;PSD时域拟合理论预计的峰值因子波动较大,峰值因子与归一化次数满足高斯分布;三角级数理论的预估精度较高,但缺乏离散峰个数的合理判据。     

中国乘用车塑料的动态物质流分析

结合行业信息并基于动态物质流模型,本文对1950~2050年间中国乘用车塑料流量与存量进行了历史测算与情景分析.历史测算表明：1950~2018年国内乘用车行业累计消耗了以聚丙烯（PP）、聚氨酯（PU）等为主的塑料3278万t,产生了337万t塑料废弃物;报废汽车拆解后的车用废塑料仅28%得到回收利用.针对未来情况,本文设计了乘用车保有量、单车塑料使用量两大关键因素下的不同情景组合.结果显示车用塑料存量及废塑料产生量将大幅增长,到2050年存量将达到0.7~2.7亿t,废塑料产生量将达到500~1600万t,汽车拆解和塑料再生等相关行业对此应充分关注.到2050年车用废塑料回收率若能提升至80%,将减少376万t/a的车用废塑料填埋或焚烧,显著减少环境风险.     

石油污染土壤多酚氧化酶的动力学及热力学特征

土壤多酚氧化酶是一种氧化还原酶,能够将土壤中芳香族化合物氧化成醌,促进土壤中石油类物质的分解转化.以距大庆油田工作区不同距离（1、5、15 km）的石油污染地为对象,研究不同温度下石油污染裸地及羊草（Leymus chinensis）修复地的土壤多酚氧化酶活性及其动力学和热力学特征的变化.结果表明:土壤多酚氧化酶活性随温度和底物浓度的增加而逐渐增大,在温度为30℃或40℃、底物浓度为80 mmol/L或160 mmol/L时达到最大值;各样地土壤酶的动力学参数K_m（Mihaelis常数）随温度的变化规律不同,V_max（酶促反应最大速度）和V_max/K_m（催化效率）随温度升高而逐渐增大,均在30℃或40℃时达到最大值;热力学参数Q₁₀（温度系数）、ΔH（活化焓）、ΔS（活化熵）随温度变化差异不显著,ΔG（活化自由能）随温度升高呈逐渐增加趋势.在同一温度下,石油污染裸地土壤多酚氧化酶活性高于羊草修复地;K_m和V_max/K_m在各样地均表现为无规律性变化,V_max最大值出现在距油田工作区5 km处的裸地（BMP）,最小值出现在距油田工作区5 km处的羊草修复地（LMP）;Q₁₀、E_a（活化能）、ΔH、ΔS的最大值均出现在距油田工作区1 km处的裸地（BVP）,最小值均出现在距油田工作区1 km处的羊草修复地（LVP）.研究显示,升温和植物修复对土壤多酚氧化酶活性的反应特征有较大影响.      

旅游目的地网络空间结构及其复杂性研究——野三坡旅游地案例实证

复杂性是旅游目的地网络化发展的必然趋势,是认识旅游地网络空间结构与组织特征的重要研究手段。论文以河北省野三坡旅游地为例,通过构建旅游联系强度模型,建立旅游地空间网络,并运用TOP网络空间分析以及复杂网络理论,揭示旅游地网络空间结构与组织的复杂性特征。研究发现：1）旅游地网络具有空间集聚性,形成了以核心景区为中心,由中心城镇、乡村社区和特色园区共同构成的空间集聚单元,并体现出“邻近连接”与“择优连接”的双重特性;2）旅游地网络服从幂律分布,具有无标度网络特性;3）每个节点的前三名和前五名旅游联系强度网络（Top3和Top5网络）具有较小的平均路径长度、较大的集聚系数,呈现出典型的“小世界网络”特征;4）旅游地网络是典型的异配型网络,度-度呈负相关,而网络节点的集聚系数与其度值之间存在近似的倒数关系,因此具有层次性。     

一种模拟动力学边界条件的环境振动试验方法研究

目的提高环境振动试验的可靠性。方法以某典型钛合金蜂窝夹芯壁板试验件为例,提出一种模拟试验件动力学边界条件的试验方法,在试验件周围引入弹性连接件,再通过刚性转接工装与振动台台面连接,以试验件在试验安装状态下的共振频率及振型节线位置为优化目标,以弹性连接件的外形尺寸及厚度为优化变量,对弹性连接件进行优化设计,从而模拟试验件真实的动力学边界条件。结果弹性连接件的优化设计使得试验件在试验安装状态下前两阶共振频率与试验要求相差小于8%,而且振型节线位置与试验要求基本重合,达到了模拟试验件真实动力学边界条件的设计目标。结论对于壁板类试验件,在传统刚性夹具的基础上引入弹性连接件的试验方法,可以较好地模拟试验件真实动力学边界条件,提高环境振动试验的可靠性,并且这种方法对试验费用及试验周期影响较小,具有良好的工程应用前景。     

铝合金的实验室盐雾试验腐蚀行为图像特征提取

目的提取铝合金材料在盐雾箱试验中可以表征腐蚀程度的表面形貌图像特征量。方法首先,对采集于表面化学清洗过的试样原始图像进行图像增强等预处理,突出腐蚀部位;其次,基于数字图像处理的分形和小波分解方法提取出分形维数和小波能量特征值。结果与以质量损失量为基础的腐蚀深度特征值进行相关性对比,基于图像分析的特征提取法的准确度和精度比较高。结论该方法可以应用于对试样的腐蚀程度进行定性和定量分析,判断并预测试样的腐蚀速度。     

Working backwards to move forwards: Graph-based connectivity metrics for reserve network selection

In this paper we apply graph theory in a reserve selection exercise to explore the tradeoffs between maintaining connectivity and minimizing the total area of a protected area network. Rather than focus on a single organism, we used a multi-species approach and looked at the tradeoff curves for organisms with varying dispersal abilities. We first generated the tradeoff curves using a graph-based metric to determine the importance of individual patches for maintaining connectivity. We then performed an analogous set of analyses using patch size as a surrogate measure of importance.     

上海市机动车污染实时排放预警系统设计与应用

研究上海市机动车污染的动态排放测算和网格化动态排放清单构建,在实时的交通数据和交通环境监测数据的基础上,结合交通模型、机动车排放清单模型等业务模型和算法,依托大数据存储、可视化和GIS等技术,开发了上海市机动车污染物实时排放预警系统,实现了上海市全市道路的机动车动态排放测算、交通环境政策实施情景模拟和网格化排放清单,更新频率为每30 min一次,包含PM、NOx、CO、SO2、VOCs等污染物和9种车型。系统建成后直接服务于首届中国国际进口博览会,为大气污染排放实时总量跟踪评估、污染源管控措施分析及监测成因分析等提供了有力的实时数据和技术支撑。