Effects of calcination temperature on physicochemical property and activity of CuSO4/TiO2 ammonia-selective catalytic reduction catalysts

CuSO_4/TiO_2 catalysts with high catalytic activity and excellent resistant to SO_2 and H_2 O,were thought to be promising catalysts used in Selective catalytic reduction of nitrogen oxides by NH_3.The performance of catalysts is largely affected by calcination temperature.Here,effects of calcination temperature on physicochemical property and catalytic activity of CuSO_4/TiO_2 catalysts were investigated in depth.Catalyst samples calcined at different temperatures were prepared first and then physicochemical properties of the catalyst were characterized by N2 adsorption-desorption,X-ray diffraction,thermogravimetric analysis,Raman spectra,Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy,temperature-pro grammed desorption of NH_3,temperature-programmed reduction of H_2 and in situ diffuse reflectance infrared Fourier transform spectroscopy.Results revealed that high calcination temperature had three main effects on the catalyst.First,sintering and anatase transform into rutile with increase of calcination temperature,causing a decrement of specific surface area.Second,decomposition of CuSO_4 under higher calcination temperature,resulting in disappears of Br(?)nsted acid sites(S-OH),which had an adverse effect on surface acidity.Third,CuO from the decomposition of CuSO_4 changed surface reducibility of the catalyst and favored the process of NH_3 oxidation to nitrogen oxides(NO_x).Thus,catalytic activity of the catalyst calcined under high temperatures(≥600℃) decreased largely.     

Synergistic effects of Cu species and acidity of Cu-ZSM-5 on catalytic performance for selective catalytic oxidation of n-butylamine

In this work, a series of Cu-ZSM-5 catalysts with different SiO₂/Al₂O₃ ratios (25, 50, 100 and 200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350°C over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5 (25) exhibited the highest selectivity to N₂, exceeding 90% at 350°C. These samples were investigated in detail by several characterizations to illuminate the dependence of the catalytic performance on redox properties, Cu species, and acidity. The characterization results proved that the redox properties and chemisorption oxygen primarily affect n-butylamine conversion. N₂ selectivity was impacted by the Brønsted acidity and the isolated Cu²⁺ species. Meanwhile, the surface acid sites over Cu-ZSM-5 catalysts could influence the formation of Cu species. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra was adopted to explore the reaction mechanism. The Cu-ZSM-5 catalysts are the most prospective catalysts for nitrogen-containing volatile organic compounds removal, and the results in this study could provide new insights into catalysts design for VOC catalytic oxidation.     

Will polycentric cities cause more CO2 emissions? A case study of 232 Chinese cities

From 2000 to 2010 China experienced rapid economic development and urbanization. Many cities in economically developed areas have developed from a single-center status to polycentricity. In this study, we used exploratory spatial data analysis (ESDA) to identify the population centers, which identified 232 cities in China as having urban centers. COMP was used to represent urban agglomeration, and POLYD (representing how far is the city's sub-centers to the main center), POLYC (representing the number of a city's centers), and POLYP (representing the population distributed between the main center and the sub-centers) were used to indicate urban polycentricity. Night light data were used to determine the CO₂ emissions from various cities in China. A mixed model was used to study the impact of urban aggregation and polycentric data on the CO₂ emission efficiency in 2000 and 2010. The study found that cities with higher compactness were distributed in coastal areas, and the cities with higher multicentricity were distributed in the Yangtze River Delta and Shandong Province. The more compact the city was, the less conducive it was to improving CO₂ emission efficiency. Polycentric development of the city was conducive to improving the CO₂ emission efficiency, but the number of urban centers had no significant relationship with the CO₂ emission efficiency. Our research showed that the compactness and multicentricity of the city had an impact on the CO₂ emission efficiency and provided some planning suggestions for the low carbon development of the city.     

Ozone pollution characteristics and sensitivity analysis using an observation-based model in Nanjing, Yangtze River Delta Region of China

Ground-level ozone (O₃) has become a critical pollutant impeding air quality improvement in Yangtze River Delta region of China. In this study, we present O₃ pollution characteristics based on one-year online measurements during 2016 at an urban site in Nanjing, Jiangsu Province. Then, the sensitivity of O₃ to its precursors during 2 O₃ pollution episodes in August was analyzed using a box model based on observation (OBM). The relative incremental reactivity (RIR) of hydrocarbons was larger than other precursors, suggesting that hydrocarbons played the dominant role in O₃ formation. The RIR values for NO_X ranged from –0.41%/% to 0.19%/%. The O₃ sensitivity was also analyzed based on relationship of simulated O₃ production rates with reductions of VOC and NO_X derived from scenario analyses. Simulation results illustrate that O₃ formation was between VOCs-limited and transition regime. Xylenes and light alkenes were found to be key species in O₃ formation according to RIR values, and their sources were determined using the Positive Matrix Factorization (PMF) model. Paints and solvent use was the largest contributor to xylenes (54%), while petrochemical industry was the most important source to propene (82%). Discussions on VOCs and NO_X reduction schemes suggest that the 5% O₃ control goal can be achieved by reducing VOCs by 20%. To obtain 10% O₃ control goal, VOCs need to be reduced by 30% with VOCs/NO_X larger than 3:1.     

Investigation to meet China II emission legislation for marine diesel engine with diesel methanol compound combustion technology

In order to reduce the pollutant emission and alleviate the pressure of petroleum resources shortage and greenhouse gas emission at the same time, the use of clean and renewable alternative fuel for marine engines is a promising option. In this study, a marine diesel engine, which was modified to run in diesel methanol compound combustion (DMCC) mode, was investigated. After the diesel injection parameters were calibrated, and combined with a sample after-treatment device DOC (diesel oxidation catalyst), the engine could meet the requirements of China II legislation. The overall MSP (methanol substitute percent) reached 54.1%. The value of each pollutant emission was much lower than that in China II emission legislation, and there was almost no methanol and formaldehyde emissions. When methanol was injected into the inlet manifold, the intake air temperature decreased a lot, as well as the exhaust gas temperature, which were beneficial to increase engine thermal efficiency and improve engine room environment. Compared with the engine running in pure diesel mode, when the engine ran in diesel/methanol dual fuel mode, the combustion phase was advanced, and the combustion duration became shorter. Therefore, the engine thermal efficiency increased, and fuel consumption decreased significantly.     

Photodegradation of Hexafluoropropylene Oxide Trimer Acid under UV Irradiation

As a novel alternative to traditional perfluoroalkyl substances (PFASs), including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), hexafluoroproplyene oxide trimer acid (HFPO-TA) has been detected worldwide in surface water. Moreover, recent researches have demonstrated that HFPO-TA has stronger bioaccumulation potential and higher hepatotoxicity than PFOA. To treat these contaminants e.g. PFOA and PFOS, some photochemical techniques by adding exogenous substances had been reported. However, there is still no report for the behavior of HFPO-TA itself under direct UV irradiation. The current study investigated the photo-transformation of HFPO-TA under UV irradiation in aqueous solution. After 72 hr photoreaction, 75% degradation ratio and 25% defluorination ratio were achieved under ambient condition. Reducing active species, i.e., hydrated electrons and active hydrogen atoms, generated from water splitting played dominant roles in degradation of HFPO-TA, which was confirmed by different effects of reaction atmospheres and quenching experiments. A possible degradation pathway was proposed based on the products identification and theoretical calculations. In general, HFPO-TA would be transformed into shorter-chain PFASs, including hexafluoropropylene oxide dimer acid (HFPO-DA), perfluoropropionic acid (PFA) and trifluoroacetate (TFA). This research provides basic information for HFPO-TA photodegradation process and is essential to develop novel remediation techniques for HFPO-TA and other alternatives with similar structures.     

Concentrations and chemical compositions of PM10 during hazy and non-hazy days in Beijing

In order to study the concentrations of major components,characteristics and comparison in hazy and non-hazy days of PM_(10) in Beijing,aerosol samples were collected at urban site in Beijing from December 29,2014 to January 22,2015.Heavy metals like Zn,Pb,Mn,Cu,As,V,Cr and Cd were deeply studied considering their toxic effects on human being;nine water-soluble inorganic ions(SO_4~(2-),NO_3~-,NH_4~+,Na~+,K~+,Cl~-,Ca~(2+) and Mg~(2+)) and carbon fractions(OC and EC) were also analyzed.The concentrations of heavy metals were 1.03–1.98 times higher in hazy days than those in non-hazy days,mainly due to biomass burning and coal burning.The trends in total heavy metals concentrations were basically consistent with the trends in PM concentrations except for two obvious periods(12.29–12.30;1.14–1.15);but when air masses accumulated locally or around Beijing,trends in PM concentrations and heavy metals were opposite.The proportion for NO_3~-/SO_4~(2-) indicated that mobile sources such as automobiles were important reasons for haze in Beijing.Correlation between OC and EC during non-hazy days was strong(R~2= 0.95) but it was low(R~2= 0.67) during hazy days,and large variations for OC/EC values occurred in hazy days.The calculated mass concentration of SOC is 2.58 μg/m~3,which only accounted for 10.1% of the OC concentration.When air masses from the far north-west,they decreased PM concentration in Beijing and they were relatively clean;however,those from the near east,south-east and south of the mainland increased PM concentration and they were dirty.     

旅游发展背景下乡村适应性演化理论框架与实证

乡村转型及适应演化路径是乡村可持续发展领域重要研究内容,对实施乡村振兴战略及其多元目标的实现具有重要理论和现实意义。通过国家制度（战略）变迁关键时间节点,梳理典型案例乡村发展阶段,明确案例乡村转型适应的体制演化特征。在乡村适应性演化理论分析框架构建基础上,以体制转换明显的乡村为实证案例,结合农户调查与深度访谈数据,评估乡村适应演化下系统适应能力（结果）及农户生计响应效果,并基于归纳法和灰色关联分析,揭示乡村体制转换与微观农户生计关联的适应演化路径及机制。研究结果表明:（1）传统农业体制乡村向旅游体制转换后出现乡村经济发展和环境破坏、社会矛盾风险并存局面,农户生计适应选择对乡村转型响应呈现多样化。（2）不同适应路径农户生计恢复力存在显著差异,升级型、扩张型生计恢复力相对较高,维持型和更替型较低。（3）乡村体制转换（R₁到R_n）与农户生计适应（P₁到P₅）呈现协同且分化的演化路径,基础设施、政策扶持以及生态环境因子是乡村转型与农户生计关联适应演化的关键影响变量。     

东平湖DOM荧光特征及与氢氧同位素指标的相关性

本研究在运用三维荧光光谱示踪平水期东平湖DOM荧光特征的基础上,进一步分析其与氢氧同位素指标的相关性,并在此基础上尝试对大气降水的DOC贡献进行估算,以期为东平湖的污染控制及治理提供依据.结果表明,东平湖平水期DOM主要由类蛋白组分（C1和C4）和类腐殖质组分（C2和C3）构成,以类酪氨酸组分C1为主,C1所占比重将近50%.平水期东平湖DOM同时受陆源、内源及大气降水的影响,但以内源输入为主;外源输入中大气降水补给与大汶河输入所占比例相当;大气降水中的溶解性有机碳输入可能会对东平湖DOM产生不可忽视的影响,需进一步系统研究.氢氧稳定同位素与溶解态有机碳以及类腐殖质荧光之间呈显著相关关系,可以在一定程度上指示DOM的变化趋势.