单原子Co修饰TiO2(101)面的结构和析氢性能的第一性原理研究

通过基于密度泛函理论（DFT）+U的第一性原理方法研究了单原子Co在TiO₂（101）面的掺杂位置和方式、几何结构和整体能量以及掺杂后产物的制氢反应机制，得到了稳定且易出现的单原子修饰结构，即单原子Co吸附在4个O组成的表面空隙的中心位，记为Co/TiO₂（101）。进一步对Co/TiO₂（101）的析氢反应过程和性能进行研究，确定了当且仅当TiO₂（101）面完成表面羟基化反应后，H原子全覆盖的TiO₂（101）表面才能进行后续的析氢反应；此时单原子Co是唯一的反应位点，整体的制氢反应自由能ΔG_H*比Co（111）面更加趋近于0，显示出其具有远优于金属Co的催化性能。此外，Co和TiO₂间的电荷转移和相互作用使TiO₂带隙出现新的掺杂能级，可带来作为光催化基材的TiO₂光吸收性能的改善。     

伊陕斜坡东南部延长组页岩气地球化学特征分析

鄂尔多斯盆地陆相页岩气勘探潜力巨大,但对于陆相页岩气成因类型的研究相对滞后,限制了对页岩气的进一步勘探和开发。通过综合化学组分分析和碳、氢同位素分析的手段对伊陕斜坡东南部延长组页岩气和原油伴生气的地球化学特征及成因进行研究。研究结果表明延长组页岩气(生产气和真空解吸气)和原油伴生气都以烷烃类气体为主,其中甲烷含量都小于95%,非烃气体含量比较低。页岩解吸气中,非烃气体比例相对较高,且氧气含量异常高,这与解吸装置密封性不好或者装置本身残留空气清除不彻底有关。页岩气和原油伴生气的甲烷含量低、干燥系数(C_1/C_(1~5))主要集中在0.6~0.9之间、C_2/C_3都小于3,δ~(13)C_1值分布于-52.0‰~-44.9‰之间、δ~(13)C_2值都小于-29‰,δ~(13)C_3值都小于-25.5‰和δD_1都小于-150‰,指示研究区页岩气和原油伴生气以陆相环境热成因的热解湿气(油型气)为主。页岩气和原油伴生气样品有相对高的正庚烷含量和正构烷烃(nC_(5-7))含量,δ~(13)C_2值分布于-41.1‰~-31.1‰之间,说明延长组页岩气与原油伴生气都属于偏腐泥型天然气。此外,延长组页岩气和原油伴生气碳同位素系列基本都属正碳同位素系列,且δ~(13)C_1与δ~(13)C_2值,δ~(13)C_2值与δ~(13)C_3值有较好的正相关关系,这也表明页岩气和原油伴生气具有相同或相似的母质来源。     

人工光合成太阳燃料制备途径及规模化

 从人工光合成太阳燃料的基本概念和反应过程、规模化太阳能分解水制氢的主要途径和可行性分析、人工光合成液态太阳燃料甲醇的技术路径及应用前景等方面，分析了人工光合成领域的发展现状。仿习自然光合作用基本过程，提出了通过“光反应”和“暗反应”耦合实现规模化人工光合成太阳燃料的新途径。     

Key technologies for polymer electrolyte membrane fuel cell systems fueled impure hydrogen

Hydrogen energy and polymer electrolyte membrane (PEM) fuel cells become concerned issues in recent years. Nevertheless, the construction of hydrogen refueling infrastructure and hydrogen storage and transportation constrains the commercial development of fuel cells. In this review, sources, production, storage, transportation, and purification methods of hydrogen are extensively reviewed and compared. The advantages of utilizing industrial by-product hydrogen and steam reforming gas in PEM fuel cell systems are analyzed. Using industrial wasted hydrogen can significantly reduce the cost of hydrogen. Also, it is indicated that the onboard hydrogen generation by steam methanol reforming can solve the difficulties of efficient storage and transportation of gaseous hydrogen, which means that methanol has great potential to be a convenient carrier of hydrogen. The effects of impurities contained in the reformate gas are generally introduced. After the methanol steam reforming and pretreatment purification processes, the reformate gas can be fed to PEM fuel cells. Thus, a fuel cell system integrated with onboard hydrogen production and impure hydrogen treatment subsystems is introduced, and key technologies therein for pretreatment purification and in-situ poisoning mitigation methods are reviewed. Finally, suggestions are proposed for further studies.     

长白山矿泉水补给径流与排泄关系

为研究长白山地区广泛分布的偏硅酸型矿泉水的补给源,通过氢氧同位素与水化学分析,结合水文地质、地球物理等资料,确定长白山泉水接受来自于西藏羌塘盆地的外源水补给。长白山泉水TDS很低但富含偏硅酸的现象表明,地下水流经的含水层是由硅酸盐等火山岩组成,结合长白山地区火山玄武岩大量的喷发事实,推断地下水导水通道由孔洞玄武岩构成。指出应加强对西藏冰川、河流与湖泊的保护,从而确保长白山优质矿泉水能够持续地开发利用。     

Effect of H2S concentration on the corrosion behavior of pipeline steel under the coexistence of H2S and CO2

The effect of H2S concentration on H2S/CO2 corrosion of API-X60 steel was studied by scanning electron microscopy, a weight-loss method, potentiodynamic polarization tests, and the electrochemical impedance spectroscopy technique. It is found that the cor-rosion process of the steel in an environment where H2S and CO2 coexist at different H2S concentrations is related to the morphological structure and stability of the corrosion product film. With the addition of a small amount of H2S, the size of the anode reaction region is de-creased due to constant adsorption and separation of more FeS sediment or more FeHS＋ions on the surface of the steel. Meanwhile, the dou-ble-layer capacitance is diminished with increasing anion adsorption capacity. Therefore, the corrosion process is inhibited. The general cor-rosion rate of the steel rapidly decreases after the addition of a small amount of H2S under the coexistence of H2S and CO2. With a further increase in H2S concentration, certain parts of the corrosion product film become loose and even fall off. Thus, the protection provided by the corrosion product film worsens, and the corrosion rate tends to increase.     

洱海水硫化物及六价铬含量的检测分析

目的:了解洱海水硫化物及六价铬含量。方法:采集洱海20个点的水样对硫化物及六价铬的含量进行检测,分别采用亚甲蓝分光光度法,二苯碳酰二肼分光光度法进行测定。结果按照《地表水环境质量标准进行评价》。结果:硫化物、六价铬合格率为100%。结论:硫化物、六价铬均达到GB 3838-2002《地表水环境质量标准》的一类水质。     

ZSM-5型分子筛上H_2选择还原NO

采用水热法合成了微米HZSM-5分子筛(HZSM-5)和纳米HZSM-5分子筛(nano-HZSM-5),通过XRD和SEM对样品进行了表征。结果表明:所得样品为纯态的HZSM-5和nano-HZSM-5分子筛。以上述样品为载体,制备了Pd基催化剂,并用于H2选择还原NO研究。在整个测试温度范围内,Pd/HZSM-5表现出良好的催化性能,优于Pd/nano-HZSM-5。当温度高于100℃时,Pd/HZSM-5上的NO可达到完全转化。此外,Pd含量仅影响低温时(100℃)Pd/HZSM-5的催化活性。上述结果说明所制备的Pd/HZSM-5是H2选择还原NO的优良催化剂。     

双氧水氧化废轮胎胶粉在改性沥青中的应用

采用双氧水对废轮胎胶粉进行表面氧化改性,将氧化改性胶粉用于制备胶粉改性沥青.通过XPS表征证明氧化改性胶粉表面的C—O和C=O的含量显著增加.通过多因素正交试验方法研究氧化剂用量、氧化温度及氧化时间对胶粉改性沥青的25,℃针入度、软化点和5,℃延度等主要性能指标的影响.运用极差分析法和方差分析法探讨了各影响因素对改性沥青性能的敏感性,发现氧化温度对改性沥青性能指标的影响最大,并提出了胶粉氧化改性的最佳反应条件为:氧化剂用量10,m L,氧化温度80,℃,氧化时间3,h.氧化胶粉改性沥青在不使用界面改性剂的条件下,能够使5,℃延度提高到11.6,cm,主要性能指标达到美国废轮胎胶粉改性沥青标准,说明废轮胎胶粉的表面氧化能够显著提高胶粉与沥青的界面结合强度.     

CH3COOH/H2O2体系氧化苯乙烯制苯甲醛

在合适条件下CH3COOH与H2O2反应生成过氧乙酸(CH3COOOH),过氧乙酸氧化苯乙烯生成苯甲醛.研究了反应温度、反应时间、过氧化氢用量、加料顺序及添加乙腈和水等对CH3COOH/H2O2体系氧化苯乙烯制苯甲醛反应的影响.结果表明:当苯乙烯为0.5mL,乙酸5mL,H2O22mL,反应时间为5h,反应温度为60℃,苯乙烯的转化率可以达到99.6%,苯甲醛的过氧乙酸选择性大于60%.