金纳米粒子修饰石墨电极上鲁米诺-过氧化氢体系电化学发光行为的研究

研究了磷酸盐缓冲溶液(pH=7.4)中金纳米粒子修饰石墨电极上鲁米诺-过氧化氢体系的电化学发光行为。实验结果表明在金纳米粒子修饰石墨电极上鲁米诺-过氧化氢的电化学发光强度增强近10倍,初步探讨了在金纳米粒子修饰石墨电极上鲁米诺-过氧化氢体系的电化学发光增强机理。在优化的实验条件下,鲁米诺浓度在4.0×10-12～1.0×1010-mol/L之间与电化学发光强度成良好的线性关系,方法的检出限为2×10-12mol/L,对5.0×10-11mol/L鲁米诺进行11次平行测定,相对标准偏差为5.3%。     

440 t/h循环流化床锅炉整体动态模型及仿真

建立循环流化床锅炉的整体动态模型对循环流化床锅炉设计、生产优化、自动控制系统的开发研究等有至关重要的影响.本文在综合分析循环流化床锅炉床温和汽包压力的动态特性的基础上,采用集中参数化的方法,分别建立了燃烧系统模型和汽水系统模型;并通过炉膛传热量,将燃烧系统模型和汽水系统模型结合起来,从而建立了以给煤、一、二给风为输入变量的循环流化床锅炉的整体动态模型.并对所建立的模型方程进行仿真,结果分析证实了该模型的正确性.     

Impact of supercritical adsorption mechanism on research of hydrogen carrier

Hydrogen storage receives the worldwide attention due to its importance in sustainable energy and the solution of greenhouse effect.Adsorption provides an efficient way to compress gases and,therefore, has been applied to the development of hydrogen storage technology.However,hydrogen is a super- critical gas at the temperature of engineering interest and follows a different adsorption mechanism compared to the sub-critical gases.The present work shows why only monolayer coverage mechanism functions at above-critical temperatures and what consequences will result in the application study. Although there are pros and cons to this point of view,understanding the adsorption mechanism is,in- deed,essential for the research of hydrogen storage method since it claims that any storage material based on adsorption will not satisfy the practical need of on board storage no matter how novel the material is.     

A comparison of transition state of phenol in H-atom abstraction by methyl and methylperoxyl radicals

DFT method was employed to locate transition state for H-atom transfer from phenol by methyl radical and methylperoxyl radical. The reaction pathway energy profiles and the structure of transition state show that a common feature is the out-of-plane structure of the transition state: in contrast to the en- ergetic minima of a hydrogen-bonded intermediate, the hydrogen bond in transition structures is con- siderably twisted out of the aromatic ring. From the values of enthalpy (△H) and activation energy (Ea) obtained, it is found that the rate of the reaction of peroxyl radical with phenolic antioxidant is higher than that of alkyl radical with antioxidant. Spin density distributions show that the electron transmis- sion is between methyl (methylperoxyl) radical and phenol.     

The genesis of H2S in the Weiyuan Gas Field, Sichuan Basin and its evidence

The Sinian Dengying Formation gas pool in Weiyuan is the oldest large-scale sulfur-bearing gas field in China, which has a H2S content ranging from 0.8% to 1.4%. The Cambrian Xixiangchi Formation gas pool discovered recently above the Dengying Formation contains gas geochemical behaviors similar to those of Dengying Formation but different in sulfur isotopes of H2S. Investigations show that though these two Sinian and Cambrian gas pools are separate ones, they share the same Cambrian source rock. The higher dry coefficient, heavier carbon isotopes, sulfur isotopes of sulfide, lower filling of gas pools, formation water characteristics, reservoir properties and H2S distribution, indicate that H2S in both the Sinian and Cambrian gas pools originates from TSR. The sulfur isotopes of sulfates have shown that H2S was formed in respective pools, namely hydrocarbons charged into the pools reacted with the Dengying Formation and the Xixiangchi Formation gypsum （TSR）, respectively, to form H2S. Compared with sulfur isotopes of sulfates in each pool, δ^34S values of H2S are 8‰ lighter for the Dengying Formation pool and 12‰ lighter for the Xixiangchi Formation pool, respectively, which is attributed to the difference in temperatures of TSR occurrence. The reservoir temperature of the Xixiangchi Formation pool is about 40℃ lower than that of the Dengying Formation pool. Temperature plays a controlling role in both the sulfur isotopic fractionation and amounts of H2S generation during TSR.     

新型有机-无机杂化材料固载烯烃环氧化催化剂

本文以新型有机-无机杂化材料“低聚苯乙烯基膦酸-磷酸氢锆（ZSPP）”为载体，设计合成了四种多胺配体钼配合物多相催化剂，并用红外、拉曼、XPS、XRD及元素分析等方法对催化剂进行了表征。以TBHP为氧源，考察了所制备催化剂催化环己烯环氧化的催化活性，结果表明，所制备的固载催化剂催化环已烯环氧化时具有较高的催化活性、选择性和重复使用性，但随着配体中N原子数的增加，转化率和选择性会逐渐降低。     

过氧化尿素的合成研究

利用高浓度双氧水与尿素反应合成过氧化尿素,考察了过氧化氢与尿素的摩尔比、反应温度、反应时间对产品性能的影响,得出了最佳反应条件。     

煤层自然发火预测预报的指标气体

煤层自然发火的指标气体是矿井煤体氧化生热、出现温度变化时可以稳定探测的气体。使用指标气体可以早期探测到煤层然发火的发生,减少不必要的经济损失。概括了火灾气体的特性,介绍了指标气体测试的实验原理和实验系统,并对典型煤样进行了实验分析,找出了适合本矿的自然发火预测预报的指标气体。根据不同阶段出现的不同指标气体,对自然发火整个过程划分了三个氧化阶段,使得自然发火预测预报工作能够更加准确无误。     

可见光照下过氧化氢氧化降解罗丹明B

通过测定在可见光照射下过氧化氢降解罗丹明B的UV-vis吸收光谱变化,探讨了可见光照的条件下过氧化氢对罗丹明B的降解情况及影响因素.实验表明:过氧化氢在碱性条件下可以有效地氧化罗丹明B,可见光能有效加快该降解过程.在pH=12的条件下,光照100min后罗丹明B(10μmol/L)降解率达到95%以上.并通过初始速率法确定了反应符合零级反应动力学.pH值对罗丹明B的氧化降解有很大的影响,当pH<9值时罗丹明B难以被氧化降解.羟基自由基和单态氧都不是该过程的活性氧化物种.     

燃烧法合成Eu2+、Dy3+、Nd3+共掺杂的硅酸盐长余辉发光材料Sr2MgSi2O7和Sr2ZnSi2O7

采用燃烧法在600~800℃合成了Sr2MgSi2O7:Eu2 、Dy3 、Nd3 ,Sr2ZnSi2O7:Eu2 、Dy3 、Nd3 和Sr2ZnSi2O7:Eu2 、Dy3 蓝色长余辉发光材料,对材料进行了XRD、TEM、激发和发射光谱、余辉亮度及余辉衰减的测定.结果表明:稀土离子的掺杂对基质晶体结构没有影响,激发和发射光谱显示它们的光谱性质是Eu2 典型的4f-5d的跃迁所致,对Sr2ZnSi2O7:Eu2 、Dy3 材料,Nd3 的共掺杂有利于提高其余辉性能.