煤气化过程中生成氮化物的研究

对煤中N在气化条件下的转化进行了研究，详细考察了在CO2和水蒸气气氛中转化生成HCN和NH3的过程，并对热解和气化条件下煤中N转化规律的差别进行了讨论。实验结果表明：在气化条件下煤中N转化为HCN和NH3的量随温度的升高而增大，在水蒸气气氛下HCN和NH3的生成量明显大于热解条件的实验结果。在本实验条件下半焦中N含量的15％－20％可以转化为NH3，水蒸汽气氛条件下NH3生成量的提高主要来源于半焦的气化反应过程。     

Syntheses,Structures and Properties of Lanthanide Coordination Polymers Constructed from Mixed Acid

Two new coordination polymers,[Ln(oba)(ox)0.5(H2O)2]n(Ln = Ho(1),Eu(2);H2oba = 4,4?-oxybis(benzoic acid),H2ox = oxalic acid) have been synthesized under hydrothermal conditions.According to single-crystal X-ray diffraction analyses,complex 1 crystallizes in the monoclinic system,space group P21/c with a = 13.783(2),b =10.0120(15),c = 12.1974(18) ,β = 105.217(2)°,V = 1624.2(4) 3,C15H12O9Ho,Mr = 501.18,Z = 4,Dc = 2.050 g/cm3,F(000) = 964,μ = 4.919 mm-1,λ(MoKα) = 0.71073 ?,GOOF = 1.124,the final R = 0.0239 and wR = 0.0570 for 3310 independent reflections with Rint = 0.0298.Complexes 2 and 1 are isostructural.Oba and ox ligands bridge the Ln(III) ions into 2D layers with(4,4) topology,which are further interlinked into a 3D supramolecular network by hydrogen bonds.TG curves of the two complexes are studied to examine their thermal stabilities.Additionally,complex 2 shows red fluorescence in the solid state at room temperature.     

一步水热合成铜纳米颗粒负载二氧化钛复合纳米管及其可见光催化活性

采用一步水热法合成了Cu纳米粒子负载二氧化钛纳米管材料. 利用透射电子显微镜(TEM)、X射线衍射仪(XRD)、能谱仪(EDS)等对材料的相组成、形貌以及形成过程进行了研究. 制得的Cu-TiO₂复合纳米材料长度约为100 nm, 直径10-15 nm, 其上负载的Cu纳米粒子尺寸约为5 nm. BET比表面积测试表明实验制备的Cu-TiO₂复合纳米管的比表面积为154.67 m²·g^-1. 通过调节水热反应时间和钛前驱体种类, 研究了该复合纳米管材料的形成机制. 结果表明: 非晶态的钛源对于成功一步合成Cu-TiO₂复合纳米管至关重要. 同时, 实验中观察到铜纳米粒子的尺寸随水热反应时间延长而减小(反奥氏陈化过程), 这一现象有助于纳米粒子的可控合成.紫外-可见吸收光谱表明该复合纳米管在350-800 nm范围内有较强的吸收, 并在550-600 nm范围观察到Cu的表面等离子激元吸收带. Cu-TiO₂界面处形成的肖特基势垒有助于加快光生载流子的输运, 提高光生电子-空穴对的分离效率. 光催化实验表明Cu-TiO₂复合纳米管在可见光下具有较高的催化活性.     

基于三维有序金掺杂纳米二氧化钛的DNA生物传感器研究

用模板法在氧化铟锡(ITO)电极上制备具有三维有序多孔结构的金掺杂纳米二氧化钛修饰电极(3DOM GTD/ITO),扫描电镜(SEM)结果表明,制备的修饰电极三维结构规整有序、孔径均一。将标记有二茂铁(Fc)的DNA探针修饰到3DOM GTD/ITO电极上构建了一种新的标记型DNA生物传感器,通过Fc在DNA探针杂交前后的电化学信号变化可识别目标靶序列。采用循环伏安(CV)、示差脉冲(DPV)和交流阻抗(EIS)等方法对DNA探针在电极表面的固定和杂交进行表征。实验结果表明,该DNA生物传感器可以成功地识别乳腺癌基因靶序列,Fc的氧化还原电流与靶序列浓度在8.0×10-7～1.0×10-5 mol/L范围内呈线性关系,线性相关系数为0.9908,检测限为5.2×10-7 mol/L。     

外围缩合四个1,10-啡啰啉单元的新氮杂酞菁的表面光伏响应及电场作用研究

通过电场诱导表面光电压谱确定外围缩合4个1,10-啡啉单元的氮杂酞菁为p型有机半导体,并对各个谱带进行合理的归属.结果发现,Soret带长波侧光电压曲线在电场作用下轻微蓝移,根据电场对高极化度n轨道基态的影响,将其归属为n-π^*     

EPR studies on H-abstractions/spin-trapping reactions of new 'magic blue' reagents with alcohols

The H-abstractions/spin-trapping reactions with primary, secondary and tertiary alcohols of new 'magic blue' reagents, namely, the blue F113 (CClF₂CCl₂F) solution containing bis{perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl} nitroxide (2) and perfluoro[1-nitroso-1-(2-fluorosulfonyl)ethoxy]ethane (3) both generated in the reaction of perfluoro[2-(2-fluorosulfonyl)ethoxy]propionyl peroxide (1) with sodium nitrite in F113 at room temperature, were studied by EPR. Based on the interpretation of the EPR spectra of the spin adducts, nitroxides, the region-selectivity of H-abstraction has been disclosed and the possible mechanistic paths of H-abstraction have also been discussed. EPR of H-abstraction by using 'magic blue' reagents can also be used for producing various hydroxyalkyl radicals from common alcohols.     

超细纳米Pd粒子与聚乙烯吡咯烷酮的相互作用

在微量聚乙烯吡咯烷酮(PVP)存在下, 利用超声还原氯化钯水溶液, 制备出超细纳米Pd颗粒, 用高分辨透射电镜、红外光谱、紫外-可见光谱和X射线光电子能谱等技术对其表面形貌及结构进行了表征. 结果表明, 纳米Pd粒子的粒径均一, 大约为3 nm. 纳米Pd/PVP复合粉末的羰基红外吸收峰比PVP的羰基吸收峰红移9 cm^-1; 且当超声反应50 min时, PVP紫外吸收波峰蓝移16 nm, 表明了纳米Pd与PVP之间存在一定的相互作用力. XPS结果证明, 纳米Pd与PVP的羰基基团通过配位作用使超细纳米Pd粒子得以稳定分散存在.     

延迟反馈法控制Genesio混沌系统

采用延迟反馈方法控制Genesio混沌系统,结果表明,延迟时间和控制强度的不同使得控制结果有较大的差异,控制方向的不同会影响控制实现的难易程度.     

固体光气法合成氯代苯基单异氰酸酯

固体光气;氯代苯胺;氯代苯基单异氰酸酯;合成     

Synthesis, structures, electrochemistry and electrocatalysis of two novel copper(II) complexes constructed with aromatic polycarboxylates and dipyrido[3,2-d:2′,3′-f]quinoxaline

Two novel coordination polymers [Cu₃(1,3-BDC)₄(Dpq)₂] (1) and [Cu₂(BTC)(OH)(Dpq)₂] · H₂O (2), have been hydrothermally synthesized by self-assembly of aromatic polycarboxylate ligands 1,3-H₂BDC (1,3-H₂BDC = 1,3-benzenedicarboxylate) or H₃BTC (H₃BTC = 1,3,5-benzenetricarboxylate), chelating ligand Dpq (Dpq = dipyrido[3,2-d:2′,3′-f]quinoxaline), and copper chloride. X-ray diffraction analysis reveals that each trinuclear Cu^II cluster is bridged by two coordination modes of 1,3-BDC ligands to form one-dimensional (1-D) chain structure in complex 1. Complex 2 possesses a two-dimensional (2-D) layer network composed of dinuclear [Cu₂(OH)(Dpq)₂] unit and bridging ligand BTC. The adjacent chains for 1 or the adjacent layers for 2 are further linked by π-π stacking interactions to form the three-dimensional (3-D) supramolecular frameworks. Moreover, the electrochemical properties of the two copper(II) complexes bulk-modified carbon paste electrodes (Cu-CPEs: 1-CPE and 2-CPE) have been studied, and the results indicate that both Cu-CPEs give one-electron quasi-reversible redox waves in potential range of 600 to −400 mV due to the metal copper ion Cu(II)/Cu(I). The Cu-CPEs have good electrocatalytic activities toward the reduction of nitrite and bromate in 0.1 M pH 2 phosphates buffer solution, and have remarkable long term stability and especially good surface renewability by simple mechanical polishing in the event of surface fouling, which is important for practical application.