光学非线性薄膜线性参数的快速测量与分析

本文提出了-种光学非线性薄膜线性参数的方便有效的测量方法,测量了ZnSe非晶态光学薄膜的线性折射率和消光系数。在此方法中,实验数据的计算与处理由-套计算机软件来完成。最后,文章对测量精度进行了简单的讨论。     

Spontaneous generation of stable pnictinyl radicals from "jack-in-the-box" dipnictines: a solid-state, gas-phase, and theoretical investigation of the origins of steric stabilization

The molecular structures of the stable phosphinyl and arsinyl radicals, .PnR(2) [Pn = P (2); As (4); R = CH(SiMe(3))(2)], have been determined by gas-phase electron diffraction (GED) in conjunction with ab initio molecular orbital calculations. The X-ray crystal structures of the corresponding dipnictines, the "dimers", R(2)PnPnR(2) [Pn = P (1), As (3)], and the chloro derivatives R(2)PnCl [Pn = P (5), As (6)] have also been determined. Collectively, these structural investigations demonstrate that large distortions of the ligands attached to Pn occur when the pnictinyl radicals unite to form the corresponding dipnictine dimers. Principally, it is the shape and flexibility of the CH(SiMe(3))(2) ligands that permit the formation of the P-P and As-As bonds in 1and 3, respectively. However, theoretical studies indicate that in the process of pnictinyl radical dimerization to form 1 and 3, both molecules accumulate substantial amounts of potential energy and are thus primed to spring apart upon release from the solid state by melting, dissolution, or evaporation. The insights gleaned from these unusual systems have permitted a deeper understanding of the functioning of sterically demanding substituents.     

废轮胎热解炭的分析及其活化特性的研究

用常规分析方法分析了废轮胎热解炭的成分和性质，用X射线能谱分析法、压汞法、N2吸附法等测定了热解炭的孔隙结构特性，并用CO2、含2％氧气的氮气流和水蒸气等活化气体对热解炭进行活化方面的研究。结果表明，热解炭灰分和硫含量比较高；两种不同粒径热解炭的比孔容积均在r≈25 nm处有最大值；在相同活化时间和活化剂流速下，温度越高，活化炭烧失率越大，比表面积也越大；在一定温度和活化剂流速下，烧失率和比表面积随着活化时间的增加而增大；对所有试验工况，烧失率越大，活化炭比表面积也越大。总体上水蒸气活化炭与CO2的活化效果较好，而含2％O2的氮气流活化的效果则次之。活化炭与商业活性炭的比较显示，前者具有较发达的孔隙结构，在进行大分子物质吸附时，具有替代商业活性炭的潜力。     

New Routes to Synthetically Useful, Sterically Encumbered Arylaluminum Halides and Hydride Halides

The synthesis and structural characterization of the compounds MesAlCl(2)(THF) (1), MesAlCl(2) (2), MesAl(H)Cl(THF) (3a), MesAl(H)Cl (4a), and (MesAlH(2))(2) (5) (Mes = 2,4,6-t-Bu(3)C(6)H(2)(-)) are described as well as those for two compounds 3b and 4b that are analogs of 3a and 4a but have H:Cl ratios that are less than 1:1. All compounds were characterized by (1)H, (13)C NMR, and IR spectroscopy, and 1, 2, 3a, and 4b were additionally characterized by X-ray crystallography. Compound 1 is best synthesized by the reaction of [(THF)(2)LiH(3)AlMes](2) (6) with 6 equiv of Me(3)SiCl. A more conventional route involving the addition of (THF)(2)LiMes to 2 equiv of AlCl(3) in toluene usually affords a mixture of 1 and AlCl(3).THF. Recrystallization of 1 from n-hexane results in a species that has less than 1 equiv of THF per MesAlCl(2). The THF free complex 2 may be obtained in quantitative yield by heating 1 for 20 min at 90 degrees C under reduced pressure. Compound 3a may be obtained by treating a 1:1 mixture of MesLi(THF)(2) and LiAlH(4) with 2 equiv of Me(3)SiCl or by the addition of slightly less than 4 equiv of Me(3)SiCl to 6. The THF can be removed from 3a by sublimation to give 4a. The related compounds 3b and 4b, which display an aluminum-bound H:Cl ratio that is deficient in H, can be obtained by reactions with slightly more than 2 equiv of Me(3)SiCl. Crystal data at 130 K with Cu Kalpha (lambda = 1.541 78 ?) radiation: 1, C(22)H(37)AlCl(2)O, a = 11.889(3) ?, b = 9.992(3) ?, c = 19.704(5) ?, orthorhombic, space group Pca2(1), Z = 4, R = 0.068 for 1556 (I > 2sigma(I)) data; 2, C(18)H(29)AlCl(2), a = 12.147(5) ?, b = 18.042(6) ?, c = 17.771(7) ?, beta = 95.77(3) degrees, monoclinic, space group P2(1)/n,Z = 8, R = 0.032 for 4610 (I > 2sigma(I)) data; 3a, C(22)H(38)AlClO, a = 16.887(7) ?, b = 16.333(6) ?, c = 8.739(3) ?, beta = 101.41(3) degrees, monoclinic, space group P2(1)/c, Z = 4, R = 0.073 for 2752 (I > 2sigma(I)) data; 4b, C(18)H(29.64)AlCl(1.36), a = 12.077(3) ?, b = 17.920(3) ?, c = 17.634(5) ?; beta = 95.21(2) ?, monoclinic, space group P2(1)/n,Z = 8, R = 0.070 for 4261 (I > 2sigma(I)) data.     

Synthesis and characterization of HC[C(Me)N(C(6)H(3)-2,6-i-Pr(2))](2)MX(2) (M = Al, X = Cl, I; M = Ga, In, X = Me, Cl, I): sterically encumbered beta-diketiminate group 13 metal derivatives

A series of group 13 metal complexes featuring the beta-diketiminate ligand [[(C(6)H(3)-2,6-i-Pr(2))NC(Me)](2)CH](-) (i.e., [Dipp(2)nacnac](-), Dipp = C(6)H(3)-2,6-i-Pr(2)) have been prepared and spectroscopically and structurally characterized. The chloride derivatives Dipp(2)nacnacMCl(2) (M = Al (3), Ga (5), In (8)) were isolated in good yield by the reaction of 1 equiv of Dipp(2)nacnacLi.Et(2)O (2) and the respective metal halides. The iodide derivatives Dipp(2)nacnacMI(2) (M = Al (4), Ga (6), In (9)), which are useful for reduction to afford M(I) species, were made by a variety of routes. Thus, 4 was obtained by treatment of the previously reported Dipp(2)nacnacAlMe(2) with I(2), whereas the gallium analogue 6 was obtained as a product of the reaction of "GaI" with Dipp(2)nacnacLi.Et(2)O, and 9 was obtained by direct reaction of InI(3) and the lithium salt. The methyl derivatives Dipp(2)nacnacMMe(2) (M = Ga (7), In (10)), which are analogous to the previously reported Dipp(2)nacnacAlMe(2), were synthesized by the reaction of GaMe(3) with Dipp(2)nacnacH (1) or by reaction of the indium chloride derivative 8 with 2 equiv of MeMgBr in diethyl ether. The compounds 3-10 exist as colorless, air- and moisture-sensitive crystalline solids. Their X-ray crystal structures feature nearly planar C(3)N(2) arrays in the Dipp(2)nacnac ligand backbone with short C-C and C-N distances that are consistent with a delocalized structure. However, there are large dihedral angles between the C(3)N(2) plane and the N(2)M metal coordination plane which have been attributed mainly to steric effects. The relatively short M-N distances are consistent with the coordination numbers of the metals and the normal/dative character of the nitrogen ligands. The compounds were also characterized by (1)H and (13)C NMR spectroscopy. (1)H NMR data for 7 revealed equivalent methyl groups whereas the spectrum of 10 displayed two In-Me signals which indicated that ring wagging was slow on the (1)H NMR time scale.     

铜及氧化铜对煤燃烧过程多环芳烃排放的影响

在实验管式炉上研究了金属铜和氧化铜对烟煤燃烧过程中PAHs生成的影响。采用气相色谱分析PAHs。实验结果表明，铜会促进PAHs的生成，而且主要是促进中高分子量PAHs的生成，这是由于铜为PAHs的合成提供了大量的活性反应中心。另一方面氧化铜对PAHs的合成和裂解具有双重催化效果，从而显著增加了中分子量PAHs的排放。在800 ℃以下，添加铜和氧化铜都减小了PAHs排放的毒性当量。在900 ℃以上，添加铜增大了PAHs排放的毒性当量。添加氧化铜时与添加铜时的规律类似，但是在1100℃以上，PAHs排放的毒性当量要比不添加时小。