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51.
甲烷部分氧化制合成气:Ⅱ.载体的影响 总被引:2,自引:2,他引:2
本文对三种催化剂(1%Rh/m-Sm2O3,1%Rh/c-Sm2O3)在甲烷部分氧化反应的催化活性与一氧化碳和氢的选择性作了比较。用二氧化碳的程序升温脱附测试了载体的相对碱性强弱;并用同位素交换反应测定了载体和负载型铑催化剂对甲烷分子中C-H和氧气分子中O-O键的解离活化能力,虽然催化活性高低与载体的碱性及解离活化能力之间没有直接的对应关系,但通过载体对反应活性影响的研究能揭示一般的规律,对研制甲 相似文献
52.
Certain aromatic diamines (the “proton sponges”) are found to have exceptionally high basicity constants: this is due to spatial interaction of the basic centers, which are in close proximity. The two factors which are most important in causing this effect are, on the one hand, the extreme steric strain in these systems and the destabilizing effect of the overlap of the nitrogen lone pairs of the neutral diamines and, on the other, the strong N?H?N hydrogen bonds which are formed on monoprotonation and which lead to a considerable relaxation of the steric strain. By the systematic variation of the structures of such aromatic diamines we have been able to study these effects as a function of steric factors, in particular of the geometry and the bond length of the N?H?N hydrogen bonds, by means of X-ray structural analysis. The hydrophobic shielding of the basic centers and the N?H?N hydrogen bonds, which was characteristic of the “proton sponge” compounds studied previously, is indeed responsible for the extremely low rate of protonation and deprotonation of these compounds; however, it apparently has no influence on their high thermodynamic basicity. The recent synthesis and basicity determination of a new type of “proton sponge” with no hydrophobic shielding whatever show that not only very strong but also kinetically active bases are accessible using the “proton sponge” concept. Their unusual properties, which are discussed here as the result of steric interactions between two basic centers, provide examples of the fact that cooperative steric interactions of reactive structural elements can lead to properties which cannot be derived from an isolated consideration of the various functional groups. Such “proximity effects” are certainly of general importance in chemistry and biochemistry; the study of their structure-function relationships is worthy of closer consideration. 相似文献
53.
阳离子掺杂水滑石的制备及其性质研究 总被引:5,自引:0,他引:5
研究了掺杂阳离子水滑石的制备及阳离子对水滑石性质的影响. 分别制备了掺杂Zn2+、Ni2+、Fe3+型的水滑石, 考察了掺杂阳离子对水滑石晶相结构、层间距、层间阴离子含量、水滑石表面形态、水滑石碱性的影响, 结果表明, 由于阳离子的引入, 导致水滑石层间距减小及层间阴离子结合量降低, 且使水滑石培烧产物电负性提高, 并最终降低其碱性. 以上述水滑石培烧产物作为固体碱催化剂促进苯甲醛和丙醛缩合, 合成α-甲基肉桂醛, 关联了水滑石培烧产物碱性与反应活性的关系. 相似文献
54.
Siddalingaiah AH Dodamani AF Kanavi PS 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2000,56(14):47-2635
The study of the adduct formation of Ni(II) di(6-chloro,2-methylphenyl)carbazonate has been undertaken by synthesising and characterizing it by magnetic susceptibility, UV-VIS, IR and 1H-NMR spectral measurements. The distorted square planar Ni(II) chelate forms adducts with heterocyclic nitrogen bases; spectrophotometric method has been employed for the study of the adduct formation in a monophase chloroform. Both bidentate and unsaturated monodentate heteronuclear nitrogen bases form hexacoordinated adducts with 1:1 and 1:2 stoichiometry, respectively (metalchelate:base). However, the saturated nitrogen bases form pentacoordinated adducts with 1:1 stoichiometry. The results are discussed in terms of basicity and steric factors of the bases. 相似文献
55.
用乙酰丙酮络钒法制备了两组不同氧化物和磷酸盐载体负载的钒载量为5%V2O5的催化剂.XRD和Raman光谱表征结果表明,钒氧化物在载体MgO,Al2O3,Mg3(PO4)2,AlPO4和Zr3(PO4)4上是高度分散的,没有生成明显的V2O5晶相;催化剂的可还原性与其氧化物或磷酸盐载体的金属还原电位序有较好的对应关系,与其丙烷氧化脱氢活性也存在较好的平行关系,表明钒氧化物与载体的阳离子形成了V—O—M桥键,该桥键氧较易移去,可能是丙烷氧化脱氢的活性氧物种;催化剂表面酸性位有利于丙烷C—H键的活化,但导致深度氧化产物增多. 相似文献
56.
Molecular electrostatic potentials computed with CNDO/2 and INDO wave functions are shown to present systematic differences with respect to ab initio potentials in the case of out-of-plane potentials and in-plane vicinal hetero atoms in planar hetero molecules. 相似文献
57.
58.
利用脱水氮化法制备了含氮HY分子筛,氮化后分子筛的结晶度和比表面积均得到较好保持.由于氮原子的电负性低于氧原子,氮原子取代氧原子进入HY分子筛的骨架,使其Lewis碱性得到增强.利用氨气吸附红外光谱、二氧化碳吸附红外光谱与二氧化碳程序升温脱附方法对氮化前后的分子筛进行表征.结果表明氮化后HY分子筛的L酸中心数量有所降低,B酸中心数量有所增加,同时生成新的碱性中心.由于新碱性中心的引入,含氮HY分子筛在Knoevenagel缩合碱性探针反应中表现出优异的活性. 相似文献
59.
SBA-15-Fe was synthesized via the incorporation of Fe0 nanoparticles (Fe(0)-Nps) in the mesoporous channels. Electron microscopy and X-ray diffraction showed that dispersion of fine iron NPs occurs mainly inside the channels of SBA-15, producing a slight structure compaction. This was accompanied by a significant improvement of both the affinity towards hydrogen and electrical conductivity, as supported by hydrogen adsorption tests and impedance measurements. CO2 thermal programmed desorption measurements revealed an attenuation of the acid character of the solid surface. This was explained in terms of strong iron interaction with the lattice oxygen atoms that reduces the SiO–H bond polarity. The close vicinity of fine Fe(0)-Nps combined with the large pore size of SBA-15 appear to contribute to a synergistic improvement of the electrical conductivity. The results reported herein open new prospects for SBA-15 as potential adsorbents for hydrogen storage and carriers for hydrogen sensors. The use of iron in lieu of noble metals for designing such materials is a novelty, because such applications of iron-loaded silica have not been envisaged so far due to the high reactivity of iron towards air and water. The development of such technologies, if any, should address this issue. 相似文献
60.
Kristen M. McGraw Greggory T. Kent Joseph R. Gonzalez Ihsan Erden Weiming Wu 《Tetrahedron letters》2017,58(20):1973-1975
The interaction of various 1,2-dibromides with NEt3 under various conditions (THF and DMF, respectively) at different temperatures was investigated. Our results from these reactions show that substrate dependent dehydrobrominations compete with reductive debrominations. A comprehensive discussion of these competitive pathways is offered. 相似文献