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NH3在选择性催化还原NO过程中的吸附与活化 总被引:15,自引:0,他引:15
通过大量文献并结合自己的工作,以NH3在催化剂表面的阶段氧化脱氢为主线,分析归纳了选择性催化还原(SCR)反应机理和该体系中可能发生的NH3氧化副反应机理的联系和共性. 对于V2O5/TiO2催化剂,大部分学者认为SCR反应与Brnsted酸性位上的NH+4有关,中间体为NH+3(ads); 而少数学者认为SCR反应与Lewis酸性位上的NH3有关,中间体为NH2(ads). 对于其它SCR催化剂,普遍认可L酸性位上NH3活化脱氢形成的NH2(ads)既是SCR反应中间体,也是NH3氧化生成N2的中间体; NH3氧化生成N2O和NO的反应源于NH2(ads)的进一步脱氢. 尽管有关SCR反应中NH3的吸附位存在分歧,但从NH3吸附后活化的角度看, NH3无论吸附在L酸性位还是B酸性位,都先经过阶段氧化脱氢,然后再参与SCR反应. 由于反应中生成的H2O可能导致L酸向B酸转化,且该转化受反应温度影响,因此不同酸性位机理可能没有本质区别, SCR反应关键是NH3吸附位的氧化性. SCR活性取决于NH3在催化剂表面的吸附量和阶段氧化程度. 催化剂应能吸附足够的NH3, 这与其表面酸碱性有关; 吸附的NH3要能被活化脱氢且程度不宜太高,这与表面氧化还原性有关. 反应温度也会影响NH3的吸附量和活化程度,因此开发高效SCR脱硝催化剂的关键是根据反应温度调控其表面酸性和吸附位的氧化性. 相似文献
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先在0.5 mol·L-1硝酸介质中活化氟离子选择性电极,再在含硝酸的总离子强度调节混合液(TISAM)中测定氟,线性范围为1×10-7~1×10-2mol·L-1,检出限为1.9μg·L-1。该方法应用于绿茶饮料、水、牛奶中痕量氟的测定,结果的RSD小于4.8%,回收率在96.1%至100.2%之间,对氟离子选择性电极在硝酸介质中的活化机理作了阐述。 相似文献
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用紧束缚EHT晶体轨道方法对银硒链状化合物〔(Ph4P)Ag(Se4)〕n及〔(Me4N)Ag(Se5)〕n进行了能带结构计算,结果表明在Fermi能级附近的能带基本上均以环上Se原子之间形成的p-pπ反键为主要成分。利用键向量近似方法对两聚合物能带的走势以及主要成分进行讨论,从而验证了该方法的可靠性。 相似文献
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近年来,过渡金属催化的C—H键官能团化反应引起了广泛的关注并得到迅速发展.作为一个不可替代的合成子,异腈已被广泛应用于合成各类含氮杂环化合物.本综述介绍了异腈参与的惰性键活化反应的最新研究进展及其在有机合成中的应用,包括异腈对C—H键或N—H键的插入反应以及异腈参与的自由基氧化成环反应等. 相似文献
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稀土氨基酸配合物的电子结构与化学键性质 总被引:4,自引:4,他引:4
本文用INDO方法研究了稀土甘氨酸配合物([Er(H_2O)_4(NH_3CH_2COO)_2]_2~(6+))的电子结构和化学键性质。配合物的HOMO由甘氨酸羧基氧O_2p轨道组成,LUMO由羧基的π*(C-O)轨道组成。在配位过程中随L→Ln电荷转移,四个桥联甘氨酸和八个配位水分子分别转移2.59和1.86个电子到铒离子上,与配合物中铒离子带0.77个正电荷结果吻合。转移至5d轨道的电荷最多。配合物具有一定的共价性。对配键有主要贡献的是5d轨道。 相似文献
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This article reports the numerical comparison of the quantities characterizing the extent of electron fluctuation and pair localization in the domains determined by the direct minimization of electron fluctuation with the domains resulting from the partitioning of the molecules based on the topological analysis of the so-called electron localization function (ELF). Such a comparison demonstrates that the ELF partitioning can be regarded as a feasible alternative to computationally much more demanding direct optimization of minimum fluctuation domains. This opened the possibility of the systematic scrutiny of the electron pair model of the chemical bond, and as it was demonstrated, the previous pessimistic claims about the applicability of this model are not completely justified. 相似文献
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We investigate, by means of ab initio calculations, the strength of electron correlations within covalent bonds: the first-row homonuclear diatomics serve as test cases. As an appropriate measure of the correlation strength, we introduce the reduction of the mean-square deviations of the electronic charges in localized orbitals forming a bond. A recently developed population analysis in terms of local operators derived from localized molecular orbitals is thereby used. The correlation-strength parameter depends only weakly on dynamical correlations as test calculations demonstrate. Therefore, the full-valence complete active space self-consistent field (CASSCF) approximation is applied in order to study the changes in the correlation strength with changing bond length for different types of bonds. A number of simple rules emerge from this discussion. In addition, we show that charge fluctuations are not only a reliable measure of intrabond correlation effects, but also can be used to monitor intraatomic quasi-degeneracy effects as well as the interdependence within multiple bonds. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 157–173, 1998 相似文献
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概述了Ru催化的碳氢键的活化反应,包括C-H/烯烃,C-H/炔径和C-H/CO/烯烃 偶联反应,加氢酰化反应,硅化反应。 相似文献
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通过理论方法研究碳氢化合物的活化及氧化,可以对不同催化剂及氧化剂的反应机理形成深刻认识,从而指导设计合成更加高效的碳氢化合物活化及氧化催化剂。本文总结了近几年在碳氢化合物的活化及氧化领域的一些新进展,涉及的底物包括从甲烷到碳原子数等于6的烃类,而催化剂及氧化剂包括有机金属化合物和无机化合物(如分子筛催化剂、金属团簇和金属氧化物等)。文章底物的碳原子数为依据进行分类编排,对每一类底物的活化及氧化介绍不同催化剂及氧化剂的反应过程,着重比较了各类催化剂及氧化剂的异同。 相似文献
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F. Albert Cotton 《Journal of Cluster Science》1994,5(1):3-9
The entire range of compounds related to, as weil as including those containing, quadruple bonds between metal atoms is reviewed, briefly and historically, and some prospects for future work are considered. 相似文献
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Ustynyuk L. Yu. Ustynyuk Yu. A. Laikov D. N. Lunin V. V. 《Russian Chemical Bulletin》2001,50(3):376-380
A DFT study of a model reaction [(5-C5H5)2MCH3]+ + RH [(5-C5H5)2MR]+ + CH4 (M = TiIV, ZrIV; R = Me, Et, Pr, Pri) was carried out with the PBE density functional. Exchange of -bonded ligand proceeds through the formation of agostic complexes [Cp2M(RH)CH3]+ followed by their isomerization into complexes [Cp2M(CH4)R]+
via an inner-sphere migration of a hydrogen atom. The calculated rate constants for such migrations involving the primary and secondary C--H bonds of propane molecule differ by 930 times for TiIV complexes and by 47 times for ZrIV complexes, which is due to the effect of steric factors. 相似文献
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KOH活化木屑生物炭制备活性炭及其表征 总被引:5,自引:2,他引:3
以木屑热裂解的生物质炭为原料,氢氧化钾为活化剂,采用化学活化法制备活性炭,探讨了碱炭比、活化温度和活化时间对活性炭吸附亚甲基蓝吸附值的影响。 利用N2吸附实验、XRD和FTIR等实验技术,对原料与制备活性炭的结构与性能进行了表征。 结果表明,在碱炭质量比为1.5、活化温度750 ℃、活化时间2 h的条件下,所制备的活性炭对亚甲基蓝吸附值为255 mg/g,BET总比表面积为1514 m2/g,中孔比表面积为110 m2/g,吸附总孔容为0.821 cm3/g,中孔孔容为0.117 cm3/g,吸附平均孔径为2.170 nm。 相似文献
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Leticia Naya Margarita López-Torres José M. Vila Nina Gómez-Blanco 《Journal of organometallic chemistry》2008,693(4):685-700
Reaction of Pd(AcO)2 with the Schiff base ligands 2-Br-4,5-(OCH2O)C6H2C(H)N(Cy) (a) and 4,5-(OCH2CH2)C6H3C(H)N(Cy) (b) leads to the cyclometallated compounds [Pd{2-Br-4,5-(OCH2O)C6HC(H)N(Cy)-C6,N}(μ-O2CMe)]2 (1a) and [Pd{4,5-(OCH2CH2)C6H2C(H)N(Cy)-C6,N}(μ-O2CMe)]2 (1b), respectively, via C-H activation. Treatment of a with Pd2(dba)3 gave [Pd{4,5-(OCH2O)C6H2C(H)N(Cy)-C2,N}(μ-Br)]2 (6a), via C-Br activation. The metathesis reaction of 1a and 1b with aqueous sodium chloride gave the corresponding cyclopalladated dimers with bridging chloride ligands, 2a and 2b, respectively. Treatment of the halogen-bridged compounds with tertiary tri- and diphosphines in the appropriate molar ratio gave the mono and dinuclear compounds 3a-5a, 7a-9a and 3b-5b. The structure of compounds 3a, 4a, 5a, 8a, 2b, 3b and 5b has been determined by X-ray diffraction analysis. 相似文献