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More than one hundred models were designed to reflect the local structure and electronic property of Ni-Fe amorphous alloys. After calculating by DFF method, a series of configurations of clusters NixFe and NiFex (x = 1 - 5) were gained. The configurations, which possessed the lowest energies and non-imaginary frequencies, were considered the most stable optimized structures. The catalytic activity, charge and magnetic properties were analyzed and discussed. The different Fe content changed the catalytic properties of clusters through altering the value of Fermi level of every cluster. However the density of state (DOS) nearby Fermi level and average 3d orbital population of atom Ni, which were also important properties related to the catalytic activation, were little changed. Based on the Fermi level, the activity of catalyst toward hydrogenation reaction would be considered best when the ratio of Ni to Fe was close to 1. The Fermi level of clusters was far distant to the level of nitrogen in singlet state. It would be the reason why the reaction condition in ammonia synthesis and nitrogen fixation process was rigorous. When Fe atom contents were higher than 75% (NiFe3), the electrons transferred from atom Fe to Ni, but when the ratio was decreased, the transfer was reversed. The ratio of atoms of local structure also played an important role in the aspect of electron transition. On the average 3d orbital population of atom Fe, the average magnetic moments of Fe atoms in clusters were calculated. When Fe atom contents were 50% nearly, the average magnetic moment achieved the highest point. 相似文献
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本文选用密度泛函B3LYP方法在Lan L2DZ基组上对Au Gen+(n=2~9)团簇的几何结构和电子性质进行了理论研究,其中包括结构优化、平均键能、HOMO-LUMO能隙和电荷转移等。结果表明,随着锗原子数的不断增加,这些掺杂团簇逐渐形成了三维立体结构,并发现Au Ge7+和Au Ge9+两个掺杂团簇是相对稳定的,而且这些掺杂团簇的电荷转移主要是由金原子到锗原子骨架上。此外,还模拟了这些掺杂团簇的红外光谱,为以后实验研究提供有价值的理论参考。 相似文献
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用DFT-B3LYP方法对低聚物(PF30T)n [n(芴)∶n(硫芴)=2∶1, 物质的量之比, n=1~4], (PF50T)n [n(芴)∶n(硫芴)=1∶1, 物质的量之比, n=1~4]体系全优化, 得到两系列低聚物的电离能(IP(a,v))、电子亲和势(EA(a,v))、空穴抽取能(HEP)、电子抽取能(EEP). 在此基础上用ZINDO和TD-DFT方法计算吸收光谱, 分析了两个系列的HOMO-LUMO能隙随着n递增的变化趋势及硫芴含量对低聚物电子结构和光谱性质的影响, 推断了高聚物的电子和光谱性质. 用ab initio CIS方法优化了低聚物的S1激发态结构并分析了其与发射光谱的关系. 研究显示: 2,8位引入的硫芴基团, 破坏了链的共轭, 而且随着硫芴含量的增加, HOMO-LUMO能隙变大, 光谱蓝移; 激发态结构趋于共面化. 相似文献
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在卡里普索(CALYPSO)结构预测的基础上,采用密度泛函理论(DFT)B3LYP方法,优化得到PdSi_n(n=1~15)团簇的基态结构,对其电子性质、红外光谱和拉曼光谱进行了讨论.结果表明,PdSi_n(n=1~15)团簇的基态构型随n值的增大由平面结构向立体结构演化;当n≤4时,PdSi_n团簇的红外与拉曼活性在450~500 cm-1范围内表现较好,当n≥5时,PdSi_n团簇的红外与拉曼活性在50~500 cm~(-1)范围内表现较好. 相似文献
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采用密度泛函理论研究了InnAsn (n≤90)管状团簇以及单壁InAs纳米管的几何结构、稳定性和电子性质. 小团簇InnAsn (n=1-3)基态结构和电子性质的计算结果与已有报道相一致. 当n≥4时优化得到了一族稳定的管状团簇, 其结构基元(In原子与As原子交替排列的四元环和六元环结构)满足共同的衍化通式. 团簇的平均结合能表明横截面为八个原子的管状团簇稳定性最好. 管状团簇前线轨道随尺寸的变化规律有效地解释了一维稳定管状团簇的生长原因, 同时也说明了实验上之所以能合成InAs纳米管的微观机理. 此外, 研究结果表明通过管状团簇的有效组装可得到宽带隙的InAs半导体单壁纳米管. 相似文献
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In order to study the electron property and the microlocal structure of Co-P amorphous alloy,a series of single-P(ConP)and two-P(ConP2)cluster models were chosen according to the experiment fact of the possible presence of direct P-P contact and short-range-ordering in the amorphous alloy. ConP and ConP2 cluster models were calculated with the DFT method and calculations showed that P(phosphor)accepted electron from Co(cobalt)in single-P(Co2P(2),Co3P(1)and Co4P(2))cluster models,which agrees well with the Pauli electronegative rule,and a very strong interaction between Co and P resulted in formation stable clusters Co2P(2),Co3P(1)and Co4P(2). However,two-P(ConP2)cluster models and single-P cluster Co5P(1)were unstable,and it was impossible to present direct P-P contact in two-P(ConP2)cluster models. It could be concluded that the clusters Co2P(2),Co3P(1)and Co4P(2) is more reasonable to represent the local structure of Co-P amorphous alloy. 相似文献
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环境法规对硫氧化物脱出的限制日益严格以及原油品质的不断下降,使得有必要研发高效的加氢脱硫催化剂。Ni2P由于具有优异的加氢脱硫活性和稳定性,引起了广泛的关注。本文综述了Ni2P加氢脱硫催化剂的特性、反应活性相、制备方法、改进和加氢脱硫活性等方面的研究进展。在Ni2P中存在两种不同的初始活性位,四面体几何构型的Ni(1)初始活性位在加氢脱硫反应中参与直接脱硫反应,四方锥几何构型的Ni(2)初始活性位则与催化剂的高加氢活性有关。在加氢脱硫反应中,催化剂表面生成的NixSyP相被认为是真正的活性相。制备Ni2P的方法主要是程序升温还原和液相合成。载体、助剂和络合剂对Ni2P活性相的形成和催化剂的活性有重要影响。相比于商用硫化物催化剂,Ni2P催化剂对噻吩、二苯并噻吩和4,6-二甲基二苯并噻吩均表现出更高的加氢脱硫活性。 相似文献
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采用程序升温还原法制备了一系列Ni2P/Ce-Al2O3催化剂,考察了制备过程中Ni2P负载量对催化剂结构及萘加氢饱和性能的影响。结果表明,Ni2P负载量可调控活性组分Ni2P与载体Ce-Al2O3之间的相互作用,进而调变催化剂的比表面积、Ni2P粒径及催化剂活性位点数量。当Ni2P负载量(质量分数)为17%时,催化剂具有较大的比表面积(40 m2/g)、较小的Ni2P粒径(26.3 nm)和最多的活性位点数量(26.7 μmol/g);同时,该催化剂萘转化率为95%,十氢萘选择性为76%,且活性稳定性良好,这主要归因于催化剂大的比表面积和高的活性位点数量为反应提供了更多的场所。 相似文献
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以氢氧化镍为镍源, 亚磷酸为磷源, TiO2柱撑海泡石(Ti-Sep)为载体, 采用浸渍法制备了含磷化镍前驱体的样品, 然后采用程序升温还原法制备了Ni质量分数(w)为5%-25%的Ni2P/Ti-Sep催化剂, 并考察了其噻吩加氢脱硫性能. 采用X射线衍射(XRD)、N2吸附-脱附、热重分析(TGA)、透射电子显微镜(TEM)和傅里叶变换红外(FTIR)光谱对催化剂样品进行了表征. 结果表明, 海泡石经TiO2柱撑之后层间距增大, 比表面积和孔容都明显变大, 热稳定性增强, 活性组分Ni2P能很好地分散在海泡石层间及表面, 并且没有破坏海泡石的层状结构. 上述原因导致Ni2P/Ti-Sep催化剂的噻吩加氢脱硫活性明显优于Ni2P/Na-Sep(NaCl改性海泡石)和Ni2P/HCl-Sep(HCl改性海泡石)催化剂. 当Ni负载量为15% (w)时, Ni2P/Ti-Sep催化剂具有最好的噻吩加氢脱硫性能; 在反应温度为400℃时, 噻吩转化率达100%. 相似文献
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With the level of B3LYP/Lanl2dz of density functional theory and advisable adsorption models designed, the adsorption properties of the most stable cluster of Ni2Fe2P were calculated, and four stable configurations with the adsorption of hydrogen were gained. The geometries and HOMO contributions of 3d orbital of metal atoms and energy level properties of adsorption configurations were concerned and their Infrared Spectrum were simulated and predicted. The bond lengths and bond orders and vibration frequencies concerned synthetically, the adsorption mechanisms of hydrogen molecular on amorphous alloys Ni40Fe40P20 surfaces were discussed in the microcosmic aspect. The hydrogen molecules adsorbing on the clusters were dissociated. In the clusters′ Infrared Spectrums of hydrogen adsorption, there were the vibration peaks with the frequency less than 500 cm-1 caused by metal atoms and other vibration peaks with the frequency more than 500 cm-1 caused by hydrogen atoms. Compared with the energy level DOS of the clusters before and after adsorption, it was found, that the new adsorption activity sites generated after the adsorption of hydrogen, as well as easy way for metal atoms providing electrons and participating subsequence reactions were gained. 相似文献
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采用10% H2S/H2对Ni2P/SiO2催化剂进行预处理,利用X射线衍射、电感耦合等离子发射光谱、X射线光电子能谱、CO化学吸附、H2程序升温脱附、NH3程序升温脱附及活性评价等方法研究了H2S预处理对催化剂结构和氯苯加氢脱氯反应性能的影响.结果表明,即使在873K进行H2S预处理,Ni2P/SiO2催化剂体相结构及Ni2P晶粒大小没有发生变化,但导致Ni2P晶粒表面形成了磷硫镍相(NiPxSy),同时使表面溢流氢数量增加.硫物种的存在不仅阻塞了部分镍中心,使催化剂表面镍中心密度降低,也导致镍中心的缺电子性进一步增加.经H2S预处理后Ni2P/SiO2催化剂上氯苯加氢脱氯反应的转化频率(TOF)明显提高,这可能与催化剂表面Ni物种的缺电子性增强及溢流氢数量增多有关. 相似文献
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Density functional calculations on the electronic structure and magnetic properties of Ni5 and Ni6 clusters are presented in this work. The geometry and spin state of clusters are optimized for several starting symmetries. Moreover, those calculations are followed by a vibrational analysis to discriminate between real minima and saddle-points on the potential energy surface of clusters. Equilibrium geometries, electronic configurations, binding energies, magnetic moments, and harmonic frequencies of stable Ni5 and Ni6 clusters are reported. 相似文献
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