负载型钯团簇上氢分子吸附和解离吸附的密度泛函理论

基于密度泛函理论考察勃姆石(AlOOH)和氧化锆(ZrO_2)负载的钯团簇表面氢分子吸附和解离吸附过程,通过分析一系列不同尺寸的钯团簇上氢吸附能以及氢分子-钯团簇-载体三者之间的电荷转移系统地研究了粒径效应和载体效应。结果表明,顶点位和面位分别是分子吸附和解离吸附的最佳吸附位置。随着钯团簇粒径的上升,氢分子吸附能和解离吸附能都下降,载体-钯团簇-被吸附氢三者之间的电荷转移量和方向也改变。氧化锆载体负载的钯团簇上分子吸附能和解离吸附能均大于勃姆石载体负载的钯团簇,说明载体对氢分子吸附过程有重要影响。     

正戊烷在钯／氢型天然丝光沸石催化剂上临氢异构化的动力学

本文采用缙云产的天然丝光沸石经铵酸法制得氢型天然丝光沸石,然后用离子交换法负载贵金属Pd,制成双功能催化剂。在加压微反色谱联合装置上进行正戊烷异构化反应。测定了反应速率常数、频率因子、活化能等动力学参数。筛选出比较合适的双位动力学模型。验证了模型的反应速率常数k,并与实验值作了比较。数据表明,该模型是适用的。     

去氢骆驼蓬碱光谱性质的密度泛函理论研究

采用密度泛函理论,M062X方法,使用6-31g(d)基组,对去氢骆驼蓬碱分子进行结构优化,通过频率计算得到该分子的红外光谱,并和实验获得的红外光谱图进行对比,实验和理论获得的红外光谱图基本一致.说明选择的DFT理论方法是可行的.对其主要振动模式进行指认和归属,分析去氢骆驼蓬碱分子前线轨道能级差及激发线波长.绘制分子静...     

乙炔氢氯化反应无汞催化剂研究进展及密度泛函理论模拟的应用

介绍了金基、铜基、钌基及非金属乙炔氢氯化反应无汞催化剂的研究进展,对比分析了 HgCl2、AuCl3、CuCl2和Ru5Cl7 4种催化剂的密度泛函理论模拟结果,得到了过渡反应数量和自由能对催化过程的影响,指出了利用密度泛函理论模拟方法寻找过渡反应数量少、自由能小的催化剂活性组分是开发乙炔氢氯化无汞催化剂的重要途径,结...     

无机物负载型钯催化剂的研究进展

钯催化剂是重要的金属催化剂,近年来,负载型钯催化剂作为一类新型催化剂广受关注。介绍了以硅胶、MCM-41分子筛、活性炭和金属氧化物等无机物为载体的负载型钯催化剂的特征及应用,并展望了其在不对称反应中的开发应用前景。     

FCC催化剂上烃分子吸附行为与其构型的关联

以稀土离子改性超稳Y分子筛、半合成FCC催化剂和原位晶化FCC催化剂为研究对象,利用智能质量分析仪(IGA)和程序升温脱附(TPD)技术考察了烃类分子(正辛烷、1-辛烯和苯)在3种吸附剂上的吸附、脱附行为。结果表明:烃类分子在FCC催化剂孔道内的吸附不仅与催化剂的孔道结构有关,客体分子的构型也是影响其吸附行为的关键因素。高吸附量下,柔性链状的正辛烷分子可在Y分子筛微孔孔道内发生分子间重排和团聚使其不易从分子筛孔道中脱附下来;而分子内双键与催化剂上B酸中心发生强化学吸附的1-辛烯分子和刚性平面结构的苯分子则无明显的分子间团聚现象。     

H2在MoxSy团簇上吸附解离的尺寸效应研究

浆态床加氢工艺可以处理不同来源的劣质重油、渣油,氢气的活化是重油加氢处理过程中发生的主要反应之一。钼基催化剂的分散性是影响重油加氢活性的关键因素。构建了Mo₇S₁₅、Mo₁₂S₂₆、Mo₁₈S₃₉、Mo₂₅S₅₄和Mo₃₃S₇₁团簇,利用密度泛函理论研究了团簇自身的稳定性、活性以及H₂在不同尺寸团簇上的吸附与解离过程。结果发现,在目前所建立的团簇中,其尺寸越小,结合能越低,最高占据分子轨道-最低未占分子轨道(HOMO-LUMO)能隙值越小,团簇稳定性越弱,活性越强。H₂在簇上的稳定吸附位点为边缘位点。随团簇尺寸增大,吸附能分别为-64.25、-34.60、-34.14、-7.20、-6.82 kJ/mol,吸附能绝对值减小,氢气分子与团簇的相互作用减弱,并且解离能逐渐增大,分别为13.76、33.14、53.64、60.75、64.47 kJ/mol。目前的结果表明,团簇尺寸越小,氢气的吸附解离越容易,显示出更高的活性。     

负载钯及非钯型Suzuki偶联反应催化剂体系的研究进展

Suzuki偶联反应是现代有机合成化学中构筑碳碳键的最有效方法之一。传统的Suzuki反应催化剂主要是Pd(PPh3)4、Pd(OAc)2等均相催化剂。这类催化剂的活性较高,但其价格高、化学稳定性较差、难以与反应液分离和回收再利用等缺点也是不容忽视的。近年来,人们开发了一系列具有不同的钯材料载体(碳材料、高分子材料以及无机材料等)的非均相催化剂体系,以及基于Ni、Cu、Mn等过渡金属的新型催化体系。这些新型的催化剂体系的发展有效地解决了上述均相催化剂的不足。综述了近来Suzuki反应在负载催化剂和非钯催化剂方面的研究进展。     

NO adsorption on Pd clusters. A density functional study

The interaction of NO with Pd clusters has been studied by means of the LCGTO-DF method. Metal cluster models (up to 13 atoms) with different size and geometry have been used to describe the atop, bridge and three-fold sites. The use of different model core potentials to increase the size of the cluster model treated and to save computational time has been discussed. The binding energies of N(1s), 4σ, 5σ and 1π electrons are calculated and compared directly to the experimental XPS and UPS data available. The NO is tilted with respect to the surface normal axis when adsorbed on top and bridge sites by about 52.6 and 46.7 degrees, respectively. On the two types of three-fold sites (hcp and fcc) the NO remains upright. The bending angle is very sensitive to the cluster size and affects the binding energies of N(1s), 4σ, 5σ and 1π orbitals. The NO adsorption energies on the different adsorption sites have been estimated using different cluster models. The vibrational frequencies have been calculated in the harmonic approximation and they are in reasonable agreement with the available experimental values. The cluster model approach is discussed in terms of its reliability to determine the adsorption energies and the favored site of adsorption. This revised version was published online in June 2006 with corrections to the Cover Date.     

Density functional theory (DFT) and microcalorimetric investigations of CO adsorption on Pt clusters

Microcalorimetric measurements were conducted at 573 K of CO adsorption on Pt clusters supported in L-zeolite. The measured heat of CO adsorption is 175 kJ/mol, and the heat decreases to 90 kJ/mol near saturation coverage. Quantum chemical calculations were performed using density functional theory to study the interaction of CO with 10-atom Pt clusters. The heat of CO adsorption on atop-sites is calculated to be 209 kJ/mol, while a lower heat of 142 kJ/mol is calculated for CO on bridge-sites. These values decrease to 197 and 102 kJ/mol for population of two atop-sites and two bridge-sites, respectively, on the same Pt₁₀ cluster. The heat of adsorption decreases to 157 kJ/mol when six CO molecules adsorb on six atop-sites of the cluster. The calculated initial heat of CO adsorption on Pt₁₀ clusters is in agreement with experimental and theoretical values reported for CO adsorption on Pt single-crystal surfaces. The higher heat of CO adsorption at atop-sites may be caused by more σ-donation from CO to sp orbitals of Pt for atop-sites. The heat of CO adsorption on bridge-sites becomes higher on negatively charged platinum clusters. The calculated C-O stretching frequencies for charged and neutral platinum clusters agree with experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

On the deactivation of supported palladium hydrogenation catalysts by thiophene poisoning

The deactivation of supported palladium catalysts for ethylbenzene hydrogenation by thiophene was studied. The presence of Pd ⁿ⁺ species on the catalyst surface, in samples prepared from acid solutions of PdCl₂, and reduced at temperatures below 450 °C, was evidenced by XPS. A correlation between the concentration of electron-deficient Pd species and the sulfur resistance was found. Thus, the higher the value of the Pd ⁿ⁺/Pd⁰ ratio, the higher the sulfur resistance. Catalysts prepared from Pd(NO₃)₂ or from PdCl₂ reduced at 450 °C, which essentially contain Pd⁰, are more quickly deactivated. Furthermore, our results also suggest that while the influence of the metal dispersion on the stability of the palladium catalysts toward sulfur is not significant, the nature of the support, on the other hand, plays an important role.     

低温吸附法分离氢同位素

液氮温度下用分子筛Y在自行设计的单塔变压吸附装置上进行氢氘气体分离的研究,考察了流量与压力对分离效果的影响,在气体总压力0.40 MPa、总流量129.79 cm3/min与吸附床长度1.0 m时氢氘气体之间的分离因子可达到1.52。然而压力为0.013 9 MPa与0.017 5 MPa时D2与H2在分子筛Y上的平衡吸附量比值仅分别为1.18和1.17。结合平衡吸附和动态分离之间的差异,表明吸附法能够有效分离氢同位素气体的机理是基于动力学效应。     

Reaction pathway studies of C6 hydrocarbons on palladium model catalysts: effects of hydrogen/hydrocarbon ratio, molecular structure, surface structure and temperature

Reaction pathways of C₆ hydrocarbons, such as hydrogenolysis, dehydrogenation, aromatization and dehydrocyclization, have been studied on small surface area palladium model catalysts, including Pd(111) single crystal and polycrystalline palladium foil. These reactions were performed in a batch reactor, at atmospheric pressure and at two different temperatures (573 and 673 K). This revised version was published online in July 2006 with corrections to the Cover Date.     

Comparative study on pressure swing adsorption system for industrial hydrogen and fuel cell hydrogen

In order to improve the design of PSA system for fuel cell hydrogen production, a non-isothermal model of eight-bed PSA hydrogen process with five-component (H₂/N₂/CH₄/CO/CO₂=74.59%/0.01%/4.2%/2.5%/18.7% (vol)) four-stage pressure equalization was developed in this article. The model adopts a composite adsorption bed of activated carbon and zeolite 5A. In this article, pressure variation, temperature field and separation performance are stimulated, and also effect of providing purge (PP) differential pressure and the ratio of activated carbon to zeolite 5A on separation performance in the process of producing industrial hydrogen (CO content in hydrogen is 10 μl·L^-1) and fuel cell hydrogen (CO content is 0.2 μl·L^-1) are compared. The results show that Run 3, when the CO content in hydrogen is 10 μl·L^-1, the hydrogen recovery is 89.8%, and the average flow rate of feed gas is 0.529 mol·s^-1; When the CO content in hydrogen is 0.2 μl·L^-1, the hydrogen recovery is 85.2%, and the average flow rate of feed gas is 0.43 mol·s^-1. With the increase of PP differential pressure, hydrogen recovery first increases and then decreases, reaching the maximum when PP differential pressure is 0.263 MPa; With the decrease of the ratio of activated carbon to zeolite 5A, the hydrogen recovery increases gradually. When the CO content in hydrogen is 0.2 μl·L^-1 the hydrogen recovery increases more obviously, from 83.96% to 86.37%, until the ratio of activated carbon to zeolite 5A decreases to 1. At the end of PP step, no large amount of CO₂ in gas or solid phase enters the zeolite 5A adsorption bed, while when the CO content in hydrogen is 10 μl·L^-1, and the ratio of carbon to zeolite 5A is less than 1.4, more CO₂ will enter the zeolite 5A bed.     

吡啶类缓蚀剂及其在Al(111)表面吸附行为的密度泛函理论分析

利用密度泛函理论方法研究了3种吡啶类缓蚀剂分子(吡啶、3-甲基吡啶和4-甲基吡啶)的反应活性及溶剂条件下在Al(111)表面的吸附行为。分子反应活性的量化计算结果表明,3种缓蚀剂分子的前线轨道均分布在吡啶环上,亲核和亲电活性中心均位于吡啶环的N原子上。分子与Al表面吸附的量化计算结果表明,3种分子均能与Al(111)面发生化学吸附,吸附强度顺序与实验测得的缓蚀效率顺序相一致,且缓蚀剂分子与Al(111)面的相互作用是由成键原子的轨道杂化所致。此外,3-甲基吡啶和4-甲基吡啶两个分子还能平行于Al(111)面发生物理吸附。     

Effect of metal‐support interface on hydrogen permeation through palladium membranes

Thin palladium membranes of different thicknesses were prepared on sol‐gel derived mesoporous γ‐alumina/α‐alumina and yttria‐stabilized zirconia/α‐alumina supports by a method combining sputter deposition and electroless plating. The effect of metal‐support interface on hydrogen transport permeation properties was investigated by comparing hydrogen permeation data for these membranes measured under different conditions. Hydrogen permeation fluxes for the Pd/γ‐Al₂O₃/α‐Al₂O₃ membranes are significantly smaller than those for the Pd/YSZ/α‐Al₂O₃ membranes under similar conditions. As the palladium membrane thickness increases, the difference in permeation fluxes between these two groups of membranes decreases and the pressure exponent for permeation flux approaches 0.5 from 1. Analysis of the permeation data with a permeation model shows that both groups of membranes have similar hydrogen permeability for bulk diffusion, but the Pd/γ‐Al₂O₃/α‐Al₂O₃ membranes exhibit a much lower surface reaction rate constant with higher activation energy, due possibly to the formation of Pd‐Al alloy, than the Pd/YSZ/α‐Al₂O₃ membranes. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

氢在多壁碳纳米管上的等量吸附热

为说明氢在多壁碳纳米管(MWCNTs)上所受吸附作用的强弱,文中基于氢和77 K氮的吸附数据,比较了由非局域密度泛函理论(NDFT)、等量吸附线和归一化等温线线性化确定的等量吸附热。结果表明,氢在MWCNTs上等量吸附热随温度变化且表现出在弱的能量不均匀表面吸附的特点,平均值约为3—4 kJ/mol;由77 K氮吸附等温线确定的孔大小分布(PSD)和比表面积影响NDFT计算初始吸附时的精度;在吸附量和吸附温度都较低时,等量吸附线标绘结果与归一化等温线线性化方程确定的等量吸附热之间的偏差较小,在200—290 K温度区间则与ND-FT计算结果更为接近。然而,当温度大于310 K时,3种方法计算结果间的偏差较大。     

煤分子结构对煤层气吸附与扩散行为的影响

对煤的芳香单元延展度、芳香单元堆砌层数以及包括不同缺陷和含氧官能团类型的表面结构对煤层气吸附与扩散的影响进行了研究。采用Monte Carlo模拟方法及分子动力学模拟方法分别得到了煤层气的吸附量与扩散系数,模拟温度为303 K,压力为10 MPa。研究结果表明,单位质量的煤对甲烷的吸附量随着芳香单元堆砌层数的增加而降低,缺陷和含氧官能团的存在不利于甲烷的吸附。甲烷的扩散随着芳香单元延展度的增加呈现出一个N形的复杂变化过程,单缺陷和羰基的存在有利于煤层气的扩散,煤结构中大的裂隙更有利于煤层气的扩散。最后,基于煤层气的微观影响因素和宏观运移行为提出了煤颗粒径向不均质的煤层气扩散微观模型。