基于密度泛函理论计算的丙烷脱氢动力学

采用乙二醇还原法制备了Pt颗粒粒径为6 nm的Pt/Al2O3催化剂,借助密度泛函理论(DFT)计算的动力学参数,建立了Pt(111)面上的微观反应动力学模型,并在此基础上建立了Pt(111)面上的Langmuir-Hinshelwood Hougen-Watson(LHHW)模型。结果表明:丙烷脱氢对丙烷的反应级数是1.00级,对氢气的反应级数是-0.51级;反应的表观活化能约为80 kJ/mol;在Pt(111)面上,氢原子是最丰富的表面吸附物种,丙烷脱氢速率受第二步脱氢控制。     

基于密度泛函理论研究H共吸附对丙烷脱氢的影响

采用密度泛函理论(DFT)考察了丙烷在Pt(111)表面上脱氢生成丙烯的反应机理。通过在Pt(111)面上预吸附一定数量H原子模拟共吸附H对丙烷脱氢过程的影响。结果表明:H共吸附能降低丙烷及其脱氢产物的吸附能,促进丙烯脱附,有利于提高丙烯的选择性;H共吸附会导致丙烷脱氢能垒变大,降低催化剂的脱氢活性;共吸附的影响随着H覆盖率增加而增大。     

镍基双金属催化剂上甲烷脱氢反应的密度泛函理论

为了从原子尺度上研究双金属的作用机理,采用基于密度泛函理论的第一性原理方法研究了甲烷在Ni-Pt和Ni-Pd双金属催化剂上的脱氢过程。计算结果表明,在Ni催化剂中引入Pt或Pd会大大减弱表面C原子的吸附,从而提高催化剂的抗积炭能力,而且甲烷第一步脱氢活化能会有所提高,反应活性略有降低。     

Propane Dehydrogenation over a Commercial Pt-Sn/Al2O3 Catalyst for Isobutane Dehydrogenation: Optimization of Reaction Conditions

The applicability of a commercial Pt-Sn/Al₂O₃ isobutane dehydrogenation catalyst in dehydrogenation of propane was studied. Catalyst performance tests were carried out in a fixed-bed quartz reactor under different operating conditions. Generally, as the factors improving propane conversion decrease the propylene selectivity, the optimal operating condition to maximize propylene yield is expected. The optimal condition was obtained by the experimental design method. The investigated parameters were temperature, hydrogen/hydrocarbon (H₂/HC) ratio and space velocity, being changed in three levels. Constrains such as the susceptibility of the catalyst components to sintering or phase transformation were also taken into account. Activity, selectivity and stability of the catalyst were considered as the measured response factors, while the space-time-yield (STY) was considered as the variable to be optimized due to its commercial interest. A STY of 16 mol·kg^-1·h^-1 was achieved under the optimal conditions of T 620℃, H₂/HC 0.6 and, weight hourly space velocity (WHSV) 2.2 h^-1. Single carbon-carbon bond rupture was found to be the main route for the formation of lower hydrocarbon byproducts.     

PtSnLi/Al_2O_3催化剂在丙烷脱氢过程中的氢气选择氧化性能

采用浸渍法制备氧化铝负载三元Pt-Sn-Li催化剂(PtSnLi/A_2O_3),采用X射线衍射(XRD)、透射电镜(TEM)和物理吸附(BET)等手段对催化剂进行表征,并在固定床反应器中评价了该催化剂在丙烷脱氢过程中对氢气选择氧化性能。结果表明,PtSnLi/Al_2O_3催化剂对氢气具有良好的选择氧化性,组分Sn和Li的加入能有效提高Pt基催化剂活性和选择性。PtSnLi/Al_2O_3催化剂在常压、550℃和质量空速为1.45 h~(-1)的条件下,氢气的选择氧化性为80%,氧气转化率大于98%,烃类损耗量0.2%。与PtSn/Al_2O_3相比,氧气转化率基本相同,氢气的选择氧化增加了29.2%,烃损耗率降低了0.9%。     

C4O7团簇的密度泛函理论研究

利用理论计算方法设计高能量密度材料(HEDM)分子是目前材料科学领域的研究热点之一.本文利用密度泛函理论(DVT)在B3LYP/6-31G(d)水平上对C4O7团簇异构体几何结构进行优化,找到了C4O7团簇的27种稳定结构.以一个C4O7团簇分子分解为3个CO2和一个CO计算,C4O7团簇分子的解离能在7.312×103～2.958×103 kJ/kg之间,放出的能量较多,是用做高能量密度材料的潜在资源.     

大环化合物密度泛函理论研究

运用量子化学密度泛函理论B3LYP/6-31G*方法对脱苯[15]轮烯和脱氢苯吡啶[15]轮烯进行了优化,用含时密度泛函(TD-DTF)计算其吸收光谱,结合前线分子轨道讨论吸收波长不同的原因。结果表明,三种构型的分子为平面共轭分子,分子Ⅰ的苯环被吡啶环取代成分子Ⅱ和Ⅲ,分子Ⅲ的最大吸收波长最长;分子Ⅱ最大吸收波长最短。     

Enhanced Stability of HZSM-5 Supported Ga2O3 Catalyst in Propane Dehydrogenation by Dealumination

Gallium oxide catalysts supported on HZSM-5 with different Si/Al ratios were characterized by pyridine adsorption FT-IR, model reactions and XPS studies. As the Si/Al ratio of the support HZSM-5 zeolite rises, the acidity of the supported catalysts decreases accordingly, which comes from two aspects: the loss of acid sites present on HZSM-5 support and the loss of the acid sites present on gallium oxides. The latter was caused by the change in the interaction between Ga₂O₃ and support. The initial activity in the propane dehydrogenation decreases with increasing Si/Al ratio while the stability increases. The enhanced stability is thought to be caused by the decrease of the acidity of the catalysts, resulting in the suppression of the side reactions, such as cracking and oligomerization.     

锡组分状态对Pt/Al2O3丙烷脱氢性能的影响

采用浸溃法制备了不同Sn组分含量以及一定量的金属钠组分的Pt-Sn/Al2O3催化剂,并采用程序升温还原(TPR),光电子能谱(XPS)和程序升温氧化(TPO)等手段对催化剂进行了表征.研究表明,Sn组分状态与Sn组分以及Na组分的相对含量有关,在Sn与Pt物质的量之比小于5(Pt质量负载量0.4%)时,Sn组分在催化剂表面以氧化态的形式存在.此种催化剂用量为0.32 g时,在常压、550℃、丙烷质量空速3.4 h-1的条件下,反应6.5 h丙烷转化率达43.1%,丙烯选择性达98.0%.若Sn含量更高,将导致Sn被还原析出,形成Sn与Pt合金.当Sn与Pt物质的量之比为1时,引入1.2%的NaCl不会影响Sn组分状态;当Sn与Pt物质的量之比为5,引入相同量的NaCl,导致催化剂表面的Sn组分容易被氢气还原.     

载体对丙烷脱氢过程中氢气选择氧化催化剂Pt/Al_2O_3性能的影响

通过X射线衍射(XRD)、透射电镜(TEM)和物理吸附(N_2吸附)等手段测定了不同合成条件下制备的Al_2O_3物性参数如比表面积,孔容和孔径等,并以合成的Al_2O_3为载体制备了单Pt/Al_2O_3催化剂,在固定床微型催化反应装置上考察了其在丙烷脱氢过程中催化氢气选择氧化性能。由相同条件下催化剂对混合气中氢气选择性氧化催化结果可知,在铝和葡萄糖物质的量比为1和弱碱条件下制备的Al_2O_3为载体,负载Pt质量分率0.5%的催化剂对烃损耗较小。NH_3的程序升温脱附(NH_3-TPD)表明,该催化剂表面碱性较强,活性较好。     

PtSnNa/Al2O3催化剂丙烷脱氢反应性能研究

采用氢化学吸附、热重和程序升温还原等多种物理化学手段结合微型催化反应研究了添加Na＋对负载型PtSn/γ-Al2O3催化剂丙烷脱氢反应性能、催化剂表面酸性、金属表面性质以及负载组分-载体相互作用的影响.发现添加一定量的Na＋可以减少催化剂的积炭量,提高催化剂的金属表面裸露度,从而改善催化剂的脱氢反应稳定性.而引入较多的Na＋虽可以提高催化剂抗积炭性能,但破坏了Pt-Sn-Al2O3之间的相互作用,锡组分易被还原,催化剂活性表面减小,从而对催化剂脱氢反应活性有抑制作用.     

过氧化麦角甾醇分子的密度泛函理论研究

采用密度泛函理论(DFT)方法,在B3LYP/6-311+G(2d,p)水平上对过氧化麦角甾醇进行了计算研究。优化得到了过氧化麦角甾醇分子的结构,给出了分子的键长、键角、二面角等参数,并对其进行了1HNMR光谱、IR光谱、UV-Vis光谱理论模拟和自然电荷分析。自然电荷计算表明,羟基O和H原子很可能是关键的活性中心。理论计算结果与实验值符合的很好。     

V–Mg–O Prepared via a Mesoporous Pathway: A Low-Temperature Catalyst for the Oxidative Dehydrogenation of Propane to Propene

The oxidative dehydrogenation of propane was investigated in a fixed-bed tubular flow reactor at 350 and 450°C over V–Mg–O catalysts prepared via a solid reaction (the mix-VMg catalysts) or from mesoporous precursors (the meso-VMg catalysts). Significantly higher selectivities and yields to propene were obtained over the meso-VMg catalysts than over the mix-VMg ones. The cooperation between a much higher BET specific surface area and a novel phase, a highly dispersed-Mg-in-V₂O₃, is suggested as responsible for the higher ODP performance of the meso-VMg catalysts than of the mix-VMg ones.     

Size Dependence of Si Nanocrystals Infrared Spectra: A Density Functional Theory Study

Infrared vibrational modes were calculated using ab initio density functional theory and coupled perturbed Hartree-Fock equations for Si nanocrystals of approximately 1.57 nm length. Frequencies of modes were analyzed against intensities, reduced masses and vibrational force constants. The present calculations were able to reproduce the red shift associated with size reduction from the original 521 cm^?1 of the bulk optical Si-Si vibrations to the present nanocrystal 493 cm^?1 high intensity mode. In order to investigate size dependence of infrared spectra a comparison is given with bulk silicon crystals and sila adamantane. A comparison revealed several changes as the nanocrystal size goes from bulk to the molecular limit. This includes a blue shift of radial breathing mode which is an acoustical mode and red shift of the optical modes. Different surface SiH₂ and SiH₃ vibrational modes were matched with experimental symmetric, asymmetric, wagging, scissor, rocking and twisting modes.     

靛族染料化合物结构与性能的密度泛函理论研究

在密度泛函理论(DFT)的B3LYP／6-31G^*水平上对一系列靛族染料化合物的几何构型进行优化计算：在获得基态稳定结构的基础上，应用含时密度泛函理论(TD-DFT)在相同水平下计算其电子吸收光谱，探讨了不同给电子基团和发色体系的延伸对电子吸收光谱的影响，得到了与实验基本一致的变化规律。结果表明，给电子能力的增强和发色体系的纵向延伸均使光谱产生一定红移，通过对前线轨道组成进行自然布居分析，揭示了靛族染料的发光均源自分子中HOMO-LUMO(П→П^*)电子跃迁。     

Probing the Positions of TeO Moieties in the Channels of the MoVNbTeO M1 Catalyst: A Density Functional Theory Model Study

Catalysis Letters - With hybrid DFT calculations applied to periodic models of the bulk MoVNbTeO M1 catalyst, we examined how [TeO]2+ species in the hexagonal channels of this material stabilize...     

乙苯脱氢催化剂制备用捏合机功率研究

针对目前乙苯脱氢催化剂捏合制备过程缺乏直接、有效的表征方法的问题,通过分析捏合过程功率曲线,考察捏合功率与催化剂产品机械强度的关联性。研究结果表明:功率曲线能直观反映捏合过程,单位物料接收的功越高,制备的催化剂其机械强度也越高,可以采用功率曲线和单位功作为直接有效地表征捏合效果的分析方法。