Packing effects on argon and methanol adsorption inside graphitic cylindrical and slit pores: a GCMC simulation study

Using Grand Canonical Monte Carlo simulation, we have studied the effects of confinement on argon and methanol adsorption in graphitic cylindrical and slit pores. Linear chain, zigzag and incomplete helical packing are observed for argon adsorption in cylindrical pores. However, for methanol adsorption different features appear because the electrostatic interactions favour configurations that maximize the hydrogen bonding among methanol molecules. We have found zigzag chains with hydrogen-bonded structures for methanol adsorption in cylindrical and slit pores. To investigate how dense the adsorbed phase is and how many molecules could be packed per unit physical volume of the solid, we consider two different definitions of pore density; one based on the physical volume and the other on the accessible volume. That based on accessible volume gives a measure of the fluid density, while that based on the physical volume gives a measure of how much adsorbate can be stored per unit volume of the adsorbent. It is found that the adsorbate is denser in cylindrical pores, but that slit pores can pack more molecules per unit solid volume. We also discuss the effects on the isosteric heat of argon and methanol of pore size, pore geometry and loading.     

Solid deformation induced by the adsorption of methane and methanol under sub- and supercritical conditions

Carbonaceous materials with some degree of flexibility in their physical structure can expand or contract under the influence of the forces exerted by adsorbed molecules. To gain insight into how adsorption of non-polar and polar fluids could deform a carbon solid, we present GCMC simulations of sub- and supercritical adsorption of methane and methanol in slit-shaped pores whose walls are made of graphene layers. Our extensive simulation study shows that there is a strong correlation between solvation pressure and solid deformation, and that the expansion or contraction of the pore strongly depends on adsorbate loading, temperature and pore size.     

沸石载体结构对甲烷无氧芳构化性能的影响

考察了担载MoO₃的沸石催化剂上甲烷的无氧芳构化性能,并与沸石结构相关联.结果表明,孔径与苯分子动态直径相当的ZSM-5、ZSM-8、ZSM-11和β沸石等是甲烷无氧芳构化催化剂的良好载体,其中3%MoO₃/HZSM-11具有最高的甲烷芳构化活性和稳定性,973K下的转化率和苯选择性分别为8.0%和90.9%;6%MoO₃/HZSM-8与7%MoO₃/H-β芳构化性能相当.以HMCM-41和HSAPO-34为载体时芳构化活性很低,以HMOR、HX和HY为载体时仅有少量乙烯生成,而以HSAPO-5和HSAPO-11为载体时未检测到烃类生成.     

分子筛催化剂上甲醇与三聚甲醛缩合制聚甲醛二甲醚

对HY、HZSM-5、Hβ和HMCM-22分子筛催化剂上甲醇与三聚甲醛缩合制聚甲醛二甲醚（PODE_n或DMM_n）的反应性能进行了研究,考察了分子筛种类和酸性对产物分布的影响。结果显示,以酸性分子筛为催化剂,甲醇与三聚甲醛可缩合得到聚甲醛二甲醚。HY分子筛上反应产物主要为短链的甲缩醛（DMM）;HZSM-5和Hβ分子筛上产物以DMM₁~3为主,其柴油添加剂组分DMM₃~8的收率分别为6.40%和13.78%;HMCM-22分子筛为催化剂时,长链的聚合物收率明显增加,其柴油添加剂组分DMM₃~8的收率可以达到29.39%。NH₃-TPD表征结果表明催化剂表面的酸性对产物分布有着明显的影响：表面弱酸位有利于短链产物DMM的生成,而中等强度的表面酸性位则能促进柴油添加组分DMM₃~8的生成。     

Calculation of the characteristics of ethanol and methanol adsorbed in a pore of activated carbon by the density functional method

Density functional theory was used to perform quantum-chemical calculations of changes in the energy and structure characteristics of methanol and ethanol molecules caused by their adsorption in model slitlike pores of activated carbon. The conclusion was made that changes in these characteristics (bond lengths, angles, charges on atoms, and harmonic vibration frequencies) is additional evidence of the validity of the Tolmachev thermodynamic model, in which adsorption is treated as a quasi-chemical reaction of the addition of adsorbate molecules to adsorption centers of an adsorbent. It was shown that the arrangement of alcohol molecules, when the C-O and C-C bonds were approximately parallel to pore walls and the hydrogen atom was directed toward a nearer pore wall, was most favorable energetically. Two adsorbed alcohol molecules are also arranged parallel to pore walls and form a hydrogen bond.     

Low temperature properties of acetonitrile confined in MCM-41

The effect of confinement on the phase changes and dynamics of acetonitrile in mesoporous MCM-41 was studied by use of adsorption, FT-IR, DSC, and quasi-elastic neutron scattering (QENS) measurements. Acetonitrile molecules in a monolayer interact strongly with surface hydroxyls to be registered and perturb the triple bond in the C[triple bond]N group. Adsorbed molecules above the monolayer through to the central part of the cylindrical pores are capillary condensed molecules (cc-acetonitrile), but they do not show the hysteresis loop in adsorption-desorption isotherms, i.e., second order capillary condensation. FT-IR measurements indicated that the condensed phase is very similar to the bulk liquid. The cc-acetonitrile freezes at temperatures that depend on the pore size of the MCM-41 down to 29.1 A (C14), below which it is not frozen. In addition, phase changes between alpha-type and beta-type acetonitriles were observed below the melting points. Application of the Gibbs-Thomson equation, assuming the unfrozen layer thickness to be 0.7 nm, gave the interface free energy differences between the interfaces, i.e., Deltagamma(l/alpha) = 22.4 mJ m(-2) for the liquid/pore surface (ps) and alpha-type/ps, and Deltagamma(alpha/beta) = 3.17 mJ m(-2) for alpha-type/ps and beta-type/ps, respectively. QENS experiments substantiate the differing behaviors of monolayer acetonitrile and cc-acetonitrile. The monolayer acetonitrile molecules are anchored so as not to translate. The two Lorentzian analysis of QENS spectra for cc-acetonitriles showed translational motion but markedly slowed. However, the activation energy for cc-acetonitrile in MCM-41 (C18) is 7.0 kJ mol(-1) compared to the bulk value of 12.7 kJ mol(-1). The relaxation times for tumbling rotational diffusion of cc-acetonitrile are similar to bulk values.     

烃在HZSM-5沸石上的程序升温脱附

本文研究了烃在HZSM-5沸石上的程序升温脱附(TPD).正己烷、环己烷和苯的TPD谱只有一个陡峰,对和间二甲苯的TPD谱均呈现出双峰.实验测得脱附活化能的次序为:正己烷>对二甲苯>苯>环己烷.水汽处理对正己烷的TPD影响不大;但对二甲苯的TPD影响较大.随着吸附量的增大,二甲苯逐渐占据孔道深处的强活性位置.     

Passivation of the calcite surface with phenylmalonate and benzylmalonate ions

We explored the affinity of calcite to adsorbed organic molecules as an approach to the conservation of cultural heritage built of marble and limestone. The utilization of phenylmalonic and benzylmalonic acids provided a hydrophobic adsorptive interface, adequate to prevent processes of aqueous weathering. Samples of marble powder (polycrystalline calcite) were impregnated with solutions of phenylmalonic and benzylmalonic acid at three concentrations (5 x 10(-2), 5 x 10(-3), and 5 x 10(-4) M) and different pH values (6.00, 7.00, and 8.00). The surface charge of the calcite suspensions was determined by potentiometric measurements under equilibrium conditions at room temperature in aqueous solution of the dicarboxylic acids, in order to understand the influence of the electrokinetic potential in the surface association. The adsorbed amounts were determined by calculation of the thermodynamic equilibria of solutions. The presence of the organic interface on the mineral surface was corroborated by Raman spectroscopy and small-angle X-ray scattering (SAXS). The results indicate effective adsorption of both dicarboxylic acids as a function of the concentration and pH, and several other conditions that favors coulombic interaction, an absence of electrophoretic mobility or surface electroneutrality related to the solid surface potentials. The coverage of pores by dicarboxylic adsorbate modified the geometrical pore shape and the pore size distribution, filling all the pores of larger than 80 A diameter, giving as a result a mesoporous structure. This change in the surface morphology by organic adsorbates constitutes a modification in the diffusional processes of the environment on the mineral surface.     

氟改性对纳米 HZSM-5 分子筛催化甲醇制丙烯的影响

 在比较了纳米和微米 HZSM-5 分子筛催化甲醇制丙烯反应性能的基础上, 对纳米 HZSM-5 分子筛进行了氟改性. 利用透射电镜、N2 吸附、X 射线衍射、氨程序升温脱附和吡啶吸附-红外光谱技术对改性前后的样品进行了表征, 并在常压、500 oC 和甲醇空速 (WHSV) 为 1.0 h–1 的反应条件下, 在连续流动固定床微型反应器上考察了其催化甲醇制丙烯的性能. 结果表明, 当氟含量<10% 时, 随氟含量的增加, 改性纳米 HZSM-5 分子筛的酸量减少, 酸强度降低, 从而使丙烯选择性和催化剂稳定性不断提高. 但过量 (15%) 氟的改性使纳米 HZSM-5 分子筛的酸量、比表面积和孔容均明显减小, 致使其稳定性反而降低. 在适量 (10%) 氟改性的纳米 HZSM-5 分子筛上, 丙烯选择性和维持甲醇完全转化的反应时间分别由原来的 30.1% 和 75 h 增加到 46.7% 和 145 h.     

Structure of methanol confined in MCM-41 investigated by large-angle X-ray scattering technique

Large-angle X-ray scattering (LAXS) measurements over a temperature range from 223 to 298 K have been made on methanol confined in mesoporous silica MCM-41 with two different pore diameters, 28 A (C14) and 21 A (C10), under both monolayer and capillary-condensed adsorption conditions. To compare the structure of methanol in the MCM-41 pores with that of bulk methanol, X-ray scattering intensities for bulk methanol in the same temperature range have also been measured. The radial distribution functions (RDFs) for the monolayer methanol samples showed that methanol molecules are strongly hydrogen bonded to the silanol groups on the MCM-41 surface, resulting in no significant change in the structure of adsorbed methanol with respect to the pore size and temperature. On the other hand, the RDFs for the capillary-condensed methanol samples showed that hydrogen-bonded chains of methanol molecules are formed in both pores. However, the distance and number of hydrogen bonds estimated from the RDFs suggested that hydrogen bonds between methanol molecules in the pores are significantly distorted or partly disrupted. It has been found that the hydrogen bonds are more distorted in the smaller pores of MCM-41. With decreasing temperature, however, the hydrogen-bonded chains of methanol in the pores were gradually ordered. A comparison of the present results on methanol in MCM-41 pores with those on water in the same pores revealed that the structural change with temperature is less significant for confined methanol than for confined water.     

水热处理对纳米HZSM-5分子筛酸性及催化甲醇制丙烯反应性能的影响

对纳米HZSM-5分子筛进行水热处理,利用N2吸附-脱附、X射线衍射(XRD)、铝固体核磁共振(27AlMASNMR)、氨-程序升温脱附(NH3-TPD)和吡啶吸附傅立叶变换红外(FT-IR)光谱等技术对改性前后样品的结构和酸性进行了详细表征,并在常压、500℃和甲醇质量空速(WHSV)为1.0h-1的反应条件下,在连续流动微型固定床反应器上考察了其催化甲醇转化制丙烯反应的性能.结果表明,适度的水热处理使纳米HZSM-5分子筛骨架脱铝并经柠檬酸洗涤而除去,酸量减少,酸强度降低,孔容和孔径增大,从而使丙烯的选择性和维持甲醇完全转化的反应时间(即催化剂寿命)分别由改性前的30.1%和75h显著提高至38.9%和160h.但过高温度的水热处理使纳米HZSM-5分子筛的酸性明显减弱,强酸中心几乎完全消失,故使丙烯的选择性和催化剂的稳定性反而大大降低.     

Influence of isotherm inflection on the loading dependence of the diffusivities of n-hexane and n-heptane in MFI zeolite. Quasi-elastic neutron scattering experiments supplemented by molecular simulations

Quasi-Elastic Neutron Scattering (QENS) experiments were carried out to determine (a) Fick diffusivity, D (b) self-diffusivity, Dself, and (c) 1/Gamma, the inverse of the thermodynamic correction factor, for n-hexane (nC6) and n-heptane (nC7) in MFI zeolite (all silica silicalite-1) at 300 K for a variety of loadings. These experimental results are compared with configurational-bias Monte Carlo (CBMC) and molecular dynamics (MD) simulations of, respectively, the adsorption isotherms and diffusivities. For n-hexane, the CBMC simulated isotherm shows a slight inflection at a loading=4 molecules per unit cell; this inflection manifests, also, in the loading dependence of 1/Gamma, obtained from QENS. The trend in the loading dependence of the Fick D and Dself of nC6 obtained from QENS matches the MD simulation results. For nC7 the CBMC simulated isotherm shows a strong inflection at a loading=4 molecules per unit cell. At this loading=4, 1/Gamma tends to zero and there is a very good match between QENS and molecular simulations for the loading dependence of 1/Gamma. Both MD simulations and QENS data on the Fick diffusivity shows a sharp maximum at a loading in the region of=4. For both nC6 and nC7 the simulated values of diffusivity are about an order of magnitude higher than those determined from QENS.     

利用原子层沉积制备Pt/HZSM-5催化剂用于乙酰丙酸水相加氢制备戊酸

利用原子层沉积（ALD）技术制备出Pt/HZSM-5催化剂，并用于乙酰丙酸（LA）水相加氢制戊酸（VA）。在HZSM-5上沉积五个循环时的5Pt/HZSM-5催化剂，其VA收率高达91.4%，且具有较高的稳定性。研究表明，Pt加氢位点和HZSM-5 酸性位点距离越近越有利于VA的选择性生成。通过延长沉积的扩散时间，ALD可将Pt沉积到HZSM-5的微孔通道中，但对HZSM-5的微孔结构和酸性位点影响较小，这体现出ALD在保护HZSM-5 结构上的优势。随着ALD沉积Pt循环数的增加，Pt纳米颗粒的平均粒径、表面Pt的电子状态、HZSM-5表面酸位点都没有发生明显的变化，分子筛孔道中的Pt比例则逐渐降低，这导致VA生成的TOF降低。同时，也通过浸渍法制备了负载在HZSM-5上的Pt催化剂作为对比，结果表明，浸渍法导致HZSM-5的孔结构受损，形成了更多的微孔，表面酸性位点数目降低，其催化活性、VA 选择性和稳定性都显著低于ALD制备的催化剂。     

Solid state 13C NMR studies of methane dehydroaromatization reaction on Mo/HZSM-5 and W/HZSM-5 catalysts

Methane dehydroaromatization on Mo/HZSM-5 and W/HZSM-5 catalysts was studied by solid state 13C NMR spectroscopy, both variation of the state of transition metal component and products such as ethane, benzene, ethene adsorbed on or in zeolite were observed after high temperature (900-1000 K) reaction.     

An experimental and molecular simulation study of the adsorption of carbon dioxide and methane in nanoporous carbons in the presence of water

The adsorption of carbon dioxide and methane in nanoporous carbons in the presence of water is studied using experiments and molecular simulations. For all amounts of adsorbed water molecules, the adsorption isotherms for carbon dioxide and methane resemble those obtained for pure fluids. The pore filling mechanism does not seem to be affected by the presence of the water molecules. Moreover, the pressure at which the maximum adsorbed amount of methane or carbon dioxide is reached is nearly insensitive to the loading of preadsorbed water molecules. In contrast, the adsorbed amount of methane or carbon dioxide decreases linearly with the number of guest water molecules. Typical molecular configurations obtained using molecular simulation indicate that the water molecules form isolated clusters within the host porous carbon due to the nonfavorable interaction between carbon dioxide or methane and water.     

Studies on hydroxy inclusion complexes. I. Host-guest interaction of the molecular complexes of 9-hydroxy-9-(1-propynyl) fluorene and 1,1-Bis (2,4-dimethylphenyl)-2-butyn-1-ol with water,methanol, ethanol,andn-propanol

Molecular inclusion by hydroxy host systems (9-hydroxy-9-(1-propynyl)fluorene+guest and 1,1-bis(2,4-dimethylphenyl)-2-butyn-1-ol+guest) has been investigated by using an empirical potential function. Water, methanol, ethanol, andn-propanol have been employed as guest molecules and their relative stabilities are considered. Alcohol is found to be more suitable than water as a guest molecule in the two tested host molecules. It is also found that the nonbonded interaction is the most important factor in determining the relative stabilities of hydroxy host systems.     

Neutron scattering study on dynamics of water molecules in MCM-41. 2. Determination of translational diffusion coefficient

Quasielastic neutron scattering (QENS) spectra of water-filled MCM-41 samples (pore diameters: 21.4 and 28.4 Angstrom) were measured over the temperature range 238-298 K and the momentum transfer range 0.31-0.99 A(-1) to investigate the dynamics of confined water molecules. The spectra, which consist mainly of contributions from the translational diffusion of water molecules, were analyzed by using the Lorentzian and the stretched exponential functions. Comparison of the fits indicated that the latter analysis is more reliable than the former one. The fraction of immobile water molecules located in the vicinity of the pore walls, which give an elastic component, was found to be 0.044-0.061 in both pores. The stretch exponent beta was determined as 0.66-0.80. It was shown that the translational diffusion of water molecules in the pores is decelerated by confinement and that the deceleration becomes marked with a decrease in pore size. The ratios of the translational diffusion coefficient D(T) of confined water to that of bulk water at room temperature were within a range of 0.47-0.63.     

Modeling the concentration dependence of the methanol self-diffusivity in faujasite systems: comparison with the liquid phase

Molecular dynamics simulations were performed to understand further the concentration dependence of the self-diffusion of methanol in the faujasite zeolite systems. The evolution of the self-diffusivity was investigated as a function of coverage for DAY and NaY systems to study the effect of both the pore confinement and the presence of the extraframework cations within the supercage. It was found that the self-diffusivity decreases with loading for DAY, whereas for NaY it passes through a maximum at intermediate coverage, in agreement with pulse-field gradient NMR and quasi elastic neutron scattering data reported in similar systems. The activation energies of the methanol diffusion corresponding to a combination of both intra- and intercage motions were evaluated as a function of the coverage. The simulated trends are interpreted on the basis of the predominant interactions which take place in both systems. Finally, the preferential arrangement of the adsorbate molecules are provided and compared with those simulated in the liquid phase. For the fully loaded materials, it was seen that the methanol molecules form a one-dimensional hydrogen-bonded chain along the channels in DAY whereas only dimers are present in NaY.     

Role of micro-structure and interfacial properties in the higher photocatalytic activity of TiO2-supported nanogold for methanol-assisted visible-light-induced splitting of water

This paper deals with the textural, microstructural and interfacial properties of Au/TiO(2) nanocomposites, in relation to their photocatalytic activity for splitting of water. TiO(2) samples of two different morphologies were employed for dispersing different cocatalysts, such as: Au, Pt, Ag or Cu, for the sake of comparison. The samples were characterized using powder XRD, XPS, UV-visible, thermoluminescence, SEM, HRTEM and SAED techniques. Compared to other metal/TiO(2) photocatalysts, Au/TiO(2) with an optimum gold loading of 1 wt% was found to exhibit considerably higher activity for visible light induced production of H(2) from splitting water in the presence of methanol. Further, the sol-gel prepared TiO(2) (s.TiO(2)), having spherical grains of 10-15 nm size, displayed better photoactivity than a Degussa P25 catalyst. The electron microscopy investigations on s.TiO(2) revealed significant heterogeneity in grain morphology of individual TiO(2) particles, exposure of the lattice planes, metal dispersion, and the interfacial metal/TiO(2) contacts. The gold particles were found to be in a better dispersed state. O(2) TPD experiments revealed that the gold nanoparticles and Au/TiO(2) interfaces may serve as distinct binding sites for adsorbate molecules. At the same time, our thermoluminescence measurements provide an insight into Au-induced new defect states that may facilitate the semiconductor-to-metal charge transfer transition. In conclusion, the superior photocatalytic activity of Au/TiO(2) may relate to the grain morphology of TiO(2), dispersion of gold particles, and the peculiar architecture of metal/oxide heterojunctions; giving rise in turn to augmented adsorption of reactant molecules and their interaction with the photo-generated e(-)/h(+) pair. The role played by methanol as a sacrificial reagent in photocatalytic splitting of water is discussed.     

甲醇催化转化制丙烯中HZSM-5分子筛的尺寸效应

甲醇催化制丙烯(MTP)是一个具有重要工业应用的研究课题, 目前普遍采用的催化剂是HZSM-5 分子筛. 通过调节分子筛合成原料的配比、晶化温度和晶化时间等参数, 对所制备的不同晶粒尺寸的HZSM-5 分子筛, 综合利用X射线衍射(XRD)、扫描电镜(SEM)、N₂吸附和氨气程序升温脱附(NH₃-TPD)等手段表征了其晶格结构、表观形貌、孔结构以及酸性质. 利用固定床反应装置对HZSM-5 分子筛甲醇催化制丙烯的活性和稳定性进行了评价, 并采用热重(TG)分析技术对催化剂的积炭性能进行了考察. 实验结果表明, HZSM-5 分子筛粒度的减小可以增加分子筛比表面积、孔体积, 同时有更多开放的孔口及短的孔道长度, 有利于反应物分子的吸附和传质,并降低了产物分子在孔道中的扩散距离及发生二次反应的几率, 提高了催化剂的抗积炭能力和容炭能力以及稳定性; 而且所合成的小尺寸分子筛单位质量的总酸量及强酸量均有不同程度的下降, 有利于提高目标产物丙烯的选择性.