Long-range diffusion in beds of nanoporous particles: pitfalls and potentials

Owing to the recent progress in the area of hardware and software of the pulsed field gradient NMR technique, molecular transport in real-life zeolite systems, such as zeolite beds and particles of formulated fluid catalytic cracking (FCC) catalysts, can be investigated in detail. These studies have revealed a number of important features of molecular transport in zeolites, which are reviewed in the present paper. In particular, the anomalous character of intracrystalline diffusion in MFI-type zeolites, dependence of the tortuosity factor in zeolite beds on diffusion regime and the role of various modes of diffusion in transport limitations arising for catalytic reactions in FCC catalysts will be discussed.     

Nanocrystalline zeolite beta and zeolite Y as catalysts in used palm oil cracking for the production of biofuel

Nanocrystalline zeolites with crystal size smaller than 100 nm are potential replacement for conventional zeolite catalysts due to their unique characteristics and advantages. In this study, the synthesis of nanocrystalline zeolite Y (FAU) and nanocrystalline zeolite beta (BEA) under hydrothermal conditions is reported. The effect of crystal size on the physico-chemical characteristics of the zeolite, Y (FAU), and beta (BEA) is reported. The properties of nanocrystalline zeolites Y and Beta with crystal size around 50 nm are compared with the microcrystalline zeolite Y and microcrystalline zeolite beta, respectively. The performance of the nanocrystalline zeolite as a catalyst was investigated in the cracking of used palm oil for the production of biofuel. The nanocrystalline zeolite catalytic activity was compared with the activity of microcrystalline zeolite in order to study the effect of crystal size on the catalytic activity. Both nanocrystalline zeolites gave better performance in terms of conversion of used palm oil as well as selectivity for the formation of gasoline fraction. The increase in surface area and improved accessibility of the reactant in nanocrystalline zeolites enhanced the cracking activity as well as the desired product selectivity.     

(K,Mo)Y分子筛中钼组分的EXAFS研究

应用同步辐射Eextended X-ray Ab sorption Fine S tructure(EXAFS)技术研究固态法制备的KHMoY分子筛的氧化态和硫化态样品以及硫化态KHY／MoO3样品中钼组分的局域配位环境结构,并与KHMoY和KHY／MoO3 样品催化加氢活性结果进行对照。结果表明,随原子比（K＋2Mo）／Al的变化,钼原子周围的配位环境有显著的差异。当（K＋2Mo）／Al时,KHMoY和KHY/MoO3硫化后,钼组分主要以MoS2小原子簇分散在分子筛超笼中;（K＋2Mo)/Al>1时,钼组分则有两种存在环境,即分子筛超笼中的和分子筛外表的钼组分。分子筛超笼中的Mo S2原子簇的催化加氢合成醇选择性较高;分子筛外表面的MoS2微小颗粒的尺寸相对于超笼中的要大许多,其合成醇选择 性较低。     

Low temperature and low pressure CO oxidation on gold clusters supported on MgO(100)

CO oxidation has been investigated on Au/MgO(100) model catalysts at RT and low pressure. The gold particles prepared by UHV evaporation on clean MgO surfaces are characterized by HRTEM. The gold particles are FCC single crystals or multiple twins with five-fold symmetry. Infrared spectroscopy indicates that two types of adsorption sites are present which correspond to loosely and strongly bound CO. The equilibrium CO coverage for the strongly bound CO is smaller than 0.1 ML. CO titration experiments show that oxygen does not dissociate on the gold nanoparticles. The CO oxidation reaction is studied at RT by molecular beam methods. A steady state CO reaction probability up to 0.50 is measured, for the first time at low pressure, for gold particles with a mean size of 1.5 nm. A reaction mechanism is proposed in which CO adsorbed on low coordinated gold atoms reacts with oxygen adsorbed molecularly, possibly at the Au/MgO interface.     

镍改性ZSM-5催化剂及其SCR催化性能

采用液态离子交换法制备了不同负载量的镍改性ZSM-5分子筛催化剂,并考察了上述催化剂的微观结构和物理化学特性及其在NH3-SCR反应中的催化性能。结果表明:在负载量<10.9%时镍在分子筛中具有高度的分散性,而随着镍负载量的进一步增加,分子筛表面开始出现较大的NiO颗粒;镍元素只以+2价存在于分子筛催化剂中;在NH₃-SCR反应中,镍负载量低于14.9%时,增加镍负载量将提高催化剂的低温活性;当反应温度超过300℃时,高温催化中心开始起作用,但随镍负载量的增加,高温活性开始下降时的温度逐渐降低。     

Exploring the surface permeability of nanoporous particles by pulsed field gradient NMR

A new method to determine the surface permeability of nanoporous particles is proposed. It is based on the comparison of experimental data on tracer exchange and intracrystalline molecular mean square displacements as obtained by the PFG NMR tracer desorption technique with the corresponding solutions of the diffusion equation via dynamical Monte Carlo simulations. The method is found to be particularly sensitive in the "intermediate" regime, when the influence of intracrystalline diffusion and surface resistances of the nanoporous crystal on molecular transport are comparable and the conventional method fails. As an example, the surface permeabilities of two samples of zeolite NaCaA with different crystal sizes are determined with methane, as a probe molecule, at room temperature.     

Surface studies of supported model catalysts

Metal particles grown by vapour deposition on clean and well-defined oxide surfaces are used as model catalysts. These new model catalysts allow, unlike metal single crystals, a study of size and support effects in heterogeneous catalysis. The structure, the electronic properties and the reactivity of these supported model catalysts have been studied, in situ, by a large number of surface science techniques. In order to get relevant information from those studies it is necessary to control the nucleation and growth in order to get uniform collections of metal particles. The preparation conditions and the characterisation methods will be reviewed. Particles with well-defined shapes are obtained by epitaxial growth at high temperature on clean ordered surfaces. The electronic properties of the small metal particles depend not only on their size but also on their shape. The chemisorption properties are strongly related to the surface structure of the particles. The interplay between the surface structure, the local electronic properties and the adsorption energy will be discussed for CO chemisorption. The presence of the support plays an important role in the control of the particle morphology. Furthermore, it can increase the adsorption rate. The intrinsic heterogeneity of the supported model catalysts has to be taken into account to understand in detail the catalytic reactions. The reaction rate cannot be considered as an average on the different crystalline facets present on the particle. Finally, we will discuss the possibility to study in situ and at the atomic level simple chemical reactions on supported catalysts.     

Surface oxides on supported Rh particles: thermal decomposition of Rh oxide under high vacuum conditions

Reduction properties of alumina-supported Rh catalysts together with a polycrystalline Rh foil were studied by a stepwise thermal decomposition in high vacuum. To investigate the progress of the oxide layer decomposition in detail, the samples were annealed in vacuum at various temperatures. After each annealing step, the changes in the chemical state of the noble metal were detected by XPS measurements. Our results show marked differences in the rate of decomposition between catalysts of different Rh loadings. In thermal decomposition, the formation of molecular oxygen and the subsequent desorption of O₂ decreases the oxygen content within the information depth of the XPS measurement. On the other hand, diffusion of oxygen from the deeper layers brings more oxygen to the selvedge. The observed decomposition properties are found to correlate with the particle size. In small particles the average diffusion length of oxygen atoms is shorter than in larger particles and the surface area is larger. These factors favor the decomposition of smaller particles in comparison with larger ones.     

红外光谱法研究甲苯在HZSM-5分子筛上的扩散

采用红外光谱法研究了甲苯在两种HZSM-5分子筛上的扩散。结果表明:甲苯分子在不同颗粒大小的分子筛吸附平衡时间不同,甲苯分子首先吸附在具有硅铝桥羟基的孔道内,而当硅铝桥羟基基本占据后,才吸附在硅羟基的吸附位上,显示了硅铝桥羟基吸附较硅羟基吸附位更强;大颗粒分子筛的甲苯扩散系数显著高于小颗粒分子筛。     

Adsorption and diffusion of argon confined in ordered and disordered microporous carbons

We use a combination of grand canonical Monte Carlo and microcanonical molecular dynamics simulations to study the adsorption and diffusion of argon at 77 K and 120 K confined in previously generated models of a disordered bituminous coal-based carbon, BPL, and an ordered carbon replica of Faujasite zeolite (C-FAU). Both materials exhibit a maximum in the diffusion coefficient as well as anomalous (sub-diffusive) behavior in the mean-squared displacements at short times at some relative pressures. In BPL, the anomalous diffusion occurs at low relative pressures, due to the trapping of argon atoms in small pores. In C-FAU, the anomalous diffusion occurs at high relative pressures, due to competitive diffusion of atoms traveling through windows and constrictions which interconnect the pores. All diffusion eventually tends to Fickian diffusion at longer times.     

Anomalous diffusion and lévy flights in a two-dimensional time periodic flow

One of the main consequences of chaos is that transport is enhanced with respect to the fluid at rest, where only molecular diffusion is present. Considering long times and spatial scales much larger than the length scale of the velocity field, particles typically diffuse with a diffusion constant, usually much bigger than the molecular one. Nevertheless there are some important physical systems in which the particle motion is not a normal diffusive process: in such a case one speaks of anomalous diffusion. In this paper, anomalous diffusion is experimentally studied in an oscillating two-dimensional vortex system. In particular, scalar enhanced diffusion due to the synchronization between different characteristic frequencies of the investigated flow (i.e., resonance) is investigated. The flow has been generated by applying an electromagnetic forcing on a thin layer of an electrolyte solution and measurements are made through image analysis. In particular, by using the Feature Tracking (FT) technique, we are able to obtain a large amount of Lagrangian data (i.e., the seeding density can be very high and trajectories can be followed for large time intervals) and transport can be characterized by analyzing the growth of the variance of particle displacements versus time and the dependence of the diffusion coefficient on the flow characteristic frequencies.     

Stabilization of catalytically active gold species in Fe-modified zeolites

The influence of iron additive on redox, electronic and catalytic properties of gold incorporated into zeolite catalysts has been studied by means of TEM, XPS, XRD, TPR, ICP and AES. The interaction of gold with iron modifier was observed in Y-zeolites and mordenites with different cations and method of Fe incorporation (impregnation or ion exchange). This interaction leads to mutual influence on redox properties of Fe and Au ionic species and facilitates their reduction. Limited diffusion of Au precursor after Fe species deposition in narrow mordenite channels does not permit to incorporate Au in adequate concentration, while in large super-cage of Y-zeolites this limitation is absent. The structure of Y-zeolites favors formation of active gold species. Catalytic tests in CO oxidation show that Fe additive stabilizes the gold active species active at low-temperature (partly charged clusters) and makes them insensitive to redox treatments.     

Crossover from normal diffusion to single-file diffusion of particles in a one-dimensional channel: LJ particles in zeolite zsm-22

The crossover from normal Fickian diffusion, where mean-squared displacement goes as t to single-file diffusion, where <z²> t?^0.5 is studied as function of particle size confined in zeolite zsm-22 using molecular dynamics simulations. The simulation results indicate that the crossover is smooth as the particle size increases and the diffusion reaches single file through a series of subdiffusion processes. A small number of mutual passage of particles can destroy the correlated single-file diffusion. The density dependence on single-file mobility obtained from molecular dynamics simulations are in very good agreement with theoretical predictions.     

Single-point magnetic resonance imaging study of water adsorption in pellets of zeolite 4A

The water uptake process in commercial type particles of zeolite 4A has been studied using a single-point MRI method. True proton density, T1, T2, and T*2 relaxation times were obtained with submillimetric resolution, overcoming the restrictions of short T*2 signals. The molecular mobility in nonequilibrium conditions has been characterized by relaxation time mapping. A clear reduction of the water sorption rate was observed by comparing MRI profiles of a loosely packed bed and gravimetric measurements of spread particles from the same sieved zeolite batch.     

Growth and morphology of carbon nanostructures on nickel oxide nanoparticles in catalytic chemical vapor deposition

The present study explores the conditions favorable for the growth of cylindrical carbon nanostructures such as multi-walled carbon nanotube (MWCNT) and carbon nanofiber by catalytic chemical vapor deposition (CCVD) method using nickel oxide-based catalyst nanoparticles of different average sizes as well as different levels of doping by copper oxide. The role of doping and the average size have been related to the observed melting behavior of nanoparticles of nickel oxide by thermal and diffraction analysis, and the importance of melting has been highlighted in the context of growth of cylindrical nanostructures. In the reducing environment prevailing in the CCVD chamber due to decomposition of flowing acetylene gas at elevated temperature, there is extensive reduction of oxide nanoparticles. Lack of melting and faster flow of carbon-bearing gases favor the formation of a carbon deposit cover over the catalyst nanoparticles giving rise to the formation of nanobeads. Melting allows rapid diffusion of carbon from the surface to inside catalyst particles, and reduced flow of gas lowers the rate of carbon deposit, both creating conditions favorable for the formation of cylindrical nanostructures, which grows around the catalyst particles. Smaller particle size and lower doping favor growth of MWCNT, while growth of fiber is commonly observed on larger particles having relatively higher level of doping.     

The surface diffusion in CO oxidation on small supported Pd particles: Experimental evidence

Thermo-programmed heterogeneous catalytic oxidation of CO on Pd small particle/mica catalysts has been used to study the influence of the Pd particle number density on the catalytic turnover rate. Rapid increase is observed in the maximum CO₂ turnover rate with decreasing particle density. This effect can be explained by the surface migration of gas molecules on the mica substrate. In previous papers devoted to CO oxidation on Pd particles we pointed out that both the initial sticking coefficient s₀ of CO on Pd and the turnover rate r_CO2 (for CO₂ formation) increase when the particles size decreased. Measurements of the CO consumation rate N_c during an oxidation reaction have also demonstrated a similar particle size dependence for Nc. If the quantities s₀ and r_CO2 are calculated relative to the impinging flux of CO molecules J_i (J_i given by the kinetic theory of gases), the obtained values are always higher than unity for particle diameter smaller than 8 nm. In the light of these results it seems that the real CO flux should be higher than J_i. Ladas, Poppa and Boudart have suggested that the edge of the particles can receive more collisions than the face atoms, which could explain an increase of the mean CO flux with decreasing particle size.     

Synthesis of nanocomposites based on nanotubes and silicates

In situ synthesis of nanocomposites based on carbon nanotubes and zeolite/montmorillonite was carried out in a hot filament CVD reactor where the precursors (methane and hydrogen) are activated by carbonized tungsten filaments heated up to 2200 °C. In nanocomposites formed both on zeolite and montmorillonite we observed cross-linking of the catalytic particles by nanotubes and creation of carbon nanotube bridges and three-dimensional networks. The length of nanotube bridges was in a range from several nm to nearly 10 μm. A high density of carbon nanotubes was observed in the whole volume of zeolite. The high catalytic efficiency of zeolite is most likely caused by its structure that allows anchoring of Fe³⁺ catalytic particles in the pores and prevents their migration from the sample. At the ends of the nanotubes grown on zeolite we observed particles of the catalyst. In montmorillonite, the particles catalyzing the growth of carbon nanotubes may be present not only on the external surface but also in the interlayer voids of the mineral. Its catalytic efficiency is enhanced as proved by the higher amount of CNTs and their bundles. In the course of CNTs synthesis probably also clumps of Fe³⁺ catalytic particles arise, which may be the reason for formation of bundles of nanotubes.     

固体核磁共振技术在锡硅分子筛表征中的应用

生物质等绿色资源的高效转化利用是催化科学的重要发展方向.锡硅分子筛因具有优良的催化性能而得到相关研究者的普遍关注.准确构建催化剂活性中心结构/酸性与催化反应性能之间的构效关系是新型高效催化剂设计与研发的基础.固体核磁共振（NMR）是研究分子筛活性中心局域结构、酸特性与催化反应机理的重要手段.本文简述了近年来固体NMR技术在锡硅分子筛研究领域的一系列主要进展,并进行了展望.     

Effect of palladium particle size on the appearance of superstructure of graphite in palladium/graphite model catalyst

Scanning tunneling microscopy images of palladium particles supported on highly oriented pyrolytic graphite as a model catalyst in ultra-high vacuum have been observed. We found superstructures on graphite lattice due to electronic interaction between palladium particles and graphite in the vicinity of small two-dimensional palladium particles (lateral size <2 nm, height <0.5 nm). However, such superstructures could not be observed near larger three-dimensional palladium particles (lateral size ∼4 nm, height ∼2 nm). The results indicate the importance of not only the size but also the dimension of metal particles in interaction between palladium and graphite, the nature of which can be interpreted by the difference in electronic properties of atomic and bulk palladium. This has important implications to the understanding of metal-support electronic interaction and its effect on the surface catalytic reactivity of supported metal catalysts.     

Effects of particle size, shape and crystal structure on the formation energy of Schottky vacancies in free-standing metal nanoparticles: A model study

A simplified model based on cohesive energy is proposed to estimate the formation energy of Schottky vacancies (VFE) in free-standing metal nanoparticles with BCC and FCC crystal structures. To study the effect of particle size and shape, the surface energy, elastic contraction and average coordination number of particles at the surface and core was considered. It is shown that the energy of vacancy formation in FCC nanoparticles increases with decreasing the size while the effect of particle shape (sphere, cubic and icosahedral) is marginal. In spite of this behavior, BCC nanoparticles exhibit a critical particle size at around 25 Å, at which a minimum VFE is attained. Additionally, the energy of vacancy formation is notably lower for BCC nanoparticles with cubic shape than spherical ones. The application of the developed model is shown for free-standing Fe and Cu nanoparticles.