Mesoporous silica supports for improved thermal stability in supported Au catalysts

In this work, we present a comprehensive review of our research on the role of mesoporous silica pore architecture, composition of the pore walls (addition of Co or Al), and silica surface chemistry (surface modification by TiO₂) to improve the hydrothermal stability of Au particles. We have found that mesoporous silica architecture plays an important role in improving Au stability, with three dimensional mesoporous architectures being less effective than one dimensional (1-D) pores. The tortuous 1-D pores in aerosol silica were found to be most effective at controlling Au particle size. Since Au particles continue to grow larger than the pore diameter, we conclude that Ostwald ripening must be the dominant sintering pathway for these Au catalysts. These catalysts are active for CO oxidation even after the Au particles have grown large enough to block the pores, suggesting that the thin walls of mesoporous silica provide easy access to gas phase molecules. Further improvements in Au stability and reactivity were obtained by surface modification of the aerosol and MCM-41 silica with TiO₂. After TiO₂ modification of the silica, the Au particles remained smaller than the pore size (< 3 nm) even after three cycles of CO oxidation at temperatures up to 400 °C.     

Anomalous reduction in surface area during mechanical activation of boehmite synthesized by thermal decomposition of gibbsite

Mechanical activation of boehmite (γ-AlOOH), synthesized by thermal decomposition of gibbsite, has been carried out in a planetary mill up to 240 min. After an initial decrease in particle size up to 15 min, the particle size shows an increase with further milling; the median size (d₅₀) has increased from 1.8 to 5 μm during 15 to 240 min of milling. Quite unexpectedly, the BET specific surface area of the sample (N₂ adsorption method) decreases continuously from 264 m²/g to 67 m²/g with milling. A detailed analysis of N₂ adsorption/desorption isotherms has indicated that the decrease in surface area is associated with: (a) change in narrow slit like pores with microporosity to slit shaped pores originating from loose aggregate of platelet type particles; and (b) shift of maxima in pore size distribution plot at ~ 2 nm and ~ 4 nm to dominantly ~ 23 nm size pores. Scanning electron microscopy (SEM) studies have revealed that during milling, initial breakage is followed by agglomeration/fusion of particles with consequent loss in porosity. Amorphisation, decrease in microcrystallite dimension (MCD) and increase in microstrain (ε) are indicated from a detailed analysis of X-ray powder diffraction patterns and Fourier Transform Infrared (FTIR) spectra. Reactivity of samples, expressed in terms of increase in dissolution in alkali (in 8 M NaOH at 90 °C) and decrease in boehmite to γ-Al₂O₃ transformation temperature, increases with milling time. The nature of correlations between reactivity and physico-chemical changes during milling has been analyzed and discussed.     

Formation and Accumulation of Intragranular Pores in the Hydrothermally Synthesized Barium Titanate Nanoparticles

As highly integrated circuits are demanded for high‐performance electric devices, small sizes of barium titanate (BaTiO₃) as a dielectric material are desirable for the application of multilayer ceramic capacitors. Since the small sizes of the particles degrade the dielectric property, especially below a certain critical size, understanding the probable cause is significant for the high‐performance capacitors. Here, we have demonstrated nanosized BaTiO₃ with average size below 30 nm and a uniform size distribution. High‐resolution transmission electron microscopy (TEM) shows that the as‐synthesized BaTiO₃ contains intragranular pores. We have analyzed the correlation between the intragranular pores inside nanoparticles and their phase ratio of cubic and tetragonal. We have found that the presence of the intragranular pores affects low tetragonality of BaTiO₃ particles, and the intragranular pores are generated by the accumulation of hydroxyl groups during hydrothermal reaction. Formation and accumulation of intragranular pores have been investigated by ex‐situ synchrotron X‐ray diffraction and TEM analysis, suggesting the phase evolution model of nanosized BaTiO₃.     

Non-shrinkage porous ceramics by In-situ hollow sphere method based on the Kirkendall effect of Al particle

The significant shrinkage of porous ceramics after sintering has produced a number of issues with their use and development. As a result, we proposed an in-situ hollow sphere method for producing non-shrinkage alumina porous ceramics. The obtained green samples were made up of Al₂O₃ and Al powders, with pores emerging inside the materials due to the Kirkendall effect of Al particles after sintering. The expansion of hollowing particles exactly offsets the shrinkage generated by sintering throughout the process. When 50 vol. % Al powder (10 µm) is added, the linear shrinkage rate of the sample after sintering at 1500 °C can reach −3.47 %, and its apparent porosity and flexural strength are 30.69 % and 44.03 MPa, respectively. According to approximate calculations, the pores formed by the oxidation of Al powder are smaller than the initial size of Al powder. This method suggests a novel approach for producing controlled shrinkage porous ceramics.     

Sulfation of high purity limestones under simulated pfbc conditions

The direct sulfation of three high purity limestones, all having more than 95% CaCO₃ but differing in petrographic texture, was studied in a thermogravimetric analyzer under simulated PFBC (Pressurized Fluidized-Bed Combustion) conditions, that is, in the presence of enough CO₂ to prevent decomposition of CaCO₃. Experiments were carried out over a wide range of particle size (53-350 μm) at two temperatures (750 and 850°C), and two concentrations (1500 and 6000 mL/m³ (ppmv) SO₂). The particle size and temperature had a strong influence on the variation of the conversion with time. In contrast, the effect of concentration was rather marginal over the whole duration of the process, and the analysis of the initial reaction rate data gave a reaction order of 0.4, with respect to SO₂, for all solids. The measured reaction rates were compared with those obtained in a past study for the sulfation of the calcines of the three solids under similar conditions. The initial rate of the calcine-SO₂ reaction was found to be higher than that of the limestone-SO₂ reaction, but since the former drops sharply as the pores at the external surface of the particles are filled with solid product, higher conversions may be obtained in some cases during direct sulfation for large reaction times.     

Fischer–Tropsch Synthesis: Morphology, Phase Transformation and Particle Size Growth of Nano-scale Particles

An unpromoted ultrafine iron nano-particle catalyst was used for Fischer–Tropsch synthesis (FTS) in a CSTR at 270 °C, 175 psig, H₂/CO = 0.7, and a syngas space velocity of 3.0 sl/h/g Fe. Prior to FTS, the catalyst was activated in CO for 24 h which converted the initial hematite into a mixture of 85% χ-Fe₅C₂ and 15% magnetite, as found by Mössbauer measurement. The activated catalyst results in an initial high conversion (ca. 85%) of CO and H₂; however the conversions decreased to ca. 10% over about 400 h of synthesis time and after that remained nearly constant up to 600 h. Mössbauer and EELS measurement revealed that the catalyst deactivation was accompanied by gradual in situ re-oxidation of the catalyst from initial nearly pure χ-Fe₅C₂ phase to pure magnetite after 400 h of synthesis time. Experimental data indicates that the nucleation for carbide/oxide transformation may initiates at the center of the particle by water produced during FTS. Small amount of ?′-Fe_2.2C phase was detected in some catalyst samples collected after 480 h of FTS which are believed to be generated by syngas during FTS. Particle size distribution (PSD) measurements indicate nano-scale growth of individual catalyst particle. Statistical average diameters were found to increase by a factor of 4 over 600 h of FTS. Large particles with the largest dimension larger than 150 nm were also observed. Chemical compositions of the larger particles were always found to be pure single crystal magnetite as revealed by EELS analysis. Small number of ultrafine carbide particles was identified in the catalyst samples collected during later period of FTS. The results suggest that carbide/oxide transformation and nano-scale growth of particles continues either in succession or at least simultaneously; but definitely not in the reverse order (in that case some larger carbide particles would have observed). EELS-STEM measurement reveals amorphous carbon rim of thickness 3–5 nm around some particles after activation and during FTS. Well ordered graphitic carbon layers on larger single crystal magnetite particles were found by EELS-STEM measurement. However the maximum thickness of the carbon (amorphous or graphitic) rim does not grow above 10 nm suggesting that the growths of particles are not due to carbon deposition.     

Evaluation of slitlike porosity of carbon adsorbents

Deviations of a pore shape from a slitlike one were analyzed for a variety of carbon adsorbents on the basis of calculations of pore size distributions (PSDs) with respect to the pore volume (f_V(x)) used for estimation of the PSDs related to the specific surface area (f_S(x)) applying several models of pores: individual slitlike pores and mixtures of slitlike and cylindrical pores and gaps between spherical particles. The use of complex pore models allows us to diminish the difference between S_BET and the specific surface area (S_sum) calculated from f_S(x).     

Particle growth mechanisms in fluidised bed granulation—I: The effect of process variables

Two types of product granule have been identified in an experimental study of batch fluidised bed granulation; agglomerates which consist of two or more, and usually several, initial particles; and layered granules, which consist of single primary particles with dried feed material adhering to the surface. Increasing the excess fluidising gas velocity, in the range U-U_mf = 0.15-0.525 m s^?1, resulted in decreased particle growth rates and, depending upon the binder material, a change in product morphology from agglomerates to layered granules. Similar changes resulted from increasing the mean size of the starting material. Thus, a mechanism of particle growth is proposed in which the strength of inter-particle bridges and the extent of fluid drag and inertial forces on particles determine the equilibrium granule form and size. However, if the initial particles are porous this mechanism may break down since liquid may enter intra-particle pores and be unavailable for the initial formation of liquid bonds.     

Synthesis of Porous α-Fe2O3 Nanorods as Catalyst Support and A Novel Method to Deposit Small Gold Colloids on Them

Two novel methods, one for preparation of porous α-Fe₂O₃ nanorod catalyst support and another for the deposition of gold (Au) particles on the catalyst support with high efficiency and high dispersion, were reported. In the former, FeO(OH) nanorods were first prepared by a mild hydrothermal synthesis using tetraethylammonium hydroxide (TEAOH) as the structure director. The FeO(OH) product was then converted to porous α-Fe₂O₃ nanorods via calcination at 300 °C. During this calcination, pores with a size distribution in the range of 1–5 nm were generated by removal of TEAOH molecules. By employing our invented Au colloid-based and sonication-assisted method, in which lysine was used as the capping agent and sonication was employed to facilitate the deposition of the Au particles, we were able to deposit very small Au particles (2–5 nm) into these pores. This method is rapid as the reaction/deposition is completed within 1 min. The prepared Au/α-Fe₂O₃-nanorod catalyst exhibited much higher catalytic activity than the Au/commercial α-Fe₂O₃ (Fluka) catalyst.     

Optimization of corrosion resistance and mechanical properties of Al2O3-Cr2O3 refractories for waste incinerator

The corrosion resistance and mechanical properties directly affects the operation and service life of Al₂O₃-Cr₂O₃ refractories used in waste incinerators. In this study, ZrO₂ particles were introduced via vacuum impregnation to adjust microstructure and properties of Al₂O₃-Cr₂O₃ refractories. The results showed that the impregnated ZrO₂ particles and increasing impregnation times resulted in the decreased median pore size and increased compactness, and mechanical strengths of refractories were elevated from the inhibited cracks propagation by ZrO₂ particles. The decreased amounts of large pores and increased amounts of small pores from the filled ZrO₂ particles inhibited penetration of low melting point phases, and the formed CaZrO₃ phase from the reactions between corrosion reagent and ZrO₂ particles increased the viscosity of penetrated corrosion reagent, resulting in the decreased penetration index from 8.57% to 2.58%. Meanwhile, the filled ZrO₂ particles around alumina particles prevented reactions between molten corrosion reagent and alumina, leading to the decreased corrosion index from 3.78% to .74%. The decreased pore size and formation of CaZrO₃ phase were primary factors that enhanced the penetration resistance. And formation of wrapped layers from ZrO₂ particles around alumina particles presented prominent effects on the strengthened corrosion resistance of Al₂O₃-Cr₂O₃ refractories.     

Fabrication of CaSiO3 bioceramics with open and unidirectional macro-channels using an ice/fiber-templated method

Porous CaSiO₃ bioceramics with open and unidirectional macro-channels of pore size more than 200 μm are of particular interest for biomedical applications. An ice/fiber-templated method was employed for the fabrication of CaSiO₃ bioceramics with interconnected lamellar pores and macro-channels of pore size more than 200 μm. The pores formed by ice crystals transformed from cellular to lamellar, while the pores formed by fibers were aligned macro-channels, which were also in alignment with the lamellar pores. Keeping the initial slurry concentration constant and increasing the packing density of fibers, the volume fraction of macro-channels and open porosity increased, and the compressive strength decreased. Maintaining the packing density of fibers and increasing the initial slurry concentration, the pore sizes of lamellar pores and open porosity decreased, and the compressive strength increased. The results indicated that it was possible to manufacture porous CaSiO₃ bioceramics with the macro-channels of 250–350 μm, lamellae spacing of 50–100 μm, open porosity of 71.12–83.94% and compressive strength of 0.87–3.59 MPa, indicating the suitability for tissue engineering.     

Laser ablation of diamond particles suspended in ethanol: Effective formation of long polyynes

Polyynes were synthesized by laser ablation of diamond particles with various sizes suspended in ethanol. Chain length distributions and total yields of polyynes produced were compared with those produced from graphitized diamond particles and graphite particles. The relative amounts of long polyynes such as C₁₄H₂ and C₁₆H₂ produced from diamond particles were found to be larger than those from graphitized diamond particles and graphite particles. From the change of the chain length distribution with the laser irradiation time, it is concluded that the long polyynes are produced directly from diamond particles at the initial stage of ablation. Furthermore, the total yield of polyynes was found to increase with the size of diamond particles and decrease as their graphitization proceeds. Possible mechanisms of these results are discussed.     

Effect of pore size and porosity on piezoelectric and acoustic properties of Pb(Zr0.53Ti0.47)O3 ceramics

We studied the effect of porosity and pore morphology on the functional properties of Pb(Zr_0.53Ti_0.47)O₃ (PZT) ceramics for application in high frequency ultrasound transducers. By sintering a powder mixture of PZT and polymethylmetacrylate spherical particles (1.5 and 10?μm) at 1080°C, we prepared ceramics with ～30% porosity with interconnected micrometer sized pores and with predominantly ～8?μm spherical pores. The acoustic impedance was ～15?MRa for both samples, which was lower than for the dense PZT. The attenuation coefficient α (at 2.25?MHz) was higher for ceramics with ～8?μm pores (0.96?dB?mm^??1?MHz^??1), in comparison to the ceramic with smaller pores (0.56?dB?mm^??1?MHz^??1). The high α value enables the miniaturisation of the transducer, which is crucial for medical imaging probes. The dielectric and piezoelectric coefficients, polarisation, and strain response decreased with increased porosity and decreased pore/grain size. We suggest a possible role of pore/grain size on the switching behaviour.     

Passive Aerosol Sampler. Part I: Principle of Operation

A method has been developed to estimate average concentrations and size distributions with a miniature passive aerosol sampler. To use the passive sampler, one exposes it to an environment for a period of hours to weeks. The passive sampler is intended to monitor ambient, indoor, or occupational aerosols and has potential utility as a personal sampler. The sampler is inexpensive and easy to operate and is capable of taking long-term samples to investigate chronic exposures. After sampling, the passive sampler is covered and brought to the lab. Scanning electron microscopy (SEM) and automated image analysis are used to count and size collected particles with d_p     

Encapsulation of titanium dioxide in styrene/n‐butyl acrylate copolymer by miniemulsion polymerization

Miniemulsion copolymerization of styrene/n‐butyl acrylate was investigated as a means of encapsulating hydrophilic titanium dioxide (TiO₂) in a film‐forming polymer. Dispersion studies of the TiO₂ were first carried out to determine the choice of stabilizer, its concentration, and the dispersion process conditions for obtaining stable TiO₂ particles with minimum particle size. Through screening studies of various functional stabilizers and shelf‐life stability studies at both room and polymerization temperatures, Solsperse 32,000 was selected to give relatively small and stable TiO₂ particles at 1 wt % stabilizer and with 20–25 min sonification. The subsequent encapsulation of the dispersed TiO₂ particles in styrene/n‐butyl acrylate copolymer (St/BA) via miniemulsion polymerization was carried out and compared with a control study using styrene monomer alone. The lattices resulting from the miniemulsion encapsulation polymerizations were characterized in terms of the encapsulation efficiencies (via density gradient column separations; DGC) and particle size (via dynamic light scattering). Encapsulation efficiencies revealed that complete encapsulation of all of the TiO₂ by all of the polymer was not achieved. The maximum encapsulation efficiencies were 79.1% TiO₂ inside 61.7% polystyrene and 63.6% TiO₂ inside 38.5% St/BA copolymer. As the density of the particles collected from the DGC increased from one layer to another, both the average particle size and the number of the TiO₂ particles contained in each latex particle increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3479–3486, 2006     

Network simulation for deep bed filtration of Brownian particles—a supplement

The track of individual particles moving through a filter bed is simulated by applying the Brownian dynamics simulation method and the modified square network model. The effect of the Raleigh-type size distribution of particles and pores on the permeability reduction of porous media is also investigated. We find that the pore size distribution of porous media has a more profound effect on the reducing of the permeability ratio than that of the particle size distribution especially at the initial period of filtration. Straining is the main mechanism to reduce the permeability at the initial period of injection for the case of Raleigh distribution of the pore size, and vice versa for the case of unique size value where the direct deposition mechanism becomes dominant.     

Effects of CaCO3 content on the densification of aluminum nitride

The effect of adding up to 13.4 wt.% CaCO₃ on the densification behavior of aluminium nitride (AlN) was investigated during pressureless sintering between 1100 and 2000 °C. The presence of second-phases, weight losses, Ca contents, and microstructures of sintered samples were correlated with the densification curves. Two microstructural aspects determined the densification of aluminum nitride with CaCO₃: second-phase evolution path and formation of large pores. Additions of small amounts of CaCO₃ caused the formation of higher melting point calcium aluminates (mainly CA₂) that increased the temperature at which liquid-phase sintering process started, but once activated rapid densification was observed. For larger CaCO₃ amounts, liquid-phase started to form at lower temperature, but the initial densification was slow, diminishing the advantage of lower C₁₂A₇ related eutectic temperature. Irrespective of the initial CaCO₃ content, all second-phase evolution paths converged to CA phase above 1600 °C, suggesting that during sintering of AlN with CaO at high temperatures, a liquid phase with composition of CA phase is more stable than others compositions. The effect of this composition changing on densification is discussed. Large pores were formed in the sites originally occupied by large particles of CaCO₃ and retarded the bulk densification in samples with high additive contents.     

Synthesis of Pt Nanowires Inside Aerosol Derived Spherical Mesoporous Silica Particles

Spherical mesoporous silica particles prepared by evaporation induced self assembly (EISA) were used as templates to form Pt nanowires. Transmission electron microscope (TEM) images of these aerosol-derived silica particles reveal hexagonally ordered pores coiled within each particle, with no obvious termination of the pores on the external surface. Near the particle surface the pores are seen to run parallel to the surface, consistent with the external constraint of spherical geometry. For MCM-41 type mesoporous materials, the pores are straight and accessible at either end for pore filling, but for spherical silica particles prepared by EISA, the pores are not open to the external surface. Hence it is remarkable that Pt nanowires can be formed within the closed pores inside these spherical silica particles, where conventional mechanisms of pore filling would not be expected to be operative. These results suggest that the silica walls in these mesoporous silica allow transport of volatile Pt complexes during wet reduction in H₂. The permeability to gases makes these spherical silica particles especially suitable for gas phase catalytic reactions, while at the same time confining metallic particles within the silica pores.     

Controllable crystallite and particle sizes of WO3 particles prepared by a spray‐pyrolysis method and their photocatalytic activity

Information about correlation of material properties parameters (i.e., crystallite and particle sizes) and photocatalytic activity of tungsten trioxide (WO₃) particles are still lacking. For this reason, the purpose of this study was to synthesize WO₃ particles with controllable crystallite (from 18 to 50 nm) and particle sizes (from 58 to 677 nm) using a spray‐pyrolysis method and to investigate correlation of crystallite/particle size and photocatalytic activity. To gain control of crystallite/particle size, synthesis temperature (120–1300^°C) and initial precursor concentration (2.5–15 mmol/L) were investigated, which were then compared with the proposal of the particle formation mechanism. The results showed that both crystallite and particle sizes played an important role in photocatalytic activity. In this research, the optimum condition to produce the highest photocatalytic performance of WO₃ particles was at the temperature of 1200^°C (crystallite size: 25 nm), and initial concentration of 10 mmol/L (particle size: 105 nm). © 2013 American Institute of Chemical Engineers AIChE J, 60: 41–49, 2014     

Pore structure control of Si3N4 ceramics based on particle-stabilized foams

Porous Si₃N₄ ceramics with open, closed pores and nest-like structures were prepared by direct foaming method, and the stability of bubbles and the microstructures of sintered Si₃N₄ foam ceramics were investigated. The bubbles produced by short-chain amphiphiles have higher stability as compared with that produced by long-chain surfactants. Si₃N₄ ceramic foams using short-chain amphiphiles are particle-stabilized one, porous Si₃N₄ ceramics with open and closed pores can be easily prepared with this method, and the nest-like microstructure in Si₃N₄ foam ceramics is achieved at high gas-pressure sintering conditions. The decrease of flexural strength due to the increase of porosity can be weakened by decreasing pore size.