Hierarchical macroporous-mesoporous SBA-15 sulfonic acid catalysts for biodiesel synthesis

Hierarchical macroporous-mesoporous SBA-15 silicas have been synthesised via dual-templating routes employing liquid crystalline surfactants and polystyrene beads. These offer high surface areas and well-defined, interconnecting macro- and mesopore networks with respective narrow size distributions around 300 nm and 3-5 nm for polystyrene:tetraethoxysilane ratios ≥2:1. Subsequent functionalisation with propylsulfonic acid yields the first organized, macro-mesoporous solid acid catalyst. The enhanced mass transport properties of these new bi-modal solid acid architectures confer significant rate enhancements in the transesterification of bulky glyceryl trioctanoate, and esterification of long chain palmitic acid, over pure mesoporous analogues. This paves the way to the wider application of hierarchical catalysts in biofuel synthesis and biomass conversion. © 2010 The Royal Society of Chemistry.

Cu and Fe oxides dispersed on SBA-15:a Fenton type bimetallic catalyst for N,N-diethyl-p-phenyl diamine degradation

A bimetallic oxidation catalyst has been synthesized via wet impregnation of copper and iron over a mesoporous SBA-15 silica support. Physicochemical properties of the resulting material were characterized by XRD, N2 physisorption, DRUVS, FTIR, Raman, SEM and HRTEM, revealing the structural integrity of the parent SBA-15, and presence of highly dispersed Cu and Fe species present as CuO and Fe2O3. The CuFe/SBA-15 bimetallic catalyst was subsequently utilized for the oxidative degradation of N,N-diethyl-p-phenyl diamine (DPD) employing a H2O2 oxidant in aqueous solution.

Alumina-grafted SBA-15 as a high performance support for Pd-catalysed cinnamyl alcohol selective oxidation

Ultrathin alumina monolayers grafted onto an ordered mesoporous SBA-15 silica framework afford a composite catalyst support with unique structural properties and surface chemistry. Palladium nanoparticles deposited onto Al-SBA-15 via wet impregnation exhibit the high dispersion and surface oxidation characteristic of pure aluminas, in conjunction with the high active site densities characteristic of thermally stable, high-area mesoporous silicas. This combination confers significant rate enhancements in the aerobic selective oxidation (selox) of cinnamyl alcohol over Pd/Al-SBA-15 compared to mesoporous alumina or silica supports. Operando, liquid-phase XAS highlights the interplay between dissolved oxygen and the oxidation state of palladium nanoparticles dispersed over Al-SBA-15 towards on-stream reduction: ambient pressures of flowing oxygen are sufficient to hinder palladium oxide reduction to metal, enabling a high selox activity to be maintained, whereas rapid PdO reduction and concomitant catalyst deactivation occurs under static oxygen. Selectivity to the desired cinnamaldehyde product mirrors these trends in activity, with flowing oxygen minimising CO cleavage of the cinnamyl alcohol reactant to trans-β-methylstyrene, and of cinnamaldehyde decarbonylation to styrene. © 2013 Elsevier B.V.

Hierarchically ordered nanoporous Pd/SBA-15 catalyst for the aerobic selective oxidation of sterically challenging allylic alcohols

The utility of a hierarchically ordered nanoporous SBA-15 architecture, comprising 270 nm macropores and 5 nm mesopores (MM-SBA-15), for the catalytic aerobic selective oxidation of sterically challenging allylic alcohols is shown. Detailed bulk and surface characterization reveals that incorporation of complementary macropores into mesoporous SBA-15 enhances the dispersion of sub 2 nm Pd nanoparticles and thus their degree of surface oxidation. Kinetic profiling reveals a relationship between nanoparticle dispersion and oxidation rate, identifying surface PdO as the catalytically active phase. Hierarchical nanoporous Pd/MM-SBA-15 outperforms mesoporous analogues in allylic alcohol selective oxidation by (i) stabilizing PdO nanoparticles and (ii) dramatically improving in-pore diffusion and access to active sites by sesquiterpenoid substrates such as farnesol and phytol. © 2013 American Chemical Society.

Support enhanced α-pinene isomerization over HPW/SBA-15

A family of mesoporous SBA-15 supported H3PW12O40 (HPW) catalysts were synthesized by wet-impregnation and compared with fumed silica analogues for the solventless isomerization of α-pinene under mild conditions. Structural and acidic properties of supported HPW materials were characterized by powder XRD, HRTEM, XPS, TGA, N2 porosimetry, DRIFTS, and ammonia and propylamine chemisorption and TPD. The high area, mesoporous SBA-15 architecture facilitates the formation of highly dispersed (isolated or low dimensional) HPW clusters and concomitant high acid site densities (up to 0.54 mmol g−1) relative to fumed silica wherein large HPW crystallites are formed even at low HPW loadings. α-Pinene exhibits a volcano dependence on HPW loading over the SBA-15 support due to competition between the number and accessibility of acid sites to the non-polar reactant, with the superior acid site accessibility for HPW/SBA-15 conferring a 10-fold rate enhancement with respect to HPW/fumed silica and pure HPW. Monocyclic limonene and terpinolene products are favoured over polycyclic camphene and β-pinene by weaker polyoxometallate analogues over SBA-15.

Octyl co-grafted PrSO3H/SBA-15:tunable hydrophobic solid acid catalysts for acetic acid esterification

Propylsulfonic acid (PrSO3H) derivatised solid acid catalysts have been prepared by post modification of mesoporous SBA-15 silica with mercaptopropyltrimethoxysilane (MPTMS), with the impact of co-derivatisation with octyltrimethoxysilane (OTMS) groups to impart hydrophobicity to the catalyst investigated. Turn over frequencies (TOF) for acetic acid esterification with methanol increase with PrSO3H surface coverage across both families suggesting a cooperative effect of adjacent acid sites at high acid site densities. Esterification activity is further promoted upon co-functionalisation with hydrophobic octyl chains, with inverse gas chromatography (iGC) measurements indicating increased activity correlates with decreased surface polarity or increased hydrophobicity.

An energy-efficient route to the rapid synthesis of organically-modified SBA-15 via ultrasonic template removal

A low energy route for the removal of Pluronic P123 surfactant template during the synthesis of SBA-15 mesoporous silicas is explored. The conventional reflux of the hybrid inorganic-organic intermediate formed during co-condensation routes to Pr-SOH-SBA-15 is slow, utilises large solvent volumes, and requires 24 h to remove ∼90% of the organic template. In contrast, room temperature ultrasonication in a small methanol volume achieves the same degree of template extraction in only 5 min, with a 99.9% energy saving and 90% solvent reduction, without compromising the textural, acidic or catalytic properties of the resultant Pr-SOH-SBA-15. © 2014 The Royal Society of Chemistry.

True liquid crystal templating of SBA-15 with reduced microporosity

Mesoporous silica SBA-15 was synthesised by the true liquid crystal templating method, yielding a material with reduced microporosity compared with that produced by the more conventional liquid crystal templating route. Further advancements allow the generation of metal nanoparticle-doped SBA-15 materials with well-defined metal particle sizes, which posses potential as catalytic systems. © 2013 Elsevier Inc. All rights reserved.

New insights in the deactivation of sulfonic modified SBA-15 catalysts for biodiesel production from low-grade oleaginous feedstock

Arenesulfonic-acid functionalized SBA-15 materials have been used in the production of biodiesel from low grade oleaginous feedstock. These materials display an outstanding catalytic activity, being able to promote the transformation of crude palm oil with methanol into fatty acid methyl esters with high yield (85%) under mild reaction conditions. However, high sensitivity of the catalyst against poisoning by different substances has also been detected. Thus, alkaline metal cations, such as sodium or potassium exert a negative influence on the catalytic activity of these materials, being necessary amounts around 500 ppm of sodium in the reaction media to decrease the catalytic activity of these materials to a half of its initial value in just two reaction runs. The deactivation of arenesulfonic acid functionalized SBA-15 materials seems to occur in this case by ion exchange of the acid protons at the sulfonic groups. Organic unsaponifiable compounds like lecithin or retinol also induce a negative influence in the catalytic activity of these sulfonic acid-based materials, though not so intense as in the case of alkaline metals. The deactivating mechanism associated to the influence of the organic compounds seems to be linked to the adsorption of such substances onto the catalytic acid sites as well as on the silica surface. The accumulation of lecithin in the surface of catalyst, observed by means of thermogravimetric analysis, suggest the creation of a strong interaction, probably by ion pair, between this compound and the sulfonic acid group.

Hydrothermal saline promoted grafting:a route to sulfonic acid SBA-15 silica with ultra-high acid site loading for biodiesel synthesis

A simple grafting protocol is reported which affords a ten-fold enhancement in acid site density of mesoporous sulfonic acid silicas compared to conventional syntheses, offering improved process efficiency and new opportunities for tailored supported solid acids in sustainable chemistry. This journal is

Thermal detemplation of SBA-15 mesophases. Effect of the activation protocol on the framework contraction

The potential use of the solvothermal extraction (SE) as a preliminary step to calcination for detemplating SBA-15 mesophases is investigated; aiming to reduce the amount of organics to be burnt and thereby the corresponding structural shrinkage. A systematic study was carried out by soxhlet extraction on mesophases hydrothermally aged between 90 and 130 C. The mesophases containing variable amounts of template were then treated by calcination or pyrolysis/calcination. TGA was applied to quantify the template amount after the various treatments. The as obtained materials were characterized by SAXS and Ar ad/desorption for structural and textural information while 1H NMR gave information about the integrity of the as-recycled template. The study shows that solvothermal conditions remove considerably the template, typically from 50 to 10-20 wt.%, mainly extracted from the primary mesopores. Possible reuse of the extracted template is questionable as it is poor in polyethyleneoxide compared to the synthesis block-copolymer, Pluronic P123. For all thermal protocols applied (direct calcination, calcination after solvent-extraction or pyrolysis/calcination after solvent extraction), the thermal shrinkage decreases with the aging temperature; that is consistent with the condensation degree of the silica. For each mesophase, it was found that the thermal shrinkage becomes less pronounced when the material is fully templated; thus the template can serve as structural support or can control the mass transfer of O2 and thereby the oxidation rate of the template burning. © 2013 Elsevier Inc. All rights reserved.

Can surface energy measurements predict the impact of catalyst hydrophobicity upon fatty acid esterification over sulfonic acid functionalised periodic mesoporous organosilicas?

Sulfonic acid functionalised periodic mesoporous organosilicas (PrSO3 H-PMOs) with tunable hydrophobicity were synthesised via a surfactant-templating route, and characterised by porosimetry, TEM, XRD, XPS, inverse gas chromatography (IGC) and ammonia pulse chemisorption. IGC reveals that incorporation of ethyl or benzyl moieties into a mesoporous SBA-15 silica framework significantly increases the non-specific dispersive surface energy of adsorption for alkane adsorption, while decreasing the free energy of adsorption of methanol, reflecting increased surface hydrophobicity. The non-specific dispersive surface energy of adsorption of PMO-SO3H materials is strongly correlated with their activity towards palmitic acid esterification with methanol, demonstrating the power of IGC as an analytical tool for identifying promising solid acid catalysts for the esterification of free fatty acids. A new parameter [-ΔGCNP-P], defined as the per carbon difference in Gibbs free energy of adsorption between alkane and polar probe molecules, provides a simple predictor of surface hydrophobicity and corresponding catalyst activity in fatty acid esterification. © 2014 Elsevier B.V.

Pore-expanded SBA-15 sulfonic acid silicas for biodiesel synthesis

Here we present the first application of pore-expanded SBA-15 in heterogeneous catalysis. Pore expansion over the range 6-14 nm confers a striking activity enhancement towards fatty acid methyl ester (FAME) synthesis from triglycerides (TAG), and free fatty acid (FFA), attributed to improved mass transport and acid site accessibility.

On the drug adsorption capacity of SBA-15 obtained from various detemplation protocols

The effect of the mild detemplation method, based on Fenton chemistry (with and without previous solvent extraction), and calcination was evaluated by the drug uptake capacity of SBA-15 materials. A number of characterization techniques were applied for evaluation and comparison of the materials properties such as TGA, CNH, N2 physisorption and 29Si NMR. The mild Fenton detemplation method rendered a nearly pristine SBA-15 without structural shrinkage, low residual template, improved surface area, pore volume and silanol concentration. The drug (ibuprofen) adsorption experiments were carried out by solution immersion in powdery form. The mild detemplated samples experienced an enhanced uptake that could be explained by the enhanced density of silanols (mmol/g), originated from the absence of calcination in the Fenton approaches. © 2014 Elsevier B.V.

Modifying the hierarchical porosity of SBA-15 via mild-detemplation followed by secondary treatments

Fenton-chemistry-based detemplation combined with secondary treatments offers options to tune the hierarchical porosity of SBA-15. This approach has been studied on a series of SBA-15 mesophases and has been compared to the conventional calcination. The as-synthesized and detemplated materials were studied with regard to their template content (TGA, CHN), structure (SAXS, TEM), surface hydroxylation (Blin-Carterets approach), and texture (high-resolution argon physisorption). Fenton detemplation achieves 99% of template removal, leading to highly hydroxylated materials. The structure is better preserved when a secondary treatment is applied after the Fenton oxidation, due to the intense capillary forces during drying in water. Two successful approaches are presented: drying in a low-surface-tension solvent (such as n-BuOH) and a hydrothermal stabilization to further condense the structure and make it structurally more robust. Both approaches give rise to remarkably low structural shrinkage, lower than calcination and the direct water-dried Fenton. Interestingly, the derived textural features are remarkably different. The n-BuOH exchange route gives rise to highly hierarchical structures with enhanced interconnecting pores and the highest surface areas. The hydrothermal stabilization produces large-pore SBA-15 structures with high pore volume, intermediate interconnectivity, and minimal micropores. Therefore, the hierarchical texture can be fine-tuned in these two fashions while the template is removed under mild conditions.