Sulfonic acid functionalized silica nanoparticles as catalysts for the esterification of linoleic acid

Aboelhassan, Mohamed M.; Peixoto, Andreia F.; Freire, Cristina

doi:10.1039/c6nj04043h

Cited by 37 publications

(45 citation statements)

References 53 publications

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“…Moderate yields (34%, after 7 h) were obtained with all the CSPTMS-functionalized clays, HNT_CSP, CLOI_CSP, and K10_CSP (entries [17][18][19]. This could be attributed to similar acidity observed for these catalysts (0.82, 0.88, and 0.80 mmol H þ g À1 ), respectively (Table S1, Supporting Information).…”

mentioning

confidence: 76%

“…According to the EA of the spent CLOI_CSP catalyst (Table ), after HMF etherification under different reaction conditions, the catalyst deactivation could be attributed to some reactants or products adsorption on the clay's surface‐restricting sulfonic acid sites’ accessibility, resulting in an inferior performance of the catalyst . This can be noted by the increase in the carbon content of the spent catalysts, observed by EA, and is more evident for the reactions where reactions occurred in continuous flow with concentrated HMF solutions (Table , entries 2, 3).…”

Section: Catalytic Activity Of the Three Selected Catalysts On The Etmentioning

confidence: 98%

“…Different types of clay materials, halloysite nanotubes (HNTs), K10, and Cloisite Na + (CLOI_Na + ) were also used to prepare sulfonic acid heterogeneous catalysts: 1) one‐pot organosilylation with CSPTMS (HNT_CSP, CLOI_CSP, K10_CSP) and 2) direct sulfonation using chlorosulfonic acid (HSO 3 Cl) to give the catalysts CLOI_SO 3 H and K10_SO 3 H . CLOI_Na + was also functionalized by two‐step methodologies using: 1) organosilylation with phenylethoxysilane (PhTES) followed by a sulfonation step with HSO 3 Cl to give the CLOI_PhSO 3 H catalyst and 2) direct condensation with benzyl alcohol followed by a reaction with HSO 3 Cl to give CLOI_BnSO 3 H.…”

Section: An Overview Of the Main Reported Catalytic Systems For The Pmentioning

confidence: 99%

“…To initiate our studies, we prepared or obtained from commercial sources a range of protic and/or Lewis acid heterogeneous catalysts. The acid resins amberlyst 15, amberlyst 16, amberlite IR120, and Keggin heteropolyacid (H 3 PW 12 [18] Sulfonated silica (SiO 2 -SO 3 H) was synthesized using the methodology proposed by Aboelhassan et al [19] Silica nanoparticles with different particle sizes (SiO 2 NPs_10 and SiO 2 NPs_100) were also functionalized with organosulfonic acid groups following the methodologies developed by Aboelhassan et al or adapted from the literature: 1) perflouroalkyl sulfonic acid-functionalized SiO 2 NPs (SiO 2 NPs10_SUL) were obtained through a one-pot synthetic reaction with 1,2,2-triflouro-2-hydroxy-1-triflouromethylethane sulfonic acid beta-sultone [20] and 2) aryl-sulfonic acid-functionalized SiO 2 NPs (SiO 2 NPs10_CSP and SiO 2 NPs100_CSP) were obtained by one-pot organosilylation with 2-(4-chlorosulfonylphenyl) ethyltrimethoxysilane (CSPTMS). [19] Different types of clay materials, halloysite nanotubes (HNTs), K10, and Cloisite Na þ (CLOI_Na þ ) were also used to prepare sulfonic acid heterogeneous catalysts: 1) one-pot organosilylation with CSPTMS [19] (HNT_CSP, CLOI_CSP, K10_CSP) and Catalyst reused three times without erosion of the yield.…”

mentioning

confidence: 99%

“…The catalytic reactivity trend of sulfated zirconia was similar or lower in the course of the first 2 h when compared with the acid resins. However, despite SO 4 /ZrO 2 (entry 10) undergoing longer reaction times, they exhibited superior (entries 5-7) or similar activity (entries [8][9][10][11][12][13][14][15][16][17][18][19] as acid resins.…”

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confidence: 99%

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Efficient Continuous Production of the Biofuel Additive 5‐(t‐Butoxymethyl) Furfural from 5‐Hydroxymethylfurfural

et al. 2019

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The catalytic etherification of 5‐hydroxymethylfurfural (HMF) with t‐butanol to a biofuel additive 5‐(t‐butoxymethyl) furfural (t‐BMF) is studied by screening 27 heterogeneous protic and/or Lewis acids. Preyssler heteropolyacid H14[NaP5W30O110] and Montmorillonite‐based CLOI_CSP catalysts are identified as the most efficient ones, allowing the etherification to reach the t‐BMF/HMF equilibrium faster (≈1:1), thus promoting minimum side reactions. Further optimization of the batch experimental conditions, namely catalyst loading, temperature, HMF concentration, time, t‐BMF stability, and additives, allows the t‐BMF/HMF equilibrium to be reached in less than 3 h with outstanding selectivity >95%. Under optimized conditions, CLOI_CSP is reused for four cycles without significant loss of efficiency. In addition, it exhibits high efficiency under flow conditions, allowing continuous production of t‐BMF up to 0.7 g t‐BMF g−1 catalyst min−1 at high concentrations of HMF.

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mentioning

confidence: 76%

Section: Catalytic Activity Of the Three Selected Catalysts On The Etmentioning

confidence: 98%

Section: An Overview Of the Main Reported Catalytic Systems For The Pmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Efficient Continuous Production of the Biofuel Additive 5‐(t‐Butoxymethyl) Furfural from 5‐Hydroxymethylfurfural

et al. 2019

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Bifunctional Janus Silica Spheres for Pickering Interfacial Tandem Catalysis

et al. 2021

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Nature provides much inspiration for the design of multistep conversion processes, with numerous reactions running simultaneously and without interference in cells, for example. A key challenge in mimicking nature's strategies is to compartmentalize incompatible reagents and catalysts, for example, for tandem catalysis. Here, we present a new strategy for antagonistic catalyst compartmentalization. The synthesis of bifunctional Janus catalyst particles carrying acid and base groups on the particle's opposite patches is reported as is their application as acid‐base catalysts in oil/water emulsions. The synthesis strategy involved the use of monodisperse, hydrophobic and amine‐functionalized silica particles (SiO2−NH2−OSi(CH3)3) to prepare an oil‐in‐water Pickering emulsion (PE) with molten paraffin wax. After solidification, the exposed patch of the silica particles was selectively etched and refunctionalized with acid groups to yield acid‐base Janus particles (Janus A–B). These materials were successfully applied in biphasic Pickering interfacial catalysis for the tandem dehydration‐Knoevenagel condensation of fructose to 5‐(hydroxymethyl)furfural‐2‐diethylmalonate (5‐HMF‐DEM) in a water/4‐propylguaiacol PE. The results demonstrate the advantage of rapid extraction of 5‐hydroxymethylfurfural (5‐HMF), a prominent platform molecule prone to side product formation in acidic media. A simple strategy to tune the acid/base balance using PE with both Janus A–B and monofunctional SiO2−NH2−OSi(CH3)3 base catalysts proved effective for antagonistic tandem catalysis.

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Analyzing the surface of functional nanomaterials—how to quantify the total and derivatizable number of functional groups and ligands

et al. 2021

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Functional nanomaterials (NM) of different size, shape, chemical composition, and surface chemistry are of increasing relevance for many key technologies of the twenty-first century. This includes polymer and silica or silica-coated nanoparticles (NP) with covalently bound surface groups, semiconductor quantum dots (QD), metal and metal oxide NP, and lanthanide-based NP with coordinatively or electrostatically bound ligands, as well as surface-coated nanostructures like micellar encapsulated NP. The surface chemistry can significantly affect the physicochemical properties of NM, their charge, their processability and performance, as well as their impact on human health and the environment. Thus, analytical methods for the characterization of NM surface chemistry regarding chemical identification, quantification, and accessibility of functional groups (FG) and surface ligands bearing such FG are of increasing importance for quality control of NM synthesis up to nanosafety. Here, we provide an overview of analytical methods for FG analysis and quantification with special emphasis on bioanalytically relevant FG broadly utilized for the covalent attachment of biomolecules like proteins, peptides, and oligonucleotides and address method- and material-related challenges and limitations. Analytical techniques reviewed include electrochemical titration methods, optical assays, nuclear magnetic resonance and vibrational spectroscopy, as well as X-ray based and thermal analysis methods, covering the last 5–10 years. Criteria for method classification and evaluation include the need for a signal-generating label, provision of either the total or derivatizable number of FG, need for expensive instrumentation, and suitability for process and production control during NM synthesis and functionalization. Graphical abstract

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Sulfonic acid functionalized silica nanoparticles as catalysts for the esterification of linoleic acid

Abstract: Sulfonic acid functionalized SiO2-nanoparticles showed excellent performance in linoleic acid esterification: 100% conversion, 2 h reaction time, TOF = 53–498 h−1.

Cited by 37 publications

References 53 publications

Efficient Continuous Production of the Biofuel Additive 5‐(t‐Butoxymethyl) Furfural from 5‐Hydroxymethylfurfural

Efficient Continuous Production of the Biofuel Additive 5‐(t‐Butoxymethyl) Furfural from 5‐Hydroxymethylfurfural

Bifunctional Janus Silica Spheres for Pickering Interfacial Tandem Catalysis

Analyzing the surface of functional nanomaterials—how to quantify the total and derivatizable number of functional groups and ligands

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