ChemInform Abstract: Sulfonic Acid Functionalized Ordered Mesoporous Materials as Catalysts for Condensation and Esterification Reactions.

Rhijn, Wim M. Van; Vos, Dirk De; Sels, Bert F.; Bossaert, Wim D.; Jacobs, Pierre

doi:10.1002/chin.199822083

Cited by 6 publications

(8 citation statements)

References 1 publication

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“…PFS nanoparticles gave a higher hydronium ion load (1.7 mmol H + /g) than the AS and BCOOH nanoparticles at 0.9 and 0.2 mmol H + /g, respectively. The acid capacity values of PFS and AS agree with the values previously reported in the literature [28,[41][42][43][44][45]. AS nanoparticles had a larger sulfur content (4.9%) than PFS nanoparticles (3.1%).…”

Section: Acid and Organic Incorporationsupporting

confidence: 89%

“…Aggregation of PFS nanoparticles could have decreased the available area for catalytic hydrolysis also. Likewise, AS nanoparticles are difficult to disperse in aqueous solutions which could be explained by the poor water affinity of AS and PFS functionalized materials [44,48]. Higher cellobiose conversion could be attained with this catalyst if a better dispersion is achieved.…”

Section: Cellobiose Hydrolysismentioning

confidence: 98%

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Cellobiose hydrolysis using acid-functionalized nanoparticles

Peña

Ikenberry

Ware

et al. 2011

Biotechnol Bioproc E

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Mineral acids have been used effectively for the pretreatment of cellulosic biomass to improve sugar recovery and promote its conversion to ethanol; however, substantial capital investment is required to enable separation of the acid, and corrosion-resistant materials are necessary. Disposal and neutralization costs are also concerns because they can decrease the economic feasibility of the process. In this work, three acid-functionalized nanoparticles were synthesized for pretreatment and hydrolysis of lignocellulosic biomass. Silica-protected cobalt spinel ferrite nanoparticles were functionalized with perfluoroalkylsulfonic acid (PFS), alkylsulfonic acid (AS), and butylcarboxylic acid (BCOOH) groups. These nanoparticles were magnetically separated from the reaction media and reused. TEM images showed that the average diameter was 2 nm for both PFS and BCOOH nanoparticles and 7 nm for AS nanoparticles. FTIR confirmed the presence of sulfonic and carboxylic acid functional groups. Ion exchange titration measurements yielded 0.9, 1.7, and 0.2 mmol H + /g of catalyst for PFS, AS, and BCOOH nanoparticles, respectively. Elemental analysis results indicated that PFS and AS nanoparticles had 3.1 and 4.9% sulfur, respectively. Cellobiose hydrolysis was used as a model reaction to evaluate the performance of acid-functionalized magnetic nanoparticles for breaking β-(1→4) glycosidic bonds. Cellobiose conversion of 78% was achieved when using AS nanoparticles as the catalyst at 175°C for 1 h, which was significantly higher than the conversion for the control experiment (52%). AS nanoparticles retained more than 60% of their sulfonic acids groups after the first run, and 65 and 60% conversions were obtained for the second and third runs, respectively.

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Section: Acid and Organic Incorporationsupporting

confidence: 89%

Section: Cellobiose Hydrolysismentioning

confidence: 98%

Cellobiose hydrolysis using acid-functionalized nanoparticles

Peña

Ikenberry

Ware

et al. 2011

Biotechnol Bioproc E

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“…However, low catalytic activity could have been a consequence of the poor water affinity observed for this catalyst. These results agree with the findings of Van Rhijn et al (1998) and Bootsma and Shanks (2007). Gill et al (2007) and Suganuma et al (2008) reported that acid groups in the PFS nanoparticles were leached into the reaction solution.…”

Section: Performance Of the Catalystssupporting

confidence: 91%

“…To increase the contact area between mesoporous materials and substrates for high conversion yield and efficiency, the present work proposes use of acidfunctionalized nanoparticles for treatment of cellulosic materials. Extensive studies have also been reported on the synthesis and evaluation of mesoporous silicas functionalized with acid groups (Harmer et al 1996;Harmer et al 1998;Van Rhijn 1998;Corma et al 2004;Alvaro 2005;Rac et al 2006;Harmer et al 2007). Monodisperse materials have an advantage that provides large surface areas.…”

Section: Acid Strength Of Sulfonic Supported Acidsmentioning

confidence: 99%

Acid Functionalized Nanoparticles for Hydrolysis of Lignocellulosic Feedstocks

Peña¹,

Wang²,

Hohn³

et al. 2009

2009 Reno, Nevada, June 21 - June 24, 2009

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Acid catalysts have been successfully used for pretreatment of cellulosic biomass to improve sugar recovery and its later conversion to ethanol. However, use of acid requires a considerable equipment investment as well as disposal of residues. Acid-functionalized nanoparticles were synthesized for pretreatment and hydrolysis of lignocellulosic biomass to increase conversion efficiency at mild conditions. Advantages of using acid-functionalized metal nanoparticles are not only the acidic properties to catalyze hydrolysis and being small enough to penetrate into the lignocellulosic structure, but also being easily separable from hydrolysis residues by using a strong magnetic field. Cobalt spinel ferrite magnetic nanoparticles were synthesized using a microemulsion method and then covered with a layer of silica to protect them from oxidation. The silanol groups of the silica serve as the support of the sulfonic acid groups that were later attached to the surface of the nanoparticles. TEM images and FTIR methods were used to characterize the properties of acid-functionalized nanoparticles in terms of nanoparticle size, presence of sulfonic acid functional groups, and pH as an indicator of acid sites present. Citric acid-functionalized magnetite nanoparticles were also synthesized and evaluated. Wheat straw and wood fiber samples were treated with the acid supported nanoparticles at 80°C for 24 h to hydrolyze their h emicellulose fraction to sugars. Further hydrolysis of the liquid fraction was carried out to account for the amount of total solubilized sugars. HPLC was used to determine the total amount of sugars obtained in the aqueous solution. The perfluroalkyl-sulfonic acid functional groups from the magnetic nanoparticles yielded significantly higher amounts of oligosaccharides from wood and wheat straw samples than the alkyl-sulfonic acid functional groups did. More stable fluorosulfonic acid functionalized nanoparticles can potentially work as an effective heterogeneous catalyst for pretreatment of lignocellulosic materials.

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“…For example, mesoporous silica having thiol groups on the pore surface showed high adsorption efficiency for heavy metals such as Hg, Ag, and Cd ions [ 80 , 81 ]. Sulfonic acid groups grafted onto mesoporous materials, as another example, exhibited high catalytic activity for selective formation of bulky organic molecules [ 82 ].…”

Section: An Overview Of Modification Of As-synthesized Mcm-41mentioning

confidence: 99%

A Review: Fundamental Aspects of Silicate Mesoporous Materials

2012

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Silicate mesoporous materials have received widespread interest because of their potential applications as supports for catalysis, separation, selective adsorption, novel functional materials, and use as hosts to confine guest molecules, due to their extremely high surface areas combined with large and uniform pore sizes. Over time a constant demand has developed for larger pores with well-defined pore structures. Silicate materials, with well-defined pore sizes of about 2.0–10.0 nm, surpass the pore-size constraint (<2.0 nm) of microporous zeolites. They also possess extremely high surface areas (>700 m2 g−1) and narrow pore size distributions. Instead of using small organic molecules as templating compounds, as in the case of zeolites, long chain surfactant molecules were employed as the structure-directing agent during the synthesis of these highly ordered materials. The structure, composition, and pore size of these materials can be tailored during synthesis by variation of the reactant stoichiometry, the nature of the surfactant molecule, the auxiliary chemicals, the reaction conditions, or by post-synthesis functionalization techniques. This review focuses mainly on a concise overview of silicate mesoporous materials together with their applications. Perusal of the review will enable researchers to obtain succinct information about microporous and mesoporous materials.

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ChemInform Abstract: Sulfonic Acid Functionalized Ordered Mesoporous Materials as Catalysts for Condensation and Esterification Reactions.

Cited by 6 publications

References 1 publication

Cellobiose hydrolysis using acid-functionalized nanoparticles

Cellobiose hydrolysis using acid-functionalized nanoparticles

Acid Functionalized Nanoparticles for Hydrolysis of Lignocellulosic Feedstocks

A Review: Fundamental Aspects of Silicate Mesoporous Materials

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