Studies on novel solid acid catalysts of niobium-based oxides with mesoporous, layered and nanosheet structures

Caio Tagusagawa, Atsushi Takagaki, Junko N. Kondo, Kazunari Domen

Research output: Chapter in Book/Report/Conference proceedingChapter

Abstract

The acidities of hydrated niobium oxide (Nb2O5·nH2O) and niobium mixed oxides have been widely studied as a promising substitute for liquid acid. Nb2O5·nH2O which is usually called niobic acid, exhibits a remarkably high acid strength corresponding to the acid strength of 70 % H2SO4. In the view of catalytic activity and stability, niobic acid exhibited excellent stabilities for acid-catalyzed reactions activities in water solution reactions including hydrolysis, hydration and esterification. In this chapter, niobium-containing mixed metal oxides with different nanostructures (nanosheet aggregates, layered and mesoporous) are presented to study the effects caused by the structure and metal combination for the acid sites and acid-catalyzed reactions. Nanosheet aggregates and protonated layered niobates (HTiNbO5, HNb3O8 and HNbWO6) are examined as potential solid acid catalysts. However, as the high charge density of the oxide sheets prevents reactants from penetrating into the interlayer region, unmodified layered transition-metal oxides are generally ineffective as solid acid catalysts. Exfoliation and aggregation of layered HTiNbO5, HNb3O8 and HNbWO6 using soft chemical processing form aggregates of nanosheets with high surface areas, making possible the access of reactants to acid sites formed by the bridged hydroxyl groups, M(OH)M' (M=Ti, Nb; M'=Nb, W). The catalytic activity for the Friedel-Crafts alkylation of anisole in the presence of benzyl alcohol increased in the order HTiNbO5 < HNb3O8 < HNbWO6, consistent with the acid strengths determined by desorption measurements and nuclear magnetic resonance spectroscopy. Layered HNbMoO6 is a very unique layered metal oxide able to intercalate different organic reactants (alcohols, saccharides, ketones, alkenes, hydroxyl acids) during the catalytic reactions. Owing to the intercalation ability and strong acidity in the interlayer, layered HNbMoO6 functioned as a highly-active solid acid catalyst. The catalytic activity for the Friedel-Crafts alkylation, acetalization and hydrolysis of saccharides exceeded the activity of zeolites and ion-exchange resins. Mesoporous NbxW(10-x) mixed oxides with different Nb and W concentrations are examined as potential solid acid catalysts. Amorphous wormhole-type mesopores are observed for samples from x = 3 to 10 whereas W-rich samples (x = 0 to 2) formed a non-mesoporous structure with presence of crystallized tungsten oxide (WO3). The acid-catalytic activity, acid strength and mesopore structure of mesoporous Nb-W oxides changed in order of W concentrations, exhibiting a very high activity for both Friedel-Crafts alkylation and hydrolysis. The results were compared with those for non-porous Nb2O5-WO3 and a range of conventional solid acids. Mesoporous Nb-W oxides obtained higher turnover rate than that of non-porous Nb2O5-WO3 led to the strong acid sites and a mesoporous structure with a high surface area and easy reactant accessibility.

Original languageEnglish
Title of host publicationNiobium
Subtitle of host publicationProperties, Production and Applications
PublisherNova Science Publishers, Inc.
Pages47-78
Number of pages32
ISBN (Print)9781611228953
Publication statusPublished - Dec 1 2011
Externally publishedYes

Fingerprint

Niobium
Nanosheets
Oxides
Catalysts
Acids
Catalyst activity
Alkylation
Hydrolysis
Metals
Acidity
Hydroxyl Radical
Alcohols
Niobium oxide

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)

Cite this

Tagusagawa, C., Takagaki, A., Kondo, J. N., & Domen, K. (2011). Studies on novel solid acid catalysts of niobium-based oxides with mesoporous, layered and nanosheet structures. In Niobium: Properties, Production and Applications (pp. 47-78). Nova Science Publishers, Inc..

Studies on novel solid acid catalysts of niobium-based oxides with mesoporous, layered and nanosheet structures. / Tagusagawa, Caio; Takagaki, Atsushi; Kondo, Junko N.; Domen, Kazunari.

Niobium: Properties, Production and Applications. Nova Science Publishers, Inc., 2011. p. 47-78.

Research output: Chapter in Book/Report/Conference proceedingChapter

Tagusagawa, C, Takagaki, A, Kondo, JN & Domen, K 2011, Studies on novel solid acid catalysts of niobium-based oxides with mesoporous, layered and nanosheet structures. in Niobium: Properties, Production and Applications. Nova Science Publishers, Inc., pp. 47-78.
Tagusagawa C, Takagaki A, Kondo JN, Domen K. Studies on novel solid acid catalysts of niobium-based oxides with mesoporous, layered and nanosheet structures. In Niobium: Properties, Production and Applications. Nova Science Publishers, Inc. 2011. p. 47-78
Tagusagawa, Caio ; Takagaki, Atsushi ; Kondo, Junko N. ; Domen, Kazunari. / Studies on novel solid acid catalysts of niobium-based oxides with mesoporous, layered and nanosheet structures. Niobium: Properties, Production and Applications. Nova Science Publishers, Inc., 2011. pp. 47-78
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N2 - The acidities of hydrated niobium oxide (Nb2O5·nH2O) and niobium mixed oxides have been widely studied as a promising substitute for liquid acid. Nb2O5·nH2O which is usually called niobic acid, exhibits a remarkably high acid strength corresponding to the acid strength of 70 % H2SO4. In the view of catalytic activity and stability, niobic acid exhibited excellent stabilities for acid-catalyzed reactions activities in water solution reactions including hydrolysis, hydration and esterification. In this chapter, niobium-containing mixed metal oxides with different nanostructures (nanosheet aggregates, layered and mesoporous) are presented to study the effects caused by the structure and metal combination for the acid sites and acid-catalyzed reactions. Nanosheet aggregates and protonated layered niobates (HTiNbO5, HNb3O8 and HNbWO6) are examined as potential solid acid catalysts. However, as the high charge density of the oxide sheets prevents reactants from penetrating into the interlayer region, unmodified layered transition-metal oxides are generally ineffective as solid acid catalysts. Exfoliation and aggregation of layered HTiNbO5, HNb3O8 and HNbWO6 using soft chemical processing form aggregates of nanosheets with high surface areas, making possible the access of reactants to acid sites formed by the bridged hydroxyl groups, M(OH)M' (M=Ti, Nb; M'=Nb, W). The catalytic activity for the Friedel-Crafts alkylation of anisole in the presence of benzyl alcohol increased in the order HTiNbO5 < HNb3O8 < HNbWO6, consistent with the acid strengths determined by desorption measurements and nuclear magnetic resonance spectroscopy. Layered HNbMoO6 is a very unique layered metal oxide able to intercalate different organic reactants (alcohols, saccharides, ketones, alkenes, hydroxyl acids) during the catalytic reactions. Owing to the intercalation ability and strong acidity in the interlayer, layered HNbMoO6 functioned as a highly-active solid acid catalyst. The catalytic activity for the Friedel-Crafts alkylation, acetalization and hydrolysis of saccharides exceeded the activity of zeolites and ion-exchange resins. Mesoporous NbxW(10-x) mixed oxides with different Nb and W concentrations are examined as potential solid acid catalysts. Amorphous wormhole-type mesopores are observed for samples from x = 3 to 10 whereas W-rich samples (x = 0 to 2) formed a non-mesoporous structure with presence of crystallized tungsten oxide (WO3). The acid-catalytic activity, acid strength and mesopore structure of mesoporous Nb-W oxides changed in order of W concentrations, exhibiting a very high activity for both Friedel-Crafts alkylation and hydrolysis. The results were compared with those for non-porous Nb2O5-WO3 and a range of conventional solid acids. Mesoporous Nb-W oxides obtained higher turnover rate than that of non-porous Nb2O5-WO3 led to the strong acid sites and a mesoporous structure with a high surface area and easy reactant accessibility.

AB - The acidities of hydrated niobium oxide (Nb2O5·nH2O) and niobium mixed oxides have been widely studied as a promising substitute for liquid acid. Nb2O5·nH2O which is usually called niobic acid, exhibits a remarkably high acid strength corresponding to the acid strength of 70 % H2SO4. In the view of catalytic activity and stability, niobic acid exhibited excellent stabilities for acid-catalyzed reactions activities in water solution reactions including hydrolysis, hydration and esterification. In this chapter, niobium-containing mixed metal oxides with different nanostructures (nanosheet aggregates, layered and mesoporous) are presented to study the effects caused by the structure and metal combination for the acid sites and acid-catalyzed reactions. Nanosheet aggregates and protonated layered niobates (HTiNbO5, HNb3O8 and HNbWO6) are examined as potential solid acid catalysts. However, as the high charge density of the oxide sheets prevents reactants from penetrating into the interlayer region, unmodified layered transition-metal oxides are generally ineffective as solid acid catalysts. Exfoliation and aggregation of layered HTiNbO5, HNb3O8 and HNbWO6 using soft chemical processing form aggregates of nanosheets with high surface areas, making possible the access of reactants to acid sites formed by the bridged hydroxyl groups, M(OH)M' (M=Ti, Nb; M'=Nb, W). The catalytic activity for the Friedel-Crafts alkylation of anisole in the presence of benzyl alcohol increased in the order HTiNbO5 < HNb3O8 < HNbWO6, consistent with the acid strengths determined by desorption measurements and nuclear magnetic resonance spectroscopy. Layered HNbMoO6 is a very unique layered metal oxide able to intercalate different organic reactants (alcohols, saccharides, ketones, alkenes, hydroxyl acids) during the catalytic reactions. Owing to the intercalation ability and strong acidity in the interlayer, layered HNbMoO6 functioned as a highly-active solid acid catalyst. The catalytic activity for the Friedel-Crafts alkylation, acetalization and hydrolysis of saccharides exceeded the activity of zeolites and ion-exchange resins. Mesoporous NbxW(10-x) mixed oxides with different Nb and W concentrations are examined as potential solid acid catalysts. Amorphous wormhole-type mesopores are observed for samples from x = 3 to 10 whereas W-rich samples (x = 0 to 2) formed a non-mesoporous structure with presence of crystallized tungsten oxide (WO3). The acid-catalytic activity, acid strength and mesopore structure of mesoporous Nb-W oxides changed in order of W concentrations, exhibiting a very high activity for both Friedel-Crafts alkylation and hydrolysis. The results were compared with those for non-porous Nb2O5-WO3 and a range of conventional solid acids. Mesoporous Nb-W oxides obtained higher turnover rate than that of non-porous Nb2O5-WO3 led to the strong acid sites and a mesoporous structure with a high surface area and easy reactant accessibility.

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