Hierarchical Porous MIL-101(Cr) Solid Acid-Catalyzed Production of Value-Added Acetals from Biomass-Derived Furfural

Considering economic and environmental impacts, catalytic biomass conversion to valuable compounds has attracted more and more attention. Of particular interest is furfural, a versatile biorefinery platform molecule used as a feedstock for the production of fuels and fine chemicals. In this study, the Cr-based metal-organic frameworks (MOFs) MIL-101 were modified by chlorosulfonic acid, and MIL-101 was changed into a hierarchical MOF structure with smaller particles and lower particle crystallinity by CTAB, which significantly improved the acidic sites of the MOFs. The original and modified MIL-101(Cr) catalysts were characterized by XRD, N2 adsorption-desorption, SEM, TEM, and FT-IR. The effects of different catalysts, reaction temperature, catalyst amount, and alcohol type on the reaction were studied. Under the action of the MOFs catalyst, a new mild route for the condensation of furfural with various alkyl alcohols to the biofuel molecules (acetals) was proposed. The conversion route includes the conversion of furfural up to 91% yield of acetal could be obtained within 1 h solvent-free and in room-temperature reaction conditions. The sulfonic acid-functionalized MIL-101(Cr) is easy to recover and reuse, and can still maintain good catalytic activity after ten runs.

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Synthesis of pyrroles catalyzed by MIL-53(Al) via Paal-Knorr reaction under mild condition

Science and Technology Development Journal - Natural Sciences ◽

10.32508/stdjns.v1it5.543 ◽

2018 ◽

Vol 1 (T5) ◽

pp. 116-125

Author(s):

Hai Truong Nguyen ◽

Phuong Hoang Tran

Keyword(s):

Catalytic Activity ◽

Metal Organic Framework ◽

Organic Ligand ◽

Molar Ratio ◽

High Yield ◽

X Ray Diffraction ◽

Benzenedicarboxylic Acid ◽

Metal Organic ◽

Ft Ir ◽

Good Catalytic Activity

Metal-organic framework MIL-53(Al) was synthesized by a solvothermal method using aluminium nitrate as the aluminium source and 1,4- benzenedicarboxylic acid (H2BDC) as the organic ligand. The structure of MIL-53(Al) was characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). The catalytic activity and recyclability of MIL-53(Al) catalyst were evaluated based on the Paal-Knorr reaction between aniline and acetonylacetone. The reaction conditions were optimized and the results showed that the MIL-53(Al) catalyst exhibited good catalytic activity and recyclability based on the PaalKnorr reaction. With the molar ratio of MIL-53(Al) catalyst of 10 mol %, the molar ratio of aniline and acetonylacetone of 1:1.2, and without solvents, the conversion of aniline could reach 100 % and the selectivity of 2,5-dimethyl-1-phenyl-1H-pyrrole has high yield (95-100 %) after 2 hours by ultrasound activation. The MIL-53(Al) catalyst can be reused five times without significant degradation in the catalytic activity.

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β-Cyclodextrin-Calcium Complex Intercalated Hydrotalcites as Efficient Catalyst for Transesterification of Glycerol

Catalysts ◽

10.3390/catal11111307 ◽

2021 ◽

Vol 11 (11) ◽

pp. 1307

Author(s):

Guanhao Liu ◽

Jingyi Yang ◽

Xinru Xu

Keyword(s):

Value Added ◽

Nitrogen Adsorption ◽

Collision Probability ◽

Molar Ratio ◽

Glycerol Carbonate ◽

Efficient Catalyst ◽

Glycerol Conversion ◽

Ft Ir ◽

Adsorption Desorption ◽

Basic Strength

β-cyclodextrin derivative intercalated MgAl-hydrotalcites (β-CD-Ca/LDH) was synthesized to convert glycerol into high value-added glycerol carbonate(GC) by transesterification of dimethyl carbonate (DMC) and glycerol in this paper. β-cyclodextrin-metal complexes and β-CD-Ca/LDH was characterized by XRD, FT-IR, SEM, XPS and nitrogen adsorption-desorption. The enrichment of organic reactants in the hydrophobic cavity of β-cyclodextrin improved the collision probability of reactants. The intercalation of β-cyclodextrin-calcium complex (β-CD-Ca) increased the pore size and basic strength of catalyst. The experiment results showed that the glycerol conversion was 93.7% and the GC yield was 91.8% catalyzed by β-CD-Ca/LDH when the molar ratio of DMC and glycerol was 3:1, the catalyst dosage was 4 wt.%, the reaction temperature was 75 °C and the reaction time was 100 min while the glycerol conversion was 49.4% and the GC yield was 48.6% catalyzed by MgAl-LDH under the same conditions.

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Study of Curcumin Adsorption of Nano Fe-based Metal-Organic Framework

Science and Technology Development Journal - Natural Sciences ◽

10.32508/stdjns.v4i4.927 ◽

2020 ◽

Vol 4 (4) ◽

pp. First

Author(s):

Trang Thị Thu Nguyễn ◽

Ý Thị Đặng ◽

Linh Hồ Thùy Nguyễn ◽

Hạnh Thị Kiều Tạ ◽

Thắng Bách Phan ◽

...

Keyword(s):

Particle Size ◽

Metal Organic Framework ◽

Crystal Formation ◽

X Ray Diffraction ◽

Isothermal Adsorption ◽

Framework Materials ◽

Metal Organic ◽

Ft Ir ◽

Adsorption Desorption ◽

Organic Framework

Highly porous and biocompatible nano metal-organic framework materials (NMOF) are increasingly being applied in biomedical fields, especially as pharmaceutical adsorbent materials. Curcumin, found in turmeric, is a widely common herb in Eastern which has recently used in many applications in supporting cancer treatment. In the synthesis of MOF materials, the use of surfactants allows to control the morphology, the process of crystal formation and development and particle size of the material. In this research, MIL-100 (Fe) nanomaterials were successfully synthesized at room temperature in the presence of polyvinylpyrrolidone surfactant (PVP) to control the nanoparticle size about 50 nm in size. The synthesized MOF structure and properties were analyzed by using characterization techniques, including powder X-ray diffraction (PXRD), fourier-transform infrared (FT-IR), thermal gravimetric analyses (TGA) and nitrogen isothermal adsorption-desorption at 77 K. The characterization results showed that MIL-100 (Fe) nanomaterials have high crystallinity, large surface area, and highly thermal stability. However, its particle size is very small, only about 50 nm. Curcumin adsorption studies exhibited that this material had the ability to adsorb curcumin with an adsorption capacity up to 64.36 mg g-1. Kinetic and mechanism studies revealed that curcumin adsorption followed the pseudo-second model. In addition, thermodynamic studies proved that this was a spontaneous and exothermic adsorption process.

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Catalytic Pyrolysis of Lignin Model Compounds (Pyrocatechol, Guaiacol, Vanillic and Ferulic Acids) over Nanoceria Catalyst for Biomass Conversion

Applied Sciences ◽

10.3390/app11167205 ◽

2021 ◽

Vol 11 (16) ◽

pp. 7205

Author(s):

Nataliia Nastasiienko ◽

Tetiana Kulik ◽

Borys Palianytsia ◽

Julia Laskin ◽

Tetiana Cherniavska ◽

...

Keyword(s):

Catalytic Pyrolysis ◽

Biomass Conversion ◽

Value Added ◽

Spectroscopic Studies ◽

Surface Complexes ◽

General Transformation ◽

Carboxylate Groups ◽

Transformation Mechanisms ◽

Ft Ir ◽

Temperature Programmed

Understanding the mechanisms of thermal transformations of model lignin compounds (MLC) over nanoscale catalysts is important for improving the technologic processes occurring in the pyrolytic conversion of lignocellulose biomass into biofuels and value-added chemicals. Herein, we investigate catalytic pyrolysis of MLC (pyrocatechol (P), guaiacol (G), ferulic (FA), and vanillic acids (VA)) over nanoceria using FT-IR spectroscopy, temperature-programmed desorption mass spectrometry (TPD MS), and thermogravimetric analysis (DTG/DTA/TG). FT-IR spectroscopic studies indicate that the active groups of aromatic rings of P, G, VA, and FA as well as carboxylate groups of VA and FA are involved in the interaction with nanoceria surface. We explore the general transformation mechanisms of different surface complexes and identify their decomposition products. We demonstrate that decomposition of carboxylate acid complexes occurs by decarboxylation. When FA is used as a precursor, this reaction generates 4-vinylguaiacol. Complexes of VA and FA formed through both active groups of the aromatic ring and decompose on the CeO2 surface to generate hydroxybenzene. The formation of alkylated products accompanies catalytic pyrolysis of acids due to processes of transalkylation on the surface.

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Phosphate Enrichment of Niobium-Based Catalytic Surfaces in Relation to Reactions of Carbohydrate Biomass Conversion: The Case Studies of Inulin Hydrolysis and Fructose Dehydration

Catalysts ◽

10.3390/catal11091077 ◽

2021 ◽

Vol 11 (9) ◽

pp. 1077

Author(s):

Mariana N. Catrinck ◽

Sebastiano Campisi ◽

Paolo Carniti ◽

Reinaldo F. Teófilo ◽

Filippo Bossola ◽

...

Keyword(s):

Biomass Conversion ◽

Acid Sites ◽

Lewis Acidity ◽

Total Acidity ◽

Biomass Hydrolysis ◽

Inulin Hydrolysis ◽

Ft Ir ◽

Fructose Dehydration ◽

Adsorption Desorption

In this work, some physical mixtures of Nb2O5·nH2O and NbOPO4 were prepared to study the role of phosphate groups in the total acidity of samples and in two reactions involving carbohydrate biomass: hydrolysis of polyfructane and dehydration of fructose/glucose to 5-hydroxymethylfurfural (HMF). The acid and catalytic properties of the mixtures were dominated by the phosphate group enrichment. Lewis and Brønsted acid sites were detected by FT-IR experiments with pyridine adsorption/desorption under dry and wet conditions. Lewis acidity decreased with NbP in the composition, while total acidity of the samples, measured by titrations with phenylethylamine in cyclohexane (~3.5 μeq m−2) and water (~2.7 μeq m−2), maintained almost the same values. Inulin conversion took advantage of the presence of surfaces rich in Brønsted sites, and NbOPO4 showed the best hydrolysis activity with glucose/fructose formation. The catalyst with a more phosphated surface showed less deactivation during the dehydration of fructose/glucose into HMF.

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Metal Organic Framework-Encapsulated Phosphotungstic Acid: An Effective Catalyst for Highly Efficient Acetalization of Vanillin Propylene Glycol

Science of Advanced Materials ◽

10.1166/sam.2020.3768 ◽

2020 ◽

Vol 12 (7) ◽

pp. 958-965

Author(s):

Jing Liu ◽

Xiaomin Li ◽

Pan Chen ◽

Yutian Mi ◽

Jiandu Lei

Keyword(s):

Propylene Glycol ◽

Metal Organic Framework ◽

Direct Synthesis ◽

Synthesis Method ◽

Empty Space ◽

Synthesis Conditions ◽

Heterogeneous Catalytic ◽

Metal Organic ◽

Ft Ir ◽

Adsorption Desorption

Metal organic frameworks (MOFs) have exhibited potential for application as heterogeneous catalytic materials because they consist of empty space, which can be used for encapsulation. Encapsulation of H3PW12O40 (HPW) in MOFs, such as the fabrication of MIL-101, by direct synthesis method or impregnation has drawn significant interest. However, few researches have used MOFs as catalysts for acetalization. This study evaluates the use of HPW encapsulated in MIL-101(Cr) to make it a catalyst in the acetalization of vanillin propylene glycol. Samples fabricated using various techniques (encapsulation and impregnation) were characterized by SEM, TEM, N2 adsorption–desorption, XRD, and FT-IR. The synthesis conditions of HPW@MIL-101 and their effects on vanillin conversion were examined. The reaction kinetics was also investigated under optimal conditions. Vanillin conversion showed that introducing HPW directly into MIL-101(Cr) during synthesis induced a 14% increase, compared with impregnation. The results indicated that HPW@MIL-101(Cr) is an effective method for vanillin propylene glycol acetal production and is reusable.

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Ni–citric acid coordination polymer as a practical catalyst for multicomponent reactions

Scientific Reports ◽

10.1038/s41598-021-03857-w ◽

2021 ◽

Vol 11 (1) ◽

Author(s):

Mostafa Koolivand ◽

Mohsen Nikoorazm ◽

Arash Ghorbani-Choghamarani ◽

Reza Azadbakht ◽

Bahman Tahmasbi

Keyword(s):

Citric Acid ◽

Multicomponent Reactions ◽

Metal Organic Frameworks ◽

Bet Surface Area ◽

Efficient Catalyst ◽

Bet Analysis ◽

Metal Organic ◽

Ft Ir ◽

Porous Microstructures ◽

Adsorption Desorption

AbstractCoordinative polymers (CP) are a subclass of Metal–organic frameworks (MOFs) with porous microstructures which have been widely synthesized in recent years and applied in various fields especially in catalysis science. In this work Coordinative polymers (CP) of nickel and citric acid (CA) was prepared as a new catalyst (Ni-CP) and applied in organic multicomponent reactions. The obtained catalyst was characterized by SEM, WDX, EDS, AAS, FT-IR, XRD and BET analysis. N2 adsorption–desorption isotherms indicate good BET surface area for Ni-CP; therefore can be employed as an efficient catalyst in multicomponent reactions for the synthesis of polyhydroquinoline and 2,3-dihydroquinazolin-4(1H)-one derivatives. Finally, this catalyst was recovered and reused several consecutive times.

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Interwrapping Distinct Metal-Organic Frameworks in Dual-MOFs for the Creation of Unique Composite Catalysts

Research ◽

10.34133/2021/9835935 ◽

2021 ◽

Vol 2021 ◽

pp. 1-12

Author(s):

Jia-Long Ling ◽

Kai Chen ◽

Chuan-De Wu

Keyword(s):

Heterogeneous Catalysts ◽

Catalytic Properties ◽

Metal Organic Frameworks ◽

Value Added ◽

Composite Catalysts ◽

Redox Active ◽

Hierarchical Porous ◽

Metal Organic ◽

Molecular Sieving

Incorporating metal nanoparticles (MNPs) inside metal-organic frameworks (MOFs) demonstrates superior catalytic properties in numerous reactions; however, the size and distribution of MNPs could not be well controlled, resulting in low product selectivity in catalysis by undergoing different catalytic reaction pathways. We report herein a facile strategy for integrating lattice-mismatched MOFs together to fabricate homogeneously distributed “dual-MOFs,” which are the ideal precursors for the preparation of MNPs@MOFs with unique catalytic properties. As a proof of concept, we successfully synthesize a dual-MOF HKUST-1/ZIF-8 for in situ creation of redox-active Cu NPs inside hierarchical porous ZIF-8 under controlled pyrolytic conditions. Combining the advantages of size-tunable Cu NPs in the molecular sieving matrix of ZIF-8, Cu@ZIF-8 demonstrates high activity and selectivity for transformation of alkynes into alkenes without overhydrogenation, which surpasses most of the catalysts in the literature. Therefore, this work paves a new pathway for developing highly efficient and selective heterogeneous catalysts to produce highly value-added chemicals.

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Metal–Organic Frameworks-Based Catalysts for Biomass Processing

Catalysts ◽

10.3390/catal8090368 ◽

2018 ◽

Vol 8 (9) ◽

pp. 368 ◽

Cited By ~ 15

Author(s):

Vera I. Isaeva ◽

Oleg M. Nefedov ◽

Leonid M. Kustov

Keyword(s):

Rational Design ◽

Biomass Conversion ◽

High Surface ◽

High Surface Area ◽

Value Added ◽

Catalytic Systems ◽

Heterogeneous Catalytic ◽

Biomass Processing ◽

Metal Organic ◽

Compositional Diversity

: Currently, metal–organic frame works (MOFs) as novel hybrid nanoporous materials are a top research interest, including endeavors in heterogeneous catalysis. MOF materials are promising heterogeneous catalytic systems due to their unique characteristics, such as a highly ordered structure, a record high surface area and a compositional diversity, which can be precisely tailored. Very recently, these metal-organic matrices have been proven as promising catalysts for biomass conversion into value-added products. The relevant publications show that the structure of MOFs can contribute essentially to the advanced catalytic performance in processes of biomass refining. This review aims at the consideration of the different ways for the rational design of MOF catalysts for biomass processing. The particular characteristics and peculiarities of the behavior of different MOF based catalytic systems including hybrid nanomaterials and composites will be also discussed by illustrating their outstanding performance with appropriate examples relevant to biomass catalytic processing.

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Synthesis of tetrazolo[1,5-a]pyrimidine-6-carbonitriles using HMTA-BAIL@MIL-101(Cr) as a superior heterogeneous catalyst

Scientific Reports ◽

10.1038/s41598-021-84379-3 ◽

2021 ◽

Vol 11 (1) ◽

Author(s):

Mohammad Hossein Abdollahi-Basir ◽

Boshra Mirhosseini-Eshkevari ◽

Farzad Zamani ◽

Mohammad Ali Ghasemzadeh

Keyword(s):

Ionic Liquid ◽

Catalytic Activity ◽

Reaction Time ◽

Metal Organic Framework ◽

One Pot ◽

Short Reaction Time ◽

Three Component Reaction ◽

Metal Organic ◽

Ft Ir ◽

Novel Catalyst

AbstractA one-pot three component reaction of benzaldehydes, 1H-tetrazole-5-amine, and 3-cyanoacetyl indole in the presence of a new hexamethylenetetramine-based ionic liquid/MIL-101(Cr) metal–organic framework as a recyclable catalyst was explored. This novel catalyst, which was fully characterized by XRD, FE-SEM, EDX, FT-IR, TGA, BET, and TEM exhibited outstanding catalytic activity for the preparation of a range of pharmaceutically important tetrazolo[1,5-a]pyrimidine-6-carbonitriles with good to excellent yields in short reaction time.

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