Heterogeneous Catalysts for the Conversion of Glucose into 5-Hydroxymethyl Furfural

Lignocellulosic biomass, a cheap and plentiful resource, could play a key role in the production of sustainable chemicals. The simple sugars contained in the renewable lignocellulosic biomass can be converted into commercially valuable products such as 5-hydroxymethyl furfural (HMF). A platform molecule, HMF can be transformed into numerous chemical products with potential applications in a wide variety of industries. Of the hexoses contained in the lignocellulosic biomass, the successful production of HMF from glucose has been a challenge. Various heterogeneous catalysts have been proposed over the last decade, ranging from zeolites to metal organic frameworks. The reaction conditions vary in the reports in the literature, which makes it difficult to compare catalysts reported in different studies. In addition, the slight variations in the synthesis of the same material in different laboratories may affect the activity results, because the selectivity towards desired products in this transformation strongly depends on the nature of the active sites. This poses another difficulty for the comparison of different reports. Furthermore, over the last decade the new catalytic systems proposed have increased profoundly. In this article, we summarize the heterogeneous catalysts: Metal Organic Frameworks (MOFs), zeolites and conventional supported catalysts, that have been reported in the recent literature and provide an overview of the observed catalytic activity, in order to provide a comparison.

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An Overview of Metal-organic Frameworks-based Acid/Base Catalysts for Biofuel Synthesis

Current Organic Chemistry ◽

10.2174/1385272824999200726230556 ◽

2020 ◽

Vol 24 (16) ◽

pp. 1876-1891

Author(s):

Qiuyun Zhang ◽

Yutao Zhang ◽

Jingsong Cheng ◽

Hu Li ◽

Peihua Ma

Keyword(s):

Alternative Fuels ◽

Heterogeneous Catalysts ◽

Supported Catalysts ◽

Metal Organic Framework ◽

Metal Organic Frameworks ◽

Flexible Structures ◽

Biodiesel Production ◽

Biodiesel Synthesis ◽

Metal Organic ◽

Organic Framework

Biofuel synthesis is of great significance for producing alternative fuels. Among the developed catalytic materials, the metal-organic framework-based hybrids used as acidic, basic, or supported catalysts play major roles in the biodiesel production. This paper presents a timely and comprehensive review of recent developments on the design and preparation of metal-organic frameworks-based catalysts used for biodiesel synthesis from various oil feedstocks, including MILs-based catalysts, ZIFs-based catalysts, UiO-based catalysts, Cu-BTC-based catalysts, and MOFs-derived porous catalysts. Due to their unique and flexible structures, excellent thermal and hydrothermal stability, and tunable host-guest interactions, as compared with other heterogeneous catalysts, metal-organic framework-based catalysts have good opportunities for application in the production of biodiesel at industrial scale.

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Selective Styrene Oxidation to Benzaldehyde over Recently Developed Heterogeneous Catalysts

Molecules ◽

10.3390/molecules26061680 ◽

2021 ◽

Vol 26 (6) ◽

pp. 1680

Author(s):

Marta A. Andrade ◽

Luísa M. D. R. S. Martins

Keyword(s):

Heterogeneous Catalysts ◽

Carbon Materials ◽

Oxygen Species ◽

Styrene Oxidation ◽

Reaction Conditions ◽

Reactive Metal ◽

Catalytic Systems ◽

Tert Butyl Hydroperoxide ◽

Metal Organic ◽

Important Intermediate

The selective oxidation of styrene under heterogeneous catalyzed conditions delivers environmentally friendly paths for the production of benzaldehyde, an important intermediate for the synthesis of several products. The present review explores heterogeneous catalysts for styrene oxidation using a variety of metal catalysts over the last decade. The use of several classes of supports is discussed, including metal–organic frameworks, zeolites, carbon materials and silicas, among others. The studied catalytic systems propose as most used oxidants tert-butyl hydroperoxide, and hydrogen peroxide and mild reaction conditions. The reaction mechanism proceeds through the generation of an intermediate reactive metal–oxygen species by catalyst-oxidant interactions. Overall, most of the studies highlight the synergetic effects among the metal and support for the activity and selectivity enhancement.

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Chiral porous metal-organic frameworks with dual active sites for sequential asymmetric catalysis

Proceedings of The Royal Society A Mathematical Physical and Engineering Sciences ◽

10.1098/rspa.2012.0100 ◽

2012 ◽

Vol 468 (2143) ◽

pp. 2035-2052 ◽

Cited By ~ 24

Author(s):

Feijie Song ◽

Teng Zhang ◽

Cheng Wang ◽

Wenbin Lin

Keyword(s):

Asymmetric Catalysis ◽

Active Sites ◽

Metal Organic Frameworks ◽

Porous Metal ◽

Dicarboxylic Acids ◽

Great Promise ◽

Epoxide Ring ◽

Potential Applications ◽

Secondary Building Units ◽

Metal Organic

Metal-organic frameworks (MOFs) are a class of organic–inorganic hybrid materials built from metal-connecting nodes and organic-bridging ligands. They have received much attention in recent years owing to the ability to tune their properties for potential applications in various areas. Properly designed MOFs with uniform, periodically aligned active sites have shown great promise in catalysing shape-, size-, chemo-, regio- and stereo-selective organic transformations. This study reports the synthesis and characterization of two chiral MOFs (CMOFs 1 and 2 ) that are constructed from Mn-salen-derived dicarboxylic acids [salen is ( R , R )- N , N ′-bis(5- tert -butylsalicylidene)-1,2-cyclohexanediamine], bis(4-vinylbenzoic acid)-salen manganese(III) chloride (H 2 L 4 ) or bis(benzoic acid)-salen manganese(III) chloride (H 2 L 3 ) and [Zn 4 (μ 4 -O)(O 2 CR) 6 ] or [Zn 5 (H 2 O) 2 (μ 3 -OH) 2 (O 2 CR) 8 ] secondary building units (SBUs), respectively. The SBUs in CMOF- 1 are connected by the linear ditopic Mn-salen-derived linkers to construct a fourfold interpenetrated isoreticular MOF (IRMOF) structure with pcu topology. In CMOF- 2 , the Mn-salen centres dimerize in a cross-linking way to form a diamondoid structure with threefold interpenetration. CMOF- 1 was examined for highly regio- and stereo-selective tandem alkene epoxidation/epoxide ring-opening reactions by using the Mn-salen andZn 4 (μ 4 -O)(carboxylate) 6 active sites, respectively. Our work demonstrated the potential utility of chiral MOFs with multiple active sites in the efficient synthesis of complex molecules with excellent regio- and stereo-controls

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Metal-Organic Frameworks for Asymmetric Catalysis and Chiral Separations

MRS Bulletin ◽

10.1557/mrs2007.104 ◽

2007 ◽

Vol 32 (7) ◽

pp. 544-548 ◽

Cited By ~ 65

Author(s):

Wenbin Lin

Keyword(s):

Asymmetric Catalysis ◽

Active Sites ◽

Heterogeneous Catalysts ◽

Metal Organic Frameworks ◽

Building Blocks ◽

Chiral Separations ◽

Bridging Ligands ◽

Guest Molecules ◽

Pure Compounds ◽

Metal Organic

Metal-organic frameworks (MOFs) are an interesting class of molecule-based hybrid materials built from metal-connecting points and bridging ligands. MOFs have received much attention, owing to their potential impact on many technological areas, including gas storage, separation, and heterogeneous catalysis. The modular nature of MOFs endows them with facile tunability, and as a result, properly designed MOFs can yield ideal heterogeneous catalysts with uniform active sites through judicious choice of the building blocks. Homochiral MOFs, which can be prepared by numerous approaches (construction from achiral components by seeding with a chiral single crystal, templating with coordinating chiral co-ligands, and building from metal-connecting nodes and chiral bridging ligands), represent a unique class of materials for the economical production of optically pure compounds, whether through asymmetric catalysis or enantioselective inclusion of chiral guest molecules in their porous frameworks. As such, homochiral MOFs promise new opportunities for developing chirotechnology. This contribution provides a brief overview of recent progress in the synthesis of homochiral porous MOFs and their applications in asymmetric catalysis and chiral separations.

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Metal-Organic Frameworks as Versatile Heterogeneous Solid Catalysts for Henry Reactions

Molecules ◽

10.3390/molecules26051445 ◽

2021 ◽

Vol 26 (5) ◽

pp. 1445

Author(s):

Francisco G. Cirujano ◽

Rafael Luque ◽

Amarajothi Dhakshinamoorthy

Keyword(s):

Active Sites ◽

Heterogeneous Catalysts ◽

Final Section ◽

Metal Organic Frameworks ◽

Henry Reaction ◽

Solid Catalysts ◽

Wide Range ◽

Metal Organic ◽

Materials Used ◽

Heterogeneous Solid

Metal–organic frameworks (MOFs) have become one of the versatile solid materials used for a wide range of applications, such as gas storage, gas separation, proton conductivity, sensors and catalysis. Among these fields, one of the more well-studied areas is the use of MOFs as heterogeneous catalysts for a broad range of organic reactions. In the present review, the employment of MOFs as solid catalysts for the Henry reaction is discussed, and the available literature data from the last decade are grouped. The review is organized with a brief introduction of the importance of Henry reactions and structural properties of MOFs that are suitable for catalysis. The second part of the review discusses the use of MOFs as solid catalysts for the Henry reaction involving metal nodes as active sites, while the third section provides data utilizing basic sites (primary amine, secondary amine, amides and urea-donating sites). While commenting on the catalytic results in these two sections, the advantage of MOFs over other solid catalysts is compared in terms of activity by providing turnover number (TON) values and the structural stability of MOFs during the course of the reaction. The final section provides our views on further directions in this field.

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A Review on Metal-Organic Frameworks as Congenial Heterogeneous Catalysts for Potential Organic Transformations

Frontiers in Chemistry ◽

10.3389/fchem.2021.747615 ◽

2021 ◽

Vol 9 ◽

Author(s):

Kranthi Kumar Gangu ◽

Sreekantha B. Jonnalagadda

Keyword(s):

Active Sites ◽

Heterogeneous Catalysts ◽

Metal Organic Frameworks ◽

Value Added ◽

Biological Molecules ◽

Full Potential ◽

Organic Transformations ◽

Solid Catalysts ◽

Metal Organic ◽

Catalytic Active Sites

Metal-organic frameworks (MOFs) have emerged as versatile candidates of interest in heterogeneous catalysis. Recent research and developments with MOFs positively endorse their role as catalysts in generating invaluable organic compounds. To harness the full potential of MOFs in value-added organic transformation, a comprehensive look at how these materials are likely to involve in the catalytic processes is essential. Mainstays of MOFs such as metal nodes, linkers, encapsulation materials, and enveloped structures tend to produce capable catalytic active sites that offer solutions to reduce human efforts in developing new organic reactions. The main advantages of choosing MOFs as reusable catalysts are the flexible and robust skeleton, regular porosity, high pore volume, and accessible synthesis accompanied with cost-effectiveness. As hosts for active metals, sole MOFs, modified MOFs, and MOFs have made remarkable advances as solid catalysts. The extensive exploration of the MOFs possibly led to their fast adoption in fabricating new biological molecules such as pyridines, quinolines, quinazolinones, imines, and their derivatives. This review covers the varied MOFs and their catalytic properties in facilitating the selective formation of the product organic moieties and interprets MOF’s property responsible for their elegant performance.

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Chiral binary metal–organic frameworks for asymmetric sequential reactions

Chemical Communications ◽

10.1039/c7cc06979k ◽

2017 ◽

Vol 53 (91) ◽

pp. 12313-12316 ◽

Cited By ~ 10

Author(s):

Zijian Li ◽

Yan Liu ◽

Qingchun Xia ◽

Yong Cui

Keyword(s):

Active Sites ◽

Heterogeneous Catalysts ◽

Metal Organic Frameworks ◽

Binary Metal ◽

Metal Organic ◽

Sequential Reactions

Two chiral MOFs with precise spatial arrangements of different metallosalen active sites are efficient heterogeneous catalysts for asymmetric sequential reactions.

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Homochiral metal–organic frameworks as heterogeneous catalysts

Inorganic Chemistry Frontiers ◽

10.1039/c8qi00063h ◽

2018 ◽

Vol 5 (7) ◽

pp. 1512-1523 ◽

Cited By ~ 17

Author(s):

Andreea Gheorghe ◽

Martijn A. Tepaske ◽

Stefania Tanase

Keyword(s):

Surface Area ◽

Asymmetric Catalysis ◽

Active Sites ◽

Heterogeneous Catalysts ◽

High Surface ◽

Metal Organic Frameworks ◽

High Surface Area ◽

Metal Organic

Homochiral metal–organic frameworks (HMOFs) are attractive materials for asymmetric catalysis because they possess high surface area and uniform active sites.

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Different synthetic approaches, design and applications of metal–organic frameworks with selected organic ligands

Scientia Bruneiana ◽

10.46537/scibru.v18i2.107 ◽

2020 ◽

Vol 18 (2) ◽

pp. 40-68

Author(s):

Ubaidullah Hj Mat Yassin ◽

Malai Haniti Sheikh Abdul Hamid ◽

Zainab Ngaini ◽

Ai Ling Tan

Keyword(s):

Heterogeneous Catalysts ◽

Antibacterial Agents ◽

Metal Organic Frameworks ◽

Organic Ligands ◽

Interlocked Molecules ◽

Potential Applications ◽

Metal Organic ◽

Photoluminescent Materials ◽

Synthetic Approaches ◽

Scientific Fields

Metal-organic frameworks (MOFs) bearing a number of organic ligands of various functional groups and substituents give rise to MOFs of unique crystal structures and topologies. A number of potential applications have been considered for these materials in a wide array of scientific fields, such as in the adsorption of industrially-relevant gases, as heterogeneous catalysts for various organic reactions, as photoluminescent materials, and as antibacterial agents. This review highlights the utility of select groups of organic ligands in the assembly of main group metals, transition metals, as well as lanthanides and actinides, to generate MOFs of diverse structures in the solid state, with special attention paid on ligands bearing the carboxylate-, pyridyl-, ether-, imine (Schiff base) moieties, as well as mechanically interlocked molecules (MIMs).

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Controlled Growth of the Non-centrosymmetric Zn(3-ptz)2 and Zn(Oh)(3-ptz) Metal-organic Frameworks

10.26434/chemrxiv.7588640.v1 ◽

2019 ◽

Author(s):

javier enriquez ◽

Ignacio Chi-Duran ◽

Carolina Manquian ◽

Felipe Herrera ◽

Ruben Fritz ◽

...

Keyword(s):

Single Crystal ◽

Nonlinear Optical ◽

Metal Organic Frameworks ◽

Molar Ratio ◽

Thermal Synthesis ◽

Small Crystals ◽

Alkaline Environments ◽

Potential Applications ◽

Metal Organic ◽

Long Rod

Non-centrosymmetric single-crystal metal-organic frameworks (MOF) are promising candidates for phase-matched nonlinear optical communication, but typical hydrothermal synthesis produces small crystals with relatively low transmittance and poor phase matching. We study the effect of the metal-to-ligand molar ratio and reaction pH on the hydro-thermal synthesis of the non-centrosymmetric Zn(3-ptz)2 and Zn(OH)(3-ptz) MOFs with in-situ ligand formation. In acidic environments, we find that decreasing the amount of ligand below the stoichiometric molar ratio 1:2 also produces highly transparent single-crystal octahedrons of Zn(3-ptz)2. In alkaline environments, we obtain long rod-like Zn(OH)(3-ptz) crystals whose length exceeds previous reports by up to four orders of magnitude. Potential applications of these results in the development of MOF-based nonlinear optical devices are discussed.

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