Heterogeneous Micro and Nanoscale Composites for the Catalysis of Organic Reactions

Heterogeneous Micro and Nanoscale Composites for the Catalysis of Organic Reactions discusses the major properties and applications of heterogeneous micro and nanoscale composites, including surface coating and functionalization capability, effective physical properties, recovery and reusability, biocompatibility and biodegradability. In addition, preparation strategies and essential analytical methods for the characterization of these materials are investigated. The effects of morphology, porosity and sizes of these composites on catalytic activity are also discussed. This book is an important reference source for materials engineers and chemical engineers who are interested in heterogeneous, thin-scaled materials and catalyzed organic synthesis reactions.

In addition, this book will help researchers design novel structures and apply them in catalytic applications.

• Provides information on the preparation, characterization and applications of catalysis of organic reactions
• Outlines the major catalytic applications of heterogenous nanocomposites
• Assesses the major challenges of manufacturing heterogenous nanocomposites on an industrial scale

• Language: English
• Publisher: Elsevier Science
• Release date: Nov 10, 2021
• ISBN: 9780323852890

Book preview

9780323852890_FC

Heterogeneous Micro and Nanoscale Composites for the Catalysis of Organic Reactions

First Edition

Ali Maleki

Full Professor, Department of Chemistry, Iran University of Science and Technology, Tehran, Iran

Table of Contents

Cover image

Title page

Copyright

Contributors

Preface

1: Classification of micro and nanoscale composites

Abstract

1.1: Metallic particles

1.2: Metal oxide particles

1.3: Metal-organic frameworks

1.4: Nonmetallic materials

1.5: Hybrid materials

1.6: Natural-based materials

1.7: Porous materials

References

2: Preparation and synthetic methods

Abstract

2.1: Liquid-liquid blending

2.2: Precipitation and co-precipitation

2.3: Complexation

2.4: Gelation

2.5: Solid-solid blending

2.6: Liquid-solid blending

2.7: Impregnation

2.8: Impregnation by soaking or with an excess of the solution

References

3: Identification and analytical methods

Abstract

3.1: Structural techniques

3.2: Surface structure and topography

3.3: Optical spectroscopies

3.4: Nuclear magnetic resonance (NMR)

3.5: Electron spin resonance (ESR)

3.6: Determination of spatial distribution of elements

3.7: Energy dispersive X-ray spectroscopy (EDS, EDX)

3.8: Electron energy loss spectroscopy (EELS)

3.9: Adsorption-desorption and thermal techniques

3.10: Surface area and pore structure

References

4: Chemistry of micro and nanoscale composites

Abstract

4.1: Acidity and basicity

4.2: Heterogeneous acid and basic composite catalysts

4.3: Synergetic catalytic effect in micro and nanocomposite catalysts

References

5: Physical aspects of micro and nanoscale composites

Abstract

5.1: Surface area and porosity

5.2: Particle size and shape

5.3: Magnetism

References

6: Effectiveness of morphology and size

Abstract

6.1: Introduction

References

7: Famous catalyzed organic reactions

Abstract

7.1: Oxidation reactions

7.2: Coupling reactions

7.3: Mizoroki-Heck couplings

7.4: Reduction reaction

References

8: Separation and purification methods in various organic reactions

Abstract

References

9: Porous micro and nanoscale composites

Abstract

References

10: Recovery and reusability of catalysts in various organic reactions

Abstract

10.1: Homogeneous and heterogeneous catalysis

References

11: Natural-based micro and nanoscale composites

Abstract

References

12: Synergistic photocatalytic effect

Abstract

12.1: Introduction

12.2: Photochemical reactions

12.3: Semiconductors

12.4: History of photocatalysis

12.5: Applications

References

13: Synergistic catalytic effects by ultrasound wave irradiation

Abstract

13.1: Introduction

13.2: History of ultrasound

13.3: Sonochemistry

13.4: Sonocatalyst

13.5: Comparison of sono, conventional, and photocatalytic mechanism

13.6: Ultrasound bath

13.7: Biological effects of ultrasound

13.8: Ultrasound effects on the synthesis

13.9: Ultrasound effects on the homogeneous and heterogeneous catalytic systems

13.10: Conclusions

References

14: Industrial view of heterogeneous micro and nanocomposites

Abstract

14.1: Introduction

14.2: Composites

14.3: Based on the phase of the matrix, composites are divided into three categories

14.4: Based on the amplifier phase

14.5: Based on size

14.6: Applications of nanocomposites

References

15: Turn over number (TON) and turn over frequency (TOF) studies for heterogeneous micro and nanocomposite catalysts

Abstract

15.1: History

15.2: Experimental method for studying active sites

15.3: The challenge of counting catalysts active sites

References

16: Future perspective

Abstract

References

Index

Copyright

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Image 1

Contributors

Nasim Arvani     Department of Medicinal Chemistry, School of Pharmacy, Hamadan University of Medical Sciences, Hamadan, Iran

Amir Ata Bahmani Asl     Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University of Science and Technology, Tehran, Iran

Fereshteh Rasouli Asl     Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University of Science and Technology, Tehran, Iran

Zoleikha Hajizadeh     Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University of Science and Technology, Tehran, Iran

Fereshte Hassanzadeh-Afruzi     Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University of Science and Technology, Tehran, Iran

Maryam Kamalzare     Department of Chemistry, Faculty of Science, Imam Khomeini International University, Qazvin, Iran

Mahdi Saeidirad     Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University of Science and Technology, Tehran, Iran

Samin Sadat Sehat     Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University of Science and Technology, Tehran, Iran

Reza Taheri-Ledari     Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University of Science and Technology, Tehran, Iran

Preface

Heterogeneity has gained considerable attention in catalysis science by its ability to provide greater convenience in the separation process. It has found great importance in organic reactions because, typically, there are complex work-up procedures for catalyst separation and further purification of the synthesized product. Today, various types of heterogeneous micro and nanoscale composites have been designed and are suggested for efficient organic reaction catalysis. Thus far, different species, such as metal oxides, natural-based materials, clay-based porous structures, polymeric composites, and hybrid systems, have been used for this purpose. Based on practical experiences gained in the laboratory, the impressive properties of micro and nanoscale catalytic systems applied in the organic reactions have been reviewed by experienced members in the following 16 chapters. Initially, a logical classification for micro and nanoscale composites is submitted based on the nature of the components. Subsequently, preparation and identification methods, and chemistry of the aforementioned systems, are discussed in detail. Furthermore, physical properties including size, shape, composition states, and their related effectiveness are discussed. Next, the role of these materials in the catalysis of notable organic reactions, such as reduction and oxidation reactions, is investigated. Later, separation methods and potential synergies with different stimuli, such as ultrasound and light waves, are discussed. Also, industrial achievements in the application of heterogeneous micro and nanoscale composites are reviewed. Finally, future perspectives of these types of catalytic systems and possible progresses in the field are reviewed.

In this text, our experienced PhD-graduated authors, with seniority of Dr. Reza Taheri-Ledari and accompaniment of our young experts, provide a beneficial collaboration by passing their knowledge to everyone interested in these micro and nano-sized heterogeneous catalytic systems.

All the best, Unlabelled Image

1: Classification of micro and nanoscale composites

Reza Taheri-Ledari    Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University of Science and Technology, Tehran, Iran

Abstract

The composition of tiny-sized materials was noticed by researchers in recent decades, because they exhibited impressive properties due to the effective arrangement of the involved ingredients. Various types of synergistic effects in different fields of science were obtained through the composition of micro and nanoscale materials. In this chapter, we submit a logical classification for micro and nanoscale catalytic systems based on their nature and structure. So far, various species of tiny-sized particles have been designed and suitably applied in chemical reactions as catalysts, which is one of the most interesting fields, especially in the industrial sciences.

Keywords

Easy separation; Green catalyst; Nanocatalyst; Metallic particles; Magnetic systems

Catalysis as a suitable strategy for facilitating chemical reactions was introduced for the first time by Jöns Jakob Berzelius in 1835 [1]. This word originates from two Greek words: "kata meaning down and lyein" meaning loosen. At the beginning of the 19th century, experimental investigations on catalytic processes revealed that small amounts of a foreign agent could be effective on the procress of chemical reactions [2]. In 1896, Henri Moissan (1906 Chemistry Nobel Prize winner) and Moureu performed the reduction reaction of acetylene by subjection of a current of acetylene on metals under a hydrogen atmosphere [3]. In 1910, Sabatier and Mailhe used metal oxides for hydration and dehydration [4, 5]. Generally, catalytic systems are divided into two main families: (1) homogeneous systems in which both catalyst and reactants are in the same phase (solution), and (2) heterogeneous systems in which the catalyst and reactants are in different physical states of the materials. Based on the nature of the homogeneous catalysts, they are classified as acid-catalyst, organometallic systems, organocatalyst, and mixed organic-metallorganic catalysts. The first species of the homogeneous catalytic systems was introduced by Jack Halpern and his colleagues in 1961, where a ruthenium complex was effectively applied for the hydrogenation of olefins [6]. Although the catalytic performance of the homogeneous systems seemed to be higher that the heterogeneous analogues due to the creation of more contacts and stronger interactions in the same physical state, the heterogeneity has been preferred in the way of catalysis evolution. This is considered an important advantage for the heterogeneous catalytic systems as they are more easily separated from the reaction mixture than their homogeneous analogues. The use of heterogeneous catalytic systems dates back to 1800, when Faraday investigated the catalytic ability of platinum for facilitating oxidation reactions [7]. It was a turning point from the world of the homogeneous catalytic systems to the heterogeneous analogues. After that, numerous novel systems were designed showing greater and faster development of the heterogeneous catalysts in chemistry science. In this regard, so many aspects of these types of materials have been precisely investigated to increase the catalytic efficiency of heterogeneous materials as well as homogeneous systems. From a well-known viewpoint, the heterogeneous catalytic systems are classified as acid- and alkaline-based systems. Acid-based systems are those that can perform their catalytic role by accepting the electron density, and as a result positive-charged centers are created in the chemical structure of the reactants. This class of heterogeneous catalytic systems are subdivided into ion-exchange resin, metal-based, and carbon-based systems. In contrast, alkaline-based catalytic systems are those that transfer electron density to the reactants by their catalytic sites and make positive changes in the organic structures, through which the structures are more prone to perform the chemical reactions. The alkaline-based family also includes metal oxides, carbon group-based, boron group-based, and waste material-based catalytic systems [8].

However, as the most effective strategy for increasing the catalytic performance of the heterogeneous materials, increasing the surface area by significantly reducing the total size of the system has been developed in recent decades. Obviously, proportional to decreasing the size of the heterogeneous particles, the surface area is expanded and, as a result, the effectiveness of the catalytic system is highly increased. This is the main reason researchers have been switching from macro to micro and nanoscale materials in the last couple of decades. Totally, there are two principal routes for preparation of micro and nanoscale materials: the first one, known as the top-down method, expresses grinding the bulk materials into tiny-sized powder via some hitting methods like ball milling.a The second one is the bottom-top method in which tiny-sized heterogeneous materials are formed from fundamental ingredients like ions. For example, some metallic ions could form nanoparticles (NPs) via a co-depositionb method [9]. However, due to the wide surface area, micro and in particular nanoscale heterogeneous materials demonstrated great catalytic efficiency in which they were gradually considered as an appropriate alternative for the homogeneous systems. The first and foremost benefit of heterogeneous catalysts is easier separation and purification processes after completion of the desired catalyzed reaction, whereas so many complex procedures for the separation of the homogeneous analogues are required. In some cases, noticeable amounts of both desired product and the applied catalyst are wasted during the purification process of the homogeneous catalytic systems. This effort is performed with more ease in the case of the heterogeneous catalytic systems that include magnetic property [10–17]. This advantage of the heterogeneous catalysts is separately discussed in more depth in future chapters of this book. In this chapter, we intend to make a logical classification for micro and nanoscale materials that have been used as efficient catalytic systems in different organic reactions. This classification is done based on the structural subunits of the materials, as discussed in the following sections.

1.1: Metallic particles

1.1.1: Palladium particles

One of the well-known catalytic systems in both homogeneous and heterogeneous types is based on palladium, and its catalytic role in organic reactions has been clearly elucidated. For someone who worked on C glyph_sbnd C coupling reactions, the Heck and Suzuki approaches are two substantial approaches in organic synthesis that can be considered for palladium [18–21]. Due to the expensiveness of palladium-based materials, using the heterogeneous analogues is preferred because it can be recycled and reused several additional times if the catalytic system is structurally stable enough. Moreover, the wasting is significantly prevented while using heterogeneous systems. Due to the afore-mentioned reasons, palladium NPs were developed as efficient catalytic systems with high heterogeneity with the same function as the homogeneous inorganic complexes [22–24]. In 2000, an effective chemical state of palladium element in C glyph_sbnd C coupling reactions was severely challenged. It was believed that palladium element in chemical state zero (Pd⁰) plays a key role for the activation of a C glyph_sbnd X bond in aryl halides. So, triphenylphosphine was used for the conversion of Pd² + ion to Pd⁰. But significant examples of the catalytic role of palladium in chemical state 2 + were reported by Jeffery [25, 26]. Jeffery exhibited that Pd(OAc)2 could be used as an efficient catalytic system in the presence of a phase-transfer agent like nBu4N+ Cl−. In the same year, Reetz and Westermann introduced Pd NPs as the first colloidal version of Pd-based catalytic systems, which showed high efficiency of intermediary palladium NPs in C glyph_sbnd C coupling reactions [27]. A substantial sample of Pd NPs was designed and introduced by Mastalir and Király in 2003 [28]. They made a dispersion of Pd NPs (with a mean size of 4 nm) onto the outer surface of hydrotalcite (a type of talc family) that was stable enough to be used as a catalytic system. They monitored the catalytic activity of their product in a semihydrogenation reaction of the alkynes. Mastalir and Király chose hydrotalcite for stabilization of the Pd NPs due to its special lamellar structure, which provides great capability for an anion-exchange process. As was expected for Pd metal, their designed catalytic system demonstrated great selectivity in the semihydrogenation of the acetylenes and also for the transformation of nonterminal alkynes to cis-alkenes. Four years later, Ananikov and co-workers produced a one-dimensional (1D) structure of Pd NPs in coordination with the organic ligands with a special shape called a nanobelt [29]. The intertwining of the Pd nanobelts with 40–80 nm thickness, as illustrated in Fig. 1A, provides a 3D network including numerous voids that are appropriate substrates for catalytic applications. They announced the nanosized organization as the key factor for high catalytic activity of the Pd nanobelts in selective addition of thiol derivatives (RSH) to the alkynes. Another structure based on Pd NPs and a binary metallic system consisting of gold (Au) and Pd NPs was suggested by Hou et al. in 2008, which was utilized in oxidation reactions of alcohols [30]. In their effort, the stabilization of the metal ions and conversion to the heterogeneous NPs was performed by poly(N-vinylpyrrolidone) (PVP). They found that making a bimetallic mixture of Au:Pd with a ratio of 1:3 showed the highest catalytic efficiency in comparison with single-metal systems. As discussed before, in the bottom-top method, the metallic ions need to be stabilized from the energy levels’ viewpoint to form the heterogeneous particles. In Hou's report, PVP was used for this aim. In addition, it was revealed that the PVP effectively inhibits the aggregation of the Au and Pd NPs during the catalytic process. Actually, the particle aggregation (sometimes called agglomeration or accumulation) is a negative phenomenon in catalysis science because the main purpose of using micro and nanoscale materials is to increase the surface area, whereas particle aggregation blocks the surfaces and reduces the active areas onto the surfaces of the particles. Fig. 1B and C respectively illustrate transmission-electron microscopy (TEM) images of the produced Pd NPs and the binary Au:Pd (1:3) metallic system by Hou's group. In the TEM images, dark spots show the formed heterogeneous metallic particles. In 2009, Sarkar and co-workers reported a preparation method for controlling the size of Pd NPs [31]. They fabricated Pd NPs in different sizes via reduction of Pd(II) ions and stabilization by polyethylene glycol (PEG). They controlled the size of the Pd NPs during the preparation process by using various concentrations of PEG in an aqueous environment. Sarkar's group found that there is an inverse relationship between the concentrations of the solved PEG and the size of the Pd particles. Fig. 1D and E clearly exhibit the key role of the PEG concentration in size controlling of the Pd particle. Sarkar and co-workers also demonstrated high catalytic efficiency of the fabricated Pd NPs in Suzuki-Miyaura coupling reactions. Years later, an environmentally benign approach for stabilization of the Pd ions and conversion to its nanoscale heterogeneous analogue was reported by Nasrollahzadeh's research band [32]. They used Salvia hydrangea plant for reducing the Pd(II) ions and apricot kernel as an environmentally benign support for Pd NPs. Briefly, Salvia hydrangea plant extract includes a catechol group in its chemical structure. The hydroxyl groups are oxidized to carbonyl during the reduction process of the Pd(II) ions. The Pd NPs formed onto the apricot kernel substrate are shown in the scanning-electron microscopy (SEM) image (Fig. 1F) as brilliant spheres. Nasrollahzadeh's research band used the fabricated Pd NPs (in the mean size 65 nm) for the catalytic reduction of organic dyes. Moreover, numerous other species of the micro and nanoscale systems have also been reported by researchers, in which Pd NPs are combined with other organic and inorganic materials. The main reason of hybridization of the materials is to add more distinguished properties to the catalytic systems. Although the main catalytic site is the metallic particles (here Pd), other agents could be added to the systems that include distinguished physical, mechanical, and chemical features. These types of catalytic systems will be comprehensively discussed in a later Section 1.5.

Fig. 1

Fig. 1 (A) Scanning-electron microscopy (SEM) image of Pd nanobelts [29]; transmission-electron microscopy (TEM) images of (B) the PVP-stabilized Pd NPs as a single-metal system; (C) the binary metallic system Au:Pd (1:3) [30]; (D) PEG-stabilized Pd NPs with Pd/PEG molar ratio 1:5 and (E) molar ratio 1:1 [31]; and SEM image of apricot kernel-stabilized Pd NPs, reduced by Salvia hydrangea plant extract [32].

1.1.2: Silver particles

Another efficient metallic catalytic system, silver (Ag) NPs have been widely discussed over the years [33]. Here again, reduction of the cationic Ag ions is needed for stabilization and conversion to the solid surfaces. Practically, Ag NPs are more easily synthesized compared with Pd NPs. One of the main reasons can be the chemical state of the cationic ions, where Pd(II) needs two steps of the reduction process and Ag(I) required just one step. Also, the nature of the metals can be effective in the preparation stage. The energy levels of the atomic orbitals in the metal ions is a determinative factor for convenient reduction and stabilization. This essential reduction process can be performed by various methods. For example, in 2001 Dong's research group introduced an electrochemical approach for reduction of Ag(I) ions on the carbon substrates [34]. In their suggested method, 4-aminophenyl-grafted pyrolytic graphite electrode surfaces were used for stabilization of the Ag(I) ions. The Ag(I) ions are attached to the electrode via effective coordination interactions with the amine groups and then reduced to Ag heterogeneous NPs via pulsed potentiostatic reduction. As discussed in the previous section, bimetallic catalytic systems could also be constructed and used for different purposes. In this case, a binary metallic system made of Ag and Pd NPs has been reported by Kunitake and co-workers, in 2003 [35]. They applied a stepwise ion-exchange/reduction approach in which the active sites for reduction of the metal ions are created on a thin TiO2-gel film. In this method, another ion (like Mg² +) is used as a template, then the primary ions are incorporated and replaced via ion exchange approach, under H2 plasma. Kunitake and co-workers observed great catalytic efficiency for the bimetallic Ag/Pd catalytic system in the hydrogenation reaction of methyl acrylate. It was observed that the catalytic activity of the Ag/Pd system was 367 and 1.6 times higher than the commercial Pd black and the single-metal system of Pd NPs, respectively. As the main reason for such fantastic synergy in the catalytic activity, giving a wider surface area by the formed Ag(core)/Pd(shell) has been mentioned. In fact, it was observed in the electron microscopy (EM) images that the tiny-sized Pd NPs are regularly distributed onto the surface of the Ag NPs. This special arrangement in the bimetallic catalytic system provides an extreme surface area, and as a result the catalytic performance is significantly increased. In an account published in 2005, it was reported that the Ag NPs with an average size of 5 nm are synthesized in the alcoholic solution of silane [36]. Reportedly, the electronic interactions between the Ag cations and the amine groups of the amino propylsilane (APS) leads to good stabilization and also prevents the irregular growth of Ag NPs. Elsewhere, Ag NPs with the mean size ca. 20 nm were produced via stabilization into the PEG matrix and reduction by H2 bubbles, as reported in 2006 by Yan et al. [37]. Then, the produced Ag NPs were used as an efficient catalytic system for three-component synthetic reactions. From the EM images, it has been disclosed that more uniform and monodispersed NPs generally result by using a polymeric substrate. Another well-known biological macromolecule that has been widely used for the stabilization of metallic cations is chitosan. There are a couple of distinguished advantages for using chitosan to stabilize the metallic ions: (1) great abundance in nature, especially in marine invertebrates, insects, fungi, and yeasts, and (2) the existence of the free amino and hydroxyl groups that provide appropriate physicochemical interactions for chelating with the cationic metals [38]. Another approach for the conversion of the Ag(I) ion into Ag NPs was introduced and applied by Begum and co-workers in 2010 [39]. In an attempt to find natural, environmentally benign, green chemical agents for