Design and Fabrication of Porous Nanostructures and Their Applications

CHAPTER 8

Design and Fabrication of Porous Nanostructures and Their Applications Arpita Hazra Chowdhury1,#, Noor Salam1,#, Rinku Debnath2,#, Sk. Manirul Islam1,* and Tanima Saha2,* 1 Department of Chemistry, University of Kalyani, Kalyani, India Department of Molecular Biology & Biotechnology, University of Kalyani, Kalyani, India

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Contents 8.1 Introduction 8.2 Classification of Porous Nanostructures 8.3 Synthesis of Porous Materials 8.3.1 Synthesis of Microporous Materials 8.3.2 Synthesis of Mesoporous Materials 8.3.3 Synthesis of Macroporous Materials 8.3.4 Synthesis of Purely Organic Porous Materials 8.3.5 Synthesis of Inorganic Nanoporous Materials 8.3.6 Synthesis of Organic
Inorganic Hybrid Polymeric Material 8.4 New Synthesis Approaches and Challenges of Porous Nanostructures 8.5 Applications of Porous Materials 8.5.1 Biomedical Use 8.5.2 Catalysis 8.5.3 Sensors and Supercapacitors 8.5.4 Adsorption, Separation, and Catalytic Conversion of CO2 8.5.5 Food Industry 8.5.6 Water Treatment 8.5.7 Gas Separation, Purification, and Storage 8.5.8 Photocatalyst 8.5.9 Agriculture 8.6 Conclusion References

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These authors contributed equally. Corresponding author.

Nanomaterials Synthesis DOI: https://doi.org/10.1016/B978-0-12-815751-0.00008-0

© 2019 Elsevier Inc. All rights reserved.

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8.1 INTRODUCTION Nowadays, porous materials with high surface area have attracted considerable attention from researchers in every field as they have the ability to interact with molecules, ions, and atoms at the external surface, as well as within the interior surface of the material. Porosity can be viewed as a thoughtful concept which helps us to understand nature and generate advanced structures. There are various interesting examples of porous structures present in nature, for example, honeycomb with hexagonal cells, hollow bamboo, and alveoli in the lungs. The design and fabrication of porous architectures have long been an important research topic. Porous polymers have various important structural characteristics which should be described, including pore size, pore geometry, pore surface functionality, and polymeric framework structure, topology, and functionality (Fig. 8.1) [1]. Porous materials have a high surface area and well-defined porosity, which are advantageous for different applications [2,3]. Porous polymers have easy processability. For example, they can be prepared in a molded monolithic form [4] or in thin films [5], which are advantageous for many applications. On the other hand, the past decade has provided substantial advances in the synthesis of new porous metal oxides, metal sulfides, metal phosphates, etc., with ordered structures, which are potentially applicable in a wide range of applications. Porous materials can be used in different fields, such as separation materials [6],

Figure 8.1 Illustration of pore size, pore surface, pore geometry, and framework structure of porous polymers.

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Classification of nanoporous materials

Depending upon pore size

Depending upon framework building blocks

Microporous materials Mesoporous materials Macroporous materials Pore diameter > 50 nm Pore diameter < 2 nm Pore diameter 2–50 nm e.g., sponge, cotton, e.g., zeolites, metal e.g., MCM-41, SBA-15, organic framework maximum reported porous recently reported some (MOF), etc. silica and metal oxides, etc. metal oxides, etc.

Purely inorganic Organic–inorganic hybrid e.g., pure silica, metal e.g., periodic mesoporous silica (PMO), organosilica, doped silica, metal metal oxophenylphosphate, oxide, mixed oxide, MOF metal phosphate

Purely organic e.g., organic porous polymer, porous carbon

Figure 8.2 Flowchart of classification of nanoporous materials.

gas storage, as encapsulation agents for controlled release of drugs [7], sensors [8], as catalysts [9,10], as supports for catalysts [11] and as precursors of nanostructured carbon materials [12], and as supports for biomolecular immobilization. These high-value applications attract researchers in the development of facile methods for preparation of porous nanomaterials, with well-designed pore architectures in addition to the customized framework as well as pore surface functionalities.

8.2 CLASSIFICATION OF POROUS NANOSTRUCTURES Porous material can be divided into three categories, depending on their porosity and the framework of their building blocks (Fig. 8.2).

8.3 SYNTHESIS OF POROUS MATERIALS 8.3.1 Synthesis of Microporous Materials Microporous materials (Fig. 8.3) can be defined as solids, containing interconnected pores of less than 2 nm in size. Thus, they possess large surface areas, typically 300
2000 m2/g as measured by gas adsorption [13].

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Figure 8.3 Structure of microporous material.

Example include zeolites, AlPO4, metal organic frameworks (MOFs), clays, carbon, etc. Zeolites are the most well-known group of microporous materials. Zeolites are the aluminosilicates commonly known as “molecular sieves.” A zeolite framework is a neutral compound, comprising exclusively oxygen-sharing SiO442 tetrahedra. Although there are natural zeolites, most of the zeolites known are synthetic. Barrer first synthesized zeolite Y in the mid-1950s. It was an attempt to imitate the conditions under which natural zeolites were supposed to have formed on the Earth [14,15]. Zeolites are prepared in the laboratory by crystallization of gels containing alumina and silica in an aqueous medium at temperatures in the range of 100°C
190°C for several days or weeks [16]. The gel can be prepared from other sources of Al, Si, and some other metals other than silica and alumina. Deville first reported the laboratory-synthesized zeolite levyne (levynite) Ca9 [Al18Si36O108], H2O in 1862 [17]. The synthetic process required heating potassium silicate and sodium aluminate in a glass ampule. Since 1950, a wide range of zeolites has been synthesized by simple isomorphous substitution of not only aluminum but also several other elements due to their excellent properties and larger pores than their counterparts. For example, the family of ZSM such as ZSM-5 [18], ZSM-12 [19] ZSM-22 [20], ZSM-23 [21], and ZSM-48 [22] have been obtained by using various templates. A germanosilicate zeolite [23] (ITQ-15) was first reported in the patent literature, which has a large pore volume with a channel system formed by 14 X12R pores [24] and has been assigned as zeotype UTL.

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8.3.2 Synthesis of Mesoporous Materials The mesoporous materials (Fig. 8.4) can be defined as the materials with monodispersed mesosized (2
50 nm) pore space, arranged in a longrange ordered array. Examples include MgO, SiO2, TiO2, ZnO, SnO2, TiPO4, AlPO4, carbon nanotubes, etc. Mesoporous materials have many attractive properties such as high surface areas, periodically arranged mesopore space, tunable pore sizes, alternative pore shapes, and large open active sites. Due to these properties, mesoporous materials are of high interest in technological applications in diverse fields such as catalysis, adsorption, drug delivery, and so on. In the 20th century materials like MCM (Mobil Composition of Matter) [25] were successfully synthesized by Mobil scientists. The discovery of an M41S family of ordered mesoporous materials with pore dimensions of 2
10 nm using quaternary alkyl ammonium surfactants (e.g., cetyltrimethylammonium bromide, CTAB) as the template is one of the most important discoveries in the history of the porous world. It suggested the huge expectations toward their applications as heterogeneous catalysts [26,27]. Mesoporous silica for example, MCM-41, MCM-48, MCM-50, FSM-16 [28], SBA-15 [29], etc. are well-known among the ordered mesoporous materials discovered initially. Although there are some differences in the synthesis conditions and structural properties of these silicas, the basic strategy for the synthesis of the materials is similar in all cases, which is based on the supramolecular self-assembly of the surfactants (or templates) [30]. Fig. 8.5 depicts a typical synthetic pathway for the formation of highly ordered 2D hexagonal mesoporous silica MCM-41 mediated by the surfactant. The structure and pore size of the silica can be modified from

Figure 8.4 Different types of 3D structures of mesoporous materials.

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Figure 8.5 Surfactant-assisted synthesis of mesoporous silica with 2D ordered hexagonal pore arrangement.

hexagonal (e.g., MCM-41), cubic (e.g., MCM-48), to lamellar (e.g., MCM-50) by varying the type of surfactant used, the surfactant
silica ratio, and the pH of the solution. Mesoporous SBA-15-type materials are another family of silica materials. They can be synthesized in the highly acidic conditions in the presence of nonionic block copolymer surfactants [29]. In addition to the cooperative pathways, nanocasting using already formed ordered mesoporous materials as hard templates has been developed to synthesize mesoporous materials [31]. This method of nanocasting is highly effective for the synthesis of other nonsiliceous porous oxide and carbon materials with ordered pore arrangements which are difficult to prepare directly by the surfactant-assisted route [32]. Nonsiliceous mesoporous materials like oxides, mixed oxides [33], metal sulfides [34], metal phosphates [35], polymers [36], carbons [37], and carbon nitrides [38] have also been synthesized successfully using surfactant templating routes. Mesoporous materials can also be synthesized without using any organic templates. Hydrothermal synthesis is one of the commonly used methods to form mesoporous materials with unique morphologies. For example, Chowdhury et al. synthesized mesoporous magnesia (MgO) with a grainy rod-like microstructure by the simple hydrothermal process at 180°C/5 h in the presence of urea, where urea has a significant role in the formation of the grainy rod with porous structure [39]. Organic surfactant molecules play an important role in generating porosity in the mesoporous material blocks and act as templates or

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structure-directing agents (SDA). This soft templating method is the most successful path for the synthesis of ordered and disordered mesoporous matrices. 8.3.2.1 Role of Template in the Formation of Porosity Template means pattern or overlay used in graphic arts (drawing, painting, etc.). In nanoporous systems template molecules help to create or design porosity in the matrix. Therefore, a template acts as a SDA in the formation of porous materials [40]. There are several kinds of SDAs. (1) Surfactants can be used as SDAs. SDA should have coexistence of a chemically bonded hydrophobic (nonpolar) hydrocarbon “tail” and a hydrophilic (polar) “head” group. These molecules possess high molecular weight and they aggregate in the solvent to form a self-assembled micelle [41,42]. (2) Some SDAs bear hydrophobic
hydrophilic groups in a single molecule. They are not surfactants but they play the role of the template in fabricating mesopores in a material. These templates may or may not form self-assembly [43]. (3) Another type of SDA is a dendrimer or polymer. They can be the macromolecular single molecule which has high molecular weight [44]. On the other hand, porous silica or colloidal silica spheres, polystyrene, etc., act as hard templates that are also used to generate porosity within the matrix [45]. The soft template SDAs can be classified as follows shown in Fig. 8.6. Template or structure directing agents

Depending upon the charge

Depending upon functionality

Cationic

Anionic

e.g., CTAB, CPC, etc.

Surfactants Large molecule, high molecular wt, form micelle, e.g., CTAB, SDS, etc.

Nonionic

e.g., SDS, lauric acid, etc.

e.g., P123, F127, etc.

Nonsurfactants

Single molecule template, no selfassembly e.g., TPA, etc.

Small molecule, low molecular wt, selfassembly, e.g., urea, sodium saliculate, etc.

Figure 8.6 Flowchart of classification of templates.

Single macromolecule template, high molecular wt, do not form micelle, e.g., dendrimers.

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Figure 8.7 A general route for the formation of a mesoporous solid [47].

8.3.2.2 Role of Surfactants as Structure-Directing Agents Surfactants possess both hydrophobic and hydrophilic groups in the molecules, which can behave specifically in polar and nonpolar solvents. These molecules form aggregates where the hydrophobic parts are oriented within the cluster and the hydrophilic parts are exposed to the solvent [46]. Such kinds of aggregates are called micelles. As the surface becomes crowded with the surfactant, more molecules will arrange into micelles. Significantly, the surface becomes completely loaded with surfactant molecules at a certain concentration and any further additions must arrange as micelles. This certain concentration is known as the critical micelle concentration (CMC). Beyond the CMC value with further increasing concentration, the self-assembly of the micelle occurs to generate a 3D spherical or 2D rod-like array, and this self-assembly helps in the pore generation. These SDA molecules act as the “placeholder,” which becomes the void space to create nanoporous material. They not only control the variation in pore size but also the shape of the pores. Therefore, the total structural design of the template molecule, its size, and shape are stamped in the porous solid (Fig. 8.7). Mesoporous materials can be classified into three categories: purely inorganic, organic
inorganic hybrid materials, and completely organic, as summarized in Table 8.1.

8.3.3 Synthesis of Macroporous Materials Macroporous materials have a pore diameter greater than 50 nm, which is the largest pore dimensions in the family of porous materials [48]. The most facile and extensively used route to prepare macroporous materials is the colloidal templating route. Macroporous metal oxides such as silica, titania, and zirconia and polymers like polyacrylamide and polyurethane with well-defined pore sizes in the submicrometer regimen have been

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Table 8.1 Possible types of mesoporous materials with examples Framework Type of materials Examples composition

Purely inorganic

Mesoporous silicas Metal-containing mesoporous silicas Mesoporous metal oxides and mixed metal oxides Mesoporous metallophosphates

Organic
inorganic hybrid

Periodic mesoporous organosilicas (PMOs) Metal oxophenylphosphates

Purely organic

Mesoporous carbons Mesoporous polymers

MCM-41/MCM-48, SBA15, etc. Ti-MCM-41, Zn-silica, etc. TiO2, AlO2, ZrO2, ZnTiO3, etc. Silicotitanium phosphate, silicoalumino phosphate, etc. Various metal-containing PMOs, etc. Iron phosphonate, chromium phosphonate, etc. CMK-3 Triazine-based polymer, triallylamine-based polymer

successfully synthesized by employing the self-assembled templates of colloidal spheres [49,50].

8.3.4 Synthesis of Purely Organic Porous Materials High surface area porous organic polymers have been attracting increasing interest over the years [51
54]. Designing chemical reactions that will facilitate the creation of pores of desired dimensions in the mesoporous organic materials is a challenging task to researchers. Such a goal can be achieved by covalent organic frameworks (COFs) because COFs are porous crystalline materials with predesigned 2D and 3D polymer structures produced by covalently linked functionalities [55,56]. There are a few reports on the soft templating strategy for the synthesis of ordered mesoporous polymers [57
59]. The choice of polymer precursor is the key to the successful organization of organic
organic mesostructures. The key conditions for the formation of polymer, which have to be fulfilled are (1) dissolution of the material in the same medium as the surfactants, (2) interaction with the template molecules, (3) organizing

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itself precisely around the template, (4) further polymerization, without losing the interaction with the template, and (5) lastly the removal of template without destroying the polymer mesostructure. Mesoporous polymers were mainly synthesized by a hard-templating method before the generation of the soft-templating approach. In this approach, a monomer is infiltrated into a hard template (e.g., an opal-like colloidal assembly of silica), which is removed after polymerization to give mesoporous polymer networks [60]. The most used method for the preparation of mesoporous polymers is the EISA (evaporation-induced self-assembly) method, usually using ethanol as solvent. On the other hand, the same kind of materials can also be prepared by a liquid crystal templating or cooperative assembling method [61].

8.3.5 Synthesis of Inorganic Nanoporous Materials Syntheses of inorganic nanoporous materials are illustrated below. 8.3.5.1 Silica-Based Mesoporous Materials Since the discovery of the M41S family of mesoporous silicas, extensive work has been on going over silica-based mesoporous materials due to their several advantages, such as a great variety of possible structures, enhanced thermal stability, as well as for the applications in various promising fields. Mesoporous silica and silica-based materials are usually prepared via the endotemplate method under hydrothermal conditions using acidic or basic media. The hydrothermal condition is actually a sol
gel process with a number of steps. The steps are: (1) formation of surfactant self-assembly to form a homogeneous surfactant solution in common solvent media (usually aqueous), (2) addition of silicate precursor, such as tetraethyl or tetramethyl orthosilicate or inorganic sodium silicate to the surfactant solution, (3) formation of silicate oligomer sol, (4) condensation of oligomers with surfactant micelle via cooperative assembly and aggregation to form an inorganic
organic hybrid, which finally precipitates in the form of a gel, and (5) hydrothermal treatment of the gel for further condensation, solidification, and reorganization of the material to an ordered arrangement [62,63]. Finally, the resultant product is cooled, filtered, washed, and dried (Fig. 8.8). Calcination or solvent extraction of the assynthesized solid leads to the formation of ordered mesostructured silica material [64,65]. This is the most well-known and convenient method of silica synthesis. Generally, CTAB and SDS are used as surfactants [66] for

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Figure 8.8 Stepwise formation of mesoporous silica material [64].

the synthesis. Mesoporous MCM-41, MCM-48 [67], etc., and different transition as well as nontransition metal-doped silica [68] are synthesized using this strategy. 8.3.5.2 Nonsilica-Based Mesoporous Materials Since 1993, the surfactant templating strategy has been commenced for the synthesis of nonsilica-based mesostructure, mainly metal oxides [69]. Nonsiliceous mesostructured materials like phosphate, sulfide materials, as well as mesoporous metals are also well developed [70,71]. Various mesoporous metal oxides of Nb, Ta, V, W, Zr, Sn, Cu, Ni, Hf, Al, Zn, Mg, etc. have been synthesized after the first successful approach toward the synthesis of mesostructured titania [72]. In the soft-templating route, mesoporous oxide materials are generally synthesized in the hydrothermal method [73], at low temperature (freezing) [74] or at room temperature [75]. In all the methods, the inorganic metal precursor forms a hydroxo species and electrostatically interacts with template molecules to form a metal
template composite in aqueous sol
gel process [76]. In the end, we get the desired solid porous metal oxide after removal of the template by calcination or solvent-extraction method. Recently, Chowdhury et al. synthesized mesoporous sheetlike MgO by a simple ammonia precipitation method maintaining the NH4OH to Mg mole ratio at 6:1, followed by calcination at 450°C [10]. Chowdhury

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et al. synthesized cube-shaped mesoporous anatase TiO2 by a simple hydrothermal technique at 180°C for 24 h in the presence of glucose followed by calcination at 600°C for 2 h. In this method, the dehydrated species of glucose was adsorbed on some specific facets of TiO2 particles and induced cube-shaped morphology to the sample [77]. Recently, Wang et al. reviewed recent advances in ordered meso/macroporous metal oxides and their applications in heterogeneous catalysis supplying clear information about the synthesis and modifications of the morphology and surface chemistry of metal oxides to get an ordered meso/macroporous structure [78] (Fig. 8.9).

Figure 8.9 (A) Stabilized highly reactive metal precursor for metal oxide synthesis and (B) interaction of metal-surfactant to form a mesostructure.

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8.3.6 Synthesis of Organic
Inorganic Hybrid Polymeric Material Organic
inorganic hybrid polymers are the combination of both organic and inorganic units. Organic functionalization of the inorganic nanoporous materials tunes the surface properties (e.g., hydrophobicity, hydrophilicity, binding to guest molecules), alters the surface reactivity, along with modifying bulk properties as well as stabilizing the materials toward hydrolysis [79]. Stein et al. reported the generalized method of preparing organic
inorganic hybrid mesoporous silicates with uniform channel structures bearing both reactive and passive organic groups in the porous solids by grafting methods or by cocondensation under surfactant control [80]. Organic
inorganic hybrid materials involve mainly the silica-based materials, though there are some reports on microporous MOFs, hybrid phosphates, phosphonates, and polymers. Few organic
inorganic hybrid mesoporous aluminophosphates have been synthesized via surfactant templating route [81]. Ghosh et al. prepared porous iron-phosphonate nanoparticles HPFP-1(NP) through a hydrothermal method via simple chemical reaction between hexamethylenediamine-N,N,N0 ,N0 -tetrakis(methylphosphonic acid) and FeCl3 (Fig. 8.10) [9]. Organic
inorganic hybrid polymers can be prepared through: (1) sol
gel process; (2) self-assembly process; (3) assembling or dispersion of nanobuilding blocks; and (4) hierarchical structures [79] and interpenetrating networks [82]. Depending upon the supramolecular templating mechanism, organic functionalized silica molecules can be prepared by three routes as shown in Fig. 8.11.

Figure 8.10 Synthetic pathway for the preparation of HPFP-1(NP) nanomaterial [9].

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Figure 8.11 Different methods for the synthesis of organic
inorganic hybrid mesoporous silica: (1) grafting, (2) cocondensation or in situ grafting, and (3) organic bridged periodic mesoporous silica.

8.4 NEW SYNTHESIS APPROACHES AND CHALLENGES OF POROUS NANOSTRUCTURES The most efficient method to synthesize porous nanostructures is the softtemplating method. In this method, generally surfactants or amphiphilic block copolymers act as a template, and are used to coassemble with organic (or inorganic) framework precursors [83]. In the past two decades, commercially available soft templates including surfactants (e.g., CTAB) and amphiphilic block copolymers (e.g., poly(ethylene oxide)-b-poly (propylene oxide)-b-poly-(ethylene oxide), PEO-b-PPO-b-PEO, such as Pluronic P123 and F127) have been intensively used to synthesize porous nanostructures with variable morphologies. The major challenge of this soft-templating approach is limited accessibility of the commercially available soft templates, which causes small pore size and amorphous (or semicrystalline) frameworks of the common porous nanostructures. It limits

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Figure 8.12 Synthetic scheme of porous metal oxide (Al2O3, MgO) layers [88].

their applications in many fields. In recent days, tailormade amphiphilic block copolymers have emerged as suitable alternative soft templates for the synthesis of new porous nanostructures with controllable molecular weights and compositions. These nanostructures have exhibited many unique features like adjustable mesostructures and framework compositions [84,85], ultra-large pores, thick pore walls, high thermal stability, and crystalline frameworks. Highly ordered mesoporous carbon has been synthesized by the selfassembly of resol (a low-molecular-weight phenol-formaldehyde resin) and commercial Pluronic block copolymers through the EISA process [86,87]. However, the pore size is below 5.0 nm. Recently, Chen et al. reported a new synthetic approach (Fig. 8.12) to prepare mesoporous Al2O3 and MgO layers with high specific surface areas up to 558 m2/g on silicon wafer substrates [88]. They have used poly(dimethylacrylamide) hydrogels as porogenic matrices. They followed the following synthetic process: (1) anchoring adhesion promoter on the Si wafer substrate, (2) spreading the polymer through spin-coating, (3) preparation of hydrogel films by photo-crosslinking and anchoring to the substrate surface, (4) swelling the hydrogels in the respective metal nitrate solutions, and (5) combustion of the hydrogel and formation of porous metal oxides by subsequent thermal conversion.

8.5 APPLICATIONS OF POROUS MATERIALS Nanoporous materials have numerous applications (Fig. 8.13) depending on their pore size, structure, type of material (organic, inorganic, or

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Biomedical Catalysis

Agriculture

Gas separation, purification and storage

Adsorption and conversion of CO2

Application of porous nanomaterials

Water treatment

Sensors, supercapacitors

Food industry

Figure 8.13 Applications of porous nanomaterials.

organic
inorganic hybrid) as well as chemical and physical properties. Nowadays the nanoporous materials have been extensively used in drug delivery and biosensing, agriculture, food industry, wastewater treatment and purification, sensors and supercapacitors, gas adsorption, separation and storage, CO2 capture, and photocatalysis, etc.

8.5.1 Biomedical Use Recent progress in biomedical sciences with development of advanced materials and technologies have rapidly expanded controlled drug-delivery applications [89,90]. Safe delivery of the drug in specific sites of the human body with their regulation for maximum therapeutic benefits is the aim of controlled drug delivery. Nanoporous particles are used in the storage and delivery of molecular therapeutics due to their large surface area and porous interior. Nanoporous anodic alumina has been used widely in electronic, optoelectronic, sensing devices, dental, and orthopedic implants due to their properties such as electrical insulation, optical transparency, chemical stability, bioinertness, and biocompatibility. Porous silica is also a biocompatible material which has optical properties, it has been used in drug-delivery applications and implantable devices. Highly porous nanostructured titania
silica ceramic has been widely used as a biomaterial by replacing commercial titanium implants [91,92]. Biocompatibility, the capacity of

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self-setting within the bone cavity, moldable ,and osteoconductive nature are some unique properties of nanostructured biomaterials, hydroxyapatite, and other calcium phosphates. These properties make them popular in drug-delivery applications and as implantable bone ceramic [93
95]. As mesoporous silica protects the molecular cargo from premature release and degradation, it is used for drug delivery. Sustained release of ibuprofen from mesoporous particles in simulated body fluid, one of the first drug deliveries using nanoporous particles, has been studied [96]. Porous nanoparticles with 1.8 nm pore-diameter release 55% of the adsorbed drug in 24 h, whereas 2.5 nm pore-diameter containing porous particles release 68% in the same time. For cellular delivery and release of camptothecin, a hydrophobic anticancer drug, nanoporous particles have been used [97]. For gene therapy, potentially dangerous and nonefficacious delivery vehicles, like viral capsids, have been used previously to deliver DNA in cells. The use of mesoporous particles may circumvent these vehicles. Lin and coworkers have shown that a plasmid DNA vector electrostatically binds and successfully transfects a number of mammalian cells by tethering second-generation poly(amidoamine) dendrimers to the surface of mesoporous particles [98]. Nanoporous membranes can act as support for kidney cells in kidney applications as well as a blood filter which retains serum proteins but flows out the smaller waste substances [99]. Nanoporous membranes used in implantable devices function as a semipermeable compartment to hold the implant or drug during the passage of the desired molecule. Nanoporous membranes are also used in diagnosis and protein separation. Many microfabricated devices have been developed which perform separation, mixing, reaction, detection, or preconcentration to automate biological analyses and reduce sample consumption and cost. In the pharmaceutical industry, food industry, and biotechnology, many techniques, including size exclusion chromatography and gel electrophoresis of biopolymers are used for isolation and purification of molecules [100,101]. Due to the biosensing property, gold nanoporous membranes with pore radius , 1 nm are used for detection of molecules and are important in the pharmaceutical industry, medical diagnosis, and detection of hazardous biomolecules [102]. A biological component with a physiochemical detection component which detects analytes is combined in the majority of biosensing devices in biological feed streams. For example, glucose oxidase immobilized in the porous nanocrystalline TiO2 film is capable of sensing the blood glucose level [103]. Similarly, cholesterol biosensors have been developed by immobilizing

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cholesterol oxidase enzyme in the ZnO nanoporous thin films [104]. Recently, a glucose-sensing system has been developed that contains a nanoporous platinum electrode embedded in a microfluidic chip comprising a microfluidic transport channel network and a miniaturized electrochemical cell [105]. It is possible to access information on the concentration, structure, size, and sequence of single- and double-stranded DNA or RNA by measuring the frequency, magnitude, and duration of blockage in the ion current of an electrolyte when biomolecules are drawn through nanopores embedded in insulating membranes [106]. For detection of biomolecules, this technique has been used by embedding membrane-bound receptors like α-hemolysin (α-HL) protein pores in a lipid membrane [107]. Micron-sized apertures in polymeric film-incorporated lipid membranes were used much earlier by researchers for analysis of single molecules. To expand the functionality of single-molecule detectors, synthetic nanopores like glass, polymers, and solid-state membranes are now used [108]. Protection of implanted cells or drug-release systems from the immune reaction is referred to as immunoisolation. Encapsulated nanoporous semipermeable membranes isolate the transplanted cells from the body’s immune system by allowing small molecules such as oxygen, glucose, and insulin but impeding the passage of much larger immune system molecules such as immunoglobulin. Nanoporous silicon interfaces prepared by microfabrication techniques have been used in the implantable artificial pancreas to treat diabetes by Desai et al. [109]. For controlled release of pharmacological agents, nanoporous membranes with suitable pore size, porosity, and membrane thickness make them an attractive route for making capsules [110]. For the sustained release of ophthalmic drugs, nanoporous inorganic membranes have been tested [111].

8.5.2 Catalysis Unique pore structure, large surface area, excellent structural stability, and high electrical conductivity of porous Pt-based nanostructured materials make them important catalysts in electrochemical reactions like oxidation of hydrogen and small organic molecules in the anode and reduction of oxygen in the cathode in fuel cells. This can eliminate the use of a carbon support in fuel cells and address the disadvantages of traditional carbonsupported catalysts [112].

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Zeolites are crystalline microporous materials that are the most widely used catalysts in different industries such as oil refining, petrochemistry, and organic synthesis in the production of fine chemicals [113
115].

8.5.3 Sensors and Supercapacitors To prepare the multifunctional materials for sensors containing uninfluenced photoluminescence and emission lifetimes, in the presence of water at ambient conditions, porous lanthanide-based metal
organic frameworks (Ln-MOFs) are appropriate materials [116
118]. Available LnMOF materials have very small pores through which the molecules of interest are not allowed and these materials are stable only up to 673K in air, so it is impossible to use them in luminescence sensors working in moisture at ambient temperature [119,120]. New possibilities will be opened for the production of low-cost sensors by MOFs that combine the magnetic and anisotropic properties with high-emission quantum yields under ambient conditions [121]. In clinical diagnoses, bioprocessing, environmental and food industries, enzyme-free amperometric detection of glucose and hydrogen peroxide is an important application. Porous Pt-based electrocatalysts are widely used to detect glucose and hydrogen peroxide [122,123]. In the fabrication of pH sensors, porous Pt-based nanomaterials are also used. From investigations, it has been revealed that nanoporous Pt material fabricated pH-sensitive electrodes exhibit near-Nernstian behavior with ignorable hysteresis, a short response time, and high precision. For example, fabrication of a solid-state reference electrode has been successfully done by combining nanoporous Pt with a polyelectrolyte (PE) junction [124]. Recently, activated carbons have become one of the most suitable electrode materials for supercapacitor preparation. Supercapacitors have a reversible electrical energy storage system with high power-energy capability and long life. All these properties make the supercapacitorcontaining devices suitable for various applications such as power electronics, backup power systems, digital electronic devices, wind turbines, electric vehicles, etc. [125].

8.5.4 Adsorption, Separation, and Catalytic Conversion of CO2 An important factor responsible for global warming is the emission of CO2 from industry and power plants. To avert the rise in CO2 levels, its

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capture, storage, and utilization (CCU) technique is one of the obvious solutions. However, during this process, further CO2 is emitted due to a certain amount of energy consumption [126,127]. Therefore, CCU techniques should be low-energy regeneration techniques with the net reduction in CO2 emission. Nanoporous materials have a high surface area and a high pore volume which make them the most suitable solid adsorbents for CO2. Zeolites are microporous crystalline materials, and have been widely used as adsorbents of CO2 due to their high surface area, specific porous structures, and availability. Other porous nanomaterials such as MOFs, mesoporous silicas, carbon nanotubes, organic cage frameworks, and COFs have also been examined for this technique [128
133]. Photocatalytic conversion of CO2 is a type of CO2 reduction reaction (CRR) using solar energy for the production of chemical fuels is considered as one of the most economical conversion. Porous carbon materials adsorb CO2 on the surface of the photocatalyst and enhance the CRR efficiency remarkably. For example, Wang et al. have shown carbon@ TiO2 hollow spheres exhibited enhanced photocatalytic conversion of CO2 compared with commercial TiO2 (P25) [134].

8.5.5 Food Industry Nanoporous materials are used in food safety for the detection of pathogenic microorganisms like Salmonella enteritidis, bacteriophage virus MS2, Escherichia coli O157:H7, Staphylococcus aureus, etc. and small organic molecules like food allergens in peanut. Nanoporous silicon has been synthesized electrochemically and functionalized with DNA probes for their utilization in biosensors capable of selective detection of S. enteritidis, which exhibit promising results in screening applications [135]. Nanoporous silicon films conjugated with antibodies detect bacteriophage virus MS2 and remove the contaminant from drinking water. Nanoporous silicon films have a detection level at 1 mg/mL and they outperform nonporous silicon-based biosensors due to their high surface area [136]. For the detection of E. coli O157:H7 and S. aureus, a polydimethylsiloxane microfluidic sensor has been developed with antibodies immobilized on an alumina nanoporous membrane [137]. Gibberellic acid is a plant growth hormone and, as a natural bioactive product, it is of great interest. However, using traditional methods, isolation and determination of gibberellic acid are difficult due to its low concentrations in plants and lack of stability during isolation. Novel sorbents have been

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developed for nondestructive isolation of small organic molecules from plant matrix, such as a nanoporous silica
sucrose material with the tunable pore structure that binds to gibberellic acid for its isolation [138]. Mesoporous silicas have been developed to remove a broad range of metal contaminants from water and beverages, and also fortified calcium in water samples during removal of uranium [139,140].

8.5.6 Water Treatment Industrial wastewater treatment and drinking water purification by the adsorption process using activated carbon is an important process. Their microporous structure, high porosities, large surface area, and chemical nature have made them efficient adsorbents for the removal of heavy metals and low-molecular-weight chemicals such as metal ions, dyes, and organic compounds from industrial wastewater. Malathion is a broadspectrum organophosphate insecticide and miticide that has various agricultural, industrial, and governmental uses. Activated carbon can be used generally for removal of malathion from water which is responsible for taste, odor, and color problems [141]. In air pollution control, pharmaceutical and chemical industries, wastewater treatment, and sugar syrup purification, activated carbon is also used as catalyst support. The mesoporous activated carbons are generally used for the separation and adsorption of bulky organic materials such as dyes and humic substances [142
145]. Silica templates generated nanoporous carbons (SMC1) with pore sizes 10
100 nm, very high pore volumes, and high surface areas, exhibited excellent adsorption capacities for bulky dyes like Acid green 20, Acid violet 17, and Direct blue 78. The adsorption capacity of these nanoporous carbons is sometimes over 10 times higher than that of commercially activated carbons [146]. Zeolites are crystalline minerals, which are formed by tetrahedral units of SiO4 and AlO4. This type of structure and higher aluminum content of zeolites, make them an effective agent for the removal of specific pollutants, catalysts, and molecular sieves used in water treatment and other applications [147]. Among the natural zeolites, clinoptilolite, mordenite, scolecite, chabazite, and phillipsite have been studied for wastewater treatment applications [148
150]. ZSM-5 and MCM-22 are synthetic zeolites used for the removal of inks and common dyes, respectively [151,152]. Zeolite mixtures of kaolin and mordenite have shown enhanced uptake of chromium compared with natural zeolites [153]. The uniform pores

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and large surface areas of mesoporous silicates make them suitable for adsorption and ion exchange. Due to these properties, they are used for removal of dyes and as the catalyst in many applications. Titaniumsubstituted mesoporous silicates have shown around 700 mg/g adsorption capacity of ionic dyes, which is much higher than any other material [154]. Nanofiber membranes such as chitosan nanofiber membranes, chloridized polyvinyl chloride nanofiber membranes, wool keratose, silk fibroin nanofiber membranes, and polyacrylonitrile nanofiber membranes have high surface areas that make them efficient candidates for removal of heavy metal ions from an aqueous solution [155
159]. Mesoporous poly (vinyl alcohol)/SiO2 composite nanofiber membranes functionalized with mercapto groups with diameters of 300
500 nm have shown high efficiency in absorbing Cu(II) ions from waste water [160].

8.5.7 Gas Separation, Purification, and Storage In cryogenic air separation units, mixtures of rare gases are usually found. The mixtures of rare gases have been separated by adsorption on MOFs (MOF-5), which is a far simpler process and can replace the cryogenic distillation. After separation of the mixture, xenon and krypton can be marketed separately, for example, in the lamp industry krypton is used as a filler and xenon is used as a narcotic medical gas [161]. Cu-BTC-MOF is used to remove sulfur odorant components from natural gas. It has the special arrangement of channels with open metalligand sites which allows a dual-type sorption behavior. For the separation of polar components from nonpolar gases, it is a powerful material [162
164]. It successfully removes amines and ammonia, water traces, alcohols, and oxygenates, etc. In MOF-filled canisters, storage of a gas can be used either to transport an equivalent amount of gas at a far lower pressure or to enhance the capacity of the gas in a given volume. Mueller et al. have shown that the volume specific uptake is higher for the rare gases, argon, krypton, and xenon in the case of a gas cylinder filled with MOF-5 [161]. Some other gases, like methane and hydrocarbons, can also be stored in the same manner [165,166]. Similarly, MOF-5-, IRMOF-8-, and Cu-BTC-MOF-filled cylinders can take up higher amounts of hydrogen compared to the pressurizing of an empty container with hydrogen [161]. For many volume-limited fuel-cell applications such as the mobile and portable cases, volume-specific data

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storage will be industrially much more relevant in comparison to weightspecific storage capacity. The high specific surface area and well-developed porous structures of activated carbon, carbon fiber, and carbon nanotubes make them excellent adsorbent materials for gas adsorption/separation and CO2 capture. Commonly used mesoporous silica for CO2 adsorption are MCM-41 and SBA-15 [167,168]. MOFs are a class of porous materials with a high specific surface area and a large amount of space both on the inside and outside. Due to these properties, they are also used in gas separation, storage, and catalysis [169,170]. Because of the better chemical and thermal stability of modified microporous organic polymers (MOPs) compared to MOFs and inorganic porous materials, they are used in gas storage, adsorption, separation, and heterogeneous catalysis [171,172].

8.5.8 Photocatalyst For the supply of clean and recyclable hydrogen energy by splitting of water, semiconductor photocatalysis is an environmentally friendly process. In this technique, solar energy decomposes harmful organic and inorganic pollutants present in the air and aqueous systems [173
176]. TiO2 is stable, cheap, and currently the most widely used highly efficient photocatalytic material. Nitrogen-doped TiO2 has recently been reported for visible-light photocatalysis [177
179]. Tungsten trioxide (WO3) also has many advantages for visible-light-driven photocatalysis, like strong adsorption within the solar spectrum, stable physicochemical properties, and resistance to photocorrosion effects [180]. Abe et al. have shown that loaded Pt in a Pt-loaded WO3 nanotubular structure (Pt/WO3) can trap photogenerated electrons from WO3 to reduce O2 to H2O2 and enhance the photocatalytic properties [181]. Metal nanoparticles loaded on nanoporous TiO2 supports are used in catalyzing reactions like photocatalytic generation of hydrogen from water, carbon monoxide oxidation, and organic pollutant photodegradation [182
184].

8.5.9 Agriculture In agriculture, nanoporous materials are used for the detection, separation, catalysis, and controlled release of materials and as sorbents, binding toxicants. Activated carbons have affinity for organic molecules, whereas zeolites have affinities for gases, ions, metals, and small organic molecules, based on this property they are used as sorbents. Zeolites are used as the

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catalyst in biofuel production [185]. Microporous clays have been used as sorbents and as additives to sequester contaminants through in-feed applications, and also reduce human exposure to the contaminants [186,187]. Aluminosilicate zeolites selectively adsorb guest molecules through their channels, cavities of a size, shape, dimension, and charge balancing cations [188,189]. Divalent cation exchanged and surfactantmodified synthetic zeolites such as zeolite X, Y, ZSM-5, and Beta have been studied as pheromone dispensers for insect attractants. They disperse the female sexual pheromone n-decanol of Agrotis segetum and Cydia pomonella, and the male synthetic attractant trimedlure for Ceratitis capitata [190]. The pheromone-loaded surfactant-modified zeolite A has dispersed pheromone for Riptortus pedestris and trapped them [191].

8.6 CONCLUSION In this chapter, we have briefly classified the porous materials as well as vividly discussed various methods to prepare a different kind of porous nanomaterial. We also discuss the possibilities for intentionally modifying the surface chemistry and morphology of the materials and their applications in various fields. After analyzing all the prospects, we can conclude that there is a broad window for future research on developing a facile, environmentally friendly green synthetic way to synthesize porous materials at an industrial scale. The green synthesis of porous materials minimizes the use of hazardous chemical reagents, making them potentially useful in commercial fields.

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