Nano Today
Volume 46,
October 2022
, 101607
Author links open overlay panel, , , ,
Abstract
Tailored mesoporous carbon nanostructures (TMCNs) featuring distinctive and tunable morphologies have gained tremendous interest over the past decades. These materials, being ambulant, have broadened the application spectrum. This review aims to provide an authoritative reference regarding the synthesis pathways, potential applications, key challenges, opportunities and future research directions. Regulating the reaction parameters, such as carbonization temperature, precursors types and concentrations, and molecular weight of structural directing agents, was crucial in this context. This review critically evaluates various techniques used to prepare TMCNs such as (i) hard templating, (ii) soft templating, (iii) modified Stöber method, (iv) space confined assembly, and (v) spray pyrolysis with an emphasis on underlying mechanisms and the impact of synthesis methods on the properties of the final product. Considering the importance of TMCN textural properties in the application spectrum, particular focus has been given to their precise tuning to obtain delicate architectural designs. Then, the applications of TMCNs with pre-defined morphologies are discussed in energy storage and conversion, catalysis, adsorption, and biomedicine. Finally, a summary of key aspects and challenges has been provided to put them into a perspective. This review presents the important research needs to foster the controlled synthesis and applications of mesoporous carbon.
Introduction
Porosity of carbon-based materials has been recognized as a profound concept to create versatile architectures. Porous carbon materials are categorized according to their pore diameters: microporous (<2nm), mesoporous (2–50nm), and macroporous (>50nm). Designing and developing porous materials to the nanoscale level is a key research topic of recent decades to attain sophisticated morphology for the desired innovative applications. Rational design and tailored synthesis of mesoporous carbon nanostructures (TMCNs) with customized pore architecture and morphologies (e.g., fibers, sheets, sphere, and rod) have been a long-standing research focus [1], [2], [3], [4], [5]. In principle, the development of versatile TMCN architecture with a unique pore size distribution, morphology, pore orientation, and chemical composition mainly depends on different reaction conditions such as; (i) combination or modification of different types of templates [4], (ii) template molecular weight [6], [7], [8], (iii) types and dosage of carbon precursors [9], (iv) concentration of pore-forming agents [9], [10], [11], (v) solvents types and contents [12], (vi) shear induced forces [1], [13], [14], and (vii) carbonization temperature [15], [16] (Fig. 1).
Generally, templating or nano-casting methods were used for the synthesis of mesoporous carbon, in which soft templating is considered to be more efficient for tailoring the external and internal interior of TMCNs [17]. In soft templating, amphiphilic surfactant and carbon precursor co-assemble in a solvent by hydrogen bonding, Coulombic interactions, or van der Waals forces in the presence of at least one pore forming agent during the assembly process [18]. The pore size and shape are defined by the template, whereas the interfacial polymerization coating mainly determines the shell thickness. Precise manipulations in the reactants concentrations and assembly process could produce versatile architectures exhibiting unique physiochemical properties, which can have a significant effect on TMCN overall performance. Customized pore architectures and the integration of specific functionality are desired while maintaining appropriate structural stability. The availability of TMCNs with carefully-controlled morphological characteristics, including inner and outer diameters, adjustable shell thickness, surface area, pore size, and volume were critical for successful applications. The surface morphology and porosity of TMCNs can be tuned for specific innovative applications by carefully regulating certain aforementioned parameters. Owing to the large surface area, high pore volume, tunable pore size, and unique meso-structures, TMCNs have been widely used in different fields such as energy sector [19], [20], [21], [22], [23], [24], environmental remediation [25], [26], [27], [28], and the biomedical industry [28], [29], [30], [31], [32].
Many excellent reviews on the topics related to conventional mesoporous carbon materials have been published. In recent years, published reviews mainly focused on a particular synthesis method and/or application of the obtained mesoporous material. For example, recent reviews by Prof. Zhao’s group focused on the synthesis of carbon mesoporous materials based on self-assembly-directed [18], [33], or single-micelle-directed routes [34], and their applications. Similarly, other reviews in this field focused on a particular group of materials like polymer-derived heteroatom-doped porous carbon materials [35], nano-porous carbons derived from waste resources [22], porous carbon spheres derived from polymer colloids [36], or nano-porous carbon materials obtained by covalent functionalization for adsorption [37]. To our best knowledge, no comprehensive review has been published so far that covers tailored mesoporous carbon nanostructures despite the immense amount of research data on this topic. The aim of this review article is to collate the results of the most relevant and up-to-date publications related to various aspects of tunable mesoporous carbon frameworks, including a critical evaluation of synthesis methods, their role in dictating the properties of these materials, and their emerging applications in various domains. To our knowledge, this is the first review that focuses on how to tailor morphological features of mesoporous carbons to obtain sophisticated pore designs for particular innovative applications. Considering the immense amount of data on mesoporous carbon nanostructures, we are convinced that this review article will be of great interest to all researchers working on various aspects related to the tailorable synthesis and applications of these materials. Owing to the rapid advancement of nanotechnology, we anticipate that this review will provide a scientific overview for beginners to the subject as well as a complete reference for expert researchers.
The goal of this review is to evaluate the synthesis and innovative applications of TMCNs. We have divided the synthesis part into five main categories including (i) hard-templating, (ii) soft-templating, (iii) modified Stöber method, (iv) space confined assembly, and (v) spray pyrolysis. These methods are critically evaluated to understand their impact on the properties of the final product. We begin by comparing and contrasting hard and soft templating strategies and their related sub-divisions, as they both operate on the same general and very simple principles, with an emphasis on tailoring morphological features. General suggestions were provided to assist in the selection of appropriate methods for synthesizing TMCNs with the desired architectures and functionalities. The role of synthesis methods when applied alone or in combination is described. This review will evaluate the advantages and limitations of each method in detail and clarify the present challenges and the ongoing efforts to overcome the limitations. In addition, we focused on customized morphological characteristics of TMCNs for specific applications including: (i) energy storage and conversion, (ii) catalysis, (iii) adsorption, and (iv) biomedical applications. Furthermore, we present the underlying challenges, prospective strategies, and possibilities in this domain for the future. We assume that this review will guide readers to gain insights into the development of functional TMCNs and their field scale applications based on tunable structural properties.
Section snippets
Synthesis strategies and underlying mechanisms
The quest for TMCNs with tunable morphology and porosity has been a driving force in the development of various synthesis strategies. To date, TMCNs is a big family including a large variety of compositions and architectures such as core-shell structures [14], [30], [38], [39], hollow [5], [40], [41], [42], [43], fibers [6], [44], [45], [46], nanotubes [47], and films [48]. TMCNs can be produced by various methods, including hard-templating (Fig. 2a), soft-templating (Fig. 2b), modified Stöber
Hard templates method
Hard templating is one of the most important and diverse pathways for assembling specified pore networks, geometry, and morphology, and it has seen significant progress in recent decades [49], [50], [51]. Pore architecture and porosity can be well controlled by this method based on the adjustable host template structural features. The pre-existing guide in this method regulates the synthesis of nanoparticles with comprehensive nanoscale features [39]. The hard template method usually has three
Soft templates method
The soft-template approach is a well-known and widely used technique for the design and synthesis of delicate TMCNs exhibiting marvelous architectures. A schematic diagram of this method is shown in Fig. 2b. Soft template technique has several benefits over conventional approaches such as its ability to produce versatile architectures, surface morphology control, and easy removal of the template. Generally, there are four fundamental requirements to obtain TMCNs by soft templates including (i)
Modified Stöber method
The Stöber method is a well-known and efficient method to obtain homogenous SiO2 colloidal microspheres (Fig. 2c) [124]. It involves the dissolution and precipitation of tetraethylorthosilicate (TEOS) in a basic alcohol-water emulsion. It has been established that TESO could easily undergo hydrolysis at the alcohol-water interface with minimum interfacial tension and generate spherical colloids. Over the past decade, the formation of mesoporous SiO2 has drawn a lot of interest in which
Space confined polymerization
The synthesis of tailored mesoporous carbon nanosphere remains a great challenge for researchers. In comparison to the previous methodologies, building a versatile mesoporous architecture in a confined space is theoretically simple, which can be achieved by tuning the polymerization parameters in the confined space (Fig. 2d). In 2013, Sun and his fellows developed novel variable microsphere structures from 2D to 3D through space confined evaporation induced self-assembly (EISA) by utilizing
Applications of TMCNs
As a huge family of programmable materials, TMCNs emerge as a potential functional material for several advanced applications due to controllable porosity, particle size, versatile morphology, higher surface area, pore-volume, and lower density. Particle size and pore size are among the most important aspects in determining physical properties and uses. In this section, we have highlighted the role of TMCNs in different fields such as energy related sector, environmental remediations, and the
Catalysis
Mesoporous carbon is considered a great choice for catalyst support owing to its tunable surface morphological features. Especially, porosity-related characteristics have great significance in the transportation of reactants and products during catalysis reactions and could also support metal nanoparticles in their frameworks. In addition, TMCNs are chemically stable under a wide range of pH (from acidic to basic) and could be used under different environmental conditions. TMCNs have poor
Adsorption
Adsorption with mesoporous carbon materials is the most common method for removing contaminants from various environmental matrices (air, water, and soil). Typically, mesoporous carbon has been extensively used for contaminant adsorption but its asymmetric irregular porous structure and limited functional groups on the surface hinder the adsorption performance. TMCNs with large surface area, good pore volume, well-connected mesoporous structure, easily tunable surface porosity, and surface
Biomedical applications
Designed and well-architected TMCNs are an important class of nanomaterials, which have been studied extensively for biomedical applications due to their unique morphological characteristics and remarkable biocompatibility. They can interact with several guest species (e.g., atoms, molecules, or bigger molecules) not just on the outer surface, but also across the channel walls, in comparison to their bulk counterparts. TMCNs have low cytotoxicity and do not have sharp edges, which means they
Summary and prospects
Over the last decade, great developments have been made in the design and synthesis of TMCNs to obtain tailored morphologies and surface chemical functionalities. The significant advancements in the synthesis techniques of TMCNs having tailored morphological characteristics and their specific innovative applications have been summarized in this review. The synthesis methods, associated mechanisms, and dominant parameters in each interfacial assembly have been addressed, which will help to
Author statements
The author states that the work described has not been published earlier, that it is not under consideration for publication elsewhere, that its publication is approved by all authors and that, if accepted, it will not be published elsewhere in the same form, in English or in any other language, including electronically without the written consent of the copyright-holder. To verify originality, this article has be checked by the originality detection service.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgment
This research was funded by the National Key R&D Program of China (2018YFC1105402), National Natural Science Foundation of China (52073230), Ningbo Natural Science Foundation (202003N4006), the Joint Research Funds of Department of Science & Technology of Shaanxi Province, Northwestern Polytechnical University (2020GXLH-Z-013, 2020GXLH-Z-017).
Atif Saleem received his B.Sc. (2014) and M.Sc (2016) from the University of Agriculture Faisalabad, Pakistan and Ph.D. from the Shaanxi University of Science and Technology, Xi'an China (2020). Now he is a postdoctoral research associate at Northwestern Polytechnical University in Xi'an China. His current research mainly focuses on the programmable self-assembly of polymers to produce [emailprotected] mesoporous nanostructures including carbon and silica nanospheres for adsorption of trace metals,
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