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Preparation of Mesoporous Carbon Materials via Emulsion Method

Zhao Xiaoxi , Wang Cong , Tian Yong , Wang Xiufang

Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (10) : 2316 -2328.

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Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (10) : 2316-2328 DOI: 10.7536/PC211220
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Preparation of Mesoporous Carbon Materials via Emulsion Method
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Abstract

Mesoporous carbons with unique features, such as high specific surface area, regular pore channels, homogeneous nano-framework, and tunable pore size, stand out from carbonaceous materials and are applied in a wide range of fields, including energy storage and conversion, catalyst, adsorption as well as drug delivery. Microemulsion method is characterized by simple preparation process, environmental friendliness, feasibility for large-scale production, and controllable product structure, which has made a breakthrough in preparation of mesoporous carbon with controllable pore structure and special morphology. Herein, the research progress of microemulsion preparation of mesoporous carbon is reviewed and the reaction mechanisms are analyzed. Besides, influencing factors controlling the pore morphology and internal structure of mesoporous carbon materials are further investigated. Finally, applications of novel mesoporous carbon materials in the fields of energy storage, catalyst, adsorption and drug delivery are summarized, and the future development prospects are put forward.

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mesoporous carbon / micro-emulsion / controllable structure / varied morphology

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Zhao Xiaoxi, Wang Cong, Tian Yong, Wang Xiufang. Preparation of Mesoporous Carbon Materials via Emulsion Method. Progress in Chemistry, 2022, 34(10): 2316-2328 DOI:10.7536/PC211220

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Contents

1 Introduction
2 Mechanism analysis of microemulsion methods for preparation of mesoporous carbon materials
2.1 Mechanism of microemulsion induced collaborative assembly
2.2 Emulsion swelling effect
2.3 Microfluidic technology
3 Morphology regulation of mesoporous carbon
3.1 Pore size adjustment
3.2 Morphology evolution
3.3 Tunable internal structure
4 Application and development trend
4.1 Energy conversion and storage
4.2 Catalyst
4.3 Adsorption
4.4 Drug delivery
5 Conclusion and outlook

1 Introduction

As one of the frontier fields of science and technology in the 21st century, materials science is closely related to the progress of human civilization and the development of modern economy and society. As the core of the field of materials, new functional materials play a supporting and promoting role in the development of high-tech. In recent years, mesoporous (2 ~ 50 nm) materials have attracted much attention due to their excellent physical and chemical properties, such as high specific surface area, regular pore structure, low density, good biocompatibility and conductivity[1⇓⇓~4]. These unique structural features make them promising for applications in catalysis, energy storage, adsorption separation, and drug delivery[5⇓⇓~8].
In 1992, Beck et al. First synthesized ordered mesoporous aluminosilicate (M41S), a series of materials with uniform channels and adjustable mesopores, which attracted the attention of many researchers[9]. In 1999, Ryoo et al. And Hyeon et al. Respectively reported the successful preparation of mesoporous carbon materials by nano-casting method (hard template method) with mesoporous silica as the hard template[10][11]. The combination of mesoporous characteristics with the excellent conductivity and chemical stability of carbon materials has opened a new era in the study of mesoporous carbon materials. In the following research, Zhao Dongyuan et al. Pioneered to obtain mesoporous carbon materials in organic solvent and aqueous solution respectively by establishing the interaction between phenolic resin and soft template based on organic-organic self-assembly, which further simplified the synthesis steps of mesoporous carbon materials[12⇓⇓~15]. Nowadays, with the deepening of research on nanomaterials and the expansion of practical applications, there is an urgent need for mesoporous materials to have new and sharp properties in structure, composition, morphology and properties. Rational design and controllable synthesis of mesoporous carbon with specific pore structure and special morphology (such as hollow, bowl-shaped, multi-cavity, layered) has become a research hotspot, and is expected to lead to a breakthrough in mesoporous materials[16⇓⇓⇓⇓~21].
Currently, various methods have been developed to fabricate mesoporous carbon materials with controlled morphology and nanostructure, including spray pyrolysis, colloid-assisted assembly, and sterically confined polymerization[22][23⇓~25][26]. However. In the spray pyrolysis method, the removal of the template and the crosslinking polymerization of the precursor molecules need to be carried out at a higher temperature (120 ~ 160 ℃), and the synthesis conditions are more stringent. Colloid-assisted assembly relies on the etching of colloidal particles to control the morphology of mesoporous materials, which often uses corrosive acid and alkali, resulting in volatile pollution and cumbersome steps. The space-limited polymerization strategy requires a dense shell (such as a silicon shell) to provide a closed space and selective etching in the subsequent process, which requires precise control of the experimental conditions. In addition, due to the uniformity of the template (micelle and colloidal particle), most of the mesoporous carbons prepared by the above methods are limited to a single structure, and it is difficult to achieve structural control in a given reaction system. Microemulsion method provides a new way to explore mesoporous carbon materials with structural diversity and controllable morphology. In 2016, Lou et al. Successfully prepared bowl-shaped mesoporous carbon nanoparticles by emulsion-induced interfacial assembly, whose asymmetric structure and radial pores shortened the proton transport path and showed strong electrocatalytic performance[27]. In addition, the transformation of mesoporous carbon morphology from bowl-like to spherical can be achieved by simply adjusting the addition of 1,3,5-trimethylbenzene (TMB). Mai et al. Further prepared anisotropic Janus nanoparticles by microemulsion method[28]. Anisotropic nanoparticles can exhibit unusual synergistic properties in certain applications due to the integration of two structures with different chemical compositions or properties into the same monomer[29]. Microemulsion method is considered to be an effective strategy for the controlled preparation of various mesoporous materials with special morphologies: (1) The preparation process is simple and green. The microemulsion template does not need an additional etching step, does not involve corrosive acid and alkali, is directly pyrolyzed in the carbonization process, has mild preparation conditions, and is suitable for large-scale production. (2) The microemulsion oil/water interface is used as a reaction space to control the growth mode of the precursor, which provides a general and simple method for the preparation of mesoporous carbon materials with asymmetric structure. (3) Microemulsion is used as a soft template to change the size, shape and hydrophobicity of the emulsion by adjusting the parameters affecting the oil-water interfacial tension, such as solvent, surfactant, additive and temperature, so as to obtain nanoparticles with adjustable structure, external morphology and particle size in the same system. Fig. 1 shows the development history of mesoporous carbon nanomaterials.
In this paper, the preparation of mesoporous materials by microemulsion method at home and abroad is reviewed, and the reaction mechanism is emphatically analyzed, and the control of microemulsion on the pore size, morphology and internal structure of mesoporous carbon materials is further discussed. Finally, the applications of mesoporous carbon materials with novel structures in various fields are summarized, and the future development directions are prospected.

2 Mechanism Analysis of Mesoporous Carbon Materials Prepared by Microemulsion Method

As a multiphase system, microemulsion is usually formed by two or more immiscible liquids, which are dispersed into another continuous phase by mechanical stirring[30]. In the microemulsion system, the internal and external interfaces of the emulsion present different environments. The precursor molecules are cross-linked or polymerized at the emulsion droplet and the oil/water interface[31,32]. As a soft template, microemulsion can not only induce the assembly of carbon precursor at its interface, but also play an auxiliary role in pore-forming. Solvent, surfactant and oil phase have a significant effect on the formation of microemulsion and droplet size[33]. Controlling the solubility of the precursor in the oil and water phases as well as the interfacial tension of the emulsion surface provides the possibility to prepare anisotropic mesoporous particles. Therefore, the microemulsion method can realize the control of the morphology, pore size and internal structure of the material. Its mechanism can be roughly divided into microemulsion-induced cooperative assembly, emulsion swelling effect and microfluidic droplet technology. Table 1 compares the preparation of mesoporous carbon nanoparticles by microemulsion method.

2.1 Microemulsion-induced cooperative assembly mechanism

In the microemulsion system, nanoscale emulsion droplets can be used to prepare mesoporous nanoparticles by cooperative assembly with carbon precursors and surfactants. The emulsion droplet was used as a spherical template to induce the nucleation and isotropic growth of the precursor on its surface[34,35]. For example, Liu et al. Prepared mesoporous carbon nanospheres in ethanol and TMB system using block copolymer F127 and fluorocarbon surfactant FC4 as template and phenolic resin as carbon precursor[36]. Among them, TMB forms supramolecular aggregates with surfactant due to hydrophobic interaction and assembles with RF resin through hydrogen bonding. The hollow mesoporous carbon nanospheres are obtained by high-temperature carbonization and hydrofluoric acid etching. By increasing the amount of ethanol and TMB, increasing the surfactant concentration or decreasing the initial reaction temperature, the properties of the hydrophobic end of the surfactant were changed, and the two-dimensional hexagonal symmetric mesoporous carbon nanospheres were converted into multilayer concave hollow nanospheres. Subsequently, Wang et al. Used the soft template method and hydrothermal carbonization system coupling, selected sodium oleate (SO) and P123 as double soft templates, and obtained mesoporous carbon nanospheres with hollow structure without adding hard templates[37]. P123 first forms mixed micelles with SO due to hydrophobic interactions. Due to the weak acidity of the precursor, the oleic acid produced by SO hydrolysis was converted into a homogeneous emulsion containing P123 and oleic acid with mixed micelles. In the subsequent hydrothermal process, 2,4-dihydroxybenzoic acid and formaldehyde interact with each other through weak acid and base and use the emulsion droplet as a template, and the isotropic growth leads to the formation of hollow structures. On this basis, Liu et al. Obtained hollow carbon bowls, hollow carbon capsules and hollow carbon spheres by adjusting the reaction time and controlling the growth process of the precursor, and further explained the dynamic formation process of hollow carbon spheres[38].
In addition, the enhancement of the interaction between the precursor and the hydrophobic droplet may change the nucleation and growth mode. With catechol and amino groups, dopamine can bind to most organic and inorganic surfaces, and properly control the interaction between emulsion droplets and polydopamine (PDA) particles, providing opportunities for island nucleation and anisotropic growth to form asymmetric mesoporous particles[39]. For example, Lou et al. Obtained bowl-shaped mesoporous carbon with asymmetric morphology by microemulsion-induced method[27]. In the emulsion system, the precursor composite micelle F127/TMB/PDA will cooperatively assemble at the oil/water interface to form PDA seeds with island mesostructure. As shown in fig. 2, the cooperative assembly of the composite micelles drives the growth of the mesoporous channels along the radial direction. Increasing the amount of TMB, F127/TMB/PDA micelles tend to form separated islands on the emulsion droplets and grow anisotropically to reduce the interfacial energy of TMB droplets, realizing the structural evolution of mesoporous carbon from nanospheres to nanobowls.
However, the above hydrothermal reaction usually needs to be carried out in an autoclave, and the reaction conditions of high temperature and high pressure limit its large-scale production, and the carbon precursor is easy to be over-crosslinked under such conditions. In 2020, Liu et al. Synthesized raspberry-like mesoporous carbon nanoparticles in one-pot aqueous solution by double soft template cooperative assembly[40]. The key of this method lies in the strong acidic environment created by hydrochloric acid, which can not only promote the hydrolysis of SO to produce oleic acid as a pore-expanding agent, but also protonate the PEO segment of F127 and phenolic resin, and use chloride ions as an anion balancer to co-assemble them into F127/oleic acid/phenolic resin composite micelles through a I+X-S+ mechanism. Subsequently, the complex micelles nucleate on the surface of oleic acid emulsion droplets and grow anisotropically in a Volmer-Weber mode, eventually forming a raspberry-like polymer. After carbonization at high temperature, raspberry-like mesoporous carbon nanoparticles with cavities (25 nm) and large mesopores (6. 9 nm) were obtained.

2.2 Emulsion swelling effect

Based on the soft characteristics of emulsion, the type and composition of solvent have a significant impact on the properties, shape and size of microemulsion droplets, which opens up a new way to construct mesoporous carbon nanoparticles with novel morphologies[41]. Stucky et al. Used polystyrene particles (PS) as the core to prepare bowl-shaped carbon nanoparticles through an expansion-induced buckling process[42]. Glucose was used as the carbon precursor for microwave-assisted hydrothermal carbonization, so that the carbon shell was uniformly coated on the surface of PS spheres (PS @ C), and then the PS @ C particles were treated by ethanol-heat treatment. Depending on the expansion effect of the PS core template, the penetration of solvent molecules at high temperatures will make it significantly larger. Subsequently, during the cooling process, the PS core recovers its original volume, and the tensile stress generated by the expanded PS core increases the plasticity of the carbon shell, which eventually leads to the buckling of the carbon shell. By controlling the temperature and solvent of the treatment, the degree of carbon shell depression can be precisely adjusted. The degree of depression of the obtained PS @ C gradually increased by using methanol, ethanol and 1-propanol as solvents in turn. This is due to the fact that polyols are more permeable to the PS core, which makes them more effective in swelling PS.
Wang Yong et al. Then extended this method to microemulsion system[43]. Homogeneous hollow carbon nanospheres were obtained in situ by hydrothermal carbonization using sodium dodecyl sulfate-derived nanoemulsion droplets as templates. These nanospheres were further post-treated with organic solvents to dissolve the oligomers in the carbon matrix, which led to the buckling of the shell and the formation of anisotropic nanobowls. Although the buckling degree of the nanoshell was achieved by changing the hydrothermal time, the post-treatment step of the organic solvent was more tedious. Chen et al. Used biomass ribose as carbon source, P123 and SO as dual surfactants to prepare hollow open vase-shaped carbon nanoparticles (HOCFs) through the synergistic effect between soft template and biomass[19]. The formation mechanism is shown in Figure 3A-B. This anisotropic structure is formed by the rupture of the polyribose shell due to the expansion of the internal emulsion as the temperature rises, and the outflow of oleic acid to form a new template surface. Some derivatives gradually dissolve into oleic acid through the opening formed and grow along the inner surface of the shell, thus building a thicker shell layer. At the same time, the derivatives at the opening of the rupture shell will nucleate, polymerize and further form the neck of the vase along the newly formed template. With the extension of hydrothermal time, the process of derivative filling and emulsion outflow continued, which eventually led to the reduction of the inner cavity of the vase-like mesoporous carbon and the lengthening of the neck of the vase. Such anisotropic vase-like mesoporous carbon nanoparticles with a specific surface area up to 2335 m2·g-1 display enhanced electrochemical performance in supercapacitors.
In 2021, our group proposed a swelling-dual permeation mechanism to obtain mesoporous carbon @ silicon composite particles (MC @ MSs) with various morphologies through microemulsion-induced interfacial self-assembly[44]. Triolein (GTO) permeates into the hydrophobic part of the F127 micelle to form the GTO @ F127 composite micelle, which acts as a template for the internal cavity. GTO @ F127 composite micelles induced the polymerization of carbon precursor to polybenzoxazine nanospheres (PBs) in alkaline solution. Then TEOS and CTAB were uniformly coated on the surface of PBs to form a silicon shell, which was transformed into MC @ MSs after high temperature carbonization. Because solvents with different polarities have different effects on the stability, interfacial properties and dispersion state of the emulsion, when the concentration of ethanol decreases, the rate of GTO migration into the interior of F127 micelles decreases (the ability to swell F127 micelles is weaker), smaller composite micelles are formed, and the polymerization with the precursor is delayed. Therefore, the volume of the cavities inside the MC @ MSs is reduced and the number of the cavities is increased.

2.3 Microfluidic droplet technology

Microfluidic droplet technology is a new technology developed on microfluidic chip to study the generation, manipulation and application of microdroplets. In recent years, it has become a new material preparation technology in the fields of chemistry, materials science and biomedicine[45⇓~47]. The emulsion is used as a template, and the size, shape, composition, and structure of the emulsion are adjusted by a specific emulsification technique to precisely control the particles produced[48⇓~50]. Compared with traditional microparticle fabrication methods, microfluidics can controllably produce microemulsion droplets for template synthesis of different functional microparticles, thus precisely controlling their size, uniformity, composition, and structure. Chu et al. Proposed water-in-oil-in-water (W/O/W) double emulsion for the synthesis of bowl-shaped particles[51]. In the experiment, a capillary device was used to obtain nanoscale droplets (fig. 4A). After these droplets are collected in the container, the inner fluid is pulled to the top of this W/O/W structure due to the density difference of the inner and outer fluids. The droplets are then polymerized under ultraviolet light, which partially reduces the oil droplet and squeezes the aqueous solution inside to form a single pore on the surface. The results show that the particle shape can be well tuned by changing the attachment energy between the inner and outer droplets. Pan et al. Prepared hollow carbon spheres in a vertical microfluidic device[52]. In which furfural, fatty acid methyl ester and Span 80 are the oil phase and sulfuric acid solution is the aqueous phase and forms aqueous droplets under shear. Then furfural was polymerized on the surface of the droplet under the catalysis of sulfuric acid to form polyfurfural microcapsules, which were further carbonized to obtain microporous hollow carbon spheres. Ge et al. Prepared mesoporous carbon spheres with adjustable particle size and pore size by microfluidic droplet technology[53]. As shown in Fig. 4 B, in the modified T-type device, the precursor solution, ionized water, and HCl solution were injected from three vertical inlets as the dispersed phase, respectively, and subsequently sheared into aqueous layered micro-droplets in the continuously flowing oil phase. When the droplets move in the serpentine channel, the precursor solution is rapidly hydrolyzed, and the collected droplets are carbonized and etched by HF to form mesoporous carbon particles. The results show that the content of deionized water affects the size of droplets, pore size, carbon spheres and surface morphology. In addition, the preheating temperature also has a direct effect on the surface morphology of carbon spheres: mesoporous carbon spheres with wrinkled or smooth surface were obtained by preheating at 70 ℃/80 ℃, respectively. The main advantages of the microfluidic droplet method are that the prepared mesoporous carbon has uniform particle size, good dispersion, and is easy to realize automation. The biggest problem is the low production[54].

3 Structure control of mesoporous carbon materials by microemulsion method

3.1 Pore size control

Pore size is an important factor in determining the physical properties and applications of mesoporous materials. SiO2 nanospheres and block copolymers (P123, F127) are often used as mesoporous templates[55⇓~57]. However, the mesoscopic structure and morphology of the mesoporous materials synthesized in the hard template are limited by the parent template, and additional post-treatment steps are needed for etching, which limits the large-scale production to a certain extent. When mesoporous carbon is synthesized by soft template method, the hydrophobic segment of the template is the key factor affecting the pore size. Among them, F127 and P123 are two commonly used surfactants. Due to the limitation of the size of the hydrophobic segment, the pore size of the mesoporous carbon materials prepared with phenolic resin as the carbon source is mostly less than 3 nm. This hinders the rapid transport and efficient loading of large-sized guest molecules (RNA, genes, and dyes) and nanoparticles (such as noble metal nanoparticles). Large mesopore sizes can be obtained by using block copolymers with long-chain hydrophobic segments as templates. Tang et al. Used polystyrene-polyethylene oxide (PS-b-PEO) as a template to adjust the mesopore size from 5.4 nm to 16.0 nm by changing the length of the hydrophobic segment of the block copolymer PS[58]. However, the block copolymer with high molecular weight has high preparation cost, which limits the industrial production of the material. In the microemulsion method, the oil phase can enter the hydrophobic section of the surfactant micelle to increase the volume of the hydrophobic core so as to achieve the purpose of pore enlargement. For example, Zhao Dongyuan et al. Introduced hexadecane into the reaction system, and the pore size of mesoporous carbon was enlarged from 3. 1 nm to 3. 8 nm[59]. When decane with longer carbon chain was used as pore expanding agent, the pore size increased to 4. 1 nm. However, the slight pore-expanding effect is not enough to fully load the guest macromolecule and carry out continuous proton transport.
In addition, the size of the micelle can be changed by adjusting the proportion of the hydrophobic phase or the content of the surfactant, and then the pore size of the mesopore can be controlled. Peng et al. Prepared mesoporous carbon nanospheres with tunable pores (5 ~ 37 nm) by nanoemulsion assembly method using F127 as template and dopamine as precursor[60]. In this strategy, TMB not only has a great influence on the pore size evolution of F127, but also plays a regulatory role in the interfacial interaction between F127 and PDA. In the alcohol/water system, TMB interacts with the hydrophobic PPO segment and PDA of F127 through van der Waals force and π-π bond, respectively, thus mediating the interfacial interaction between them. Due to the swelling effect, the size of nanoemulsion increases from 8 nm to 52 nm with the increase of TMB content in the system, which changes the morphology of mesoporous carbon from non-porous nanospheres to ultra-large mesoporous (37 nm) dendrites (Figure 5A).
Recently, Zhao Dongyuan et al. Proposed the strategy of shear-induced dynamic assembly to regulate the internal structure[61]. By adjusting the stirring speed to control the shear force, the size of the micelle can be accurately and dynamically controlled, so that the self-assembly process of the micelle can be programmed by setting the on-demand stirring mode. When the stirring speed was low, the formed F127/TMB/DA composite micelles were small and continuously assembled on the pre-synthesized PDA nanospheres to form a double mesoporous structure. As the assembly process proceeds, the pores gradually evolve into columnar mesoscopic channels, forming a gradient core-shell structure. During this step, the micelles undergo contact, deformation, coalescence, and fusion processes in the radial direction, eventually forming a cylindrical structure (Fig. 5 B, C).

3.2 Morphological transformation

While the microstructure of materials has been studied, the macroscopic morphology of materials has also made some progress, and the contour design of nanomaterials morphology is one of the most attractive fields at present. Carbon materials with different morphologies have many special uses, for example, the large through holes on the shell of hollow mesoporous materials are beneficial to the rapid penetration of guest molecules, and the larger internal voids can improve the guest loading[37,62,63]; Compared with spherical isotropic carbon particles, bowl-shaped or hemispherical carbon particles have higher volume packing density and specific surface area, and are ideal electrode materials for small-volume portable energy storage devices[64⇓~66]; Each component of the asymmetric Janus composite can operate independently without interacting with each other, making it a truly multifunctional entity[67⇓⇓~70]. The synthesis of mesoporous carbon materials with novel morphologies and the exploration of their structural evolution mechanisms can further broaden their practical applications.
In recent years, the research on the preparation of mesoporous carbon materials based on interfacial assembly has been gradually deepened. In the microemulsion system, researchers have achieved the regulation of the morphology and structure of mesoporous carbon by introducing different dimensional substrates. Zhu et al. Synthesized carbon nanotubes @ mesoporous carbon (CNTs @ mesoNC) nanofibers with core-shell structure by molecule-mediated interfacial assembly[71]. Under the mediation of TMB molecules, TMB/F127/PDA complex micelles will be deposited and self-assembled on the surface of CNTs. With the progress of the reaction, the spherical composite micelles gradually fused into cylindrical micelles, and then formed vertical mesoporous channels. CNTs @ mesoNC nanofibers were obtained by carbonization in an anoxic atmosphere. Subsequently, Yamauchi et al. Extended the interfacial assembly strategy to the synthesis of two-dimensional (2D) mesoporous materials[72]. 2D sandwich-like mesoporous nanosheets were prepared using MXene nanosheets, graphene oxide, and imidazolate acid zeolite frameworks as substrates, respectively. Lou et al. Used three-dimensional (3D)SiO2 spheres as substrates to form polymer shells through the assembly of composite micelles at the interface of spheres, and obtained hollow mesoporous carbon spheres after carbonization and HF etching[73]. Based on the interfacial assembly, the introduction of different dimensional substrates into the microemulsion system provides a general strategy for the morphology control of mesoporous carbon materials.
Guan et al. Reported an anisotropic assembly strategy to generate bowl-shaped mesoporous carbon nanoparticles on the surface of TMB droplets via emulsion interfacial induction[74]. The strong interaction of dopamine molecules with catechol and amine groups with block copolymer and TMB emulsion droplets provides the possibility for island nucleation and anisotropic growth. Subsequently, in a similar reaction system, they introduced two block copolymers (P123 and F127) with different hydrophilic chain lengths as dual soft templates, and TMB as a pore-expanding agent. By fine-tuning the mass ratio of P123 to F127 in the reaction system and precisely controlling the filling parameters of the surfactant, the evolution of nanoparticles from bowl-like to dendritic and finally to sheet-like was achieved (Figure 6A). This shape transition originates from the shorter hydrophilic chain of P123. With the increase of the mass ratio of P123/F127 in the reaction system, the filling parameter of the surfactant in the system increases, which leads to the transition of the pore structure from columnar structure to bicontinuous structure, and finally to layered structure.
Similarly, using TMB oil/water mixture as emulsion system, Mai et al. Used P123 as surfactant and m-phenylenediamine (mPD) as monomer to synthesize anisotropic nanoparticles with adjustable structure by one-pot emulsification method, including mushroom-like, gear-like and acorn-like[28]. The polymerization of mPD in the oil phase produced PmPD lipophilic particles, which were anchored at the O/W interface based on the Pickering effect. At the three-phase contact line, the polymer sphere continues to grow along the O/W interface, forming a hemispherical shell around the core and eventually growing into mushroom-shaped nanoparticles. However, the addition of ethanol reduces the oil/water interfacial tension and increases the average size of oil droplets, so that the polymerization of mPD is gradually transferred from the oil droplet interface to the oil droplet, and the structural transformation to gear-like and acorn-like is realized.

3.3 Tunable internal structure

In addition to the external morphology, nanoparticles with complex internal structures have also been born[75]. Based on the surface free energy induced assembly method, Lu et al. Used triolein (GTO) nanoemulsion droplets as soft templates to synthesize multi-cavity structured carbon spheres[76]. Among them, the small-sized GTO nanoemulsion serves as the primary structural unit. The carbon precursor is then polymerized around the nanoemulsion to form substructural units with high surface free energy. In the subsequent hydrothermal treatment, these substructural units tend to aggregate and assemble, so that the surface free energy reaches the low energy state. Finally, the multi-chamber mesoporous carbon is obtained through high-temperature pyrolysis polymerization. By changing the amount of GTO and the concentration of polymer, the cavity size of the multi-cavity nanoparticle can be adjusted, which is the first time to synthesize multi-cavity carbon nanospheres by soft template method. The internal multi-cavity structure connected with the mesoporous shell can prevent the migration of long-chain lithium polysulfides into the electrolyte during charge and discharge, resulting in excellent cycling stability of lithium-sulfur batteries (Figure 7 a).
Yang et al. Proposed a method to finely control the internal structure of mesoporous carbon spheres based on the confined space assembly of surfactant emulsion droplets using emulsion as a template[77]. According to the theory of phase transition in the confined space of emulsion droplets and the study of the preparation process, the formation mechanism of the internal structure of carbon spheres was proposed: the droplets of Pickering emulsion stabilized by nano-SiO2 were used to form the shell, while F127, toluene and carbon precursors were aggregated in the droplets of Pickering emulsion to form the corresponding internal structure. The temperature and phenol content of the system have important effects on the surface and internal structure of mesoporous carbon spheres. The stability of the toluene oil droplet in the droplet was changed by changing the polymerization temperature, and the internal structure was transformed from a run-through bicontinuous (bijel) to a multinucleate and finally to a honeycomb structure. By adjusting the content of phenol, the mesoporous carbon spheres with wrinkled hollow, multi-chamber and multi-core structures were formed, respectively. This study reveals the formation mechanism of the internal structure of mesoporous carbon spheres and the droplet confinement effect, which provides a general rule for the preparation of particles with complex internal structure.

4 Application and Development Trend

Mesoporous carbon materials have been widely explored and applied in catalysis, energy storage and conversion, adsorption and separation, biomedicine and other fields due to their inherent advantages such as high specific surface area and large pore volume, good biocompatibility and thermal stability. The microemulsion method provides an idea for the construction of novel mesoporous carbon materials with controllable pore size, multi-morphology conversion and anisotropic structure. The unique structure of these nanomaterials changes the interaction between them and the surrounding environment (such as guest molecules, cell membrane, emulsion interface, etc.), thus improving their performance[78⇓⇓~81]. In this section, several typical application examples of these mesoporous carbon materials in the fields of energy storage and conversion, catalysis, adsorption, biomedicine, etc. Will be shown.

4.1 Energy storage and conversion

The high specific surface area, large pore volume, tunable pore size, and controllable geometry characteristics of mesoporous carbon materials increase the active reaction sites and improve the transport efficiency of reactants. At the same time, mesoporous structures can better adapt to strain relaxation and prevent structural collapse during repeated electrochemical or electrocatalytic cycles, making them ideal candidates for energy conversion and storage, which have been widely used in various types of fuel cells, supercapacitors and solar cells in recent years[5,82]. Guo et al. Introduced melamine as an in situ N-doped precursor in a microemulsion system, and synthesized mesoporous carbon nanospheres with 3D open pore size (8.1 nm), large specific surface area (883 m2·g-1), and ultra-high nitrogen content (15.6 wt%)[83]. This unique mesoporous carbon nanosphere as a sodium storage anode exhibits ultrahigh discharge capacity (834 mAh·g-1), outstanding reversible capacity (373 mAh·g-1,0.06 ag-1), and cycling performance, that is, a specific capacity of 116 mAh·g-1 is maintained after 1000 cycles at a high current density of 1.5 A·g-1. The excellent reversible sodium ion storage capacity and excellent cycle performance are mainly attributed to its open large pores and ultra-high nitrogen content. The porous hollow open vase-shaped carbon nanoparticles (PHOCFs) reported by Wang et al. Have a large specific surface area (2335 m2·g-1) and have great potential for application in supercapacitors[19]. In 6 M KOH solution, the cyclic voltammetry curve shows a nearly rectangular shape in the range of 10 – 1000 mV/s, indicating that the PHOCFs have a nearly ideal capacitance. The specific capacitance of PHOCFs is 263 F·g-1 at 0.1 Ag-1 and remains 222 F·g-1 at 1 Ag-1, which is one of the best values reported for mesoporous carbon materials. In addition, a capacitance retention of 76% was still achieved with a 200-fold increase in current density. This result is due to the fast ion transport achieved by PHOCFs by integrating the advantages of open and porous shells.

4.2 Catalysis field

Mesoporous carbon materials are ideal catalyst supports because of their high porosity and large pore volume, which provide a large number of reaction centers for heterogeneous catalysis[84]. Sch Schüth et al. Reported Pt/Co bimetallic supported hollow mesoporous carbon nanoparticles[37]. Pt @ HCS was obtained by adding platinum salt into the microemulsion system, reducing to Pt nanocrystals by hydrothermal method, and carbonizing. Co2C was further introduced to prepare the bell-shaped PtCo @ HCS nanospheres, which were used to catalyze 5-hydroxymethylfurfural to 2,5-dimethylfuran. The results showed that the conversion of 5-hydroxymethylfurfural was 100% within 10 min, and the yield reached 98% after 2 H (Fig. 8A). Deng et al. Prepared dendritic macroporous mesoporous carbon spheres by microemulsion-induced interfacial assembly, and further loaded Au nanoparticles (Au/RA-MC) as a novel heterogeneous catalyst[85]. The 3D dendritic radially aligned mesopores in mesoporous carbon spheres not only provide a large number of accessible attachment sites for Au nanoparticles, but also facilitate the diffusion and migration of reactant and product molecules. The Au/RA-MC-2 catalyst exhibited a high catalytic rate in the hydrogenation of 4-nitrophenol to 4-aminophenol with a K value of 0.28 min-1, which is much higher than that of Au supported on non-porous carbon nanospheres. In addition, in the cycling test, the Au/RA-MC catalyst demonstrated high stability and recyclability, maintaining a high catalytic rate over 9 cycles (Fig. 8B).
Mesoporous carbon materials have a good development prospect in improving the redox reaction (ORR) activity because of their high specific surface area and pore volume, which accelerate the charge transfer and proton transport. Liu et al. Prepared nitrogen-doped hollow mesoporous carbon nanospheres in microemulsion system[86]. Among them, the conjugation effect of nitrogen lone pair electrons and graphitized carbon produces unique electronic characteristics, which makes it an excellent electrocatalytic performance as a metal-free ORR electrocatalyst. The rotating disk electrode test in 0.1 M KOH showed that the ORR activity was comparable to that of the commercial Pt/C catalyst, and the catalyst exhibited superior ORR stability and methanol resistance. In addition, mesoporous carbon materials, as the support of photocatalyst, can significantly improve the photocatalytic efficiency. Bi et al. Employed a solvothermal method to introduce TiO2 catalyst into mesoporous carbon materials (MC-TiO2), which showed enhanced response in both UV and visible light regions[87]. The MC-TiO2 was used to degrade simulated phenol wastewater, and the photodegradation efficiency was more than 81% after 150 min of reaction, and the photodegradation efficiency was still more than 75% after 5 times of reuse.

4.3 Adsorption field

Over the past few decades, the increasing concentration of CO2 in the atmosphere has led to global climate change, which is the most challenging problem in the 21st century. From the point of view of environmental protection, it is of great significance to capture the generated CO2 and convert them into clean fuels or chemicals without pollution, so as to realize the simultaneous conversion and utilization of CO2, which is of great significance to achieve the goal of "carbon neutrality"[88]. Mesoporous materials have been widely used in the field of CO2 adsorption due to their high void content and low cost. In addition, mesoporous materials can act as catalysts, providing a platform with multiple catalytic sites and high porosity for the conversion of CO2 to CO, HCOO, and CH3OH for high charge transfer. Nitrogen-doped mesoporous carbon materials, in particular, play a key role in driving the CO2 reduction activity through the nitrogen defect sites constructed in the hexagonal graphite framework[89,90]. In addition, mesoporous carbon with basic functional groups such as nitrogen element can enhance the adsorption capacity and adsorption selectivity for CO2 acid gas through acid-base interaction or hydrogen bonding[91⇓⇓~94]. Yuan et al. Prepared mesoporous carbon with rich microporous structure by replacing corrosive acid such as hydrochloric acid with environmentally friendly citric acid and phenolic resin as carbon precursor[95]. The abundant carboxyl groups of citric acid can enhance the hydrogen bonding force between the block copolymer and the precursor, and introduce more micropores in the synthesized carbon materials, which is more conducive to the adsorption of CO2. The carbonized mesoporous carbon material is nitrided in an ammonia atmosphere, and the ammonia decomposes into a plurality of transition state products at a high temperature, and the excited state substances can react with the surface of the carbon to generate nitrogen-containing functional groups, such as —NH2, — CN, pyridyl, pyrrolyl and four-coordinated nitrogen, which can improve the CO2 capture. The CO2 adsorption capacity of the sample after nitridation at 650 ° C was 2.43mmol·L-1. With the increase of nitriding temperature, the content of introduced nitrogen increases, which further increases the adsorption capacity of the material for CO2, and the CO2 adsorption capacity of the sample nitrided at 1000 ℃ increases to 3.46mmol·L-1. Dai et al. Used biomass tannic acid as carbon precursor and amino acid, urea, melamine, guanine, etc. As nitrogen sources to achieve in situ nitrogen doping of mesoporous carbon under the action of a high-energy ball mill[56]. The as-synthesized mesoporous carbon has a high specific surface area of up to 707 m2·g-1, with high CO2 adsorption capacity and adsorption selectivity. In addition to the field of CO2 adsorption, some mesoporous carbon materials have also been used for pollution treatment. Yu et al. Developed dendriform mesoporous carbon nanoparticles with large open radial pore channels and highly accessible surface area (1218 m2·g-1), which have efficient anthracene adsorption ability (947.9mg·g-1)[96]. Moreover, this large radial porosity and bimodal pore size distribution (2.1 nm and 18.4 nm), allow it to exhibit fast adsorption kinetics. Kalantari et al. Prepared mesoporous carbon with hollow structure and used it to study the adsorption of organic pollutant di-n-butyl phthalate[97]. The results showed that it had a strong adsorption capacity, and the adsorption capacity decreased by only 12% after five times of reuse. In addition, in addition to the excellent adsorption properties of mesoporous nanospheres, our group also introduced metal elements (such as Fe) into mesoporous carbon to prepare magnetic mesoporous nanomaterials[98]. The magnetic separation capability of this adsorbent material enables the recovery of the adsorbent and the reprocessing of pollutants. In addition, the reduction characteristics of Fe element can reduce pollutants and reduce their chemical toxicity.

4.4 Field of drug delivery

Mesoporous carbon materials have unique physical and chemical properties, such as easily modified surface, photothermal conversion ability, supramolecular π-π stacking, ideal compatibility, high adsorption capacity and therapeutic function, which have good application prospects in drug delivery, multimodal bioimaging, chemo-photothermal synergistic therapy, biosensors and other medical fields[99⇓⇓~102]. The steric hindrance effect provided by the mesoporous channels can inhibit the recrystallization of drugs, improve the dispersion of drug molecules, and control the release of drugs. Compared with mesoporous silicon materials, mesoporous carbon materials have sp2 hybrid frameworks, and their high drug loading rate is favored by many people[103,104]. The drug can be in direct contact with the hot spots on the pore wall to adjust the drug release performance. Zhao Dongyuan et al. Prepared amphiphilic mesoporous carbon/silicon composite nanospheres (MC@MSiO2) with core-shell structure[105]. As a drug carrier, MC@MSiO2 can be loaded with hydrophilic drug cisplatin and hydrophobic drug paclitaxel, and the loading amount is 12.6% and 10.2%, respectively. The double drug-loaded material realizes the synergistic effect of drugs, has obvious inhibitory effect on human ovarian cancer cells, and even has more than 50% killing effect on drug-resistant cells.
Liu et al. Synthesized raspberry-like mesoporous carbon nanoparticles (RS-NMCNs) in a dual-template system by emulsion method[40]. The RS-NMCNs exhibited low cytotoxicity and good biocompatibility due to the large cavity and hierarchical pores, which are different from those of ordinary spherical mesoporous carbon. FITC-labeled RS-NMCNs were co-cultured with human immortalized epidermal (HaCaT) cells, and laser confocal images showed that they could be well taken up by the cells. As a drug carrier, RS-NMCNs greatly improved the in vitro dissolution of the poorly soluble drug carbamazepine, up to 90% within 180 min, providing a successful example for improving the in vitro performance of poorly soluble drugs (Figure 9 A). Using the microemulsion-induced strategy, our research group also prepared mesoporous carbon @ silicon composite nanoparticles with multiple morphologies for the delivery of anticancer drug 5-fluorouracil (Fig. 9b)[44]. Hemolysis experiments showed that hollow, multi-cavity and bowl-shaped mesoporous carbon @ silicon nanoparticles had good biocompatibility. Bowl-shaped mesoporous carbon @ silicon shows better ability to be taken up by cells, which is due to its special structure similar to red blood cells with greater mechanical strength, which is conducive to intracellular transport. This also illustrates that the structure of mesoporous materials plays an important role in their practical applications. Rational design of functionalized mesoporous carbon nanoparticles with easy cell internalization, multi-morphology and multi-drug loading is the future development direction.

5 Conclusion and prospect

Mesoporous carbon with structural diversity and controllable morphology has become a research hotspot because of its superior performance. At present, researchers have prepared a variety of mesoporous carbon nanoparticles with novel morphologies by microemulsion method. Mesoporous carbon materials have developed new properties based on their inherent advantages through the control of pore size, external morphology and internal structure of particles. It is widely used in the fields of energy storage and conversion, catalysis, adsorption and separation, and drug delivery, and has broad prospects for development. Although great progress has been made, the preparation of mesoporous carbon materials by emulsion method is still in the research stage, and there are still many difficulties to be solved in the design of special mesoporous structure, the establishment of structure-function relationship, and related theories. These obstacles, while hampering development, point the way to the future of the field.
(1) With the deepening of research, it is a hot spot and development direction of mesoporous carbon materials to explore environmentally friendly, mild conditions and large-scale production synthetic routes to prepare mesoporous carbon. At present, the preparation of mesoporous carbon materials is mostly based on the organic-organic self-assembly of precursors and templates. Among them, the interaction between precursor and template mostly depends on strict hydrothermal conditions or corrosive acid and alkali to construct. This makes the synthesis process more cumbersome and potentially harmful to the environment and human body. The use of non-toxic and inexpensive carbon precursors (such as biomass polysaccharides and polyphenols) and catalysts to achieve the green synthesis of mesoporous carbon is a goal that needs to be pursued.
(2) Preparation of multicomponent anisotropic mesoporous carbon nanoparticles with precisely controlled structure. A single material or structure limits the multifunctional use of the material, so composite materials that fuse multiple components or structures are needed. Anisotropic nanostructures can provide more opportunities to tune their properties due to increased complexity, contributing to improved performance compared to isotropic structures. At present, most of the anisotropic materials developed by microemulsion method are dominated by interfacial energy, and exploring more routes to construct complex multi-morphology and multi-chamber mesoporous nanoparticles will lead the future research direction. On the other hand, precise manipulation of nucleation sites (number, location, orientation, etc.) is also crucial. If the position of anisotropic assembly can be precisely controlled, different mesoporous units can be used as modular units to prepare multi-unit mesoporous nanomaterials in the true sense.

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Funding

Natural Science Foundation of Guangdong Province(2022A1515011225)

Key Project for Innovation/ Enhancing Guangdong Pharmaceutical University(2020ZDZX2023)

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