Macroscopic-scale template synthesis of robust carbonaceous nanofiber hydrogels and aerogels and their applications.

Hydrogels and aerogels are two typical families of gels, classified according to the medium they encompass, that is, water and air, respectively. Hydrogels have not only pervaded our everyday life in a variety of forms (e.g., fruit jellies, toothpaste, contact lenses, and hair gel), but have also been extensively explored as functional soft materials for use in various scientific fields. Replacing the liquid solvent in hydrogels or other wet gels by air without collapsing the network structure can lead to a new type of porous materials, namely, aerogels. Particularly, 3D nanoscale networks with open pores in the gels allow access and fast diffusion of ions and molecules, and thus hydrogels/aerogels have exhibited excellent performance as super adsorbents, electrode materials for batteries and supercapacitors, catalyst supports, and chemical and biological sensors. Despite their outstanding potential, several challenges in aerogel synthesis still must be addressed prior to their extensive practical application. The major problem associated with conventional aerogels is poor mechanical stability. The mechanical strength of aerogels could be enhanced by nanocasting conformal polymer coatings on preformed 3D networks, but this was accompanied by dramatic decreases in their porosity. Furthermore, to prevent the network from collapsing in a gel, supercritical drying is the most widely used technique for solvent removal. It is difficult to prepare low-cost aerogels on a large scale due to the limitations of industrial supercritical drying. Although several nanomaterials including carbon nanotubes, cellulose nanofibers, and the newly discovered graphene have been recently used as building blocks and assembled into monolithic gels, there is a lack of precise control of their physicochemical properties, particularly the size of building blocks, the porosity, and their surface chemistry, which are crucial in the further design and functionalization of aerogels for various applications. Here we report a new class of monolithic hydrogels/aerogels consisting of highly uniform carbonaceous nanofibers (CNFs), based on the recent, well-developed templatedirected hydrothermal carbonization (HTC) process. Compared with the conventional process for aerogel preparation, our synthetic method has some significant advantages: 1) Direct scaleup from 30 mL to 12 L just by using a large autoclave and without changing reactant concentrations and reaction time; 2) Easy and precise control of the structural parameters and mechanical strength of the CNF hydrogels/ aerogels over a wide range; and 3) Extraordinary flexibility and high chemical reactivity of the CNF gels give them great application potential. The synthesis of CNF gels is illustrated in Figure 1a. Ultrathin Te nanowire (TeNWs) templates are first dispersed in glucose solution to form a homogenous mixture (step 1 in Figure 1a). Hydrothermal treatment of the mixture at 180 8C for 12–48 h results in a mechanically robust monolithic gel-like product, which occupies the whole Teflon container and can be taken out directly without any damage (step 2 in Figure 1a; see also Supporting Information Figure S1a). The as-prepared wet gel can be easily cut into the desired shape (Supporting Information Figure S1b). After washing and chemical etching to remove TeNWs (Supporting Information Figure S2), the CNF hydrogel is formed (step 3 in Figure 1a). To obtain the CNF aerogel, water in the hydrogel is removed by freeze-drying (step 4 in Figure 1a and Supporting Information Figure S1c). A low-magnification SEM image of the aerogel reveals a highly porous network structure consisting of disordered nanofibers with uniform size (Figure 1c, left). There is no apparent difference in CNF size and distribution over the whole monolithic gel (Supporting Information Figure S3), that is, the network structure is homogeneous. Further SEM observations indicate that these highly uniform nanofibers interconnect with each other to a high degree through numerous junctions (Figure 1c, right). We hypothesize that these junctions are responsible for the outstanding mechanical properties of the gels. Formation of junctions between CNFs is not difficult to understand. In the original mixture before hydrothermal treatment, it was unavoidable that the TeNWs physically contacted or approached each other if their concentration reached a critical [*] Dr. H. W. Liang, Q. F. Guan, L. F. Chen, Z. Zhu, W. J. Zhang, Prof. S. H. Yu Division of Nanomaterials and Chemistry, Hefei National Laboratory for Physical Sciences at Microscale, Department of Chemistry, National Synchrotron Radiation Laboratory, University of Science and Technology of China Hefei, Anhui 230026 (China) E-mail: [email protected] Homepage: http://staff.ustc.edu.cn/~ yulab/