Min‐Sik Kim

Nanostructured porous carbon materials have diverse applications including sorbents, catalyst supports for fuel cells, electrode materials for capacitors, and hydrogen storage systems. When these materials have hierarchical porosity, interconnected pores of different dimensions, their potential application is increased. Hierarchical nanostructured carbons (HNCs) that contain 3D-interconnected macroporous/mesoporous and mesoporous/microporous structures have enhanced properties compared with single-sized porous carbon materials, because they have improved mass transport through the macropores/mesopores and enhanced selectivity and increased specific surface area on the level of fine pore systems through mesopores/micropores. The HNCs with macro/mesoporosity are of particular interest because chemists can tailor specific applications through controllable synthesis of HNCs with designed nanostructures. An efficient and commonly used technique for creating HNCs is "nanocasting", a technique that first involves the creation of a sacrificial silica template with hierarchical porous nanostructure and then the impregnation of the silica template with an appropriate carbon source. This is followed by carbonization of the filled carbon precursor, and subsequent removal of the silica template. The resulting HNC is an inverse replica of its parent hierarchical nanostructured silica (HNS). Through such nanocasting, scientists can create different HNC frameworks with tailored pore structures and narrow pore size distribution. Generally, HNSs with specific structure and 3D-interconnected porosity are needed to fabricate HNCs using the nanocasting strategy. However, how can we fabricate a HNS framework with tailored structure and hierarchical porosity of meso-macropores? This Account reports on our recent work in the development of novel HNCs and their interesting applications. We have explored a series of strategies to address the challenges in synthesis of HNSs and HNCs. Through careful control of experimental parameters, we found we could readily create new HNSs and HNCs with tailored structure and hierarchical porosity. In this Account, we describe the applications of the HNCs in low-temperature fuel cells, in Li ion batteries, in quantum-dot-sensitized solar cells (QDSSCs) and as hydrogen storage materials. Fuel cell and QDSSC polarization performance data reveal that both the ordered HNC and spherical HNC with uniform macro- and mesoporosity demonstrate superior catalyst support effect and considerably enhanced photovoltaic performance due to their incredible structural characteristics. For hydrogen and lithium storage applications, primary experimental results show that spherical HNCs with uniform macroporous core/mesoporous shell and ordered HNC are highly beneficial in terms of a high hydrogen (or Li) uptake, good rate capability and excellent cycling retainability. These data suggest that the innovative HNCs with tailored nanostructure may find promising applications in the rapid and efficient storage of hydrogen (or Li).

A simple and efficient approach has been developed for synthesis of carbon-supported Pt nanoparticles (NPs) that combines homogeneous deposition (HD) of Pt complex species through a gradual increase of pH realized by in situ hydrolysis of urea and subsequent uniform reduction by ethylene glycol (EG) in a polyol process, giving control over the size and dispersion of Pt NPs. With increasing amount of urea in the starting Pt salt aqueous solution, the size of Pt complex species decreases and so does that of the metallic Pt NPs. The decrease in size of the Pt species is likely attributable to two determining factors: the steric contraction effect and the electrostatic charge effect. The excellent electrocatalysis ability of the Pt catalysts produced by HD-EG is demonstrated through the determination of electrochemical surface area and fuel-cell polarization performance. The Pt NPs deposited on Vulcan XC-72 (VC) carbon black by the HD-EG strategy show smaller size with more uniform dispersion, higher Pt utilization efficiency, and considerably improved fuel-cell polarization performance compared with the Pt NPs prepared by conventional sodium borohydride reduction or by a microwave-assisted polyol approach. Particularly important and significant is that this HD-EG method is very efficient for the synthesis of high Pt loading catalysts with tunable NP size and uniform particle dispersion. A high metal loading catalyst such as Pt(60 wt %)/VC fabricated by the HD-EG method outperforms ones with mid-to-low metal loadings (i.e., 40 and 20 wt %), even at a very low catalyst loading of 0.2 mg of Pt cm−2 at the cathode, which is for the first time reported for the VC-supported Pt catalysts.