Tim Biemelt

Nanocasting Hierarchical Carbide-Derived Carbons in Nanostructured Opal Assemblies for High-Performance Cathodes in Lithium–Sulfur Batteries

Silica nanospheres are used as templates for the generation of carbide-derived carbons with monodisperse spherical mesopores (d=20-40 nm) and microporous walls. The nanocasting approach with a polycarbosilane precursor and subsequent pyrolysis, followed by silica template removal and chlorine treatment, results in carbide-derived carbons DUT-86 (DUT=Dresden University of Technology) with remarkable textural characteristics, monodisperse, spherical mesopores tunable in diameter, and very high pore volumes up to 5.0 cm3 g(-1). Morphology replication allows these nanopores to be arranged in a nanostructured inverse opal-like structure. Specific surface areas are very high (2450 m2 g(-1)) due to the simultaneous presence of micropores. Testing DUT-86 samples as cathode materials in Li-S batteries reveals excellent performance, and tailoring of the pore size allows optimization of cell performance, especially the active center accessibility and sulfur utilization. The outstanding pore volumes allow sulfur loadings of 80 wt %, a value seldom achieved in composite cathodes, and initial capacities of 1165 mAh gsulfur(-1) are reached. After 100 cycle capacities of 860 mAh gsulfur(-1) are retained, rendering DUT-86 a high-performance sulfur host material.

Unusual Ultra‐Hydrophilic, Porous Carbon Cuboids for Atmospheric‐Water Capture

There is significant interest in high-performance materials that can directly and efficiently capture water vapor, particularly from air. Herein, we report a class of novel porous carbon cuboids with unusual ultra-hydrophilic properties, over which the synergistic effects between surface heterogeneity and micropore architecture is maximized, leading to the best atmospheric water-capture performance among porous carbons to date, with a water capacity of up to 9.82 mmol g(-1) at P/P0 =0.2 and 25 °C (20% relative humidity or 6000 ppm). Benefiting from properties, such as defined morphology, narrow pore size distribution, and high heterogeneity, this series of functional carbons may serve as model materials for fundamental research on carbon chemistry and the advance of new types of materials for water-vapor capture as well as other applications requiring combined highly hydrophilic surface chemistry, developed hierarchical porosity, and excellent stability.

Polymer-derived nanoporous silicon carbide with monodisperse spherical pores

The synthesis of polymer-derived nanoporous silicon carbide with monodisperse spherical pores is described. An incipient wetness method was used to fill the interparticle voids of microemulsion-derived silica nanospheres with the polycarbosilane SMP-10. The spheres have a very narrow diameter distribution in the mesoscale that could be replicated as pores of the silicon carbide materials by performing pyrolysis in an inert atmosphere and subsequent HF etching. Using a pyrolysis temperature between 973 K and 1573 K control of the pore sizes, the specific surface areas as well as the silicon carbide structure was achieved. Shrinkage of the system due to crystallization and structure transformations seems to occur. Even for temperatures as high as 1573 K SiC with uniform spherical pores and specific surface areas up to 433.1 m2 g−1 could be synthesized. This class of silicon carbides (named DUT-45, DUT = Dresden University of Technology) is characterized by unique nitrogen physisorption performance and small angle X-ray scattering curves.

Nanoporous and Highly Active Silicon Carbide Supported CeO2-Catalysts for the Methane Oxidation Reaction

CeOx @SiO2 nanoparticles are used for the first time for the generation of porous SiC materials with tailored pore diameter in the mesopore range containing encapsulated and catalytically active CeO2 nanoparticles. The nanocasting approach with a preceramic polymer and subsequent pyrolysis is performed at 1300 °C, selective leaching of the siliceous part results in CeOx /SiC catalysts with remarkable characteristics like monodisperse, spherical pores and specific surface areas of up to 438 m(2) ·g(-1) . Porous SiC materials are promising supports for high temperature applications. The catalysts show excellent activities in the oxidation of methane with onset temperatures of the reaction 270 K below the onset of the homogeneous reaction. The synthesis scheme using core-shell particles is suited to functionalize silicon carbide with a high degree of stabilization of the active nanoparticles against sintering in the core of the template even at pyrolysis temperatures of 1300 °C rendering the novel synthesis principle as an attractive approach for a wide range of catalytic reactions.

Synthesis of Ordered Mesoporous Carbon Materials by Dry Etching

A novel synthesis method for ordered mesoporous carbons is presented. The inverse replication of a silica template was achieved using the carbonization of sucrose within mesoporous KIT-6. Instead of liquid acid etching, as in classical nanocasting, a novel dry chlorine etching procedure for template removal is presented for the first time. The resultant ordered mesostructured carbon material outperforms carbons obtained by conventional hard templating with respect to high specific micro- and mesopore volumes (0.6 and 1.6 cm(3) g(-1) , respectively), due to the presence of a hierarchical pore system. A high specific surface area of 1671 m(2) g(-1) was achieved, rendering this synthesis route a highly convenient method to produce ordered mesoporous carbons.