When High-Temperature Cesium Chemistry Meets Self-Templating: Metal Acetates as Building Blocks of Unusual Highly Porous Carbons.

Self-templating is a facile strategy for synthesizing porous carbons by direct pyrolysis of organic metal salts. However, the method typically suffers from low yields (<4%) and limited specific surface areas (SSA<2000 m2 g-1 ) originating from low activity of metal cations (e.g., K+ or Na+ ) in promoting construction and activation of carbon frameworks. Here we use cesium acetate as the only precursor of oxo-carbons with large SSA of the order of 3000 m2 g-1 , pore volume approaching 2 cm3 g-1 , tunable oxygen contents, and yields of up to 15 %. We unravel the role of Cs+ as an efficient promoter of framework formation, templating and etching agent, while acetates act as carbon/oxygen sources of carbonaceous frameworks. The oxo-carbons show record-high CO2 uptake of 8.71 mmol g-1 and an ultimate specific capacitance of 313 F g-1 in the supercapacitor. This study helps to understand and rationally tailor the materials design by a still rare organic solid-state chemistry.

"Red Carbon": A Rediscovered Covalent Crystalline Semiconductor.

Carbon suboxide (C3 O2 ) is a unique molecule able to polymerize spontaneously into highly conjugated light-absorbing structures at temperatures as low as 0 °C. Despite obvious advantages, little is known about the nature and the functional properties of this carbonaceous material. In this work, the aim is to bring "red carbon," a forgotten polymeric semiconductor, back to the community's attention. A solution polymerization process is adapted to simplify the synthesis and control the structure. This allows one to obtain this crystalline covalent material at low temperatures. Both spectroscopic and elemental analyses support the chemical structure represented as conjugated ladder polypyrone ribbons. Density functional theory calculations suggest a crystalline structure of AB stacks of polypyrone ribbons and identify the material as a direct bandgap semiconductor with a medium bandgap that is further confirmed by optical analysis. The material shows promising photocatalytic performance using blue light. Moreover, the simple condensation-aromatization route described here allows the straightforward fabrication of conjugated ladder polymers and can be inspiring for the synthesis of carbonaceous materials at low temperatures in general.

Mn(II) sub-nanometric site stabilization in noble, N-doped carbonaceous materials for electrochemical CO2 reduction.

The preparation of stable and efficient electrocatalysts comprising abundant and non-critical row-materials is of paramount importance for their industrial implementation. Herein, we present a simple synthetic route to prepare Mn(II) sub-nanometric active sites over a highly N-doped noble carbonaceous support. This support not only promotes a strong stabilization of the Mn(II) sites, improving its stability against oxidation, but also provides a convenient coordination environment in the Mn(II) sites able to produce CO, HCOOH and CH3COOH from electrochemical CO2 reduction.

Ultrahigh water sorption on highly nitrogen doped carbonaceous materials derived from uric acid.

HYPOTHESIS: Developing materials for thermally driven adsorption chillers and adsorption heat pumps is a growing research field due to the potential of these technologies to address up to 50% of the world's total energy demand. These materials must be abundant, easy to synthesize, hydrophilic, and low in cost. Bare carbon materials are hydrophobic and therefore usually not considered for these applications. However, by introducing heteroatoms and tuning their porosity, the hydrophilicity of carbonaceous networks can be increased significantly. EXPERIMENTAL: Herein, a series of highly nitrogen doped carbonaceous materials (CNs) have been synthesized by submitting uric acid to heat treatment at different temperatures in the presence of an inorganic salt mix as solvent and pore template. The effect of the thermal treatment on the materials composition, pore network, and water sorption capability has been studied. FINDINGS: At 800 °C, a nitrogen depleted carbonaceous material with a maximal water uptake of 1.38gH2O g-1 is obtained. Condensation at 750 °C creates an ultra-hydrophilic CN with a water uptake of 0.8 gH2O g-1 at already much lower partial pressures. While the maximum uptake is mainly ascribed to the mesopore volume of the material, the differences in hydrophilicity can be controlled by functionality.

Guanine-Derived Porous Carbonaceous Materials: Towards C1 N1.

Herein, the basic nature of noble covalent, sp2-conjugated materials prepared via direct condensation of guanine in the presence of an inorganic salt melt as structure directing agent was studied. At temperatures below 700 °C stable and more basic addition products with at C/N ratio of 1 (C1 N1 adducts) and with rather uniform micropore sizes were formed. Carbonization at higher temperatures broke the structural motif, and N-doped carbons with 11 wt % and surface areas of 1900 m2 g-1 were obtained. The capability for CO2 sorption and catalytic activity of the materials depended of both their basicity and their pore morphology. The optimization of the synthetic parameters led to very active (100 % conversion) and highly selective (99 % selectivity) heterogeneous base catalysts, as exemplified with the model Knoevenagel condensation of benzaldehyde with malononitrile. The high stability upon oxidation of these covalent materials and their basicity open new perspectives in heterogeneous organocatalysis.