Heterogeneous acid catalysts were prepared by sulfonation of nanoporous carbons (NPCs). The NPCs were produced by pyrolysis of resorcinol–formaldehyde nanoporous resins (NPRs). The NPRs were synthesized as wet gels by condensation of resorcinol and formaldehyde in a sol–gel polycondensation using Na2CO3 as catalyst. A cationic polyelectrolyte (poly(diallyl dimethyl ammonium chloride)) was used as pore stabilizer, allowing to dry the gels in air without any special procedures. Five NPRs with different properties were synthesized by varying the monomer to catalyst ratio (Resorcinol/Na2CO3, R/C). The morphological and textural characterizations of the NPCs were performed by scanning electron microscopy and nitrogen adsorption–desorption isotherms. The results indicate that using a molar ratio of R/C=200, a nanoporous carbon NPC with large surface area (695m2/g) is obtained. This NPC was sulfonated by reaction with three different sulfonating agents: (i) concentrated sulfuric acid; (ii) fuming sulfuric acid and (iii) chlorosulfonic acid in order to obtain a novel Fischer esterification catalyst. The amount of acid groups attached to the NPC surface was determined by titration using a modified Boehm method. The catalytic activity, for Fischer esterification reaction of different sulfonated NPCs, was compared with sulfonated NPRs, sulfonated commercial porous carbons and polymeric acid catalyst (cationic ion exchange resins, sulfonated fluoropolymers). The modification of NPCs with concentrated sulfuric acid seems to render the materials with more catalytic activity. The best sulfonated material NPC (PC200-H2SO4) shows a high catalytic activity for the esterification of acetic acid (90.8%) and oleic acid (60.6%) with ethanol. The conversion and conversion rate values are better than commercial acid catalysts. The results suggest that sulfonated NPC catalysts are promising materials for the synthesis of biodiesel and related reactions

The interactions between a series of dendrimers with a porphyrin core (Pf-Ds) and alkaline cations (Li⁺, Na⁺ and K⁺) in DMF solution were studied by absorption and fluorescence spectroscopies. The solutions basified with an excess of NaOH or KOH showed spectral shifts that could be ascribed to the complexes formed between the Pf-Ds anions and the cations. Subsequent spectral shifts were observed by adding an aqueous solution of LiCl to the basic Pf-Ds solutions, at lithium concentrations several orders of magnitude lower than those of Na⁺ or K⁺. This striking preference towards Li⁺ was interpreted based on the formation of a more stable complex, since the smallest size of this ion fits in the deprotonated porphyrin core. Linear increases in the fluorescence emission were detected with sub-micromolar lithium concentrations, for all Pf-Ds studied. One of the compounds, namely C9, showed a linear fluorescence response at lithium concentrations as low as a few tens of nanomoles per liter. Both the selectivity and sensitivity observed suggest that the Pf-Ds analyzed have potential to be applied in sensing of Li⁺ in solution.