Promotional mechanism of nitrogen-doping in activated carbon for formaldehyde removal: Enhanced attractive noncovalent interactions coupled with Cannizzaro-type disproportionation reaction

Abstract

Inserting nitrogen (N) heteroatoms into the carbonaceous adsorbents has been confirmed to be one of efficient strategies for enhancing HCHO removal. However, the essential promotion mechanisms of specific N-containing groups (such as pyridinic-N, pyrrolic-N, and quaternary-N) remain blurred. Herein, a series of N-doped activated carbons were prepared by annealing the melamine impregnated activated carbons at 600–900 °C and used for HCHO elimination. It manifested that the HCHO elimination performance of samples was remarkably improved after N-doping and their HCHO adsorption capacities were in the order of ACN-600 (16.37 mg/g) > ACN-750 (9.87 mg/g) > ACN-900 (7.28 mg/g) > AC (5.09 mg/g). DFT calculation results revealed that there existed stronger attractive noncovalent interactions between pyrrolic-N doped carbon and HCHO due to the formation of stronger H-bonds. Therefore, the HCHO physisorption energy on pyrrolic-N doped carbon was the highest (−32.83 kJ/mol). Compared with the single physisorption mechanism of previous studies, the in-situ DRIFTS results manifested that the pyridinic-N atom (as a typical strong Lewis base) could trigger the Cannizzaro-type disproportionation reaction, which would transform toxic HCHO into relatively less toxic methanol and formic acid. Benefiting from the dual enhanced mechanisms of attractive noncovalent interactions and Cannizzaro-type disproportionation reaction, the ACN-600 manifested excellent HCHO removal performance. This study not only intrinsically discloses the promotion mechanism of specific N-containing groups on HCHO removal at molecular level but also provides guidelines for rational design and development of carbonaceous materials for effective HCHO elimination.