Constructing a fragmentary g-C3N4 framework with rich nitrogen defects as a highly efficient metal-free catalyst for acetylene hydrochlorination
Graphitic carbon nitride (denoted as “g-C3N4”), as a graphite-like CN material, is widely used in catalysis. In this paper, a fragmentary g-C3N4 framework with a porous structure and rich nitrogen defects was synthesized for acetylene hydrochlorination, using melamine formaldehyde (MF) resin as an oxygen-containing precursor. The fragmentary g-C3N4 shows a highly efficient activity with acetylene conversion reaching 94.5%, which is 30 times higher than that of pure g-C3N4 prepared by direct pyrolysis of melamine. Both experimental and characterization studies by XRD, XPS and TG-MS reveal that the high activity of the catalyst is mainly derived from the porous structure and rich nitrogen defects, which are attributed to the etching of the g-C3N4 framework by oxygen species in the MF resin. Moreover, density functional theory (DFT) calculations demonstrated that the nitrogen defects in the g-C3N4 framework greatly improved the adsorption of HCl and acetylene, and at the same time significantly reduced the energy barrier from 62.0 to 38.1 kcal mol−1 at the rate-determining step.