Engineering of Edge-Enriched Nitrogen-Doped Porous Carbon as a High-Performance Metal-Free Catalyst for Acetylene Hydrochlorination.

The development of efficient catalysts for acetylene hydrochlorination is critical for replacing the industrially prevalent mercury chloride catalysts. Herein, a defective nitrogen-doped carbon material (NC-APT) is engineered via a facile co-polymerization of pyrrole, aniline, and thiophene, followed by a controlled calcination procedure. This co-polymerization strategy introduces abundant structural defects compared to mono-polymerization processes, primarily due to the lattice mismatch and steric hindrance between the distinct monomers, which disrupts the regularity of the polymer chain and prevents graphitic ordering. The resulting NC-APT catalyst features a high specific surface area of 375.7 m2·g-1 and a substantial nitrogen dopant content of 14.4%, with 81% of the nitrogen existing as catalytically active edge structures (pyrrolic and pyridinic N). Consequently, the catalyst delivers exceptional performance, achieving 92% acetylene conversion at 220 °C with a C2H2 gas hourly space velocity (GHSV) of 80 h-1. This performance significantly outperforms many reported metal-free counterparts and rivals that of traditional metal-based catalysts. This work offers new insights into the rational design of carbon-based, metal-free catalysts through monomer mismatch engineering.