Borocarbonitrides (BCNs) have emerged as highly selective catalysts for the oxidative dehydrogenation (ODH) reaction. However, there is a lack of in-depth understanding of the catalytic mechanism over BCN catalysts due to the complexity of the surface oxygen functional groups. Here, BCN nanotubes with multiple active sites are synthesized for oxygen-assisted methanol conversion reaction. The catalyst shows a notable activity improvement for methanol conversion (29%) with excellent selectivity to formaldehyde (54%). Kinetic measurements indicate that carboxylic acid groups on BCN are responsible for the formation of dimethyl ether, while the redox catalysis to formaldehyde occurs on both ketonic carbonyl and boron hydroxyl (B─OH) sites. The ODH reaction pathway on the B─OH site is further revealed by in situ infrared, x-ray absorption spectra, and density functional theory. The present work provides physical-chemical insights into the functional mechanism of BCN catalysts, paving the way for further development of the underexplored nonmetallic catalytic systems.

硼碳氮化物（BCN）已经成为用于氧化脱氢（ODH）反应的高选择性催化剂。然而，由于表面氧官能团的复杂性，对BCN催化剂的催化机理缺乏深入的了解。在此，合成具有多个活性位点的BCN纳米管用于氧辅助甲醇转化反应。该催化剂在甲醇转化率（29％）方面表现出显着的活性提高，对甲醛（54％）的选择性也极好。动力学测量表明，BCN上的羧酸基团负责形成二甲醚，而酮基羰基和硼羟基（B-OH）上均发生氧化还原催化甲醛的反应。通过原位红外，x射线吸收光谱进一步揭示了B‑OH位点上的ODH反应途径，和密度泛函理论 本工作提供了对BCN催化剂功能机理的物理化学见解，为进一步开发未开发的非金属催化体系铺平了道路。