The borocarbonitrides (BCNs) have exhibited enormous potential as non-metallic catalysts for alkane oxidative dehydrogenation (ODH) reactions. However, the poor electron transportation ability in BCN leads to a low reactivity of oxygen functional groups (CO and BOH). Herein, we present a generalized strategy to promote the catalytic activity of BCN through in situ encapsulation of transition-metal (Fe, Co, Ni) nanoparticles within BCN nanotubes (BCNNTs). Among them, individual metal particles themselves do not contribute directly on ODH reactions and mainly serve as electron modulators to tune the electron density of CO and BOH active sites on BCNNTs. As a result, catalytic activities of all metal@BCNNTs catalysts surpass pure BCN in ethylbenzene (EB) ODH reactions, among which Fe@BCNNTs displays a significant activity enhancement with 36 % EB conversion with the styrene (ST) selectivity remaining >98% under gentle reaction conditions. Structural and kinetic analyses proved that the promotion effect originated from the strong interactions between metal nanoparticles and BCNNTs. The theoretical calculations disclosed that the enhanced ODH activity was due to the electron transfer from the encapsulated metal to BCNNTs, which increases the electron transportation ability and electron density of BCNNTs, thus promoting the nucleophilicity of CO and BOH active sites, leading to the reduced activation energy barrier for CH bond dissociation. The present work sets forth the structure-function relationship, identifying opportunities for rational design of highly efficient BCN catalysts for ODH reactions.

硼碳氮化物 (BCN) 作为烷烃氧化脱氢 (ODH) 反应的非金属催化剂显示出巨大的潜力。然而，差电子输送能力在BCN导致氧的官能团（一个低反应性Ç O和乙OH）。在此，我们提出了一种通用策略，通过在BCN 纳米管 (BCNNT) 内原位封装过渡金属（Fe、Co、Ni）纳米颗粒来提高 BCN 的催化活性。其中，单独的金属颗粒本身不上ODH反应直接贡献，主要作为电子调制器以调谐的电子密度Ç O和乙BCNNT 上的 OH 活性位点。因此，所有金属@BCNNTs 催化剂在乙苯（EB）ODH 反应中的催化活性都超过了纯 BCN，其中 Fe@BCNNTs 表现出显着的活性增强，EB 转化率为 36%，苯乙烯（ST）选择性保持>98%温和的反应条件。结构和动力学分析证明，促进作用源于金属纳米粒子与 BCNNT 之间的强相互作用。理论计算公开了增强ODH活性是由于来自包封的金属的电子转移到BCNNTs，这增加了电子输送能力和BCNNTs的电子密度，从而促进的亲核Ç O和乙OH 活性位点，导致C H 键解离的活化能垒降低。目前的工作阐述了结构 - 功能关系，确定了合理设计用于 ODH 反应的高效 BCN 催化剂的机会。