College of Chemical and Biological Engineering, Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, Zhejiang University, 310027, Hangzhou, P. R. China.
Institute of Zhejiang University - Quzhou, Zheda Rd. #99, 324000, Quzhou, P.R. China.
Chemphyschem. 2023 Jun 1;24(11):e202200949. doi: 10.1002/cphc.202200949. Epub 2023 Mar 16.
The performance of heteronuclear clusters [AlXO ] (X=Al, AlO , AlMg O , AlZnO, AlAu , Mg, Y, VO, NbO, TaO) in activating methane has been explored by a combination of high-level quantum calculations with reported and supplementary gas-phase experiments. With different dopants in [AlXO ] , the mechanism, reactivity and selectivity towards methane activation varies accordingly. The classic HAT competes with PCET, depending on the composition of intramolecular interactions. Although the existence of terminal oxygen radical is beneficial for classic HAT, the Al -C interaction in the [AlXO ] clusters as enhanced by the strongly electronegative doping groups (X=Al, AlZnO, Mg, Zn, VO, NbO, TaO) favors the PCET process, facilitating C-H bond breaking. In addition, with different dopants, the destiny of the split methyl group varies accordingly. While strong interaction between Al and CH results in the formation of the Al -C bond, dopants with variable valance may promote the formation of deep-oxidation products like formaldehyde. It has been discussed in detail how to regulate the activity and selectivity of the active center of the catalyst via rational doping.
通过将高水平量子计算与报道和补充的气相实验相结合，研究了杂核簇[AlXO]（X=Al、AlO、AlMgO、AlZnO、AlAu、Mg、Y、VO、NbO、TaO）激活甲烷的性能。在[AlXO]中使用不同的掺杂剂，甲烷激活的机理、反应性和选择性会相应变化。经典的 HAT 与 PCET 竞争，这取决于分子内相互作用的组成。虽然末端氧自由基的存在有利于经典 HAT，但[AlXO]簇中 Al-C 相互作用（通过强电负性掺杂基团增强，X=Al、AlZnO、Mg、Zn、VO、NbO、TaO）有利于 PCET 过程，促进 C-H 键断裂。此外，不同的掺杂剂会导致分裂甲基基团的命运也不同。虽然 Al 和 CH 之间的强相互作用导致 Al-C 键的形成，但变价掺杂剂可能会促进像甲醛这样的深度氧化产物的形成。详细讨论了如何通过合理掺杂来调节催化剂活性中心的活性和选择性。
