Tan Hao, Kong Peng, Zhang Riguang, Gao Mengting, Liu Meixian, Gu Xianmo, Liu Weifeng, Zheng Zhanfeng
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
Innovation (Camb). 2021 Feb 6;2(1):100089. doi: 10.1016/j.xinn.2021.100089. eCollection 2021 Feb 28.
The controlled generation of reactive oxygen species (ROS) to selectively epoxidize styrene is a grand challenge. Herein, cyano-group-modified carbon nitrides (CNCY and CN-T ) are prepared, and the catalysts show better performance in regulating ROS and producing styrene oxide than the cyano-free sample. The diffuse reflectance infrared and density functional theory calculation results reveal that the cyano group acts as the adsorption and activation site of oxygen. X-ray photoelectron spectroscopy and NMR spectrum results confirm that the cyano group bonds with the intact heptazine ring. This unique structure could inhibit HO and OH formation, resulting in high selectivity of styrene oxide. Furthermore, high catalytic activity is still achieved when the system scales up to 2.7 L with 100 g styrene under solar light irradiation. The strategy of cyano group modification gives a new insight into regulating spatial configuration for tuning the utilization of oxygen-active species and shows potential applications in industry.
可控地生成活性氧（ROS）以选择性地环氧化苯乙烯是一项巨大的挑战。在此，制备了氰基修饰的碳氮化物（CNCY和CN-T），与无氰样品相比，这些催化剂在调节ROS和生成环氧苯乙烷方面表现出更好的性能。漫反射红外和密度泛函理论计算结果表明，氰基作为氧的吸附和活化位点。X射线光电子能谱和核磁共振光谱结果证实，氰基与完整的七嗪环键合。这种独特的结构可以抑制HO和OH的形成，从而实现环氧苯乙烷的高选择性。此外，当系统在太阳光照射下扩大到2.7 L并使用100 g苯乙烯时，仍能实现高催化活性。氰基修饰策略为调节空间构型以调控氧活性物种的利用提供了新的思路，并显示出在工业中的潜在应用。
