Yang Qihao, Peng Huaitao, Zhang Qiuju, Qian Xu, Chen Xu, Tang Xuan, Dai Sheng, Zhao Jiajun, Jiang Kun, Yang Qiu, Sun Jian, Zhang Linjuan, Zhang Nian, Gao Honglin, Lu Zhiyi, Chen Liang
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, 315201, P. R. China.
University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Adv Mater. 2021 Nov;33(45):e2103186. doi: 10.1002/adma.202103186. Epub 2021 Sep 18.
Highly active catalysts that can directly utilize renewable energy (e.g., solar energy) are desirable for CO value-added processes. Herein, aiming at improving the efficiency of photodriven CO cycloaddition reactions, a catalyst composed of porous carbon nanosheets enriched with a high loading of atomically dispersed Al atoms (≈14.4 wt%, corresponding to an atomic percent of ≈7.3%) coordinated with N (AlN motif, Al-N-C catalyst) via a versatile molecule-confined pyrolysis strategy is reported. The performance of the Al-N-C catalyst for catalytic CO cycloaddition under light irradiation (≈95% conversion, reaction rate = 3.52 mmol g h ) is significantly superior to that obtained under a thermal environment (≈57% conversion, reaction rate = 2.11 mmol g h ). Besides the efficient photothermal conversion induced by the carbon matrix, both experimental and theoretical analysis reveal that light irradiation favors the photogenerated electron transfer from the semiconductive Al-N-C catalyst to the epoxide reactant, facilitating the formation of a ring-opened intermediate through the rate-limiting step. This study not only provides an advanced Al-N-C catalyst for photodriven CO cycloaddition, but also furnishes new insight for the rational design of superior photocatalysts for diverse heterogeneous catalytic reactions in the future.
对于CO增值过程而言，能够直接利用可再生能源（如太阳能）的高活性催化剂是非常理想的。在此，为了提高光驱动CO环加成反应的效率，本文报道了一种通过通用的分子限域热解策略制备的催化剂，该催化剂由富含高负载量原子分散Al原子（≈14.4 wt%，对应原子百分比≈7.3%）且与N配位（AlN motif，Al-N-C催化剂）的多孔碳纳米片组成。Al-N-C催化剂在光照下催化CO环加成的性能（≈95%转化率，反应速率 = 3.52 mmol g⁻¹ h⁻¹）显著优于在热环境下的性能（≈57%转化率，反应速率 = 2.11 mmol g⁻¹ h⁻¹）。除了碳基体诱导的高效光热转换外，实验和理论分析均表明，光照有利于光生电子从半导体Al-N-C催化剂转移至环氧化物反应物，从而通过限速步骤促进开环中间体的形成。本研究不仅为光驱动CO环加成提供了一种先进的Al-N-C催化剂，也为未来合理设计用于各种多相催化反应的优质光催化剂提供了新的见解。
