Catalytic Ethylene Oligomerization over Imine-Linked Covalent-Organic Frameworks with Coordinative Ni(II) and Cr(III)

作者：Lijun Guo, Yingchuan Zhang, Wei Chen, Yang Li, Da Song, Weiwei Yang, Jin Huang, Feng Li, Cuiqin Li, Zhengxiao Guo · 发表于：ACS Sustainable Chemistry & Engineering · 年份：2025 · DOI：10.1021/acssuschemeng.5c01284 · 被引用次数：10 · 研究领域：Covalent Organic Framework Applications、Metal-Organic Frameworks: Synthesis and Applications、Advanced Photocatalysis Techniques

High Resolution Image Download MS PowerPoint Slide Covalent-organic frameworks (COFs) hold great promise for heterogeneous catalysis due to their porous structure for gas adsorption and tunable functionality for bond activation. This study reports two flower-like shaped imine-linked COFs with coordinative Ni(II) and Cr(III) species, to endow Ni/PD-TPA COF and Cr/PD-TPA COF, for catalytic ethylene oligomerization. The synergy between imine nitrogen atoms and coordinated metals enables an exceptional activity (16.70 × 10 5 and 19.90 × 10 5 g/(mol M·h)) with high selectivity of butene and hexane (∼98.5%) in long-span catalytic processes, respectively. To optimize multiple reaction parameters (e.g., cocatalyst dosage, temperature, and time), Box–Behnken design (BBD) is employed as a statistical tool to establish a precise model integrating process parameters, catalyst structures, and catalytic performance. The optimized models exhibit high precision (indicated by high R values) in predicting the activity and selectivity of ethylene oligomerization over Cr/PD-TPA COF and Ni/PD-TPA COF, indicating the promise of BBD in reaction engineering and process design. M/PD-TPA COFs are highly active after three recycles and deliver the highest activity at ambient temperature and low pressure with a minimal quantity of cocatalysts compared with other catalysts. These findings demonstrate the potential of metal-loaded COFs for sustainable heterogeneous catalysis and provide insights into the ...