Tuning the microenvironment surrounding single atom metals is an effective but challenging way to regulate the performance of single atom catalysts (SACs). Herein, we prepared a series of P, N-abundant porous organic polymers (P&N-POPs) with diverse framework flexibility and coordination ability to serve as SACs’ carriers. The microenvironment (coordination site, coordination number) surrounding Rh and the equilibrium of ea/ee-HRh(CO)₂P₂ active species were effectively regulated in Rh/P&N-POPs catalysts. Our study shows that the specific active ee-HRh(CO)₂(P)₂ species confined in the flexible polymeric skeleton endowed the Rh/mPPh₃&PPD-POP with superior activity (TOF = 2000 h⁻¹), selectivity of aldehydes (93.5 %), ratio of linear aldehyde to branched aldehyde (l/b ratio = 15.9), favorable stability (10 recycling runs without activity loss) and extensive substrate applicability (19 kinds of olefins) in hydroformylation reactions. Multiple characterization techniques (EXAFS, STEM, in-situ FTIR etc.) were employed to get insights into this effective strategy to regulate the performance of single atom catalysts (SACs).

调节单原子金属周围的微环境是调节单原子催化剂（SAC）性能的有效但具有挑战性的方法。在此，我们制备了一系列具有多种骨架灵活性和配位能力的富含P、N的多孔有机聚合物（P&N-POPs）作为SAC的载体。Rh/P&N-POPs催化剂中Rh周围的微环境（配位位点、配位数）和ea / ee -HRh(CO) ₂ P _{2活性物种的平衡得到有效调节。}我们的研究表明，限制在柔性聚合物骨架中的特定活性ee -HRh(CO) ₂ (P) _{2物种赋予了 Rh/} m PPh₃ &PPD-POP 具有优异的活性 (TOF = 2000 h ^-1 )、醛的选择性 (93.5 %)、直链醛与支链醛的比率 (l/b 比率 = 15.9)、良好的稳定性（10 次回收运行，无活性损失）加氢甲酰化反应中底物的广泛适用性（19 种烯烃）。采用多种表征技术（EXAFS、STEM、原位FTIR 等）来深入了解这种调节单原子催化剂 (SAC) 性能的有效策略。