The challenge of light-driven controlled radical polymerization through non-noble metal catalyst remains the most significant issue. Ferrocene-bearing microporous aromatic polymer nanosheets (termed “FeMAP-11”) that feature high chemical stability were reported here to synergistically combine the advantageous properties of the redox-active ferrocene units and the conjugated microporous polymers (CMPs), and to be able to serve as photocatalyst for activators regenerated by electron transfer atom transfer radical polymerization (AGET-ATRP). It succeeded in initiating polymerizations of 3 common vinyl monomers, i.e. methyl methacrylate (MMA), methacrylate (MA) and styrene (St), and produced polymers with controlled molecular weight and relatively low molecular weight dispersity (˜1.3). Benefiting from steric hindrance through ketone-amine chemistry, the microporous catalyst with tolerance to acidic and basic media was found stable under the AGET-ATRP conditions. It showed negligible metal leaching and good recyclability for at least 10 cycles without sacrifice of its catalytic performance. Our tests proved that FeMAP-11 exceeded the state-of-the-art ATRP photocatalysts such as UiO-66-NH₂, titanium MOF-901 and the commercial P-25 Titania, demonstrating promising potential in catalysis in view of green chemistry.

通过非贵金属催化剂进行光驱动受控自由基聚合的挑战仍然是最重要的问题。据报道，具有高化学稳定性的带有二茂铁的微孔芳族聚合物纳米片（称为“ FeMAP-11”）可协同结合氧化还原活性二茂铁单元和共轭微孔聚合物（CMP）的有利性能，并能够用作通过电子转移原子转移自由基聚合（AGET-ATRP）再生的活化剂的光催化剂。它成功引发了3种常见的乙烯基单体的聚合反应，即甲基丙烯酸甲酯（MMA），甲基丙烯酸酯（MA）和苯乙烯（St），并生产了具有可控制的分子量和相对较低的分子量分散度（〜1.3）的聚合物。通过酮胺化学从空间位阻中受益，在AGET-ATRP条件下发现对酸性和碱性介质具有耐受性的微孔催化剂是稳定的。它显示出可忽略不计的金属浸出和至少10个循环的良好可回收性，而没有牺牲其催化性能。我们的测试证明，FeMAP-11超过了最先进的ATRP光催化剂，例如UiO-66-NH参照图₂，MOF-901钛和市售的P-25二氧化钛，从绿色化学的角度证明了在催化方面的有前途的潜力。