Nowadays, the photochemical conversion of CO₂ to high-value products is attracting tremendous research interest. Developing artificial photocatalysts with excellent catalytic activity and long-term stability is still a challenge. This work demonstrates that solution-processable naphthalenedimide (NDI)-based conjugated polymers, PNDI-BT, PNDI-DTBT, and PNDI-BP, which are copolymerization products of NDI with bithiophene (BT), 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (DTBT), and biphenyl (BP), respectively, were capable of catalyzing the photochemical reduction of CO₂ to produce CO in the presence of water without the need for metal-containing co-catalysts or sacrificial agents. In particular, the PNDI-BP-catalyzed reaction generated CH₄ as well as CO. Results from time-resolved photoluminescence, photovoltage decay, electrochemical impedance spectroscopy, and transient photocurrent response experiments indicate that PNDI-BP with the largest dihedral angles along the conjugated backbone possessed the longest electron lifetime, the lowest charge-carrier recombination rate, and the smallest interfacial charge transfer resistance. Consequently, it had the best catalytic performance. Notably, PNDI-BP exhibited excellent recyclability, robust structural stability, and extremely steady catalytic activity for more than 330 h during a photocatalytic CO₂ reaction. Furthermore, the solution-processability of the linear polymer allows the incorporation of porous substrates, which improve the reaction interface. The catalyst system of PNDI-BP@molecular sieves with H₂O/triethylamine doubled the CO yield to 214.8 μmol·g_cat^–1 and enhanced the CH₄ yield by ∼36 times to 61.4 μmol·g_cat^–1 in an 18 h reaction.

中文翻译：

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可溶液加工的萘二亚胺基共轭聚合物作为光催化 CO2 反应的有机催化剂，具有超过 330 小时的极其稳定的催化活性

目前，CO ₂光化学转化为高价值产品的研究引起了极大的关注。开发具有优异催化活性和长期稳定性的人工光催化剂仍然是一个挑战。这项工作证明了可溶液加工的萘酰亚胺 (NDI) 基共轭聚合物 PNDI-BT、PNDI-DTBT 和 PNDI-BP，它们是 NDI 与二噻吩 (BT)、4,7-di(thiophen-2) 的共聚产物-yl)benzo[c][1,2,5]thiadiazole (DTBT) 和联苯 (BP) 分别能够在水的存在下催化 CO ₂的光化学还原生成 CO，而不需要金属-含有助催化剂或牺牲剂。特别是，PNDI-BP 催化的反应生成 CH ₄时间分辨光致发光、光电压衰减、电化学阻抗谱和瞬态光电流响应实验的结果表明，沿共轭骨架具有最大二面角的 PNDI-BP 具有最长的电子寿命，最低的电荷载流子复合率和最小的界面电荷转移电阻。因此，它具有最好的催化性能。_{值得注意的是，PNDI-BP 在光催化 CO 2}过程中表现出优异的可回收性、稳健的结构稳定性和极其稳定的催化活性超过 330 小时。反应。此外，线性聚合物的溶液加工性允许掺入多孔基材，从而改善反应界面。PNDI-BP@分子筛与H ₂ O/三乙胺的催化剂体系在18小时内将CO产率提高了一倍，达到214.8 μmol·g _cat ^–1，将CH ₄产率提高了约36倍，达到61.4 μmol·g _cat ^–1反应。