Abstract：
Artificial photosynthesis of hydrogen peroxide (H2O2) is a hopeful alternative to the industrial anthraquinone process. However, rational fabrication of the photocatalysts for the production of H2O2 without any sacrificial agents is still a formidable challenge. Herein, two kinds of linear conjugated polymers (LCPs) including pyridinic N functionalized polymer (DEB-N2) and pyridinic N non-contained polymer (DEB-N0) were successfully synthesized. DEB-N2 displays enhanced light capturing ability and good dispersion in water, leading to a substantial initial H2O2 generation rate of 3492μmol g-1h-1 as well as remarkable photocatalytic stability in pure water. Furthermore, the temperature programmed desorption (TPD) and density functional theory (DFT) analysis reveal that highly electronegative pyridine-N atoms in DEB-N2 boost the adsorption affinity of oxygen molecules, which facilitates the occurrence of the oxygen reduction reaction, therefore enhancing the performance of photocatalytic H2O2 production. This study unveils that the presence of pyridinic N in DEB-N2 has a significant impact on photocatalytic H2O2 production, suggesting the precise manipulation of the chemical structure of polymer photocatalysts is essential to achieve efficient solar-to-chemical energy conversion.
摘要：
过氧化氢（H2O2）的人工光合作用是工业蒽醌工艺的有希望的替代方案。然而,在没有任何牺牲剂的情况下，合理制造用于生产H2O2的光催化剂仍然是一个巨大的挑战。在这里，成功合成了两种线性共轭聚合物（LCP），包括吡啶N官能化聚合物（DEB-N2）和吡啶N不含聚合物（DEB-N0）。DEB-N2显示增强的光捕获能力和在水中的良好分散性，导致H2O2的初始生成速率为3492μmolg-1h-1，并且在纯水中具有显着的光催化稳定性。此外，程序升温脱附(TPD)和密度泛函理论(DFT)分析表明,DEB-N2中的高电负性吡啶-N原子增强了氧分子的吸附亲和力,这促进了氧还原反应的发生，因此提高了光催化H2O2生产的性能。这项研究揭示了吡啶N在DEB-N2中的存在对光催化H2O2的产生有显著的影响，这表明对聚合物光催化剂的化学结构的精确操纵对于实现有效的太阳能到化学能转换至关重要。
