Ma Jin, Peng Cheng, Peng Xiaoxiao, Liang Sicheng, Zhou Zhixin, Wu Kaiqing, Chen Ran, Liu Songqin, Shen Yanfei, Ma Haibo, Zhang Yuanjian
Jiangsu Engineering Laboratory of Smart Carbon-Rich Materials and Device, Jiangsu Province Hi-Tech Key Laboratory for Bio-Medical Research, School of Chemistry and Chemical Engineering, Medical School, Southeast University, Nanjing 211189, China.
Qingdao Institute for Theoretical and Computational Sciences, School of Chemistry and Chemical Engineering, Shandong University, Qingdao 266237, China.
J Am Chem Soc. 2024 Jul 31;146(30):21147-21159. doi: 10.1021/jacs.4c07170. Epub 2024 Jul 16.
Driven by the essential need of a green, safe, and low-cost approach to producing HO, a highly valuable multifunctional chemical, artificial photosynthesis emerges as a promising avenue. However, current catalyst systems remain challenging, due to the need of high-density sunlight, poor selectivity and activity, or/and unfavorable thermodynamics. Here, we reported that an indirect 2e water oxidation reaction (WOR) in photocatalytic HO production was unusually activated by CN with piezoelectric effects. Interestingly, under ultrasonication, CN exhibited an overall HO photosynthesis rate of 918.4 μM/h and an exceptionally high solar-to-chemical conversion efficiency of 2.6% after calibration under weak light (0.1 sun). Mechanism studies showed that the piezoelectric effect of carbon nitride overcame the high uphill thermodynamics of *OH intermediate generation, which enabled a new pathway for 2e WOR, the kinetic limiting step in the overall HO production from HO and O. Benefiting from the outstanding sonication-assisted photocatalytic HO generation under weak light, the concept was further successfully adapted to biomedical applications in efficient sono-photochemodynamic therapy for cancer treatment and water purification.
受生产高价值多功能化学品过氧化氢所需的绿色、安全且低成本方法这一基本需求的驱动，人工光合作用成为一条有前景的途径。然而，由于需要高密度阳光、选择性和活性差，或/且热力学不利，目前的催化剂体系仍然具有挑战性。在此，我们报道了在光催化过氧化氢生产中，间接的2e水氧化反应（WOR）被具有压电效应的氮化碳异常激活。有趣的是，在超声处理下，氮化碳在弱光（0.1太阳）校准后表现出918.4 μM/h的总过氧化氢光合作用速率和2.6%的异常高的太阳能到化学能的转换效率。机理研究表明，氮化碳的压电效应克服了*OH中间体生成的高上坡热力学，这为2e WOR开辟了一条新途径，而2e WOR是从过氧化氢和氧气整体生产过氧化氢中的动力学限制步骤。受益于在弱光下出色的超声辅助光催化过氧化氢生成，该概念进一步成功应用于生物医学领域，用于癌症治疗和水净化的高效声-光化学动力疗法。
