Peng Yu, Zhang Yang, Wang Xing, Sui Xin Yuan, Lin Miao Yu, Zhu Yan, Jing Changfei, Yuan Hai Yang, Yang Shuang, Liu Peng Fei, Dai Sheng, Zheng Zhaoke, Yang Hua Gui, Hou Yu
Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Center, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
Angew Chem Int Ed Engl. 2024 Apr 8;63(15):e202319882. doi: 10.1002/anie.202319882. Epub 2024 Feb 26.
Polar materials with spontaneous polarization (P) have emerged as highly promising photocatalysts for efficient photocatalytic H evolution owing to the P-enhanced photogenerated carrier separation. However, traditional inorganic polar materials often suffer from limitations such as wide band gaps and poor carrier transport, which hinders their photocatalytic H evolution efficiency. Here, we rationally synthesized a series of isostructural two-dimensional (2D) aromatic Dion-Jacobson (DJ) perovskites, namely (2-(2-Aminoethyl)pyridinium)PbI (2-APDPI), (3-(2-Aminoethyl)pyridinium)PbI (3-APDPI), and (4-(2-Aminoethyl)pyridinium)PbI (4-APDPI), where 2-APDPI and 4-APDPI crystalize in polar space groups with piezoelectric constants (d) of approximately 40 pm V and 3-APDPI adopts a centrosymmetric structure. Strikingly, owing to the P-facilitated separation of photogenerated carriers, polar 2-APDPI and 4-APDPI exhibit a 3.9- and 2.8-fold increase, respectively, in photocatalytic H evolution compared to the centrosymmetric 3-APDPI. As a pioneering study, this work provides an efficient approach for exploring new polar photocatalysts and highlights their potential in promoting photocatalytic H evolution.
由于自发极化（P）增强了光生载流子的分离，具有自发极化的极性材料已成为高效光催化析氢极具前景的光催化剂。然而，传统的无机极性材料常常存在诸如宽带隙和载流子传输差等局限性，这阻碍了它们的光催化析氢效率。在此，我们合理合成了一系列同构的二维（2D）芳香狄翁 - 雅各布森（DJ）钙钛矿，即（2 - （2 - 氨基乙基）吡啶鎓）PbI（2 - APDPI）、（3 - （2 - 氨基乙基）吡啶鎓）PbI（3 - APDPI）和（4 - （2 - 氨基乙基）吡啶鎓）PbI（4 - APDPI），其中2 - APDPI和4 - APDPI在极性空间群中结晶，压电常数（d）约为40 pm V，而3 - APDPI采用中心对称结构。引人注目的是，由于自发极化促进了光生载流子分离，与中心对称的3 - APDPI相比，极性的2 - APDPI和4 - APDPI的光催化析氢分别提高了3.9倍和2.8倍。作为一项开创性研究，这项工作为探索新型极性光催化剂提供了一种有效方法，并突出了它们在促进光催化析氢方面的潜力。
