Interlayer anions modulated ZnAl-layered double hydroxides for enhanced photocatalytic CO2 reduction

Photocatalytic CO2 reduction has drawn widespread attention across all sectors of society. Layered double hydroxides (LDHs) have emerged as promising photocatalysts, renowned for their adjustable bandgaps and reaction sites. As a typical anionic layered material, LDHs exhibit intricate interactions between interlayer anions and brucite-like metal layers, greatly influencing their inherent physicochemical properties. In this work, we synthesized ZnAl-LDH samples intercalated with four distinct anions: carbonate (CO32–), chloridion (Cl–), nitrate (NO3–), and dodecyl sulfate (DS–), denoted as LDH-CO3, LDH-Cl, LDH-NO3, and LDH-DS, respectively. These LDHs samples have comparable crystallinity and morphology but differ in their interlayer spacing. XRD results reveal interlayer spacings of 0.77 nm for LDH-CO3, 0.78 nm for LDH-Cl, 0.88 nm for LDH-NO3, and 1.24 nm for LDH-DS, bwtween adjacent brucite-like ZnAl hydroxide layers. Remarkably, LDH-NO3 demonstrates the highest photocatalytic CO2 reduction performance, with CO as the primary reduction product. Specifically, the average CO production rate of LDH-NO3 are 3.80 μmol g–1 h–1, surpassing that of LDH-CO3, LDH-Cl, and LDH-DS by 1.9, 2.1, and 2.5 times, respectively. This superior performance can be attributed to the intermediate interlayer spacing of LDH-NO3, which facilitates strong light absorption and a robust local built-in electric field. Theses properties enhance charge generation and separation abilities, leading to efficient photocatalytic reactions. The obtained results highlight the critical role of controlling small molecules within the interlayer, alongside defects, in the design and fabrication of layered-structure photocatalysts. This study provides valuable insights into optimizing the performance of LDH-based photocatalysts for CO2 reduction and potentially other photocatalytic applications.