Wu Lijun, Zheng Song, Lin Heng, Zhou Shun, Mahmoud Idris Ahmed, Wang Jin, Li Sheng, Li Zhengquan
Department of Physics, Zhejiang Normal University, Jinhua, Zhejiang 321004, PR China.
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, Zhejiang 321004, PR China.
J Colloid Interface Sci. 2023 Jan;629(Pt A):233-242. doi: 10.1016/j.jcis.2022.08.152. Epub 2022 Aug 27.
All-inorganic lead-free halide double perovskites have emerged as rising star photocatalysts to substitute the toxic lead-based hailed perovskites (LHPs) owing to their unique photophysical properties. Nevertheless, their photocatalytic activities toward CO reduction are still far from comparable with the LHPs, associated with severe charge recombination and sluggish surface catalytic reaction. Herein, a delicate 0D/2D heterojunction of CsAgBiBr/BiWO (CABB/BWO) was assembled by in-situ growing cubic CABB nanocrystals on the flat surface of BWO nanosheets via a facile hot-injection method. Density functional theory (DFT) calculations disclose that the work function and Fermi level difference between CABB and BWO give rise to charge redistribution at the interface upon the formation of the heterojunction, creating an internal electric field (IEF). Upon light irradiation, the IEF enables the photogenerated electron transfer from BWO to CABB via direct Z-scheme electron transfer mode with striking spatial charge separation as verified by in-situ X-ray photoelectron (XPS) and electron spin resonance (ESR) spectra. Consequently, the CABB/BWO heterojunction realizes 7-fold higher photocatalytic activity than pristine CABB with significant electron consumption rate of 87.66 µmol gh under simulated solar light (AM 1.5G).
全无机无铅卤化物双钙钛矿因其独特的光物理性质,已成为替代有毒铅基卤化物钙钛矿(LHP)的新兴光催化剂。然而,它们对CO还原的光催化活性仍远不及LHP,这与严重的电荷复合和缓慢的表面催化反应有关。在此,通过简便的热注入法在BWO纳米片的平坦表面上原位生长立方CABB纳米晶体,组装了一种精细的CsAgBiBr/BiWO(CABB/BWO)0D/2D异质结。密度泛函理论(DFT)计算表明,CABB和BWO之间的功函数和费米能级差导致异质结形成时界面处的电荷重新分布,产生内建电场(IEF)。光照下,IEF使光生电子通过直接Z型电子转移模式从BWO转移到CABB,原位X射线光电子能谱(XPS)和电子自旋共振(ESR)光谱证实了显著的空间电荷分离。因此,CABB/BWO异质结在模拟太阳光(AM 1.5G)下实现了比原始CABB高7倍的光催化活性,电子消耗速率高达87.66 μmol g⁻¹ h⁻¹。