Tsai I-Hua, Huang Chun-Wei, Chang Chun-Fu, Diau Eric Wei-Guang
Department of Applied Chemistry, Institute of Molecular Science, National Yang Ming Chiao Tung University, 1001 Ta-Hseuh Rd., Hsinchu, 300093, Taiwan.
Center for Emergent Functional Matter Science, National Yang Ming Chiao Tung University, 1001 Ta-Hseuh Rd., Hsinchu, 300093, Taiwan.
Small. 2025 Jan;21(3):e2409023. doi: 10.1002/smll.202409023. Epub 2024 Nov 28.
A pseudohalide (SCN) tin-based perovskite material using a solvent-free ball milling method is developed. The synthesized perovskite exhibits long-term water stability and demonstrated significant photocatalytic activity in reducing CO to CO under light irradiation. The structural transition from nanoparticles to planar perovskites is achieved by varying the ratios of dimethylammonium (DMA) and formamidinium (FA) cations, which is confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses. The surface elemental distribution, absorption spectra, band gap and energy levels estimations using energy-dispersive X-ray spectroscopy (EDS), Kubelka-Munk function, and ultraviolet photoelectron spectroscopy (UPS) are thoroughly investigated. These findings indicated that the incorporation of DMA cations increased the band gap and shifted the absorption spectra toward the blue region. The optimal photocatalytic performance is observed for the perovskite composition with a 50% DMA cation ratio (DMAFASnI(SCN)), achieving a CO production yield of 285 µmol g with 12 hours irradiation in humid environment. The efficiency is critically dependent on the ball milling speed and duration, with 400 rpm and 1 hour being the optimal conditions. This research highlights the potential of environmentally friendly synthesis methods in developing stable and efficient lead-free perovskites as photocatalytic materials, contributing to the goal of net-zero carbon emissions.
通过无溶剂球磨法制备了一种拟卤化物（SCN）基锡钙钛矿材料。合成的钙钛矿具有长期的水稳定性，并且在光照下将CO还原为CO时表现出显著的光催化活性。通过改变二甲基铵（DMA）和甲脒（FA）阳离子的比例实现了从纳米颗粒到平面钙钛矿的结构转变，这通过X射线衍射（XRD）和扫描电子显微镜（SEM）分析得到证实。使用能量色散X射线光谱（EDS）、库贝尔卡-蒙克函数和紫外光电子能谱（UPS）对表面元素分布、吸收光谱、带隙和能级估计进行了深入研究。这些发现表明，DMA阳离子的掺入增加了带隙，并使吸收光谱向蓝色区域移动。对于DMA阳离子比例为50%的钙钛矿组合物（DMAFASnI（SCN）），观察到了最佳的光催化性能，在潮湿环境中光照12小时，CO产率达到285 µmol g。效率严重依赖于球磨速度和时间，400 rpm和1小时是最佳条件。这项研究突出了环境友好合成方法在开发稳定高效的无铅钙钛矿光催化材料方面的潜力，有助于实现净零碳排放目标。
