Chandra Moumita, Guharoy Utsab, Pradhan Debabrata
Materials Science Centre, Indian Institute of Technology Kharagpur, Kharagpur, West Bengal 721302, India.
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China.
ACS Appl Mater Interfaces. 2022 May 18;14(19):22122-22137. doi: 10.1021/acsami.2c03230. Epub 2022 May 4.
The present research aims at the elevation of solar-to-chemical energy conversion with extortionate performance and sustainability. The nanostructured materials are revolutionizing the water splitting technology into decoupled hydrogen with simultaneous value-added organic chemical production. Yet, the bottleneck in semiconductor photocatalysis is rapid charge recombination and sluggish reaction kinetics. Herein, we demonstrate an efficient and non-noble metal-based catalyst for successful redox reaction with a theoretical modeling through density functional theory (DFT) study. Implementing this robust approach on 2/1D ultrathin g-CN nanosheets and TiO nanowires heterojunction, we achieved H production of 5.1 mmol g h with apparent quantum efficiency of 7.8% under visible light illumination and 93% of benzylamine conversion to -benzylidene benzylamine in situ. The interface of 2D g-CN nanosheets and 1D nanowires provide ample active sites and extends the visible light absorption with requisite band edge position for the separation of photoinduced charge carriers with superior stability. The electronic properties, band structure, and stability of the heterojunction are further investigated via DFT calculations which corroborate the experimental results and in good agreement for the enhanced activity of the heterojunction.
本研究旨在以优异的性能和可持续性提升太阳能到化学能的转换。纳米结构材料正在将水分解技术变革为同时生产增值有机化学品的解耦制氢。然而，半导体光催化的瓶颈在于快速的电荷复合和缓慢的反应动力学。在此，我们通过密度泛函理论（DFT）研究的理论建模，展示了一种用于成功氧化还原反应的高效非贵金属基催化剂。在二维/一维超薄石墨相氮化碳（g-CN）纳米片和二氧化钛（TiO）纳米线异质结上采用这种稳健方法，我们在可见光照射下实现了5.1 mmol g⁻¹ h⁻¹的产氢量，表观量子效率为7.8%，并且苄胺原位转化为亚苄基苄胺的转化率达到93%。二维g-CN纳米片和一维纳米线的界面提供了充足的活性位点，并通过必要的能带边缘位置扩展了可见光吸收，以实现具有卓越稳定性的光生电荷载流子分离。通过DFT计算进一步研究了异质结的电子性质、能带结构和稳定性，这些计算结果证实了实验结果，并与异质结活性增强的结果高度吻合。
