Ghosh Rapti, Singh Mukesh, Chang Li Wei, Lin Hung-I, Chen Yu Siang, Muthu Jeyavelan, Papnai Bhartendu, Kang Yi Sun, Liao Yu-Ming, Bera Krishna Prasad, Guo Guang-Yu, Hsieh Ya-Ping, Hofmann Mario, Chen Yang-Fang
Molecular Science and Technology Program, Taiwan International Graduate Program, Academia Sinica, Taipei 106, Taiwan.
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 115, Taiwan.
ACS Nano. 2022 Apr 26;16(4):5743-5751. doi: 10.1021/acsnano.1c10772. Epub 2022 Apr 4.
The clean production of hydrogen from water using sunlight has emerged as a sustainable alternative toward large-scale energy generation and storage. However, designing photoactive semiconductors that are suitable for both light harvesting and water splitting is a pivotal challenge. Atomically thin transition metal dichalcogenides (TMD) are considered as promising photocatalysts because of their wide range of available electronic properties and compositional variability. However, trade-offs between carrier transport efficiency, light absorption, and electrochemical reactivity have limited their prospects. We here combine two approaches that synergistically enhance the efficiency of photocarrier generation and electrocatalytic efficiency of two-dimensional (2D) TMDs. The arrangement of monolayer WS and MoS into a heterojunction and subsequent nanostructuring into a nanoscroll (NS) yields significant modifications of fundamental properties from its constituents. Spectroscopic characterization and simulation demonstrate the beneficial effects of straining and wall interactions on the band structure of such a heterojunction-NS that enhance the electrochemical reaction rate by an order of magnitude compared to planar heterojunctions. Phototrapping in this NS further increases the light-matter interaction and yields superior photocatalytic performance compared to previously reported 2D material catalysts and is comparable to noble-metal catalyst systems in the photoelectrochemical hydrogen evolution reaction (PEC-HER) process. Our approach highlights the potential of morphologically varied TMD-based catalysts for PEC-HER.
利用阳光从水中清洁制氢已成为大规模能源生产和储存的一种可持续替代方案。然而，设计适用于光捕获和水分解的光活性半导体是一项关键挑战。原子级薄的过渡金属二硫属化物（TMD）因其广泛的可用电子性质和成分可变性而被视为有前景的光催化剂。然而，载流子传输效率、光吸收和电化学反应性之间的权衡限制了它们的前景。我们在此结合了两种方法，协同提高二维（2D）TMD的光载流子产生效率和电催化效率。将单层WS和MoS排列成异质结，随后纳米结构化形成纳米卷（NS），会使其基本性质与其组成成分相比产生显著变化。光谱表征和模拟表明，应变和壁相互作用对这种异质结-NS的能带结构具有有益影响，与平面异质结相比，其电化学反应速率提高了一个数量级。与之前报道的二维材料催化剂相比，这种NS中的光捕获进一步增强了光与物质的相互作用，并产生了优异的光催化性能，在光电化学析氢反应（PEC-HER）过程中与贵金属催化剂体系相当。我们的方法突出了形态多样的基于TMD的催化剂在PEC-HER方面的潜力。
