非贵金属肖特基结的强电子耦合效应增强了平方米级光催化氢进化

Wei Deng, Xuqiang Hao, Jiaqi Yang, Zhiliang Jin
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摘要

光催化制氢技术利用太阳能将水分解成氢气,有助于缓解能源枯竭的压力。将非贵金属纳米材料作为协同催化剂,可在低成本、可持续和大规模光催化制氢方面发挥重要作用。本文采用两步水热法制备了具有强电子耦合效应的 MnCdS-Vs/NiCoS (MCSN) 肖特基结纳米材料,并成功应用于平方米氢气进化装置。优化后的 MCSN 材料具有 34.28 mmol g h 的高氢气进化活性,分别是纯 MnCdS-Vs 和 NiCoS 的 9.34 倍和 685.60 倍。更重要的是,在一平方米(1 m)的平板反应器中,MCSN 在 5 小时内产生了约 201 mmol 的氢气进化,展示了其大规模应用的潜力。XPS 和 DFT 计算表明,MnCdS-V 与 NiCoS 相互作用,产生了强烈的电子耦合效应,形成了一个肖特基结。它不仅促进了光生电子从 MnCdS-Vs 向 NiCoS 的定向迁移,还有效抑制了电子通过肖特基势垒的回流。此外,丰富的硫空位增强了可见光吸收能力,进一步提高了光催化氢气进化性能。这项研究深入探讨了缺陷工程和肖特基结设计在提高光催化性能方面的作用,为光催化制氢技术从小规模实验室实验过渡到大规模实际应用提供了新的见解。
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Strong electron coupling effect of non-precious metal Schottky junctions enhanced square meter level photocatalytic hydrogen evolution
Photocatalytic hydrogen production technology utilizes solar energy to decompose water into hydrogen, helping to alleviate the pressure of energy depletion. Engineering of non-precious metal nanomaterials as cocatalysts can play a significant role in low-cost, sustainable, and large-scale photocatalytic hydrogen production. Herein, MnCdS-Vs/NiCoS (MCSN) Schottky junction nanomaterials with strong electron coupling effect were prepared by a two-step hydrothermal method and successfully applied to a square meter hydrogen evolution device. The optimized MCSN material demonstrated high hydrogen evolution activity of 34.28 mmol g h, which is 9.34 and 685.60 times higher than that of pure MnCdS-Vs and NiCoS, respectively. More importantly, in a square meter (1 m) flat-plate reactor, MCSN produced H evolution approximately 201 mmol in 5 h, showcasing its potential for large-scale applications. XPS and DFT calculations demonstrated that MnCdS-V interacts with NiCoS to produce a strong electron coupling effect and form a Schottky junction. It promotes the facilitated the directional migration of photogenerated electrons from MnCdS-Vs to NiCoS, but also effectively suppressed electron backflow through the Schottky barrier. Furthermore, the abundance of sulfur vacancies enhanced visible light absorption capability, further improving photocatalytic hydrogen evolution performance. This work delves into the role of defect engineering and Schottky junction design in enhancing photocatalytic performance, providing new insights into transitioning photocatalytic hydrogen production technologies from small-scale laboratory experiments to large-scale practical applications.
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