Lai Ting-Hsuan, Tsao Chun-Wen, Fang Mei-Jing, Wu Jhen-Yang, Chang Yu-Peng, Chiu Yi-Hsuan, Hsieh Ping-Yen, Kuo Ming-Yu, Chang Kao-Der, Hsu Yung-Jung
Department of Materials Science and Engineering, National Chiao Tung University, Hsinchu 30010, Taiwan.
Department of Materials Science and Engineering, National Yang Ming Chiao Tung University, Hsinchu 30010, Taiwan.
ACS Appl Mater Interfaces. 2022 Sep 14;14(36):40771-40783. doi: 10.1021/acsami.2c07145. Epub 2022 Aug 30.
In this work, we demonstrated the practical use of Au@CuO core-shell and Au@CuSe yolk-shell nanocrystals as photocatalysts in photoelectrochemical (PEC) water splitting and photocatalytic hydrogen (H) production. The samples were prepared by conducting a sequential ion-exchange reaction on a Au@CuO core-shell nanocrystal template. Au@CuO and Au@CuSe displayed enhanced charge separation as the Au core and yolk can attract photoexcited electrons from the CuO and CuSe shells. The localized surface plasmon resonance (LSPR) of Au, on the other hand, can facilitate additional charge carrier generation for CuO and CuSe. Finite-difference time-domain simulations were carried out to explore the amplification of the localized electromagnetic field induced by the LSPR of Au. The charge transfer dynamics and band alignment of the samples were examined with time-resolved photoluminescence and ultraviolet photoelectron spectroscopy. As a result of the improved interfacial charge transfer, Au@CuO and Au@CuSe exhibited a substantially larger photocurrent of water reduction and higher photocatalytic activity of H production than the corresponding pure counterpart samples. Incident photon-to-current efficiency measurements were conducted to evaluate the contribution of the plasmonic effect of Au to the enhanced photoactivity. Relative to Au@CuO, Au@CuSe was more suited for PEC water splitting and photocatalytic H production by virtue of the structural advantages of yolk-shell architectures. The demonstrations from the present work may shed light on the rational design of sophisticated metal-semiconductor yolk-shell nanocrystals, especially those comprising metal selenides, for superior photocatalytic applications.
在本工作中，我们展示了Au@CuO核壳纳米晶体和Au@CuSe蛋黄壳纳米晶体作为光催化剂在光电化学（PEC）水分解和光催化制氢中的实际应用。通过在Au@CuO核壳纳米晶体模板上进行连续离子交换反应制备了样品。Au@CuO和Au@CuSe表现出增强的电荷分离，因为Au核和蛋黄可以吸引来自CuO和CuSe壳层的光激发电子。另一方面，Au的局域表面等离子体共振（LSPR）可以促进为CuO和CuSe产生额外的电荷载流子。进行了时域有限差分模拟，以探索由Au的LSPR引起的局域电磁场的增强。用时间分辨光致发光和紫外光电子能谱研究了样品的电荷转移动力学和能带排列。由于界面电荷转移得到改善，Au@CuO和Au@CuSe相对于相应的纯样品表现出显著更大的水还原光电流和更高的光催化产氢活性。进行了入射光子到电流效率测量，以评估Au的等离子体效应对增强光活性的贡献。相对于Au@CuO，由于蛋黄壳结构的结构优势，Au@CuSe更适合PEC水分解和光催化产氢。本工作的演示可能为设计复杂的金属 - 半导体蛋黄壳纳米晶体，特别是那些包含金属硒化物的纳米晶体，用于卓越的光催化应用提供启示。
