Metal–organic frameworks (MOFs), which are composed of crystalline microporous materials with metal ions, have gained considerable interest as promising substrate materials for surface-enhanced Raman scattering (SERS) detection via charge transfer. Research on MOF-based SERS substrates has advanced rapidly because of the MOFs’ excellent structural tunability, functionalizable pore interiors, and ultrahigh surface-to-volume ratios. Compared with traditional noble metal SERS plasmons, MOFs exhibit better biocompatibility, ease of operation, and tailorability. However, MOFs cannot produce a sufficient limit of detection (LOD) for ultrasensitive detection, and therefore, developing an ultrasensitive MOF-based SERS substrate is imperative. To the best of our knowledge, this is the first study to develop an MOFs/heterojunction structure as an SERS enhancing material. We report an in situ ZIF-67/Co(OH)₂ heterojunction-based nanocellulose paper (nanopaper) plate (in situ ZIF-67 nanoplate) as a device with an LOD of 0.98 nmol/L for Rhodamine 6G and a Raman enhancement of 1.43 × 10⁷, which is 100 times better than that of the pure ZIF-67-based SERS substrate. Further, we extend this structure to other types of MOFs and develop an in situ HKUST-1 nanoplate (with HKUST-1/Cu(OH)₂). In addition, we demonstrate that the formation of heterojunctions facilitates efficient photoinduced charge transfer for SERS detection by applying the M_x(OH)_y-assisted (where M = Co, Cu, or other metals) MOFs/heterojunction structure. Finally, we successfully demonstrate the application of medicine screening on our nanoplates, specifically for omeprazole. The nanoplates we developed still maintain the tailorability of MOFs and perform high anti-interference ability. Our approach provides customizing options for MOF-based SERS detection, catering to diverse possibilities in future research and applications.

中文翻译：

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用于表面增强拉曼散射的金属有机框架/异质结结构，具有增强的灵敏度和可定制性


金属有机框架（MOF）由带有金属离子的结晶微孔材料组成，作为通过电荷转移进行表面增强拉曼散射（SERS）检测的有前景的基底材料，引起了人们的广泛关注。由于 MOF 优异的结构可调性、可功能化的孔内部以及超高的表面积与体积比，基于 MOF 的 SERS 基底的研究取得了迅速进展。与传统的贵金属SERS等离子体相比，MOF表现出更好的生物相容性、易于操作和可定制性。然而，MOF 无法产生足够的检测限 (LOD) 来进行超灵敏检测，因此，开发基于 MOF 的超灵敏 SERS 基底势在必行。据我们所知，这是第一项开发 MOF/异质结结构作为 SERS 增强材料的研究。我们报道了一种原位 ZIF-67/Co(OH) ₂ 基于异质结的纳米纤维素纸（纳米纸）板（原位 ZIF-67 纳米板）作为罗丹明 LOD 为 0.98 nmol/L 的装置6G 和 1.43 × 10 ⁷ 的拉曼增强，比纯 ZIF-67 基 SERS 基底好 100 倍。此外，我们将此结构扩展到其他类型的 MOF 并开发了原位 HKUST-1 纳米板（使用 HKUST-1/Cu(OH) ₂ ）。此外，我们证明，通过应用 M _x (OH) _y 辅助（其中 M = Co、Cu 或其他金属）MOF/异质结结构。最后，我们成功展示了纳米片上药物筛选的应用，特别是奥美拉唑。 我们开发的纳米板仍然保持了MOF的可定制性并具有高抗干扰能力。我们的方法为基于 MOF 的 SERS 检测提供定制选项，满足未来研究和应用中的多种可能性。