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地球上丰富的二硫化钼(MoS2)作为一种有前景的表面增强拉曼光谱(SERS)基底引起了人们的广泛关注, 但由于其半导体特性而限制了其发展. 因此, 本文设计了一种MoS2/沸石咪唑酯骨架-67(ZIF-67)异质结构作为SERS基底, 该基底具有优异的灵敏度, 增强因子可达6.68×106. 此外, 利用MoS2/ZIF-67对胆红素进行无标记检测, 检测限低至10–10 mol/L. 同时, 该基底暴露在空气中4个月后, SERS性能基本保持不变, 表明该基底具有较高的稳定性和可重复使用性. 该基底优秀的性能主要是由于MoS2的垂直分布结构能暴露出更多的活性位点. 同时, ZIF-67具有较大的比表面积和丰富的孔洞结构, 这也为分子提供了大量的吸附位点. 此外, 内部电荷转移诱导了高比例稳定1T相的形成, 从而提高了电导率. 本文为合理设计用于高灵敏SERS检测的无贵金属材料提供了有价值的参考.Earth-abundant molybdenum disulfide (MoS2), as a promising substrate for surface-enhanced Raman spectroscopy (SERS), has attracted considerable attention. Naturally occurring MoS2 primarily exists in the semiconducting 2H phase, but its SERS performance is limited because active sites are typically confined to its edges. Furthermore, the irregular agglomeration of MoS2 can lead to performance degradation, making natural semiconducting material unsuitable for practical applications. Therefore, enhancing the performance of MoS2 in the field of SERS is of great significance. Metal-organic frameworks (MOFs) are ideal materials for building efficient SERS substrates due to their tunable pore structures. Among various MOF materials, zeolitic imidazolate frameworks (ZIFs) have aroused significant interest due to their well-defined polyhedral structures, homogeneity, and small particle sizes. Therefore, in this study, MoS2/zeolitic imidazolate framework-67 (ZIF-67) heterostructures are prepared by the hydrothermal method as SERS substrates, which exhibits exceptionaly high sensitivity to rhodamine 6G with an enhancement factor of up to 6.68×106. Moreover, after SERS is exposed to air for four months, its performance remains almost unchanged, demonstrating high stability and reusability. To evaluate the actual detection ability of this substrate, bilirubin is selected as the analyte, which is a clinically relevant metabolic waste. Since both high and low concentrations of free bilirubin can lead to cardiovascular and cerebrovascular diseases, accurate monitoring of bilirubin levels is crucial for diagnosing bilirubin-induced disorders. Using the MoS2/ZIF-67 substrate, the label-free detection of bilirubin is achieved with a limit of detection (LOD) as low as 10–10 mol/L. The outstanding performance of this substrate can be attributed to the vertically aligned MoS2 nanostructure, which exposes more active sites. Additionally, ZIF-67 provides a high specific surface area and abundant porous structures, providing numerous adsorption sites for target molecules. Furthermore, the internal charge transfer facilitates the formation of a highly conductive 1T phase, thereby improving electrical conductivity. This work provides valuable insights into the rational designing of noble-metal-free materials for highly sensitive SERS detection.
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Keywords:
- surface-enhanced Raman spectroscopy /
- MoS2 /
- ZIF-67 /
- heterostructure
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图 1 ZIF-67, MoS2和xMoS2/ZIF-67的合成流程示意图
Fig. 1. Schematic diagram of the synthesis of ZIF-67, MoS2 and xMoS2/ZIF-67.
图 2 MoS2, ZIF-67和MoS2/ZIF-67的(a) XRD图、(b)拉曼光谱和(c)傅里叶变换红外光谱
Fig. 2. (a) XRD patterns, (b) Raman spectra, and (c) FT-IR spectra of MoS2, ZIF-67 and MoS2/ZIF-67.
图 3 基底的SEM, TEM和EDS图 (a) MoS2, (b) ZIF-67和(c) 0.3 MoS2/ZIF-67的SEM图像; (d) MoS2, (e) ZIF-67和(f) 0.3 MoS2/ZIF-67的TEM图像; (g) 0.3 MoS2/ZIF-67的HRTEM; (h) 图(g)中蓝色矩形区域放大后的图片; (i)—(l) Co, Mo, S, O的EDS元素映射图
Fig. 3. SEM images of (a) MoS2, (b) ZIF-67 and (c) 0.3 MoS2/ZIF-67; TEM images of (d) MoS2, (e) ZIF-67 and (f) 0.3 MoS2/ZIF-67; (g) HRTEM of 0.3 MoS2/ZIF-67; (h) magnified domains of the blue rectangle; (i)–(l) EDS element mapping images of Co, Mo, S and O.
图 4 基底的XPS图 (a) MoS2和0.3 MoS2/ZIF-67的Mo 3d谱、(c) S 2p谱和(d) O 1s谱; (b) MoS2和0.3 MoS2/ZIF-67的Co 2p谱
Fig. 4. (a) Mo 3d spectrum, (c) S 2p spectrum and (d) O 1s spectrum of MoS2 and 0.3 MoS2/ZIF-67; (b) Co 2p spectrum of MoS2 and 0.3 MoS2/ZIF-67.
图 5 基底的拉曼光谱和SERS性能图 (a) R6G(10–3 mol/L)吸附在MoS2, ZIF-67和xMoS2/ZIF-67上的SERS谱图; (b) 0.3 MoS2/ZIF-67基底上不同浓度R6G的SERS光谱; (c) 1653 cm–1处SERS强度与对数浓度的线性关系; (d) 0.3 MoS2/ZIF-67的可重复性、(e)循环性和(f)稳定性表征
Fig. 5. (a) SERS spectra of R6G (10–3 mol/L) adsorbed on MoS2, ZIF-67 and xMoS2/ZIF-67; (b) SERS spectra of R6G of various concentrations enhanced by 0.3 MoS2/ZIF-67; (c) linear relationship of SERS intensities at 1653 cm–1 versus logarithm of concentration; (d) reproducibility, (e) cyclicity and (f) stability of 0.3 MoS2/ZIF-67.
图 6 R6G-0.3 MoS2/ZIF-67的能级和电荷转移示意图
Fig. 6. Diagram of the energy level and charge transfer in the R6G-0.3 MoS2/ZIF-67.
图 7 复合后的基底与非复合基底的SERS性能对比图 (a)不同浓度胆红素在0.3 MoS2/ZIF-67基底上的SERS光谱和(b) 1614 cm–1处信号强度与胆红素对数浓度的关系; (c)不同浓度胆红素在MoS2基底上的SERS光谱和(d) 1614 cm–1处信号强度与胆红素对数浓度的关系
Fig. 7. SERS spectra of (a) 0.3 MoS2/ZIF-67 and (c) MoS2 substrates with various concentrations of bilirubin. Plot of the intensity at 1614 cm–1 against the logarithmic concentration of bilirubin in the presence of (b) 0.3 MoS2/ZIF-67 and (d) MoS2.
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