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Tailoring Crystal Facets of Metal-Organic to Enhance Sensing Performance for Aromatic Vapors Detection
Journal of Hazardous Materials ( IF 12.2 ) Pub Date : 2024-12-17 , DOI: 10.1016/j.jhazmat.2024.136859 Zhiheng Ma, Yu Zhang, Tongwei Yuan, Yu Fan, Xiaowu Wang, Zhenggang Xue, Aihua Zhong, Jiaqiang Xu
Journal of Hazardous Materials ( IF 12.2 ) Pub Date : 2024-12-17 , DOI: 10.1016/j.jhazmat.2024.136859 Zhiheng Ma, Yu Zhang, Tongwei Yuan, Yu Fan, Xiaowu Wang, Zhenggang Xue, Aihua Zhong, Jiaqiang Xu
It is well known that metals and metal oxides with different crystal facets exhibit varying sensitivity in gas sensors, but this strategy is rarely used in metal-organic frameworks (MOFs). Herein, we proved for the first time that Cu metal-organic with high energy crystal facets (Cu-MOF-74-300) shows a much higher sensitivity than the low energy crystal facets (Cu-MOF-74-110), with a up to 2 times response more than Cu-MOF-74-110 and ultra-low limit of detection (LOD) of 68 ppb to toluene vapors. In addition, this strategy was further demonstrated on MOF-14 and HKUST-1, which are also Cu-centered and exhibit clear recognition effects on benzene and xylene, respectively. Furthermore, the Cu-MOF-74-300 shows high selectivity (92%) and excellent stability, with a minor reduction in response of less than 1.9% after 6 months. Additionally, the sensitive mechanism is explored by DFT and GCMC methods. The simulations reveal that Cu-MOF-74 includes two adsorption sites, one is Cu site with adsorption enthalpy (ΔH) of -58.76 kJ/mol, another is the benzene ring site (ΔH is -65.7 kJ/mol) in the ligand. The difference in charge densities reveal that the Cu2+ and benzene ring on the surface of Cu-MOF-74-300 enables synergistic sensing, leading to more electron transfer in toluene than that of Cu-MOF-74-110 (only benzene ring site). Finally, based on the temperature-varying experiments, the experimental adsorption energy (-51.35 kJ/mol) was obtained by calculations. Combined quasi-in-situ XPS, implying Cu is the critical role to the improvement of Cu-MOF-74-300 sensitivity to toluene.
中文翻译:
定制金属有机物的晶体刻面,以增强芳烃蒸气检测的传感性能
众所周知,具有不同晶体刻面的金属和金属氧化物在气体传感器中表现出不同的灵敏度,但这种策略很少用于金属有机框架 (MOF)。在此,我们首次证明,具有高能晶体刻面的有机铜 (Cu-MOF-74-300) 显示出比低能晶体刻面 (Cu-MOF-74-110) 高得多的灵敏度,响应比 Cu-MOF-74-110 高 2 倍,对甲苯蒸气的超低检测限 (LOD) 为 68 ppb。此外,这种策略在 MOF-14 和 HKUST-1 上得到了进一步验证,它们也是以铜为中心的,分别对苯和二甲苯表现出明显的识别作用。此外,Cu-MOF-74-300 显示出高选择性 (92%) 和出色的稳定性,6 个月后响应略有降低,不到 1.9%。此外,通过 DFT 和 GCMC 方法探索了敏感机制。模拟结果表明,Cu-MOF-74 包括两个吸附位点,一个是吸附焓 (ΔH) 为 -58.76kJ/mol 的 Cu 位点,另一个是配体中的苯环位点 (ΔH 为 -65.7kJ/mol)。电荷密度的差异表明,Cu-MOF-74-300 表面的 Cu 2+ 和苯环能够协同感应,导致甲苯中的电子转移比 Cu-MOF-74-110 更多(仅苯环位点)。最后,基于温变实验,通过计算得到实验吸附能 (-51.35kJ/mol)。结合准原位 XPS,意味着 Cu 是提高 Cu-MOF-74-300 对甲苯敏感性的关键作用。
更新日期:2024-12-18
中文翻译:
定制金属有机物的晶体刻面,以增强芳烃蒸气检测的传感性能
众所周知,具有不同晶体刻面的金属和金属氧化物在气体传感器中表现出不同的灵敏度,但这种策略很少用于金属有机框架 (MOF)。在此,我们首次证明,具有高能晶体刻面的有机铜 (Cu-MOF-74-300) 显示出比低能晶体刻面 (Cu-MOF-74-110) 高得多的灵敏度,响应比 Cu-MOF-74-110 高 2 倍,对甲苯蒸气的超低检测限 (LOD) 为 68 ppb。此外,这种策略在 MOF-14 和 HKUST-1 上得到了进一步验证,它们也是以铜为中心的,分别对苯和二甲苯表现出明显的识别作用。此外,Cu-MOF-74-300 显示出高选择性 (92%) 和出色的稳定性,6 个月后响应略有降低,不到 1.9%。此外,通过 DFT 和 GCMC 方法探索了敏感机制。模拟结果表明,Cu-MOF-74 包括两个吸附位点,一个是吸附焓 (ΔH) 为 -58.76kJ/mol 的 Cu 位点,另一个是配体中的苯环位点 (ΔH 为 -65.7kJ/mol)。电荷密度的差异表明,Cu-MOF-74-300 表面的 Cu 2+ 和苯环能够协同感应,导致甲苯中的电子转移比 Cu-MOF-74-110 更多(仅苯环位点)。最后,基于温变实验,通过计算得到实验吸附能 (-51.35kJ/mol)。结合准原位 XPS,意味着 Cu 是提高 Cu-MOF-74-300 对甲苯敏感性的关键作用。