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摘要: 總結了將MOFs材料與金屬氧化物、紡織品以及碳基導電纖維材料相結合，并在電阻式氣體傳感器領域的研究與應用。其中金屬氧化物結合MOFs過程中，MOFs主要有兩個作用：一是作為分散劑提高金屬氧化物的分散性；二是利用MOFs本身具有較大的比表面積和大量的活性位點，來提高材料對于氣體分子的吸附量和選擇性。當紡織品與MOFs結合的過程中，由于紡織品的導電性相對較差，所以需要結合一些導電性及氣體選擇性較好的MOFs來作為傳感器。碳基導電纖維一般具有較好的機械性能和導電性能，因此將其與MOFs材料復合后用于柔性電阻氣體傳感器具有一定的優勢。Abstract: Metal-organic frameworks (MOFs) are a new class of organic–inorganic hybrid materials that show great potential for gas adsorption and storage. However, the powder form of these materials limits the range of their applications. Integration of MOFs on polymer fiber scaffolds to increase the contact area between these frameworks and target molecules and improve the performance of the resulting material is expected to provide new application prospects in gas adsorption, membrane separation, catalysis, and toxic gas sensing. Electrochemical sensors with good flexibility and high sensitivity and selectivity are needed in environmental detection, disease diagnosis, food safety, and other fields. Flexible resistance sensors are sensitive, low cost, and can be produced on a large scale; thus, these sensors have received extensive attention from researchers. Preparing flexible resistance sensors with high sensitivity, high stability, and good wearing comfort is a current and popular area of research. In this paper, we summarized the research and application of MOFs materials combined with metal oxides, textiles and carbon-based conductive fiber materials in the field of resistance gas sensors. Metal oxides act as a conductive material in resistance sensors bearing a metal oxide-and-MOF design. In this design, MOFs play two roles. First, MOFs can wrap precious metals and form nanoparticles encasing these precious metals when calcined. Here, the precious metal functions as a catalyst while the MOF is used as a dispersant to distribute the metal evenly on the surface of the sensing material. Second, the MOFs are combined with the metal oxide by in situ growth or doping on the metal oxide surface. The MOF surface has a large specific surface area and numerous active sites that can bind with the target gas. Resistance sensing is achieved by changing the electronic distribution within the sensing material. When textiles and MOFs are combined, the resulting resistive sensing materials must have a certain electrical conductivity. However, common MOF materials have poor electrical conductivity. Therefore, developing a conductive MOF material in which 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and 2,3,6,7,10,11-hexaaminotriphenylene (HATP) show strong sensing performance for NO, H2S, and H2O is necessary. Carbon nanotube fibers and MOF materials can also be combined to obtain resistive sensor materials. Carbon nanotube materials are characterized by cross contact at the nanoscale and have good mechanical and electrical conductive properties. Thus, they feature certain advantages over other materials when applied to flexible resistive sensors.
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Key words:
- metal-organic frameworks /
- fiber /
- flexible /
- gas sensor /
- resistance
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圖 1 （a）SnO2傳感器的制備流程圖，插圖為煅燒前后的掃描電子顯微鏡圖像對比；（b）比較未負載和負載30% Pd–SnO2對于H2的響應值；（c） PdO@ZnO?WO2纖維的合成工藝圖；（d） 350 ℃時PdO@ZnO?WO2對甲苯的傳感性能[8, 12]
Figure 1. (a) Schematic diagram illustrating the fabrication process of our SnO2 sensor prototypes, the inset shows images of the materials in the as-spun state and after hot-pressing and calcination obtained by confocal microscopy; (b) electrical responses of unloaded and 30% Pd-loaded SnO2 sensors to H2; (c) schematic illustration of the synthetic process of PdO@ZnO?WO2 nanoparticles; (d) sensitivity of PdO@ZnO?WO2 nanoparticles to toluene at 350 ℃[8, 12]
圖 2 （a） PdO@ZnO–SnO2納米纖維合成工藝示意圖；（b） 400 ℃下不同材料對0.1×10?6～5×10?6體積分數丙酮的響應值；（c） Pd@ZnO–WO3納米纖維的掃描電鏡圖像，插圖為表面放大圖像；（d） PdO@ZnO-SnO2的掃描電鏡圖像[13]。
Figure 2. (a) Schematic illustration of the synthetic process of PdO@ZnO-SnO2 nanoparticles; (b) Transition of dynamic responses to acetone in the volume fraction range of 0.1×10?6?5.0×10?6 at 400 ℃; (c) SEM images of Pd@ZnO–WO3 nanofibers and magnified image of the material surface; (d) SEM image of PdO@ZnO–SnO2 nanotubes[13]
圖 4 （a） Pd@ZnO–WO3納米纖維在350 ℃下對于不同氣體的選擇性；（b） PdO@ZnO–SnO2納米纖維在400 ℃下對于不同氣體的選擇性；（c） ZnO和ZIF-8/ZnO對于不同氣體的選擇性[12-14]
Figure 4. (a) Selective detection characteristics of Pd@ZnO-WO3 nanofibers toward toluene in the presence of multiple interfering analytes at 350 °C; (b) selective sensing characteristics of PdO@ZnO–SnO2 nanoparticles at 400 ℃; (c) selective of ZnO and ZIF-8/ZnO for different gases[12-14]
圖 5 （a） ZnO@ZIF–CoZn氣體傳感器的制備原理圖；（b） ZnO and ZnO@ ZIF–CoZn的平面圖和截面圖；（c） ZnO@5 nm ZIF–CoZn對不同體積分數丙酮的響應值，并且在10×10?6體積分數下測試對于不同濕度的響應值[4]
Figure 5. (a) Schematic illustration of the preparation of ZnO@ZIF–CoZn gas sensors; (b) plan and cross-sectional views of ZnO and ZnO@ ZIF–CoZn nanowire arrays: (1,3) HRTEM image of pure ZnO and SAED patterns of a single ZnO nanowire (in inset), (2,4) ZnO@15 nm ZIF–CoZn；(c) response–recovery curves of ZnO@5 nm ZIF–CoZn toward acetone of different volume fraction in dry air and 10×10?6 acetone at different relative humidities[4]
圖 6 （a）通過噴墨印刷技術，將HKUST-1合成在柔性基材上；（b） HKUST-1暴露在不同氣體前后的對比照片；（c） HKUST-1的掃描電鏡圖像；（d） HKUST-1對于NH3的傳感響應曲線[24]。
Figure 6. (a) Inkjet printing of SURMOFs onto flexible substrates using a HKUST-1 precursor solution as “ink”; (b) photographs of a dot of HKUST-1 printed onto textiles before and after exposure to different gases; (c) SEM images of a HKUST-1 printed paper fiber; (d) partial reversible adsorption/desorption of NH3 on HKUST-1 film[24]
圖 8 （a）校準曲線在體積分數范圍為(10～500)×10?6時用于分析物（甲醇，乙醇和異丙醇）的傳感器；（b）MIL-53(Cr-Fe)/Ag/CNT三元納米復合材料的傳感機理[29]
Figure 8. (a) Calibration curves of the sensors for different analytes (methanol, ethanol, and iso-propanol) in the volume fraction range of (10–500)×10?6; (b) sensing mechanism of the MIL-53(Cr-Fe)/Ag/CNT ternary nanocomposite[29]
圖 9 （a）傳感器示意圖；0 V （22 ℃）（b），0.7 V （36 ℃） （c）和2.1 V （100 ℃） （d）下傳感器的響應和恢復動力學曲線[30]
Figure 9. (a) Schematic illustrations of the overall sensing platform; response and recovery kinetics of SWCNT-loaded PdO–Co3O4 HNCs on cPI film toward the Ni/Au-cPI heater at 0 V (22 °C) (b), 0.7 V (36 °C) (c), and 2.1 V (100 °C) (d)[30]
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