Semiconducting MOFs on Laser-Induced Graphene for NO2 Monitoring

We report a hybrid structure of Cu3HHTP2, 2D semiconducting metal-organic frameworks (MOFs), and laser-induced graphene (LIG) for high-performance NO2 sensing. LIG@Cu3HHTP2 shows one of the fastest responses and the lowest limit of detection (LoD) compared with state-of-the-art NO2 sensors.
Semiconducting MOFs on Laser-Induced Graphene for NO2 Monitoring
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Safeguarding a livable environment from air pollution is a global challenge due to the rapid pace of urbanization. In particular, the WHO has set the exposure limit for NO2 to ~5 ppb due to its detrimental effects on human health, such as cardiovascular deaths and even degenerative brain diseases1. Accordingly, there is an urgent need to develop technology to monitor NO2 at the ppb level in real time to provide personalized pollutant information. However, previous NO2 sensing materials (metal oxides, transition metal dichalcogenides, and carbon-based nanomaterials) have limitations in sensitivity, response time, and high-temperature operation2. To overcome these obstacles, researchers have recently explored the use of semiconducting MOFs as highly sensitive NO2 sensing material, which has a designable topology, record-breaking large surface area, and uniform pore size distribution3.

Here, we introduce LIG as a growth platform for Cu3HHTP2 2D semiconducting MOFs to accomplish real-time monitoring of ppb-level NO2 (Fig. 1). LIG is an emerging 3D macroporous material that can be produced by direct laser irradiation of various polymers and organic substrates4. Through the combination of Cu3HHTP2 and LIG (denoted LIG@Cu3HHTP2), we demonstrated a synergistic effect that could not be achieved when MOFs were used alone.

Figure 1 Fabrication of LIG@Cu3HHTP2. a Schematic of LIG@Cu3HHTP2 processing. Irradiation by the 355 nm laser directly converted PI to LIG. Subsequently, Cu3HHTP2 MOF is grown on LIG by a layer-by-layer process. b Schematic of the structure of Cu3HHTP2 on LIG.

First, the nanostructured MOFs grown on LIG enabled accelerated mass transport of the exposed gas due to the lung-mimicking hierarchical macro-/microporous architecture (Fig. 2). Furthermore, the increased exposed area maximized the advantage of the MOFs, which have abundant open metal sites and edge ligands to which guest molecules can adsorb. Therefore, the LIG@Cu3HHTP2 structure exhibited one of the shortest response/recovery times (16 s/15 s) and lowest LoD (0.168 ppb) among state-of-the-art NO2 sensors, even at room temperature and atmospheric conditions.

Figure 2 Effect of the hierarchical porous structure. a Comparison of the response and recovery time of LIG@Cu3HHTP2 hybrids and dense Cu3HHTP2 films toward 10 ppb NO2. b Repeatability tests with cyclic NO2 exposure. c Mass transport of the hierarchical porous structure compared to the dense MOF film. d Comparison with other state-of-the-art NO2 sensing materials operating in air at room temperature in terms of the limit of detection and response time.

Second, we validated the patterning strategy of solution-based MOF growth, which is one of the most significant challenges in the fabrication of MOF-based electronic devices. Figure 3 shows the spatial mapping of the graphitic G bands and metal-ligand vibration peaks only in the laser-irradiated region, which means selective growth of Cu3HHTP2 on LIG. The rGO-like chemical environment of LIG provides abundant defect sites and dangling hydroxyl functional groups, which provide an ideal platform for MOF nucleation by anchoring metal ions.

Figure 3. Vibrational spectroscopy analysis of LIG@Cu3HHTP2. Raman mapping of graphitic G bands and the M-O vibration mode after the formation of Cu3HHTP2 in a locally laser-irradiated region, displaying the selective growth of MOF on LIG. The inset shows an optical microscopic image of the same position.

 Finally, MOF-based electronic devices, mostly limited to rigid substrates, could be applied to lightweight and flexible substrates through formation on LIG. The sensor endured 10,000 repetitive bending cycles even at a harsh radius of curvature of 2.5 mm (Fig. 4). Therefore, we demonstrated a unique strategy for applying MOFs as personalized wearable sensors. These findings will help guide applications in MOFtronics, which remain at the laboratory level, as a high-performance sensor that could be implemented in the real world.

Figure 4. Stress analysis and flexibility tests. a Simulation of the stress distribution of the film by finite element analysis when the radius of curvature is 2.5 mm and the thickness is 25 μm. b The fatigue test shows no variation in resistance during the cyclic bending process (n = 0, 1000, 5000, and 10000, when the radius of curvature is 2.5 mm and the thickness is 25 μm)

To learn more, please check out our publication “Semiconducting MOFs on ultraviolet laser-induced graphene with a hierarchical pore architecture for NO2 monitoring” in Nature Communications: https://doi.org/10.1038/s41467-023-38918-3

 

References

  1. World Health Organization. WHO Global Air Quality Guidelines: Particulate Matter (PM2. 5 and PM10), Ozone, Nitrogen Dioxide, Sulfur Dioxide and Carbon Monoxide (World Health Organization, Geneva, Switzerland 2021).
  2. Kumar, S. et al. A review on 2D transition metal di-chalcogenides and metal oxide nanostructures based NO2 gas sensors. Materials Science in Semiconductor Processing 107, (2020).
  3. Allendorf, M. D. et al. Electronic Devices Using Open Framework Materials. Chem Rev 120, 8581-8640 (2020).
  4. Vivaldi, F. M. et al. Three-Dimensional (3D) Laser-Induced Graphene: Structure, Properties, and Application to Chemical Sensing. ACS Appl Mater Interfaces 13, 30245-30260 (2021).

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