Gas sensing behavior of metal-catecholates based MOFs.

We report on the usability aspect of triphenylene ligand-based metal-organic frameworks (MOF) as the potential gas sensing element in chemiresistive devices. Among various possibilities, we explored mono-metallic (Nickel-based) and bi-metallic (Nickel and copper-based) in room temperature gas sensing. Our investigations suggest that the chemiresistive device based on nickel catecholate MOFs were highly sensitive to ethyl alcohol gas in the concentration range of 5-100 ppm with decent sensing parameters such as response time, recovery time, repeatability, stability, etc. We also investigated bimetallic (Nickel and copper) catecholate based MOFs in gas sensing with different metallic content ratios (Cu: Ni:: 60:40 and 40:60). We found that the 1D Cu0.6Ni0.4-CAT nanostructures-based gas sensor to be selective towards H2gas (0.2-7 ppm) at room temperature. We further explored the gas sensing abilities of Cu0.4Ni0.6-CAT based devices, and we found them to be selective towards NO2gas. However, it was not possible to obtain the current versus concentration curve due to the gas molecules' aggressive chemisorption. However, the device could perform well (with a hysteresis error of ∼10%) for detecting NO gas (which has the 2nd best absolute response after NO2). These results indicate that the ratio of metal ions in the MOF directly influences the sensing capabilities. Hence, rational synthetic variations in the metal content in MOF can lead to the design and develop highly selective and sensitive chemiresistive sensors.

Growth-Temperature Dependent Unpassivated Oxygen Bonds Determine the Gas Sensing Abilities of Chemical Vapor Deposition-Grown CuO Thin Films.

CuO is a multifunctional metal oxide excellent for chemiresistive gas sensors. In this work, we report CuO-based NO2 sensors fabricated via chemical vapor deposition (CVD). CVD allows great control on composition, stoichiometry, impurity, roughness, and grain size of films. This endows sensors with high selectivity, responsivity, sensitivity, and repeatability, low hysteresis, and quick recovery. All these are achieved without the need of expensive and unscalable nanostructures, or heterojunctions, with a technologically mature CVD. Films deposited at very low temperatures (≤350 °C) are sensitive but slow due to traps and small grains. Films deposited at high temperatures (≥550 °C) are not hysteretic but suffer from low sensitivity and slow response due to lack of surface states. Films deposited at optimum temperatures (350-450 °C) combine the best aspects of both regimes to yield NO2 sensors with a response of 300 % at 5 ppm, sensitivity limit of 300 ppb, hysteresis of <20%, repeatable performance, and recovery time of ∼1 min. The work demonstrates that CVD might be a more effective way to deposit oxide films for gas sensors.

Ultrasonication assisted fabrication of a tungsten sulfide/tungstite heterostructure for ppb-level ammonia detection at room temperature.

A heterostructure of WS2/WO3·H2O has been prepared by partial oxidation of WS2 nanosheets by exposing bulk WS2 micron powder to ultrasonic waves in a bath sonicator. The as-prepared nanomaterial was used as a sensing film in an interdigitated electrode-based gas detecting device. The device was found to be specific towards ammonia gas among a group oxidizing and reducing gases. In particular, a response of as high as 11.36-254.66% was recorded for ammonia concentrations of 50 ppb to 2 ppm with excellent repeatability and reproducibility at room temperature. The response time and recovery time of the device was found to be a few tens of seconds suggesting its practicability. A plausible mechanism based on different active sites present in the receptor film is proposed and a logical reason behind its specificity towards ammonia gas is also inferred based on the Lewis acidic centers on the nano-surfaces. Overall, this proposed nanomaterial has very high potential for practical use as a room temperature ammonia sensor.

Boron nanostructures obtained via ultrasonic irradiation for high performance chemiresistive methane sensors.

We report on a chemiresistive gas sensor using boron nanostructures as the sensing layer, to detect methane gas down to 50 ppm. The sensor showed an excellent response of 43.5-153.1% for a methane concentration of 50 ppm to 105 ppm, with linear behaviour and good response and recovery time. The stability, repeatability, reproducibility, and shelf life of the sensor are promising for next generation methane gas detection.

Liquid exfoliated pristine WS2 nanosheets for ultrasensitive and highly stable chemiresistive humidity sensors.

WS2 nanosheets have been synthesized by ultrasonication in a binary mixture of acetone and 2-propanol, with a volume ratio of 80:20. Hansen solubility parameters were taken into consideration as part of the process. These nanosheets have been characterized by electron microscopy, atomic force microscopy, and x-ray diffraction, along with spectroscopy such as ultraviolet-visible spectroscopy, Raman spectroscopy, and x-ray photoelectron spectroscopy. The nanosheets were further used as a sensing material to fabricate a humidity sensor on interdigitated aluminum electrodes, realized over Si/SiO2 substrate using a conventional photolithography technique. The response for our sensor varied from 11.9 for 40% RH to as high as 37.5 for 80% RH. Response and recovery time were found to be 13 ± 2 s and 17 ± 2 s respectively. The suspended nanosheets were also treated with UV light in a nitrogen environment. The response for UV treated nanosheets shows better linearity, however its response decreases in the presence of humidity. This is due to a decrease in oxygen content of the UV treated sample. Furthermore, the effect of sonication time has been investigated, and it was found that samples with 10 h sonication are better than others due to their high surface-to-volume ratio. The repeatability and stability of the sensor have been investigated and found to be excellent. The hysteresis in the sensors was also explored. The mechanism of humidity sensing has been discussed in detail.