Humidity Dependence of Commercial Thick and Thin-Film MOX Gas Sensors under UV Illumination

Enhancing the performance of a chemo-resistive gas sensor is often challenging due to environmental humidity influencing its sensitivity and baseline resistance. One of the most promising ways of overcoming this challenge is through ultraviolet (UV) illumination of the sensing material. Most research has focused on using UV with in-house developed sensors, which has limited their widespread use. In this work, we have evaluated if UV can enhance the performance of commercially available MOX-based gas sensors. The performance of five different MOX sensors has been evaluated, specifically SGX Microtech MiCS6814 (thin-film triple sensor), FIGARO TGS2620 (n-type thick film), and Alphasense VOC sensor (p-type thick film). These sensors were tested towards isobutylene gas under UV light at different wavelengths (UV-278 nm and UV-365 nm) to investigate its effect on humidity, sensitivity, baseline drift, and recovery time of each sensor. We found the response time of thin-film sensors for reducing gases was improved by 70 s under UV- 365 nm at normal operating temperatures. In addition, all the sensors were left in a dirty environment and the humid-gas testing was repeated. However, due to their robust design, the sensitivity and baseline drift of all the sensors remained the same. This indicates that UV has only limited uses with commercial gas sensors.

Water Capture Mechanisms at Zeolitic Imidazolate Framework Interfaces

Water capture mechanisms of zeolitic imidazolate framework ZIF-90 are revealed by differentiating the water clustering and the center pore filling step, using vibrational sum-frequency generation spectroscopy (VSFG) at a one-micron spatial resolution and state-of-the-art molecular dynamics (MD) simulations. Through spectral lineshape comparison between VSFG and IR spectra, the relative humidity dependence of VSFG intensity, and MD simulations, based on MB-pol, we found water clustering and center pore filling happen nearly simultaneously within each pore, with water filling the other pores sequentially. The integration of nonlinear optics with MD simulations provides critical mechanistic insights into the pore filling mechanism and suggests that the relative strength of the hydrogen bonds governs the water uptake mechanisms. This molecular-level detailed mechanism can inform the rational optimization of metal-organic frameworks for water harvesting.

Iodide CIMS and <i>m</i>∕<i>z</i> 62: the detection of HNO₃ as NO₃⁻ in the presence of PAN, peroxyacetic acid and ozone

Chemical ionisation mass spectrometry (CIMS) using I− (the iodide anion), hereafter I-CIMS, as a primary reactant ion has previously been used to measure NO3 and N2O5 both in laboratory and field experiments. We show that reports of large daytime mixing ratios of NO3 and N2O5 (both usually present in detectable amounts only at night) are likely to be heavily biased by the ubiquitous presence of HNO3 in the troposphere and lower stratosphere. We demonstrate in a series of laboratory experiments that the CIMS detection of HNO3 at m/z 62 using I− ions is efficient in the presence of peroxy acetyl nitric anhydride (PAN) or peroxyacetic acid (PAA) and especially O3. We have characterised the dependence of the sensitivity to HNO3 detection on the presence of acetate anions (CH3CO2-, m/z 59, from either PAN or PAA). The loss of CH3CO2- via conversion to NO3- in the presence of HNO3 may represent a significant bias in I-CIMS measurements of PAN and PAA in which continuous calibration (e.g. via addition of isotopically labelled PAN) is not carried out. The greatest sensitivity to HNO3 at m/z 62 is achieved in the presence of ambient levels of O3 whereby the thermodynamically disfavoured, direct reaction of I− with HNO3 to form NO3- is bypassed by the formation of IOx-, which reacts with HNO3 to form, for example, iodic acid and NO3-. The ozone and humidity dependence of the detection of HNO3 at m/z 62 was characterised in laboratory experiments and applied to daytime, airborne measurements in which good agreement with measurements of the I−(HNO3) cluster ion (specific for HNO3 detection) was obtained. At high ozone mixing ratios, we show that the concentration of I− ions in our ion–molecule reactor (IMR) is significantly depleted. This is not reflected by changes in the measured I− signal at m/z 127 as the IOx- formed does not survive passage through the instrument but is likely detected after fragmentation to I−. This may result in a bias in measurements of trace gases using I-CIMS in stratospheric air masses unless a calibration gas is continuously added or the impact of O3 on sensitivity is characterised.

Iodide-CIMS and <i>m/z</i> 62: The detection of HNO₃ as NO₃⁻ in the presence of PAN, peracetic acid and O₃

Chemical Ionisation Mass Spectrometry (CIMS) using I− (the iodide anion) as primary chemi-ion has previously been used to measure NO3 and N2O5 both in laboratory and field experiments. We show that reports of the large daytime mixing ratios of NO3 and N2O5 (usually only present in detectable amounts at night-time) are likely to be heavily biased by the ubiquitous presence of HNO3 in the troposphere and lower stratosphere. We demonstrate in a series of laboratory experiments that the CIMS detection of HNO3 at m/z 62 using I− ions is efficient in the presence of PAN or peracetic acid (PAA) and especially O3. We have characterised the dependence of the sensitivity to HNO3 detection on the presence of acetate anions (CH3CO2−, m/z 59, from either PAN or PAA). The loss of CH3CO2− via conversion to NO3− in the presence of HNO3 may represent a significant bias in I-CIMS measurements of PAN and CH3C(O)OOH. The largest sensitivity to HNO3 at m/z 62 is achieved in the presence of ambient levels of O3 whereby the thermodynamically disfavoured, direct reaction of I− with HNO3 to form NO3− is bypassed by the formation of IOX− which react with HNO3 to form e.g. iodic acid and NO3−. The ozone and humidity dependence of the detection of HNO3 at m/z 62 was characterised in laboratory experiments and applied to daytime, airborne measurements in which very good agreement with measurements of the I−(HNO3) cluster-ion (specific for HNO3 detection) was obtained.