Rapid and Selective NH3 Sensing by Porous CuBr.

Fast and selective detection of NH3 at parts-per-billion (ppb) concentrations with inexpensive and low-power sensors represents a long-standing challenge. Here, a room temperature, solid-state sensor is presented consisting of nanostructured porous (78%) CuBr films. These are prepared by flame-aerosol deposition of CuO onto sensor substrates followed by dry reduction and bromination. Each step is monitored in situ through the film resistance affording excellent process control. Such porous CuBr films feature an order of magnitude higher NH3 sensitivity and five times faster response times than conventional denser CuBr films. That way, rapid (within 2.2 min) sensing of even the lowest (e.g., 5 ppb) NH3 concentrations at 90% relative humidity is attained with outstanding selectivity (30-260) over typical confounders including ethanol, acetone, H2, CH4, isoprene, acetic acid, formaldehyde, methanol, and CO, superior to state-of-the-art sensors. This sensor is ideal for hand-held and battery-driven devices or integration into wearable electronics as it does not require heating. From a broader perspective, the process opens exciting new avenues to also explore other bromides and classes of semiconductors (e.g., sulfides, nitrides, carbides) currently not accessible by flame-aerosol technology.

Palladium embedded in SnO2 enhances the sensitivity of flame-made chemoresistive gas sensors.

Palladium is used commonly to enhance the performance of chemoresistive metal-oxide gas sensors. Typically, this enhancement is attributed to the presence of Pd clusters on the surface of their metal-oxide support (i.e. SnO2). Possible Pd incorporation or embedding into the support rarely has been considered. Here, SnO2 particles (15 - 21 nm in diameter measured by N2 adsorption) with different Pd contents (0 - 3 mol%) were prepared by flame spray pyrolysis (FSP). Leaching these particles with HNO3 and characterization by inductively coupled plasma - optical emission spectrometry (ICP-OES) indicated that only 36 - 60% of Pd have been removed (e.g., from the SnO2 surface). The rest was embedded within the SnO2 particles. Annealing prior to leaching decreased by ~30% that Pd surface content. Most interestingly, such SnO2 particles (with only embedded Pd) show higher sensor response to acetone, ethanol and CO at 350 °C compared to SnO2 particles containing both surface and embedded Pd (i.e. before leaching). As a result, such sensors can detect acetone with high (> 25) signal-to-noise ratio at levels down to 5 ppb at 50% relative humidity. Graphical abstractFlame-made SnO2 nanoparticles with embedded and surface Pd (triangles) exhibit lower sensor response to acetone, ethanol and CO than SnO2 from which the surface Pd had been removed by leaching (circles).

Orthogonal gas sensor arrays by chemoresistive material design.

Gas sensor arrays often lack discrimination power to different analytes and robustness to interferants, limiting their success outside of research laboratories. This is primarily due to the widely sensitive (thus weakly-selective) nature of the constituent sensors. Here, the effect of orthogonality on array accuracy and precision by selective sensor design is investigated. Therefore, arrays of (2-5) selective and non-selective sensors are formed by systematically altering array size and composition. Their performance is evaluated with 60 random combinations of ammonia, acetone and ethanol at ppb to low ppm concentrations. Best analyte predictions with high coefficients of determination (R2) of 0.96 for ammonia, 0.99 for acetone and 0.88 for ethanol are obtained with an array featuring high degree of orthogonality. This is achieved by using distinctly selective sensors (Si:MoO3 for ammonia and Si:WO3 for acetone together with Si:SnO2) that improve discrimination power and stability of the regression coefficients. On the other hand, arrays with collinear sensors (Pd:SnO2, Pt:SnO2 and Si:SnO2) hardly improve gas predictions having R2 of 0.01, 0.86 and 0.28 for ammonia, acetone and ethanol, respectively. Sometimes they even exhibited lower coefficient of determination than single sensors as a Si:MoO3 sensor alone predicts ammonia better with a R2 of 0.68. Graphical abstract Conventional arrays (red) with weakly-selective sensors span a significantly smaller volume in the analyte space than arrays containing distinctly-selective sensors (orthogonal array, green). Orthogonal arrays feature better accuracy and precision than conventional arrays in mixtures of ammonia, acetone and ethanol.

Sniffing Entrapped Humans with Sensor Arrays.

Earthquakes are lethal natural disasters frequently burying people alive under collapsed buildings. Tracking entrapped humans from their unique volatile chemical signature with hand-held devices would accelerate urban search and rescue (USaR) efforts. Here, a pilot study is presented with compact and orthogonal sensor arrays to detect the breath- and skin-emitted metabolic tracers acetone, ammonia, isoprene, CO2, and relative humidity (RH), all together serving as sign of life. It consists of three nanostructured metal-oxide sensors (Si-doped WO3, Si-doped MoO3, and Ti-doped ZnO), each specifically tailored at the nanoscale for highly sensitive and selective tracer detection along with commercial CO2 and humidity sensors. When tested on humans enclosed in plethysmography chambers to simulate entrapment, this sensor array rapidly detected sub-ppm acetone, ammonia, and isoprene concentrations with high accuracies (19, 21, and 3 ppb, respectively) and precision, unprecedented by portable sensors but required for USaR. These results were in good agreement (Pearson's correlation coefficients ≥0.9) with benchtop selective reagent ionization time-of-flight mass spectrometry (SRI-TOF-MS). As a result, an inexpensive sensor array is presented that can be integrated readily into hand-held or even drone-carried detectors for first responders to rapidly screen affected terrain.

Monitoring of selected skin- and breath-borne volatile organic compounds emitted from the human body using gas chromatography ion mobility spectrometry (GC-IMS).

Human smuggling and associated cross-border crimes have evolved as a major challenge for the European Union in recent years. Of particular concern is the increasing trend of smuggling migrants hidden inside shipping containers or trucks. Therefore, there is a growing demand for portable security devices for the non-intrusive and rapid monitoring of containers to detect people hiding inside. In this context, chemical analysis of volatiles organic compounds (VOCs) emitted from the human body is proposed as a locating tool. In the present study, an in-house made ion mobility spectrometer coupled with gas chromatography (GC-IMS) was used to monitor the volatile moieties released from the human body under conditions that mimic entrapment. A total of 17 omnipresent volatile compounds were identified and quantified from 35 ion mobility peaks corresponding to human presence. These are 7 aldehydes (acrolein, 2-methylpropanal, 3-methylbutanal, 2-ethacrolein, n-hexanal, n-heptanal, benzaldehyde), 3 ketones (acetone, 2-pentanone, 4-methyl-2-pentanone), 5 esters (ethyl formate, ethyl propionate, vinyl butyrate, butyl acetate, ethyl isovalerate), one alcohol (2-methyl-1-propanol) and one organic acid (acetic acid). The limits of detection (0.05-7.2 ppb) and relative standard deviations (0.6-11%) should be sufficient for detecting these markers of human presence in field conditions. This study shows that GC-IMS can be used as a portable field detector of hidden or entrapped people.