Electrochemical sensors have been used for many decades. However, the modeling of such sensors used in electrolysis mode is poorly documented, especially in the case of multiple gases’ parallel actions. These are of great interest since they constitute the first brick to bring information on the natures and concentrations of gaseous mixture compositions, thanks to gray box modeling of sensor arrays, for example. Based on Butler–Volmer’s equations, a model assuming parallel reactions at gold cathode has been introduced in this article and confronted with experimental results. The establishment of the model is based on the extraction of three variables: the charge transfer coefficient “α”, the reaction order γ, and the reaction constant rate k0. Tests performed without pollutants and with different concentrations of oxygen could be nicely fitted using the model. The influence of the polarization current on the three variables of the model has been evaluated, showing a clear influence on the constant rate and the reaction order. Moreover, increasing the polarization current enabled us to obtain selectivity for oxidant gases. Similarly, the effect of the oxygen concentration was evaluated. Results showed that, in this case, the charge transfer coefficients “α” obtained for oxidant gases are quite different from the ones obtained in the polarization current varying conditions. Therefore, the model will be interesting in situations where polarization current and oxygen content are not varied together. Variation of polarization current can be quite interesting to obtain increased information for multivariate analysis purposes in constant oxygen content situations. Additionally, other parameters have to be considered for applications in which the oxygen content is bound to change, such as exhaust gases or combustion.

Among the conventional inks used for inkjet printing, metals, oxides, or polymers have been deposited in order to form functional coatings. Gold is one of the most used metals for electrode fabrication in the gas sensor field due to its inert behavior when exposed to reactive gases and conductive properties. However, only a few commercial gold inks are commercially available, and the combination of excessive price, a high minimum purchase quantity, and an unknown composition renders the actual products unappealing. To meet these shortcomings, gold inks were formulated with different solvents in order to reach sufficient properties for the inkjet printing process, such as surface tension and viscosity. On the one hand, gold ink was developed using a gold nanoparticle (AuNP) solution as the metal. This ink was optimized from nanoparticle synthesis, with the ink formulation obtaining a 32 mN·m−1 surface tension and 11.2 mPa·s viscosity in order to be inkjet-printed onto polyimide foil. On the other hand, a particle-free ink, called a precursor based of ink, was also developed. In this case, ink was made by solubilizing gold salt in aqueous medium in order to reach jettable properties. Surface tension was measured at 32 mN·m−1 while viscosity was 14.0 mPa·s. Then, printing and deposition parameters were optimized in order to obtain a highly conductive gold coating. The measured resistivity was 2 × 10−7 Ω·m which is close to the bulk gold conductive value. These coatings could be used for the fabrication of various devices in different working fields.

New process developments linked to Power to X (energy storage or energy conversion to another form of energy) require tools to perform process monitoring. The main gases involved in these types of processes are H2, CO, CH4, and CO2. Because of the non-selectivity of the sensors, a multi-sensor matrix has been built in this work based on commercial sensors having very different transduction principles, and, therefore, providing richer information. To treat the data provided by the sensor array and extract gas mixture composition (nature and concentration), linear (Multi Linear Regression—Ordinary Least Square “MLR-OLS” and Multi Linear Regression—Partial Least Square “MLR-PLS”) and non-linear (Artificial Neural Network “ANN”) models have been built. The MLR-OLS model was disqualified during the training phase since it did not show good results even in the training phase, which could not lead to effective predictions during the validation phase. Then, the performances of MLR-PLS and ANN were evaluated with validation data. Good concentration predictions were obtained in both cases for all the involved analytes. However, in the case of methane, better prediction performances were obtained with ANN, which is consistent with the fact that the MOX sensor’s response to CH4 is logarithmic, whereas only linear sensor responses were obtained for the other analytes. Finally, prediction tests performed on one-year aged sensor platforms revealed that PLS model predictions on aged platforms mainly suffered from concentration offsets and that ANN predictions mainly suffered from a drop of sensitivity.

Electrochemical sensors have been used for many decades. Yet, modeling of such sensors used in electrolysis mode is poorly documented, especially in the case parallel action of multiple gases. Those ones are of great interest since they constitute the first brick to bring information on natures and concentrations of a gaseous mixture composition thanks to grey box modeling of sensors array for example. Based on Butler Volmer’s equations, a model assuming parallel reactions at gold cathode has been introduced in this article and confronted to experimental results. Establishment of the model is based on the extraction of 3 variables: the charge transfer coefficient “α”, the reaction order γ, and the reaction constant rate k0. Tests performed without pollutants and with different concentrations of oxygen could be nicely fitted by the model. Then, the influence of polarization current on the 3 variables of the model has been evaluated showing a clear influence on the constant rate and the reaction order. Also, increasing the polarization current enabled us to get selectivity to oxidant gases. Similarly, the effect of the oxygen concentration was evaluated. Results showed that, in this case, the charge transfer coefficients “α” obtained for oxidant gases is quite different that the ones obtained in the polarization current varying conditions. Therefore, the model will be interesting in situations where polarization current and oxygen content are not varied together. Variation of polarization current can be quite interesting to get increased information for multivariate analysis purpose in constant oxygen content situations. Besides, other parameters have are required for applications in which the oxygen content is bound to change like exhaust gases or combustion.

Printing graphene-based nanomaterials on flexible substrates has become a burgeoning platform for next-generation technologies. Combining graphene and nanoparticles to create hybrid nanomaterials has been proven to boost device performance, thanks to their complementary physical and chemical properties. However, high growth temperatures and long processing times are often required to produce high-quality graphene-based nanocomposites. For the first time, we report a novel scalable approach for additive manufacturing of Sn patterns on polymer foil and their selective conversion into nanocomposite films under atmospheric conditions. A combination of inkjet printing and intense flashlight irradiation techniques is studied. Light pulses that are selectively absorbed by the printed Sn patterns cause a temperature of over 1000 °C to be reached locally in a split second without damaging the underlying polymer foil. The top surface of the polymer foil at the interface with printed Sn becomes locally graphitized and acts as a carbon source, transforming printed Sn into Sn@graphene (Sn@G) core-shell patterns. Our results revealed a decrease in electrical sheet resistance, with an optimal value (Rs = 72 ± 2 Ω/sq) reached when light pulses with an energy density of 12.8 J/cm2 were applied. These graphene-protected Sn nanoparticle patterns exhibit excellent resistance against air oxidation for months. Finally, we demonstrate the implementation of Sn@G patterns as electrodes for Li-ion microbatteries (LIBs) and triboelectric nanogenerators (TENGs), showing remarkable performance. This work offers new insight into the development of a versatile, eco-friendly, and cost-effective technique for producing well-defined patterns of graphene-based nanomaterials directly on a flexible substrate using different light-absorbing nanoparticles and carbon sources.

Electrochemical NOx sensors based on yttria-stabilized zirconia (YSZ) provide a reliable onboard way to control NOx emissions from glass-melting furnaces. The main limitation is the poisoning of this sensor by sulfur oxides (SOx) contained in the stream. To overcome this drawback, an “SO2 trap” with high SOx storage capacity and low affinity to NOx is required. Two CuO/BaO/SBA-15 traps with the same CuO loading (6.5 wt.%) and different BaO loadings (5 and 24.5 wt.%, respectively) were synthetized, thoroughly characterized and evaluated as SO2 traps. The results show that the 6.5%CuO/5%BaO/SBA-15 trap displays the highest SO2 adsorption capacity and can fully adsorb SO2 for a specific period of time, while additionally displaying a very low NO adsorption capacity. A suitable quantity of this material located upstream of the sensor could provide total protection of the NOx sensor against sulfur poisoning in glass-furnace exhausts.

To promote the diffusion on the market of solid oxide fuel cell (SOFC) devices, the use of fuels other than the most appealing hydrogen and also decreasing the working temperature could show the way forward. In the first part, we concentrated our efforts on cathodes; hereby, we focused on anodes and concentrated our efforts to develop a sustainable multifuel anode. We decided to develop LSGF (La0.6Sr0.4Ga0.3Fe0.7O3)-based nanocomposites by depositing manganite oxide to enhance the performance toward propane. MnOx has been deposited by a wet impregnation method, and the powders have been largely characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, hydrogen temperature-programmed reduction, oxygen temperature-programmed desorption, and N2 adsorption. Cell performances were first collected in hydrogen as a function of both the temperature and hydrogen content. EIS measurements were studied using Nyquist and Bode plots, and they show two processes at high frequency, assigned to charge transfer at the electrode/electrolyte interface, and at low frequency due to the dissociative adsorption of hydrogen. The Arrhenius plot of area specific resistance suggests two different trends, and the activation energy decreases from 117 kJ/mol at 750 °C to 46 kJ/mol above that temperature. This behavior is often connected to chemical modification of the catalyst or changes in the limiting step processes. Power densities in hydrogen and propane were determined at 744 °C after 1 h of operation, achieving 70 mW/cm2 in H2 and 67 mW/cm2 in C3H8. The open-circuit voltage increases from 1.10 V in hydrogen to 1.13 V in propane.

In this contribution brownmillerite-based nanocomposite cathode for Single-Chamber Solid Oxide Fuel Cells is developed. These cells can be very attractive especially for small and cheap devices because of the absence of seals. The efficiency of SC-SOFCs is strictly connected to the selectivity of anode and cathode, the bottleneck for this technology. The development of a cathode inert in fuel oxidation is particularly challenging. Our strategy is to start from a catalytically un-active support (CFA = Ca2FeAl0.95Mg0.05O5) and induce the formation of iron oxide based nanoparticles, expected to activate oxygen. Symmetric (CFA thorn FeOx/CGO/CFA + FeOx) and complete cells (CFA + FeOx/CGO/Ni-CGO) are studied in air and methane/oxygen 2:1 mixture. The Area Specific Resistance of CFA + FeOx is less than 1/3 that of CFA. The high selectivity allows to reach an efficiency of 25%; power still needs to be increased but we demonstrated the possibility to develop selective low cost electrodes. The effect of air, methane/oxygen exposure and the heat treatments were carefully investigated. (C) 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Ethylene oxide (EO) is industrially produced by epoxidation of ethylene on Ag-based heterogeneous cata-lysts. Electrophilic oxygen species are assumed to be active key species in the EO production. This study explores the possibility to electrochemically produced these oxygen species in a solid oxide electrochem-ical cell. Two series of Ag based cermet electrodes were prepared either with Yttria Stabilized Zirconia (YSZ), a pure oxygen ionic conductor, or with Gadolinia-Doped Ceria (GDC), a mixed ionic and electronic conductor. Ag/YSZ cermet layers were deposited on planar and tubular YSZ dense substrates by using a conventional chemical method while Ag/GDC cermets were coated on GDC dense pellets by reactive magnetron sputtering. We evidenced a self-redispersion of Ag in the ethylene/oxygen mixture in Ag/YSZ cermet layers leading to the formation of small Ag clusters in close interaction with YSZ which are selec-tive for epoxidation. However, the sintering process of these small Ag clusters is too fast even at 260 degrees C to maintain the EO selectivity. On the other hand, the selectivity towards EO and the ethylene conversion of Ag/GDC cermet coatings were found to linearly increase with the applied current, demonstrating for the first time, the direct electrooxidation of ethylene into EO. (c) 2021 Elsevier Ltd. All rights reserved.

In the present study, Au-V2O5 sensing material was tested as a sensing electrode for developing mixed-potential ammonia gas sensors. The results of gas sensing measurements indicated selective responses to NH3 while this selectivity was highly dependent on the temperature. Different V2O5 contents were tested in the sensing electrode. The results showed that by increasing V2O5 content from 15 wt.% to 50 wt.%, selective ammonia sensors could be achieved at 550 ?C. The selectivity of Au-50 %V2O5 sensor was also confirmed in gas mixtures of CO, NH3, NO, and NO2 gases. Modeling of the sensor responses in the ammonia concentration range 2?40 ppm at four oxygen concentrations was performed based on mixed-potential theory. Nernst and Butler-Volmer equations with an electron transfer assumption were used for data modeling.

Ammonia detection at ambient with low-cost sensors is a challenge for various applications like breath analysis and agriculture. Such a challenge can be reached with functionalized SnO2 based gas sensors using silanization by 3-aminopropyltriethoxysilane (APTES) as an intermediate step before grafting with functional end group providing selectivity for the target gas. Moreover, operation at room temperature gives the opportunity to develop a sensor on a plastic substrate entirely manufactured by inkjet technology, by developing suitable inks, in particular to obtain SnO2 sensing element.

This study reports the catalytic properties of Ag nanoparticles dispersed on mixed ionic and electronic conducting layers of LSCF (La0.6Sr0.4Co0.2Fe0.8O3) for propene combustion. A commercial and a synthesized LSCF powder were deposited by screen-printing or spin-coating on dense yttria-stabilized zirconia (YSZ) substrates, an oxygen ion conductor. Equal loadings (50 µg) of Ag nanoparticles were dispersed via drop-casting on the LSCF layers. Electrochemical and catalytic properties have been investigated up to 300 °C with and without Ag in a propene/oxygen feed. The Ag nanoparticles do not influence the electrochemical reduction of oxygen, suggesting that the rate-determining step is the charge transfer at the triple phase boundaries YSZ/LSCF/gas. The anodic electrochemical performances correlate well with the catalytic activity for propene oxidation. This suggests that the diffusion of promoting oxygen ions from YSZ via LSCF grains can take place toward Ag nanoparticles and promote their catalytic activity. The best specific catalytic activity, achieved for a LSCF catalytic layer prepared by screen-printing from the commercial powder, is 800 times higher than that of a pure Ag screen-printed film.

In this study, we have investigated, for the very first time, the oxygen electrode reactions on Ag/YSZ electrochemical catalysts both in oxygen and under reaction conditions compatible with the ethylene epoxidation reaction. Electrochemical Impedance Spectroscopy (EIS) in combination with in-situ Raman spectroscopy and catalytic activity measurements were used to identify and understand the main oxygen reaction pathways. The results obtained suggested that the rate limiting step under an O-2 reaction atmosphere (at 300 degrees C) is the O-2 adsorption/dissociation process on the Ag catalyst-electrode. In addition, the polarization resistance increased with time under the presence of O-2. This was attributed to the formation of Ag2O on the catalyst surface or near surface, which limits the oxygen electrode reactions. Finally, we observed that the addition of ethylene in the feed stream hinders the electrode reaction, due to its competitive chemisorption with oxygen on Ag. These results give new insights into the design of selective Ag/YSZ catalyst for ethylene epoxidation.

The feasibility of room temperature ammonia gas sensors based on tin dioxide (SnO2) functionalization has been demonstrated. 3-aminopropyltriethoxysilane (APTES) was used as an intermediate step, followed by functionalization with molecules having acyl chloride with different end functional groups molecules such as alkyl, acid and ester groups. Modified films were characterized by attenuated total reflectance infra-red spectroscopy (ATR-FTIR). Upon exposure to ammonia gas, the electrical conductance of alkyl, acid and ester modified SnO2-APTES increases, whereas other reducing gases such as ethanol, carbon monoxide and acetone show no change in conductance. Furthermore, ester modified SnO2 is more selective than acid modified sensor regarding ethanol and carbon monoxide gases

One of the most effective technologies in decreasing large-scale NOx emission produced by diesel engine vehicles is Urea-SCR (selective catalytic reduction) system. In order to prevent inducing excessive ammonia to the environment, an NH3 sensor is required at the exit of this system [1, 2]. In this study, highly selective ammonia sensors were developed to detect ammonia emissions from automotive exhaust. The sensors were fabricated with 8-YSZ electrolyte, a platinum reference electrode and a working electrode of Au-V2O5 (mass ratio 85/15), screen-printed on an alumina substrate. A platinum resistor was printed at the backside of the support to control the sensor temperature. The measured sensor’ response (ΔV) is the potential difference between reference and working electrodes. Figure 1 shows the responses of two identical sensors to 100 ppm CO, NO2, NO and 20 ppm of NH3 at four different temperatures. It can be seen that the sensors respond to all gases at lower temperatures while by increasing temperature to 600°C, the selectivity to NH3 is greatly improved. The selectivity of sensors was also confirmed by testing other possible interfering gases: no responses were observed for 20ppm of hydrogen and 100ppm of a hydrocarbon mixture. The stability of such sensors was studied at 550°C and 600°C. Since the sensors show no long-term stability at 600°C (electrode degradation), but remain stable at 550 °C, investigations were made to decrease the working temperature while maintaining selectivity. After testing different mass percentages of V2O5 in working electrode, we observed that by increasing this value to 50%, the working temperature of selective ammonia sensors could be decreased to 550°C with stable responses. Further investigations will be performed in order to gain deeper insight in sensing mechanism of V2O5 based working electrodes, which governs the sensor’s performance. References [1] K. Shimizu, I. Chinzei, et al. "Doped-vanadium oxides as sensing materials for high temperature operative selective ammonia gas sensors," Sensors and Actuators B, 141, 2009, pp. 410-416. [2] M. Van Nieuwstadt, I. Dpadhyay, et al. "Control of Urea SCR Systems for US Diesel Applications" in IFP Energies Nouvelles International Conference, Dearborn, USA, 2011, pp. 655-665. Figure 1

In recent years, printed and flexible gas sensors have quickly emerged as an innovative area of great interest because of their lightness and low cost.

Surface functionalization has numerous applications worldwide. Silicon oxide has been a research material of choice. However, tin dioxide (SnO2) films are employed in many applications especially in gas sensors, and little studied in regard to functionalization. Thus, they were chosen to be functionalized via 3-aminopropyltriethoxysilane (APTES). Different synthesis parameters were tested such as APTES grafting by vapor or liquid phases deposition. In liquid, many parameters were investigated: water presence, reaction times, and APTES concentration. The presence and reactivity of grafted amine-terminated film on SnO2 were carried out by Alexa Fluor® molecules. In addition, APTES grafting was characterized using attenuated total reflectance Fourier transform infrared spectroscopy and X-ray photoelectron spectrometry techniques. These characterizations showed how synthesis parameters affect the amount and thickness of APTES films. Optimal liquid silanization parameters were determined in order to obtain a saturated SnO2 surface with APTES molecules. Importantly, the addition of 5 vol% H2O to the APTES solution provided denser surface coverage, by hydrolyzing the ethoxy groups to silanol. An almost 50% improvement over anhydrous liquid and vapor methods was obtained.