Recent progress on nanomaterial-based electrochemical dissolved oxygen sensors

Dissolved oxygen(DO)usually refers to the amount of oxygen dissolved in water.In the environment,medicine,and fermentation industries,the DO level needs to be accurate and capable of online monitoring to guide the precise control of water quality,clinical treatment,and microbial metabolism.Compared with other analytical methods,the electrochemical strategy is superior in its fast response,low cost,high sensitivity,and portable device.However,an electrochemical DO sensor faces a trade-off between sensitivity and long-term stability,which strongly limits its practical applications.To solve this problem,various advanced nanomaterials have been proposed to promote detection performance owing to their excellent electrocatalysis,conductivity,and chemical stability.Therefore,in this review,we focus on the recent progress of advanced nanomaterial-based electrochemical DO sensors.Through the comparison of the working principles on the main analysis techniques toward DO,the advantages of the electrochemical method are discussed.Emphasis is placed on recently developed nanomaterials that exhibit special characteristics,including nanostructures and preparation routes,to benefit DO determination.Specifically,we also introduce some interesting research on the configuration design of the electrode and device,which is rarely introduced.Then,the different requirements of the electrochemical DO sensors in different application fields are included to provide brief guidance on the selection of appropriate nanomaterials.Finally,the main challenges are evaluated to propose future development prospects and detection strategies for nanomaterial-based electrochemical sensors.

Microarrow sensor array with enhanced skin adhesion for transdermal continuous monitoring of glucose and reactive oxygen species

Conventional blood sampling for glucose detection is prone to cause pain and fails to continuously record glucose fluctuations in vivo.Continuous glucose monitoring based on implantable electrodes could induce pain and potential tissue inflammation,and the presence of reactive oxygen species(ROS)due to inflammationmay affect glucose detection.Microneedle technology is less invasive,yet microneedle adhesion with skin tissue is limited.In this work,we developed a microarrow sensor array(MASA),which provided enhanced skin surface adhesion and enabled simultaneous detection of glucose and H_(2)O_(2)(representative of ROS)in interstitial fluid in vivo.The microarrows fabricated via laser micromachining were modified with functional coating and integrated into a patch of a three-dimensional(3D)microneedle array.Due to the arrow tip mechanically interlocking with the tissue,the microarrow array could better adhere to the skin surface after penetration into skin.The MASA was demonstrated to provide continuous in vivo monitoring of glucose and H_(2)O_(2) concentrations,with the detection of H_(2)O_(2) providing a valuable reference for assessing the inflammation state.Finally,the MASA was integrated into a monitoring system using custom circuitry.This work provides a promising tool for the stable and reliable monitoring of blood glucose in diabetic patients.

Self-Healing,Self-Adhesive and Stable Organohydrogel-Based Stretchable Oxygen Sensor with High Performance at Room Temperature

With the advent of the 5G era and the rise of the Internet of Things,various sensors have received unprecedented attention,especially wearable and stretchable sensors in the healthcare field.Here,a stretchable,self-healable,self-adhesive,and room-temperature oxygen sensor with excellent repeatability,a full concentration detection range(0-100%),low theoretical limit of detection(5.7 ppm),high sensitivity(0.2%/ppm),good linearity,excellent temperature,and humidity tolerances is fabricated by using polyacrylamide-chitosan(PAM-CS)double network(DN)organohydrogel as a novel transducing material.The PAM-CS DN organohydrogel is transformed from the PAM-CS composite hydrogel using a facile soaking and solvent replacement strategy.Compared with the pristine hydrogel,the DN organohydrogel displays greatly enhanced mechanical strength,moisture retention,freezing resistance,and sensitivity to oxygen.Notably,applying the tensile strain improves both the sensitivity and response speed of the organohydrogel-based oxygen sensor.Furthermore,the response to the same concentration of oxygen before and after self-healing is basically the same.Importantly,we propose an electrochemical reaction mechanism to explain the positive current shift of the oxygen sensor and corroborate this sensing mechanism through rationally designed experiments.The organohydrogel oxygen sensor is used to monitor human respiration in real-time,verifying the feasibility of its practical application.This work provides ideas for fabricating more stretchable,self-healable,self-adhesive,and high-performance gas sensors using ion-conducting organohydrogels.

Solid Reference Electrode of Metallurgical Oxygen Sensor

The thermal equilibrium state of the reference electrode was investigated. The results show that the temperature difference between the inside and the outside of zirconia tube was very small and the Seebeck effect can be ignored after the sensor was dipped into liquid steel for more than 2 s. A special sensor was designed to test the relation between the EMF （electromotive force） of sensor and the thermal equilibrium state of the reference elec- trode. Based on these results, it is suggested that the peak in EMF curve was caused by the change of oxygen potential in reference electrode before the thermal equilibrium was reached. If NiO was added by 2 M- 5 M to the Cr/Cr2O3 reference electrode, the peak in EMF curve could be eliminated.

Effect of ZrO_2 (9mol% Y_2O_3) coating thickness on the electronic conductivity of Mg-PSZ oxygen sensors

The ZrO2 (9mol% Y2O3) coating was prepared evenly on the surface of MgO partially stabilized zirconia (Mg-PSZ) tube (oxygen sensor probe) by dipping the green Mg-PSZ tube in a ZrO2 (9mol% Y2O3) slurry and then co-firing at 1750°C for 8 h. The double-cell method was employed to measure the electronic conductivity parameter and exam the reproducibility of the coated Mg- PSZ tube. The experimental results indicate that the good thermal shock resistance of the Mg-PSZ tube can be retained when the coating thickness is not more than 3.4 μm. The ZrO2 (9mol% Y2O3) coating reduces the electronic conductivity parameter remarka- bly, probably due to the lower electronic conductivity of Y2O,-stabilized ZrO2 than that of MgO-stabilized ZrO2. Moreover, the ZrO2 (9mol% Y2O3) coating can improve the reproducibility and accuracy of the Mg-PSZ tube significantly in the low oxygen measure- ment. The smooth surface feature and lower electronic conductivity of the coated Mg-PSZ tube should be responsible for this im- provement.

The performance of Pt/air oxygen sensors in stagnant Pb-Bi eutectic at high temperatures

Oxygen control technology is a critical issue for compatibility of candidate structural materials with liquid lead-bismuth eutectic(LBE) in accelerator driven systems. Performances of a self-developed Pt/air sensor and another one from Karlsruher Institute of Technology(KIT) were tested in stagnant oxygen-saturated liquid LBE.Calibrations showed that the trend and values of corrected electromotive force(EMF) of the self-developed sensor, with a bias voltage of 20 mV, were consistent with theoretical results above 425℃, and similar results were obtained in cross-calibration test with EMF value of KIT sensor as reference. In stability test at 450℃ for 100 hours, the KIT sensor performed better than the self-developed one, which showed signal fluctuations.Both sensors exhibited quick response to temperature variations in the responsiveness test.

Real Time Dynamic Study of Amperometric Exhaust Oxygen Sensors

Previously,we had identified the various dynamic mechanisms of a wide range air to fuel ratio sensor operated in the engine exhaust by using the transfer function approach.In this study,we utilized these results to model the real time sensor response to an engine exhaust excursion.In the fitting,we identified a new dynamic mechanism,which was not detected in the previous transfer function study.This new dynamic occurred at the stoichiometric point when the engine changed from rich to lean.This new mechanism involved the depletion of the adsorbed fuel species on the electrode surface by an oxidation process. The dynamics of this effect depends on the ratio of the diffusion flux of the sensor-coating layer to the total adsorbed gas species on the electrode surface.The smaller the ratio is,the slower the dynamic mechanism will be.

Research on Oxygen Sensor for Metallurgical Process

A new technique for manufacture of the oxygen sensor used for metallurgical process has been developed.The powder of MgO-PSZ was prepared by coprecipitation.The MgOPSZ tube was prepared by powder injection molding(PIM).The final sintered tube was assembled into oxygen cell,then tested in laboratory and on RH vessel.The results showed that the thermal shock resistance of MgO-PSZ matrix is strong enough for determining the active oxygen concentration in steel melt.The reproducibility of the EMF measurement is very good.The structure of the tube has been analysed by means of SEM and XRD.In addition,the characteristics such as the density and phase ratio in the product were compared with that of Shijiazhuang Maple Wood Sensor Company s product.

Properties of Zirconia Material as Oxygen Sensor

The properties and applications of ZrO_2-Y_2O_3 material used as oxygen sensor were studied.Oxygen sensors are studied by X-ray diffraction technique,microstructure determination and thermal shock resistance test,and are tested on the spot.Oxygen sensors made from the sintered dense ZrO_2 stabilized by Y_2O_3 can be used to measure the oxygen concentration in molten steel at 1600℃.The data obtained are stable and reliable, and the thermal shock resistance is high.The oxygen concentration is measured at(1～150)×10^(-4)% with re- sponse time of 2～3s.

A Novel Electrochemical Oxygen Sensor for Determination of Ultra-low Oxygen Contents in Molten Metal

A novel electrochemical oxygen sensor has been developed by using La beta -Al2O3 as solid electrolyte and Cr+Cr2O3 as reference electrode. The sensor not only can be used as normal oxygen sensor but also as an ultra-low oxygen sensor. Especially, it is very sensitive to measure ultra-low oxygen in molten metal. For estimating the accuracy of La beta -Al2O3 oxygen sensor, two series of oxygen activities in molten iron at different oxygen contents and different temperature were measured by both La beta -Al2O3 oxygen sensor and ZrO2 oxygen sensor. The theoretical values of oxygen activities in molten iron (3.30%C, in mass fraction) at 1723K and 1745K were also evaluated for comparing the measuring results of two sensors. At last, the error of measurement for La beta -Al2O3 oxygen sensor was discussed too.

Preparation and Properties of Sensing Membrane for Fiber Optic Oxygen Sensor

Four sensing membranes based on fluorescence quenching were prepared by sol-gel method and CA membrane method, and the Ru(Ⅱ) complexes, Ru( bpy)3 Cl2 and Ru(phen)3 Cl2 , were used as the indicators . The results indicate that the volume fraction of oxygen o2 have a linear relationship in large scale with tan0/tanfor all of the sensing membranes. They have super properties such as excellent limit of detection ,fast response time and good reproducibility. The stability of the sensing membranes made by sol-gel method is better than those by CA membranes, but the uniformity of the latter is better than that of the former.

Preparation and Characterization of Zireonia Oxygen Sensors

A thimble zirconia oxygen sensor electrolyte and their interface were observed with was prepared with YSZ. The surfaces of the Pt electrode, a scanning electron microscope （SEM）.The sensor was examined with engine bench test to evaluate the essential performance. The basic function such as electromotive force output and response time was discussed. The oscillograph trace was also obtained and analyzed with four different frequencies. The experimental results reveal that the oxygen sensor has high performances meeting the demands of practical applications..

Dissolved oxygen sensor based on sol-gel matrix doped with tris(2,2'-bipyridine)ruthenium dichloride

To establish a immobilization method of oxygen sensitive dye, a dissolved oxygen sensor based on a sol-gel matrix doped with ruthenium complex ([Ru(bpy)3]2+) as the oxygen-sensitive material is reported. The results indicate that the I0 /I100 value of the [Ru(bpy)3]2+-doped in tetraethylorthosilane (TEOS) composite films are estimated to be 10.6, where I0 and I100 correspond to the detected fluorescence intensities in pure nitrogen saturated water and pure oxygen saturated water, respectively. Also, the Stern-Volmer plot shows a very good linearity at low dissolved oxygen concentrations. The response time of the composite films is 5 s upon switching from nitrogen saturated water to oxygen saturated water and 10 s from oxygen saturated water to nitrogen saturated water. The dissolved oxygen sensors based on the ruthenium complex/TEOS composite films exhibit greater sensitivity, stability and faster response time as compared to the existing ones. Furthermore, the thin films possess greatly minimized dye leaching effect.

Preparation and Properties of Modified Sol-Gel Sensing Membrane for Fiber Optic Oxygen Sensor

Modified sensing membranes based on fluorescence quenching were prepared by the sol-gel method,using formamide as the drying control chemical additive,tetraethoxysilane as the main material,Ru(phen) 3Cl 2 as the indicator.The membrane with the optimum thickness of 20-50μm is uniform and crack-free,in which the indicator has a very small leaking rate.The membrane is immersed in water for 50h,the membrane sensing parameter M decreases by less than 5%.The fiber optic oxygen sensor with the sensing membrane has a detection limit of 5×10 -6M(ppm),a response time of less than 30s,excellent reproducibility and stability.

Highly sensitive ratiometric fluorescent fiber matrices for oxygen sensing with micrometer spatial resolution

Oxygen(O_(2))-sensing matrices are promising tools for the live monitoring of extracellular O_(2) consumption levels in long-term cell cultures.In this study,ratiometric O_(2)-sensing membranes were prepared by electrospinning,an easy,low-cost,scalable,and robust method for fabricating nanofibers.Poly(ε-caprolactone)and poly(dimethyl)siloxane polymers were blended with tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II)dichloride,which was used as the O_(2)-sensing probe,and rhodamine B isothiocyanate,which was used as the reference dye.The functionalized scaffolds were morphologically characterized by scanning electron microscopy,and their physicochemical profiles were obtained by Fourier transform infrared spectroscopy,thermogravimetric analysis,and water contact angle measurement.The sensing capabilities were investigated by confocal laser scanning microscopy,performing photobleaching,reversibility,and calibration curve studies toward different dissolved O_(2)(DO)concentrations.Electrospun sensing nanofibers showed a high response to changes in DO concentrations in the physiological-pathological range from 0.5%to 20%and good stability under ratiometric imaging.In addition,the sensing systems were highly biocompatible for cell growth promoting adhesiveness and growth of three cancer cell lines,namely metastatic melanoma cell line SK-MEL2,breast cancer cell line MCF-7,and pancreatic ductal adenocarcinoma cell line Panc-1,thus recreating a suitable biological environment in vitro.These O_(2)-sensing biomaterials can potentially measure alterations in cell metabolism caused by changes in ambient O_(2)content during drug testing/validation and tissue regeneration processes.

Sintering Caβ″/β/α-Al_2O_3 High Temperature Oxygen Sensor

An extended-life and ultra-low oxygen sensor has been fabricated by using polycrystalline Caβ″/β/α-Al2O3 as a solid electrolyte. Five reference electrodes CaO+O2, Caβ″/β/α-Al2O3 (powder)+O2,Cr+Cr2O3, Nb+NbO and Mo+MoO2 were tested in order to select a better reference electrode for this sensor. The limit of determining oxygen activity and the extended-life of the sensor were also tested in this study.

Preparation and analysis of zirconia oxygen sensors

Thimble zirconia oxygen sensors were prepared with yttria stabilized zirconia(YSZ). The surfaces of the electrode, electrolyte and their interface were observed by scanning electron microscope(SEM). The sensor was examined with engine bench test to evaluate the essential performance. The results show that the oxygen sensor has good performance, which can meet the demand of practical applications. Chemical equilibrium theory was introduced to explain electromotive force of the sensors and the influence of temperature on the signals. The educed theoretical model of electromotive force agrees well with testing results.

A Fiber Optic Sensor for 2-cholrophenol Analysis based on Oxygen Sensing System

A fiber optic 2-cholrophenol（2-CP） sensor was developed based on the fluorescence quenching of molecular oxygen on the oxygen-sensitive membrane and O2 consumption during catalytic oxidation reaction of 2-CP. The 2-CP concentration can be determined by utilizing a lock-in amplifier to measure the change in the fluorescence lifetime of an oxygen-sensitive membrane, in which the tris（2,2′-bipyridyl） ruthenium（II） chloride complexes（Ru（II）（byp）3Cl2） were immobilized in cellulose acetate（CA） via simple hybridized approach. The experimental results show the good linear relationship between the phase delay of sensitive membrane and 2-CP concentration in its detection range of 1×10-7 to 1×10-5 mol/L and 1×10-5 to 1×10-4 mol/L. The detection limit of the sensor is 7×10-8 mol/L（S/N=3） and the response time is 5 min. Our experimental measurements confirmed good response characteristics of the as-prepared fiber optic 2-CP sensor, as well as its capability to detect the 2-CP concentration in practical water samples.