Iron and nitrogen co-modified multi-walled carbon nanotubes for efficient electrocatalytic oxygen reduction.

Multi-walled carbon nanotubes (MWCNTs) with one-dimensional nanostructure are an ideal support for oxygen reduction reaction (ORR) catalysts thanks to their intrinsic outstanding electrical conductivity and high specific surface area. Iron and nitrogen doping could alter the local electronic structure and therefore enhance the ORR activity of MWCNTs, but the preparation process always includes complicated growth conditions and post-treatment. Herein, an iron and nitrogen co-modified multi-walled carbon nanotubes (Fe-N-MWCNTs) with hierarchical nanostructure is engineered and synthesized via a simple two-step pyrolysis approach. Large specific surface area, low resistivity, and intensified charge density near the Fermi level synergistically endow the Fe-N-MWCNTs with outstanding ORR activity. The optimal Fe-N-MWCNTs exhibit a higher onset potential value of 0.92 V (versus RHE) and half-wave potential (E1/2) of 0.85 V (versus RHE) in 0.1 M KOH medium, which exceeds the benchmark Pt/C electrocatalyst (E1/2= 0.84 V). This strategy of modifying MWCNTs support by a simple calcination process provides a feasible method to prepare cost-efficient ORR electrocatalysts.

Efficient mixed-potential acetone sensor with yttria-stabilized zirconia and porous Co3O4 nanofoam sensing electrode for hazardous gas monitoring and breath analysis.

For hazardous gas monitoring and non-invasive diagnosis of diabetes using breath analysis, porous foams assembled by Co3O4 nanoparticles were designed as sensing electrode materials to fabricate efficient yttria-stabilized zirconia (YSZ)-based acetone sensors. The sensitivity of the sensors was improved by varying the sintering temperature to regulate the morphology. Compared to other materials sintered at different temperatures, the porous Co3O4 nanofoams sintered at 800 °C exhibited the highest electrochemical catalytic activity during the electrochemical test. The response of the corresponding Co3O4-based sensor to 10 ppm acetone was -77.2 mV and it exhibited fast response and recovery times. Moreover, the fabricated sensor achieved a low detection limit of 0.05 ppm and a high sensitivity of -56 mV/decade in the acetone concentration range of 1-20 ppm. The sensor also exhibited excellent repeatability, acceptable selectivity, good O2/humidity resistance, and long-term stability during continuous measurements for over 30 days. Moreover, the fabricated sensor was used to determine the acetone concentration in the exhaled breaths of patients with diabetic ketosis. The results indicated that it could distinguish between healthy individuals and patients with diabetic ketosis, thereby proving its abilities to diagnose and monitor diabetic ketosis. Based on its excellent sensitivity and exhaled breath measurement results, the developed sensor has broad application prospects.

Ultrasonic-assisted Fenton reaction inducing surface reconstruction endows nickel/iron-layered double hydroxide with efficient water and organics electrooxidation.

Nickel/iron-layered double hydroxide (NiFe-LDH) tends to undergo an electrochemically induced surface reconstruction during the water oxidation in alkaline, which will consume excess electric energy to overcome the reconstruction thermodynamic barrier. In the present work, a novel ultrasonic wave-assisted Fenton reaction strategy is employed to synthesize the surface reconstructed NiFe-LDH nanosheets cultivated directly on Ni foam (NiFe-LDH/NF-W). Morphological and structural characterizations reveal that the low-spin states of Ni2+ (t2g6eg2) and Fe2+ (t2g4eg2) on the NiFe-LDH surface partially transform into high-spin states of Ni3+ (t2g6eg1) and Fe3+ (t2g3eg2) and formation of the highly active species of NiFeOOH. A lower surface reconstruction thermodynamic barrier advantages the electrochemical process and enables the NiFe-LDH/NF-W electrode to exhibit superior electrocatalytic water oxidation activity, which delivers 10 mA cm-2 merely needing an overpotential of 235 mV. Besides, surface reconstruction endows NiFe-LDH/NF-W with outstanding electrooxidation activities for organic molecules of methanol, ethanol, glycerol, ethylene glycol, glucose, and urea. Ultrasonic-assisted Fenton reaction inducing surface reconstruction strategy will further advance the utilization of NiFe-LDH catalyst in water and organics electrooxidation.

Insight into the effect of the continuous testing and aging on the SO2 sensing characteristics of a YSZ (Yttria-stabilized Zirconia)-based sensor utilizing ZnGa2O4 and Pt electrodes.

In this paper, YSZ-based mixed potential SO2 sensor with ZnGa2O4 and Pt electrodes was developed and the effect of the continuous testing and aging process on the sensing characteristics was discussed. The results showed that with this process the response of the sensor to SO2 performed an opposite direction to that in the sensor's initial state. The reason might be that the PtS produced at the Pt electrode increased the electrochemical catalytic activity of the Pt electrode, leading to the mixed potential of the Pt electrode higher than that of the ZnGa2O4 electrode. XPS and EDS results proved that a lot of Pt2+ and S2- were produced at Pt electrode after this process. Moreover, vulcanized sensor also performed similar sensing properties to the above aging sensor, which indicated that the produced PtS should be the reason that the sensor performed reverse deflection on sensing properties. In addition, the sensor after sulfuration can detect 0.05-500 ppm SO2 with the sensitivity being 5 mV/decade to 0.05-1 ppm and 41 mV/decade to 1-500 ppm. The sensor also had a reliable stability during the continuous measurement.

Highly sensitive detection of Pb2+ and Cu2+ based on ZIF-67/MWCNT/Nafion-modified glassy carbon electrode.

A series of different facile modification layers (MLs) was designed to gradually increase the electrochemical sensing performance of glassy carbon electrode (GCE) for simultaneously detecting Pb2+ and Cu2+. ML designs were mainly a different combination of ZIF-67, MWCNT and Nafion, and their different electrochemical sensing performances were investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), square wave stripping voltammetry (SWSV) and chronocoulometry. The fabricated sensor, which modified with ZIF-67/MWCNT and Nafion layer, exhibited the biggest response peak current to Pb2+ and Cu2+. In addition, it displayed a wide linear detection range of 1.38 nM-5 µM for Pb2+ and 1.26 nM-5 µM for Cu2+, a detection accuracy of about 1 nM for both Pb2+ and Cu2+, and an excellent stability for both Pb2+ and Cu2+. We also analyzed the real water sample taken from Changchun's Sanjia Lake and Yan Lake. We believe this ML design provides instruction for building high-performance electrochemical sensing systems.

Fabrication of Well-Ordered Three-Phase Boundary with Nanostructure Pore Array for Mixed Potential-Type Zirconia-Based NO2 Sensor.

A well-ordered porous three-phase boundary (TPB) was prepared with a polystyrene sphere as template and examined to improve the sensitivity of yttria-stabilized zirconia (YSZ)-based mixed-potential-type NO2 sensor due to the increase of the electrochemical reaction active sites. The shape of pore array on the YSZ substrate surface can be controlled through changing the concentration of the precursor solution (Zr(4+)/Y(3+) = 23 mol/L/4 mol/L) and treatment conditions. An ordered hemispherical array was obtained when CZr(4+) = 0.2 mol/L. The processed YSZ substrates were used to fabricate the sensors, and different sensitivities caused by different morphologies were tested. The sensor with well-ordered porous TPB exhibited the highest sensitivity to NO2 with a response value of 105 mV to 100 ppm of NO2, which is approximately twice as much as the smooth one. In addition, the sensor also showed good stability and speedy response kinetics. All these enhanced sensing properties might be due to the structure and morphology of the enlarged TPB.