The instability of the surface chemistry in transition metal oxide perovskites is the main factor hindering the long-term durability of oxygen electrodes in solid oxide electrochemical cells. The instability of surface chemistry is mainly due to the segregation of A-site dopants from the lattice to the surface. Here we report that cathodic potential can remarkably improve the stability in oxygen reduction reaction and electrochemical activity, by decomposing the near-surface region of the perovskite phase in a porous electrode made of La1-xSrxCo1-xFexO3mixed with Sm0.2Ce0.8O1.9. Our approach combines X-ray photoelectron spectroscopy and secondary ion mass spectrometry for surface and sub-surface analysis. Formation of Ruddlesden-Popper phase is accompanied by suppression of the A-site dopant segregation, and exsolution of catalytically active Co particles onto the surface. These findings reveal the chemical and structural elements that maintain an active surface for oxygen reduction, and the cathodic potential is one way to generate these desirable chemistries.
Electrospun porous La–Sr–Co–Ni–O nanofibers for highly sensitive non-enzymatic glucose detection
Glucose biosensors are widely used for clinical, industrial, and environmental applications. Nonenzymatic electrochemical glucose biosensors based on metal oxides with a perovskite structure have exhibited high sensitivity, excellent stability, and cost efficiency. In this work, porous La–Sr–Co–Ni–O (LSCNO) nanofibers, with an ABO 3 -type perovskite structure, were prepared through optimizing the A-site and B-site elements by electrospinning, followed with calcination at 700 °C for 5 h. Characterized by scanning and transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, fabricated nanofibers were confirmed to be porous and nanosized polycrystalline grains with high crystallinity. A novel La 0.75 Sr 0.25 Co 0.5 Ni 0.5 O 3 -based nonenzymatic electrochemical biosensor was developed, which is sensitive to glucose because of an electrochemically catalytic mechanism, a mediated electron transfer involving Ni( ii )/Ni( iii ) or Co( ii )/Co( iii ), accompanying with gluconic acid complexation. The glucose biosensor presented a linear response in the range of 0.1–1.0 mM with a calibration sensitivity of 924 ± 28 μA mM −1 , a proportion of the variance of 0.9926, and a lower limit of detection of 0.083 mM, respectively, demonstrating an outstanding analytical performance. The biosensor showed no response to the most widely used anionic surfactant, sodium dodecyl sulfate, and low sensitivity to other biomolecules, such as fructose, lactose, galactose, mannose, dopamine, and ascorbic acid. A urine sample was tested by this novel nonenzymatic electrochemical biosensor by standard addition method, suggesting a potential application for clinical test.
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- Award ID(s):
- 1900837
- NSF-PAR ID:
- 10348146
- Date Published:
- Journal Name:
- Materials Advances
- Volume:
- 3
- Issue:
- 4
- ISSN:
- 2633-5409
- Page Range / eLocation ID:
- 2096 to 2103
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract -
Sr(Ti 1−x Fe x )O 3−δ (STF) has recently been explored as an oxygen electrode for solid oxide electrochemical cells (SOCs). Model thin film electrode studies show oxygen surface exchange rates that generally improve with increasing Fe content when x < 0.5, and are comparable to the best Co-containing perovskite electrode materials. Recent results on porous electrodes with the specific composition Sr(Ti 0.3 Fe 0.7 )O 3−δ show excellent electrode performance and stability, but other compositions have not been tested. Here we report results for porous electrodes with a range of compositions from x = 0.5 to 0.9. The polarization resistance decreases with increasing Fe content up to x = 0.7, but increases for further increases in x . This results from the interaction of two effects – the oxygen solid state diffusion coefficient increases with increasing x , but the electrode surface area and surface oxygen exchange rate decrease due to increased sinterability and Sr surface segregation for the Fe-rich compositions. Symmetric cells showed no degradation during 1000 h life tests at 700 °C even at a current density of 1.5 A cm −2 , showing that all the STF electrode compositions worked stably in both fuel cell mode and electrolysis modes. The excellent stability may be explained by X-ray Photoelectron Spectroscopy (XPS) results showing that the amount of surface segregated Sr did not change during the long-term testing, and by relatively low polarization resistances that help avoid electrode delamination.more » « less
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Water electrolysis can use renewable electricity to produce green hydrogen, a portable fuel and sustainable chemical precursor. Improving electrolyzer efficiency hinges on the activity of the oxygen evolution reaction (OER) catalyst. Earth-abundant, ABO3-type perovskite oxides offer great compositional, structural, and electronic tunability, with previous studies showing compositional substitution can increase the OER activity drastically. However, the relationship between the tailored bulk composition and that of the surface, where OER occurs, remains unclear. Here, we study the effects of electrochemical cycling on the OER activity of La 0.5 Sr 0.5 Ni 1-x Fe x O 3-δ (x = 0-0.5) epitaxial films grown by oxide molecular beam epitaxy as a model Sr-containing perovskite oxide. Electrochemical testing and surface-sensitive spectroscopic analyses show Ni segregation, which is affected by electrochemical history, along with surface amorphization, coupled with changes in OER activity. Our findings highlight the importance of surface composition and electrochemical cycling conditions in understanding OER performance on mixed metal oxide catalysts, suggesting common motifs of the active surface with high surface area systems.more » « less
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Transition metals have been explored extensively for non-enzymatic electrochemical detection of glucose. However, to enable glucose oxidation, the majority of reports require highly alkaline electrolytes which can be damaging to the sensors and hazardous to handle. In this work, we developed a non-enzymatic sensor for detection of glucose in near-neutral solution based on copper-nickel electrodes which are electrochemically modified in phosphate-buffered saline (PBS). Nickel and copper were deposited using chronopotentiometry, followed by a two-step annealing process in air (Step 1: at room temperature and Step 2: at 150 °C) and electrochemical stabilization in PBS. Morphology and chemical composition of the electrodes were characterized using scanning electron microscopy and energy-dispersive X-ray spectroscopy. Cyclic voltammetry was used to measure oxidation reaction of glucose in sodium sulfate (100 mM, pH 6.4). The PBS-Cu-Ni working electrodes enabled detection of glucose with a limit of detection (LOD) of 4.2 nM, a dynamic response from 5 nM to 20 mM, and sensitivity of 5.47 ± 0.45 μA cm−2/log10(mole.L−1) at an applied potential of 0.2 V. In addition to the ultralow LOD, the sensors are selective toward glucose in the presence of physiologically relevant concentrations of ascorbic acid and uric acid spiked in artificial saliva. The optimized PBS-Cu-Ni electrodes demonstrate better stability after seven days storage in ambient compared to the Cu-Ni electrodes without PBS treatment.more » « less
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null (Ed.)Sr(Ti 0.3 Fe 0.7 )O 3−δ (STF) and the associated exsolution electrodes Sr 0.95 (Ti 0.3 Fe 0.63 Ru 0.07 )O 3−δ (STFR), or Sr 0.95 (Ti 0.3 Fe 0.63 Ni 0.07 )O 3−δ (STFN) are alternatives to Ni-based cermet fuel electrodes for solid oxide electrochemical cells (SOCs). They can provide improved tolerance to redox cycling and fuel impurities, and may allow direct operation with hydrocarbon fuels. However, such perovskite-oxide-based electrodes present processing challenges for co-sintering with thin electrolytes to make fuel electrode supported SOCs. Thus, they have been mostly limited to electrolyte-supported SOCs. Here, we report the first example of the application of perovskite oxide fuel electrodes in novel oxygen electrode supported SOCs (OESCs) with thin YSZ electrolytes, and demonstrate their excellent performance. The OESCs have La 0.8 Sr 0.2 MnO 3−δ –Zr 0.92 Y 0.16 O 2−δ (LSM–YSZ) oxygen electrode-supports that are enhanced via infiltration of SrTi 0.3 Fe 0.6 Co 0.1 O 3−δ , while the fuel electrodes are either Ni-YSZ, STF, STFN, or STFR. Fuel cell power density as high as 1.12 W cm −2 is obtained at 0.7 V and 800 °C in humidified hydrogen and air with the STFR electrode, 60% higher than the same cell made with a Ni-YSZ electrode. Electrolysis current density as high as −1.72 A cm −2 is obtained at 1.3 V and 800 °C in 50% H 2 O to 50% H 2 mode; the STFR cell yields a value 72% higher than the same cell made with a Ni-YSZ electrode, and competitive with the widely used conventional Ni-YSZ-supported cells. The high performance is due in part to the low resistance of the thin YSZ electrolyte, and also to the low fuel electrode polarization resistance, which decreases with fuel electrode in the order: Ni-YSZ > STF > STFN > STFR. The high performance of the latter two electrodes is due to exsolution of catalytic metal nanoparticles; the results are discussed in terms of the microstructure and properties of each electrode material, and surface oxygen exchange resistance values are obtained over a range of conditions for STF, STFN, and STFN. The STF fuel electrodes also provide good stability during redox cycling.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d1ma00984b
