Chromium evaporation and oxidation characteristics of alumina-forming austenitic stainless steels for balance of plant applications in solid oxide fuel cells

The chromium (Cr) evaporation behavior of several different types of iron (Fe)-based AFA alloys and benchmark Cr₂O₃-forming Fe-based 310 and Ni-based 625 alloys was investigated for 500 h exposures at 800 °C to 900 °C in air with 10% H₂O. The Cr evaporation rates from alumina-forming austenitic (AFA) alloys were ~5 to 35 times lower than that of the Cr₂O₃-forming alloys depending on alloy and temperature. The Cr evaporation behavior was correlated with extensive characterization of the chemistry and microstructure of the oxide scales, which also revealed a degree of quartz tube Si contamination during the test. Long-term oxidation kinetics were also assessed at 800 to 1000 °C for up to 10,000 h in air with 10% H₂O to provide further guidance for SOFC BOP component alloy selection.     

Evaluation of bismuth doped La2-xBixNiO4+δ (x = 0, 0.02 and 0.04) as cathode materials for solid oxide fuel cells

Bismuth doped La_2-xBi_xNiO_4+δ (x = 0, 0.02 and 0.04) oxides are investigated as SOFC cathodes. The effects of Bi doping on the phase structure, thermal expansion, electrical conduction behavior as well as electrochemical performance are studied. All the samples exist as a tetragonal Ruddlesden-Popper structure. Bi-doped LBNO-0.02 and LBNO-0.04 have good chemical and thermal compatibility with LSGM electrolyte. The average TEC over 20–900°С was 13.4 × 10^?6 and 14.2 × 10^?6 K^?1 for LBNO-0.02 and LBNO-0.04, respectively. The electrical conductivity was decreasing with the rise of Bi doping content. EIS measurement indicates Bi doping can decrease the ASR values. At 750 °C, the obtained ASR for LBNO-0.04 is 0.18 Ωcm², which is 56% lower than that of the sample without Bi doping, suggesting Bi doping is beneficial to the electrochemical catalytic activity of LBNO cathodes.     

Fabrication and characterization of In doped Li13.9Sr0.1Zn(GeO4+δ)4 electrolytes for proton-conducting solid oxide fuel cells

Li_13.9Sr_0.1Zn(GeO_4+δ)₄ (LSZG) materials can exhibit proton conduction by Li⁺/H⁺ ion exchange in hydrogen atmosphere. It can be used in solid oxide fuel cells (SOFCs) as an electrolyte. In this study, In³⁺ doped LSZG powders are synthesized by sol-gel method. X-ray diffraction, scanning electron microscopy, thermal gravimetric analyzer, and electrochemical impedance spectroscopy are used to investigate the effects of In doping on LSZG. All Li_13.9-xIn_xSr_0.1Zn(GeO_4+δ)₄ (LISZG, 0 ≤ x ≤ 0.3) ceramics exhibit the same phase with LSZG. The dopant of In promotes the sintering activity and Li⁺/H⁺ ion exchange rate of LSZG. The optimum doping of In is x = 0.2. At 600 °C, Li_13.7In_0.2Sr_0.1Zn(GeO_4+δ)₄ (0.2LISZG) shows a proton conductivity of 0.094 S/cm under 0.9 V direct current bias voltage. In addition, the single cell based on 0.2LISZG electrolyte is prepared, and it has been demonstrated that the practical utilization of 0.2LISZG in IT-SOFCs is feasible.     

Charge injection in metal/organic/metal structures with ZnO:Al/organic interface modified by Zn1−xMgxO:Al layer

Aluminum-doped zinc oxide (ZnO:Al, AZO) electrodes were covered with very thin (∼6 nm) Zn_1−xMg_xO:Al (AMZO) layers grown by atomic layer deposition. They were tested as hole blocking/electron injecting contacts to organic semiconductors. Depending on the ALD growth conditions, the magnesium content at the film surface varied from x = 0 to x = 0.6. Magnesium was present only at the ZnO:Al surface and subsurface regions and did not diffuse into deeper parts of the layer. The work function of the AZO/AMZO (x = 0.3) film was 3.4 eV (based on the ultraviolet photoelectron spectroscopy). To investigate carrier injection properties of such contacts, single layer organic structures with either pentacene or 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl] squaraine layers were prepared. Deposition of the AMZO layers with x = 0.3 resulted in a decrease of the reverse currents by 1–2 orders of magnitude and an improvement of the diode rectification. The AMZO layer improved hole blocking/electron injecting properties of the AZO electrodes. The analysis of the current-voltage characteristics by a differential approach revealed a richer injection and recombination mechanisms in the structures containing the additional AMZO layer. Among those mechanisms, monomolecular, bimolecular and superhigh injection were identified.     

Hierarchical Ni-BDC coated FeOOH nanosheets: A coordination tuning synergistic electrocatalyst with enhanced activity for water oxidation

Hierarchical composites represent a class of efficient electrocatalysts for renewable energy storage and conversion technologies owing to the porous structure and additional exposure of metal sites. Herein, a Ni-based metal organic frameworks (MOFs) (marked as Ni-BDC, BDC stands for 1,4-benzenedicarboxylic acid) nanosheet is successfully fabricated on hydroxyl iron oxide (FeOOH) array with carbon fiber cloth (CFC) as substrate. Benefit from the coordination tuning synergistic effect of the distinct chemical composition and the hierarchical structure for fast mass transportation, the as-obtained FeOOH@Ni-BDC illustrates excellent catalytic ability for electrochemical water oxidation with low overpotential of 270 mV to reach 10 mA/cm² current and good durability in alkaline electrolyte. The novelty of this work lies in the modulation of electronic structure of the FeOOH with Ni-BDC through coordination effect to enhance the activity of the hierarchical composite electrocatalyst. This work is expected to guide the preparation of efficient electrocatalyst for new type alternative energy sources exploitation in near future.     

Enhancement of optical and electrical properties of SILAR deposited ZnO thin films through fluorine doping and vacuum annealing for photovoltaic applications

Undoped and fluorine doped ZnO thin films were deposited onto glass substrates using successive ionic layer adsorption and reaction (SILAR) technique and then annealed at 350 °C in vacuum ambience. The F doping level was varied from 0 to 15 at% in steps of 5 at%. The XRD analysis showed that all the films are polycrystalline with hexagonal wurtzite structure and preferentially oriented along the (002) plane. Crystallite sizes were found to increase when 5 at% of F is doped and then decreased with further doping. It was seen from the SEM images that the doping causes remarkable changes in the surface morphology and the annealing treatment results in well-defined grains with an improvement in the grain size irrespective of doping level. All the films exhibit good transparency (>70%) after vacuum annealing. Electrical resistivity of the film was found to be minimum (1.32×10⁻³ Ω cm) when the fluorine doping level was 5 at%.     

Studies on influence of hydrogen and carbon monoxide concentration on reduction progression behavior of molybdenum oxide catalyst

Temperature programmed reduction (TPR) analysis was applied to investigate the chemical reduction progression behavior of molybdenum oxide (MoO₃) catalyst. The composition and morphology of the reduced phases were characterized by X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FE-SEM). The reduction progression of MoO₃ catalyst was attained with different reductant types and concentration (10% H₂/N₂, 10% and 20% CO/N₂ (%, v/v)). Two different modes of reduction process were applied. The first approach of reduction involved non-isothermal mode reduction up to 700 °C, while the second approach of reduction involved the isothermal mode reduction for 60 min at 700 °C. Hydrogen temperature programmed reduction (H₂-TPR) results showed the reduction progression of three-stage reduction of MoO₃ (Mo⁶⁺ → Mo⁵⁺ → Mo⁴⁺ → Mo⁰) with Mo⁵⁺ and Mo⁴⁺. XRD analysis confirmed the formation of Mo₄O₁₁ phase as an intermediate phase followed by MoO₂ phase. After 60 min of isothermal reduction, peaks of metallic molybdenum (Mo) appeared. Whereas, FESEM analysis showed porous crater-like structure on the surface cracks of MoO₂ layer which led to the growth of Mo phase. Meanwhile, the reduction of MoO₃ catalyst in 10% carbon monoxide (CO) showed the formation of unstable intermediate phase of Mo₉O₂₆ at the early stage of reduction. Furthermore, by increasing 20% CO led to the carburization of MoO₂ phase, resulted in the formation of Mo₂C rather than the formation of metallic Mo, as confirmed by XPS analysis. Therefore, the presented study shows that hydrogen gave better reducibility due to smaller molecular size, which contributed to high diffusion rate and achieved deeper penetration into the MoO₃ catalyst compared to carbon monoxide reductant. Hence, the reduction of MoO₃ in carbon monoxide atmosphere promoted the formation of Mo₂C which was in agreement with the thermodynamic assessment.     

A distributed energy system integrating SOFC-MGT with mid-and-low temperature solar thermochemical hydrogen fuel production

Solar thermochemical hydrogen production with energy level upgraded from solar thermal to chemical energy shows great potential. By integrating mid-and-low temperature solar thermochemistry and solid oxide fuel cells, in this paper, a new distributed energy system combining power, cooling, and heating is proposed and analyzed from thermodynamic, energy and exergy viewpoints. Different from the high temperature solar thermochemistry (above 1073.15 K), the mid-and-low temperature solar thermochemistry utilizes concentrated solar thermal (473.15–573.15 K) to drive methanol decomposition reaction, reducing irreversible heat collection loss. The produced hydrogen-rich fuel is converted into power through solid oxide fuel cells and micro gas turbines successively, realizing the cascaded utilization of fuel and solar energy. Numerical simulation is conducted to investigate the system thermodynamic performances under design and off-design conditions. Promising results reveal that solar-to-hydrogen and net solar-to-electricity efficiencies reach 66.26% and 40.93%, respectively. With the solar thermochemical conversion and hydrogen-rich fuel cascade utilization, the system exergy and overall energy efficiencies reach 59.76% and 80.74%, respectively. This research may provide a pathway for efficient hydrogen-rich fuel production and power generation.     

Transesterification of Palm-based Methyl Palmitate into Esteramine Catalyzed by Calcium Oxide Catalyst

The technology for transesterification reactions between methyl esters and alcohols is well established by using classical homogeneous alkaline catalysts, which provide high conversion of methyl esters to specialty or nonindigenous esters. However, in certain products where the purity of the esters is of concern, the removal of homogeneous catalysts after the completion of the reaction is a challenge in terms of production cost and water footprint. Therefore, a study to investigate the potential of heterogeneous catalysts was conducted on reactions between methyl palmitate and triethanolamine. The degree of basicity and active surface area of calcium oxide (CaO), zinc oxide (ZnO), and magnesium oxide (MgO) were first characterized by using temperature-programmed desorption (TPD-CO₂) and Brunauere–Emmett–Teller (BET), respectively. Among the metal oxides investigated, the CaO catalyst showed the best catalytic activity toward the transesterification process as it gave the highest conversion of methyl palmitate and yielded fatty esteramine compositions similar to the conventional homogeneous catalyst. The optimum transesterification condition by using the CaO catalyst utilized a lower vacuum system of approximately 200 mbar, which could minimize a considerable amount of energy consumption. Furthermore, low CaO dosage of 0.1% was able to give a conversion of 94.5% methyl ester and formed esteramine at 170 °C for 2 h. Therefore, the production of esterquats from esteramine may become more economically feasible through the methyl ester route by using the CaO catalyst, which can be recycled three times.