Surface Chemistry Modulation of BaGd0.8La0.2Co2O6-δ As Active Air Electrode for Solid Oxide Cells.

Modulation of the surface chemistry of air electrodes makes it possible to significantly improve the electrocatalytic performance of solid oxide cells (SOCs). Here, the surface chemistry of BaGd0.8La0.2Co2O6-δ (BGLC) double perovskite is modulated by treatment in an acidic citric acid solution. The treatment leads to corrosion on the surface of BGLC particles, and the effect is dependent on the acidity of the solution. As the acidity of solution is low, Ba cations are selectively dissolved out of the BGLC surface, while as the acidity increases, the corrosion becomes more homogeneous. The Ba surface deficiency remarkably increases the concentration of surface oxygen vacancies and electrocatalytic activity of BGLC. To avoid the loss of Ba-deficient surface during the conventional high temperature sintering process, a sintering-free fabrication route is utilized to directly assemble the Ba-deficient BGLC powder into an air electrode. A single cell with the surface Ba-deficient BGLC electrode shows a peak power density of 1.04 W cm-2 at 750 °C and an electrolysis current density of 1.48 A cm-2 at 1.3 V, much greater than 0.64 W cm-2 and 1.02 A cm-2 of the cell with the pristine BGLC, respectively. This work provides a simple and effective surface chemistry modulation strategy for the development of an efficient air electrode for SOCs.

Development of Nanostructured Lanthanum Strontium Cobalt Ferrite/Gadolinian-Doped Ceria Composite Electrodes of Solid Oxide Cells Formed by In Situ Polarization.

In the development of nanoscale oxygen electrodes of high-temperature solid oxide cells (SOCs), the interface formed between the nanoelectrode particles and the electrolyte or electrolyte scaffolds is the most critical. In this work, a new synthesis technique for the fabrication of nanostructured electrodes via in situ electrochemical polarization treatment is reported. The lanthanum strontium cobalt ferrite (LSCF) precursor solution is infiltrated into a gadolinia-doped ceria (GDC) scaffold presintered on a yttria-stabilized zirconia (YSZ) electrolyte, followed by in situ polarization current treatment at SOC operation temperatures. Electrode ohmic and polarization resistances decrease with an increase in the polarization current treatment. Detailed microstructure analysis indicates the formation of a convex-shaped interface between the LSCF nanoparticles (NPs) and the GDC scaffold, very different from the flat contact between LSCF and GDC observed after heating at 800 °C with no polarization current treatment. The embedded LSCF NPs on the GDC scaffold contribute to the superior stability under both fuel cell and electrolysis operation conditions at 750 °C and a high peak power density of 1.58 W cm-2 at 750 °C. This work highlights a novel and facile route to in situ construct a stable and high-performing nanostructured electrode for SOCs.

Smart Dual-Exsolved Self-Assembled Anode Enables Efficient and Robust Methane-Fueled Solid Oxide Fuel Cells.

Perovskite oxides have emerged as alternative anode materials for hydrocarbon-fueled solid oxide fuel cells (SOFCs). Nevertheless, the sluggish kinetics for hydrocarbon conversion hinder their commercial applications. Herein, a novel dual-exsolved self-assembled anode for CH4 -fueled SOFCs is developed. The designed Ru@Ru-Sr2 Fe1.5 Mo0.5 O6-δ (SFM)/Ru-Gd0.1 Ce0.9 O2-δ (GDC) anode exhibits a unique hierarchical structure of nano-heterointerfaces exsolved on submicron skeletons. As a result, the Ru@Ru-SFM/Ru-GDC anode-based single cell achieves high peak power densities of 1.03 and 0.63 W cm-2 at 800 °C under humidified H2 and CH4 , surpassing most reported perovskite-based anodes. Moreover, this anode demonstrates negligible degradation over 200 h in humidified CH4 , indicating high resistance to carbon deposition. Density functional theory calculations reveal that the created metal-oxide heterointerfaces of Ru@Ru-SFM and Ru@Ru-GDC have higher intrinsic activities for CH4 conversion compared to pristine SFM. These findings highlight a viable design of the dual-exsolved self-assembled anode for efficient and robust hydrocarbon-fueled SOFCs.

Electrochemically Assisted Construction of a La2NiO4+δ@Pt Core-Shell Structure for Enhancing the Performance and Durability of La2NiO4+δ Cathodes.

Ruddlesden-Popper oxide La2NiO4+δ (LNO) has a high ionic conductivity and good thermal match with the electrolyte of solid oxide fuel cells (SOFCs); however, LNO suffers from performance decay owing to the La surface segregation under the operation conditions of SOFCs. Herein, we report an in situ electrochemical decoration strategy to improve the electrocatalytic activity and durability of LNO cathodes. We show that the electrochemical polarization leads to in situ construction of the LNO@Pt core-shell structure, significantly suppressing the detrimental effect of La surface segregation on the LNO cathode. The initial peak power density of a single cell with the LNO cathode is 0.71 W cm-2 at 750 °C, increasing to 1.39 W cm-2 by the in situ construction of the LNO@Pt core-shell structure after polarization at 0.5 A cm-2 for 20 h. The LNO@Pt core-shell structure is also highly durable without noticeable performance degradation over the duration of the test for 180 h. The findings shed light on the design and fabrication of highly active and durable LNO-based cathodes for SOFCs.

Facile Construction of Nanostructured Cermet Anodes with Strong Metal-Oxide Interaction for Efficient and Durable Solid Oxide Fuel Cells.

Nanostructured anodes generate massive reaction sites to oxidize fuels in solid oxide fuel cells (SOFCs); however, the nonexistence of a practically viable approach for the construction of nanostructures and the retention of these nanostructures under the harsh operating conditions of SOFCs poses a significant challenge. Herein, a simple procedure is reported for the construction of a nanostructured Ni-Gd-doped CeO2 anode based on the direct assembly of pre-formed nanocomposite powder with strong metal-oxide interaction. The directly assembled anode forms heterointerfaces with the electrolyte owing to the electrochemical polarization current and exhibits excellent structural robustness against thermal ripening. An electrolyte-supported cell with the directly assembled anode produces a peak power density of 0.73 W cm-2 at 800 °C, while maintaining stability for 100 h, which is in contrast to the drastic degradation of the cermet anode prepared using the conventional method. These findings provide clarity on the design and construction of durable nanostructured anodes and other electrodes for SOFCs.

Facile Approach for Improving the Interfacial Adhesion of Nanofiber Air Electrodes of Reversible Solid Oxide Cells.

Nanofibers have great promise as a highly active air electrode for reversible solid oxide cells (ReSOCs); however, one thorny issue is how to adhesively stick nanofibers to electrolyte with no damage to the original morphology. Herein, PrBa0.8Ca0.2Co2O5+δ (PBCC) nanofibers are applied as an air electrode by a facile direct assembly approach that leads to the retention of most of the unique microstructure of nanofibers, and firm adhesion of the nanofiber electrode onto the electrolyte is achieved by applying electrochemical polarization. A single cell with the PBCC nanofiber air electrode exhibits excellent maximum power density (1.97 W cm-2), electrolysis performance (1.3 A cm-2 at 1.3 V), and operating stability at 750 °C for 200 h. These findings provide a facile means for the utilization of nanofiber electrodes for high-performance and durable ReSOCs.

Ultrafine, Dual-Phase, Cation-Deficient PrBa0.8Ca0.2Co2O5+δ Air Electrode for Efficient Solid Oxide Cells.

Nanostructured air electrodes play a crucial role in improving the electrocatalytic activity of oxygen reduction and evolution reactions in solid oxide cells (SOCs). Herein, we report the fabrication of a nanostructured BaCoO3-decorated cation-deficient PrBa0.8Ca0.2Co2O5+δ (PBCC) air electrode via a combined modification and direct assembly approach. The modification approach endows the dual-phase air electrode with a large surface area and abundant oxygen vacancies. An intimate air electrode-electrolyte interface is in situ constructed with the formation of a catalytically active Co3O4 bridging layer via electrochemical polarization. The corresponding single cell exhibits a peak power density of 2.08 W cm-2, an electrolysis current density of 1.36 A cm-2 at 1.3 V, and a good operating stability at 750 °C for 100 h. This study provides insights into the rational design and facile utilization of an active and stable nanostructured air electrode of SOCs.

A critical review of the nano-structured electrodes of solid oxide cells.

Renewable energies from solar and wind power are playing an ever increasing role in meeting the tremendous global energy demand with substantially reduced carbon emissions; however, their intermittent nature poses a critical challenge for sustainability and practical applications. The capability of solid oxide cells (SOCs) to operate in both fuel cell and electrolysis modes makes them one of the most important candidates for efficient storage and regeneration of renewable energies. Here we present a critical review and prospects on the development of key fabrication techniques, e.g. wet infiltration, exsolution and direct assembly, for nanostructured electrodes, one of the most critical issues affecting the performance and stability of SOC technologies. The traits and challenges of these techniques are thoroughly discussed, with an aim to provide a critical guide for future design and development of more refined, high-performing nanostructured electrodes for SOCs.

Recent Progress in Pd-Based Nanocatalysts for Selective Hydrogenation.

Selective hydrogenation plays an important role in the chemical industry and has a wide range of applications, including the production of fine chemicals and petrochemicals, pharmaceutical synthesis, healthcare product development, and the synthesis of agrochemicals. Pd-based catalysts have been widely applied for selective hydrogenation due to their unique electronic structure and ability to adsorb and activate hydrogen and unsaturated substrates. However, the exclusive and comprehensive summarization of the size, composition, and surface and interface effect of metal Pd on the performance for selective hydrogenation is still lacking. In this perspective, the research progress on selective hydrogenation using Pd-based catalysts is summarized. The strategies for improving the catalytic hydrogenation performance over Pd-based catalysts are investigated. Specifically, the effects of the size, composition, and surface and interfacial structure of Pd-based catalysts, which could influence the dissociation mode of hydrogen, the adsorption, and the reaction mode of the catalytic substrate, on the performance have been systemically reviewed. Then, the progress on Pd-based catalysts for selective hydrogenation of unsaturated alkynes, aldehydes, ketones, and nitroaromatic hydrocarbons is revealed based on the fundamental principles of selective hydrogenation. Finally, perspectives on the further development of strategies for chemical selective hydrogenation are provided. It is hoped that this perspective would provide an instructive guideline for constructing efficient heterogeneous Pd-based catalysts for various selective hydrogenation reactions.

Analysis of a multiple-quantum-dots embedded ring structure for potential optically-controlled quantum switch or spin filter.

We theoretically study the average current through a ring embedded with multiple quantum dots in each arm subjected to a time-dependent external field. A current resonance band can be observed in a six-quantum-dot system. In the presence of a time-dependent external field, mutual transformation occurs between the resonance band and antiresonance band, indicating an effective optically-controlled quantum switch can be realized in a wider quantum dot's energy regime. As the Zeeman effect is introduced, the conversion between 100 and - 100% for spin polarization [Formula: see text] can be realized by adjusting the frequency of time-dependent external field, suggesting a physical scheme of an optically-controlled spin filter. The present work sheds lights onto the design and quantum computation of future nano-devices.

Molten Salt Synthesis of High-Performance, Nanostructured La0.6Sr0.4FeO3-δ Oxygen Electrode of a Reversible Solid Oxide Cell.

Nanoscale perovskite oxides with enhanced electrocatalytic activities have been widely used as oxygen electrodes of reversible solid oxide cells (RSOC). Here, La0.6Sr0.4FeO3-δ (LSF) nanoscale powder is synthesized via a novel molten salt method using chlorides as the reaction medium and fired at 850 °C for 5 h after removing the additives. A direct assembly method is employed to fabricate the LSF electrode without a pre-sintering process at high temperature. The microstructure characterization ensures that the direct assembly process will not damage the porosity of LSF. When operating as a solid oxide fuel cell (SOFC), the LSF cell exhibits a peak power density of 1.36, 1.07 and 0.7 W/cm2 at 800, 750 and 700 °C, respectively, while in solid oxide electrolysis cell (SOEC) mode, the electrolysis current density reaches 1.52, 0.98 and 0.53 A/cm2 under an electrolysis voltage of 1.3 V, respectively. Thus, it indicates that the molten salt routine is a promising method for the synthesis of highly active perovskite LSF powders for directly assembled oxygen electrodes of RSOC.

Study on the enhanced electron-hole separation capability of IrxZn1-xO/Ti electrodes with high photoelectrocatalysis efficiency.

Making full use of low-energy photons and reducing photogenerated carriers' recombination rate have been considered important ways to raise photoelectrocatalysis (PEC) efficiency. In this study, Ir-doped ZnO PEC electrodes were prepared by thermal decomposition method, first principles calculations were used to study the effects of Ir content on the electronic structure and optical properties of IrxZn1-xO coatings, the PEC degradation mechanism of the IrxZn1-xO/Ti electrodes was also tentatively presented. The results indicated that with numbers of Zn atoms replaced by Ir atoms, impurity energy level appeared in ZnO band gap, which reduced the electron transition barriers and increased the number of photogenerated carriers. Besides, IrO2 nanoparticles covered on ZnO nanorods surface, acting as highly efficient electron transfer channels and electrocatalytic active sites, could separate photogenerated electron-hole pairs and enhance PEC performance effectively. PEC performance of IrxZn1-xO/Ti electrodes with different Ir contents under UV irradiation was evaluated by rhodamine B (RhB) removal rate. Compared with pure ZnO electrodes, IrxZn1-xO/Ti ones exhibited much stronger degradation capacity. Specifically, Ir0.09375Zn0.90625O/Ti electrodes showed the highest degradation rate of 99.4 %, and a relatively high rate of 95.2 % after working 100 h continuously, indicating its excellent long-term stability.

Remarkable adsorption performance of MOF-199 derived porous carbons for benzene vapor.

Volatile organic compounds (VOCs) are perceived as serious pollutants due to their great threat to both environment and human health. Recovery and removal of VOCs is of great significance. Herein, novel MOF-199 derived porous carbon materials (MC-T-n) were prepared by using MOF-199 as precursor, glucose as additional carbon source and KOH as activator, and then characterized. Adsorption performance of MC-T-n materials for benzene vapor was investigated. Isotherms of MC-T-n samples towards benzene and water vapor were measured. The adsorption selectivities of benzene/water were estimated by DIH (difference of the isosteric heats) equation. Results indicated that BET surface area and pore volume of MC-T-n materials reached separately 2320 m2/g and 1.05 m3/g. Benzene adsorption capacity of MC-T-n materials reached as high as 12.8 mmol/g at 25 °C, outperforming MOF-199 and some conventional adsorbents. Moreover, MC-T-n materials presented type-V isotherms of water vapor, suggesting their excellent water resistance. The isosteric heats of benzene adsorption on MC-500-6 were much greater than that of water adsorption, leading to a preferential adsorption for C6H6 over H2O. The adsorption selectivity of C6H6/H2O on MC-500-6 reached up to 16.3 superior to some previously reported MOFs. Therefore, MC-500-6 was a promising candidate for VOC adsorption and seperation. This study provides a strong foundation for MOF derived porous carbons as adsorbents for VOC removal.

In Situ Formation of Er0.4Bi1.6O3 Protective Layer at Cobaltite Cathode/Y2O3-ZrO2 Electrolyte Interface under Solid Oxide Fuel Cell Operation Conditions.

Bismuth-based oxides exhibit outstanding oxygen ionic conductivity and fast oxygen surface kinetics and have shown great potential as a highly active component for electrode materials in solid oxide fuel cells (SOFCs). Herein, a Nb-doped La0.6Sr0.4Co0.2Fe0.7Nb0.1O3-δ (LSCFNb) electrode with 40% Er0.4Bi1.6O3 (ESB) composite electrode was successfully fabricated by decoration method and directly assembled on barrier-layer-free yttrium-stabilized zirconia (YSZ) electrolyte cells, achieving a peak power density of 1.32 W cm-2 and excellent stability at 750 °C and 250 mA cm-2 for 100 h. ESB decoration also significantly reduces the activation energy from 214 kJ mol-1 for the O2 reduction on pristine LSCFNb electrode to 98 kJ mol-1. Further microstructural analysis reveals that there is a redistribution and migration of the ESB phase in the ESB-LSCFNb composite toward the YSZ electrolyte under the influence of cathodic polarization, forming a thin ESB layer at the cathode/YSZ electrolyte interface. The in situ formed ESB layer not only prevents the direct contact and subsequent reaction between segregated SrO and YSZ electrolytes, but also remarkably promotes the oxygen migration/diffusion at the interface for O2 reduction reaction, resulting in a remarkable increase in power output and a decrease in activation energy. The present study clearly demonstrated the in situ formation of a highly functional and active ESB protective layer at LSCFNb cobaltite cathode and YSZ electrolyte interface via ESB-decorated LSCFNb composite cathode under SOFC operation conditions.

Cellular Structure Fabricated on Ni Wire by a Simple and Cost-Effective Direct-Flame Approach and Its Application in Fiber-Shaped Supercapacitors.

Cellular metals with the large surface/volume ratios and excellent electrical conductivity are widely applicable and have thus been studied extensively. It is highly desirable to develop a facile and cost-effective process for fabrication of porous metallic structures, and yet more so for micro/nanoporous structures. A direct-flame strategy is developed for in situ fabrication of micron-scale cellular architecture on a Ni metal precursor. The flame provides the required heat and also serves as a fuel reformer, which provides a gas mixture of H2 , CO, and O2 for redox treatment of metallic Ni. The redox processes at elevated temperatures allow fast reconstruction of the metal, leading to a cellular structure on Ni wire. This process is simple and clean and avoids the use of sacrificial materials or templates. Furthermore, nanocrystalline MnO2 is coated on the microporous Ni wire (MPNW) to form a supercapacitor electrode. The MnO2 /MPNW electrode and the corresponding fiber-shaped supercapacitor exhibit high specific capacitance and excellent cycling stability. Moreover, this work provides a novel strategy for the fabrication of cellular metals and alloys for a variety of applications, including catalysis, energy storage and conversion, and chemical sensing.

Effect of Nb2O5 doping on improving the thermo-mechanical stability of sealing interfaces for solid oxide fuel cells.

Nb2O5 is added to a borosilicate sealing system to improve the thermo-mechanical stability of the sealing interface between the glass and Fe-Cr metallic interconnect (Crofer 22APU) in solid oxide fuel cells (SOFCs). The thermo-mechanical stability of the glass/metal interface is evaluated experimentally as well as by using a finite element analysis (FEA) method. The sealing glass doped with 4 mol.% Nb2O5 shows the best thermo-mechanical stability, and the sealing couple of Crofer 22APU/glass/GDC (Gd0.2Ce0.8O1.9) remains intact after 50 thermal cycles. In addition, all sealing couples show good joining after being held at 750 °C for 1000 h. Moreover, the possible mechanism on the thermo-mechanical stability of sealing interface is investigated in terms of stress-based and energy-based perspectives.

Highly Stable Sr-Free Cobaltite-Based Perovskite Cathodes Directly Assembled on a Barrier-Layer-Free Y2 O3 -ZrO2 Electrolyte of Solid Oxide Fuel Cells.

Direct assembly is a newly developed technique in which a cobaltite-based perovskite (CBP) cathode can be directly applied to a barrier-layer-free Y2 O3 -ZrO2 (YSZ) electrolyte with no high-temperature pre-sintering steps. Solid oxide fuel cells (SOFCs) based on directly assembled CBPs such as La0.6 Sr0.4 Co0.2 Fe0.8 O3-δ show high performance initially but degrade rapidly under SOFC operation conditions at 750 °C owing to Sr segregation and accumulation at the electrode/electrolyte interface. Herein, the performance and interface of Sr-free CBPs such as LaCoO3-δ (LC) and Sm0.95 CoO3-δ (SmC) and their composite cathodes directly assembled on YSZ electrolyte was studied systematically. The LC electrode underwent performance degradation, most likely owing to cation demixing and accumulation of La on the YSZ electrolyte under polarization at 500 mA cm-2 and 750 °C. However, the performance and stability of LC electrodes could be substantially enhanced by the formation of LC-gadolinium-doped ceria (GDC) composite cathodes. Replacement of La by Sm increased the cell stability, and doping of 5 % Pd to form Sm0.95 Co0.95 Pd0.05 O3-δ (SmCPd) significantly improved the electrode activity. An anode-supported YSZ-electrolyte cell with a directly assembled SmCPd-GDC composite electrode exhibited a peak power density of 1.4 W cm-2 at 750 °C, and an excellent stability at 750 °C for over 240 h. The higher stability of SmC as compared to that of LC is most likely a result of the lower reactivity of SmC with YSZ. This study demonstrates the new opportunities in the design and development of intermediate-temperature SOFCs based on the directly assembled high-performance and durable Sr-free CBP cathodes.

Polarization-Induced Interface and Sr Segregation of in Situ Assembled La0.6Sr0.4Co0.2Fe0.8O3-δ Electrodes on Y2O3-ZrO2 Electrolyte of Solid Oxide Fuel Cells.

Application of cobaltite-based electrodes such as La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) on Y2O3-ZrO2 (YSZ) electrolyte in solid oxide fuel cells (SOFCs) generally requires the use of a doped ceria barrier layer to prevent the interaction between LSCF and YSZ during sintering at high temperatures. In this paper, we report for the first time an in situ assembly approach to directly incorporate LSCF cathode to YSZ electrolyte without the use of a doped ceria barrier layer and without presintering at high temperatures. A Ni-YSZ anode-supported YSZ electrolyte cell with an in situ assembled LSCF electrode exhibits a peak power density of 1.72 W cm-2 at 750 °C. However, the cell performance degrades significantly at 500 mAcm-2 and 750 °C. The results indicate that cathodic polarization not only induces the formation of the interface but also accelerates the Sr segregation. The segregated Sr migrates to the LSCF electrode/YSZ electrolyte surface and forms an SrO layer. Using a Sr-free LaCoO3-δ composite cathode overcomes the Sr segregation problem, showing an excellent peak power density of 1.2 Wcm-2 and good stability at 750 °C for over 100 h. The present study shows that cobaltite-based perovskites can be directly used on YSZ-based electrolyte via the in situ assembly providing an effective means to advance the application of highly active mixed ionic/electronic conducting cathodes to YSZ electrolyte-based SOFCs.

Electrochemically Driven Deactivation and Recovery in PrBaCo2 O5+δ Oxygen Electrodes for Reversible Solid Oxide Fuel Cells.

The understanding of surface chemistry changes on oxygen electrodes is critical for the development of reversible solid oxide fuel cell (RSOFC). Here, we report for the first time that the electrochemical potentials can drastically affect the surface composition and hence the electrochemical activity and stability of PrBaCo2 O5+δ (PBCO) electrodes. Anodic polarization degrades the activity of the PBCO electrode, whereas the cathodic bias could recover its performance. Alternating anodic/cathodic polarization for 180 h confirms this behavior. Microstructure and chemical analysis clearly show that anodic bias leads to the accumulation and segregation of insulating nanosized BaO on the electrode surface, whereas cathodic polarization depletes the surface species. Therefore, a mechanism based on the segregation and incorporation of BaO species under electrochemical potentials is considered to be responsible for the observed deactivation and recovery process, respectively.

Why solid oxide cells can be reversibly operated in solid oxide electrolysis cell and fuel cell modes?

High temperature solid oxide cells (SOCs) are attractive for storage and regeneration of renewable energy by operating reversibly in solid oxide electrolysis cell (SOEC) and solid oxide fuel cell (SOFC) modes. However, the stability of SOCs, particularly the deterioration of the performance of oxygen electrodes in the SOEC operation mode, is the most critical issue in the development of high performance and durable SOCs. In this study, we investigate in detail the electrochemical activity and stability of La0.8Sr0.2MnO3 (LSM) oxygen electrodes in cyclic SOEC and SOFC modes. The results show that the deterioration of LSM oxygen electrodes caused by anodic polarization can be partially or completely recovered by subsequent cathodic polarization. Using in situ assembled LSM electrodes without pre-sintering, we demonstrate that the deteriorated LSM/YSZ interface can be repaired and regenerated by operating the cells under cathodic polarization conditions. This study for the first time establishes the foundation for the development of truly reversible and stable SOCs for hydrogen fuel production and electricity generation in cyclic SOEC and SOFC operation modes.