Search

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 BaGd 0.8 La 0.2 Co 2 O 6-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.

Ruddlesden-Popper oxide La 2 NiO 4+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.

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, PrBa 0.8 Ca 0.2 Co 2 O 5+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.

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 BaCoO 3 -decorated cation-deficient PrBa 0.8 Ca 0.2 Co 2 O 5+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 Co 3 O 4 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.

Enhancing charge-carrier dynamics is imperative to achieve efficient photoelectrodes for practical photoelectrochemical devices. However, a convincing explanation and answer for the important question which has thus far been absent relates to the precise mechanism of charge-carrier generation by solar light in photoelectrodes. Herein, to exclude the interference of complex multi-components and nanostructuring, we fabricate bulky TiO 2 photoanodes through physical vapor deposition. Integrating photoelectrochemical measurements and in situ characterizations, the photoinduced holes and electrons are transiently stored and promptly transported around the oxygen-bridge bonds and 5-coordinated Ti atoms to form polarons on the boundaries of TiO 2 grains, respectively. Most importantly, we also find that compressive stress-induced internal magnetic field can drastically enhance the charge-carrier dynamics for the TiO 2 photoanode, including directional separation and transport of charge carriers and an increase of surface polarons. As a result, bulky TiO 2 photoanode with high compressive stress displays a high charge-separation efficiency and an excellent charge-injection efficiency, leading to 2 orders of magnitude higher photocurrent than that produced by a classic TiO 2 photoanode. This work not only provides a fundamental understanding of the charge-carrier dynamics of the photoelectrodes but also provides a new paradigm for designing efficient photoelectrodes and controlling the dynamics of charge carriers., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The lack of low-cost catalysts with high activity leads to the unsatisfactory electrochemical performance of Li-CO 2 batteries. Single-atom catalysts (SACs) with metal-N x moieties have great potential to improve battery reaction kinetics and cycling ability. However, how to rationally select and develop highly efficient electrocatalysts remains unclear. Herein, we used density functional theory (DFT) calculations to screen SACs on N-doped graphene (SAMe@NG, Me = Cr, Mn, Fe, Co, Ni, Cu) for CO 2 reduction and evolution reaction. Among them, SACr@NG shows the promising potential as an effective electrocatalyst for the reversible Li-CO 2 batteries. To verify the validity of the DFT calculations, a two-step method has been developed to fabricate SAMe@NG on a porous carbon foam (SAMe@NG/PCF) with similar loading of ∼8 wt %. Consistent with the theoretical calculations, batteries with the SACr@NG/PCF cathodes exhibit a superior rate performance and cycling ability, with a long cycle life and a narrow voltage gap of 1.39 V over 350 cycles at a rate of 100 μA cm -2 . This work not only demonstrates a principle for catalysts selection for the reversible Li-CO 2 batteries but also a controllable synthesis method for single atom catalysts.

Lithium-sulfur (Li-S) batteries are promising next-generation energy storage technologies due to their high theoretical energy density, environmental friendliness, and low cost. However, low conductivity of sulfur species, dissolution of polysulfides, poor conversion from sulfur reduction, and lithium sulfide (Li 2 S) oxidation reactions during discharge-charge processes hinder their practical applications. Herein, under the guidance of density functional theory calculations, we have successfully synthesized large-scale single atom vanadium catalysts seeded on graphene to achieve high sulfur content (80 wt % sulfur), fast kinetic (a capacity of 645 mAh g -1 at 3 C rate), and long-life Li-S batteries. Both forward (sulfur reduction) and reverse reactions (Li 2 S oxidation) are significantly improved by the single atom catalysts. This finding is confirmed by experimental results and consistent with theoretical calculations. The ability of single metal atoms to effectively trap the dissolved lithium polysulfides (LiPSs) and catalytically convert the LiPSs/Li 2 S during cycling significantly improved sulfur utilization, rate capability, and cycling life. Our work demonstrates an efficient design pathway for single atom catalysts and provides solutions for the development of high energy/power density Li-S batteries.

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 La 0.6 Sr 0.4 Co 0.2 Fe 0.7 Nb 0.1 O 3-δ (LSCFNb) electrode with 40% Er 0.4 Bi 1.6 O 3 (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 O 2 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 O 2 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.

Carbon nanotubes (CNTs) are excellent supports for electrocatalysts because of their large surface area, excellent electronic conductivity, and high chemical and structural stability. In the present study, the activity of CNTs on direct electron transfer (DET) and on immobilized glucose oxidase (GO X ) is studied as a function of number of walls of CNTs. The results indicate that the GO X immobilized by the CNTs maintains its electrocatalytic activity toward glucose; however, the DET and electrocatalytic activity of GO X depend strongly on the number of inner tubes of CNTs. The GO X immobilized on triple-walled CNTs (TWNTs) has the highest electron-transfer rate constant, 1.22 s -1 , for DET, the highest sensitivity toward glucose detection, 66.11 ± 5.06 μA mM -1 cm -2 , and the lowest apparent Michaelis-Menten constant, 6.53 ± 0.58 mM, as compared to GO X immobilized on single-walled and multiwalled CNTs. The promotion effect of CNTs on the GO X electrocatalytic activity and DET is most likely due to the electron-tunneling effect between the outer wall and inner tubes of TWNTs. The results of this study have general implications for the fundamental understanding of the role of CNT supports in DET processes and can be used for the better design of more effective electrocatalysts for biological processes including biofuel cells and biosensors., Competing Interests: The authors declare no competing financial interest.

As differentiated from conventional synthetic processes, amino-functionalized hollow mesoporous silica (NH 2 -HMS) has been synthesized using a new and facile strategy of ion-exchange-induced selective etching of amino-functionalized mesoporous silica (NH 2 -meso-silica) by an alkaline solution. Nuclear magnetic resonance (NMR) spectroscopy and in situ time-resolved small-angle X-ray scattering (SAXS) reveal that ion-exchange-induced selective etching arises from the gradient distribution of OH - in the NH 2 -meso-silica nanospheres. Moreover, the ion-exchange-induced selective etching mechanism is verified through a successful synthesis of hollow mesoporous silica. After infiltration with phosphotungstic acid (PWA), PWA-NH 2 -HMS nanoparticles are dispersed in the poly(ether sulfone)-polyvinylpyrrolidone (PES-PVP) matrix, forming a hybrid PWA-NH 2 -HMS/PES-PVP nanocomposite membrane. The resultant nanocomposite membrane with an optimum loading of 10 wt % of PWA-NH 2 -HMS showed an enhanced proton conductivity of 0.175 S cm -1 and peak power density of 420 mW cm -2 at 180 °C under anhydrous conditions. Excellent durability of the hybrid composite membrane fuel cell has been demonstrated at 200 °C. The results of this study demonstrated the potential of the facile synthetic strategy in the fabrication of NH 2 -HMS with controlled mesoporous structure for application in nanocomposite membranes as a technology platform for elevated-temperature proton exchange membrane fuel cells.

It is known that hierarchical structure plays a key role in many unique material properties such as self-cleaning effect of lotus leaves and the antifogging property of the compound eyes of mosquitoes. This study reports a series of highly ordered mesoporous Nafion membranes with unique hierarchical structural features at the nanometer scale. Using NMR, we show for the first time that, at low RH conditions, the proton in the ionic domains migrates via a surface diffusion mechanism and exhibits approximately 2 orders of magnitude faster transport than that in the nanopores, whereas the nanopores play a role of reservoir and maintain water and thereby conductivity at higher temperature and lower humidities. Thereby creating hierarchical nanoscale structures is a feasible and promising strategy to develop PEMs that would enable efficient electrochemical performance in devices such as fuel cells, even in the absence of high humidity and at elevated temperatures.

Rechargeable Zn-air battery is limited by the sluggish kinetics and poor durability of the oxygen catalysts. In this Research Article, a new bifunctional oxygen catalyst has been developed through embedding the ultrafine NiFeO nanoparticles (NPs) in a porous amorphous MnO x layer, in which the NiFeO-core contributes to the high activity for the oxygen evolution reaction (OER) and the amorphous MnO x -shell functions as active phase for the oxygen reduction reaction (ORR), promoted by the synergistic effect between the NiFeO core and MnO x shell. The synergistic effect is related to the electron drawing of NiFeO core from MnO x shell, which decreases the affinity and adsorption energy of oxygen on MnO x shell and significantly increases the kinetics of ORR. The electrocatalytic activity and durability of NiFeO@MnO x depends strongly on the NiFeO:MnO x ratio. NiFeO@MnO x with NiFeO:MnO x weight ratio of 1:0.8 shows the best performance for reversible ORR and OER, with a potential gap (ΔE) of 0.792 V to achieve a current density of 3 mA cm -2 for ORR (E ORR=3 ) and 5 mA cm -2 for OER (E OER=5 ) in 0.1 M KOH solution. The high activity of the NiFeO@MnO x (1:0.8) has been demonstrated in a Zn-air battery. Zn-air battery fabricated using the NiFeO@MnO x (1:0.8) oxygen electrode shows similar initial performance with that of Pt-Ir/C oxygen electrode but a much better durability under charge and discharge cycles as the result of the structure confinement effect of amorphous MnO x . The results demonstrate NiFeO@MnO x as an effective bifunctional oxygen catalysts for rechargeable metal-air batteries.

Application of cobaltite-based electrodes such as La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) on Y 2 O 3 -ZrO 2 (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 LaCoO 3-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.

Conventional anode materials for solid oxide fuel cells (SOFCs) are Ni-based cermets, which are highly susceptible to deactivation by contaminants in hydrocarbon fuels. Hydrogen sulfide is one of the commonly existed contaminants in readily available natural gas and gasification product gases of pyrolysis of biomasses. Development of sulfur tolerant anode materials is thus one of the critical challenges for commercial viability and practical application of SOFC technologies. Here we report a viable approach to enhance substantially the sulfur poisoning resistance of a Ni-gadolinia-doped ceria (Ni-GDC) anode through impregnation of proton conducting perovskite BaCe0.9Yb0.1O3-δ (BCYb). The impregnation of BCYb nanoparticles improves the electrochemical performance of the Ni-GDC anode in both H2 and H2S containing fuels. Moreover, more importantly, the enhanced stability is observed in 500 ppm of H2S/H2. The SEM and XPS analysis indicate that the infiltrated BCYb fine particles inhibit the adsorption of sulfur and facilitate sulfur removal from active sites, thus preventing the detrimental interaction between sulfur and Ni-GDC and the formation of cerium sulfide. The preliminary results of the cell with the BCYb+Ni-GDC anode in methane fuel containing 5000 ppm of H2S show the promising potential of the BCYb infiltration approach in the development of highly active and stable Ni-GDC-based anodes fed with hydrocarbon fuels containing a high concentration of sulfur compounds.

Oxygen evaluation reaction (OER) is the most important reaction in hydrogen production from water splitting. Here we developed metal-carbon nanotubes (M-CNTs) hybrids with high metal oxide catalyst loading synthesized by arc-discharge and chemical vapor deposition (CVD) methods as electrocatalysts for OER in alkaline solutions. The M-CNTs hybrids produced by arc-discharge (M-CNTs-Arc) and CVD (M-CNTs-CVD) exhibit a core-shell-like structure, in which metal nanoparticles (NPs) encapsulated by graphite shells are connected by carbon nanotubes (CNTs), forming M-CNTs network hybrids. M-CNTs-Arc has NiCo0.16Fe0.34 metal core and shows very high activity and superior stability for OER, achieving 100 A g(-1) at an overpotential (η) of 0.29 V and 500 A g(-1) at η = 0.37 V in 1 M KOH solution. This is probably the highest activity reported for OER in alkaline solutions. The reaction follows the first-order kinetics with respect to OH(-) concentration and Tafel slope of 34 mV dec(-1). The results demonstrate a highly efficient, scalable, and low-cost one-step synthesis method for developing highly active and stable catalysts for electrochemical water splitting in alkaline solutions.

We have developed for fuel cells a novel proton exchange membrane (PEM) using inorganic phosphotungstic acid (HPW) as proton carrier and mesoporous silica as matrix (HPW-meso-silica) . The proton conductivity measured by electrochemical impedance spectroscopy is 0.11 S cm(-1) at 90 °C and 100% relative humidity (RH) with a low activation energy of ∼14 kJ mol(-1). In order to determine the energetics associated with proton migration within the HPW-meso-silica PEM and to determine the mechanism of proton hopping, we report density functional theory (DFT) calculations using the generalized gradient approximation (GGA). These DFT calculations revealed that the proton transfer process involves both intramolecular and intermolecular proton transfer pathways. When the adjacent HPWs are close (less than 17.0 Å apart), the calculated activation energy for intramolecular proton transfer within a HPW molecule is higher (29.1-18.8 kJ/mol) than the barrier for intermolecular proton transfer along the hydrogen bond. We find that the overall barrier for proton movement within the HPW-meso-silica membranes is determined by the intramolecular proton transfer pathway, which explains why the proton conductivity remains unchanged when the weight percentage of HPW on meso-silica is above 67 wt %. In contrast, the activation energy of proton transfer on a clean SiO2 (111) surface is computed to be as high as ∼40 kJ mol(-1), confirming the very low proton conductivity on clean silica surfaces observed experimentally.

A novel inorganic proton exchange membrane based on phosphoric acid (PA)-functionalized sintered mesoporous silica, PA-meso-silica, has been developed and investigated. After sintering at 650 °C, the meso-silica powder forms a dense membrane with a robust and ordered mesoporous structure, which is critical for retention of PA and water within the porous material. The PA-meso-silica membrane achieved a high proton conductivity of 5 × 10(-3) to 5 × 10(-2) S cm(-1) in a temperature range of 80-220 °C, which is between 1 and 2 orders of magnitudes higher than a typical membrane Nafion 117 or polybenzimidazole (PBI)/PA in the absence of external humidification. Furthermore, the PA-meso-silica membranes exhibited good chemical stability along with high performance at elevated temperatures, producing a peak power density of 632 mW cm(-2) using a H2 fuel at 190 °C in the absence of external humidification. The high membrane proton conductivity and excellent fuel cell performance demonstrate the utility of PA-meso-silica as a new class of inorganic proton exchange membranes for use in the high-temperature proton exchange membrane fuel cells (PEMFCs).

The effect of an amorphous TiO(x) interlayer on layered graphene/quantum dots photochemical cells has been investigated. The addition of the TiO(x) interlayer eliminates the decay of photocurrent in the initial seconds after light illumination and significantly increases the slope of the steady-state photocurrent versus the light intensity. The open-circuit voltage decay measurements further illustrate a longer electron lifetime when an amorphous TiO(x) interlayer is applied. Consequently, the photocurrent and photovoltage of the photovoltaic cell with a TiO(x) interlayer are greatly increased. This work demonstrates that the graphene/amorphous TiO(x) composite structure effectively inhibits charge recombination while enhancing charge transfer, providing a promising scaffold for quantum dots and dye-sensitized photovoltaic cells., (© 2011 American Chemical Society)

A new synthesis method for the preparation of high-performance PtRu electrocatalysts on multiwalled carbon nanotubes (MWCNTs) is reported. In this method, bimetallic PtRu electrocatalysts are deposited onto 1-aminopyrene (1-AP)-functionalized MWCNTs by a microwave-assisted polyol process. The noncovalent functionalization of MWCNTs by 1-AP is simple and can be carried out at room temperature without the use of expensive chemicals or corrosive acids, thus preserving the integrity and the electronic structure of MWCNTs. PtRu electrocatalysts on 1-AP-functionalized MWCNTs show much better distribution with no formation of aggregates, higher electrochemically active surface area, and higher electrocatalytic activity for the electrooxidation of methanol in direct methanol fuel cells as compared to that on conventional acid-treated MWCNTs and carbon black supported PtRu electrocatalysts. PtRu electrocatalysts on 1-AP-functionalized MWCNTs also show significantly enhanced stability.