Metal exsolution from perovskite-based anodes in solid oxide fuel cells.

Solid oxide fuel cells (SOFCs) are highly efficient and environmentally friendly devices for converting fuel into electrical energy. In this regard, metal nanoparticles (NPs) loaded onto the anode oxide play a crucial role due to their exceptional catalytic activity. NPs synthesized through exsolution exhibit excellent dispersion and stability, garnering significant attention for comprehending the exsolution process mechanism and consequently improving synthesis effectiveness. This review presents recent advancements in the exsolution process, focusing on the influence of oxygen vacancies, A-site defects, lattice strain, and phase transformation on the variation of the octahedral crystal field in perovskites. Moreover, we offer insights into future research directions to further enhance our understanding of the mechanism and achieve significant exsolution of NPs on perovskites.

Enhanced Oxygen Evolution Rate and Anti-interfacial Delamination Property of the SrCo0.9Ta0.1O3-δ@La0.6Sr0.4Co0.2Fe0.8O3-δ Oxygen-Electrode for Solid Oxide Electrolysis Cells.

Interfacial delamination between the oxygen-electrode and electrolyte is a significant factor impacting the reliability of solid oxide electrolysis cells (SOECs) when operating at high voltages. The most effective method to mitigate this delamination is to decrease the interfacial oxygen partial pressure, which can be accomplished by amplifying the oxygen exsolution rate and the O2- transport rate of the oxygen-electrode. In this study, a SrCo0.9Ta0.1O3-δ (SCT) film with an outstanding oxygen surface exchange coefficient and an outstanding O2- conductivity was introduced onto the La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) surface by infiltration. This composite oxygen-electrode exhibited a notably high electrochemical catalytic activity primarily due to the significantly improved O2- transport and oxygen surface exchange rate. Single cells with a 15-LSCF oxygen-electrode achieved a peak power density of 1.33 W cm-2 at 700 °C and a current density of 1.25 A cm-2 at 1.3 V (60% H2O-H2) at 750 °C. Additionally, an electrolysis cell with a 15 wt % SCT-infiltrated LSCF oxygen-electrode demonstrated stable operation even at high current densities for over 330 h with no noticeable delamination. The remarkable durability of the 15-LSCF oxygen-electrode can be attributed to the boosted oxygen exsolution reaction (OER) activity and the suppression of Sr segregation due to SCT infiltration. The impressive OER activity and resistance to interfacial delamination make the 15-LSCF a promising candidate for a composite oxygen-electrode in SOECs.

Failure Mechanism and Optimization of Metal-Supported Solid Oxide Fuel Cells.

A solid oxide fuel cell (SOFC) is a clean, efficient energy conversion device with wide fuel applicability. Metal-supported solid oxide fuel cells (MS-SOFCs) exhibit better thermal shock resistance, better machinability, and faster startup than traditional SOFCs, making them more suitable for commercial applications, especially in mobile transportation. However, many challenges remain that hinder the development and application of MS-SOFCs. High temperature may accelerate these challenges. In this paper, the existing problems in MS-SOFCs, including high-temperature oxidation, cationic interdiffusion, thermal matching, and electrolyte defects, as well as lower temperature preparation technologies, including the infiltration method, spraying method, and sintering aids method, are summarized from different perspectives, and the improvement strategy of existing material structure optimization and technology integration is put forward.

Coupling MnS and CoS Nanocrystals on Self-Supported Porous N-doped Carbon Nanofibers to Enhance Oxygen Electrocatalytic Performance for Flexible Zn-Air Batteries.

Seeking highly efficient, stable, and cost-effective bifunctional electrocatalysts of rechargeable Zn-air batteries (ZABs) is the top-priority for developing new generation portable electronic devices. For this, the rational and effective structural design, interface engineering, and electron recombination on electrocatalysts should be taken into account to reduce the reaction overpotential and expedite the kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Herein, we construct a MnCo-based metal organic framework-derived heterogeneous MnS-CoS nanocrystals, which are anchored on free-standing porous N-doped carbon fibers (PNCFs) by the in situ growth method and vulcanization process. Benefiting from the abundant vacancies and active sites, strong interfacial coupling as well as favorable conductivity, the MnS-CoS/PNCFs composite electrode delivers a mentionable oxygen electrocatalytic activity and stability with a half-wave potential of 0.81 V for ORR and an overpotential of 350 mV for OER in the alkaline medium. Of note, the flexible rechargeable ZAB using MnS-CoS/PNCFs as binder-free air cathode offers high power density of 86.7 mW cm-2, large specific capacity of 563 mA h g-1, and adapts to different bending degree of operation. In addition, the density functional theory calculation clarifies that the heterogeneous MnS-CoS nanocrystals reduces the reaction barrier and enhances the conductivity of the catalyst and the adsorption capacity of the intermediates during the ORR and OER process. This study opens up a new insight to the design of the self-supported air cathode for flexible electronic devices.

Construction of ZnIn2 S4 /CdS/PdS S-Scheme Heterostructure for Efficient Photocatalytic H2 Production.

It is facing a tremendous challenge to develop the desirable hybrids for photocatalytic H2 generation by integrating the advantages of a single semiconductor. Herein, an all-sulfide ZnIn2 S4 /CdS/PdS heterojunction is constructed for the first time, where CdS and PdS nanoparticles anchor in the spaces of ZnIn2 S4 micro-flowers due to the confinement effects. The morphology engineering can guarantee rapid charge transfer owing to the short carrier migration distances and the luxuriant reactive sites provided by ZnIn2 S4 . The S-scheme mechanism between ZnIn2 S4 and CdS assisted by PdS cocatalyst is testified by in situ irradiated X-ray photoelectron spectroscopy and electron paramagnetic resonance (EPR), where the electrons and holes move in reverse driven by work function difference and built-in electric field at the interfaces. The optimal ZnIn2 S4 /CdS/PdS performs a glaring photocatalytic activity of 191.9 µmol h-1 (10 mg of catalyst), and the largest AQE (apparent quantum efficiency) can reach a high value of 26.26%. This work may afford progressive tactics to design multifunctional photocatalysts.

Ni-Doped BiVO4 photoanode for efficient photoelectrochemical water splitting.

BiVO4 (BVO) based photoanode is one of the most mega-potential materials for solar water splitting while suffers from poor charge transfer and separation efficiency limit its practical application. Herein, FeOOH/Ni-BiVO4 photoanode synthesized by the facile wet chemical method were investigated for improved charge transport and separation efficiency. The photoelectrochemical (PEC) measurements demonstrate that the water oxidation photocurrent density can reach as high as 3.02 mA cm-2 at 1.23 V vs RHE, and the surface separation efficiency can be boosted to 73.3 %, which increases around 4 times comparing with that of pure sample. Further depth studies showed that the Ni doping can effectively promote hole transport/trapping and introduce more active sites for the oxidation of water, while FeOOH co-catalyst could passivate the Ni-BiVO4 photoanode surface. This work provides a model for the design of BiVO4-based photoanodes with combined thermodynamic and kinetic advantages.

Boosting photoelectrochemical water splitting of bismuth vanadate photoanode via novel co-catalysts of amorphous manganese oxide with variable valence states.

Bismuth vanadate (BVO) is a promising photoanode while suffers from sluggish oxygen evolution kinetics. Herein, an ultra-thin manganese oxide (MnOx) is selected as co-catalyst to modify the surface of BVO photoanode by a facile spray pyrolysis method. The photoelectrochemical measurements demonstrate that surface charge transport efficiency (ηsurface) of MnOx modified BVO photoanode (BVO/MnOx) is strikingly increased from 6.7 % to 22.3 % at 1.23 VRHE (reversible hydrogen electrode (VRHE)). Moreover, the ηsurface can be further boosted to 51.3 % at 1.23 VRHE after applying Ar plasma on the BVO/MnOx sample, which is around 7 times higher comparing with that of pristine BVO samples. Additional characterizations reveal that the remarkable PEC performance of the Ar-plasma treated BVO/MnOx photoanode (BVO/MnOx/Ar plasma) could be attributed to the increased charge carrier density, extended carrier lifetime and additional exposed Mn3+ active sites on the BVO surface. This investigation could provide a new understanding for the design of BVO photoanode with superior PEC performance based on the modification of MnOx and plasma surface treatment.

Defected tungsten disulfide decorated CdS nanorods with covalent heterointerfaces for boosted photocatalytic H2 generation.

Owing to their intrinsic and pronounced charge carrier transport when facing the formidable challenge of inhibiting severe surface charge recombination, one-dimensional (1D) CdS nanostructures are promising for advancing high-yield hydrogen production. We herein demonstrate an efficient strategy of boosting interfacial carrier separation by heterostructuring 1D CdS with defective WS2. This process yields solid covalent interfaces for high flux carrier transfer that differ distinctively from those reported structures with physical contacts. As a nonnoble cocatalyst, WS2 can accept photogenerated electrons from CdS, and the sulfur vacancies existing at its edges can effectively trap electrons as active sites for H2 evolution. Moreover, due to its strong negative property, the H+ from the aqueous solution can gather around WS2. WS2 possesses a lower reaction barrier than CdS, which expedites the kinetic process for the reaction. The optimized sample exhibits a high photocatalytic H2 evolution rate of 183.4 µmol/h (10 mg photocatalyst), which is as far as we know among the top in the records for CdS-based photocatalysts. We believe this present work will be inspiring in addressing the interfacial charge carrier transfer by constructing covalent heterointerfaces.

Activating a Semiconductor-Liquid Junction via Laser-Derived Dual Interfacial Layers for Boosted Photoelectrochemical Water Splitting.

The semiconductor-liquid junction (SCLJ), the dominant place in photoelectrochemical (PEC) catalysis, determines the interfacial activity and stability of photoelectrodes, whcih directly affects the viability of PEC hydrogen generation. Though efforts dedicated in past decades, a challenge remains regarding creating a synchronously active and stable SCLJ, owing to the technical hurdles of simultaneously overlaying the two advantages. The present work demonstrates that creating an SCLJ with a unique configuration of the dual interfacial layers can yield BiVO4 photoanodes with synchronously boosted photoelectrochemical activity and operational stability, with values located at the top in the records of such photoelectrodes. The bespoke dual interfacial layers, accessed via grafting laser-generated carbon dots with phenolic hydroxyl groups (LGCDs-PHGs), are experimentally verified effective, not only in generating the uniform layer of LGCDs with covalent anchoring for inhibited photocorrosion, but also in activating, respectively, the charge separation and transfer in each layer for boosted charge-carrier kinetics, resulting in FeNiOOH-LGCDs-PHGs-MBVO photoanodes with a dual configuration with the photocurrent density of 6.08 mA cm-2 @ 1.23 VRHE , and operational stability up to 120 h @ 1.23 VRHE . Further work exploring LGCDs-PHGs from catecholic molecules warrants the proposed strategy as being a universal alternative for addressing the interfacial charge-carrier kinetics and operational stability of semiconductor photoelectrodes.

Atomic cerium modulated palladium nanoclusters exsolved ferrite catalysts for lean methane conversion.

The active and stable palladium (Pd) based catalysts for CH4 conversion are of great environmental and industrial significance. Herein, we employed N2 as an optimal activation agent to develop a Pd nanocluster exsolved Ce-incorporated perovskite ferrite catalyst toward lean methane oxidation. Replacing the traditional initiator of H2, the N2 was found as an effective driving force to selectively touch off the surface exsolution of Pd nanocluster from perovskite framework without deteriorating the overall material robustness. The catalyst showed an outstanding T50 (temperature of 50% conversion) plummeting down to 350°C, outperforming the pristine and H2-activated counterparts. Further, the combined theoretical and experimental results also deciphered the crucial role that the atomically dispersed Ce ions played in both construction of active sites and CH4 conversion. The isolated Ce located at the A-site of perovskite framework facilitated the thermodynamic and kinetics of the Pd exsolution process, lowering its formation temperature and promoting its quantity. Moreover, the incorporation of Ce lowered the energy barrier for cleavage of C─H bond, and was dedicated to the preservation of highly reactive PdOx moieties during stability measurement. This work successfully ventures uncharted territory of in situ exsolution to provide a new design thinking for a highly performed catalytic interface.

Electrospun Bi-doped SnO2 porous nanosheets for highly sensitive nitric oxide detection.

The real-time monitoring of NO in the low-concentration range from the ppb- to ppm-level is of great importance in the field of healthcare; however, accomplishing this is still challenging owing to the technical issues regarding highly efficient and selective sensing materials. In this study, we demonstrate the highly sensitive and selective detection of NO by Bi-doped SnO2 two-dimensional ultrathin nanosheets with porous structures, fabricated using a facile one-step electrospinning method. It was found that the SnO2 with 0.75 mol% Bi exhibits the highest sensitivity of 217-10 ppm of NO at a relatively low temperature of 75 °C. Further, a low detection limit of 50 ppb; high selectivity; and good stability have also been achieved. Further detailed analysis indicates that the promising sensing properties can be attributed to the ultrathin nanosheet structure, which has a high surface area and abundant pores. These results indicate that 2D metal-oxide ultrathin nanosheets achieve superior gas-sensing performance, and Bi-doped SnO2 is a potential material for use in the real-time and low-power detection of NO.

Surface defect passivation of Ta3N5 photoanode via pyridine grafting for enhanced photoelectrochemical performance.

Tantalum nitride (Ta3N5) is a promising photoanode material for photoelectrochemical (PEC) water splitting, while the Ta3N5/Ta photoanode synthesized via general thermal oxidation and nitridation on a Ta foil method usually has serious carrier recombination at the surface, which usually reduces the PEC activities. Herein, we demonstrate an efficient strategy of decorating pyridine, a small organic molecule at the surface of the Ta3N5/Ta photoanode, to alleviate the surface recombination. Such decoration yields a stable photocurrent density of 4.4 mA cm-2 at 1.23 VRHE under AM 1.5G (air mass 1.5 global, 100 mW cm-2) simulated sunlight, which is about 1.4 times higher than that of Ta3N5/Ta without modification, and the photocurrent density still remained ∼100% of its original value after a 5 h stability test. Further characterization of the incident photon-to-current conversion efficiency and absorbed photon-to-current efficiency of the pyridine/Ta3N5/Ta photoanode showed a significant increase to 62% and 72% at 500 nm, respectively. The enhanced pyridine/Ta3N5/Ta PEC performance can be attributed to minimizing the density of nitrogen vacancies due to the passivation of pyridine grafting, which results in the decreased recombination centers and improved charge separation efficiency at the surface. We thus believe that our study of surface passivation by using small organic molecules provides an alternative to address the surface recombination of Ta3N5 based photoelectrodes.

LaCrO3-Coated La0.6Sr0.4Co0.2Fe0.8O3-δ Core-Shell Structured Cathode with Enhanced Cr Tolerance for Intermediate-Temperature Solid Oxide Fuel Cells.

La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) is a common cathode material for intermediate-temperature solid oxide fuel cells because of its excellent oxygen reduction reaction catalytic activity. However, the Cr-poisoning effect is a severe issue, causing electrochemical performance degradation. For the development of a LSCF-based cathode with excellent Cr tolerance, a LaCrO3-coated LSCF core-shell structured (LCr@LSCF) cathode was prepared via the solution infiltration method. After the cathode was coated with a LCr shell, the long-term stability and Cr tolerance were obviously improved, at the price of sacrificing some electrochemical performance. The development of a LCr@LSCF cathode with eye-catching Cr tolerance is of great significance to the commercialization of LSCF.

Laser-generated BiVO4 colloidal particles with tailoring size and native oxygen defect for highly efficient gas sensing.

To alleviate the poor sensing performance of BiVO4, developing new strategies for the fabrication of unique device with improved sensing properties is very necessary and has great practical significance. In this work, size-tailored and uniform black BiVO4 colloids with abundant oxygen vacancy were synthesized by a unique method of pulsed laser irradiation of colloidal nanoparticles (PLICN). The corresponding laser irradiation effects on the sensing properties are comparatively investigated. The results indicate that the BiVO4 nanospheres with average size of 50 nm shows best sensing properties with high sensitivity, superior selectivity, low detection limit (44 ppb) to H2S at low working temperature (75 °C). Its sensing response is over 4 times higher when comparing with that of the raw material. Further investigation manifests that laser irradiation could induce quantity of the oxygen vacancy and decrease the resistance of the sensing device, which is mainly responsible for the enhanced sensing performance. Moreover, the density functional theories (DFT) calculations suggest that the oxygen vacancies can greatly decrease the surface absorption energy with enhanced H2S absorption capability on BiVO4 surface and lower the bader charger transfer from the absorbed H2S molecules to the BiVO4, thus enabling the implementation for the enhanced gas-sensing properties.

Redox-Reversible Electrode Material for Direct Hydrocarbon Solid Oxide Fuel Cells.

Solid oxide fuel cells (SOFCs) can directly operate on hydrocarbon fuels such as natural gas; however, the widely used nickel-based anodes face grand challenges such as coking, sulfur poisoning, and redox instability. We report a novel double perovskite oxide Sr2Co0.4Fe1.2Mo0.4O6-δ (SCFM) that possesses excellent redox reversibility and can be used as both the cathode and the anode. When heat-treated at 900 °C in a reducing environment, double perovskite phase SCFM transforms into a composite of the Ruddlesden-Popper structured oxide Sr3Co0.1Fe1.3Mo0.6O7-δ (RP-SCFM) with the Co-Fe alloy nanoparticles homogeneously distributed on the surface of RP-SCFM. At 900 °C in an oxidizing atmosphere, the composite transforms back into the double perovskite phase SCFM. The excellent oxygen reduction reaction catalytic activity and mixed ionic-electronic conductivity make SCFM an excellent cathode material for SOFCs. When SCFM is used as the anode, excellent performance and stability are achieved upon either direct oxidation of methane as a fuel or operation with sulfur-containing fuels. The excellent redox reversibility coupled with outstanding electrical and catalytic properties manifested by SCFM will enable a broad application in energy conversion applications.

In Situ Exsolved Ni-Decorated Ba(Ce0.9Y0.1)0.8Ni0.2O3-δ Perovskite as Carbon-Resistant Composite Anode for Hydrocarbon-Fueled Solid Oxide Fuel Cells.

In this study, in situ exsolved Ni-Ba(Ce0.9Y0.1)0.8Ni0.2O3-δ+Gd0.1Ce0.9O1.9 (Ni-BCYN+GDC) perovskite anode is studied for application in hydrocarbon-fueled solid oxide fuel cell (SOFC). The electrocatalytic activities of the oxidation reaction of anode in hydrogen and methane atmospheres are studied. The results show that the surface-exsolved Ni nanoparticles can significantly improve the electrochemical properties of the anode. The polarization resistances of the studied anode in hydrogen and methane atmospheres at 750 °C are as low as 0.0042 and 0.0054 Ω·cm-2, respectively. At the same time, a 36 h short-term open-circuit voltage test under a methane atmosphere confirms that the Ni-BCYN+GDC composite anode exhibits a good carbon deposition resistance. These results demonstrate that the Ni-BCYN+GDC composite anode is a potential novel anode material candidate for hydrocarbon-fueled SOFC.

Pristine-Graphene-Supported Nitrogen-Doped Carbon Self-Assembled from Glucaminium-Based Ionic Liquids as Metal-Free Catalyst for Oxygen Evolution.

For the first time, graphene-supported N-doped carbon (G@NC) with a high degree of N doping was synthesized by in situ self-assembly of a glucaminium-based ionic liquid on pristine graphene under hydrothermal conditions. This 2D, metal-free nanohybrid exhibited much higher catalytic activity than most reported metal-free catalysts for the oxygen evolution reaction (OER) and even state-of-the-art Ir- and Ru-based catalysts because the high content of graphitic N greatly increased the number of OER-active sites, the pristine graphene significantly promoted the OER activity of the C sites adjacent to the graphitic N atoms, and N-doped graphitic carbon remarkably enhanced the charge-transfer rate. This work not only creates a facile and economical approach to controllably fabricate pristine-graphene-supported carbon with a high N-doping level for the development of highly efficient metal-free OER catalysts but also provides insight into the mechanisms for both the in situ self-assembly and the high OER catalytic activity of G@NC.

Embedding laser generated nanocrystals in BiVO4 photoanode for efficient photoelectrochemical water splitting.

Addressing the intrinsic charge transport limitation of metal oxides has been of significance for pursuing viable PEC water splitting photoelectrodes. Growing a photoelectrode with conductive nanoobjects embedded in the matrix is promising for enhanced charge transport but remains a challenge technically. We herein show a strategy of embedding laser generated nanocrystals in BiVO4 photoanode matrix, which achieves photocurrent densities of up to 5.15 mA cm-2 at 1.23 VRHE (from original 4.01 mA cm-2) for a single photoanode configuration, and 6.22 mA cm-2 at 1.23 VRHE for a dual configuration. The enhanced performance by such embedding is found universal owing to the typical features of laser synthesis and processing of colloids (LSPC) for producing ligand free nanocrystals in desired solvents. This study provides an alternative to address the slow bulk charge transport that bothers most metal oxides, and thus is significant for boosting their PEC water splitting performance.

City-level climate change mitigation in China.

As national efforts to reduce CO2 emissions intensify, policy-makers need increasingly specific, subnational information about the sources of CO2 and the potential reductions and economic implications of different possible policies. This is particularly true in China, a large and economically diverse country that has rapidly industrialized and urbanized and that has pledged under the Paris Agreement that its emissions will peak by 2030. We present new, city-level estimates of CO2 emissions for 182 Chinese cities, decomposed into 17 different fossil fuels, 46 socioeconomic sectors, and 7 industrial processes. We find that more affluent cities have systematically lower emissions per unit of gross domestic product (GDP), supported by imports from less affluent, industrial cities located nearby. In turn, clusters of industrial cities are supported by nearby centers of coal or oil extraction. Whereas policies directly targeting manufacturing and electric power infrastructure would drastically undermine the GDP of industrial cities, consumption-based policies might allow emission reductions to be subsidized by those with greater ability to pay. In particular, sector-based analysis of each city suggests that technological improvements could be a practical and effective means of reducing emissions while maintaining growth and the current economic structure and energy system. We explore city-level emission reductions under three scenarios of technological progress to show that substantial reductions (up to 31%) are possible by updating a disproportionately small fraction of existing infrastructure.

Enhanced methane steam reforming activity and electrochemical performance of Ni0.9Fe0.1-supported solid oxide fuel cells with infiltrated Ni-TiO2 particles.

Ni0.9Fe0.1 alloy-supported solid oxide fuel cells with NiTiO3 (NTO) infiltrated into the cell support from 0 to 4 wt.% are prepared and investigated for CH4 steam reforming activity and electrochemical performance. The infiltrated NiTiO3 is reduced to TiO2-supported Ni particles in H2 at 650 °C. The reforming activity of the Ni0.9Fe0.1-support is increased by the presence of the TiO2-supported Ni particles; 3 wt.% is the optimal value of the added NTO, corresponding to the highest reforming activity, resistance to carbon deposition and electrochemical performance of the cell. Fueled wet CH4 at 100 mL min-1, the cell with 3 wt.% of NTO demonstrates a peak power density of 1.20 W cm-2 and a high limiting current density of 2.83 A cm-2 at 650 °C. It performs steadily for 96 h at 0.4 A cm-2 without the presence of deposited carbon in the Ni0.9Fe0.1-support and functional anode. Five polarization processes are identified by deconvoluting and data-fitting the electrochemical impedance spectra of the cells under the testing conditions; and the addition of TiO2-supported Ni particles into the Ni0.9Fe0.1-support reduces the polarization resistance of the processes ascribed to CH4 steam reforming and gas diffusion in the Ni0.9Fe0.1-support and functional anode.