Molybdenum tailored Co^(0)/Co^(2+)active pairs on a perovskite-type oxide for direct ethanol synthesis from syngas

Selective synthesis of ethanol from syngas under the Co-based catalysts is still challenging due to the hard of regulating the active site Co^(0) and Co^(2+)ratio.In this work,a series of CaTi_(0.9-x)Co_(x)Mo_(0.1)O_(3)(x=0,0.1-0.4)and CaTi_(0.7)Co_(0.3)O_(3) catalysts were prepared by using citric acid complexation method to promote the synthesis of ethanol.It was found that Mo species in the perovskite lattice can regulate the Co^(0) and Co^(2+)ratio through the domain-limiting effect of perovskite and the degree of Co reduction could be adjusted by changing the Co/Mo molar ratio.Among these investigated catalysts,the total selectivity of alcohols over the catalyst with the optimal Co/Mo ratio CaTi_(0.6)Co_(0.3)Mo_(0.1)O_(3) reached 39.1%,with ethanol accounting for 74.7%,which was ascribed to the moderate and tightly bound ratio of dissociative to non-dissociative adsorption sites on the surface and the balance of CH_(x)-CH_(y) coupling and C^(O) insertion.

Total conductivity,oxygen permeability and stability of perovskite-type oxide BaCo_(0.7)Fe_(0.2)Nb_(0.1)O_(3-δ)

The total conductivity,oxygen sorption property,oxygen permeability and stability of pure perovskite-type oxide BaCo0.7Fe0.2Nb0.1O3-δ (BCFNO) in real operating conditions were investigated. Its total conductivity was measured to be 3.6 S·cm-1 at 600°C. Though the total conductivity of the BCFNO membrane is much smaller than that of the Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCFO) membrane,the oxygen permeability of the BCFNO membrane is similar to that of the BSCFO membrane. SEM observation and EDX analysis of the BCFN...

Highly Dispersed Pt Species with Excellent Stability and Catalytic Performance by Reducing a Perovskite-Type Oxide Precursor for CO Oxidation

A new scheme for the preparation of highly dispersed precious metal catalysts is proposed in this work. Samples of LaCol-xPtxO3/SiO2 （x = 0.03, 0.05, 0.07, 0.09, and 0.10） were prepared through a simple method of citrate acid complexa-tion combined with impregnation. In a nanocrystallite of LaCOl-xPtxO3, ions of lanthanum, cobalt, and platinum are evenly mixed at the atomic level and confined within the nanocrystallite. In the reduction process, platinum ions were reduced and migrated onto the surface of the nanocrystallite, and the platinum should be highly dispersed owing to the even mixing of the platinum ions in the precursor. When x = 0.05 or lower, the highest dispersion of Pt could be achieved. The highly dispersed Pt is stable, because of the strong interaction between Pt atoms and the support. The catalysts were characterized by BET surface area, temperature-programmed reduction, X-ray diffraction, transmission electron microscopy, CO temperature-programmed desorption, and turnover frequency. Compared with general precious metal Pt catalysts, the LaCo0.95Pt0.05O3/ SiO2 catalyst exhibited better activity for CO oxidation, and it maintained stability at a high temperature of 400 ℃ for 250 h with complete CO conversion.

Review of magnetocaloric effect in perovskite-type oxides

We survey the magnetocaloric effect in perovskite-type oxides （including doped ABO3-type manganese oxides, A3B2OT-type two-layered perovskite oxides, and A2B＇B＇＇O6-type ordered double-perovskite oxides）. Magnetic entropy changes larger than those of gadolinium can be observed in polycrystalline La1-xCaxMnO3 and alkali-metal （Na or K） doped La0.8Ca0.2MnO3 perovskite-type manganese oxides. The large magnetic entropy change produced by an abrupt reduction of magnetization is attributed to the anomalous thermal expansion at the Curie temperature. Considerable mag- netic entropy changes can also be observed in two-layered perovskites Lal.6Cal.4Mn207 and La2.5-xK0.5＋xMn2O7＋6 （0 〈 x 〈 0.5）, and double-perovskite Ba2Fe1＋xMol-xO6 （0 〈 x 〈 0.3） near their respective Curie temperatures. Com- pared with rare earth metals and their alloys, the perovskite-type oxides are lower in cost, and they exhibit higher chemical stability and higher electrical resistivity, which together favor lower eddy-current heating. They are potential magnetic refrigerants at high temperatures, especially near room temperature.

Preparation and application of perovskite-type oxides for electrocatalysis in oxygen/air electrodes

Recent advances in the preparation and application of perovskite-type oxides as bifunctional electrocatalysts for oxygen reaction and oxygen evolution reaction in rechargeable metal-air batteries are presented in this review.Various fabrication methods of these oxides are introduced in detail,and their advantages and disadvantages are analyzed.Different preparation methods adopted have great influence on the morphologies and physicochemical properties of perovskite-type oxides.As a bifunctional electrocatalyst,perovskite-type oxides are widely used in rechargeable metal-air batteries.The relationship between the preparation methods and the performances of oxygen/air electrodes are summarized.This work is concentrated on the structural stability,the phase compositions,and catalytic performance of perovskite-type oxides in oxygen/air electrodes.The main problems existing in the practical application of perovskite-type oxides as bifunctional electrocatalysts are pointed out and possible research directions in the future are recommended.

High performance and stability of double perovskite-type oxide NdBa0.5Ca0.5Co1.5Fe0.5O5+δas an oxygen electrode for reversible solid oxide electrochemical cell

In this study,we successfully synthesized double perovskite-type oxide NdBa0.5Ca0.5Co1.5Fe0.5O5+δ(NBCCF)using a conventional wet chemical method as the oxygen electrode for reversible solid oxide electrochemical cells(RSOCs).The polarization resistance(Rp)of the composite electrode NBCCFGd0.1Ce0.9O2(GDC)is only 0.079Ωcm^2 at 800℃under air.The single cell based on NBCCF-GDC electrode displays a peak power density of 0.941 W/cm^2 in fuel cell mode and a low Rp value of 0.134Ωcm^2.In electrolysis cell mode,the cell displays an outstanding oxygen evolution reaction(OER)activity and shows current density as high as 0.92 A/cm^2 with 50 vol%AH(Absolute Humidity)at 800℃and applied voltage of 1.3 V.Most importantly,the cell exhibits admirable durability of 60 h both in electrolysis mode and fuel cell mode with distinguished reversibility.All these results suggest that NBCCF is a promising candidate electrode for RSOC.

Fabrication of Sm-Based Perovskite-Type Oxide Thin-Films and Gas Sensing Properties to Acetylene

Sm-based perovskite-type oxide (SmMeO3: Me = Cr, Mn, Fe, Co) thin-films could be synthesized by a wet-chemical method using an acetylacetone—Poly(Vinyl Pyrrolidone) (PVP) polymeric precursor method at 750℃. The perovskite-type oxide thin-films were tried to apply an acetylene gas sensor based on AC impedance spectroscopy. Among the oxides tested, SmFeO3 thin-film sensor showed good sensor responses in which the AC impedance at 20 kHz was depending on acetylene gas concentration between 2 ppm and 80 ppm at 400℃.

Characterization and Stability of La0.5Sr0.5CoO2.91 Perovskite-Type Oxide

Compositely doped oxide La0.5Sr0.5CoO2.91 （LSC） was synthesized using solid state reaction and citric acid-nitrate low temperature self-propagating combustion methods. The crystal structure and the particle size micrograph of LSC powders synthesized by different methods were investigated with XRD and SEM. The experimental results show that the single perovskite phase of LSC can be synthesized by solid state reaction method, but LaSrCoO4 phase appears in LSC powder synthesized by citric acid-nitrate low temperature self-propagating combustion method. The LSC particle by citric acid-nitrate low temperature self- propagating combustion method has smaller size. To analyze the character of cathode material based on Ceo.gGdo.101.95（GDC） electrolyte, two types of cathode wafers were fabricated with the two kinds of LSC and GDC powders at the mass rate of 6：4, respectively. The electrical conductivity of the sintered samples was measured by four probe DC method from 300 to 800 ℃. The cathode with LSC particle by citric acid- nitrate low temperature self-propagating combustion method has higher electrical conductivity. In order to investigate the stability, the two samples were put into the muffle furnace to heat up in air at 800℃for 800 h. To analysis the reason for reduced electrical conductivity, the crystal structure and the particle micrograph of the cathode wafers before and after an exposure were investigated with XRD and SEM. The result shows that new crystal structure appears in both the two kinds of cathode wafers and crystal micrographs change a lot.

Removal of NO_x and Diesel Soot Particulates Catalyzed byPerovskite-type Oxide La_(0.9)K_(0.1)CoO_3

The catalytic performance of perovskite composite oxide catalyst La0.9 K0.1 CoO3 coated on catalyst supports by traditional solid state reaction method and sol-gel method were investigated by a series of experiments. The restdt shows that the catalytic performance of the La0.9 K0.1 CoO3 perovskite composite oxide catalyst synthesized by sol-gel method is superior to that synthesized by solid state reaction method, having lower ignition temperature of the diesel soot particulates, lower start temperature of NOx treatment, and lower concentration of byproduct CO.

Macroporous perovskite-type complex oxide catalysts of La_(1-x)K_xCo_(1-y)Fe_yO_3 for diesel soot combustion

A facile procedure was carried out to prepare macroporous perovskite-type complex oxide catalysts of La1–xKxCo1–yFeyO3(x=0,0.1,y=0,0.1) by using the combined method of organic ligation and solution combustion.This method could ensure the formation of the desired macroporous structures and the desired crystal phases of the prepared catalysts.It was found that the macroporous catalysts showed higher catalytic activities for soot combustion than that of the corresponding nanometric samples,and the macroporous ...

Layered Potassium Titanium Niobate/Reduced Graphene Oxide Nanocomposite as a Potassium‑Ion Battery Anode

With graphite currently leading as the most viable anode for potassium-ion batteries(KIBs),other materials have been left relatively underexamined.Transition metal oxides are among these,with many positive attributes such as synthetic maturity,longterm cycling stability and fast redox kinetics.Therefore,to address this research deficiency we report herein a layered potassium titanium niobate KTiNbO5(KTNO)and its rGO nanocomposite(KTNO/rGO)synthesised via solvothermal methods as a high-performance anode for KIBs.Through effective distribution across the electrically conductive rGO,the electrochemical performance of the KTNO nanoparticles was enhanced.The potassium storage performance of the KTNO/rGO was demonstrated by its first charge capacity of 128.1 mAh g^(−1) and reversible capacity of 97.5 mAh g^(−1) after 500 cycles at 20 mA g^(−1),retaining 76.1%of the initial capacity,with an exceptional rate performance of 54.2 mAh g^(−1)at 1 A g^(−1).Furthermore,to investigate the attributes of KTNO in-situ XRD was performed,indicating a low-strain material.Ex-situ X-ray photoelectron spectra further investigated the mechanism of charge storage,with the titanium showing greater redox reversibility than the niobium.This work suggests this lowstrain nature is a highly advantageous property and well worth regarding KTNO as a promising anode for future high-performance KIBs.

High‑Entropy Layered Oxide Cathode Enabling High‑Rate for Solid‑State Sodium‑Ion Batteries

Na-ion O3-type layered oxides are prospective cathodes for Na-ion batteries due to high energy density and low-cost.Nevertheless,such cathodes usually suffer from phase transitions,sluggish kinetics and air instability,making it difficult to achieve high performance solid-state sodium-ion batteries.Herein,the high-entropy design and Li doping strategy alleviate lattice stress and enhance ionic conductivity,achieving high-rate performance,air stability and electrochemically thermal stability for Na_(0.95)Li_(0.06)Ni_(0.25)Cu_(0.05)Fe_(0.15)Mn_(0.49)O_(2).This cathode delivers a high reversible capacity(141 mAh g^(−1)at 0.2C),excellent rate capability(111 mAh g^(−1)at 8C,85 mAh g^(−1)even at 20C),and long-term stability(over 85%capacity retention after 1000 cycles),which is attributed to a rapid and reversible O3–P3 phase transition in regions of low voltage and suppresses phase transition.Moreover,the compound remains unchanged over seven days and keeps thermal stability until 279℃.Remarkably,the polymer solid-state sodium battery assembled by this cathode provides a capacity of 92 mAh g^(−1)at 5C and keeps retention of 96%after 400 cycles.This strategy inspires more rational designs and could be applied to a series of O3 cathodes to improve the performance of solid-state Na-ion batteries.

Laser‑Induced and MOF‑Derived Metal Oxide/Carbon Composite for Synergistically Improved Ethanol Sensing at Room temperature

Advancements in sensor technology have significantly enhanced atmospheric monitoring.Notably,metal oxide and carbon(MO_(x)/C)hybrids have gained attention for their exceptional sensitivity and room-temperature sensing performance.However,previous methods of synthesizing MO_(x)/C composites suffer from problems,including inhomogeneity,aggregation,and challenges in micropatterning.Herein,we introduce a refined method that employs a metal–organic framework(MOF)as a precursor combined with direct laser writing.The inherent structure of MOFs ensures a uniform distribution of metal ions and organic linkers,yielding homogeneous MO_(x)/C structures.The laser processing facilitates precise micropatterning(<2μm,comparable to typical photolithography)of the MO_(x)/C crystals.The optimized MOF-derived MO_(x)/C sensor rapidly detected ethanol gas even at room temperature(105 and 18 s for response and recovery,respectively),with a broad range of sensing performance from 170 to 3,400 ppm and a high response value of up to 3,500%.Additionally,this sensor exhibited enhanced stability and thermal resilience compared to previous MOF-based counterparts.This research opens up promising avenues for practical applications in MOF-derived sensing devices.

Recent progresses in the development of tubular segmented-in-series solid oxide fuel cells:Experimental and numerical study

Solid oxide fuel cells(SOFCs)have attracted a great deal of interest because they have the highest efficiency without using any noble metal as catalysts among all the fuel cell technologies.However,traditional SOFCs suffer from having a higher volume,current leakage,complex connections,and difficulty in gas sealing.To solve these problems,Rolls-Royce has fabricated a simple design by stacking cells in series on an insulating porous support,resulting in the tubular segmented-in-series solid oxide fuel cells(SIS-SOFCs),which achieved higher output voltage.This work systematically reviews recent advances in the structures,preparation methods,perform-ances,and stability of tubular SIS-SOFCs in experimental and numerical studies.Finally,the challenges and future development of tubular SIS-SOFCs are also discussed.The findings of this work can help guide the direction and inspire innovation of future development in this field.

Advancements,strategies,and prospects of solid oxide electrolysis cells(SOECs):Towards enhanced performance and large-scale sustainable hydrogen production

Solid oxide electrolysis cells(SOECs)represent a crucial stride toward sustainable hydrogen generation,and this review explores their current scientific challenges,significant advancements,and potential for large-scale hydrogen production.In SOEC technology,the application of innovative fabrication tech-niques,doping strategies,and advanced materials has enhanced the performance and durability of these systems,although degradation challenges persist,implicating the prime focus for future advancements.Here we provide in-depth analysis of the recent developments in SOEC technology,including Oxygen-SOECs,Proton-SOECs,and Hybrid-SOECs.Specifically,Hybrid-SOECs,with their mixed ionic conducting electrolytes,demonstrate superior efficiency and the concurrent production of hydrogen and oxygen.Coupled with the capacity to harness waste heat,these advancements in SOEC technology present signif-icant promise for pilot-scale applications in industries.The review also highlights remarkable achieve-ments and potential reductions in capital expenditure for future SOEC systems,while elaborating on the micro and macro aspects of sOECs with an emphasis on ongoing research for optimization and scal-ability.It concludes with the potential of SOEC technology to meet various industrial energy needs and its significant contribution considering the key research priorities to tackle the global energy demands,ful-fillment,and decarbonization efforts.

Phase-engineering modulation of Mn-based oxide cathode for constructing super-stable sodium storage

The Mn-based oxide cathode with enriched crystal phase structure and component diversity can provide the excellent chemistry structure for Na-ion batteries.Nevertheless,the broad application prospect is obstructed by the sluggish Na^(+)kinetics and the phase transitions upon cycling.Herein,we establish the thermodynamically stable phase diagram of various Mn-based oxide composites precisely controlled by sodium content tailoring strategy coupling with co-doping and solid-state reaction.The chemical environment of the P2/P'3 and P2/P3 biphasic composites indicate that the charge compensation mechanism stems from the cooperative contribution of anions and cations.Benefiting from the no phase transition to scavenge the structure strain,P2/P'3 electrode can deliver long cycling stability(capacity retention of 73.8%after 1000 cycles at 10 C)and outstanding rate properties(the discharge capacity of 84.08 mA h g^(-1)at 20 C)than P2/P3 electrode.Furthermore,the DFT calculation demonstrates that the introducing novel P'3 phase can significantly regulate the Na^(+)reaction dynamics and modify the local electron configuration of Mn.The effective phase engineering can provide a reference for designing other high-performance electrode materials for Na-ion batteries.

Porous metal oxides in the role of electrochemical CO_(2) reduction reaction

The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.

Enhancing the stability of Ni Fe-layered double hydroxide nanosheet array for alkaline seawater oxidation by Ce doping

Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability caused by detrimental chlorine chemistry.Herein,we present our recent discovery that the incorporation of Ce into Ni Fe layered double hydroxide nanosheet array on Ni foam(Ce-Ni Fe LDH/NF)emerges as a robust electrocatalyst for seawater oxidation.During the seawater oxidation process,CeO_(2)is generated,effectively repelling Cl^(-)and inhibiting the formation of Cl O-,resulting in a notable enhancement in the oxidation activity and stability of alkaline seawater.The prepared Ce-Ni Fe LDH/NF requires only overpotential of 390 m V to achieve the current density of 1 A cm^(-2),while maintaining long-term stability for 500 h,outperforming the performance of Ni Fe LDH/NF(430 m V,150 h)by a significant margin.This study highlights the effectiveness of a Ce-doping strategy in augmenting the activity and stability of materials based on Ni Fe LDH in seawater electrolysis for oxygen evolution.

Boosting oxygen reduction activity and CO_(2) resistance on bismuth ferrite-based perovskite cathode for low-temperature solid oxide fuel cells below 600℃

Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)FeO_(3-δ) perovskites as highly-active catalysts for LT-SOFCs.Sm doping can significantly enhance the electrocata lytic activity and chemical stability of cathode.At 600℃,Bi_(0.675)Sm_(0.025)Sr_(0.3)FeO_(3-δ)(BSSF25) cathode has been found to be the optimum composition with a polarization resistance of 0.098 Ω cm^2,which is only around 22.8% of Bi_(0.7)Sr_(0.3)FeO_(3-δ)(BSF).A full cell utilizing BSSF25 displays an exceptional output density of 790 mW cm^(-2),which can operate continuously over100 h without obvious degradation.The remarkable electrochemical performance observed can be attributed to the improved O_(2) transport kinetics,superior surface oxygen adsorption capacity,as well as O_(2)p band centers in close proximity to the Fermi level.Moreover,larger average bonding energy(ABE) and the presence of highly acidic Bi,Sm,and Fe ions restrict the adsorption of CO_(2) on the cathode surface,resulting in excellent CO_(2) resistivity.This work provides valuable guidance for systematic design of efficient and durable catalysts for LT-SOFCs.

Photoelectrochemical seawater oxidation with metal oxide materials:Challenges and opportunities

Photocatalytic water oxidation is a crucial counter-electrode reaction in the process of photoelectrochemical energy conversion.Despite its importance,challenges remain in effectively and sustainably converting water to oxygen,particularly with readily available and inexpensive electrolyte solutions such as seawater.While metal oxide materials have demonstrated their advantages in promoting efficiency by reducing overpotential and improving light utilization,stability remains limited by corrosion in multicomponent seawater.In this paper,we reviewed the relationship between four basic concepts including photoelectrochemistry,metal oxide,water oxidation and seawater to better understand the challenges and opportunities in photoelectrochemical(PEC)seawater oxidation.To overcome these challenges,the advances in material design,interfacial modification,local environment control and reactor design have been further reviewed to benefit the industrial PEC seawater oxidation.Noticeably,we demonstrate engineered layered metal oxide electrodes and cell structures that enable powerful and stable seawater oxidation.We also outline and advise on the future direction in this area.