Supported nanoparticles have attracted considerable attention as a promising catalyst for achieving unique properties in numerous applications,including fuel cells,chemical conversion,and batteries.Nanocatalysts demon...Supported nanoparticles have attracted considerable attention as a promising catalyst for achieving unique properties in numerous applications,including fuel cells,chemical conversion,and batteries.Nanocatalysts demonstrate high activity by expanding the number of active sites,but they also intensify deactivation issues,such as agglomeration and poisoning,simultaneously.Exsolution for bottomup synthesis of supported nanoparticles has emerged as a breakthrough technique to overcome limitations associated with conventional nanomaterials.Nanoparticles are uniformly exsolved from perovskite oxide supports and socketed into the oxide support by a one-step reduction process.Their uniformity and stability,resulting from the socketed structure,play a crucial role in the development of novel nanocatalysts.Recently,tremendous research efforts have been dedicated to further controlling exsolution particles.To effectively address exsolution at a more precise level,understanding the underlying mechanism is essential.This review presents a comprehensive overview of the exsolution mechanism,with a focus on its driving force,processes,properties,and synergetic strategies,as well as new pathways for optimizing nanocatalysts in diverse applications.展开更多
Solid oxide electrolysis cell(SOEC) could be a potential technology to afford chemical storage of renewable electricity by converting water and carbon dioxide.In this work,we present the Ni-doped layered perovskite ox...Solid oxide electrolysis cell(SOEC) could be a potential technology to afford chemical storage of renewable electricity by converting water and carbon dioxide.In this work,we present the Ni-doped layered perovskite oxides,(La_(4)Sr_(n-4))_(0.9)Ti_(0.9n)Ni_(0.1n)O_(3n+2) with n=5,8,and 12(LSTNn) for application as catalysts of CO_(2) electrolysis with the exsolution of Ni nanoparticles through a simple in-situ growth method.It is found that the density,size,and distribution of exsolved Ni nanoparticles are determined by the number of n in LSTNn due to the different stack structures of TiO_6 octahedra along the c axis.The Ni doping in LSTNn significantly improved the electrochemical activity by increasing oxygen vacancies,and the Ni metallic nanoparticles afford much more active sites.The results show that LSTNn cathodes can successfully be manipulated the activity by controlling both the n number and Ni exsolution.Among these LSTNn(n=5,8,and 12),LSTN8 renders a higher activity for electrolysis of CO_(2) with a current density of 1.50A cm^(-2)@2.0 V at 800℃ It is clear from these results that the number of n in(La_(4)Sr_(n-4))_(0.9)Ti_(0.9n)Ni_(0.1n)O_(3n+2)with Ni-doping is a key factor in controlling the electrochemical performance and catalytic activity in SOEC.展开更多
In this paper, the partial oxidation of methane to synthesis gas using lattice oxygen of La1- SrxMO3-λ (M=Fe, x ...In this paper, the partial oxidation of methane to synthesis gas using lattice oxygen of La1- SrxMO3-λ (M=Fe, x Mn) perovskite oxides instead of molecular oxygen was investigated. The redox circulation between 11% O2/Ar flow and 11% CH4/He flow at 900℃ shows that methane can be oxidized to CO and H2 with a selectivity of over 90.7% using the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite oxides in an appropriate reaction condition, while the lost lattice x oxygen can be supplemented by air re-oxidation. It is viable for the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite x oxides instead of molecular oxygen to react with methane to synthesis gas in the redox mode.展开更多
Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9CO0.1O3 perovskite oxides as oxygen carrier for partial oxidation of methane in the absence of gaseous oxygen was investigated by continuous flow reaction and s...Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9CO0.1O3 perovskite oxides as oxygen carrier for partial oxidation of methane in the absence of gaseous oxygen was investigated by continuous flow reaction and sequential redox reaction, Methane was oxidized to syngas with high selectivity by oxygen species of perovskite oxides in the absence of gaseous oxygen. The sequential redox reaction revealed that the structural stability and continuous oxygen supply in redox reaction decreased over La0.8Sr0.2Fe0.9Co0. 1O3 oxide, while LaFeO3 and La0.8Sr0.2FeO3 exhibited excellent structural stability and continuous oxygen supply.展开更多
The oxygen evolution reaction (OER) dominates the efficiency of electrocatalytic water splitting owing to its sluggish kinetics.Perovskite oxides (ABO_(3)) have emerged as promising candidates to accelerate the OER pr...The oxygen evolution reaction (OER) dominates the efficiency of electrocatalytic water splitting owing to its sluggish kinetics.Perovskite oxides (ABO_(3)) have emerged as promising candidates to accelerate the OER process owing to their high intrinsic activities and tailorable properties.Fe ions in perovskite oxides have been proved to be a highly catalytic element for OER,while some Fe-based perovskites such as SrTi_(0.8)Fe_(0.2)O_(3-δ)(STF) and La_(0.66)Ti_(0.8)Fe_(0.2)O_(3-δ)(LTF) exhibit inferior OER activity.Yet the essential reason is still unclear and the effective method to promote the activity of such perovskite is also lacking.Herein,an in-situ exsolution strategy was proposed to boost the OER by migrating Fe from the bulk to the surface.Significantly enhanced OER activity was achieved on STF and LTF perovskites with surfacedecorated oxygen vacancies and Fe nanoparticles.In addition,theoretical calculation confirmed that the oxygen vacancies and Fe nanoparticle on surface could lower the overpotential of OER by facilitating the adsorption of OH^(-).From this study,migration of the active elements in perovskite is found to be an effective strategy to increase the quantity and activity of active sites,providing new insights and understanding for designing efficient OER catalysts.展开更多
Volatile organic compounds are a kind of important indoor and outdoor air pollutants.In recent years,more and more attention has been paid to the ways of volatile organic compound elimination because of its potential ...Volatile organic compounds are a kind of important indoor and outdoor air pollutants.In recent years,more and more attention has been paid to the ways of volatile organic compound elimination because of its potential long-term effects on human health.Among the various available methods for volatile organic compound elimination,the catalytic combustion is the most attractive method due to its high efficiency,low cost,simple operation,and easy scale-up.Perovskite oxides,as a large family of metal oxides with their A-site mainly of lanthanide element and/or alkaline earth metal element and B-site of transition metal element,have been extensively investigated as active and stable catalysts for volatile organic compound removal reactions due to their abundant compositional elements,high thermal/chemical stability,and compositional/structural flexibility.The catalytic performance of perovskite oxides is strongly depended on its material composition,morphology,and surface/bulk properties,while the doping,tailored synthesis route,and composite construction may have a significant effect on the bulk(oxygen vacancy concentration,lattice structure),surface(oxygen species,defect)properties,and particulate morphology,consequently the catalytic activity and stability for volatile organic compound removal.Herein,a comprehensive review about the recent advances in perovskite oxides for volatile organic compound elimination reactions based on catalytic combustion is presented from different aspects with a special emphasis on the material design strategies,such as compositional tuning,morphology control,nanostructure building,hybrid construction,and surface modification.At last,some perspectives are presented on the development and design of perovskite oxide-based catalysts for volatile organic compound removal applications by highlighgting the critical issues and challenges.展开更多
All-solid-state batteries equipped with solid-state electrolytes(SSEs)havegained significant interest due to their enhanced safety,energy density,andlongevity in comparison to traditional liquid organic electrolyte-ba...All-solid-state batteries equipped with solid-state electrolytes(SSEs)havegained significant interest due to their enhanced safety,energy density,andlongevity in comparison to traditional liquid organic electrolyte-based batteries.However,many SSEs,such as sulfides and hydrides,are highly sensitiveto water,limiting their practical use.As one class of important perovskites,theRuddlesden–Popper perovskite oxides(RPPOs),show great promise as SSEsdue to their exceptional stability,particularly in terms of water resistance.Inthis review,the crystal structure and synthesis methods of RPPOs SSEs are firstintroduced in brief.Subsequently,the mechanisms of ion transportation,including oxygen anions and lithium-ions,and the relevant strategies forenhancing their ionic conductivity are described in detail.Additionally,theprogress made in developing flexible RPPOs SSEs,which are critical for flexibleand wearable electronic devices,has also been summarized.Furthermore,thekey challenges and prospects for exploring and developing RPPOs SSEs in allsolid-state batteries are suggested.This review presents in detail the synthesismethods,the ion transportation mechanism,and strategies to enhance theroom temperature ionic conductivity of RPPOs SSEs,providing valuableinsights on enhancing their ionic conductivity and thus for their practicalapplication in solid-state batteries.展开更多
High-entropy oxides(HEOs)have gained great attention as an emerging kind of highperformance anode materials for lithium-ion batteries(LIBs)due to the entropy stabilization and multi-principal synergistic effect.Herein...High-entropy oxides(HEOs)have gained great attention as an emerging kind of highperformance anode materials for lithium-ion batteries(LIBs)due to the entropy stabilization and multi-principal synergistic effect.Herein,the porous perovskite-type RE(Co_(0.2)Cr_(0.2)Fe_(0.2)Mn_(0.2)Ni_(0.2))O_(3)(RE(=La,Sm,and Gd)is the abbreviation of rare earth)HEOs were successfully synthesized by a solution combustion synthesis(SCS)method.Owing to the synergistic effect of lattice distortion and oxygen vacancies(Ov),the Gd(Co_(0.2)Cr_(0.2)Fe_(0.2)Mn_(0.2)Ni_(0.2))O_(3) electrode exhibits superior high-rate lithium-ion storage performance and excellent cycling stability.A reversible capacity of 403 mAh·g^(-1) at a current rate of 0.2 A·g^(-1) after 500 cycles and a superior high-rate capacity of 394 mAh·g^(-1)even at 1.0 A·g^(-1)after 500 cycles are achieved.Meanwhile,the Gd(Co_(0.2)Cr_(0.2)Fe_(0.2)Mn_(0.2)Ni_(0.2))O_(3) electrode also exhibits a pronounced pseudo-capacitive behavior,contributing to an additional capacity.By adjusting and balancing the lattice distortion and oxygen vacancies of the electrode materials,the lithium-ion storage performance can be further regulated.展开更多
Emerging new applications of antiferroelectric perovskite oxides based on their fascinating phase transformation between polar and nonpolar states have provided considerable attention to this class of materials even d...Emerging new applications of antiferroelectric perovskite oxides based on their fascinating phase transformation between polar and nonpolar states have provided considerable attention to this class of materials even decades after the discovery of antiferroelectricity.After presenting the challenge of formulating a precise definition of antiferroelectric materials,we briefly summarize proposed applications.In the following,we focus on the crystallographic structures of the antiferroelectric and ferroelectric phases of NaNbO_(3),which is emerging as a promising alternative to PbZrO_(3)-based systems.The field-induced phase transition behavior of NaNbO_(3)-based AFE materials in the form of single crystals,bulk ceramics,and multilayer ceramic capacitors is reviewed.Recent advances in a group of materials exhibiting high energy storage performance and relaxor-like behavior are also covered.The influence of electrode geometry on phase transition behavior and thus on the energy storage property is briefly addressed.The review concludes with an overview of the remaining challenges related to the fundamental understanding of the scientific richness of AFE materials in terms of structure,microstructure,defect transport under high fields,and phase transition dynamics required for their future development and applications.展开更多
With the rapid development of industry,volatile organic compounds(VOCs)are gaining attention as a class of pollutants that need to be eliminated due to their adverse effects on the environment and human health.Catalyt...With the rapid development of industry,volatile organic compounds(VOCs)are gaining attention as a class of pollutants that need to be eliminated due to their adverse effects on the environment and human health.Catalytic combustion is the most popular technology used for the removal of VOCs as it can be adapted to different organic emissions under mild conditions.This review first introduces the hazards of VOCs,their treatment technologies,and summarizes the treatment mechanism issues.Next,the characteristics and catalytic performance of perovskite oxides as catalysts for VOC removal are expounded,with a special focus on lattice distortions and surface defects caused by metal doping and surface modifications,and on the treatment of different VOCs.The challenges and the prospects regarding the design of perovskite oxides catalysts for the catalytic combustion of VOCs are also discussed.This review provides a reference base for improving the performance of perovskite catalysts to treat VOCs.展开更多
Stimulus-responsive materials are fundamental to the broad and ever-growing field of intelligence research,which bridge intelligent systems with the Internet of Things(loT)in future lifestyles.Among these materials,wr...Stimulus-responsive materials are fundamental to the broad and ever-growing field of intelligence research,which bridge intelligent systems with the Internet of Things(loT)in future lifestyles.Among these materials,writable materials have received great interest;however,carbonization and irreversible writing processes are generally inevitable for extensively investigated organic compounds.Photochromism is a potential mode of composing information.Nevertheless,inorganic materials usually exhibit weak photochromic effects.Here,a novel strategy of designing high-entropy perovskite(HEP)oxides is put forward to develop a new inorganic photochromic system with satisfying performance.A series of HEP oxides are synthesized for the first time.Benefiting from excellent photochromic features,real-time information encoding was achieved.The mechanism-related photochromism is also discussed.Distinct from the previous works,it is believed that the present photochromic-based HEP oxides provide a new and manyfold research space for the future development of conventional writable materials and the disclosing of unprecedented properties and phenomena.展开更多
The magnetic functional materials play a particularly important role in our modern society and daily life.The magnetocaloric effect(MCE)is at the basis of a solid state magnetic refrigeration(MR)technology which may e...The magnetic functional materials play a particularly important role in our modern society and daily life.The magnetocaloric effect(MCE)is at the basis of a solid state magnetic refrigeration(MR)technology which may enhance the efficiency of cooling systems,both for room temperature and cryogenic appli-cations.Despite numerous experimental and theoretical MCE studies,commercial MR systems are still at developing stage.Designing magnetic solids with outstanding magnetocaloric performances remains therefore a most urgent task.Herein,recent progresses on characterizing the crystal structure,magnetic properties and cryogenic MCE of rare earths(RE)-based RE_(2)TMTM’O_(6)double perovskite(DP)oxides,where TM and TM’are different 3d transition metals,are summarized.Some Gd-based DP oxides are found to exhibit promising cryogenic magnetocaloric performances which make them attractive for active MR ap-plications.展开更多
Magnesia modified LaCoO3 was prepared by a facile one-step sol-gel method and used for removal of dilute methane.Compared with the conventional doping technique,the obtained LaCoO3@MgO-x exhibits pseudo core-shell str...Magnesia modified LaCoO3 was prepared by a facile one-step sol-gel method and used for removal of dilute methane.Compared with the conventional doping technique,the obtained LaCoO3@MgO-x exhibits pseudo core-shell structure and shows superior catalytic activity.The methane conversion exceeds90%at 532℃on LaCoO3@MgO-0.1,while only 60%of methane is conversed using the doped perovskite LaCo0.9Mg0.1O3.The high catalytic performance of LaCoO3@MgO-0.1 is mainly attributed to the adjustment of surface acid-base properties by the MgO shell structure.According to density functional theory(DFT)calculation,the methane is more likely to be adsorbed and cracked on LaCoO3@MgO-0.1.The in situ DRIFTS shows that CH3-O-CH3 intermediate specie is formed.The pseudo core-shell structure also enhances the stability and the LaCoO3@MgO-0.1 maintains high activity after working for 100 h.The above results demonstrate that surface modification by magnesia is an effective strategy for improving LaCoO3 catalytic performance.展开更多
Developing highly-active,earth-abundant non-precious-metal catalysts for hydrogen evolution reaction(HER)in alkaline solution would be beneficial to sustainable energy storage.Perovskite oxides are generally regarded ...Developing highly-active,earth-abundant non-precious-metal catalysts for hydrogen evolution reaction(HER)in alkaline solution would be beneficial to sustainable energy storage.Perovskite oxides are generally regarded as low-active HER catalysts,due to their inapposite hydrogen adsorption and water dissociation.Here,we report a detailed study on perovskite LaCoO_(3)epitaxial thin films as a model catalyst to significantly enhance the HER performance via an electrochemical activation process.As a result,the overpotential for the activation films to achieve a current density of 0.36 m A/cm^(2)is 238 m V,reduced by more than 200 m V in comparison with that of original samples.Structural characterization revealed the activation process dramatically increases the concentration of oxygen vacancies(Vo)on the surface of LaCoO_(3).We established the relationship between the electronic structure induced by Vo and the enhanced HER activity.Further theoretical calculations revealed that the Vo optimizes the hydrogen adsorption and dissociation of water on the surface of LaCoO_(3)thin films,thus improving the HER catalytic activity.This work may promote a deepened understanding of perovskite oxides for HER mechanism by Vo adjusting and a new avenue for designing highly active electrochemical catalysts in alkaline solution.展开更多
Electrochemical carbon dioxide(CO_(2))reduction(ECR)is a promising technology to produce valuable fuels and feedstocks from CO_(2).Despite large efforts to develop ECR catalysts,the investigation of the catalytic perf...Electrochemical carbon dioxide(CO_(2))reduction(ECR)is a promising technology to produce valuable fuels and feedstocks from CO_(2).Despite large efforts to develop ECR catalysts,the investigation of the catalytic performance and electrochemical behavior of complex metal oxides,especially perovskite oxides,is rarely reported.Here,the inorganic perovskite oxide Ag-doped(La_(0.8)Sr_(0.2))_(0.95)Ag_(0.05)MnO_(3-δ)(LSA0.05M)is reported as an efficient electrocatalyst for ECR to CO for the first time,which exhibits a Faradaic efficiency(FE)of 84.3%,a remarkable mass activity of 75Ag^(-1)(normalized to the mass of Ag),and stability of 130 h at a moderate overpotential of 0.79 V.The LSA0.05M catalyst experiences structure reconstruction during ECR,creating the in operando-formed interface between the perovskite and the evolved Ag phase.The evolved Ag is uniformly distributed with a small particle size on the perovskite surface.Theoretical calculations indicate the reconstruction of LSA0.05M during ECR and reveal that the perovskite-Ag interface provides adsorption sites for CO_(2) and accelerates the desorption of the*CO intermediate to enhance ECR.This study presents a novel high-performance perovskite catalyst for ECR andmay inspire the future design of electrocatalysts via the in operando formation of metal-metal oxide interfaces.展开更多
This work aims to study the effect of redox property and surface morphology of perovskite oxides on the catalytic activity of CO oxidation and CO+NO reduction, with the redox property being tuned by doping Fe at the ...This work aims to study the effect of redox property and surface morphology of perovskite oxides on the catalytic activity of CO oxidation and CO+NO reduction, with the redox property being tuned by doping Fe at the Co site of La0.8Sr0.2Co1-xFexO3 and the surface morphology being modified by supporting La0.8Sr0.2CoO3 on various mesoporous silicas(i.e., SBA-16, SBA-15, MCF). Characteristic results show that the Fe doping improves the match of redox potentials, and SBA-16 is the best support of La0.8Sr0.2CoO3 when referring to the oxidation ability(e.g., the Co^3+/Co^2+ molar ratio). A mechanism for oxygen desorption from perovskite oxides is proposed based on O2-TPD experiments, showing the evolution process of oxygen released from oxygen vacancy and lattice framework. Catalytic tests indicate that La0.8Sr0.2CoO3 is the best for CO oxidation, and La0.8Sr0.2FeO3 is the best for CO+NO reduction. The mechanism of CO+NO reduction changes as the reaction temperature increases, with XNO/XCO value decreases from 2.4 at 250℃ to 1.0 at 400℃. As for the surface morphology, La0. Sr0.2CoO3 supported on SBA-16 possesses the highest surface Co^3+/Co^2+ molar ratio as compared to the other two, and shows the best activity for CO oxidation.展开更多
Orthorhombic perovskite oxides are studied by high-throughput first-principles calculations to explore new thermal barrier coating(TBC)materials with low thermal conductivities.The mechanical and thermal properties ar...Orthorhombic perovskite oxides are studied by high-throughput first-principles calculations to explore new thermal barrier coating(TBC)materials with low thermal conductivities.The mechanical and thermal properties are predicted for 160 orthorhombic perovskite oxides.The average atomic volume is identified as a possible predictor of the thermal conductivity for the perovskite oxides,as it has a good correlation with the thermal conductivity.Five compounds,i.e.,LaTmO_(3),LaErO_(3),LaHoO_(3),SrCeO_(3),and SrPrO_(3),having thermal conductivities under 1 W·m^(-1)·K^(-1) and good damage tolerance,are proposed as novel TBC materials.The obtained data are expected to inspire the design of perovskite oxide-based TBC materials and also support their future functionality investigations.展开更多
Heterogeneous catalytic combustion provides a feasible technique for high efficient methane utilization.Perovskites ABO_3-type materials have received renewed attention as a potential alternative for noble metals supp...Heterogeneous catalytic combustion provides a feasible technique for high efficient methane utilization.Perovskites ABO_3-type materials have received renewed attention as a potential alternative for noble metals supported catalysts in catalytic methane combustion due to excellent hydrothermal stability and sulfur resistance. Recently, the emergence of nanostructured perovskite oxides(such as threedimensional ordered nanostructure, nano-array structure) with outstanding catalytic activity has further driven methane catalytic combustion research into spotlight. In this review, we summarize the recent development of nanostructured perovskite oxide catalysts for methane combustion, and shed some light on the rational design of high efficient nanostructured perovskite catalysts via lattice oxygen activation,lattice oxygen mobility and materials morphology engineering. The emergent issues needed to be addressed on perovskite catalysts were also proposed.展开更多
The growth of electrochemically inert segregation layers on the surface of solid oxide fuel cell cathodes has become a bottleneck restricting the development of perovskite-structured oxygen reduction catalysts.Here,we...The growth of electrochemically inert segregation layers on the surface of solid oxide fuel cell cathodes has become a bottleneck restricting the development of perovskite-structured oxygen reduction catalysts.Here,we report a new discovery in which enriched Ba and Fe ions on the near-surface of Nd_(1/2)Ba_(1/2)Co_(1/3)Fe_(1/3)Mn_(1/3)O_(3-δ)spontaneously agglomerate into dispersed Ba_(5)Fe_(2)O_(8) nanoparticles and maintain a highly active and durable perovskite structure on the surface.This unique surface selfcleaning phenomenon is related to the low average potential energy of Ba_(5)Fe_(2)O_(8),which is grown on the near-surface layer.The electrochemically inert Ba_(5)Fe_(2)O_(8) segregation layer on the near-surface of the perovskite catalyst achieves self-cleaning by regulating the formation energy of enriched metal oxides.This self-cleaned perovskite surface exhibits an ultrafast oxygen exchange rate,high catalytic activity for the oxygen reduction reaction,and good adaptability to the actual working conditions of solid oxide fuel cell stacks.This study paves a new way for overcoming the stubborn problem of perovskite catalyst surface deactivation and enriches the scientific knowledge of surface catalysis.展开更多
The crystal structure of CaSrFe<sub>0.75</sub>Co<sub>0.75</sub>Mn<sub>0.5</sub>O<sub>6−δ</sub> is investigated through neutron diffraction techniques in this study. The...The crystal structure of CaSrFe<sub>0.75</sub>Co<sub>0.75</sub>Mn<sub>0.5</sub>O<sub>6−δ</sub> is investigated through neutron diffraction techniques in this study. The material is synthesized using a solid-state synthesis method at a temperature of 1200˚C. Neutron diffraction data is subjected to Rietveld refinement, and a comparative analysis with X-ray diffraction (XRD) data is performed to unravel the structural details of the material. The findings reveal that the synthesized material exhibits a cubic crystal structure with a Pm-3m phase. The neutron diffraction results offer valuable insights into the arrangement of atoms within the lattice, contributing to a comprehensive understanding of the material’s structural properties. This research enhances our knowledge of CaSrFe0.75</sub>Co0.75</sub>Mn0.5</sub>O6−δ</sub>, with potential implications for its applications in various technological and scientific domains.展开更多
基金This study was supported by the National Research Foundation of Korea(NRF-2021R1C1C1010233)funded by the Korean government(MSIT)+1 种基金This research was also supported by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)Grant(No.G032542411)funded by the Korea Ministry of Trade,Industry,and Energy(MOTIE).
文摘Supported nanoparticles have attracted considerable attention as a promising catalyst for achieving unique properties in numerous applications,including fuel cells,chemical conversion,and batteries.Nanocatalysts demonstrate high activity by expanding the number of active sites,but they also intensify deactivation issues,such as agglomeration and poisoning,simultaneously.Exsolution for bottomup synthesis of supported nanoparticles has emerged as a breakthrough technique to overcome limitations associated with conventional nanomaterials.Nanoparticles are uniformly exsolved from perovskite oxide supports and socketed into the oxide support by a one-step reduction process.Their uniformity and stability,resulting from the socketed structure,play a crucial role in the development of novel nanocatalysts.Recently,tremendous research efforts have been dedicated to further controlling exsolution particles.To effectively address exsolution at a more precise level,understanding the underlying mechanism is essential.This review presents a comprehensive overview of the exsolution mechanism,with a focus on its driving force,processes,properties,and synergetic strategies,as well as new pathways for optimizing nanocatalysts in diverse applications.
基金supported by the National Natural Science Foundation of China (51877173)the Key R&D Project of Shaanxi Province (2023-YBGY-057)+1 种基金the State Key Laboratory of Electrical Insulation and Power Equipment (EIPE22314, EIPE22306)the Natural Science Basic Research Program of Shaanxi (2023-JC-QN-0483)。
文摘Solid oxide electrolysis cell(SOEC) could be a potential technology to afford chemical storage of renewable electricity by converting water and carbon dioxide.In this work,we present the Ni-doped layered perovskite oxides,(La_(4)Sr_(n-4))_(0.9)Ti_(0.9n)Ni_(0.1n)O_(3n+2) with n=5,8,and 12(LSTNn) for application as catalysts of CO_(2) electrolysis with the exsolution of Ni nanoparticles through a simple in-situ growth method.It is found that the density,size,and distribution of exsolved Ni nanoparticles are determined by the number of n in LSTNn due to the different stack structures of TiO_6 octahedra along the c axis.The Ni doping in LSTNn significantly improved the electrochemical activity by increasing oxygen vacancies,and the Ni metallic nanoparticles afford much more active sites.The results show that LSTNn cathodes can successfully be manipulated the activity by controlling both the n number and Ni exsolution.Among these LSTNn(n=5,8,and 12),LSTN8 renders a higher activity for electrolysis of CO_(2) with a current density of 1.50A cm^(-2)@2.0 V at 800℃ It is clear from these results that the number of n in(La_(4)Sr_(n-4))_(0.9)Ti_(0.9n)Ni_(0.1n)O_(3n+2)with Ni-doping is a key factor in controlling the electrochemical performance and catalytic activity in SOEC.
文摘In this paper, the partial oxidation of methane to synthesis gas using lattice oxygen of La1- SrxMO3-λ (M=Fe, x Mn) perovskite oxides instead of molecular oxygen was investigated. The redox circulation between 11% O2/Ar flow and 11% CH4/He flow at 900℃ shows that methane can be oxidized to CO and H2 with a selectivity of over 90.7% using the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite oxides in an appropriate reaction condition, while the lost lattice x oxygen can be supplemented by air re-oxidation. It is viable for the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite x oxides instead of molecular oxygen to react with methane to synthesis gas in the redox mode.
基金the Chinese Natural Science Foundation(Project No.20306016)
文摘Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9CO0.1O3 perovskite oxides as oxygen carrier for partial oxidation of methane in the absence of gaseous oxygen was investigated by continuous flow reaction and sequential redox reaction, Methane was oxidized to syngas with high selectivity by oxygen species of perovskite oxides in the absence of gaseous oxygen. The sequential redox reaction revealed that the structural stability and continuous oxygen supply in redox reaction decreased over La0.8Sr0.2Fe0.9Co0. 1O3 oxide, while LaFeO3 and La0.8Sr0.2FeO3 exhibited excellent structural stability and continuous oxygen supply.
基金financial supports from the Youth Innovation Fund of Dalian Institute of Chemical Physics (DICP I202126)the Strategic Priority Research Program of Chinese Academy of Sciences (XDB17020400)。
文摘The oxygen evolution reaction (OER) dominates the efficiency of electrocatalytic water splitting owing to its sluggish kinetics.Perovskite oxides (ABO_(3)) have emerged as promising candidates to accelerate the OER process owing to their high intrinsic activities and tailorable properties.Fe ions in perovskite oxides have been proved to be a highly catalytic element for OER,while some Fe-based perovskites such as SrTi_(0.8)Fe_(0.2)O_(3-δ)(STF) and La_(0.66)Ti_(0.8)Fe_(0.2)O_(3-δ)(LTF) exhibit inferior OER activity.Yet the essential reason is still unclear and the effective method to promote the activity of such perovskite is also lacking.Herein,an in-situ exsolution strategy was proposed to boost the OER by migrating Fe from the bulk to the surface.Significantly enhanced OER activity was achieved on STF and LTF perovskites with surfacedecorated oxygen vacancies and Fe nanoparticles.In addition,theoretical calculation confirmed that the oxygen vacancies and Fe nanoparticle on surface could lower the overpotential of OER by facilitating the adsorption of OH^(-).From this study,migration of the active elements in perovskite is found to be an effective strategy to increase the quantity and activity of active sites,providing new insights and understanding for designing efficient OER catalysts.
基金supported by the National Natural Science Foundation of China(Project No.21908106 and 21878158)the Jiangsu Natural Science Foundation(Project No.BK20190682)+2 种基金the Program for Jiangsu Specially Appointed Professorsthe Funding from State Key Laboratory of Materials-Oriented Chemical Engineering(Project No.ZK201808)a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)。
文摘Volatile organic compounds are a kind of important indoor and outdoor air pollutants.In recent years,more and more attention has been paid to the ways of volatile organic compound elimination because of its potential long-term effects on human health.Among the various available methods for volatile organic compound elimination,the catalytic combustion is the most attractive method due to its high efficiency,low cost,simple operation,and easy scale-up.Perovskite oxides,as a large family of metal oxides with their A-site mainly of lanthanide element and/or alkaline earth metal element and B-site of transition metal element,have been extensively investigated as active and stable catalysts for volatile organic compound removal reactions due to their abundant compositional elements,high thermal/chemical stability,and compositional/structural flexibility.The catalytic performance of perovskite oxides is strongly depended on its material composition,morphology,and surface/bulk properties,while the doping,tailored synthesis route,and composite construction may have a significant effect on the bulk(oxygen vacancy concentration,lattice structure),surface(oxygen species,defect)properties,and particulate morphology,consequently the catalytic activity and stability for volatile organic compound removal.Herein,a comprehensive review about the recent advances in perovskite oxides for volatile organic compound elimination reactions based on catalytic combustion is presented from different aspects with a special emphasis on the material design strategies,such as compositional tuning,morphology control,nanostructure building,hybrid construction,and surface modification.At last,some perspectives are presented on the development and design of perovskite oxide-based catalysts for volatile organic compound removal applications by highlighgting the critical issues and challenges.
基金National Natural Science Foundation of China,Grant/Award Numbers:21671106,22371043,62288102Priority Academic Program Development of Jiangsu Higher Education Institutions+1 种基金Minjiang Scholars Award Program(2023),Fujian ProvinceStart-Up Fund for High-Leveled Talents from Fujian Normal University,Grant/Award Numbers:Y0720316K13,Y0720320K13。
文摘All-solid-state batteries equipped with solid-state electrolytes(SSEs)havegained significant interest due to their enhanced safety,energy density,andlongevity in comparison to traditional liquid organic electrolyte-based batteries.However,many SSEs,such as sulfides and hydrides,are highly sensitiveto water,limiting their practical use.As one class of important perovskites,theRuddlesden–Popper perovskite oxides(RPPOs),show great promise as SSEsdue to their exceptional stability,particularly in terms of water resistance.Inthis review,the crystal structure and synthesis methods of RPPOs SSEs are firstintroduced in brief.Subsequently,the mechanisms of ion transportation,including oxygen anions and lithium-ions,and the relevant strategies forenhancing their ionic conductivity are described in detail.Additionally,theprogress made in developing flexible RPPOs SSEs,which are critical for flexibleand wearable electronic devices,has also been summarized.Furthermore,thekey challenges and prospects for exploring and developing RPPOs SSEs in allsolid-state batteries are suggested.This review presents in detail the synthesismethods,the ion transportation mechanism,and strategies to enhance theroom temperature ionic conductivity of RPPOs SSEs,providing valuableinsights on enhancing their ionic conductivity and thus for their practicalapplication in solid-state batteries.
基金supported by the Natural Science Foundation of Anhui Province(Grant No.2008085ME125)University Natural Science Research Project of Anhui Province(Grant Nos.KJ2020A0268 and KJ2020A0270).
文摘High-entropy oxides(HEOs)have gained great attention as an emerging kind of highperformance anode materials for lithium-ion batteries(LIBs)due to the entropy stabilization and multi-principal synergistic effect.Herein,the porous perovskite-type RE(Co_(0.2)Cr_(0.2)Fe_(0.2)Mn_(0.2)Ni_(0.2))O_(3)(RE(=La,Sm,and Gd)is the abbreviation of rare earth)HEOs were successfully synthesized by a solution combustion synthesis(SCS)method.Owing to the synergistic effect of lattice distortion and oxygen vacancies(Ov),the Gd(Co_(0.2)Cr_(0.2)Fe_(0.2)Mn_(0.2)Ni_(0.2))O_(3) electrode exhibits superior high-rate lithium-ion storage performance and excellent cycling stability.A reversible capacity of 403 mAh·g^(-1) at a current rate of 0.2 A·g^(-1) after 500 cycles and a superior high-rate capacity of 394 mAh·g^(-1)even at 1.0 A·g^(-1)after 500 cycles are achieved.Meanwhile,the Gd(Co_(0.2)Cr_(0.2)Fe_(0.2)Mn_(0.2)Ni_(0.2))O_(3) electrode also exhibits a pronounced pseudo-capacitive behavior,contributing to an additional capacity.By adjusting and balancing the lattice distortion and oxygen vacancies of the electrode materials,the lithium-ion storage performance can be further regulated.
基金This work was supported by the Hessian State Ministry for Higher Education,Research and the Arts under the LOEWE collaborative project FLAME(Fermi level engineering of antiferro-electric materials for energy storage and insulation systems).
文摘Emerging new applications of antiferroelectric perovskite oxides based on their fascinating phase transformation between polar and nonpolar states have provided considerable attention to this class of materials even decades after the discovery of antiferroelectricity.After presenting the challenge of formulating a precise definition of antiferroelectric materials,we briefly summarize proposed applications.In the following,we focus on the crystallographic structures of the antiferroelectric and ferroelectric phases of NaNbO_(3),which is emerging as a promising alternative to PbZrO_(3)-based systems.The field-induced phase transition behavior of NaNbO_(3)-based AFE materials in the form of single crystals,bulk ceramics,and multilayer ceramic capacitors is reviewed.Recent advances in a group of materials exhibiting high energy storage performance and relaxor-like behavior are also covered.The influence of electrode geometry on phase transition behavior and thus on the energy storage property is briefly addressed.The review concludes with an overview of the remaining challenges related to the fundamental understanding of the scientific richness of AFE materials in terms of structure,microstructure,defect transport under high fields,and phase transition dynamics required for their future development and applications.
基金the following organisations is gratefully acknowledged:the National Natural Science Foundation of China(Grant Nos.21976141,22102123,42277485)the Department of Science and Technology of Hubei Province(Grant No.2021CFA034)+3 种基金the Department of Education of Hubei Province(Grant Nos.T2020011,Q20211712)the Opening Project of Hubei Key Laboratory of Biomass Fibers and Eco-Dyeing&Finishing(Grant No.STRZ202101)and the South Africa National Research Foundation(No.137947)SACC acknowledges Fundação para a Ciência e a Tecnologia(FCT),Portugal for Scientific Employment Stimulus-Institutional Call(Grant No.CEECINST/00102/2018)Associate Laboratory for Green Chemistry-LAQV financed by national funds from FCT/MCTES(Grant Nos.UIDB/50006/2020 and UIDP/5006/2020).
文摘With the rapid development of industry,volatile organic compounds(VOCs)are gaining attention as a class of pollutants that need to be eliminated due to their adverse effects on the environment and human health.Catalytic combustion is the most popular technology used for the removal of VOCs as it can be adapted to different organic emissions under mild conditions.This review first introduces the hazards of VOCs,their treatment technologies,and summarizes the treatment mechanism issues.Next,the characteristics and catalytic performance of perovskite oxides as catalysts for VOC removal are expounded,with a special focus on lattice distortions and surface defects caused by metal doping and surface modifications,and on the treatment of different VOCs.The challenges and the prospects regarding the design of perovskite oxides catalysts for the catalytic combustion of VOCs are also discussed.This review provides a reference base for improving the performance of perovskite catalysts to treat VOCs.
基金supported by the National Natural Science Foundation of China(Nos.51772326 and 62105235)Natural Science Foundation of Tianjin City(No.22JCZDJC00010)+1 种基金Tianjin Research Innovation Project for Postgraduate Students(No.2022SKY153)the National Undergraduate Training Programs for Innovation and Entrepreneurship(No.202210059005).
文摘Stimulus-responsive materials are fundamental to the broad and ever-growing field of intelligence research,which bridge intelligent systems with the Internet of Things(loT)in future lifestyles.Among these materials,writable materials have received great interest;however,carbonization and irreversible writing processes are generally inevitable for extensively investigated organic compounds.Photochromism is a potential mode of composing information.Nevertheless,inorganic materials usually exhibit weak photochromic effects.Here,a novel strategy of designing high-entropy perovskite(HEP)oxides is put forward to develop a new inorganic photochromic system with satisfying performance.A series of HEP oxides are synthesized for the first time.Benefiting from excellent photochromic features,real-time information encoding was achieved.The mechanism-related photochromism is also discussed.Distinct from the previous works,it is believed that the present photochromic-based HEP oxides provide a new and manyfold research space for the future development of conventional writable materials and the disclosing of unprecedented properties and phenomena.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.52171174 and 91963123)the Ten Thousand Talents Plan of Zhejiang Province(No.2018R52003)the Fundamental Research Funds for the Provincial University of Zhejiang(No.GK199900299012-022).
文摘The magnetic functional materials play a particularly important role in our modern society and daily life.The magnetocaloric effect(MCE)is at the basis of a solid state magnetic refrigeration(MR)technology which may enhance the efficiency of cooling systems,both for room temperature and cryogenic appli-cations.Despite numerous experimental and theoretical MCE studies,commercial MR systems are still at developing stage.Designing magnetic solids with outstanding magnetocaloric performances remains therefore a most urgent task.Herein,recent progresses on characterizing the crystal structure,magnetic properties and cryogenic MCE of rare earths(RE)-based RE_(2)TMTM’O_(6)double perovskite(DP)oxides,where TM and TM’are different 3d transition metals,are summarized.Some Gd-based DP oxides are found to exhibit promising cryogenic magnetocaloric performances which make them attractive for active MR ap-plications.
基金Project supported by the Ministry of Education Blue Fire Program(XZJH201717)。
文摘Magnesia modified LaCoO3 was prepared by a facile one-step sol-gel method and used for removal of dilute methane.Compared with the conventional doping technique,the obtained LaCoO3@MgO-x exhibits pseudo core-shell structure and shows superior catalytic activity.The methane conversion exceeds90%at 532℃on LaCoO3@MgO-0.1,while only 60%of methane is conversed using the doped perovskite LaCo0.9Mg0.1O3.The high catalytic performance of LaCoO3@MgO-0.1 is mainly attributed to the adjustment of surface acid-base properties by the MgO shell structure.According to density functional theory(DFT)calculation,the methane is more likely to be adsorbed and cracked on LaCoO3@MgO-0.1.The in situ DRIFTS shows that CH3-O-CH3 intermediate specie is formed.The pseudo core-shell structure also enhances the stability and the LaCoO3@MgO-0.1 maintains high activity after working for 100 h.The above results demonstrate that surface modification by magnesia is an effective strategy for improving LaCoO3 catalytic performance.
基金funding support by the National Natural Science Foundation of China(Grant No.21872116 and 22075232)the Mobility Program of the Sino-German Center for Research Promotion(Grant No.M-0377)the financial support by National Natural Science Foundation of China(Grant No.21991151,21991150,22021001)。
文摘Developing highly-active,earth-abundant non-precious-metal catalysts for hydrogen evolution reaction(HER)in alkaline solution would be beneficial to sustainable energy storage.Perovskite oxides are generally regarded as low-active HER catalysts,due to their inapposite hydrogen adsorption and water dissociation.Here,we report a detailed study on perovskite LaCoO_(3)epitaxial thin films as a model catalyst to significantly enhance the HER performance via an electrochemical activation process.As a result,the overpotential for the activation films to achieve a current density of 0.36 m A/cm^(2)is 238 m V,reduced by more than 200 m V in comparison with that of original samples.Structural characterization revealed the activation process dramatically increases the concentration of oxygen vacancies(Vo)on the surface of LaCoO_(3).We established the relationship between the electronic structure induced by Vo and the enhanced HER activity.Further theoretical calculations revealed that the Vo optimizes the hydrogen adsorption and dissociation of water on the surface of LaCoO_(3)thin films,thus improving the HER catalytic activity.This work may promote a deepened understanding of perovskite oxides for HER mechanism by Vo adjusting and a new avenue for designing highly active electrochemical catalysts in alkaline solution.
基金Australian Centre for Neutron ScatteringAustralian Nuclear Science and Technology Organisation,Grant/Award Number:MI8046+1 种基金Max Planck-POSTECH-Hsinchu Center for Complex Phase MaterialsHigh-Performance Computing Center of Nanjing Tech University。
文摘Electrochemical carbon dioxide(CO_(2))reduction(ECR)is a promising technology to produce valuable fuels and feedstocks from CO_(2).Despite large efforts to develop ECR catalysts,the investigation of the catalytic performance and electrochemical behavior of complex metal oxides,especially perovskite oxides,is rarely reported.Here,the inorganic perovskite oxide Ag-doped(La_(0.8)Sr_(0.2))_(0.95)Ag_(0.05)MnO_(3-δ)(LSA0.05M)is reported as an efficient electrocatalyst for ECR to CO for the first time,which exhibits a Faradaic efficiency(FE)of 84.3%,a remarkable mass activity of 75Ag^(-1)(normalized to the mass of Ag),and stability of 130 h at a moderate overpotential of 0.79 V.The LSA0.05M catalyst experiences structure reconstruction during ECR,creating the in operando-formed interface between the perovskite and the evolved Ag phase.The evolved Ag is uniformly distributed with a small particle size on the perovskite surface.Theoretical calculations indicate the reconstruction of LSA0.05M during ECR and reveal that the perovskite-Ag interface provides adsorption sites for CO_(2) and accelerates the desorption of the*CO intermediate to enhance ECR.This study presents a novel high-performance perovskite catalyst for ECR andmay inspire the future design of electrocatalysts via the in operando formation of metal-metal oxide interfaces.
基金Supported by the National Natural Science Foundation of China(No.21203254), the Natural Science Foundation of Hubei Province of China(No.2015CFA138), the Natttral Science Foundation of Liaoning Province of Ctfina(No.201602681), the Shenyang Municipal Science and Technology Planning Project, China(No.17-76-1-00) and the Shenyang Normal University Excellent Talent Support Program, China(No.51600203).
文摘This work aims to study the effect of redox property and surface morphology of perovskite oxides on the catalytic activity of CO oxidation and CO+NO reduction, with the redox property being tuned by doping Fe at the Co site of La0.8Sr0.2Co1-xFexO3 and the surface morphology being modified by supporting La0.8Sr0.2CoO3 on various mesoporous silicas(i.e., SBA-16, SBA-15, MCF). Characteristic results show that the Fe doping improves the match of redox potentials, and SBA-16 is the best support of La0.8Sr0.2CoO3 when referring to the oxidation ability(e.g., the Co^3+/Co^2+ molar ratio). A mechanism for oxygen desorption from perovskite oxides is proposed based on O2-TPD experiments, showing the evolution process of oxygen released from oxygen vacancy and lattice framework. Catalytic tests indicate that La0.8Sr0.2CoO3 is the best for CO oxidation, and La0.8Sr0.2FeO3 is the best for CO+NO reduction. The mechanism of CO+NO reduction changes as the reaction temperature increases, with XNO/XCO value decreases from 2.4 at 250℃ to 1.0 at 400℃. As for the surface morphology, La0. Sr0.2CoO3 supported on SBA-16 possesses the highest surface Co^3+/Co^2+ molar ratio as compared to the other two, and shows the best activity for CO oxidation.
基金financially supported by the Natural Science Foundation of Shanghai(No.20ZR1419200)the National Natural Science Foundation of China(No.52172071)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning(No.GZ2020012).
文摘Orthorhombic perovskite oxides are studied by high-throughput first-principles calculations to explore new thermal barrier coating(TBC)materials with low thermal conductivities.The mechanical and thermal properties are predicted for 160 orthorhombic perovskite oxides.The average atomic volume is identified as a possible predictor of the thermal conductivity for the perovskite oxides,as it has a good correlation with the thermal conductivity.Five compounds,i.e.,LaTmO_(3),LaErO_(3),LaHoO_(3),SrCeO_(3),and SrPrO_(3),having thermal conductivities under 1 W·m^(-1)·K^(-1) and good damage tolerance,are proposed as novel TBC materials.The obtained data are expected to inspire the design of perovskite oxide-based TBC materials and also support their future functionality investigations.
基金the financial support from the Recruitment Program of Global Young Experts Start-up Fundthe Program of Introducing Talents of Discipline to Universities of China(111 Program, No. B17019)
文摘Heterogeneous catalytic combustion provides a feasible technique for high efficient methane utilization.Perovskites ABO_3-type materials have received renewed attention as a potential alternative for noble metals supported catalysts in catalytic methane combustion due to excellent hydrothermal stability and sulfur resistance. Recently, the emergence of nanostructured perovskite oxides(such as threedimensional ordered nanostructure, nano-array structure) with outstanding catalytic activity has further driven methane catalytic combustion research into spotlight. In this review, we summarize the recent development of nanostructured perovskite oxide catalysts for methane combustion, and shed some light on the rational design of high efficient nanostructured perovskite catalysts via lattice oxygen activation,lattice oxygen mobility and materials morphology engineering. The emergent issues needed to be addressed on perovskite catalysts were also proposed.
基金financially supported by the National Natural Science Foundation of China (U2032157)the Natural Science Foundation of Jiangsu Province (BK20201425)。
文摘The growth of electrochemically inert segregation layers on the surface of solid oxide fuel cell cathodes has become a bottleneck restricting the development of perovskite-structured oxygen reduction catalysts.Here,we report a new discovery in which enriched Ba and Fe ions on the near-surface of Nd_(1/2)Ba_(1/2)Co_(1/3)Fe_(1/3)Mn_(1/3)O_(3-δ)spontaneously agglomerate into dispersed Ba_(5)Fe_(2)O_(8) nanoparticles and maintain a highly active and durable perovskite structure on the surface.This unique surface selfcleaning phenomenon is related to the low average potential energy of Ba_(5)Fe_(2)O_(8),which is grown on the near-surface layer.The electrochemically inert Ba_(5)Fe_(2)O_(8) segregation layer on the near-surface of the perovskite catalyst achieves self-cleaning by regulating the formation energy of enriched metal oxides.This self-cleaned perovskite surface exhibits an ultrafast oxygen exchange rate,high catalytic activity for the oxygen reduction reaction,and good adaptability to the actual working conditions of solid oxide fuel cell stacks.This study paves a new way for overcoming the stubborn problem of perovskite catalyst surface deactivation and enriches the scientific knowledge of surface catalysis.
文摘The crystal structure of CaSrFe<sub>0.75</sub>Co<sub>0.75</sub>Mn<sub>0.5</sub>O<sub>6−δ</sub> is investigated through neutron diffraction techniques in this study. The material is synthesized using a solid-state synthesis method at a temperature of 1200˚C. Neutron diffraction data is subjected to Rietveld refinement, and a comparative analysis with X-ray diffraction (XRD) data is performed to unravel the structural details of the material. The findings reveal that the synthesized material exhibits a cubic crystal structure with a Pm-3m phase. The neutron diffraction results offer valuable insights into the arrangement of atoms within the lattice, contributing to a comprehensive understanding of the material’s structural properties. This research enhances our knowledge of CaSrFe0.75</sub>Co0.75</sub>Mn0.5</sub>O6−δ</sub>, with potential implications for its applications in various technological and scientific domains.