Iron-based perovskite-type compounds modified by Ru were prepared through sol-gel process to study its catalytic activity of NOx direct decomposition at low temperature and evaluate the conversion of NO under the expe...Iron-based perovskite-type compounds modified by Ru were prepared through sol-gel process to study its catalytic activity of NOx direct decomposition at low temperature and evaluate the conversion of NO under the experimental conditions. The catalytic activity of La 0.9Ce 0.1Fe 0.8-nCo 0.2RunO3 (n=0.01,0.03,0.05,0.07,0.09)series for the NO, NO-CO two components, CO-HC-NO three components were also analyzed. The catalytic investigation evidenced that the presence of Ru is necessary for making highly activity in decomposition of nitric oxide even at low temperature(400 ℃)and La 0.9Ce 0.9Fe 0.75Co 0.2Ru 0.05O3 (n=0.05) has better activity in all the samples, the conversion of it is 58.5%. With the reducing gas(CO,C3H6)added into the gas, the catalyst displayed very high activity in decomposition of NO and the conversion of it is 80% and 92.5% separately.展开更多
La<sup>0.8 Cu<sup>0.2 MnO<sup>3±δ perovskite-type catalyst for methane combustion prepared through sol-gel process was characterized by X-ray Diffractometry(XRD), X-ray Photoelectron Spectros...La<sup>0.8 Cu<sup>0.2 MnO<sup>3±δ perovskite-type catalyst for methane combustion prepared through sol-gel process was characterized by X-ray Diffractometry(XRD), X-ray Photoelectron Spectroscopy(XPS) and Scanning Electron Microscopy(SEM). XPS analyses reveal that the surface characteristics of the catalyst are changed. The lattice defects and oxygen vacancies on the catalyst surface are enhanced due to a part of La3+ being substituted by Cu2+ . Temperature-programmed-desorption(TPD) and temperature-programmed-reduction(TPR) analyses were carried out to study the catalytic behavior. It is found that there are two O2-desorption peaks at 350℃ and 650℃ in the TPD pattern, and two CH4-consumption peaks at 420℃ and 750℃ in the TPR patterns respectively, which indicates that the two kinds of oxygen species, so-called α and β oxygen, can react with the methane during catalytic combustion process. The catalytic activity tests were performed in a fixed-bed reactor, and the results show that the T<sup>1/2 at which the conversion of methane attains 50% of La<sup>0.8 Cu<sup>0.2 MnO<sup>3±δ is lower by 55℃ than that of LaMnO3. This indicates that the catalytic activity of-La<sup>0.8 Cu<sup>0.2 MnO<sup>3±δ is increased with partial substitution of Cu2+ for La3+ .-展开更多
Double perovskite-type catalysts including La2 CoMnO6 and La2 CuMnO6 are first evaluated for the effectiveness in removing volatile organic compounds(VOCs), and single perovskites(La CoO3, LaMnO3, and La Cu O3) ar...Double perovskite-type catalysts including La2 CoMnO6 and La2 CuMnO6 are first evaluated for the effectiveness in removing volatile organic compounds(VOCs), and single perovskites(La CoO3, LaMnO3, and La Cu O3) are also tested for comparison. All perovskites are tested with the gas hourly space velocity(GHSV) of 30,000 hr^-1, and the temperature range of100–600℃ for C7H8 removal. Experimental results indicate that double perovskites have better activity if compared with single perovskites. Especially, toluene(C7H8) can be completely oxidized to CO2 at 300℃ as La2 Co MnO6 is applied. Characterization of catalysts indicates that double perovskites own unique surface properties and are of higher amounts of lattice oxygen,leading to higher activity. Additionally, apparent activation energy of 68 k J/mol is calculated using Mars-van Krevelen model for C7 H8 oxidation with La2 Co Mn O6 as catalyst. For durability test, both La2 Co Mn O6 and La2 CuMnO6 maintain high C7 H8 removal efficiencies of 100% and98%, respectively, at 300℃ and 30,000 hr^-1, and they also show good resistance to CO2(5%) and H2 O(g)(5%) of the gas streams tested. For various VOCs including isopropyl alcohol(C3H8 O),ethanal(C2H4O), and ethylene(C2H4) tested, as high as 100% efficiency could be achieved with double perovskite-type catalysts operated at 300–350℃, indicating that double perovskites are promising catalysts for VOCs removal.展开更多
A series of perovskite type oxides and supported Ag catalysts were prepared, and characterized by X ray diffraction (XRD) and X ray photoelectron spectroscopy (XPS). The catalytic activities of the catalyst...A series of perovskite type oxides and supported Ag catalysts were prepared, and characterized by X ray diffraction (XRD) and X ray photoelectron spectroscopy (XPS). The catalytic activities of the catalysts as well as influencing factors on catalytic activity have been investigated for the simultaneous removal of NOx and diesel soot particulate. An increase in catalytic activity for the selective reduction of NOx was observed with Ag addition in these perovskite oxides, especially with 5% Ag loading. This catalyst could be a promising candidate of catalytic material for the simultaneous elimination of NOx and diesel soot.展开更多
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 m...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 ...展开更多
Clean energy and a sustainable environment are grand challenges that the world is facing which can be addressed by converting solar energy into transportable and storable fuels(chemical fuel).The main scientific and t...Clean energy and a sustainable environment are grand challenges that the world is facing which can be addressed by converting solar energy into transportable and storable fuels(chemical fuel).The main scientific and technological challenges for efficient solar energy conversion,energy storage,and environmental applications are the stability,durability,and performance of low-cost functional materials.Among different nanomaterials,perovskite type LaFeO_(3)has been extensively investigated as a photocatalyst due to its abundance,high stability,compositional and structural fexibility,high electrocatalytic activity,efficient sunlight absorption,and tunable band gap and band edges.Hence,it is urgent to write a comprehensive review to highlight the trend,challenges,and prospects of LaFeO_(3)in the field of photocatalytic solar energy conversion and environment purification.This critical review summarizes the history and basic principles of photocatalysis.Further,it reviews in detail the LaFeO_(3),applications,shortcomings,and activity enhancement strategies including the design of nanostructures,elemental doping,and heterojunctions construction such as Type-I,Type-II,Z-Type,and uncommon heterojunctions.Besides,the optical and electronic properties,charge carriers separation,electron transport phenomenon and alignment of the band gaps in LaFeO_(3)-based heterostructures are comprehensively discussed.展开更多
I.INTRODUCTION The perovskite-type compounds, as one kind of new functional materials has received more and more attention owing to their perfect crystal structure, unique electromagnetic properties, and high catalyti...I.INTRODUCTION The perovskite-type compounds, as one kind of new functional materials has received more and more attention owing to their perfect crystal structure, unique electromagnetic properties, and high catalytic activities for oxidation and hydrogena-展开更多
Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by ...Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by single-atom catalysts(SACs),which exhibit unique and intricate interactions between atomically dispersed metal atoms and their supports.Recently,bimetallic SACs(bimSACs)have garnered significant attention for leveraging the synergistic functions of two metal ions coordinated on appropriately designed supports.BimSACs offer an avenue for rich metal–metal and metal–support cooperativity,potentially addressing current limitations of SACs in effectively furnishing transformations which involve synchronous proton–electron exchanges,substrate activation with reversible redox cycles,simultaneous multi-electron transfer,regulation of spin states,tuning of electronic properties,and cyclic transition states with low activation energies.This review aims to encapsulate the growing advancements in bimSACs,with an emphasis on their pivotal role in hydrogen generation via water splitting.We subsequently delve into advanced experimental methodologies for the elaborate characterization of SACs,elucidate their electronic properties,and discuss their local coordination environment.Overall,we present comprehensive discussion on the deployment of bimSACs in both hydrogen evolution reaction and oxygen evolution reaction,the two half-reactions of the water electrolysis process.展开更多
Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3...Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.展开更多
Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal int...Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.展开更多
The current single-atom catalysts(SACs)for medicine still suffer from the limited active site density.Here,we develop a synthetic method capable of increasing both the metal loading and mass-specific activity of SACs ...The current single-atom catalysts(SACs)for medicine still suffer from the limited active site density.Here,we develop a synthetic method capable of increasing both the metal loading and mass-specific activity of SACs by exchanging zinc with iron.The constructed iron SACs(h^(3)-FNC)with a high metal loading of 6.27 wt%and an optimized adjacent Fe distance of~4 A exhibit excellent oxidase-like catalytic performance without significant activity decay after being stored for six months and promising antibacterial effects.Attractively,a“density effect”has been found at a high-enough metal doping amount,at which individual active sites become close enough to interact with each other and alter the electronic structure,resulting in significantly boosted intrinsic activity of single-atomic iron sites in h^(3)-FNCs by 2.3 times compared to low-and medium-loading SACs.Consequently,the overall catalytic activity of h^(3)-FNC is highly improved,with mass activity and metal mass-specific activity that are,respectively,66 and 315 times higher than those of commercial Pt/C.In addition,h^(3)-FNCs demonstrate efficiently enhanced capability in catalyzing oxygen reduction into superoxide anion(O_(2)·^(−))and glutathione(GSH)depletion.Both in vitro and in vivo assays demonstrate the superior antibacterial efficacy of h^(3)-FNCs in promoting wound healing.This work presents an intriguing activity-enhancement effect in catalysts and exhibits impressive therapeutic efficacy in combating bacterial infections.展开更多
S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB...S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB)degradation.The effects of two different mixing routes were identified on the MB degradation performance.Particularly,the catalyst obtained by the alcohol solvent evaporation(MOF-AEP)mixing route could degrade 95.60%MB(50 mg/L)within 4 min(degradation rate:K=0.78 min^(-1)),which was faster than that derived from the direct grinding method(MOF-DGP,80.97%,K=0.39 min^(-1)).X-ray photoelectron spectroscopy revealed that the Co-S content of MOF-AEP(43.39at%)was less than that of MOF-DGP(54.73at%),and the proportion of C-S-C in MOF-AEP(13.56at%)was higher than that of MOF-DGP(10.67at%).Density functional theory calculations revealed that the adsorption energy of Co for PMS was -2.94 eV when sulfur was doped as C-S-C on the carbon skeleton,which was higher than that when sulfur was doped next to cobalt in the form of Co-S bond(-2.86 eV).Thus,the C-S-C sites might provide more contributions to activate PMS compared with Co-S.Furthermore,the degradation parameters,including pH and MOF-AEP dosage,were investigated.Finally,radical quenching experiments and electron paramagnetic resonance(EPR)measurements revealed that ^(1)O_(2)might be the primary catalytic species,whereas·O~(2-)might be the secondary one in degrading MB.展开更多
Two perovskite-type fluorides K2NaVF6 and (NH4)3VF6 were synthesized under mild hydrothermal con- ditions. The structures of the compounds were determined by means of powder X-ray diffraction analysis. The Riet- vel...Two perovskite-type fluorides K2NaVF6 and (NH4)3VF6 were synthesized under mild hydrothermal con- ditions. The structures of the compounds were determined by means of powder X-ray diffraction analysis. The Riet- veld refinement indicates that K2NaVF6 has a cubic elpasolite-type structure and crystallizes in space group Fm3m with lattice constant a=8.3180(2) nm. (NH4)3VF6 has a cubic cryolite-type structure and crystallizes in space group Fm3m with lattice parameter a=9.090(1) rim. The compounds were further characterized by scanning electron micro- scopy(SEM), thermogravimetric(TG) and differential thermal analysis(DTA). The variable temperature magnetic susceptibility of these two compounds was characterized for the first time and the result shows that the magnetic or- dering is related to the crystallographic features and isolated magnetic unit with the temperature decreasing.展开更多
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...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...展开更多
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 ci...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.展开更多
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...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.展开更多
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...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.展开更多
Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utiliz...Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.展开更多
The emerging of single-atom catalysts(SACs)offers a great opportunity for the development of advanced energy storage and conversion devices due to their excellent activity and durability,but the actual mass production...The emerging of single-atom catalysts(SACs)offers a great opportunity for the development of advanced energy storage and conversion devices due to their excellent activity and durability,but the actual mass production of high-loading SACs is still challenging.Herein,a facile and green boron acid(H_(3)BO_(3))-assisted pyrolysis strategy is put forward to synthesize SACs by only using chitosan,cobalt salt and H_(3)BO_(3)as precursor,and the effect of H_(3)BO_(3)is deeply investigated.The results show that molten boron oxide derived from H_(3)BO_(3)as ideal high-temperature carbonization media and blocking media play important role in the synthesis process.As a result,the acquired Co/N/B tri-doped porous carbon framework(Co-N-B-C)not only presents hierarchical porous structure,large specific surface area and abundant carbon edges but also possesses high-loading single Co atom(4.2 wt.%),thus giving rise to outstanding oxygen catalytic performance.When employed as a catalyst for air cathode in Zn-air batteries,the resultant Co-N-B-C catalyst shows remarkable power density and long-term stability.Clearly,our work gains deep insight into the role of H_(3)BO_(3)and provides a new avenue to synthesis of high-performance SACs.展开更多
基金Sponsored by the National Natural Science Foundation of China(Grant No.20271019 and 20576027), Natural Science Foundation of Heilongjiang Prov-ince(Grant No.B200504), Postdoctoral Foundationof Heilongjiang Province(Grant No.LBH-Z05066) and Education Department Foundation of Hei-longjiang Province(Grant No.11511270).
文摘Iron-based perovskite-type compounds modified by Ru were prepared through sol-gel process to study its catalytic activity of NOx direct decomposition at low temperature and evaluate the conversion of NO under the experimental conditions. The catalytic activity of La 0.9Ce 0.1Fe 0.8-nCo 0.2RunO3 (n=0.01,0.03,0.05,0.07,0.09)series for the NO, NO-CO two components, CO-HC-NO three components were also analyzed. The catalytic investigation evidenced that the presence of Ru is necessary for making highly activity in decomposition of nitric oxide even at low temperature(400 ℃)and La 0.9Ce 0.9Fe 0.75Co 0.2Ru 0.05O3 (n=0.05) has better activity in all the samples, the conversion of it is 58.5%. With the reducing gas(CO,C3H6)added into the gas, the catalyst displayed very high activity in decomposition of NO and the conversion of it is 80% and 92.5% separately.
文摘La<sup>0.8 Cu<sup>0.2 MnO<sup>3±δ perovskite-type catalyst for methane combustion prepared through sol-gel process was characterized by X-ray Diffractometry(XRD), X-ray Photoelectron Spectroscopy(XPS) and Scanning Electron Microscopy(SEM). XPS analyses reveal that the surface characteristics of the catalyst are changed. The lattice defects and oxygen vacancies on the catalyst surface are enhanced due to a part of La3+ being substituted by Cu2+ . Temperature-programmed-desorption(TPD) and temperature-programmed-reduction(TPR) analyses were carried out to study the catalytic behavior. It is found that there are two O2-desorption peaks at 350℃ and 650℃ in the TPD pattern, and two CH4-consumption peaks at 420℃ and 750℃ in the TPR patterns respectively, which indicates that the two kinds of oxygen species, so-called α and β oxygen, can react with the methane during catalytic combustion process. The catalytic activity tests were performed in a fixed-bed reactor, and the results show that the T<sup>1/2 at which the conversion of methane attains 50% of La<sup>0.8 Cu<sup>0.2 MnO<sup>3±δ is lower by 55℃ than that of LaMnO3. This indicates that the catalytic activity of-La<sup>0.8 Cu<sup>0.2 MnO<sup>3±δ is increased with partial substitution of Cu2+ for La3+ .-
基金the Ministry of Science and Technology(MOST),Republic of China(ROC)(No.102WFA0700516)National Central University(No.105G910-9)for fundingfinancial support from the Industrial Technology Research Institute(No.105G910-8)
文摘Double perovskite-type catalysts including La2 CoMnO6 and La2 CuMnO6 are first evaluated for the effectiveness in removing volatile organic compounds(VOCs), and single perovskites(La CoO3, LaMnO3, and La Cu O3) are also tested for comparison. All perovskites are tested with the gas hourly space velocity(GHSV) of 30,000 hr^-1, and the temperature range of100–600℃ for C7H8 removal. Experimental results indicate that double perovskites have better activity if compared with single perovskites. Especially, toluene(C7H8) can be completely oxidized to CO2 at 300℃ as La2 Co MnO6 is applied. Characterization of catalysts indicates that double perovskites own unique surface properties and are of higher amounts of lattice oxygen,leading to higher activity. Additionally, apparent activation energy of 68 k J/mol is calculated using Mars-van Krevelen model for C7 H8 oxidation with La2 Co Mn O6 as catalyst. For durability test, both La2 Co Mn O6 and La2 CuMnO6 maintain high C7 H8 removal efficiencies of 100% and98%, respectively, at 300℃ and 30,000 hr^-1, and they also show good resistance to CO2(5%) and H2 O(g)(5%) of the gas streams tested. For various VOCs including isopropyl alcohol(C3H8 O),ethanal(C2H4O), and ethylene(C2H4) tested, as high as 100% efficiency could be achieved with double perovskite-type catalysts operated at 300–350℃, indicating that double perovskites are promising catalysts for VOCs removal.
文摘A series of perovskite type oxides and supported Ag catalysts were prepared, and characterized by X ray diffraction (XRD) and X ray photoelectron spectroscopy (XPS). The catalytic activities of the catalysts as well as influencing factors on catalytic activity have been investigated for the simultaneous removal of NOx and diesel soot particulate. An increase in catalytic activity for the selective reduction of NOx was observed with Ag addition in these perovskite oxides, especially with 5% Ag loading. This catalyst could be a promising candidate of catalytic material for the simultaneous elimination of NOx and diesel soot.
基金supported by the National Natural Science Foundation of China (20833011 and 20803093)the 863 Project of China (2006AA06Z346)
文摘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 ...
基金financially supported by the Ministry of Science and Technology of China(Grant No.2018YFA0702100)the National Natural Science Foundation of China(Grant Nos.11874169,51972129)+3 种基金the National Key R&D Program of China(Grant No.2017YFE0120500)the Key Research and Development Program of Hubei(Grant No.2020BAB079)the South Xinjiang Innovation and Development Program of Key Industries of Xinjiang Production and Construction Corps(Grants No.2020DB002)the Hubei‘‘Chu-Tian Young Scholar”program.
文摘Clean energy and a sustainable environment are grand challenges that the world is facing which can be addressed by converting solar energy into transportable and storable fuels(chemical fuel).The main scientific and technological challenges for efficient solar energy conversion,energy storage,and environmental applications are the stability,durability,and performance of low-cost functional materials.Among different nanomaterials,perovskite type LaFeO_(3)has been extensively investigated as a photocatalyst due to its abundance,high stability,compositional and structural fexibility,high electrocatalytic activity,efficient sunlight absorption,and tunable band gap and band edges.Hence,it is urgent to write a comprehensive review to highlight the trend,challenges,and prospects of LaFeO_(3)in the field of photocatalytic solar energy conversion and environment purification.This critical review summarizes the history and basic principles of photocatalysis.Further,it reviews in detail the LaFeO_(3),applications,shortcomings,and activity enhancement strategies including the design of nanostructures,elemental doping,and heterojunctions construction such as Type-I,Type-II,Z-Type,and uncommon heterojunctions.Besides,the optical and electronic properties,charge carriers separation,electron transport phenomenon and alignment of the band gaps in LaFeO_(3)-based heterostructures are comprehensively discussed.
文摘I.INTRODUCTION The perovskite-type compounds, as one kind of new functional materials has received more and more attention owing to their perfect crystal structure, unique electromagnetic properties, and high catalytic activities for oxidation and hydrogena-
基金support from the Czech Science Foundation,project EXPRO,No 19-27454Xsupport by the European Union under the REFRESH—Research Excellence For Region Sustainability and High-tech Industries project number CZ.10.03.01/00/22_003/0000048 via the Operational Programme Just Transition from the Ministry of the Environment of the Czech Republic+1 种基金Horizon Europe project EIC Pathfinder Open 2023,“GlaS-A-Fuels”(No.101130717)supported from ERDF/ESF,project TECHSCALE No.CZ.02.01.01/00/22_008/0004587).
文摘Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by single-atom catalysts(SACs),which exhibit unique and intricate interactions between atomically dispersed metal atoms and their supports.Recently,bimetallic SACs(bimSACs)have garnered significant attention for leveraging the synergistic functions of two metal ions coordinated on appropriately designed supports.BimSACs offer an avenue for rich metal–metal and metal–support cooperativity,potentially addressing current limitations of SACs in effectively furnishing transformations which involve synchronous proton–electron exchanges,substrate activation with reversible redox cycles,simultaneous multi-electron transfer,regulation of spin states,tuning of electronic properties,and cyclic transition states with low activation energies.This review aims to encapsulate the growing advancements in bimSACs,with an emphasis on their pivotal role in hydrogen generation via water splitting.We subsequently delve into advanced experimental methodologies for the elaborate characterization of SACs,elucidate their electronic properties,and discuss their local coordination environment.Overall,we present comprehensive discussion on the deployment of bimSACs in both hydrogen evolution reaction and oxygen evolution reaction,the two half-reactions of the water electrolysis process.
基金Research Institute for Smart Energy(CDB2)the grant from the Research Institute for Advanced Manufacturing(CD8Z)+4 种基金the grant from the Carbon Neutrality Funding Scheme(WZ2R)at The Hong Kong Polytechnic Universitysupport from the Hong Kong Polytechnic University(CD9B,CDBZ and WZ4Q)the National Natural Science Foundation of China(22205187)Shenzhen Municipal Science and Technology Innovation Commission(JCYJ20230807140402006)Start-up Foundation for Introducing Talent of NUIST and Natural Science Foundation of Jiangsu Province of China(BK20230426).
文摘Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.
基金financially supported by the National Natural Science Foundation of China(22309137,22279095)Open subject project State Key Laboratory of New Textile Materials and Advanced Processing Technologies(FZ2023001).
文摘Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFB3804500)the National Natural Science Foundation of China(Grant No.52202352,22335006)+4 种基金the Shanghai Municipal Health Commission(Grant No.20224Y0010)the CAMS Innovation Fund for Medical Sciences(Grant No.2021-I2M-5-012)the Basic Research Program of Shanghai Municipal Government(Grant No.21JC1406000)the Fundamental Research Funds for the Central Universities(Grant No.22120230237,2023-3-YB-11,22120220618)the Basic Research Program of Shanghai Municipal Government(23DX1900200).
文摘The current single-atom catalysts(SACs)for medicine still suffer from the limited active site density.Here,we develop a synthetic method capable of increasing both the metal loading and mass-specific activity of SACs by exchanging zinc with iron.The constructed iron SACs(h^(3)-FNC)with a high metal loading of 6.27 wt%and an optimized adjacent Fe distance of~4 A exhibit excellent oxidase-like catalytic performance without significant activity decay after being stored for six months and promising antibacterial effects.Attractively,a“density effect”has been found at a high-enough metal doping amount,at which individual active sites become close enough to interact with each other and alter the electronic structure,resulting in significantly boosted intrinsic activity of single-atomic iron sites in h^(3)-FNCs by 2.3 times compared to low-and medium-loading SACs.Consequently,the overall catalytic activity of h^(3)-FNC is highly improved,with mass activity and metal mass-specific activity that are,respectively,66 and 315 times higher than those of commercial Pt/C.In addition,h^(3)-FNCs demonstrate efficiently enhanced capability in catalyzing oxygen reduction into superoxide anion(O_(2)·^(−))and glutathione(GSH)depletion.Both in vitro and in vivo assays demonstrate the superior antibacterial efficacy of h^(3)-FNCs in promoting wound healing.This work presents an intriguing activity-enhancement effect in catalysts and exhibits impressive therapeutic efficacy in combating bacterial infections.
基金financially supported by the National Natural Science Foundation of China(Nos.51602018 and 51902018)the Natural Science Foundation of Beijing Municipality(No.2154052)+3 种基金the China Postdoctoral Science Foundation(No.2014M560044)the Fundamental Research Funds for the Central Universities(No.FRF-MP-20-22)USTB Research Center for International People-to-people Exchange in Science,Technology and Civilization(No.2022KFYB007)Education and Teaching Reform Foundation at University of Science and Technology Beijing(Nos.2023JGC027,KC2022QYW06,and KC2022TS09)。
文摘S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB)degradation.The effects of two different mixing routes were identified on the MB degradation performance.Particularly,the catalyst obtained by the alcohol solvent evaporation(MOF-AEP)mixing route could degrade 95.60%MB(50 mg/L)within 4 min(degradation rate:K=0.78 min^(-1)),which was faster than that derived from the direct grinding method(MOF-DGP,80.97%,K=0.39 min^(-1)).X-ray photoelectron spectroscopy revealed that the Co-S content of MOF-AEP(43.39at%)was less than that of MOF-DGP(54.73at%),and the proportion of C-S-C in MOF-AEP(13.56at%)was higher than that of MOF-DGP(10.67at%).Density functional theory calculations revealed that the adsorption energy of Co for PMS was -2.94 eV when sulfur was doped as C-S-C on the carbon skeleton,which was higher than that when sulfur was doped next to cobalt in the form of Co-S bond(-2.86 eV).Thus,the C-S-C sites might provide more contributions to activate PMS compared with Co-S.Furthermore,the degradation parameters,including pH and MOF-AEP dosage,were investigated.Finally,radical quenching experiments and electron paramagnetic resonance(EPR)measurements revealed that ^(1)O_(2)might be the primary catalytic species,whereas·O~(2-)might be the secondary one in degrading MB.
基金Supported by the Science and Technology Development Planning of Jilin Province,China(Nos.20100116,201105005)the Specialized Research Fund for the Doctoral Program of Higher Education of China(No.20100061120089)+1 种基金the Open Project of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry(No.2011-01)the Open Project of State Key Laboratory of Superhard Materials(No.2011-04),China
文摘Two perovskite-type fluorides K2NaVF6 and (NH4)3VF6 were synthesized under mild hydrothermal con- ditions. The structures of the compounds were determined by means of powder X-ray diffraction analysis. The Riet- veld refinement indicates that K2NaVF6 has a cubic elpasolite-type structure and crystallizes in space group Fm3m with lattice constant a=8.3180(2) nm. (NH4)3VF6 has a cubic cryolite-type structure and crystallizes in space group Fm3m with lattice parameter a=9.090(1) rim. The compounds were further characterized by scanning electron micro- scopy(SEM), thermogravimetric(TG) and differential thermal analysis(DTA). The variable temperature magnetic susceptibility of these two compounds was characterized for the first time and the result shows that the magnetic or- dering is related to the crystallographic features and isolated magnetic unit with the temperature decreasing.
基金the National High-Tech Research and Development Program of China (No. 2006AA11A189)the Science and Technology Commission of Shanghai Municipality (No. 07DZ12036)+1 种基金the National Engineering Research Center of Advanced Steel Technology (NERCAST, No. 050209)the Education Commission of Shanghai Municipality.
文摘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...
基金supported by the National Natural Science Foundation of China(Nos.21576192,21776214)
文摘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.
基金Projects(51504212,21573184,51703061)supported by the National Natural Science Foundation of ChinaProject(2018J01521)supported by the Natural Science Foundation of Fujian Province,ChinaProject(fma2017202)supported by the Open Fund of Fujian Provincial Key Laboratory of Functional Materials and Applications(Xiamen University of Technology),China
文摘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.
基金Project supported by the National Natural Science Foundation of China (Grant No. 11174132)the National Basic Research Program of China (Grant Nos. 2011CB922102 and 2012CB932304)the Priority Academic Program Development of Jiangsu Higher Education Institutions, China
文摘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.
基金supported by the National Natural Science Foundation of China(22234005,21974070)the Natural Science Foundation of Jiangsu Province(BK20222015)。
文摘Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.
基金supported by National Natural Science Foundation of China(Nos.52274298,51974114,51672075 and 21908049)China Postdoctoral Science Foundation(2020M682560)+4 种基金International Postdoctoral Exchange Fel owship Program(Grant No.PC2022020)Science&Technology innovation program of Hunan province(2020RC2024 and 2022RC3037)Hunan Provincial Natural Science Foundation of China(No.2020JJ4175)Science&Technology talents lifting project of Hunan Province(No.2022TJ-N16)Scientific Research Fund of Hunan Provincial Education Department(No.21A0392)
文摘The emerging of single-atom catalysts(SACs)offers a great opportunity for the development of advanced energy storage and conversion devices due to their excellent activity and durability,but the actual mass production of high-loading SACs is still challenging.Herein,a facile and green boron acid(H_(3)BO_(3))-assisted pyrolysis strategy is put forward to synthesize SACs by only using chitosan,cobalt salt and H_(3)BO_(3)as precursor,and the effect of H_(3)BO_(3)is deeply investigated.The results show that molten boron oxide derived from H_(3)BO_(3)as ideal high-temperature carbonization media and blocking media play important role in the synthesis process.As a result,the acquired Co/N/B tri-doped porous carbon framework(Co-N-B-C)not only presents hierarchical porous structure,large specific surface area and abundant carbon edges but also possesses high-loading single Co atom(4.2 wt.%),thus giving rise to outstanding oxygen catalytic performance.When employed as a catalyst for air cathode in Zn-air batteries,the resultant Co-N-B-C catalyst shows remarkable power density and long-term stability.Clearly,our work gains deep insight into the role of H_(3)BO_(3)and provides a new avenue to synthesis of high-performance SACs.