Heterogeneous photocatalysed reduction of aqueous Na_2CO_3 was carried out by using nano LaCoO_3 semiconductor powders. Formic acid and formaldehyde were identified as photoproducts,and were measured spectrophotometri...Heterogeneous photocatalysed reduction of aqueous Na_2CO_3 was carried out by using nano LaCoO_3 semiconductor powders. Formic acid and formaldehyde were identified as photoproducts,and were measured spectrophotometrically using Nash reagent. The effect of different parameters such as sodium carbonate concentration,amount of photocatalyst and different light sources on the yield of photoproducts was also investigated. It shows that nano LaCoO_3 has photocatalytic activity. Irradiation leads to the production of electrons in the conduction band of the LaCoO_3 semiconductor. It is likely that the photoproduced electrons initially reduce CO_3 (2-) to HCOO -,and then to HCHO and CH_3OH.展开更多
High-temperature X-ray diffraction (HTXRD) measurements of LaCoO_3 powder was carried out in a temperature range from 298 to 1273 K. The experimental data obtained were adopted to evaluate the lattice parameters and c...High-temperature X-ray diffraction (HTXRD) measurements of LaCoO_3 powder was carried out in a temperature range from 298 to 1273 K. The experimental data obtained were adopted to evaluate the lattice parameters and cell volume. In this temperature range, the linear and volume expansion coefficients calculated using these cell parameters are 24.160～23.610×10^(-6)·K^(-1) and 59.601～63.218×10^(-6)·K^(-1) respectively. There is no discontinuity found in the cell parameters through the proposed first-order transition at 1210 K.展开更多
Rationally manipulating the in‐situ formed catalytically active surface of catalysts remains a great challenge for a highly efficient water electrolysis.Here,we report a cationic oxidation method which can adjust the...Rationally manipulating the in‐situ formed catalytically active surface of catalysts remains a great challenge for a highly efficient water electrolysis.Here,we report a cationic oxidation method which can adjust the leaching of the in‐situ catalyst and promote the reconstruction of dynamic surface for the oxygen evolution reaction(OER).The chlorine doping can reduce the possibility of triggering in‐situ cobalt oxidation and chlorine leaching,leading to a transformation of the surface chlorine doped LaCoO_(3)(Cl‐LaCoO_(3))into an intricate amorphous(oxygen)hydroxide phase.And thus,Cl‐LaCoO_(3)nanocrystals shows an ultralow overpotential of 342 mV at the current density of 10 mA cm^(–2)and Tafel slope of 76.2 mV dec–1.Surface reconstructed Cl‐LaCoO_(3)is better than many of the most advanced OER catalysts and has proven significant stability.This work provides a new prospect for designing a high‐efficiency electrocatalyst with optimized perovskite‐structure in renewable energy system.展开更多
Herein, we attempted to engineer oxygen vacancies on the surface of LaCoO_(3) perovskite through simple post-treatments(acid or reductive thermal treatments). Acid treatment induces oxygen vacancies through the select...Herein, we attempted to engineer oxygen vacancies on the surface of LaCoO_(3) perovskite through simple post-treatments(acid or reductive thermal treatments). Acid treatment induces oxygen vacancies through the selective etching of the La cations, whereas thermal treatment in a reducing atmosphere generates oxygen vacancies by directly removing lattice oxygen. The characterization results confirm that the number of surface oxygen vacancies, which are crucial in various catalytic oxidation reactions,considerably increases in the LaCoO_(3) catalysts treated with acid or reducing gas. Acid treatment enriches the oxygen vacancies while maintaining the structure of the LaCoO_(3) catalysts, which can not be achieved through reductive thermal treatment. Therefore, the acid treatment is considered a promising technique for oxygen vacancy engineering of perovskite catalysts for tuning their catalytic activities. Furthermore,the catalytic activities of the posttreated LaCoO_(3) catalysts for CO oxidation were evaluated and are noted to be considerably better than those of the pristine LaCoO_(3) catalyst due to their abundant oxygen vacancies. Consequently, we conclude that the oxygen vacancies of perovskite catalysts can be effectively engineered via two simple methods and play a significant role in CO oxidation.展开更多
In the quest for the development of thermally stable,highly active and low-cost catalysts for use in catalyzed diesel particulate filter,nano-composites are new areas of research.Therefore,we reported the easy synthes...In the quest for the development of thermally stable,highly active and low-cost catalysts for use in catalyzed diesel particulate filter,nano-composites are new areas of research.Therefore,we reported the easy synthesis of spinel NiCo_(2)O_(4)/perovskite LaCoO_(3) nano-composite,and its individual oxides NiCo_(2)O_(4)and LaCoO_(3) for comparison.The detailed insights into the physio-chemical characteristics of formed NiCo_(2)O_(4)/LaCoO_(3) nano-composite were done based on various characterization analysis such as X-ray diffraction(XRD),Fourier transform infrared(FT-IR),N_(2) physiosorption,scanning electron microscopy-energy dispersive spectroscopy(SEM-EDX),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).The characterization analysis of NiCo_(2)O_(4)/LaCoO_(3) revealed the successful formation of a chemical interface possessing strong interfacial interaction,resulting in desirable physicochemical characteristics such as small crystallite size,abundant mesoporosity,high specific surface area and activation of surface lattice oxygen.Owing to the desirable characteristics,the activity results over NiCo_(2)O_(4)/LaCoO_(3) nano-composite showed the excellent CO oxidation performance and high soot oxidation activity,recyclability and thermal stability.This work mainly attempts to emphasize the effectiveness of the facile,inexpensive and conventionally used precipitation method for the successful formation of highly efficient nano-composites.展开更多
Perovskite LaCoO_(3)is of great potential in electromagnetic wave absorption considering its outstanding dielectric loss as well as the existing magnetic response with the magnetic doping.However,the dissipation mecha...Perovskite LaCoO_(3)is of great potential in electromagnetic wave absorption considering its outstanding dielectric loss as well as the existing magnetic response with the magnetic doping.However,the dissipation mechanism of the magnetic doping on the microwave absorption is lack of sufficient investigated.In this paper,LaCo_(1-x)Fe_(x)O_(3)(x=0,0.05,0.1,0.15,0.2,0.25,0.3,LCFOs)perovskites with different Fe doping amounts were prepared successfully by the sol-gel method and subsequent heat treatment in the air atmosphere.The structure characterization carried out by the frst-principles calculations shows the effect of Fe doping on the dielectric and magnetic properties of LCFOs and the strong hybridization of Co/Fe-3d with O-2p in the LCFOs system was successfully demonstrated.Particularly,when x=0.1 and the thickness is only 1.95 mm,the LaCo_(0.9)Fe_(0.1)O_(3)exhibits the best microwave absorption performance with the minimum reflection loss(RL)value of about-41 dB.The typical samples achieve a broad effective absorption bandwidth(EAB)of 5.16 GHz(7.92-13.08 GHz),which covers the total X band(8-12 GHz).Considering that,the especial Fe doping perovskite is promising to be a candidate as efficient microwave absorbers.展开更多
The correlation between crystal facets and electronic configurations of perovskite is closely related to the intrinsic activity for water splitting.Herein,we proposed a unique molten-salt method(MSM)to manipulate the ...The correlation between crystal facets and electronic configurations of perovskite is closely related to the intrinsic activity for water splitting.Herein,we proposed a unique molten-salt method(MSM)to manipulate the electronic properties of LaCoO_(3) by fine-tuning its crystal facet and atomic doping.LaCoO_(3) samples with oriented(110)(LCO(110))and(111)(LCO(111))facets were motivated by a capping agent(Sr^(2+)).Compared with the LCO(111)plane,the LCO(110)and Sr-doped LCO(111)(LSCO(111))planes possessed higher O 2p positions,stronger Co 3d-O 2p covalencies,and higher Co spin states by inducing CoO_(6) distortion,thus leading to superior oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)performances.Specifically,the overpotentials at 10 mA cm^(−2) were 299,322,and 289 mV for LCO(110),LCO(111),and LSCO(111),respectively.In addition,the(110)crystal facet and Sr substitution bestowed enhanced stability on LaCoO_(3) due to the strengthened Co-O bonding.The present work enlightens new avenues of regulating electronic properties by crystal facet engineering and atom doping and provides a valuable reference for the electron structure-electrocatalytic activity connection for OER and HER.展开更多
In the present work, dense perovskite ceramics were successfully prepared from a series of La1-xBaxCoO3 solid solutions in the range of substitution 0 ≤ x ≤ 0.75 using solid state reaction and conventional sintering...In the present work, dense perovskite ceramics were successfully prepared from a series of La1-xBaxCoO3 solid solutions in the range of substitution 0 ≤ x ≤ 0.75 using solid state reaction and conventional sintering. Structural properties of La1-xBaxCoO3 were systematically investigated and thermoelectric properties were measured in the temperature range of 330–1000 K. The results show that the thermoelectric properties of Ba-substituted LaCoO3 depend on x. Indeed, at 330 K, electrical conductivity presents an optimum value for x = 0.25 with a value of σmax ≈ 2.2×105 S·m–1 whereas the Seebeck coefficient decreases when x and/or the temperature increases. The Ba-substituted LaCoO3 samples exhibit p-type semiconducting behaviour. The best power factor value found is 3.4×10–4 W·m–1·K–2 at 330 K for x = 0.075, which is 10% higher than the optimum value measured in La1–xSrxCoO3 for x = 0.05. The thermal diffusivity and thermal conductivity increase with increasing temperature and Ba concentration. La1-xBaxCoO3 shows a maximum figure of merit(ZT = 0.048) for x = 0.05 at 330 K, 25% higher than the best value in La1–xSrxCoO3 compounds.展开更多
文摘Heterogeneous photocatalysed reduction of aqueous Na_2CO_3 was carried out by using nano LaCoO_3 semiconductor powders. Formic acid and formaldehyde were identified as photoproducts,and were measured spectrophotometrically using Nash reagent. The effect of different parameters such as sodium carbonate concentration,amount of photocatalyst and different light sources on the yield of photoproducts was also investigated. It shows that nano LaCoO_3 has photocatalytic activity. Irradiation leads to the production of electrons in the conduction band of the LaCoO_3 semiconductor. It is likely that the photoproduced electrons initially reduce CO_3 (2-) to HCOO -,and then to HCHO and CH_3OH.
文摘High-temperature X-ray diffraction (HTXRD) measurements of LaCoO_3 powder was carried out in a temperature range from 298 to 1273 K. The experimental data obtained were adopted to evaluate the lattice parameters and cell volume. In this temperature range, the linear and volume expansion coefficients calculated using these cell parameters are 24.160～23.610×10^(-6)·K^(-1) and 59.601～63.218×10^(-6)·K^(-1) respectively. There is no discontinuity found in the cell parameters through the proposed first-order transition at 1210 K.
文摘Rationally manipulating the in‐situ formed catalytically active surface of catalysts remains a great challenge for a highly efficient water electrolysis.Here,we report a cationic oxidation method which can adjust the leaching of the in‐situ catalyst and promote the reconstruction of dynamic surface for the oxygen evolution reaction(OER).The chlorine doping can reduce the possibility of triggering in‐situ cobalt oxidation and chlorine leaching,leading to a transformation of the surface chlorine doped LaCoO_(3)(Cl‐LaCoO_(3))into an intricate amorphous(oxygen)hydroxide phase.And thus,Cl‐LaCoO_(3)nanocrystals shows an ultralow overpotential of 342 mV at the current density of 10 mA cm^(–2)and Tafel slope of 76.2 mV dec–1.Surface reconstructed Cl‐LaCoO_(3)is better than many of the most advanced OER catalysts and has proven significant stability.This work provides a new prospect for designing a high‐efficiency electrocatalyst with optimized perovskite‐structure in renewable energy system.
基金Project supported by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)the Ministry of Trade,Industry&Energy(MOTIE),Republic of Korea(No.20214810100010)。
文摘Herein, we attempted to engineer oxygen vacancies on the surface of LaCoO_(3) perovskite through simple post-treatments(acid or reductive thermal treatments). Acid treatment induces oxygen vacancies through the selective etching of the La cations, whereas thermal treatment in a reducing atmosphere generates oxygen vacancies by directly removing lattice oxygen. The characterization results confirm that the number of surface oxygen vacancies, which are crucial in various catalytic oxidation reactions,considerably increases in the LaCoO_(3) catalysts treated with acid or reducing gas. Acid treatment enriches the oxygen vacancies while maintaining the structure of the LaCoO_(3) catalysts, which can not be achieved through reductive thermal treatment. Therefore, the acid treatment is considered a promising technique for oxygen vacancy engineering of perovskite catalysts for tuning their catalytic activities. Furthermore,the catalytic activities of the posttreated LaCoO_(3) catalysts for CO oxidation were evaluated and are noted to be considerably better than those of the pristine LaCoO_(3) catalyst due to their abundant oxygen vacancies. Consequently, we conclude that the oxygen vacancies of perovskite catalysts can be effectively engineered via two simple methods and play a significant role in CO oxidation.
文摘In the quest for the development of thermally stable,highly active and low-cost catalysts for use in catalyzed diesel particulate filter,nano-composites are new areas of research.Therefore,we reported the easy synthesis of spinel NiCo_(2)O_(4)/perovskite LaCoO_(3) nano-composite,and its individual oxides NiCo_(2)O_(4)and LaCoO_(3) for comparison.The detailed insights into the physio-chemical characteristics of formed NiCo_(2)O_(4)/LaCoO_(3) nano-composite were done based on various characterization analysis such as X-ray diffraction(XRD),Fourier transform infrared(FT-IR),N_(2) physiosorption,scanning electron microscopy-energy dispersive spectroscopy(SEM-EDX),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).The characterization analysis of NiCo_(2)O_(4)/LaCoO_(3) revealed the successful formation of a chemical interface possessing strong interfacial interaction,resulting in desirable physicochemical characteristics such as small crystallite size,abundant mesoporosity,high specific surface area and activation of surface lattice oxygen.Owing to the desirable characteristics,the activity results over NiCo_(2)O_(4)/LaCoO_(3) nano-composite showed the excellent CO oxidation performance and high soot oxidation activity,recyclability and thermal stability.This work mainly attempts to emphasize the effectiveness of the facile,inexpensive and conventionally used precipitation method for the successful formation of highly efficient nano-composites.
基金fnancial support from the National Natural Science Foundation of China(No.51971111)。
文摘Perovskite LaCoO_(3)is of great potential in electromagnetic wave absorption considering its outstanding dielectric loss as well as the existing magnetic response with the magnetic doping.However,the dissipation mechanism of the magnetic doping on the microwave absorption is lack of sufficient investigated.In this paper,LaCo_(1-x)Fe_(x)O_(3)(x=0,0.05,0.1,0.15,0.2,0.25,0.3,LCFOs)perovskites with different Fe doping amounts were prepared successfully by the sol-gel method and subsequent heat treatment in the air atmosphere.The structure characterization carried out by the frst-principles calculations shows the effect of Fe doping on the dielectric and magnetic properties of LCFOs and the strong hybridization of Co/Fe-3d with O-2p in the LCFOs system was successfully demonstrated.Particularly,when x=0.1 and the thickness is only 1.95 mm,the LaCo_(0.9)Fe_(0.1)O_(3)exhibits the best microwave absorption performance with the minimum reflection loss(RL)value of about-41 dB.The typical samples achieve a broad effective absorption bandwidth(EAB)of 5.16 GHz(7.92-13.08 GHz),which covers the total X band(8-12 GHz).Considering that,the especial Fe doping perovskite is promising to be a candidate as efficient microwave absorbers.
基金supported by the National Natural Science Foundation of China(52174283)。
文摘The correlation between crystal facets and electronic configurations of perovskite is closely related to the intrinsic activity for water splitting.Herein,we proposed a unique molten-salt method(MSM)to manipulate the electronic properties of LaCoO_(3) by fine-tuning its crystal facet and atomic doping.LaCoO_(3) samples with oriented(110)(LCO(110))and(111)(LCO(111))facets were motivated by a capping agent(Sr^(2+)).Compared with the LCO(111)plane,the LCO(110)and Sr-doped LCO(111)(LSCO(111))planes possessed higher O 2p positions,stronger Co 3d-O 2p covalencies,and higher Co spin states by inducing CoO_(6) distortion,thus leading to superior oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)performances.Specifically,the overpotentials at 10 mA cm^(−2) were 299,322,and 289 mV for LCO(110),LCO(111),and LSCO(111),respectively.In addition,the(110)crystal facet and Sr substitution bestowed enhanced stability on LaCoO_(3) due to the strengthened Co-O bonding.The present work enlightens new avenues of regulating electronic properties by crystal facet engineering and atom doping and provides a valuable reference for the electron structure-electrocatalytic activity connection for OER and HER.
基金Programme d‘Investissment d’Avenir PIA“Tours 2015”for the financial support
文摘In the present work, dense perovskite ceramics were successfully prepared from a series of La1-xBaxCoO3 solid solutions in the range of substitution 0 ≤ x ≤ 0.75 using solid state reaction and conventional sintering. Structural properties of La1-xBaxCoO3 were systematically investigated and thermoelectric properties were measured in the temperature range of 330–1000 K. The results show that the thermoelectric properties of Ba-substituted LaCoO3 depend on x. Indeed, at 330 K, electrical conductivity presents an optimum value for x = 0.25 with a value of σmax ≈ 2.2×105 S·m–1 whereas the Seebeck coefficient decreases when x and/or the temperature increases. The Ba-substituted LaCoO3 samples exhibit p-type semiconducting behaviour. The best power factor value found is 3.4×10–4 W·m–1·K–2 at 330 K for x = 0.075, which is 10% higher than the optimum value measured in La1–xSrxCoO3 for x = 0.05. The thermal diffusivity and thermal conductivity increase with increasing temperature and Ba concentration. La1-xBaxCoO3 shows a maximum figure of merit(ZT = 0.048) for x = 0.05 at 330 K, 25% higher than the best value in La1–xSrxCoO3 compounds.
