A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potenti...A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potential between Pt （Ⅳ） and Fe （Ⅱ） precursors as driving force. The formed Fe3O4 nanoparticles （NPs） effectively prevent the aggregation of Pt nanocrystallites and promote the dispersion of Pt NPs on the surface of catalyst, which will be favorable for the exposure of Pt active sites for high-efficient adsorption and contact of substrate and hydrogen donor. The electron-enrichment state of Pt NPs donated by Fe304 nanocrystallites is corroborated by XPS measurement, which is responsible for promoting and activating the terminal C=O bond of adsorbed substrate via a vertical configuration. The experimental results show that the activated charcoal supported Pt/Fe3O4 catalyst exhibits 94.8% selectivity towards cinnamyl alcohol by the transfer hydrogenation of einnamaldehyde with Pt loading of 2.46% under the optimum conditions of 120 ℃ for 6 h, and 2-propanol as a hydrogen donor. Additionally, the present study demonstrates that a high-efficient and recyclable catalyst can be rapidly separated from the mixture due to its natural magnetism upon the application of magnetic field.展开更多
Fe3O4/MWCNTs nanocomposites were prepared by chemical oxidation coprecipitation method and developed as highly efficient heterogeneous Fenton-like catalyst. XRD results revealed that Fe3O4 nanoparticles deposited onto...Fe3O4/MWCNTs nanocomposites were prepared by chemical oxidation coprecipitation method and developed as highly efficient heterogeneous Fenton-like catalyst. XRD results revealed that Fe3O4 nanoparticles deposited onto MWCNTs surface remained the inverse spinel crystal structure of cubic Fe3O4 phase. The FTIR characteristic peaks of MWCNTs weakened or disappeared due to the anchor of Fe3O4 nanoparticles and Fe-O peak at 570 cm^-1 was indicative of the formation of Fe3O4. TEM observation revealed that Fe3O4 nanoparticles were tightly anchored by MWCNTs. The Fenton-like catalytic activity of Fe3O4/MWCNTs nanocomposites for the discoloration of methyl orange （MO） was much higher than that of Fe3O4 nanoparticles. The process optimization of this heterogeneous Fenton-like system was implemented by response surface methodology （RSM）. The optimum conditions for MO discoloration were determined to be of 12.3 mmoi/L H2O2 concentration, 2.9 glL catalyst dosage, solution pH 2.7 and 39.3 min reaction time, with the maximum predicted value for MO discoloration ratio of 101.85%. The corresponding experimental value under the identical conditions was obtained as 99.86%, which was very close to the predicted one with the absolute deviation of 1.99%.展开更多
Multi-walled carbon nanotubes （MWCNTs） can act not only as a support for Fe3O4 nanoparticles （NPs） but also as a coworker with synergistic effect, accordingly improving the heterogeneous Fenton-like efficiency of ...Multi-walled carbon nanotubes （MWCNTs） can act not only as a support for Fe3O4 nanoparticles （NPs） but also as a coworker with synergistic effect, accordingly improving the heterogeneous Fenton-like efficiency of Fe3O4 NPs. In this study, Fe3O4 NPs were in situ anchored onto MWCNTs by a moderate co-precipitation method and the as-prepared Fe3O4/MWCNTs nanocomposites were employed as the highly efficient Fenton-like catalysts. The analyses of XRD, FTIR, Raman, FESEM, TEM and HRTEM results indicated the formation of Fe3O4 crystals in Fe3O4/MWCNTs nanocomposites prepared at different conditions and the interaction between Fe3O4 NPs and MWCNTs. Over a wide pH range, the surface of modified MWCNTs possessed negative charges. Based on these results, the possible combination mechanism between Fe3O4 NPs and MWCNTs was discussed and proposed. Moreover, the effects of preparation and catalytic conditions on the Fenton-like catalytic efficiency were investigated in order to gain further insight into the heterogeneous Fenton-like reaction catalyzed by Fe3O4/MWCNTs nanocomposites.展开更多
The kinetics and Fenton-like mechanism are two challenging tasks for heterogeneous Fenton-like catalytic oxidation of organic pollutants. In this study, three kinetic models were used for the kinetic studies of Fe3O4/...The kinetics and Fenton-like mechanism are two challenging tasks for heterogeneous Fenton-like catalytic oxidation of organic pollutants. In this study, three kinetic models were used for the kinetic studies of Fe3O4/MWCNTs-H2O2 Fenton-like reaction for MO degradation. The results indicated that this reaction followed the first- order kinetic model. The relationship of reaction rate constant and temperature followed the Arrhenius equation. The activation energy and frequency factor of this system were calculated as 8.2 kJ.mo1-1 and 2.72 s-1, respectively. The quantifications of Fe ions dissolution and ,OH radicals generation confirmed that the homogeneous and hetero- geneous catalyses were involved in Fe3O4/MWCNTs＇H2O2 Fenton-like reaction. The reaction rate constant was closely related with Fe ions dissolution and ,OH radicals generation. Fe3O4/MWCNTs nanocomposites had typical ferromagnetic property and could be easily separated from solution by an external magnet after being used. Furthermore, Fe3O4/MWCNTs nanocomposites exhibited good stability and recyclability. Finally, the Fenton-like mechanisms on homogeneous and heterogeneous catalyses were described.展开更多
A composite paste electrode based on Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF)—initially synthesized by solgel method—and multiwall carbon nanotube (MWCNT) as a cathode in fuel cells is developed. The composite pastes are pr...A composite paste electrode based on Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF)—initially synthesized by solgel method—and multiwall carbon nanotube (MWCNT) as a cathode in fuel cells is developed. The composite pastes are prepared by the direct mixing of BSCF:MWCNT at 90:10, 80:20 and 70:30 (% w/W). These electrodes are then characterized by the x-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption-desorption isotherm, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The XRD and SEM confirm the inclusion and the uniform dispersal of the MWCNT within BSCF, respectively. The nitrogen adsorption isotherm study shows that the porosity of the composite paste electrode has been improved by two-fold from the BSCF electrode. The EIS and CV demonstrate that the higher ratios of MWCNT in the composites are critical in improving the electronic conductivity as well as the kinetics. It is also noticeable that the electrode has increased the catalysis of oxygen in 0.1 M KOH (pH 12.0). Cyclic voltammetric studies on the oxygen reduction reaction (ORR) suggest that the incorporation of MWCNT is vital in improving the electrode (cathode) properties of a fuel cell.展开更多
CO adsorption microcalorimetry was employed in the study of γ-Al-2O-3-supported Pt, Pt-Sn and Pt-Fe catalysts. The results indicated that the initial differential heat of CO adsorption of the Pt/γ-Al-2O-3 catalyst w...CO adsorption microcalorimetry was employed in the study of γ-Al-2O-3-supported Pt, Pt-Sn and Pt-Fe catalysts. The results indicated that the initial differential heat of CO adsorption of the Pt/γ-Al-2O-3 catalyst was 125 kJ/mol. As CO coverage increased, the differential heat of adsorption decreased. At higher coverages, the differential heat of adsorption decreased significantly. 60% of the differential heat of CO adsorption on the Pt/γ-Al-2O-3 catalyst was higher than 100 kJ/mol. No significant effect on the initial differential heat was found after adding Sn and Fe to the Pt/γ-Al-2O-3 catalyst. The amount of strong CO adsorption sites decreased, while the portion of CO adsorption sites with differential heat of 60110 kJ/mol increased after increasing the Sn or Fe content. This indicates that the surface adsorption energy was changed by adding Sn or Fe to Pt/γ-Al-2O-3. The distribution of differential heat of CO adsorption on the Pt-Sn（C）/γ-Al-2O-3 catalyst was broad and homogeneous. Comparison of the dehydrogenation performance of C-4 alkanes with the number of CO adsorption sites with differential heat of 60110 kJ/mol showed a good correlation. These results indicate that the surface Pt centers with differential heats of 60110 kJ/mol for CO adsorption possess superior activity for the dehydrogenation of alkanes.展开更多
Methylcyclohexane(MCH)serves as an ideal hydrogen carrier in hydrogen storage and transportation process.In the continuous production of hydrogen from MCH dehydrogenation,the rational design of energy-efficient cataly...Methylcyclohexane(MCH)serves as an ideal hydrogen carrier in hydrogen storage and transportation process.In the continuous production of hydrogen from MCH dehydrogenation,the rational design of energy-efficient catalytic way with good performance remains an enormous challenge.Herein,an internal electric heating(IEH)assisted mode was designed and proposed by the directly electrical-driven catalyst using the resistive heating effect.The Pt/Al2O_(3)on Fe foam(Pt/Al2O_(3)/FF)with unique threedimensional network structure was constructed.The catalysts were studied in a comprehensive way including X-ray diffraction(XRD),scanning electron microscopy(SEM)-mapping,in situ extended X-ray absorption fine structure(EXAFS),and in situ COFourier transform infrared(FTIR)measurements.It was found that the hydrogen evolution rate in IEH mode can reach up to above 2060 mmol·gPt^(−1)·min^(−1),which is 2–5 times higher than that of reported Pt based catalysts under similar reaction conditions in conventional heating(CH)mode.In combination with measurements from high-resolution infrared thermometer,the equations of heat transfer rate,and reaction heat analysis results,the Pt/Al2O_(3)/FF not only has high mass and heat transfer ability to promote catalytic performance,but also behaves as the heating component with a low thermal resistance and heat capacity offering a fast temperature response in IEH mode.In addition,the chemical adsorption and activation of MCH molecules can be efficiently facilitated by IEH mode,proved by the operando MCH-FTIR results.Therefore,the as-developed IEH mode can efficiently reduce the heat and mass transfer limitations and prominently boost the dehydrogenation performance,which has a broad application potential in hydrogen storage and other catalytic reaction processes.展开更多
基金This work is supported by the National Natural Science Foundation of China （No.51372248, No.51432009 and No.51502297）, Instrument Developing Project of the Chinese Academy of Sciences （No.yz201421）, the CAS/SAFEA International Partnership Program for Creative Research Teams of Chinese Academy of Sciences, China.
文摘A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potential between Pt （Ⅳ） and Fe （Ⅱ） precursors as driving force. The formed Fe3O4 nanoparticles （NPs） effectively prevent the aggregation of Pt nanocrystallites and promote the dispersion of Pt NPs on the surface of catalyst, which will be favorable for the exposure of Pt active sites for high-efficient adsorption and contact of substrate and hydrogen donor. The electron-enrichment state of Pt NPs donated by Fe304 nanocrystallites is corroborated by XPS measurement, which is responsible for promoting and activating the terminal C=O bond of adsorbed substrate via a vertical configuration. The experimental results show that the activated charcoal supported Pt/Fe3O4 catalyst exhibits 94.8% selectivity towards cinnamyl alcohol by the transfer hydrogenation of einnamaldehyde with Pt loading of 2.46% under the optimum conditions of 120 ℃ for 6 h, and 2-propanol as a hydrogen donor. Additionally, the present study demonstrates that a high-efficient and recyclable catalyst can be rapidly separated from the mixture due to its natural magnetism upon the application of magnetic field.
基金Acknowledgements This work was kindly supported by the National Natural Science Foundation of China （Grant Nos. 51404083 and 21273060）, the Natural Science Foundation of Heilongjiang Province （E2015065） and the Program for New Century Excellent Talents in Heilongjiang Provincial Universities （1253-NCET-010）.
文摘Fe3O4/MWCNTs nanocomposites were prepared by chemical oxidation coprecipitation method and developed as highly efficient heterogeneous Fenton-like catalyst. XRD results revealed that Fe3O4 nanoparticles deposited onto MWCNTs surface remained the inverse spinel crystal structure of cubic Fe3O4 phase. The FTIR characteristic peaks of MWCNTs weakened or disappeared due to the anchor of Fe3O4 nanoparticles and Fe-O peak at 570 cm^-1 was indicative of the formation of Fe3O4. TEM observation revealed that Fe3O4 nanoparticles were tightly anchored by MWCNTs. The Fenton-like catalytic activity of Fe3O4/MWCNTs nanocomposites for the discoloration of methyl orange （MO） was much higher than that of Fe3O4 nanoparticles. The process optimization of this heterogeneous Fenton-like system was implemented by response surface methodology （RSM）. The optimum conditions for MO discoloration were determined to be of 12.3 mmoi/L H2O2 concentration, 2.9 glL catalyst dosage, solution pH 2.7 and 39.3 min reaction time, with the maximum predicted value for MO discoloration ratio of 101.85%. The corresponding experimental value under the identical conditions was obtained as 99.86%, which was very close to the predicted one with the absolute deviation of 1.99%.
基金This work was financially supported by the Natural Science Foundation of Heilongjiang Province, China （No. E2015065）.
文摘Multi-walled carbon nanotubes （MWCNTs） can act not only as a support for Fe3O4 nanoparticles （NPs） but also as a coworker with synergistic effect, accordingly improving the heterogeneous Fenton-like efficiency of Fe3O4 NPs. In this study, Fe3O4 NPs were in situ anchored onto MWCNTs by a moderate co-precipitation method and the as-prepared Fe3O4/MWCNTs nanocomposites were employed as the highly efficient Fenton-like catalysts. The analyses of XRD, FTIR, Raman, FESEM, TEM and HRTEM results indicated the formation of Fe3O4 crystals in Fe3O4/MWCNTs nanocomposites prepared at different conditions and the interaction between Fe3O4 NPs and MWCNTs. Over a wide pH range, the surface of modified MWCNTs possessed negative charges. Based on these results, the possible combination mechanism between Fe3O4 NPs and MWCNTs was discussed and proposed. Moreover, the effects of preparation and catalytic conditions on the Fenton-like catalytic efficiency were investigated in order to gain further insight into the heterogeneous Fenton-like reaction catalyzed by Fe3O4/MWCNTs nanocomposites.
基金This work was financially supported by the Natural Science Foundation of Heilongjiang Province, China （Grant No. E2015065）.
文摘The kinetics and Fenton-like mechanism are two challenging tasks for heterogeneous Fenton-like catalytic oxidation of organic pollutants. In this study, three kinetic models were used for the kinetic studies of Fe3O4/MWCNTs-H2O2 Fenton-like reaction for MO degradation. The results indicated that this reaction followed the first- order kinetic model. The relationship of reaction rate constant and temperature followed the Arrhenius equation. The activation energy and frequency factor of this system were calculated as 8.2 kJ.mo1-1 and 2.72 s-1, respectively. The quantifications of Fe ions dissolution and ,OH radicals generation confirmed that the homogeneous and hetero- geneous catalyses were involved in Fe3O4/MWCNTs＇H2O2 Fenton-like reaction. The reaction rate constant was closely related with Fe ions dissolution and ,OH radicals generation. Fe3O4/MWCNTs nanocomposites had typical ferromagnetic property and could be easily separated from solution by an external magnet after being used. Furthermore, Fe3O4/MWCNTs nanocomposites exhibited good stability and recyclability. Finally, the Fenton-like mechanisms on homogeneous and heterogeneous catalyses were described.
文摘A composite paste electrode based on Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF)—initially synthesized by solgel method—and multiwall carbon nanotube (MWCNT) as a cathode in fuel cells is developed. The composite pastes are prepared by the direct mixing of BSCF:MWCNT at 90:10, 80:20 and 70:30 (% w/W). These electrodes are then characterized by the x-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption-desorption isotherm, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The XRD and SEM confirm the inclusion and the uniform dispersal of the MWCNT within BSCF, respectively. The nitrogen adsorption isotherm study shows that the porosity of the composite paste electrode has been improved by two-fold from the BSCF electrode. The EIS and CV demonstrate that the higher ratios of MWCNT in the composites are critical in improving the electronic conductivity as well as the kinetics. It is also noticeable that the electrode has increased the catalysis of oxygen in 0.1 M KOH (pH 12.0). Cyclic voltammetric studies on the oxygen reduction reaction (ORR) suggest that the incorporation of MWCNT is vital in improving the electrode (cathode) properties of a fuel cell.
文摘CO adsorption microcalorimetry was employed in the study of γ-Al-2O-3-supported Pt, Pt-Sn and Pt-Fe catalysts. The results indicated that the initial differential heat of CO adsorption of the Pt/γ-Al-2O-3 catalyst was 125 kJ/mol. As CO coverage increased, the differential heat of adsorption decreased. At higher coverages, the differential heat of adsorption decreased significantly. 60% of the differential heat of CO adsorption on the Pt/γ-Al-2O-3 catalyst was higher than 100 kJ/mol. No significant effect on the initial differential heat was found after adding Sn and Fe to the Pt/γ-Al-2O-3 catalyst. The amount of strong CO adsorption sites decreased, while the portion of CO adsorption sites with differential heat of 60110 kJ/mol increased after increasing the Sn or Fe content. This indicates that the surface adsorption energy was changed by adding Sn or Fe to Pt/γ-Al-2O-3. The distribution of differential heat of CO adsorption on the Pt-Sn（C）/γ-Al-2O-3 catalyst was broad and homogeneous. Comparison of the dehydrogenation performance of C-4 alkanes with the number of CO adsorption sites with differential heat of 60110 kJ/mol showed a good correlation. These results indicate that the surface Pt centers with differential heats of 60110 kJ/mol for CO adsorption possess superior activity for the dehydrogenation of alkanes.
基金the National Natural Science Foundation of China(Nos.22225807,21961132026,21878331,22021004,and 22109177)the National Key Research and Development Program(Nos.2020YFA0210903 and 2021YFA1501304)+4 种基金the PetroChina research institute of petroleum processing program(Nos.PRIKY21057 and PRIKY 21199)the Fundamental Research Funds for the Central Universities(No.2462020BJRC008)the support of Energy Internet Research Center,China University of Petroleum(Beijing),Haihe Laboratory of Sustainable Chemical Transformations(No.CYZC202105)the Beijing Synchrotron Radiation Facility(BSRF)Shanghai Synchrotron Radiation Facility(SSRF)during the XAFS measurements at the beamline of 1W1B,1W2B,and BL11B.
文摘Methylcyclohexane(MCH)serves as an ideal hydrogen carrier in hydrogen storage and transportation process.In the continuous production of hydrogen from MCH dehydrogenation,the rational design of energy-efficient catalytic way with good performance remains an enormous challenge.Herein,an internal electric heating(IEH)assisted mode was designed and proposed by the directly electrical-driven catalyst using the resistive heating effect.The Pt/Al2O_(3)on Fe foam(Pt/Al2O_(3)/FF)with unique threedimensional network structure was constructed.The catalysts were studied in a comprehensive way including X-ray diffraction(XRD),scanning electron microscopy(SEM)-mapping,in situ extended X-ray absorption fine structure(EXAFS),and in situ COFourier transform infrared(FTIR)measurements.It was found that the hydrogen evolution rate in IEH mode can reach up to above 2060 mmol·gPt^(−1)·min^(−1),which is 2–5 times higher than that of reported Pt based catalysts under similar reaction conditions in conventional heating(CH)mode.In combination with measurements from high-resolution infrared thermometer,the equations of heat transfer rate,and reaction heat analysis results,the Pt/Al2O_(3)/FF not only has high mass and heat transfer ability to promote catalytic performance,but also behaves as the heating component with a low thermal resistance and heat capacity offering a fast temperature response in IEH mode.In addition,the chemical adsorption and activation of MCH molecules can be efficiently facilitated by IEH mode,proved by the operando MCH-FTIR results.Therefore,the as-developed IEH mode can efficiently reduce the heat and mass transfer limitations and prominently boost the dehydrogenation performance,which has a broad application potential in hydrogen storage and other catalytic reaction processes.
