A series of K-promoted Pt/Al2O3 catalysts were tested for CO oxidation. It was found that the addition of K significantly enhanced the activity. A detailed kinetic study showed that the activation energies of the K-co...A series of K-promoted Pt/Al2O3 catalysts were tested for CO oxidation. It was found that the addition of K significantly enhanced the activity. A detailed kinetic study showed that the activation energies of the K-containing catalysts were lower than those of the K-free ones, particularly for catalysts with high Pt contents （51.6 k）/mol for 0.42K-2.0Pt/Al2O3 and 6：3.6 kJ/mol for 2.0Pt/Al2O3 ）. The CO reaction orders were higher for the K-containing catalysts （about -0.2） than for the K-free ones （about -0.5）, with the former having much lower equilibrium constants for CO adsorption than the latter. In situ Fourier-transform infrared spectroscopy showed that surface CO desorption from the 0.42K-2.0Pt/Al2O3 catalyst was easier than from 2.0Pt/Al2O3. The promoting effect of K was therefore caused by weakening of the interactions between CO and surface Pt atoms. This decreased coverage of the catalyst with CO and facilitated competitive O2 chemisorption on the Pt surface, and significantly lowered the reaction barrier between chemisorbed CO and O2 species.展开更多
Eco-physiological responses of seedlings of eight species, Pinus koraiensis, Picea koraiensis, Larix olgensis, Populus ussuriensis, Betula platyphylla, Tilia amurensis, Traxinus mandshurica and Acer mono from broadlea...Eco-physiological responses of seedlings of eight species, Pinus koraiensis, Picea koraiensis, Larix olgensis, Populus ussuriensis, Betula platyphylla, Tilia amurensis, Traxinus mandshurica and Acer mono from broadleaved/Korean pine forest, to elevated CO2 were studied by using open-top chambers under natural sunlight in Changbai Mountain, China in two growing seasons (1998-1999). Two concentrations of CO2 were designed: elevated CO2 (700 祄olmol-1) and ambient CO2 (400 祄olmol-1). The study results showed that the height growth of the tree seedlings grown at elevated CO2 increased by about 10%-40% compared to those grown at ambient CO2. And the water using efficiency of seedlings also followed the same tendency. However, the responses of seedlings in transpiration and chlorophyll content to elevated CO2 varied with tree species. The broad-leaf tree species were more sensitive to the elevated CO2 than conifer tree species. All seedlings showed a photosynthetic acclimation to long-term elevated CO2.展开更多
Elucidation of the CuOx-CeO2 interactions is of great interest and importance in understanding complex CuOx-CeO2 interfacial catalysis in various reactions. In the present work, we have investigated structures and cat...Elucidation of the CuOx-CeO2 interactions is of great interest and importance in understanding complex CuOx-CeO2 interfacial catalysis in various reactions. In the present work, we have investigated structures and catalytic activity in CO oxidation of CuOx species on CeO2 rods, cubes and polyhedra predominantly exposing {110}+{100}, {100} and {111} facets by the incipient wetness impregnation method with the lowest Cu loading of 0.025%. The structural evolution of CuOx species was found to depend on both the Cu loading and the CeO2 morphology. As the Cu loading increases, CuOx species are deposited preferentially on the surface defect of CeO2 and then aggregate and grow, accompanied by the formation of isolated Cu ions, CuOx clusters strongly/weakly interacting with the CeO2, highly dispersed Cu O nanoparticles, and large Cu O nanoparticles. The isolated Cu^+ species and CuOx clusters weakly interacting with the CeO2 were observed mainly on the O-terminated CeO2{100} facets. Meanwhile, more Cu(I) species are stabilized during CO reduction processes in CuOx/c-CeO2 catalysts than in CuOx/r-CeO2 and CuOx/p-CeO2 catalysts. The catalytic activities of various CuOx/CeO2 catalysts in CO oxidation vary with both the CuOx species and the CeO2 morphology. These results comprehensively elucidate the CuOx-CeO2 interactions and exemplify their morphology-dependence.展开更多
MXenes have attracted considerable attention owing to their versatile and excellent physicochemi‐cal properties.Especially,they have potential applications as robust support for single atom cata‐lysts.Here,quantum c...MXenes have attracted considerable attention owing to their versatile and excellent physicochemi‐cal properties.Especially,they have potential applications as robust support for single atom cata‐lysts.Here,quantum chemical studies with density functional theory are carried out to systemati‐cally investigate the geometries,stability,electronic properties of oxygen functionalized Ti_(2)C(Ti_(2)CO_(2))supported single‐atom catalysts M_(1)/Ti_(2)CO_(2)(M=Fe,Co,Ni,Cu Ru,Rh,Pd,Ag Os,Ir,Pt,Au).A new non‐noble metal SAC Fe_(1)/Ti_(2)CO_(2) has been found to show excellent catalytic performance for low‐temperature CO oxidation after screening the group 8‐11 transition metals.We find that O_(2) and CO adsorption on Fe_(1) atom of Fe_(1)/Ti_(2)CO_(2) is favorable.Accordingly,five possible mechanisms for CO oxidation on this catalyst are evaluated,including Eley‐Rideal,Langmuir‐Hinshelwood,Mars-van Krevelen,Termolecular Eley‐Rideal,and Termolecular Langmuir‐Hinshelwood(TLH)mechanisms.Based on the calculated reaction energies for different pathways,Fe_(1)/Ti_(2)CO_(2) shows excellent kinet‐ics for CO oxidation via TLH mechanism,with distinct low‐energy barrier(0.20 eV)for the rate‐determining step.These results demonstrate that Fe_(1)/Ti_(2)CO_(2) MXene is highly promising 2D materials for building robust non‐noble metal catalysts.展开更多
The mixed metal/metal sulphide(Ag@CoS)with reduced graphene oxide(rGO)nanocomposite(Ag@CoS/rGO)was synthesized for the possible electrode in supercapacitors.Ag@CoS was successfully deposited on the rGO nanosheets by h...The mixed metal/metal sulphide(Ag@CoS)with reduced graphene oxide(rGO)nanocomposite(Ag@CoS/rGO)was synthesized for the possible electrode in supercapacitors.Ag@CoS was successfully deposited on the rGO nanosheets by hydrothermal method,implying the growth of 2D Ag and CoS-based hexagonal-like structure on the rGO framework.The synthesized nanocomposite was subjected to structural,morphological and electrochemical studies.The XRD results show that the prepared nanocomposite material exhibits a combination of hexagonal and cubic phase due to the presence of CoS and Ag phases together.The band appearing at nearly 470.33 cm^−1 in FTIR spectra can be ascribed to the absorption of S—S bond in the Ag@CoS/rGO nanocomposite.The clear hexagonal structure was analysed by SEM and TEM with the grain sizes ranging from nanometer to micrometer.The electrode material exhibits excellent cyclic stability with a specific capacitance of 1580 F/g at a current density of 0.5 A/g without any loss of capacitive retention even after 1000 cycles.Based on the electrochemical performance,it can be inferred that the prepared novel nanocomposite material is very suitable for using as an electrode for electrochemical supercapacitor applications.展开更多
Large surface areas nano-scale zirconia was prepared by the self-assembly route and was employed as support in nickel catalysts for the CO selective methanation. The effects of Ni loading and the catalyst calcination ...Large surface areas nano-scale zirconia was prepared by the self-assembly route and was employed as support in nickel catalysts for the CO selective methanation. The effects of Ni loading and the catalyst calcination temperature on the performance of the catalyst for CO selective methanation reaction were investigated. The cata- lysts were characterized by Brunauer-Emmett-Teller （BET）, transmission electron microscope （TEM）, X-ray dif- fraction （XRD） and temperature-programmed reduction （TPR）. The results showed that the as-synthesized Ni/nano-ZrO2 catalysts presented high activity for CO methanation due to the interaction between Ni active particle and nano zir- conia support. The selectivity for the CO methanation influenced significantly by the particle size of the active Ni species. The exorbitant calcination resulted in the conglomeration of dispersive Ni particles and led to the decrease of CO methanation selectivity. Among the catalysts studied, the 7.5% （by mass） Ni/ZrO2 catalyst calcinated at 500℃ was the most effective for the CO selective methanation. It can preferentially catalyze the CO methanation with a higher 99% conversion in the CO/CO2 competitive methanation system over the temperature range of 260-280℃, while keeping the CO2 conversion relatively low.展开更多
基金financially supported by the National Natural Science Foundation of China(21173195)~~
文摘A series of K-promoted Pt/Al2O3 catalysts were tested for CO oxidation. It was found that the addition of K significantly enhanced the activity. A detailed kinetic study showed that the activation energies of the K-containing catalysts were lower than those of the K-free ones, particularly for catalysts with high Pt contents （51.6 k）/mol for 0.42K-2.0Pt/Al2O3 and 6：3.6 kJ/mol for 2.0Pt/Al2O3 ）. The CO reaction orders were higher for the K-containing catalysts （about -0.2） than for the K-free ones （about -0.5）, with the former having much lower equilibrium constants for CO adsorption than the latter. In situ Fourier-transform infrared spectroscopy showed that surface CO desorption from the 0.42K-2.0Pt/Al2O3 catalyst was easier than from 2.0Pt/Al2O3. The promoting effect of K was therefore caused by weakening of the interactions between CO and surface Pt atoms. This decreased coverage of the catalyst with CO and facilitated competitive O2 chemisorption on the Pt surface, and significantly lowered the reaction barrier between chemisorbed CO and O2 species.
基金The project was supported by National Key Basic Development of China (G1999043400) and the grant KZCX-406-4 KZCX1SW01 of the Chinese Academy of Sciences
文摘Eco-physiological responses of seedlings of eight species, Pinus koraiensis, Picea koraiensis, Larix olgensis, Populus ussuriensis, Betula platyphylla, Tilia amurensis, Traxinus mandshurica and Acer mono from broadleaved/Korean pine forest, to elevated CO2 were studied by using open-top chambers under natural sunlight in Changbai Mountain, China in two growing seasons (1998-1999). Two concentrations of CO2 were designed: elevated CO2 (700 祄olmol-1) and ambient CO2 (400 祄olmol-1). The study results showed that the height growth of the tree seedlings grown at elevated CO2 increased by about 10%-40% compared to those grown at ambient CO2. And the water using efficiency of seedlings also followed the same tendency. However, the responses of seedlings in transpiration and chlorophyll content to elevated CO2 varied with tree species. The broad-leaf tree species were more sensitive to the elevated CO2 than conifer tree species. All seedlings showed a photosynthetic acclimation to long-term elevated CO2.
文摘Elucidation of the CuOx-CeO2 interactions is of great interest and importance in understanding complex CuOx-CeO2 interfacial catalysis in various reactions. In the present work, we have investigated structures and catalytic activity in CO oxidation of CuOx species on CeO2 rods, cubes and polyhedra predominantly exposing {110}+{100}, {100} and {111} facets by the incipient wetness impregnation method with the lowest Cu loading of 0.025%. The structural evolution of CuOx species was found to depend on both the Cu loading and the CeO2 morphology. As the Cu loading increases, CuOx species are deposited preferentially on the surface defect of CeO2 and then aggregate and grow, accompanied by the formation of isolated Cu ions, CuOx clusters strongly/weakly interacting with the CeO2, highly dispersed Cu O nanoparticles, and large Cu O nanoparticles. The isolated Cu^+ species and CuOx clusters weakly interacting with the CeO2 were observed mainly on the O-terminated CeO2{100} facets. Meanwhile, more Cu(I) species are stabilized during CO reduction processes in CuOx/c-CeO2 catalysts than in CuOx/r-CeO2 and CuOx/p-CeO2 catalysts. The catalytic activities of various CuOx/CeO2 catalysts in CO oxidation vary with both the CuOx species and the CeO2 morphology. These results comprehensively elucidate the CuOx-CeO2 interactions and exemplify their morphology-dependence.
文摘MXenes have attracted considerable attention owing to their versatile and excellent physicochemi‐cal properties.Especially,they have potential applications as robust support for single atom cata‐lysts.Here,quantum chemical studies with density functional theory are carried out to systemati‐cally investigate the geometries,stability,electronic properties of oxygen functionalized Ti_(2)C(Ti_(2)CO_(2))supported single‐atom catalysts M_(1)/Ti_(2)CO_(2)(M=Fe,Co,Ni,Cu Ru,Rh,Pd,Ag Os,Ir,Pt,Au).A new non‐noble metal SAC Fe_(1)/Ti_(2)CO_(2) has been found to show excellent catalytic performance for low‐temperature CO oxidation after screening the group 8‐11 transition metals.We find that O_(2) and CO adsorption on Fe_(1) atom of Fe_(1)/Ti_(2)CO_(2) is favorable.Accordingly,five possible mechanisms for CO oxidation on this catalyst are evaluated,including Eley‐Rideal,Langmuir‐Hinshelwood,Mars-van Krevelen,Termolecular Eley‐Rideal,and Termolecular Langmuir‐Hinshelwood(TLH)mechanisms.Based on the calculated reaction energies for different pathways,Fe_(1)/Ti_(2)CO_(2) shows excellent kinet‐ics for CO oxidation via TLH mechanism,with distinct low‐energy barrier(0.20 eV)for the rate‐determining step.These results demonstrate that Fe_(1)/Ti_(2)CO_(2) MXene is highly promising 2D materials for building robust non‐noble metal catalysts.
文摘The mixed metal/metal sulphide(Ag@CoS)with reduced graphene oxide(rGO)nanocomposite(Ag@CoS/rGO)was synthesized for the possible electrode in supercapacitors.Ag@CoS was successfully deposited on the rGO nanosheets by hydrothermal method,implying the growth of 2D Ag and CoS-based hexagonal-like structure on the rGO framework.The synthesized nanocomposite was subjected to structural,morphological and electrochemical studies.The XRD results show that the prepared nanocomposite material exhibits a combination of hexagonal and cubic phase due to the presence of CoS and Ag phases together.The band appearing at nearly 470.33 cm^−1 in FTIR spectra can be ascribed to the absorption of S—S bond in the Ag@CoS/rGO nanocomposite.The clear hexagonal structure was analysed by SEM and TEM with the grain sizes ranging from nanometer to micrometer.The electrode material exhibits excellent cyclic stability with a specific capacitance of 1580 F/g at a current density of 0.5 A/g without any loss of capacitive retention even after 1000 cycles.Based on the electrochemical performance,it can be inferred that the prepared novel nanocomposite material is very suitable for using as an electrode for electrochemical supercapacitor applications.
基金Supported by the National Natural Science Foundation of China(21276054,21376280)
文摘Large surface areas nano-scale zirconia was prepared by the self-assembly route and was employed as support in nickel catalysts for the CO selective methanation. The effects of Ni loading and the catalyst calcination temperature on the performance of the catalyst for CO selective methanation reaction were investigated. The cata- lysts were characterized by Brunauer-Emmett-Teller （BET）, transmission electron microscope （TEM）, X-ray dif- fraction （XRD） and temperature-programmed reduction （TPR）. The results showed that the as-synthesized Ni/nano-ZrO2 catalysts presented high activity for CO methanation due to the interaction between Ni active particle and nano zir- conia support. The selectivity for the CO methanation influenced significantly by the particle size of the active Ni species. The exorbitant calcination resulted in the conglomeration of dispersive Ni particles and led to the decrease of CO methanation selectivity. Among the catalysts studied, the 7.5% （by mass） Ni/ZrO2 catalyst calcinated at 500℃ was the most effective for the CO selective methanation. It can preferentially catalyze the CO methanation with a higher 99% conversion in the CO/CO2 competitive methanation system over the temperature range of 260-280℃, while keeping the CO2 conversion relatively low.
