The preferential oxidation of CO (CO‐PROX) is a hot topic because of its importance in pro‐ton‐exchange membrane fuel cells (PEMFCs). Au catalysts are highly active in CO oxidation. Howev‐er, their activities ...The preferential oxidation of CO (CO‐PROX) is a hot topic because of its importance in pro‐ton‐exchange membrane fuel cells (PEMFCs). Au catalysts are highly active in CO oxidation. Howev‐er, their activities still need to be improved at the PEMFC operating temperatures of 80–120 °C. In the present study, Au nanoparticles of average size 2.6 nm supported on ceria‐modified Al2O3 were synthesized and characterized using powder X‐ray diffraction, nitrogen physisorption, transmission electron and scanning transmission electron microscopies, temperature‐programmed hydrogen reduction (H2‐TPR), Raman spectroscopy, and in situ diffuse‐reflectance infrared Fourier‐transform spectroscopy. Highly dispersed Au nanoparticles and strong structures formed by Au–support in‐teractions were the main active species on the ceria surface. The Raman and H2‐TPR results show that the improved catalytic performance of the Au catalysts can be attributed to enhanced strong metal–support interactions and the reducibility caused by ceria doping. The formation of oxygen vacancies on the catalysts increased their activities in CO‐PROX. The synthesized Au catalysts gave excellent catalytic performances with high CO conversions (>97%) and CO2 selectivities (>50%) in the temperature range 80–150 °C.展开更多
Chemical modification(CM)and deposition-precipitation(DP)methods were used for the dispersion of active Au nanoparticles on mesoporous silica materials in this work.XRD,TEM,N2 adsorption isotherms and UV-Vis absorptio...Chemical modification(CM)and deposition-precipitation(DP)methods were used for the dispersion of active Au nanoparticles on mesoporous silica materials in this work.XRD,TEM,N2 adsorption isotherms and UV-Vis absorption spectra were used to characterize in detail Au-SBA-15 materials prepared by the two methods. The analysis results showed that high loading(1.7%,by mass)and uniform Au nanoparticles(approximately 3 nm) were dispersed in the channels of mesoporous SBA-15 by the CM method.While for the DP method,most of Au nanoparticles with the size of 10—15nm were aggregated outside of the channels of SBA-15 and the actual loading of Au was only 0.38%(by mass).展开更多
Knowledge of the equilibrium bed-concentration is vital to mathematic a l modeling of the river-bed deformation associated with suspended load but prev i ous investigations only dealt with the reference concentration ...Knowledge of the equilibrium bed-concentration is vital to mathematic a l modeling of the river-bed deformation associated with suspended load but prev i ous investigations only dealt with the reference concentration of uniform sedime nt because of difficulties in observation of the bed-concentration. This work i s a first attempt to develop a theoretical formula for the equilibrium bed-conce n tration of any fraction of nonuniform sediment defined at the bed-surface. The f ormula is based on a stochastic-mechanistic model for the exchange of nonunifor m sediment near the bed, and described as a function of incipient motion probabil ity, non-ceasing probability, pick-up probability, and the ratio of the averag e single-step continuous motion time to static time. Comparison of bed-concentra ti on calculated from the proposed formula with the measured data showed satisfacto ry agreement, indicating the present formula can be used for solving the differe ntial equation governing the motion of suspended load.展开更多
Silica-dispersed NiMo hydrodesulfurization catalysts were synthesized by the deposition-precipitation method. For comparative purposes, bulk NiMo catalysts were obtained by co-precipitation. The silica-dispersed NiMo ...Silica-dispersed NiMo hydrodesulfurization catalysts were synthesized by the deposition-precipitation method. For comparative purposes, bulk NiMo catalysts were obtained by co-precipitation. The silica-dispersed NiMo catalyst had highly active metals content. Silica was employed to disperse active metals for full utilization of active components. The BET analysis showed that the silica-dispersed NiMo catalysts had a high surface area (147.0 m2/g) and pore volume (0.27 mL/g), whereas the bulk NiMo catalysts exhibited a very low surface area (87.5 m2/g). Transmission electron microscopy results proved that the active components were dispersed on the SiO2 substrate. X-ray diffraction patterns of the silicadispersed NiMo catalyst and the bulk NiMo catalyst were indexed to NiMoO4. The hydrodesulfurization activity of silicadispersed NiMo catalysts was much higher than that of reference catalysts and could be up to twice greater than those of commercial NiMo alumina-supported systems per gram of catalyst. The activity testing results also demonstrated that the silica-dispersed NiMo catalyst was an effective hydrodesulflarization catalyst.展开更多
Redox-sensitive elements in sediments, such as manganese (Mn), vanadium (V), molybdenum (Mo), and uranium (U), are promising indicators of past redox conditions during sedimentation and early diagenesis. Howev...Redox-sensitive elements in sediments, such as manganese (Mn), vanadium (V), molybdenum (Mo), and uranium (U), are promising indicators of past redox conditions during sedimentation and early diagenesis. However, in the Ontong Java Plateau, west equatorial Pacific, there are sparse datasets of redox-sensitive elements in sediment cores. Here, we present a 250 ka record of redox sensitive elements from a 460 cm gravity core at site WP7 (3~56'S, 156^.E, water depth 1 800 m), which was recovered from the southwest Ontong Java Plateau during the 1993 cruise of R/V Science I of the Institute of Oceanology, Chinese Academy of Sciences (IOCAS). Relative to the Post-Archean Australian Shale (PAAS), authigenic Mn, cobalt (Co), nickel (Ni), Mo, V, U, and cadmium (Cd) were found at constantly low levels except when peaks occurred at several depth intervals. Manganese, Co, Ni, and Mo concentrations were elevated at 25-35 cm due to Mn redox cycling. The core was divided into three distinct sections, the top 0-25 cm being oxic, a suboxic section at 25-35 cm and from 35-460 cm which was anoxic. Differential authigenic enrichments of Co, Ni, Mo, V, U, and Cd at the same depth intervals were observed indicating that the enrichments happened during sedimentation or diagenesis and suffered no post settlement redox changes. Therefore, no significant changes in redox conditions during sedimentation must have happened. The water at depth on the Ontong Java Plateau during past 250 ka must have been well oxygenated, possibly resulted from the more or less continuous presence of oxygen-rich deep water like the modem Antarctic Intermediate Water (AAIW) and Antarctic Circumpolar Water (ACW); while it's slightly less oxygenated in glacial intervals, possibly due to ventilation weakening and/or the surface productivity increase.展开更多
The largest Mesozoic northward transgression in Qangtang Basin of Qinghai-Xizang (Tibet) Plateau occurred during the Buqu Stage, Middle Jurassic. Mainly filled with carbonate rocks, the whole basin is composed of tran...The largest Mesozoic northward transgression in Qangtang Basin of Qinghai-Xizang (Tibet) Plateau occurred during the Buqu Stage, Middle Jurassic. Mainly filled with carbonate rocks, the whole basin is composed of transgression-regression sedimentary cycle. Field outcrops and indoor analysis revealed 8 types of sedimentary facies markers in this region. 4 types of sedimentary facies have been recognized: platform facies, platform marginal facies, foreslope facies and basin facies. Influenced by the northern Lazhuglung-Jinshajiang suture zone, central uplift region and southern Bangongco-Nujiang suture zone, these facies belts extended east-west. The sedimentary model was established based on observed depositional features. From their biological features and sedimentary characteristics, it is suggested that the paleoclimate was warm and humid at that time. The Buqu Formation is a promising target for oil and gas exploration in Shuanghu-Duoyong area in future.展开更多
Deposition-precipitation(DP)method is commonly used to prepare the supported metal catalysts.In this study,the modification effect of the mild DP method on the photocatalytic performance of TiO_(2)was investigated.The...Deposition-precipitation(DP)method is commonly used to prepare the supported metal catalysts.In this study,the modification effect of the mild DP method on the photocatalytic performance of TiO_(2)was investigated.The TiO_(2)samples with DP treatment,as well as Au/TiO_(2)prepared under the same conditions,showed enhanced photocatalytic performance of the degradation of methylene blue(MB).·OH generated by photoexcited holes is identified as the main intermediate reactive species during the degradation reaction.X-ray photoelectron spectroscopy(XPS)and Fourier transform infrared spectroscopy(FTIR)show that TiO_(2)(A)-17 after DP treatment has the most amount of surface OH^(-)_(ad)species.The presence of surface OH^(-)_(ad)species not only changes the surface zeta potential,favoring the attraction of cationic MB;but also depresses the electron-hole recombination,favoring photodegradation of MB by hole-produced·OH.An implication of these findings is that the modification of support properties should be taken into account while preparing supported metal catalysts using DP methods.展开更多
The Badain Jaran Desert exhibits the greatest difference in altitude of all of the world's deserts.On the slopes of megadunes in the desert,there are physical and chemical deposits produced by surface runoff.In ad...The Badain Jaran Desert exhibits the greatest difference in altitude of all of the world's deserts.On the slopes of megadunes in the desert,there are physical and chemical deposits produced by surface runoff.In addition,we have observed rarely-seen infiltration-excess surface runoff in the megadune depressions as well as spring streams at the base of megadunes.We used electron microscopy,energy spectrum analysis,infiltration experiments,moisture content determinations and grain-size analysis to study the mineral and chemical composition of the runoff precipitates,and grain-size of the deposits associated with the runoff,together with the hydrological balance in the megadune area,and the atmospheric precipitation mechanism responsible for groundwater recharge and for supplying water to lakes.The observations of shallow runoff and infiltration-excess surface runoff indicate the occurrence of strong and effective precipitation in summer,which would provide an important source for groundwater recharge.Several lines of evidence,such as the physical and chemical deposits resulting from shallow subsurface runoff,spring streams,infiltration-excess runoff,and gravity capillary water with a moisture content of 3-6%,demonstrate that precipitation reaches the base of the megadunes through infiltration and subsequently becomes groundwater.The chemical deposits,such as newly-formed calcite and gypsum,and gray-black physical deposits,as well as different stages in the development of fan-shaped landforms resulting from shallow subsurface runoff,indicate that groundwater recharge in the area is the result of long-term precipitation,rather than intermittent individual major rainfall events.Fine sand layers with a low infiltration capacity lead to subsurface runoff emerging at the ground surface.Five factors play an important role in maintaining a positive water balance and in replenishing groundwater via rainfall:effective rainfall as a water source,the high infiltration capacity of the sands enabling rainfall to rapidly become capillary water in the dunes,low evapotranspiration rates due to the sparse vegetation,the fact that the depth of the sand layer influenced by evaporation is shallow enough to maximize the deep infiltration of rainfall,and rapidly-moving gravity capillary water in the sandy dunes.These five factors together constitute a mechanism for groundwater recharge from rainfall,and explain the origin of the groundwater and lakes in the area.Our findings represent a significant advance in research on the hydrological cycle,including groundwater recharge conditions and recharge mechanisms,in this desert region.展开更多
基金supported by the National Basic Research Program of China (973 Program, 2013CB934104)the National Natural Science Founda-tion of China (21225312, U1303192)~~
文摘The preferential oxidation of CO (CO‐PROX) is a hot topic because of its importance in pro‐ton‐exchange membrane fuel cells (PEMFCs). Au catalysts are highly active in CO oxidation. Howev‐er, their activities still need to be improved at the PEMFC operating temperatures of 80–120 °C. In the present study, Au nanoparticles of average size 2.6 nm supported on ceria‐modified Al2O3 were synthesized and characterized using powder X‐ray diffraction, nitrogen physisorption, transmission electron and scanning transmission electron microscopies, temperature‐programmed hydrogen reduction (H2‐TPR), Raman spectroscopy, and in situ diffuse‐reflectance infrared Fourier‐transform spectroscopy. Highly dispersed Au nanoparticles and strong structures formed by Au–support in‐teractions were the main active species on the ceria surface. The Raman and H2‐TPR results show that the improved catalytic performance of the Au catalysts can be attributed to enhanced strong metal–support interactions and the reducibility caused by ceria doping. The formation of oxygen vacancies on the catalysts increased their activities in CO‐PROX. The synthesized Au catalysts gave excellent catalytic performances with high CO conversions (>97%) and CO2 selectivities (>50%) in the temperature range 80–150 °C.
基金Supported by the National Natural Science Foundation of China (No.20490204), Shanghai Municipal Science and Technology Commission of China (No.05DJ 14002) and Shanghai Municipal Education Commission of China.
文摘Chemical modification(CM)and deposition-precipitation(DP)methods were used for the dispersion of active Au nanoparticles on mesoporous silica materials in this work.XRD,TEM,N2 adsorption isotherms and UV-Vis absorption spectra were used to characterize in detail Au-SBA-15 materials prepared by the two methods. The analysis results showed that high loading(1.7%,by mass)and uniform Au nanoparticles(approximately 3 nm) were dispersed in the channels of mesoporous SBA-15 by the CM method.While for the DP method,most of Au nanoparticles with the size of 10—15nm were aggregated outside of the channels of SBA-15 and the actual loading of Au was only 0.38%(by mass).
文摘Knowledge of the equilibrium bed-concentration is vital to mathematic a l modeling of the river-bed deformation associated with suspended load but prev i ous investigations only dealt with the reference concentration of uniform sedime nt because of difficulties in observation of the bed-concentration. This work i s a first attempt to develop a theoretical formula for the equilibrium bed-conce n tration of any fraction of nonuniform sediment defined at the bed-surface. The f ormula is based on a stochastic-mechanistic model for the exchange of nonunifor m sediment near the bed, and described as a function of incipient motion probabil ity, non-ceasing probability, pick-up probability, and the ratio of the averag e single-step continuous motion time to static time. Comparison of bed-concentra ti on calculated from the proposed formula with the measured data showed satisfacto ry agreement, indicating the present formula can be used for solving the differe ntial equation governing the motion of suspended load.
基金the financial support from the National Basic Research Program(No. 2010CB226905) of China.
文摘Silica-dispersed NiMo hydrodesulfurization catalysts were synthesized by the deposition-precipitation method. For comparative purposes, bulk NiMo catalysts were obtained by co-precipitation. The silica-dispersed NiMo catalyst had highly active metals content. Silica was employed to disperse active metals for full utilization of active components. The BET analysis showed that the silica-dispersed NiMo catalysts had a high surface area (147.0 m2/g) and pore volume (0.27 mL/g), whereas the bulk NiMo catalysts exhibited a very low surface area (87.5 m2/g). Transmission electron microscopy results proved that the active components were dispersed on the SiO2 substrate. X-ray diffraction patterns of the silicadispersed NiMo catalyst and the bulk NiMo catalyst were indexed to NiMoO4. The hydrodesulfurization activity of silicadispersed NiMo catalysts was much higher than that of reference catalysts and could be up to twice greater than those of commercial NiMo alumina-supported systems per gram of catalyst. The activity testing results also demonstrated that the silica-dispersed NiMo catalyst was an effective hydrodesulflarization catalyst.
基金Supported by the Pilot Project of the National Knowledge Innovation Program of the Chinese Academy of Sciences(No.KZCX2-YW-221)the National Basic Research Program of China(973 Program)(No.2007CB815903)+2 种基金the Pilot Project of the National Knowledge Innovation Program of Institute of Oceanology,Chinese Academy of Sciences(No.2007-10)the National Natural Science Foundation of China(No.40906038)the Open Foundation of the State Key Laboratory of Marine Geology(No.MG0903)
文摘Redox-sensitive elements in sediments, such as manganese (Mn), vanadium (V), molybdenum (Mo), and uranium (U), are promising indicators of past redox conditions during sedimentation and early diagenesis. However, in the Ontong Java Plateau, west equatorial Pacific, there are sparse datasets of redox-sensitive elements in sediment cores. Here, we present a 250 ka record of redox sensitive elements from a 460 cm gravity core at site WP7 (3~56'S, 156^.E, water depth 1 800 m), which was recovered from the southwest Ontong Java Plateau during the 1993 cruise of R/V Science I of the Institute of Oceanology, Chinese Academy of Sciences (IOCAS). Relative to the Post-Archean Australian Shale (PAAS), authigenic Mn, cobalt (Co), nickel (Ni), Mo, V, U, and cadmium (Cd) were found at constantly low levels except when peaks occurred at several depth intervals. Manganese, Co, Ni, and Mo concentrations were elevated at 25-35 cm due to Mn redox cycling. The core was divided into three distinct sections, the top 0-25 cm being oxic, a suboxic section at 25-35 cm and from 35-460 cm which was anoxic. Differential authigenic enrichments of Co, Ni, Mo, V, U, and Cd at the same depth intervals were observed indicating that the enrichments happened during sedimentation or diagenesis and suffered no post settlement redox changes. Therefore, no significant changes in redox conditions during sedimentation must have happened. The water at depth on the Ontong Java Plateau during past 250 ka must have been well oxygenated, possibly resulted from the more or less continuous presence of oxygen-rich deep water like the modem Antarctic Intermediate Water (AAIW) and Antarctic Circumpolar Water (ACW); while it's slightly less oxygenated in glacial intervals, possibly due to ventilation weakening and/or the surface productivity increase.
基金Sponsored by National Ninth Five Year Plan Science and Technology Project (970204-01-01).
文摘The largest Mesozoic northward transgression in Qangtang Basin of Qinghai-Xizang (Tibet) Plateau occurred during the Buqu Stage, Middle Jurassic. Mainly filled with carbonate rocks, the whole basin is composed of transgression-regression sedimentary cycle. Field outcrops and indoor analysis revealed 8 types of sedimentary facies markers in this region. 4 types of sedimentary facies have been recognized: platform facies, platform marginal facies, foreslope facies and basin facies. Influenced by the northern Lazhuglung-Jinshajiang suture zone, central uplift region and southern Bangongco-Nujiang suture zone, these facies belts extended east-west. The sedimentary model was established based on observed depositional features. From their biological features and sedimentary characteristics, it is suggested that the paleoclimate was warm and humid at that time. The Buqu Formation is a promising target for oil and gas exploration in Shuanghu-Duoyong area in future.
基金supported by the National Key Research and Development Program of China(No.2021YFA1500403)the National Natural Science Foundation of China(No.21773047 and No.U1832180)partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication.
文摘Deposition-precipitation(DP)method is commonly used to prepare the supported metal catalysts.In this study,the modification effect of the mild DP method on the photocatalytic performance of TiO_(2)was investigated.The TiO_(2)samples with DP treatment,as well as Au/TiO_(2)prepared under the same conditions,showed enhanced photocatalytic performance of the degradation of methylene blue(MB).·OH generated by photoexcited holes is identified as the main intermediate reactive species during the degradation reaction.X-ray photoelectron spectroscopy(XPS)and Fourier transform infrared spectroscopy(FTIR)show that TiO_(2)(A)-17 after DP treatment has the most amount of surface OH^(-)_(ad)species.The presence of surface OH^(-)_(ad)species not only changes the surface zeta potential,favoring the attraction of cationic MB;but also depresses the electron-hole recombination,favoring photodegradation of MB by hole-produced·OH.An implication of these findings is that the modification of support properties should be taken into account while preparing supported metal catalysts using DP methods.
基金supported by the Major Projects of International Cooperation of National Natural Science Foundation of China(Grant Nos.41210002 & 40672108)the Cheung Kong Scholars Programme of the Ministry of Education of China(Grant No.801813)
文摘The Badain Jaran Desert exhibits the greatest difference in altitude of all of the world's deserts.On the slopes of megadunes in the desert,there are physical and chemical deposits produced by surface runoff.In addition,we have observed rarely-seen infiltration-excess surface runoff in the megadune depressions as well as spring streams at the base of megadunes.We used electron microscopy,energy spectrum analysis,infiltration experiments,moisture content determinations and grain-size analysis to study the mineral and chemical composition of the runoff precipitates,and grain-size of the deposits associated with the runoff,together with the hydrological balance in the megadune area,and the atmospheric precipitation mechanism responsible for groundwater recharge and for supplying water to lakes.The observations of shallow runoff and infiltration-excess surface runoff indicate the occurrence of strong and effective precipitation in summer,which would provide an important source for groundwater recharge.Several lines of evidence,such as the physical and chemical deposits resulting from shallow subsurface runoff,spring streams,infiltration-excess runoff,and gravity capillary water with a moisture content of 3-6%,demonstrate that precipitation reaches the base of the megadunes through infiltration and subsequently becomes groundwater.The chemical deposits,such as newly-formed calcite and gypsum,and gray-black physical deposits,as well as different stages in the development of fan-shaped landforms resulting from shallow subsurface runoff,indicate that groundwater recharge in the area is the result of long-term precipitation,rather than intermittent individual major rainfall events.Fine sand layers with a low infiltration capacity lead to subsurface runoff emerging at the ground surface.Five factors play an important role in maintaining a positive water balance and in replenishing groundwater via rainfall:effective rainfall as a water source,the high infiltration capacity of the sands enabling rainfall to rapidly become capillary water in the dunes,low evapotranspiration rates due to the sparse vegetation,the fact that the depth of the sand layer influenced by evaporation is shallow enough to maximize the deep infiltration of rainfall,and rapidly-moving gravity capillary water in the sandy dunes.These five factors together constitute a mechanism for groundwater recharge from rainfall,and explain the origin of the groundwater and lakes in the area.Our findings represent a significant advance in research on the hydrological cycle,including groundwater recharge conditions and recharge mechanisms,in this desert region.