如果说由Lasaga和Kirkpatrick编篡的Kinetics of Geochemical l’rocesses(矿物学论评之八,1981)标志着以均匀相溶液化学为理论基础的传统地球化学时代的结束,地球化学家逐渐认识并承认绝大多数地质作用都发生在固、液、气相共存的不均...如果说由Lasaga和Kirkpatrick编篡的Kinetics of Geochemical l’rocesses(矿物学论评之八,1981)标志着以均匀相溶液化学为理论基础的传统地球化学时代的结束,地球化学家逐渐认识并承认绝大多数地质作用都发生在固、液、气相共存的不均匀多相体系中,表面反应控制着地球化学作用的话,那么Hochella和White编辑出版的Mineral—Water Interface Geochemistry(矿物学论评之二十三,1990)则是这一研究的深化。展开更多
MoS_2 samples with controllable morphologies and structures were synthesized using surfactantassisted hydrothermal processes.The effects of surfactants（PEG,PVP,P123,SDS,AOT,and CTAB）on the morphologies and structure...MoS_2 samples with controllable morphologies and structures were synthesized using surfactantassisted hydrothermal processes.The effects of surfactants（PEG,PVP,P123,SDS,AOT,and CTAB）on the morphologies and structures of MoS_2 samples were investigated.The results revealed that spherical,bulk-like,and flower-like MoS_2 particles assembled by NH4~＋-intercalated MoS_2 nano-sheets were synthesized.The morphologies of the MoS_2 samples and their structures（including the slab length and the number of stacked layers） of MoS_2 nano-sheets in these samples could be controlled by adjusting the surfactants.Mono-dispersed spherical MoS_2 particles could be synthesized with PEG via the creation of MoS_2 nano-sheets with slab lengths shorter than 15 nm and fewer than six stacked layers.Possible formation mechanisms of these MoS_2 samples created via surfactant-assisted hydrothermal processes are proposed.Further,the catalytic activities of MoS_2 samples for anthracene hydrogenation were evaluated in a slurry-bed reactor.The catalyst synthesized with the surfactant PEG exhibited the highest catalytic hydrogenation activity.Compared with the other catalysts,it had a smaller particle size,mono-dispersed spherical morphology,shorter slab length,and fewer stacked layers;these were all beneficial to exposing its active edges.This work provides an efficient approach to synthesize transition metal sulfides with controllable morphologies and structures.展开更多
The interaction of O2 with pyrite, marcasite and pyrrhotite surfaces was studied using first-principle calculations to obtain the oxidization mechanisms of these minerals. The results show that the adsorption energy o...The interaction of O2 with pyrite, marcasite and pyrrhotite surfaces was studied using first-principle calculations to obtain the oxidization mechanisms of these minerals. The results show that the adsorption energy of O2 on pyrrhotite surface is the largest, followed by that on marcasite surface and then pyrite surface. O2 molecules adsorbed on pyrite, marcasite and pyrrhotite surfaces are all dissociated. The oxygen atoms and surface atoms of pyrite, marcasite and pyrrhotite surfaces have different bonding structures. Due to more atoms on pyrrhotite and marcasite surfaces interaction with oxygen atoms, the adsorption energies of O2 on pyrrhotite and marcasite surfaces are larger than that on pyrite surface. Larger values of Mulliken populations for O？Fe bond of pyrrhotite surface result in relative larger adsorption energy compared with that on marcasite surface.展开更多
Novel silver/silver molybdate（Ag/Ag2MoO4） composites with surface plasmon resonance（SPR）-enhanced photocatalytic performance were successfully fabricated via a facile one-pot hydrothermal route with the presence o...Novel silver/silver molybdate（Ag/Ag2MoO4） composites with surface plasmon resonance（SPR）-enhanced photocatalytic performance were successfully fabricated via a facile one-pot hydrothermal route with the presence of sodium dodecyl sulfate（SDS） in this study.The as prepared silver/silver molybdate（Ag/Ag2MoO4） composites were systematically characterized by X-ray diffraction（XRD）,scanning electron microscopy（SEM） and ultraviolet-visible diffuse reflectance absorption spectroscopy（DRS） in order to investigate their crystal structure,morphology and optical property as well.The photocatalytic activities of the composites were subsequently evaluated by their ability to degrade rhodamine B（RhB） under visible-light irradiation.Varies of controlled experiments were then carefully operated to gain a deep insight into the assembling of Ag/Ag2MoO4composites.It was found that preparation conditions such as pH,reaction time,and the amount of surfactant played important roles in the formation of composites with octahedral microstructures.And the composite obtained at 160 ℃ using 0.5 g of sodium dodecyl sulfate exhibited the highest photocatalytic performance under visible-light irradiation.Capture experiments were also conducted to clarify the function of different active species generated on the surface of Ag/Ag2MoO4during the photocatalytic process,in which both holes and ·OH radicals were found to play crucial role in photocatalytic removal of RhB under visible light irradiation.A possible photocatalytic mechanism of Ag/Ag2MoO4 was finally proposed on the basis of all the results to explain the higher photocatalytic activity of the octahedral Ag/Ag2MoO4 composites.It was inferred that the photoinduced ＂hot＂ electrons can quickly transfer from the Ag NPs to the conduction band of Ag2MoO4 and react with oxygen and H2O to generate a large quality of active radicals such as ·OH and ·O2^- because of the SPR effects.Besides,this SPR effects of Ag nanoparticles deposited on the surface of Ag2MoO4 can not only dramatically amplify its light absorption,especially in the visible region,but also promote the separation of photoexcited electron-hole pairs and effectively decrease electron-hole recombination.展开更多
Hydrogen peroxide was used as an oxidant to modify the cuprite surface and enhance its sulfidization.Surface-adsorption and infrared spectroscopy measurements indicated that the modification of the cuprite surface wit...Hydrogen peroxide was used as an oxidant to modify the cuprite surface and enhance its sulfidization.Surface-adsorption and infrared spectroscopy measurements indicated that the modification of the cuprite surface with hydrogen peroxide before sulfidization increased the adsorption capacity of xanthate.Zeta potential,scanning electron microscopy-energy dispersive X-ray spectroscopy,X-ray photoelectron spectroscopy,and time-of-flight secondary ion mass spectrometry results showed that the modification with hydrogen peroxide increased the contents of S^(2−)and Sn^(2−)species on the cuprite surface.Microflotation tests showed that the recovery of cuprite increased from 61.74%to 83.30%after the modification of the surface with hydrogen peroxide.These results confirm that the modification of the cuprite surface with hydrogen peroxide enhances the sulfidization of cuprite,which in turn improves its flotation.展开更多
The effect of molybdenum oxide on the activity and durability of Ce O2-Ti O2 catalyst for NO reduction by NH3 was examined. It was found that the introduction of Mo could improve the low-temperature NH3-SCR activity a...The effect of molybdenum oxide on the activity and durability of Ce O2-Ti O2 catalyst for NO reduction by NH3 was examined. It was found that the introduction of Mo could improve the low-temperature NH3-SCR activity and SO2/H2 O durability of the Ce O2-Ti O2 catalyst and an optimal loading of Mo was 4?wt.%. The best Mo O3/Ce O2-Ti O2 catalyst displayed over 90% NO conversion from 200 °C to 400 °C and obtained 4-fold increase in NO conversion compared to Ce O2-Ti O2 at 150 °C. The characterization results revealed that the number of Br?nsted acid sites over Mo O3/Ce O2-Ti O2 was significantly increased, and the adsorption of nitrate species was dramatically weakened because of the coverage of Mo O3, which were favorable for the high NH3-SCR performance. It is believed that the Mo O3/Ce O2-Ti O2 catalyst is a suitable substitute for the NH3-SCR reaction.展开更多
Pyrite （FeS2） bulk and （100） surface properties and the oxygen adsorption on the surface were studied by using density functional theory methods. The results show that in the formation of FeS2 （100） surface, the...Pyrite （FeS2） bulk and （100） surface properties and the oxygen adsorption on the surface were studied by using density functional theory methods. The results show that in the formation of FeS2 （100） surface, there exists a process of electron transfer from Fe dangling bond to S dangling bond. In this situation, surface Fe and S atoms have more ionic properties. Both Fe2+ and S2- have high electrochemistry reduction activity, which is the base for oxygen adsorption. From the viewpoint of adsorption energy, the parallel form oxygen adsorption is in preference. The result also shows that the state of oxygen absorbed on FeS2 surface acts as peroxides rather than O2.展开更多
Highly selective electrocatalytic semihydrogenation of alkynes to alkenes with water as the hydrogen source over palladium-based electrocatalysts is significant but remains a great challenge because of the excessive h...Highly selective electrocatalytic semihydrogenation of alkynes to alkenes with water as the hydrogen source over palladium-based electrocatalysts is significant but remains a great challenge because of the excessive hydrogenation capacity of palladium.Here,we propose that an ideal palladium catalyst should possess weak alkene adsorption and inhibit subsurface hydrogen formation to stimulate the high selectivity of alkyne semihydrogenation.Therefore,sulfur-modified Pd nanowires(Pd-S NWs)are designedly prepared by a solid-solution interface sulfuration method with KSCN as the sulfur source.The introduction of S weakens the alkene adsorption and prevents the diffusion of active hydrogen(H^(*))into the Pd lattice to form unfavorable subsurface H^(*).As a result,electrocatalytic alkyne semihydrogenation is achieved over a Pd-S NWs cathode with wide substrate scopes,potential-independent up to 99%alkene selectivity,good fragile groups compatibility,and easily synthesized deuterated alkenes.An adsorbed hydrogen addition mechanism of this semihydrogenation reaction is proposed.Importantly,an easy modification of commercial Pd/C by in situ addition of SCN–enabling the gram-scale synthesis of an alkene with 99%selectivity and 95%conversion highlights the promising potential of our method.展开更多
基金supported by the National Natural Science Foundation of China(21303186)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA07020300)~~
文摘MoS_2 samples with controllable morphologies and structures were synthesized using surfactantassisted hydrothermal processes.The effects of surfactants（PEG,PVP,P123,SDS,AOT,and CTAB）on the morphologies and structures of MoS_2 samples were investigated.The results revealed that spherical,bulk-like,and flower-like MoS_2 particles assembled by NH4~＋-intercalated MoS_2 nano-sheets were synthesized.The morphologies of the MoS_2 samples and their structures（including the slab length and the number of stacked layers） of MoS_2 nano-sheets in these samples could be controlled by adjusting the surfactants.Mono-dispersed spherical MoS_2 particles could be synthesized with PEG via the creation of MoS_2 nano-sheets with slab lengths shorter than 15 nm and fewer than six stacked layers.Possible formation mechanisms of these MoS_2 samples created via surfactant-assisted hydrothermal processes are proposed.Further,the catalytic activities of MoS_2 samples for anthracene hydrogenation were evaluated in a slurry-bed reactor.The catalyst synthesized with the surfactant PEG exhibited the highest catalytic hydrogenation activity.Compared with the other catalysts,it had a smaller particle size,mono-dispersed spherical morphology,shorter slab length,and fewer stacked layers;these were all beneficial to exposing its active edges.This work provides an efficient approach to synthesize transition metal sulfides with controllable morphologies and structures.
基金Project supported by the High Level Innovation Team and Outstanding Scholar Program in Guangxi Colleges(the second batch),ChinaProjects(51304054+1 种基金51364002)supported by the National Natural Science Foundation of ChinaProject supported by the Open Foundation of Guangxi Colleges and University Key Laboratory of Minerals Engineering in Guangxi University,China
文摘The interaction of O2 with pyrite, marcasite and pyrrhotite surfaces was studied using first-principle calculations to obtain the oxidization mechanisms of these minerals. The results show that the adsorption energy of O2 on pyrrhotite surface is the largest, followed by that on marcasite surface and then pyrite surface. O2 molecules adsorbed on pyrite, marcasite and pyrrhotite surfaces are all dissociated. The oxygen atoms and surface atoms of pyrite, marcasite and pyrrhotite surfaces have different bonding structures. Due to more atoms on pyrrhotite and marcasite surfaces interaction with oxygen atoms, the adsorption energies of O2 on pyrrhotite and marcasite surfaces are larger than that on pyrite surface. Larger values of Mulliken populations for O？Fe bond of pyrrhotite surface result in relative larger adsorption energy compared with that on marcasite surface.
基金supported by Fundamental Research Funds for the Central Universities (2662014BQ061, 2015PY120, 2015PY047, 2016PY088)the National Natural Science Foundation of China (51572101, 21502059, 21607047)~~
文摘Novel silver/silver molybdate（Ag/Ag2MoO4） composites with surface plasmon resonance（SPR）-enhanced photocatalytic performance were successfully fabricated via a facile one-pot hydrothermal route with the presence of sodium dodecyl sulfate（SDS） in this study.The as prepared silver/silver molybdate（Ag/Ag2MoO4） composites were systematically characterized by X-ray diffraction（XRD）,scanning electron microscopy（SEM） and ultraviolet-visible diffuse reflectance absorption spectroscopy（DRS） in order to investigate their crystal structure,morphology and optical property as well.The photocatalytic activities of the composites were subsequently evaluated by their ability to degrade rhodamine B（RhB） under visible-light irradiation.Varies of controlled experiments were then carefully operated to gain a deep insight into the assembling of Ag/Ag2MoO4composites.It was found that preparation conditions such as pH,reaction time,and the amount of surfactant played important roles in the formation of composites with octahedral microstructures.And the composite obtained at 160 ℃ using 0.5 g of sodium dodecyl sulfate exhibited the highest photocatalytic performance under visible-light irradiation.Capture experiments were also conducted to clarify the function of different active species generated on the surface of Ag/Ag2MoO4during the photocatalytic process,in which both holes and ·OH radicals were found to play crucial role in photocatalytic removal of RhB under visible light irradiation.A possible photocatalytic mechanism of Ag/Ag2MoO4 was finally proposed on the basis of all the results to explain the higher photocatalytic activity of the octahedral Ag/Ag2MoO4 composites.It was inferred that the photoinduced ＂hot＂ electrons can quickly transfer from the Ag NPs to the conduction band of Ag2MoO4 and react with oxygen and H2O to generate a large quality of active radicals such as ·OH and ·O2^- because of the SPR effects.Besides,this SPR effects of Ag nanoparticles deposited on the surface of Ag2MoO4 can not only dramatically amplify its light absorption,especially in the visible region,but also promote the separation of photoexcited electron-hole pairs and effectively decrease electron-hole recombination.
基金Project funded by Ten Thousand Talent Plans for Young Top-notch Talents of Yunnan Province, China (No. YNWR-QNBJ-2018-051)。
文摘Hydrogen peroxide was used as an oxidant to modify the cuprite surface and enhance its sulfidization.Surface-adsorption and infrared spectroscopy measurements indicated that the modification of the cuprite surface with hydrogen peroxide before sulfidization increased the adsorption capacity of xanthate.Zeta potential,scanning electron microscopy-energy dispersive X-ray spectroscopy,X-ray photoelectron spectroscopy,and time-of-flight secondary ion mass spectrometry results showed that the modification with hydrogen peroxide increased the contents of S^(2−)and Sn^(2−)species on the cuprite surface.Microflotation tests showed that the recovery of cuprite increased from 61.74%to 83.30%after the modification of the surface with hydrogen peroxide.These results confirm that the modification of the cuprite surface with hydrogen peroxide enhances the sulfidization of cuprite,which in turn improves its flotation.
基金supported by the National Natural Science Foundation of China(21773106,21707066,21677069,and 21806077)the China Postdoctoral Science Foundation(2018M642206)~~
文摘The effect of molybdenum oxide on the activity and durability of Ce O2-Ti O2 catalyst for NO reduction by NH3 was examined. It was found that the introduction of Mo could improve the low-temperature NH3-SCR activity and SO2/H2 O durability of the Ce O2-Ti O2 catalyst and an optimal loading of Mo was 4?wt.%. The best Mo O3/Ce O2-Ti O2 catalyst displayed over 90% NO conversion from 200 °C to 400 °C and obtained 4-fold increase in NO conversion compared to Ce O2-Ti O2 at 150 °C. The characterization results revealed that the number of Br?nsted acid sites over Mo O3/Ce O2-Ti O2 was significantly increased, and the adsorption of nitrate species was dramatically weakened because of the coverage of Mo O3, which were favorable for the high NH3-SCR performance. It is believed that the Mo O3/Ce O2-Ti O2 catalyst is a suitable substitute for the NH3-SCR reaction.
文摘Pyrite （FeS2） bulk and （100） surface properties and the oxygen adsorption on the surface were studied by using density functional theory methods. The results show that in the formation of FeS2 （100） surface, there exists a process of electron transfer from Fe dangling bond to S dangling bond. In this situation, surface Fe and S atoms have more ionic properties. Both Fe2+ and S2- have high electrochemistry reduction activity, which is the base for oxygen adsorption. From the viewpoint of adsorption energy, the parallel form oxygen adsorption is in preference. The result also shows that the state of oxygen absorbed on FeS2 surface acts as peroxides rather than O2.
文摘Highly selective electrocatalytic semihydrogenation of alkynes to alkenes with water as the hydrogen source over palladium-based electrocatalysts is significant but remains a great challenge because of the excessive hydrogenation capacity of palladium.Here,we propose that an ideal palladium catalyst should possess weak alkene adsorption and inhibit subsurface hydrogen formation to stimulate the high selectivity of alkyne semihydrogenation.Therefore,sulfur-modified Pd nanowires(Pd-S NWs)are designedly prepared by a solid-solution interface sulfuration method with KSCN as the sulfur source.The introduction of S weakens the alkene adsorption and prevents the diffusion of active hydrogen(H^(*))into the Pd lattice to form unfavorable subsurface H^(*).As a result,electrocatalytic alkyne semihydrogenation is achieved over a Pd-S NWs cathode with wide substrate scopes,potential-independent up to 99%alkene selectivity,good fragile groups compatibility,and easily synthesized deuterated alkenes.An adsorbed hydrogen addition mechanism of this semihydrogenation reaction is proposed.Importantly,an easy modification of commercial Pd/C by in situ addition of SCN–enabling the gram-scale synthesis of an alkene with 99%selectivity and 95%conversion highlights the promising potential of our method.
