Catalytic converting CO2 into fuels with the help of solar energy is regarded as‘dream reaction’,as both energy crisis and environmental issue can be mitigated simultaneously.However,it is still suffering from low e...Catalytic converting CO2 into fuels with the help of solar energy is regarded as‘dream reaction’,as both energy crisis and environmental issue can be mitigated simultaneously.However,it is still suffering from low efficiency due to narrow solar-spectrum utilization and sluggish heterogeneous reaction kinetics.In this work,we demonstrate that catalytic reduction of CO2 can be achieved over Au nanoparticles(NPs)deposited rutile under full solar-spectrum irradiation,boosted by solar-heating effect.We found that UV and visible light can initiate the reaction,and the heat from IR light and local surface-plasmon resonance relaxation of Au NPs can boost the reaction kinetically.The apparent activation energy is determined experimentally and is used to explain the superior catalytic activity of Au/rutile to rutile in a kinetic way.We also find the photo-thermal synergy in the Au/rutile system.We envision that this work may facilitate understanding the kinetics of CO2 reduction and developing feasible catalytic systems with full solar spectrum utilization for practical artificial photosynthesis.展开更多
Experimental data are presented for the void fraction and the shear stresses of stratified gas-liquid flow in a pipe. A new technique was used to measure the interface shear stress. The interfacial shear stress was de...Experimental data are presented for the void fraction and the shear stresses of stratified gas-liquid flow in a pipe. A new technique was used to measure the interface shear stress. The interfacial shear stress was determined by using two methods: a momentum balance of gas and an extrapolation of the Reynolds shear stress profile at the gas-liquid interface. A new formula , relating to the interfacial friction factor with the void fraction and superficial gas Reynold number, was developed to predict the interface shear stress . The predicted values are in good agreement with experimental data.展开更多
Preconsolidation stress （ σP） is the maximum effective stress that a soil has suffered throughout its life. From a geotech- nical point of view, pre-consolidation stress has great importance because it separates el...Preconsolidation stress （ σP） is the maximum effective stress that a soil has suffered throughout its life. From a geotech- nical point of view, pre-consolidation stress has great importance because it separates elastic and reversible deformations from inelastic and only partially irreversible deformations and marks the starting point of high compressibility. In this study we calculated the preconsolidation stress for 72 undisturbed soil samples from the Yellow River Delta, using the oedometer test and applying the method proposed by Casagrande. The results showed that the over-consolidation ratio （OCR-the ratio of pre-consolidation stress to current natural overburden stress） values of the soil from soil surface to 6m depth varied from 1.72 to 15.34 and the maximum pre- consolidation stress was above 200 kPa. In consequence, the soils of the Yellow River Delta are highly over-consolidated within the upper 6m, the OCR decreasing gradually with depth from 6 to 12m. For samples from deeper than 12m the soils were found to be under-consolidated, which was proved by standard penetration tests （SPTs）. The main causes of this type of consolidation are the mineral composition and the designability of the soil body.展开更多
Binuclear ruthenium complexes bearing the2,2'‐bipyridine‐6,6'‐dicarboxylate(bda)ligand have been demonstrated to be highly active catalysts towards water oxidation with CeIV as an oxidant.However,the cataly...Binuclear ruthenium complexes bearing the2,2'‐bipyridine‐6,6'‐dicarboxylate(bda)ligand have been demonstrated to be highly active catalysts towards water oxidation with CeIV as an oxidant.However,the catalytic properties of ruthenium dimers have not yet been explored for visible light‐driven water oxidation.Herein,the photocatalytic performance of a dipyridyl propane‐bridged ruthenium dimer2was investigated in comparison with its monomeric precursor,[Ru(bda)(pic)2](1),in CH3CN/phosphate buffer mixed solvent in a three‐component system including a photosensitizer and a sacrificial electron acceptor.Experimental results showed that the activity of each catalyst was strongly dependent on the content of CH3CN in the phosphate buffer,which not only affected the driving force for water oxidation,but also altered the kinetics of the reaction,probably through different mechanisms associated with the O–O bond formation.As a result,dimer2showedsignificantly higher activity than monomer1in the solvent containing a low content of CH3CN,and comparable activities were attained with a high content of CH3CN in the solvent.Under the optimal conditions,complex2achieved a turnover number of638for photocatalytic O2evolution.展开更多
Density functional theory method was employed to study the effect of the nitroamino group as a substituent in cyclopentane and cyclohexane, which usually construct polycyclic or caged nitramines. Based on the optimize...Density functional theory method was employed to study the effect of the nitroamino group as a substituent in cyclopentane and cyclohexane, which usually construct polycyclic or caged nitramines. Based on the optimized molecular structures of two groups of monocyclic nitramines at the B3LYP/6-31G^＊＊ level, the infrared （IR） spectra were obtained and assigned by harmonic vibrational analysis. The calculated results agree reasonably with the available experimental data. According to the principles of statistic thermodynamics, thermodynamic properties were derived from the IR spectra, which were linearly correlated with the number of nitroamino groups as well as the temperature. The contributions of nitroamino groups to thermodynamic properties are in accord with the group additivity.展开更多
基金supported by the Belt and Road Initiative by Chinese Academy of Sciencesthe National Natural Science Foundation of China(21673052,11404074)
文摘Catalytic converting CO2 into fuels with the help of solar energy is regarded as‘dream reaction’,as both energy crisis and environmental issue can be mitigated simultaneously.However,it is still suffering from low efficiency due to narrow solar-spectrum utilization and sluggish heterogeneous reaction kinetics.In this work,we demonstrate that catalytic reduction of CO2 can be achieved over Au nanoparticles(NPs)deposited rutile under full solar-spectrum irradiation,boosted by solar-heating effect.We found that UV and visible light can initiate the reaction,and the heat from IR light and local surface-plasmon resonance relaxation of Au NPs can boost the reaction kinetically.The apparent activation energy is determined experimentally and is used to explain the superior catalytic activity of Au/rutile to rutile in a kinetic way.We also find the photo-thermal synergy in the Au/rutile system.We envision that this work may facilitate understanding the kinetics of CO2 reduction and developing feasible catalytic systems with full solar spectrum utilization for practical artificial photosynthesis.
基金Supported by the National Natural Science Foundation of China(No.59236130).
文摘Experimental data are presented for the void fraction and the shear stresses of stratified gas-liquid flow in a pipe. A new technique was used to measure the interface shear stress. The interfacial shear stress was determined by using two methods: a momentum balance of gas and an extrapolation of the Reynolds shear stress profile at the gas-liquid interface. A new formula , relating to the interfacial friction factor with the void fraction and superficial gas Reynold number, was developed to predict the interface shear stress . The predicted values are in good agreement with experimental data.
基金supported by the National Natural Science Foundation of China (Nos. 40472137 and 40606020)
文摘Preconsolidation stress （ σP） is the maximum effective stress that a soil has suffered throughout its life. From a geotech- nical point of view, pre-consolidation stress has great importance because it separates elastic and reversible deformations from inelastic and only partially irreversible deformations and marks the starting point of high compressibility. In this study we calculated the preconsolidation stress for 72 undisturbed soil samples from the Yellow River Delta, using the oedometer test and applying the method proposed by Casagrande. The results showed that the over-consolidation ratio （OCR-the ratio of pre-consolidation stress to current natural overburden stress） values of the soil from soil surface to 6m depth varied from 1.72 to 15.34 and the maximum pre- consolidation stress was above 200 kPa. In consequence, the soils of the Yellow River Delta are highly over-consolidated within the upper 6m, the OCR decreasing gradually with depth from 6 to 12m. For samples from deeper than 12m the soils were found to be under-consolidated, which was proved by standard penetration tests （SPTs）. The main causes of this type of consolidation are the mineral composition and the designability of the soil body.
基金supported by the National Basic Research Program of China (973 Program, 2014CB239402)the National Natural Science Foundation of China (21476043)+1 种基金the Fundamental Research Funds for the Central Universities (DUT17ZD204)the Swedish Energy Agency and K&A Wallenberg Foundation~~
文摘Binuclear ruthenium complexes bearing the2,2'‐bipyridine‐6,6'‐dicarboxylate(bda)ligand have been demonstrated to be highly active catalysts towards water oxidation with CeIV as an oxidant.However,the catalytic properties of ruthenium dimers have not yet been explored for visible light‐driven water oxidation.Herein,the photocatalytic performance of a dipyridyl propane‐bridged ruthenium dimer2was investigated in comparison with its monomeric precursor,[Ru(bda)(pic)2](1),in CH3CN/phosphate buffer mixed solvent in a three‐component system including a photosensitizer and a sacrificial electron acceptor.Experimental results showed that the activity of each catalyst was strongly dependent on the content of CH3CN in the phosphate buffer,which not only affected the driving force for water oxidation,but also altered the kinetics of the reaction,probably through different mechanisms associated with the O–O bond formation.As a result,dimer2showedsignificantly higher activity than monomer1in the solvent containing a low content of CH3CN,and comparable activities were attained with a high content of CH3CN in the solvent.Under the optimal conditions,complex2achieved a turnover number of638for photocatalytic O2evolution.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.10576030 and No.10576016） and the National Basic Research Program of China （No.61337）.
文摘Density functional theory method was employed to study the effect of the nitroamino group as a substituent in cyclopentane and cyclohexane, which usually construct polycyclic or caged nitramines. Based on the optimized molecular structures of two groups of monocyclic nitramines at the B3LYP/6-31G^＊＊ level, the infrared （IR） spectra were obtained and assigned by harmonic vibrational analysis. The calculated results agree reasonably with the available experimental data. According to the principles of statistic thermodynamics, thermodynamic properties were derived from the IR spectra, which were linearly correlated with the number of nitroamino groups as well as the temperature. The contributions of nitroamino groups to thermodynamic properties are in accord with the group additivity.
