Supercritical fluids play a crucial role in material transport within Earth's deep interior.Investigating the pressure-dependent atomic structures and transport properties of such fluids is essential for understan...Supercritical fluids play a crucial role in material transport within Earth's deep interior.Investigating the pressure-dependent atomic structures and transport properties of such fluids is essential for understanding their petrological,chemical,and geophysical behaviors.In this study,we employed first-principles molecular dynamics simulations to explore the structures,self-diffusion coefficients(D),and viscosities(η)of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids under conditions of 2000 K and 3-10 GPa,with water contents of 30 wt% and 50 wt%.Our calculations indicate that at a water content of 30 wt%,Q^(2) and Q^(3) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species(n represents the number of bridging oxygens connected to Si/Al)show minimal changes.At a water content of 50 wt%,Q^(2) and Q^(0) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species show minimal changes.At both water contents,Si-O-H and molecular water in the system exhibit negative pressure dependence,suggesting that the migration of supercritical fluids from deep to shallow regions is accompanied by the release of water.The self-diffusion coefficients in the supercritical NaAlSi_(3)O_(8)-H_(2)O fluid follow the order D_(Na)≈D_(H)>D_(O)>D_(Al)≈D_(Si),with an overall weak negative pressure dependence.By comparing the viscosities of anhydrous and hydrous silicate melts from previous studies,we found that the addition of water caused a transition from negative to positive pressure dependence of viscosity,corresponding to a structural change from polymerization to depolymerization.Additionally,we calculated the fluid mobility Δp/η of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids and found that their mobility is several orders of magnitude higher than that of basalt melt and is also significantly greater than that of carbonate melt.As supercritical fluids ascend from deeper to shallower regions,their mobility is further enhanced,significantly contributing to the transport of elements from subducting slabs to the overlying mantle wedge.展开更多
The dispersion of K\-2CO\-3 on \%γ\%\|Al\-2O\-3 and the adsorption performance of K\-2CO\-3/\%γ\%\|Al\-2O\-3 to SO\-2 are investigated.The results show that K\-2CO\-3 can disperse onto the surface of \%γ\%\|Al\-2O\...The dispersion of K\-2CO\-3 on \%γ\%\|Al\-2O\-3 and the adsorption performance of K\-2CO\-3/\%γ\%\|Al\-2O\-3 to SO\-2 are investigated.The results show that K\-2CO\-3 can disperse onto the surface of \%γ\%\|Al\-2O\-3 as a monolayer and the dispersion threshold is 0.31\[\%m\%(K\-2CO\-3)/\%m\%(\%γ\%\|Al\-2O\-3), \%m\%/g\], which is close to the theoretical value calculated by assuming a bidentate vertical dispersion model of CO\-2 on the \%γ\%\|Al\-2O\-3 surface . The SO\-2 adsorption\|capacity on K\-2CO\-3/\%γ\%\|Al\-2O\-3 sample increases with the K\-2CO\-3 loading and reaches an extremum at its threshold. The adsorbent conversion of K\-2CO\-3/\%γ\%\|Al\-2O\-3 at the threshold is up to 72%. When the loading is higher than the threshold, the SO\-2 adsorption capacity decreases at first, then increases again. This phenomenon is caused by the reaction between SO\-2 and the bulk phase of K\-2CO\-3 crystallites. The sample decreases with the loading, and the sample with \{0.10\}\[\%m\%(K\-2CO\-3)/\%m(γ\%\|Al\-2O\-3), \%m\%/g\] loading shows the highest regeneration percentage of 63%. Compared with Na\-2CO\-3/\%γ\%\|Al\-2O\-3, K\-2CO\-3/\%γ\%\|Al\-2O\-3 might have some advantages.展开更多
The novel polyoxometalate, 32[Mo8ⅣMo4ⅤV2ⅣO38(PO4)], was synthesized and characterized by elementary analysis, EPR, IR spectra and X ray diffraction. The compoundcrystallizes in triclinic system, space group with a=...The novel polyoxometalate, 32[Mo8ⅣMo4ⅤV2ⅣO38(PO4)], was synthesized and characterized by elementary analysis, EPR, IR spectra and X ray diffraction. The compoundcrystallizes in triclinic system, space group with a= 1.41999(2)nm, b=1.43467(2)nm, c=1.694610(10)nm, α=95.7250(10)°, β=92.2110(10)°, γ=92.6060(10)°, V=3.42829(7)nm3, Z=2, Dc=2.388g·cm-3, Mr=2465.10g·mol-1, μ=2.489mm-1, F(000)=2388, R1=0.0584, wR2=0.1461, S=1.164. The heteropolyanion is a bi capped pseudo Keggin complex. CCDC: 186645.展开更多
基金funded by National Natural Science Foundation of China(42373033,Yicheng Sun)Fundamental Research Funds for the Central Universities(B240201111,Yicheng Sun)。
文摘Supercritical fluids play a crucial role in material transport within Earth's deep interior.Investigating the pressure-dependent atomic structures and transport properties of such fluids is essential for understanding their petrological,chemical,and geophysical behaviors.In this study,we employed first-principles molecular dynamics simulations to explore the structures,self-diffusion coefficients(D),and viscosities(η)of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids under conditions of 2000 K and 3-10 GPa,with water contents of 30 wt% and 50 wt%.Our calculations indicate that at a water content of 30 wt%,Q^(2) and Q^(3) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species(n represents the number of bridging oxygens connected to Si/Al)show minimal changes.At a water content of 50 wt%,Q^(2) and Q^(0) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species show minimal changes.At both water contents,Si-O-H and molecular water in the system exhibit negative pressure dependence,suggesting that the migration of supercritical fluids from deep to shallow regions is accompanied by the release of water.The self-diffusion coefficients in the supercritical NaAlSi_(3)O_(8)-H_(2)O fluid follow the order D_(Na)≈D_(H)>D_(O)>D_(Al)≈D_(Si),with an overall weak negative pressure dependence.By comparing the viscosities of anhydrous and hydrous silicate melts from previous studies,we found that the addition of water caused a transition from negative to positive pressure dependence of viscosity,corresponding to a structural change from polymerization to depolymerization.Additionally,we calculated the fluid mobility Δp/η of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids and found that their mobility is several orders of magnitude higher than that of basalt melt and is also significantly greater than that of carbonate melt.As supercritical fluids ascend from deeper to shallower regions,their mobility is further enhanced,significantly contributing to the transport of elements from subducting slabs to the overlying mantle wedge.
文摘The dispersion of K\-2CO\-3 on \%γ\%\|Al\-2O\-3 and the adsorption performance of K\-2CO\-3/\%γ\%\|Al\-2O\-3 to SO\-2 are investigated.The results show that K\-2CO\-3 can disperse onto the surface of \%γ\%\|Al\-2O\-3 as a monolayer and the dispersion threshold is 0.31\[\%m\%(K\-2CO\-3)/\%m\%(\%γ\%\|Al\-2O\-3), \%m\%/g\], which is close to the theoretical value calculated by assuming a bidentate vertical dispersion model of CO\-2 on the \%γ\%\|Al\-2O\-3 surface . The SO\-2 adsorption\|capacity on K\-2CO\-3/\%γ\%\|Al\-2O\-3 sample increases with the K\-2CO\-3 loading and reaches an extremum at its threshold. The adsorbent conversion of K\-2CO\-3/\%γ\%\|Al\-2O\-3 at the threshold is up to 72%. When the loading is higher than the threshold, the SO\-2 adsorption capacity decreases at first, then increases again. This phenomenon is caused by the reaction between SO\-2 and the bulk phase of K\-2CO\-3 crystallites. The sample decreases with the loading, and the sample with \{0.10\}\[\%m\%(K\-2CO\-3)/\%m(γ\%\|Al\-2O\-3), \%m\%/g\] loading shows the highest regeneration percentage of 63%. Compared with Na\-2CO\-3/\%γ\%\|Al\-2O\-3, K\-2CO\-3/\%γ\%\|Al\-2O\-3 might have some advantages.
文摘The novel polyoxometalate, 32[Mo8ⅣMo4ⅤV2ⅣO38(PO4)], was synthesized and characterized by elementary analysis, EPR, IR spectra and X ray diffraction. The compoundcrystallizes in triclinic system, space group with a= 1.41999(2)nm, b=1.43467(2)nm, c=1.694610(10)nm, α=95.7250(10)°, β=92.2110(10)°, γ=92.6060(10)°, V=3.42829(7)nm3, Z=2, Dc=2.388g·cm-3, Mr=2465.10g·mol-1, μ=2.489mm-1, F(000)=2388, R1=0.0584, wR2=0.1461, S=1.164. The heteropolyanion is a bi capped pseudo Keggin complex. CCDC: 186645.
