The ionic transport in sub-nanochannels plays a key role in energy storage,yet suffers from a high energy barrier.Wetting sub-nanochannels is crucial to accelerate ionic transport,but the introduction of water is chal...The ionic transport in sub-nanochannels plays a key role in energy storage,yet suffers from a high energy barrier.Wetting sub-nanochannels is crucial to accelerate ionic transport,but the introduction of water is challenging because of the hydrophobic extreme confinement.We propose wetting the channels by the exothermic hydration process of pre-intercalated ions,the effect of which varies distinctly with different ionic hydration structures and energies.Compared to the failed pre-intercalation of SO_(4)^(2-),HSO_(4)^(-) with weak hydration energy results in a marginal effect on the HOMO(Highest Occupied Molecular Orbital)level of water to avoid water splitting during the electrochemical intercalation.Meanwhile,the ability of water introduction is reserved by the initial incomplete dissociation state of HSO_(4)^(-),so the consequent exothermic reionization and hydration processes of the intercalated HSO_(4)^(-) promote the water introduction into sub-nanochannels,finally forming the stable confined water through hydrogen bonding with functional groups.The wetted channels exhibit a significantly enhanced ionic diffusion coef-ficient by~9.4 times.展开更多
Specific ion effects play a vital role in a variety of colloidal and interfacial processes.However,few studies have reported the specific ion effects in the humus aggregation process,which strongly influence the trans...Specific ion effects play a vital role in a variety of colloidal and interfacial processes.However,few studies have reported the specific ion effects in the humus aggregation process,which strongly influence the transport and fate of environmental pollutants.In this study,soil humus colloids were prepared and characterized,and the specific ion effects on humus aggregation in electrolyte solutions were investigated at a variety of concentrations and pH values using dynamic light scattering methods.Activation energy(ΔE),which is known to reflect the dynamics and stability of a colloidal system,was used to quantitatively characterize the specific ion effects.The results showed that given ΔE value of 2.48×10^(3) J mol^(-1) at pH 3.0,the electrolyte concentrations were 91.6,58.2,3.8,and 0.8 mmol L^(-1) for Na^(+),K^(+),Mg^(2+),and Ca_(2+),respectively,thus indicating significant specific ion effects in the humus aggregation process.Most importantly,decreasing the electrolyte concentrations increased the differences in the ΔE value between two cation species with the same valence(i.e.,ΔE_(Na)-ΔE_(K) and ΔE_(Mg)-ΔE_(Ca)),while increasing the pH increased the magnitude of ΔE_(Mg)-ΔE_(Ca).However,the classic Derjaguin,Landau,Verwey,and Overbeek(DLVO)theory and the double layer theory,as well as the currently widely used ionic hydration and dispersion effects,failed to predict the experimentally observed increase in the specific ion effects with decreasing electrolyte concentrations in a quantitative sense.These results have implications for the necessity of involving specific ion effects for a better understanding of humus aggregation and interactions in aqueous and soil systems.展开更多
基金supported by the National Key Research and Development Program of China(2021YFA1101300)the National Natural Science Foundation of China(Grant No.22225801,21776197,22078214,and 21905206)Special Fund for Science and Technology Innovation Team of Shanxi Province(No.202204051001009).
文摘The ionic transport in sub-nanochannels plays a key role in energy storage,yet suffers from a high energy barrier.Wetting sub-nanochannels is crucial to accelerate ionic transport,but the introduction of water is challenging because of the hydrophobic extreme confinement.We propose wetting the channels by the exothermic hydration process of pre-intercalated ions,the effect of which varies distinctly with different ionic hydration structures and energies.Compared to the failed pre-intercalation of SO_(4)^(2-),HSO_(4)^(-) with weak hydration energy results in a marginal effect on the HOMO(Highest Occupied Molecular Orbital)level of water to avoid water splitting during the electrochemical intercalation.Meanwhile,the ability of water introduction is reserved by the initial incomplete dissociation state of HSO_(4)^(-),so the consequent exothermic reionization and hydration processes of the intercalated HSO_(4)^(-) promote the water introduction into sub-nanochannels,finally forming the stable confined water through hydrogen bonding with functional groups.The wetted channels exhibit a significantly enhanced ionic diffusion coef-ficient by~9.4 times.
基金supported by the National Natural Science Foundation of China(Nos.41501241 and 41877026)the Fundamental Research Funds for the Central Universities of China(Nos.XDJK2019B037 and SWU116049)。
文摘Specific ion effects play a vital role in a variety of colloidal and interfacial processes.However,few studies have reported the specific ion effects in the humus aggregation process,which strongly influence the transport and fate of environmental pollutants.In this study,soil humus colloids were prepared and characterized,and the specific ion effects on humus aggregation in electrolyte solutions were investigated at a variety of concentrations and pH values using dynamic light scattering methods.Activation energy(ΔE),which is known to reflect the dynamics and stability of a colloidal system,was used to quantitatively characterize the specific ion effects.The results showed that given ΔE value of 2.48×10^(3) J mol^(-1) at pH 3.0,the electrolyte concentrations were 91.6,58.2,3.8,and 0.8 mmol L^(-1) for Na^(+),K^(+),Mg^(2+),and Ca_(2+),respectively,thus indicating significant specific ion effects in the humus aggregation process.Most importantly,decreasing the electrolyte concentrations increased the differences in the ΔE value between two cation species with the same valence(i.e.,ΔE_(Na)-ΔE_(K) and ΔE_(Mg)-ΔE_(Ca)),while increasing the pH increased the magnitude of ΔE_(Mg)-ΔE_(Ca).However,the classic Derjaguin,Landau,Verwey,and Overbeek(DLVO)theory and the double layer theory,as well as the currently widely used ionic hydration and dispersion effects,failed to predict the experimentally observed increase in the specific ion effects with decreasing electrolyte concentrations in a quantitative sense.These results have implications for the necessity of involving specific ion effects for a better understanding of humus aggregation and interactions in aqueous and soil systems.