限域传递机制初探：以限域状态为切入点描述传递阻力

doi:10.11949/0438-1157.20221080

摘要/Abstract

摘要：

纳米限域空间中分子的传递是新一代化工过程的共性问题。限域空间引入界面润湿性与限域自由度，导致固体-流体受到的非对称相互作用显著，使得流体状态大幅度偏离均一主体相，经典传递理论不再适用。面向限域的传递理论的缺失，已不能满足现代化工发展的需求。本文综述本团队及前沿的限域传递研究工作，并基于统计力学与非平衡热力学方法进行分析，发现前沿研究分别涵盖三个角度：新自由度下分子间相互作用力决定流体反常状态，反常状态描述流体限域传递物性，反常传递物性描述限域传递阻力实现通量描述。针对三个角度，总结出限域传递阻力雏形，并从三个角度对限域热点工作初探分析，以限域状态为起点，将三个角度贯通是发展限域传递模型的方向，进而为现代化工发展基础数据和模型。

关键词: 纳米限域空间, 限域传递, 限域状态, 传递阻力

Abstract:

Molecule transfer in the nanoconfined space is a common issue in the modern chemical process. However, surface wettability and confined degree in nanoconfined space lead to the effect of asymmetry of the molecular interaction. Such symmetric interaction induces the inhomogeneous and further causes the unavailable of the classical transfer theory. The lack of the transfer theory oriented to the limit can no longer meet the needs of the development of modern industry. This paper summarizes the research work of our team and the frontier of confined transport, and analyzes it based on statistical mechanics and non-equilibrium thermodynamic methods. It is found that the frontier research covers three perspectives. Namely, molecular interaction determines the abnormal fluid state in new free degrees, the abnormal fluid state-dependent fluid transfer phenomenon further decides the confined fluid resistance of fluid transfer. Based on three perspectives, the primary theory of confined transfer resistance is concluded. Furthermore, the primary theory of confined transfer resistance is used to analyze hot research in nanoconfinement conducted by advanced experimental and theoretical works. Finally, this work proposed that combining three perspectives, in terms of the fluid state in the space, may give a framework to develop the nanoconfined transfer theory for guiding the development of modern chemical engineering.

Key words: nanoconfined space, confined transfer, fluid state, transfer resistance

中图分类号:

TQ 021.4

覃瑶, 张禹萌, 潘雪玲, 王文强, 戴正兴, 朱育丹, 陆小华. 限域传递机制初探：以限域状态为切入点描述传递阻力[J]. 化工学报, 2023, 74(1): 74-85.

Yao QIN, Yumeng ZHANG, Xueling PAN, Wenqiang WANG, Zhengxing DAI, Yudan ZHU, Xiaohua LU. Preliminary study on mechanism of transfer in confined space: description of confined transfer resistance based on confined fluid state[J]. CIESC Journal, 2023, 74(1): 74-85.

图/表 8

参考文献 78

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流体、界面类型及受限尺寸	反常现象	相态变化	文献
流体：水界面类型：碳圆形孔 d=2.5σ、3σ、5σ	随着受限尺寸的减小，气液相共存区缩小，临界温度下降	气-液相之间	[61]
流体：水界面类型：石墨烯 d=0.79、0.99、1.69、4.5 nm	水形成特殊的三维水簇结构网络	—	[62]
流体：水界面类型：羟基化二氧化硅、石墨烯 d=0.4~1.6 nm	液相、气相和双层冰等状态转变	气-液-固三相	[63]
流体：水界面类型：氧化硅 d=0.6~1.2 nm	d=0.8 nm时，双层冰和三层非均质水的密度增加，一阶相变发生	液-固相之间	[42]
流体：冰界面类型：碳纳米管 d=1.1~1.4 nm	d=1.19 nm的碳纳米管内一阶冰相变化到六角形和七边形的纳米管形状, 并且可以连续转变成固态方形结构或五角冰纳米管形状	液-固相之间	[21]
流体：冰界面类型：石墨烯 d=0.7~0.9 nm	d=0.78 nm的石墨烯狭缝中出现双层极低密度无定形冰的新状态	液-固相之间	[64]
流体：甲烷、乙烷、丁烷、正丁烷界面类型：石墨烯、云母 d= 0.5~1.5 nm	随着受限尺寸变小，气液表面张力下降，饱和蒸气压增大	气-液相之间	[65]
流体：水界面类型：石墨烯、云母 d=1~6 nm	随着尺寸变小，水的气液相临界温度下降，水的密度呈非均一分布，气液相共存	气-液相之间	[65]
流体：甲烷、乙烷界面类型：石墨烯 d=4、7、10 nm	随着受限尺寸的减小，气液相共存区缩小，临界温度下降	气-液相之间	[66]
流体：辛烷、癸烷界面类型：碳纳米管 d=4.3、38.1 nm	当d=4.3 nm时，出现两个不同的泡点，气液相共存	气-液相之间	[67]

流体、界面类型及受限尺寸	反常现象	相态变化	文献
流体：水界面类型：碳圆形孔 d=2.5σ、3σ、5σ	随着受限尺寸的减小，气液相共存区缩小，临界温度下降	气-液相之间	[61]
流体：水界面类型：石墨烯 d=0.79、0.99、1.69、4.5 nm	水形成特殊的三维水簇结构网络	—	[62]
流体：水界面类型：羟基化二氧化硅、石墨烯 d=0.4~1.6 nm	液相、气相和双层冰等状态转变	气-液-固三相	[63]
流体：水界面类型：氧化硅 d=0.6~1.2 nm	d=0.8 nm时，双层冰和三层非均质水的密度增加，一阶相变发生	液-固相之间	[42]
流体：冰界面类型：碳纳米管 d=1.1~1.4 nm	d=1.19 nm的碳纳米管内一阶冰相变化到六角形和七边形的纳米管形状, 并且可以连续转变成固态方形结构或五角冰纳米管形状	液-固相之间	[21]
流体：冰界面类型：石墨烯 d=0.7~0.9 nm	d=0.78 nm的石墨烯狭缝中出现双层极低密度无定形冰的新状态	液-固相之间	[64]
流体：甲烷、乙烷、丁烷、正丁烷界面类型：石墨烯、云母 d= 0.5~1.5 nm	随着受限尺寸变小，气液表面张力下降，饱和蒸气压增大	气-液相之间	[65]
流体：水界面类型：石墨烯、云母 d=1~6 nm	随着尺寸变小，水的气液相临界温度下降，水的密度呈非均一分布，气液相共存	气-液相之间	[65]
流体：甲烷、乙烷界面类型：石墨烯 d=4、7、10 nm	随着受限尺寸的减小，气液相共存区缩小，临界温度下降	气-液相之间	[66]
流体：辛烷、癸烷界面类型：碳纳米管 d=4.3、38.1 nm	当d=4.3 nm时，出现两个不同的泡点，气液相共存	气-液相之间	[67]

流体、界面类型及受限尺寸	反常现象	机制解释	解释机制所用模型	文献
流体：氦气、氢气、氮气等有机溶剂；水界面类型：GO 受限尺寸：约1 nm	水分子以超快速度渗透过狭缝宽度为1 nm的GO膜，流速约为He的10¹⁰倍	考虑滑移长度为10~100 nm范围的Hagen-Poiseuille方程能够合理描述水的传输通量，即滑移长度的增加，产生了无摩擦流动，解释了水的快速传输机制	滑移修正的HP 方程	[15]
流体：苯甲酸、DMSO、甲苯、CuCl₂、MgCl₂、NaCl、丙醇、甲苯、辛醇等界面类型：GO 受限尺寸：层间距0.34 nm，孔径0.9~1.3 nm	小离子和有机分子可以快速渗透而大的离子和有机分子无法渗透过孔径极小的GO膜	结合分子模拟构象分析，水合半径大于0.45 nm的渗透受到通道内两层水区域的限制，水合离子不易脱水，而水合半径小于0.45 nm的水合离子位阻效应更小，解释了精确离子筛分特性	Fick定律	[14]
流体：氦气、水界面类型：GO 受限尺寸：层间距0.34 nm	水在层间距为0.34 nm的通道内具有超快传输速度，达到1 m·s^-1	考虑了超高渗透压以及滑移修正的Hagen-Poiseuille方程能够合理描述水的传输通量，即超高渗透压以及滑移长度的增加，解释了水的快速传输机制	含有压力修正和滑移修正项的HP方程	[70]
流体：KCl、AlCl₃溶液等；水界面类型：GO、h-BN、MoS₂ 受限尺寸：0.66~0.67 nm	半径大于埃米级通道尺寸的水合离子仍然可以以较低的速度进行传输和渗透	通过考虑了离子有效体积贡献和表面电荷贡献的总电导方程，解释了大于二维通道的尺寸水合离子可以以较低的速度进行传输和渗透	离子有效体积贡献和表面电荷贡献的电导方程	[71]
流体：氦气界面类型：GO、 h-BN、MoS₂ 受限尺寸：1.4 nm	气体分子(He)在受限尺寸为1.4 nm二维通道中的传输速度极快，表现出近似于无阻碍的“弹道”(Ballistic)输运特征	考虑漫反射的Knudsen扩散理论(计算结果与实验值相差几个数量级)，考虑漫反射和镜面反射的弹道输运理论能够合理描述He的传输，解释其快速传输机制是由于产生大量的镜面反射	同时考虑漫反射和镜面反射的弹道(Ballistic)输运理论	[72]
流体：水界面类型：GO 受限尺寸：1 nm	在GO膜中制造导电细丝实现水的超快渗透到完全堵塞精确控制——调控水的弹道输运	考虑漫反射的Knudsen扩散理论(计算结果与实验值相差几个数量级)，考虑漫反射和镜面反射的弹道输运理论能够合理描述He的传输，解释其快速传输机制是由于产生大量的镜面反射	同时考虑漫反射和镜面反射的弹道(Ballistic)输运理论	[73]
流体：水界面类型：h-BN 受限尺寸：1~1.4 nm	首次通过实验证明了1 nm h-BN通道中,界面水的介电常数在2左右，远低于普通环境中水的介电常数(约80)	通过与光学频率下的介电常数测定比较，结合模拟结果，发现偶极作用以及氢键作用被抑制对于介电常数减少的贡献，解释了受限水的超低介电常数成因主要归因于变化不大的电子贡献	介电常数是离子传递模型如Poisson-Boltzmann方程等的重要参数	[74]
流体：水、质子H⁺、离子水溶液界面类型：GO、h-BN 受限尺寸：层间距0.34 nm	使用石墨烯或h-BN作为间隔层制成的致密空腔，允许单层水的存在，但阻碍所有水合离子的通过。只有质子H⁺能够通过这种毛细血管内的单层水扩散通道	水合离子由于位阻效应无法通过。通过Grotthuss机制，解释了质子H⁺的传输，其能够在水分子间跳跃且不需要随身携带大水化壳层	Grotthuss机制：质子通过氢键和分子重排的方式实现质子的跳变 Nernst方程	[75]

流体、界面类型及受限尺寸	反常现象	机制解释	解释机制所用模型	文献
流体：氦气、氢气、氮气等有机溶剂；水界面类型：GO 受限尺寸：约1 nm	水分子以超快速度渗透过狭缝宽度为1 nm的GO膜，流速约为He的10¹⁰倍	考虑滑移长度为10~100 nm范围的Hagen-Poiseuille方程能够合理描述水的传输通量，即滑移长度的增加，产生了无摩擦流动，解释了水的快速传输机制	滑移修正的HP 方程	[15]
流体：苯甲酸、DMSO、甲苯、CuCl₂、MgCl₂、NaCl、丙醇、甲苯、辛醇等界面类型：GO 受限尺寸：层间距0.34 nm，孔径0.9~1.3 nm	小离子和有机分子可以快速渗透而大的离子和有机分子无法渗透过孔径极小的GO膜	结合分子模拟构象分析，水合半径大于0.45 nm的渗透受到通道内两层水区域的限制，水合离子不易脱水，而水合半径小于0.45 nm的水合离子位阻效应更小，解释了精确离子筛分特性	Fick定律	[14]
流体：氦气、水界面类型：GO 受限尺寸：层间距0.34 nm	水在层间距为0.34 nm的通道内具有超快传输速度，达到1 m·s^-1	考虑了超高渗透压以及滑移修正的Hagen-Poiseuille方程能够合理描述水的传输通量，即超高渗透压以及滑移长度的增加，解释了水的快速传输机制	含有压力修正和滑移修正项的HP方程	[70]
流体：KCl、AlCl₃溶液等；水界面类型：GO、h-BN、MoS₂ 受限尺寸：0.66~0.67 nm	半径大于埃米级通道尺寸的水合离子仍然可以以较低的速度进行传输和渗透	通过考虑了离子有效体积贡献和表面电荷贡献的总电导方程，解释了大于二维通道的尺寸水合离子可以以较低的速度进行传输和渗透	离子有效体积贡献和表面电荷贡献的电导方程	[71]
流体：氦气界面类型：GO、 h-BN、MoS₂ 受限尺寸：1.4 nm	气体分子(He)在受限尺寸为1.4 nm二维通道中的传输速度极快，表现出近似于无阻碍的“弹道”(Ballistic)输运特征	考虑漫反射的Knudsen扩散理论(计算结果与实验值相差几个数量级)，考虑漫反射和镜面反射的弹道输运理论能够合理描述He的传输，解释其快速传输机制是由于产生大量的镜面反射	同时考虑漫反射和镜面反射的弹道(Ballistic)输运理论	[72]
流体：水界面类型：GO 受限尺寸：1 nm	在GO膜中制造导电细丝实现水的超快渗透到完全堵塞精确控制——调控水的弹道输运	考虑漫反射的Knudsen扩散理论(计算结果与实验值相差几个数量级)，考虑漫反射和镜面反射的弹道输运理论能够合理描述He的传输，解释其快速传输机制是由于产生大量的镜面反射	同时考虑漫反射和镜面反射的弹道(Ballistic)输运理论	[73]
流体：水界面类型：h-BN 受限尺寸：1~1.4 nm	首次通过实验证明了1 nm h-BN通道中,界面水的介电常数在2左右，远低于普通环境中水的介电常数(约80)	通过与光学频率下的介电常数测定比较，结合模拟结果，发现偶极作用以及氢键作用被抑制对于介电常数减少的贡献，解释了受限水的超低介电常数成因主要归因于变化不大的电子贡献	介电常数是离子传递模型如Poisson-Boltzmann方程等的重要参数	[74]
流体：水、质子H⁺、离子水溶液界面类型：GO、h-BN 受限尺寸：层间距0.34 nm	使用石墨烯或h-BN作为间隔层制成的致密空腔，允许单层水的存在，但阻碍所有水合离子的通过。只有质子H⁺能够通过这种毛细血管内的单层水扩散通道	水合离子由于位阻效应无法通过。通过Grotthuss机制，解释了质子H⁺的传输，其能够在水分子间跳跃且不需要随身携带大水化壳层	Grotthuss机制：质子通过氢键和分子重排的方式实现质子的跳变 Nernst方程	[75]

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