气固界面吸附团簇分布及相变机制研究

doi:10.11949/0438-1157.20201394

摘要/Abstract

摘要：

为了深入探讨气固界面吸附过程中团簇分布及其演化规律，结合实验测量和理论分析研究了水蒸气在二氧化硅和石墨表面的吸附特征，获取了不同压比下的团簇分布，确定了吸附相变及润湿转变的临界条件。结果表明，实验测量结果和Zeta吸附理论预测吸附曲线吻合很好，明确了气体分子以团簇形式吸附在固体表面，在低压比区，小分子团簇和零吸附单元占主导地位，随着压比的增加，吸附团簇类型增多，当压比达到某一临界值时，吸附熵达到极大值，界面发生吸附相变。确定了零吸附情况下石墨和二氧化硅表面张力及界面润湿临界条件，润湿压比下，性质均一的大分子团簇聚集，形成类液膜润湿界面。

关键词: 气固界面, 吸附相变, 团簇分布, 吸附熵, 界面张力

Abstract:

To explore the cluster distribution and evolution during the process of adsorption at solid-vapor interface, a series of experimental measurements and theoretical analysis are hybrid to study the characteristics of water vapor adsorption on silica and graphite surfaces. The adsorption isotherms in the full pressure range are obtained based on the Zeta adsorption model, the cluster distributions at different pressure ratios are obtained, the critical conditions for the adsorption phase change and wetting are determined. The results showed that Zeta adsorption isotherm has no singularity at saturation pressure. The adsorption measurements are in good agreement with the theoretical prediction by Zeta adsorption model. Meanwhile, the vapor adsorbate is formed as clusters with different number of molecules. In the low pressure ratio zone, small molecular clusters and zero adsorption units dominate the adsorption site. As the pressure ratio increases, the types of adsorption clusters increase. Once the pressure exceeds a certain value, the entropy reaches a maximum value, indicating the occurrence of phase transition at the interface. The surface tension of graphite and silica and the critical conditions of interfacial wetting under the condition of zero adsorption are determined. Under the wetting pressure ratio, homogeneous macromolecular clusters gather to form a liquid-film-like wetting interface.

Key words: solid-vapor interface, adsorption phase change, cluster distribution, entropy, surface tension

中图分类号:

TK 121

宋本南, 吴春梅, 李友荣. 气固界面吸附团簇分布及相变机制研究[J]. 化工学报, 2021, 72(5): 2680-2687.

SONG Bennan, WU Chunmei, LI Yourong. Investigation on cluster distribution and phase transition of adsorption at solid-vapor interface[J]. CIESC Journal, 2021, 72(5): 2680-2687.

图/表 10

图1 等温吸附曲线

Fig.1 Adsorption isotherms of water vapor on silica and graphite surfaces

表1 Zeta等温吸附参数

Table 1 Zeta isothermal parameters

吸附质

吸附剂

(μmol/m²)

ζ_m

图2 二氧化硅表面零吸附单元(a)及团簇(b)分布演化过程

Fig.2 Empty adsorption sites (a) and cluster distribution (b) for water vapor adsorption on silica

图3 石墨表面零吸附单元(a)及团簇(b)分布演化过程

Fig.3 Empty adsorption sites (a) and cluster distribution (b) for water vapor adsorption on graphite

图4 饱和压力附近团簇演化过程

Fig.4 Cluster distribution when the pressure is around the saturation pressure

图5 压比为1/α及1.14时不同团簇类型分布

Fig.5 The number of different clusters when xV=1/α and xV=1.14

图6 全压比区间Zeta等温吸附曲线

Fig.6 Zeta adsorption isotherm in the full pressure range

图7 吸附熵及吸附量变化率随压比的变化规律

Fig.7 Variations of entropy of adsorption clusters and the adsorption increasing rate with thepressure ratio

图8 气固界面张力随压比变化规律

Fig.8 Variations of surface tension at solid-vapor interface with pressure ratio

图9 不同压比下界面张力变化率随压比变化情况

Fig.9 Pressure ratio dependence of the variation of surface tension

参考文献 37

1	刘有毅, 黄艳, 何嘉杰, 等. CO/N₂/CO₂在MOF-74(Ni)上吸附相平衡和选择性[J]. 化工学报, 2015, 66(11): 4469-4475.
	Liu Y Y, Huang Y, He J J, et al. Adsorption isotherms and selectivity of CO/N₂/CO₂ on MOF-74(Ni)[J]. CIESC Journal, 2015, 66(11): 4469-4475.
2	张所瀛, 刘红, 刘朋飞, 等. 金属有机骨架材料在CO₂/CH₄吸附分离中的研究进展[J]. 化工学报, 2014, 65(5): 1563-1570.
	Zhang S Y, Liu H, Liu P F, et al. Progress of adsorption-based CO₂/CH₄ separation by metal organic frameworks[J]. CIESC Journal, 2014, 65(5): 1563-1570.
3	罗仙平, 李健昌, 严群, 等. 处理低浓度氨氮废水吸附材料的筛选[J]. 化工学报, 2010, 61(1): 216-222.
	Luo X P, Li J C, Yan Q, et al. Screening of optimum adsorbents for treating wastewater containing low concentration ammonia-nitrogen[J]. CIESC Journal, 2010, 61(1): 216-222.
4	任南琪, 周显娇, 郭婉茜, 等. 染料废水处理技术研究进展[J]. 化工学报, 2013, 64(1): 84-94.
	Ren N Q, Zhou X J, Guo W Q, et al. A review on treatment methods of dye wastewater[J]. CIESC Journal, 2013, 64(1): 84-94.
5	Ishihara K, Ziats N P, Tierney B P, et al. Protein adsorption from human plasma is reduced on phospholipid polymers[J]. Journal of Biomedical Materials Research, 1991, 25(11): 1397-1407.
6	Lord M S, Foss M, Besenbacher F. Influence of nanoscale surface topography on protein adsorption and cellular response[J]. Nano Today, 2010, 5(1): 66-78.
7	Narayanan S, Yang S, Kim H, et al. Optimization of adsorption processes for climate control and thermal energy storage[J]. International Journal of Heat and Mass Transfer, 2014, 77: 288-300.
8	Langmuir I. The dissociation of hydrogen into atoms(Ⅲ): The mechanism of the reaction[J]. Journal of the American Chemical Society, 1916, 38(6): 1145-1156.
9	Brunauer S, Emmett P H, Teller E. Adsorption of gases in multimolecular layers[J]. Journal of the American Chemical Society, 1938, 60(2): 309-319.
10	Tompkins F C. Physical adsorption on non-uniform surfaces[J]. Transactions of the Faraday Society, 1950, 46: 569.
11	Hill T L. Theory of physical adsorption[J]. Advances in Catalysis, 1952, 4: 211-258.
12	Scheufele F B, Módenes A N, Borba C E, et al. Monolayer-multilayer adsorption phenomenological model: kinetics, equilibrium and thermodynamics[J]. Chemical Engineering Journal, 2016, 284: 1328-1341.
13	Laaksonen A. A unifying model for adsorption and nucleation of vapors on solid surfaces[J]. The Journal of Physical Chemistry A, 2015, 119(16): 3736-3745.
14	Anderson R B, Hall W K. Modifications of the Brunauer, Emmett and Teller equation [J]. Journal of the American Chemical Society, 1948, 70(5): 1727-1734.
15	Foo K Y, Hameed B H. Insights into the modeling of adsorption isotherm systems[J]. Chemical Engineering Journal, 2010, 156(1): 2-10.
16	Kong L L, Adidharma H. A new adsorption model based on generalized van der Waals partition function for the description of all types of adsorption isotherms[J]. Chemical Engineering Journal, 2019, 375: 122112.
17	Buttersack C. Modeling of type IV and V sigmoidal adsorption isotherms[J]. Physical Chemistry Chemical Physics, 2019, 21(10): 5614-5626.
18	Petsev N D, Leal L G, Shell M S. Universal gas adsorption mechanism for flat nanobubble morphologies[J]. Physical Review Letters, 2020, 125(14): 146101.
19	Talu O, Myers A L. Rigorous thermodynamic treatment of gas adsorption[J]. AIChE Journal, 1988, 34(11): 1887-1893.
20	Toth J. State equations of the solid gas interface layer[J]. Acta Chimica Academiae Scientiarum Hungaricae, 1971, 69: 311-317.
21	Schlangen L J M, Koopal L K, Cohen Stuart M A, et al. Wettability: thermodynamic relationships between vapour adsorption and wetting[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 1994, 89(2/3): 157-167.
22	Kaplan W D, Chatain D, Wynblatt P, et al. A review of wetting versus adsorption, complexions, and related phenomena: the Rosetta stone of wetting[J]. Journal of Materials Science, 2013, 48(17): 5681-5717.
23	Laaksonen A, Malila J. An adsorption theory of heterogeneous nucleation of water vapour on nanoparticles[J]. Atmospheric Chemistry and Physics, 2016, 16(1): 135-143.
24	Wang Z J, Qin F H, Luo X S. Numerical investigation of effects of curvature and wettability of particles on heterogeneous condensation[J]. The Journal of Chemical Physics, 2018, 149(13): 134306.
25	Zandavi S H, Ward C A. Vapour adsorption kinetics: statistical rate theory and zeta adsorption isotherm approach[J]. Physical Chemistry Chemical Physics, 2016, 18(36): 25538-25545.
26	Wu C M, Zandavi S H, Ward C A. Prediction of the wetting condition from the Zeta adsorption isotherm[J]. Physical Chemistry Chemical Physics, 2014, 16(46): 25564-25572.
27	Ward C A, Wu J Y. Effect of adsorption on the surface tensions of solid-fluid interfaces[J]. The Journal of Physical Chemistry B, 2007, 111(14): 3685-3694.
28	Wongkoblap A, Do D D. Adsorption of water in finite length carbon slit pore: comparison between computer simulation and experiment[J]. The Journal of Physical Chemistry B, 2007, 111(50): 13949-13956.
29	Zandavi S H, Ward C A. Characterization of the pore structure and surface properties of shale using the zeta adsorption isotherm approach[J]. Energy & Fuels, 2015, 29(5): 3004-3010.
30	Zargarzadeh L, Elliott J A W. Thermodynamics of surface nanobubbles[J]. Langmuir, 2016, 32(43): 11309-11320.
31	Ghaffarizadeh S A, Zandavi S H, Ward C A. Specific surface area from nitrogen adsorption data at 77 K using the zeta adsorption isotherm [J]. The Journal of Physical Chemistry C, 2017, 121(41): 23011-23016.
32	Wei X, Wu C M, Li Y R. Molecular insight into the formation of adsorption clusters based on the zeta isotherm[J]. Physical Chemistry Chemical Physics, 2020, 22(18): 10123-10131.
33	汪志诚. 热力学·统计物理[M]. 5版. 北京: 高等教育出版社, 2013.
	Wang Z C. Thermodynamics:Statistical Physics [M]. 5th ed. Beijing: Higher Education Press, 2013.
34	Argyris D, Tummala N R, Striolo A, et al. Molecular structure and dynamics in thin water films at the silica and graphite surfaces[J]. The Journal of Physical Chemistry C, 2008, 112(35): 13587.
35	苏长荪. 高等工程热力学[M]. 北京: 高等教育出版社, 1987.
	Su C S. Advanced Engineering Thermodynamics [M]. Beijing: Higher Education Press, 1987.
36	Ghasemi H, Ward C A. Surface tension of solids in the absence of adsorption[J]. The Journal of Physical Chemistry B, 2009, 113(38): 12632-12634.
37	Barton S S, Evans M J B, MacDonald J A F. Adsorption of water vapor on nonporous carbon[J]. Langmuir, 1994, 10(11): 4250-4252.

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