Thermodynamic mechanism of complex fluid–solid interfacial interaction
(2.Herbert Gleiter Institute of Nanoscience, School of Materials Science and Engineering, Nanjing University of Science & Technology, Nanjing, Jiangsu, China 210094)
(3.Energy Engineering, Division of Energy Science, Luleå University of Technology, Luleå, Sweden)
【Abstract】Interfacial transfer at mesoscale is a common issue for all the multi-phase chemical processes, and the related study remains as a scientific challenge due to the complexities. Investigating the interfacial interactions at mesoscale to find out the regulation strategies is the key to the realization of process intensification of mass transfer and reaction for the advanced chemical industries. To accurately describe the behavior of fluids at the interface, a new molecular thermodynamic model that can describe the complex fluid–solid interfacial interaction is established. When the molecular thermodynamic modeling method is extended to the nano/micro-interfacial transfer, the coordination of advanced experiments at nano/micro-scale and molecular thermodynamic modeling is needed. Atomic force microscopy (AFM), which possesses the sensitivity down to nanoscale, can directly obtain the interfacial interaction at nano/micro-scale. The quantification of AFM-measured forces can be used to construct the coarse-grained molecular model and describe complex interfacial interactions. Then, the coarse-grained molecular model can reveal the molecular thermodynamic mechanism of nano- and micro-interface transfer, realizing quantitative prediction.
【Keywords】 thermodynamics; complex fluids; model; interface; molecular simulation; AFM;
(Translated by WANG YX)
 Park H B, Kamcev J, Robeson L M, et al. Maximizing the right stuff: the trade-off between membrane permeability and selectivity [J]. Science, 2017, 356 (6343): eaab0530.
 Wang S, Wu Y, Zhang N, et al. A highly permeable graphene oxide membrane with fast and selective transport nanochannels for efficient carbon capture [J]. Energy & Environmental Science, 2016, 9 (10): 3107–3112.
 Zhang H, Sun J M, Ma D, et al. Unusual mesoporous SBA-15 with parallel channels running along the short axis [J]. Journal of the American Chemical Society, 2004, 126 (24): 7440–7441.
 Pan X L, Fan Z L, Chen W, et al. Enhanced ethanol production inside carbon-nanotube reactors containing catalytic particles [J]. Nature Materials, 2007, 6 (7): 507–511.
 Corma A. From microporous to mesoporous molecular sieve materials and their use in catalysis [J]. Chemical Reviews, 1997, 97 (6): 2373–2419.
 Tome L C, Marrucho I M. Ionic liquid-based materials: a platform to design engineered CO2 separation membranes [J]. Chemical Society Reviews, 2016, 45 (10): 2785–2824.
 Oztop H F, Al-Salem K. A review on entropy generation in natural and mixed convection heat transfer for energy systems [J]. Renewable & Sustainable Energy Reviews, 2012, 16 (1): 911–920.
 Smith A E, Zhou L Z, Gorensek A H, et al. In-cell thermodynamics and a new role for protein surfaces [J]. Proceedings of the National Academy of Sciences of the United States of America, 2016, 113 (7): 1725–1730
 Yang H G, Sun C H, Qiao S Z, et al. Anatase TiO2 single crystals with a large percentage of reactive facets [J]. Nature, 2008, 453 (7195): 638–641.
 Xie W L, Ji X Y, Feng X, et al. Mass-transfer rate enhancement for CO2 separation by ionic liquids: theoretical study on the mechanism [J]. AIChE Journal, 2015, 61 (12): 4437–4444.
Lu X H, Ji Y H, Liu H L. Non-equilibrium thermodynamics analysis and its application for interfacial mass transfer [J]. Scientia Sinica Chimica, 2011, (9): 1540–1547 (in Chinese).
 Bair S, McCabe C, Cummings P T. Comparison of nonequilibrium molecular dynamics with experimental measurements in the nonlinear shear-thinning regime [J]. Physical Review Letters, 2002, 88 (5): 058302.
 Hapala P, Svec M, Stetsovych O, et al. Mapping the electrostatic force field of single molecules from high-resolution scanning probe images [J]. Nature Communications, 2016, 7: 11560.
 Kim E H, Lee B J. Size dependency of melting point of crystalline nano particles and nano wires: a thermodynamic modeling [J]. Metals and Materials International, 2009, 15 (4): 531–537.
 Luo W H, Hu W Y, Su K L, et al. Gibbs free energy approach to the prediction of melting points of isolated, supported, and embedded nanoparticles [J]. Journal of Applied Physics, 2012, 112 (1): 014302.
 Shibuta Y, Suzuki T. Effect of wettability on phase transition in substrate–supported bcc–metal nanoparticles: a molecular dynamics study [J]. Chemical Physics Letters, 2010, 486 (4/5/6): 137–143.
 Gubbins K E, Long Y, Sliwinska-Bartkowiak M. Thermodynamics of confined nano-phases [J]. Journal of Chemical Thermodynamics, 2014, 74: 169–183.
 Wu N H, Ji X Y, An R, et al. Generalized Gibbs free energy of confined nanoparticles [J]. AIChE Journal, 2017, 63 (10): 4595–4603.
 Wu N H, Ji X Y, Xie W L, et al. Confinement phenomenon effect on the CO2 absorption working capacity in ionic liquids immobilized into porous solid supports [J]. Langmuir, 2017, 33 (42): 11719–11726.
 Wang Y, Jiang W, Yan T, et al. Understanding ionic liquids through atomistic and coarse-grained molecular dynamics simulations [J]. Accounts of Chemical Research, 2007, 40 (11): 1193–1199.
 Maginn E J. Atomistic simulation of the thermodynamic and transport properties of ionic liquids [J]. Accounts of Chemical Research, 2007, 40 (11): 1200–1207.
 Zhou J, Lu X H, Wang Y R, et al. Molecular dynamics study on ionic hydration [J]. Fluid Phase Equilibria, 2002, 194: 257–270.
 Yamnitz C R, Negin S, Carasel I A, et al. Dianilides of dipicolinic acid function as synthetic chloride channels [J]. Chemical Communications, 2010, 46 (16): 2838–2840.
 Shao Q, Zhou J, Lu L H, et al. Anomalous hydration shell order of Na+ and K+ inside carbon nanotubes [J]. Nano Letters, 2009, 9 (3): 989–994.
 Gong X J, Li J C, Xu K, et al. A controllable molecular sieve for Na+ and K+ ions [J]. Journal of the American Chemical Society, 2010, 132 (6): 1873–1877.
 Zhou X B, Liu G D, Yamato K, et al. Self–assembling subnanometer pores with unusual mass-transport properties [J]. Nature Communications, 2012, 3: 8.
 Wang J, Zhu Y, Zhou J, et al. Diameter and helicity effects on static properties of water molecules confined in carbon nanotubes [J]. Physical Chemistry Chemical Physics, 2004, 6 (4): 829–835.
 Cambre S, Schoeters B, Luyckx S, et al. Experimental observation of single–file water filling of thin single-wall carbon nanotubes down to chiral index (5, 3) [J]. Physical Review Letters, 2010, 104 (20): 4.
 Tang Z Q, Lu L H, Dai Z Y, et al. CO2 absorption in the ionic liquids immobilized on solid surface by molecular dynamics simulation [J]. Langmuir, 2017, 33: 11658–11669.
 Dai Z Y, You Y J, Zhu Y D, et al. Atomistic insights into the layered microstructure and time-dependent stability of [BMIM][PF6] confined within the meso-slit of carbon [J]. Journal of Physical Chemistry B, 2019, 123 (31): 6857–6869.
 Dai Z Y, Shi L L, Lu L H, et al. Unique structures and vibrational spectra of protic ionic liquids confined in TiO2 slits: the role of interfacial hydrogen bonds [J]. Langmuir, 2018, 34 (44): 13449–13458.
 Nguyen H D, Hall C K. Spontaneous fibril formation by polyalanines: discontinuous molecular dynamics simulations [J]. Journal of the American Chemical Society, 2006, 128 (6): 1890–1901.
 Jalili N, Laxminarayana K. A review of atomic force microscopy imaging systems: application to molecular metrology and biological sciences [J]. Mechatronics, 2004, 14 (8): 907–945.
 Fang T H, Chang W J, Weng C I. Surface analysis of nanomachined films using atomic force microscopy [J]. Materials Chemistry and Physics, 2005, 92 (2/3): 379–383.
 Binnig G, Quate C F, Gerber C. Atomic force microscopy [J]. Physical Review Letters, 1986, 56 (9): 930–933.
 Jahanmir J, Haggar B G, Hayes J B. The scaning probe microscopy [J]. Scanning Microscopy, 1992, 6 (3): 625–660.
 Butt H J, Cappella B, Kappl M. Force measurements with the atomic force microscope: technique, interpretation and applications [J]. Surface Science Reports, 2005, 59 (1/2/3/4/5/6): 1–152.
 Ederth T. Computation of lifshitz—van der Waals forces between alkylthiol monolayers on gold films [J]. Langmuir, 2001, 17 (11): 3329–3340.
 Johnson K L, Johnson K L. Contact Mechanics [J]. Cambridge: Cambridge University Press, 1987.
 Johnson K L, Greenwood J A. An adhesion map for the contact of elastic spheres [J]. Journal of Colloid and Interface Science, 1997, 192 (2): 326–333.
 Derjaguin B V, Muller V M, Toporov Y P. Effect of contact deformations on the adhesion of particles [J]. Journal of Colloid and Interface Science, 1975, 53 (2): 314–326.
 Johnson K L, Kendall K, Roberts A D. Surface energy and the contact of elastic solids [J]. Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences, 1971, 324 (1558): 301–313.
 You H X, Lowe C R. AFM studies of protein adsorption (2): Characterization of immunoglobulin G adsorption by detergent washing [J]. Journal of Colloid and Interface Science, 1996, 182 (2): 586–601.
 Xu L C, Logan B E. Interaction forces measured using AFM between colloids and surfaces coated with both dextran and protein [J]. Langmuir, 2006, 22 (10): 4720–4727.
 Tencer M, Charbonneau R, Lahoud N. et al. AFM study of BSA adlayers on Au stripes [J]. Applied Surface Science, 2007, 253 (23): 9209–9214.
 An R, Yu Q M, Zhang L Z, et al. Simple physical approach to reducing frictional and adhesive forces on a TiO2 surface via creating heterogeneous nanopores [J]. Langmuir, 2012, 28 (43): 15270–15277.
 An R, Zhu Y D, Wu N H, et al. Wetting behavior of ionic liquid on mesoporous titanium dioxide surface by atomic force microscopy [J]. ACS Applied Materials & Interfaces, 2013, 5 (7): 2692–2698.
 Nel A E, Madler L, Velegol D, et al. Understanding biophysicochemical interactions at the nano–bio interface [J]. Nature Materials, 2009, 8 (7): 543–557.
 Tu X, Manohar S, Jagota A, et al. DNA sequence motifs for structure-specific recognition and separation of carbon nanotubes [J]. Nature, 2009, 460 (7252): 250–253.
 Ma C D, Wang C, Acevedo-Velez C, et al. Modulation of hydrophobic interactions by proximally immobilized ions [J]. Nature, 2015, 517 (7534): 347–350.
 Shao M, Ning F, Zhao J, et al. Preparation of Fe3O4@SiO2@layered double hydroxide core–shell microspheres for magnetic separation of proteins [J]. Journal of the American Chemical Society, 2012, 134 (2): 1071–1077.
 Leslie D C, Waterhouse A, Berthet J B, et al. A bioinspired omniphobic surface coating on medical devices prevents thrombosis and biofouling [J]. Nature Biotechnology, 2014, 32 (11): 1134–1140.
 Zhen X, Wang X, Xie C, et al. Cellular uptake, antitumor response and tumor penetration of cisplatin-loaded milk protein nanoparticles [J]. Biomaterials, 2013, 34 (4): 1372–1382.
 Walkey C D, Chan W C. Understanding and controlling the interaction of nanomaterials with proteins in a physiological environment [J]. Chemical Society Reviews, 2012, 41 (7): 2780–2799.
 Elter P, Lange R, Beck U. Atomic force microscopy studies of the influence of convex and concave nanostructures on the adsorption of fibronectin [J]. Colloids And Surfaces B—Biointerfaces, 2012, 89: 139–146.
 Tsapikouni T S, Missirlis Y F. pH and ionic strength effect on single fibrinogen molecule adsorption on mica studied with AFM [J]. Colloids and Surfaces B—Biointerfaces 2007, 57 (1): 89–96
 Dupont-Gillain C C, Fauroux C M J, Gardner D C J, et al. Use of AFM to probe the adsorption strength and time-dependent changes of albumin on self-assembled monolayers [J]. Journal of Biomedical Materials Research Part A, 2003, 67A (2): 548–558.
 Cao T, Tang H Y, Liang X M, et al. Nanoscale investigation on adhesion of E. coli surface modified silicone using atomic force microscopy [J]. Biotechnology and Bioengineering, 2006, 94 (1): 167–176.
 Beckwitt E C, Kong M, van Houten B. Studying protein–DNA interactions using atomic force microscopy [J]. Seminars in Cell & Developmental Biology, 2018, 73: 220–230.
 Tsapikouni T S, Missirlis Y F. Protein–material interactions: from micro- to -nano scale [J]. Materials Science and Engineering B—Advanced Functional Solid-State Materials, 2008, 152 (1/2/3): 2–7.
 An R, Zhuang W, Yang Z H, et al. Protein adsorptive behavior on mesoporous titanium dioxide determined by geometrical topography [J]. Chemical Engineering Science, 2014, 117: 146–155.
 An R, Dong Y H, Zhu J H, et al. Adhesion and friction forces in biofouling attachments to nanotube- and PEG-patterned TiO2 surfaces [J]. Colloids and Surfaces B—Biointerfaces, 2017, 159: 108–117.
 Ma L, Cai Y Y, Li Y H. et al. Single-molecule force spectroscopy of protein–membrane interactions [J]. eLife, 2017, 6: 30493.
 Verdorfer T, Bernardi R C, Meinhold A. et al. Combining in vitro and in silico single-molecule force spectroscopy to characterize and tune cellulosomal scaffoldin mechanics [J]. Journal of the American Chemical Society, 2017, 139 (49): 17841–17852.
 Dong Y H, An R, Zhao S L, et al. Molecular interactions of protein with TiO2 by the AFM-measured adhesion force [J]. Langmuir, 2017, 33: 11626–11634.
 Moerz S T, Huber P. pH-dependent selective protein adsorption into mesoporous silica [J]. The Journal of Physical Chemistry C, 2015, 119 (48): 27072–27079.
 Aramesh M, Shimoni O, Ostrikov K, et al. Surface charge effects in protein adsorption on nanodiamonds [J]. Nanoscale, 2015, 7 (13): 5726–5736
 Kumar S, Aswal V K, Callow P. pH-dependent interaction and resultant structures of silica nanoparticles and lysozyme protein [J]. Langmuir, 2014, 30 (6): 1588–1598.
 Dong Y H, Laaksonen A, Cao W, et al. AFM study of pH-dependent adhesion on single protein to TiO2 surface [J]. Advanced Materials Interfaces, 2019, 6: 1900411.
 Zhou J, Zhang L Z, Leng Y S, et al. Unbinding of the streptavidinbiotin complex by atomic force microscopy: a hybrid simulation study [J]. Journal of Chemical Physics, 2006, 125 (10): 104905.
 Wang H, Fertala A, Ratner B D, et al. Identifying the SPARC binding sites on collagen I and procollagen I by atomic force microscopy [J]. Analytical Chemistry, 2005, 77 (21): 6765–6771.
 Zhang L Z, Li L Y, Chen S F, et al. Measurements of friction and adhesion for alkyl monolayers on Si(111) by scanning force microscopy [J]. Langmuir, 2002, 18 (14): 5448–5456.
 Lee C, Li Q Y, Kalb W, et al. Frictional characteristics of atomically thin sheets [J]. Science, 2010, 328 (5974): 76–80.
 Muller J, Hartke B. REAXFF reactive force field for disulfide mechanochemistry, fitted to multireference ab initio data [J]. Journal of Chemical Theory and Computation, 2016, 12 (8): 3913–3925.
 An R, Huang L L, Long Y, et al. Liquid–solid nanofriction and interfacial wetting [J]. Langmuir, 2016, 32 (3): 743–750
 An R, Zhou G B, Zhu Y D, et al. Friction of ionic liquid–glycol ether mixtures at titanium interfaces: negative load dependence [J]. Advanced Materials Interfaces, 2018, 5: 1800263.
 Dong Y H, Ji X Y, Laaksonen A, et al. Determination of the small amount of proteins interacting with TiO2 nanotubes by AFM measurement [J]. Biomaterials, 2019, 192: 368–376.