Publications by authors named "Rahul Prasanna Misra"

8 Publications

  • Page 1 of 1

Diameter Dependence of Water Filling in Lithographically Segmented Isolated Carbon Nanotubes.

ACS Nano 2021 Feb 29;15(2):2778-2790. Epub 2021 Jan 29.

Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.

Although the structure and properties of water under conditions of extreme confinement are fundamentally important for a variety of applications, they remain poorly understood, especially for dimensions less than 2 nm. This problem is confounded by the difficulty in controlling surface roughness and dimensionality in fabricated nanochannels, contributing to a dearth of experimental platforms capable of carrying out the necessary precision measurements. In this work, we utilize an experimental platform based on the interior of lithographically segmented, isolated single-walled carbon nanotubes to study water under extreme nanoscale confinement. This platform generates multiple copies of nanotubes with identical chirality, of diameters from 0.8 to 2.5 nm and lengths spanning 6 to 160 μm, that can be studied individually in real time before and after opening, exposure to water, and subsequent water filling. We demonstrate that, under controlled conditions, the diameter-dependent blue shift of the Raman radial breathing mode (RBM) between 1 and 8 cm measures an increase in the interior mechanical modulus associated with liquid water filling, with no response from exterior water exposure. The observed RBM shift with filling demonstrates a non-monotonic trend with diameter, supporting the assignment of a minimum of 1.81 ± 0.09 cm at 0.93 ± 0.08 nm with a nearly linear increase at larger diameters. We find that a simple hard-sphere model of water in the confined nanotube interior describes key features of the diameter-dependent modulus change of the carbon nanotube and supports previous observations in the literature. Longer segments of 160 μm show partial filling from their ends, consistent with pore clogging. These devices provide an opportunity to study fluid behavior under extreme confinement with high precision and repeatability.
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http://dx.doi.org/10.1021/acsnano.0c08634DOI Listing
February 2021

Predicting Gas Separation through Graphene Nanopore Ensembles with Realistic Pore Size Distributions.

ACS Nano 2021 Jan 13;15(1):1727-1740. Epub 2021 Jan 13.

Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.

The development of nanoporous single-layer graphene membranes for gas separation has prompted increasing theoretical investigations of gas transport through graphene nanopores. However, computer simulations and theories that predict gas permeances through individual graphene nanopores are not suitable to describe experimental results, because a realistic graphene membrane contains a large number of nanopores of diverse sizes and shapes. With this need in mind, here, we generate nanopore ensembles by etching carbon atoms away from pristine graphene with different etching times, using a kinetic Monte Carlo algorithm developed by our group for the isomer cataloging problem of graphene nanopores. The permeances of H, CO, and CH through each nanopore in the ensembles are predicted using transition state theory based on classical all-atomistic force fields. Our findings show that the total gas permeance through a nanopore ensemble is dominated by a small fraction of large nanopores with low energy barriers of pore crossing. We also quantitatively predict the increase of the gas permeances and the decrease of the selectivities between the gases as functions of the etching time of graphene. Furthermore, by fitting the theoretically predicted selectivities to the experimental ones reported in the literature, we show that nanopores in graphene effectively expand as the temperature of permeation measurement increases. We propose that this nanopore "expansion" is due to the desorption of contaminants that partially clog the graphene nanopores. In general, our study highlights the effects of the pore size and shape distributions of a graphene nanopore ensemble on its gas separation properties and calls into attention the potential effect of pore-clogging contamination in experiments.
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http://dx.doi.org/10.1021/acsnano.0c09420DOI Listing
January 2021

Uncovering a Universal Molecular Mechanism of Salt Ion Adsorption at Solid/Water Interfaces.

Langmuir 2021 Jan 4;37(2):722-733. Epub 2021 Jan 4.

Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.

Solid/water interfaces, in which salt ions come in close proximity to solids, are ubiquitous in nature. Because water is a polar solvent and salt ions are charged, a long-standing puzzle involving solid/water interfaces is how do the electric fields exerted by the salt ions and the interfacial water molecules polarize the charge distribution in the solid and how does this polarization, in turn, influence ion adsorption at any solid/water interface. Here, using state-of-the-art polarizable force fields derived from quantum chemical simulations, we perform all-atomistic molecular dynamics simulations to investigate the adsorption of various ions comprising the well-known Hofmeister series at the graphene/water interface, including comparing with available experimental data. Our findings reveal that, , the ionic electric field-induced polarization of graphene results in a significantly large graphene-ion polarization energy, which drives all salt ions to adsorb to graphene. On the contrary, , we show that the ions and the water molecules exert waves of molecular electric fields on graphene which destructively interfere with each other. This remarkable phenomenon is shown to cause a water-mediated screening of more than 85% of the graphene-ion polarization energy. Finally, by investigating superhydrophilic and superhydrophobic model surfaces, we demonstrate that this phenomenon occurs universally at all solid/water interfaces and results in a significant weakening of the ion-solid interactions, such that ion specific effects are governed primarily by a competition between the ion-water and water-water interactions, irrespective of the nature of the solid/water interface.
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http://dx.doi.org/10.1021/acs.langmuir.0c02829DOI Listing
January 2021

Analytical Prediction of Gas Permeation through Graphene Nanopores of Varying Sizes: Understanding Transitions across Multiple Transport Regimes.

ACS Nano 2019 Oct 23;13(10):11809-11824. Epub 2019 Sep 23.

Department of Chemical Engineering , Massachusetts Institute of Technology , Cambridge , Massachusetts 02139 , United States.

Nanoporous graphene is a promising candidate material for gas separation membranes, due to its atomic thickness and low cross-membrane transport resistance. The mechanisms of gas permeation through graphene nanopores, in both the large and small pore size limits, have been reported in the literature. However, mechanistic insights into the crossover from the small pore size limit to the large pore size limit are still lacking. In this study, we develop a comprehensive theoretical framework to predict gas permeance through graphene nanopores having a wide range of diameters using analytical equations. We formulate the transport kinetics associated with the direct impingement from the bulk and with the surface diffusion from the adsorption layer on graphene and then combine them to predict the overall gas permeation rate using a reaction network model. We also utilize molecular dynamics simulations to validate and calibrate our theoretical model. We show that the rates of both the direct impingement and the surface diffusion pathways need to be corrected using different multiplicative factors, which are functions of temperature, gas kinetic diameter, and pore diameter. Further, we find a minor spillover pathway that originates from the surface adsorption layer, but is not included in our theoretical model. Finally, we utilize the corrected model to predict the permeances of CO, CH, and Ar through graphene nanopores. We show that as the pore diameter increases, gas transport through graphene nanopores can transition from being translocation dominated (pore diameter 0.7 nm), to surface pathway dominated (pore diameter 1-2 nm), and finally to direct pathway dominated (pore diameter 4 nm). The various gas permeation mechanisms outlined in this study will be particularly useful for the rational design of membranes made out of two-dimensional materials such as graphene for gas separation applications.
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http://dx.doi.org/10.1021/acsnano.9b05779DOI Listing
October 2019

Theory of Surface Forces in Multivalent Electrolytes.

Langmuir 2019 Sep 20;35(35):11550-11565. Epub 2019 Aug 20.

Department of Chemical Engineering , Massachusetts Institute of Technology , 25 Ames Street , Cambridge , Massachusetts 02142 , United States.

Aqueous electrolyte solutions containing multivalent ions exhibit various intriguing properties, including attraction between like-charged colloidal particles, which results from strong ion-ion correlations. In contrast, the classical Derjaguin-Landau-Verwey-Overbeek theory of colloidal stability, based on the Poisson-Boltzmann mean-field theory, always predicts a repulsive electrostatic contribution to the disjoining pressure. Here, we formulate a general theory of surface forces, which predicts that the contribution to the disjoining pressure resulting from ion-ion correlations is always attractive and can readily dominate over entropic-induced repulsions for solutions containing multivalent ions, leading to the phenomenon of like-charge attraction. Ion-specific short-range hydration interactions, as well as surface charge regulation, are shown to play an important role at smaller separation distances but do not fundamentally change these trends. The theory is able to predict the experimentally observed strong cohesive forces reported in cement pastes, which result from strong ion-ion correlations involving the divalent calcium ion.
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http://dx.doi.org/10.1021/acs.langmuir.9b01110DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6750839PMC
September 2019

Multi-scale approach for modeling stability, aggregation, and network formation of nanoparticles suspended in aqueous solutions.

Nanoscale 2019 Feb;11(9):3979-3992

Department of Energy, Politecnico di Torino, Torino, Italy.

Suspensions of nanoparticles (NPs) in aqueous solutions hold promise in many research fields, including energy applications, water desalination, and nanomedicine. The ability to tune NP interactions, and thereby to modulate the NP self-assembly process, holds the key to rationally synthesize NP suspensions. However, traditional models obtained by coupling the DLVO (Derjaguin, Landau, Verwey, and Overbeek) theory of NP interactions, or suitable modifications of it, with the kinetic theory of colloidal aggregation are inadequate to precisely model NP self-assembly because they neglect hydration forces and discrete-size effects predominant at the nanoscale. By synergistically blending molecular dynamics and stochastic dynamics simulations with continuum theories, we develop a multi-scale (MS) model, which is able to accurately predict suspension stability, timescales for NP aggregation, and macroscopic properties (e.g., the thermal conductivity) of bare and surfactant-coated NP suspensions, in good agreement with the experimental data. Our results enable the formulation of design rules for engineering NP aqueous suspensions in a wide range of applications.
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http://dx.doi.org/10.1039/c8nr08782bDOI Listing
February 2019

Mechanism and Prediction of Gas Permeation through Sub-Nanometer Graphene Pores: Comparison of Theory and Simulation.

ACS Nano 2017 08 19;11(8):7974-7987. Epub 2017 Jul 19.

Department of Chemical Engineering, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.

Due to its atomic thickness, porous graphene with sub-nanometer pore sizes constitutes a promising candidate for gas separation membranes that exhibit ultrahigh permeances. While graphene pores can greatly facilitate gas mixture separation, there is currently no validated analytical framework with which one can predict gas permeation through a given graphene pore. In this work, we simulate the permeation of adsorptive gases, such as CO and CH, through sub-nanometer graphene pores using molecular dynamics simulations. We show that gas permeation can typically be decoupled into two steps: (1) adsorption of gas molecules to the pore mouth and (2) translocation of gas molecules from the pore mouth on one side of the graphene membrane to the pore mouth on the other side. We find that the translocation rate coefficient can be expressed using an Arrhenius-type equation, where the energy barrier and the pre-exponential factor can be theoretically predicted using the transition state theory for classical barrier crossing events. We propose a relation between the pre-exponential factor and the entropy penalty of a gas molecule crossing the pore. Furthermore, on the basis of the theory, we propose an efficient algorithm to calculate CO and CH permeances per pore for sub-nanometer graphene pores of any shape. For the CO/CH mixture, the graphene nanopores exhibit a trade-off between the CO permeance and the CO/CH separation factor. This upper bound on a Robeson plot of selectivity versus permeance for a given pore density is predicted and described by the theory. Pores with CO/CH separation factors higher than 10 have CO permeances per pore lower than 10 mol s Pa, and pores with separation factors of ∼10 have CO permeances per pore between 10 and 10 mol s Pa. Finally, we show that a pore density of 10 m is required for a porous graphene membrane to exceed the permeance-selectivity upper bound of polymeric materials. Moreover, we show that a higher pore density can potentially further boost the permeation performance of a porous graphene membrane above all existing membranes. Our findings provide insights into the potential and the limitations of porous graphene membranes for gas separation and provide an efficient methodology for screening nanopore configurations and sizes for the efficient separation of desired gas mixtures.
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http://dx.doi.org/10.1021/acsnano.7b02523DOI Listing
August 2017

Electric double layer force between charged surfaces: effect of solvent polarization.

J Chem Phys 2013 Mar;138(11):114703

Department of Mechanical Engineering, University of Alberta, Edmonton, Alberta T6G 2G8, Canada.

In this paper, we develop a theory to delineate the consequences of finite solvent polarization in electric double layer interaction or the osmotic pressure between two similar or oppositely charged surfaces. We use previously published Langevin-Bikerman equations to calculate this electric double layer interaction force or the osmotic pressure between the charged surfaces. The osmotic pressure between oppositely charged surfaces is found to be much larger than that between similarly charged surfaces, and for either case, the influence of solvent polarization ensures a larger pressure than that predicted by the Poisson-Boltzmann (PB) model. We derive distinct scaling relationships to explain the increase of the pressure as a function of the separation between the surfaces, the solvent polarizability, and the number density of water molecules. Most importantly, we demonstrate that our theory can successfully reproduce the experimental results of interaction force between similar and oppositely charged surfaces, by accounting for the large under-prediction made by the corresponding PB model.
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http://dx.doi.org/10.1063/1.4794784DOI Listing
March 2013