publications

Journal Articles

2025

1. From slit pores to 3D frameworks: Advances in molecular modeling of adsorption in nanoporous carbons

   Nicholas J. Corrente, and Alexander V. Neimark

   Advances in Colloid and Interface Science, 2025

   Abs DOI Bib

   Recent advances in computational capabilities have revolutionized the modeling of nanoporous carbons, enabling a transition from idealized pore descriptions to versatile three-dimensional molecular models. This review traces the evolution from traditional continuous potential methods and simple pore models to modern simulation techniques that generate realistic carbon structures incorporating surface heterogeneity, pore connectivity, and framework flexibility. We examine various approaches including Hybrid Reverse Monte Carlo, Quench Molecular Dynamics, and Annealed Molecular Dynamics methods, discussing their respective strengths and limitations. Particular attention is given to the choice of interatomic potentials and their impact on structural predictions. The development of million-atom models captures long-range ordering effects previously inaccessible to simulation. Applications of the 3D models demonstrate their ability to quantitatively predict adsorption behavior and provide the improved characterization of practical carbons using novel methods such as 3D-VIS and APDM. Recent hybrid MD/MC approaches, which incorporate the effects of structure flexibility, offer new insights into adsorbate-induced structural changes. This review highlights how advancing computational methods are bridging the gap between molecular-level understanding and practical applications in the carbon materials design and modeling of adsorption processes.

   @article{corrente2024slit,
     title = {From slit pores to 3D frameworks: Advances in molecular modeling of adsorption in nanoporous carbons},
     journal = {Advances in Colloid and Interface Science},
     volume = {342},
     pages = {103502},
     year = {2025},
     issn = {0001-8686},
     doi = {https://doi.org/10.1016/j.cis.2025.103502},
     url = {https://www.sciencedirect.com/science/article/pii/S0001868625001137},
     author = {Corrente, Nicholas J. and Neimark, Alexander V.},
     keywords = {Nanoporous carbons, Adsorption, Adsorption-induced deformation, Monte Carlo simulation, Molecular dynamics simulation, Density functional theory},
   }

2. Modeling structural flexibility in 3D carbon models: A hybrid MC/MD approach to adsorption-induced deformation

   Nicholas J Corrente, Shivam Parashar, Raleigh Gough, and 3 more authors

   Carbon, 2025

   Abs DOI Bib

   Predicting adsorption-induced deformation in nanoporous carbons is crucial for applications ranging from gas separations and energy storage to carbon capture and enhanced natural gas recovery, where structural changes can significantly impact material performance and process efficiency. The interplay between adsorption and material deformation presents both challenges and opportunities, particularly for CO2–CH4 displacement processes in geological structures where matrix swelling can alter reservoir permeability. We investigate adsorption-induced deformation of nanoporous carbons using an original hybrid Monte Carlo/Molecular Dynamics (MC/MD) simulation approach that couples adsorption sampling with structural relaxation. By studying CH4 and CO2 adsorption on 3D carbon structures of varying densities (0.5–1.0 g/cm3), we demonstrate characteristic non-monotonic deformation behavior, with initial contraction at low pressures followed by expansion at higher pressures. A key contribution is the direct calculation of isothermal compressibility of adsorbate saturated porous structures from the volume fluctuations during NPT-MD simulations, which reveals dramatic mechanical property changes during adsorption. In the process of adsorption, carbon structures exhibit initial softening followed by substantial hardening, with a dramatic increase of the volumetric modulus in denser carbons. Using elastic theory relationships, we estimate the adsorption stresses reaching 175 MPa, that provides crucial insights into potential material degradation mechanisms. For binary CH4/CO2 mixtures, increasing CO2 content amplifies both contraction and expansion effects due to stronger fluid-wall interactions. The iterative MC/MD methodology enables direct observation of the structural evolution and quantitative estimates of the mechanical properties, which are difficult to measure experimentally, advancing our understanding of coupled adsorption-deformation processes in nanoporous materials.

   @article{CORRENTE2025120160,
     title = {Modeling structural flexibility in 3D carbon models: A hybrid MC/MD approach to adsorption-induced deformation},
     journal = {Carbon},
     volume = {238},
     pages = {120160},
     year = {2025},
     issn = {0008-6223},
     doi = {https://doi.org/10.1016/j.carbon.2025.120160},
     url = {https://www.sciencedirect.com/science/article/pii/S0008622325001769},
     author = {Corrente, Nicholas J and Parashar, Shivam and Gough, Raleigh and Hinks, Elizabeth L. and Ravikovitch, Peter I. and Neimark, Alexander V.},
     keywords = {Nanoporous carbons, Adsorption, Adsorption-induced deformation, Monte Carlo simulation, Molecular dynamics simulation},
   }

3. Unveiling non-monotonic deformation of flexible MOFs during gas adsorption: From contraction and softening to expansion and hardening

   Shivam Parashar, Nicholas J Corrente, and Alexander V. Neimark

   Journal of Colloid and Interface Science, 2025

   Abs DOI Bib

   Flexibility of metal–organic frameworks (MOFs) plays an important role in their applications, particularly in adsorption separations, energy and gas storage, and drug delivery. As an important practical example, we study adsorption of CH4, and CO2 on isoreticular MOF-1 (IRMOF-1) crystal at different temperatures using an original computational scheme of iterative grand canonical Monte Carlo (GCMC) and isothermal-isobaric ensemble molecular dynamics (NPT-MD) simulations. Our findings reveal that thermal fluctuations and flexibility of the host framework affect adsorption of guest molecules, which in turn exert a significant adsorption stress, up to 0.1 GPa, on the framework causing its deformation that occurs in a counterintuitive manner. Contrary to the expected gradual swelling during adsorption, we observe non-monotonic deformation, characterized by sharp contraction during the pore filling, followed by partial expansion. During the pore-filling process, guest molecules engender softening of the host structure to a nearly 100% increase in compressibility. However, upon the pore filling and further densification of the adsorbed phase, the structure hardens and compressibility decreases. These findings are supported by quantitative agreement with adsorption experiments on IRMOF-1 and are expected to be applicable to various degrees, to other MOFs and nanoporous materials.

   @article{PARASHAR202588,
     title = {Unveiling non-monotonic deformation of flexible MOFs during gas adsorption: From contraction and softening to expansion and hardening},
     journal = {Journal of Colloid and Interface Science},
     volume = {686},
     pages = {88-95},
     year = {2025},
     issn = {0021-9797},
     doi = {https://doi.org/10.1016/j.jcis.2025.01.228},
     url = {https://www.sciencedirect.com/science/article/pii/S0021979725002796},
     author = {Parashar, Shivam and Corrente, Nicholas J and Neimark, Alexander V.},
     keywords = {Metal–organic frameworks, Adsorption, Monte Carlo simulations, Adsorption induced deformation}
   }

4. Phase Transformations in MOFs Induced by Adsorbate Exchange

   Alexander V. Neimark, Nicholas J Corrente, and François-Xavier Coudert

   Langmuir, 2025

   PMID: 39957601

   Abs DOI Bib

   Deformation of nanoporous materials induced by gas adsorption is a ubiquitous phenomenon that plays an important role in adsorption separations, gas and energy storage, nanosensors, actuators, secondary gas recovery, and carbon dioxide sequestration in coal and shale reservoirs. One of the most prominent examples is the breathing phase transformation in metal–organic frameworks (MOF) associated with significant volume variations upon adsorption and desorption of guest molecules. Here, we present a theoretical framework for the quantitative description of the breathing transitions upon adsorption of binary mixtures, drawing on the practically important example of the displacement of methane by carbon dioxide in the MIL-53 MOF. The proposed approach, which is based on the concept of adsorption stress, reveals the mechanisms of framework deformation and breathing phase transformation between the large pore (LP) and narrow pore (NP) conformations. We show that when pure CH4 adsorption proceeds entirely in the LP phase, even a small addition of CO2 makes the LP phase unstable and triggers conversion to the NP phase, and the reverse NP–LP transformation occurs upon further displacement of CH4 by CO2. The theoretical predictions of adsorption and strain isotherms are confirmed by an agreement with the literature experimental studies performed on MIL-53(Al) at different CH4–CO2 mixture pressures and temperatures. The proposed general approach is applicable to other flexible nanoporous structures and gas mixtures.

   @article{doi:10.1021/acs.langmuir.4c04626,
     author = {Neimark, Alexander V. and Corrente, Nicholas J and Coudert, Fran{\c{c}}ois-Xavier},
     title = {Phase Transformations in MOFs Induced by Adsorbate Exchange},
     journal = {Langmuir},
     volume = {41},
     number = {7},
     pages = {4720-4729},
     year = {2025},
     doi = {10.1021/acs.langmuir.4c04626},
     note = {PMID: 39957601},
     url = {https://doi.org/10.1021/acs.langmuir.4c04626},
     eprint = {https://doi.org/10.1021/acs.langmuir.4c04626}
   }

2024

1. Surface area and porosity analysis in nanoporous carbons by atomistic pore domain model

   Piotr Kowalczyk, Sylwester Furmaniak, Artur P. Terzyk, and 2 more authors

   Carbon, 2024

   Abs DOI Bib

   We present a new atomistic model for evaluating the surface area and porosity of micro-mesoporous carbons. This method, referred to as the atomistic pore domain model (APDM), advances the adsorption porosity methodology by calculating textural properties of micro-mesoporous carbons without relying on assumptions about pore geometry. A thorough analysis of porosity across eleven porous carbons demonstrates a robust correlation between the surface area accessible to N2 molecules, as computed using APDM and the Brunauer-Emmett-Teller method with Rouquerol criterium. This correlation is observed across a spectrum of nanoporous carbons, ranging from ultramicroporous activated carbon fibers and nanoporous carbon beads to supermicro-mesoporous activated carbons and activated carbon fibers. APDM facilitates the extraction of the information regarding the N2 surface area accessibility and the intrinsic geometric surface area of micro-mesoporous carbons. The N2-to-He surface area accessibility ratio of the investigated porous carbons varies from approximately 57 %–94 %, indicating varying degrees of pore sieving among studied carbon samples. Except for ACF-25 micro-mesoporous activated carbon fiber, the intrinsic geometric surface areas of the studied micro-mesoporous carbons are smaller than the geometrical surface area of a single graphene sheet (2640 m2/g).

   @article{KOWALCZYK2024119510,
     title = {Surface area and porosity analysis in nanoporous carbons by atomistic pore domain model},
     journal = {Carbon},
     volume = {229},
     pages = {119510},
     year = {2024},
     issn = {0008-6223},
     doi = {https://doi.org/10.1016/j.carbon.2024.119510},
     url = {https://www.sciencedirect.com/science/article/pii/S0008622324007292},
     author = {Kowalczyk, Piotr and Furmaniak, Sylwester and Terzyk, Artur P. and Corrente, Nicholas J. and Neimark, Alexander V.}
   }

2. Deformation of Nanoporous Carbons Induced By Multicomponent Adsorption: Insight from the SAFT-DFT Model

   Nicholas J. Corrente, Elizabeth L. Hinks, Aastha Kasera, and 2 more authors

   The Journal of Physical Chemistry C, 2024

   Abs DOI Bib

   Deformation of nanoporous materials during gas adsorption has been attracting considerable attention due to various applications, including energy and gas storage, carbon capture, and separation. While most practical applications involve multicomponent mixtures, most experimental and theoretical works deal with single-component adsorption. Here, we study the specifics of adsorption-induced deformation during the displacement of methane by carbon dioxide from carbon nanopores, a process of paramount importance for secondary gas recovery and carbon sequestration in shale and coal formations. Density functional theory calculations augmented by the perturbed-chain statistical associating fluid theory (SAFT-DFT) and grand canonical Monte Carlo (GCMC) simulations are employed to model the adsorption of CH4–CO2 mixtures on carbon slit nanopores of various sizes. We found a nonmonotonic behavior of adsorption deformation with increasing pressure and varying mixture composition that is explained by the peculiarities of molecule packings confined in nanoscale pores. The SAFT-DFT method is shown to produce results in agreement with atomistic GCMC simulations at a fraction of the computational cost. The SAFT-DFT method can be extended to study the adsorption selectivity and deformation effects for complex mixtures, including hydrocarbons and CO2.

   @article{doi:10.1021/acs.jpcc.4c00833,
     author = {Corrente, Nicholas J. and Hinks, Elizabeth L. and Kasera, Aastha and Liu, Jinlu and Neimark, Alexander V.},
     title = {Deformation of Nanoporous Carbons Induced By Multicomponent Adsorption: Insight from the SAFT-DFT Model},
     journal = {The Journal of Physical Chemistry C},
     volume = {128},
     number = {20},
     pages = {8458-8466},
     year = {2024},
     doi = {10.1021/acs.jpcc.4c00833},
     url = {https://doi.org/10.1021/acs.jpcc.4c00833},
     eprint = {https://doi.org/10.1021/acs.jpcc.4c00833},
   }

2023

1. 3D nanostructure prediction of porous carbons via gas adsorption

   Fernando Vallejos-Burgos, Carla de Tomas, Nicholas J. Corrente, and 11 more authors

   Carbon, 2023

   Abs DOI Bib

   Structural characterization of porous carbon materials is critical for the evaluation of their synthesis procedures and performance. Throughout the last decades, many methods have been employed to determine porosity properties from gas adsorption such as surface area, pore size distribution (PSD) and real density. However, gas adsorption models use 1D structures of carbon nanopores, although adsorption and separation properties of nanoporous carbons are governed by 3D pore parameters. Estimating the 3D nanostructure of nanoporous carbons using gas adsorption would accelerate progress in research and implementation of nanoporous carbons. We report here a promising 3D pore nanostructural characterization from gas adsorption. Using atomistic simulations, we have generated a database of realistic 3D porous carbon structures spanning a wide range of pore sizes and geometries. After calculating their gas adsorption isotherms, we employed a numerical procedure to find the relative contribution for each of the structures to the adsorption isotherm of a nanoporous carbon sample. These contributions allowed us to estimate the surface area and pore size distribution of carbon materials; moreover (and perhaps more importantly!), we will show that the plausible 3D pore structures correlate very well with the local carbon structure as experimentally determined by high-resolution TEM observations and can successfully predict adsorption of different molecules. This is a powerful procedure that can be extended to other materials, and with enough computer power, to larger pore sizes.

   @article{VALLEJOSBURGOS2023118431,
     title = {3D nanostructure prediction of porous carbons via gas adsorption},
     journal = {Carbon},
     volume = {215},
     pages = {118431},
     year = {2023},
     issn = {0008-6223},
     doi = {https://doi.org/10.1016/j.carbon.2023.118431},
     url = {https://www.sciencedirect.com/science/article/pii/S0008622323006760},
     author = {Vallejos-Burgos, Fernando and {de Tomas}, Carla and Corrente, Nicholas J. and Urita, Koki and Wang, Shuwen and Urita, Chiharu and Moriguchi, Isamu and Suarez-Martinez, Irene and Marks, Nigel and Krohn, Matthew H. and Kukobat, Radovan and Neimark, Alexander V. and Gogotsi, Yury and Kaneko, Katsumi},
     keywords = {Gas adsorption, Nanoporous carbons, Surface area, Pore size distribution, Adsorption prediction, Nanoscale imaging}
   }

2022

1. Modeling adsorption of simple fluids and hydrocarbons on nanoporous carbons

   Nicholas J. Corrente, Elizabeth L. Hinks, Aastha Kasera, and 3 more authors

   Carbon, 2022

   Abs DOI Bib

   Predicting adsorption on nanoporous carbonaceous materials is important for developing various adsorption and membrane separations, as well as for oil and gas recovery from shale reservoirs. Here, we explore the capabilities of 3D molecular models of disordered carbon structures to reproduce the morphological and adsorption features of practical adsorbents. Using grand canonical Monte Carlo simulations, we construct a series of adsorption isotherms of simple fluids (N2, Ar, CO2, and SO2) and a series of alkanes from methane to hexane on two model 3D structures, purely microporous structure A and micro-mesoporous structure B. We show that structure A reproduces the morphological properties of commercial Norit R1 Extra activated carbon and demonstrates outstanding agreement between the simulated and experimental adsorption isotherms reported in the literature for all adsorbates considered. Good agreement is also found for simulated and measured isosteric heats. Taking into account inherent variability of structural properties of commercial carbons and experimental adsorption data from different literature sources, the correlations with experiments are truly amazing. This work provides a new insight into the specifics of structural and adsorption properties of nanoporous carbons and demonstrates the advantages of using 3D molecular models for predicting adsorption hydrocarbons and other chemicals by MC simulations.

   @article{CORRENTE2022526,
     title = {Modeling adsorption of simple fluids and hydrocarbons on nanoporous carbons},
     journal = {Carbon},
     volume = {197},
     pages = {526-533},
     year = {2022},
     issn = {0008-6223},
     doi = {https://doi.org/10.1016/j.carbon.2022.06.071},
     url = {https://www.sciencedirect.com/science/article/pii/S0008622322005103},
     author = {Corrente, Nicholas J. and Hinks, Elizabeth L. and Kasera, Aastha and Gough, Raleigh and Ravikovitch, Peter I. and Neimark, Alexander V.},
     keywords = {Gas adsorption, Pore size characterization, Nanoporous materials, Carbons, Hydrocarbons},
   }

2021

1. Deformation of Nanoporous Materials in the Process of Binary Adsorption: Methane Displacement by Carbon Dioxide from Coal

   Nicholas J. Corrente, Katarzyna Zarȩbska, and Alexander V. Neimark

   The Journal of Physical Chemistry C, 2021

   Abs DOI Bib

   The phenomenon of adsorption-induced deformation of nanoporous materials has recently attracted a lot of attention in chemical, materials, and geoscience communities. Various theoretical and molecular simulation approaches have been suggested to predict the stress and strain induced by single component gas adsorption. Here, we develop a thermodynamic method based on the notion of the adsorption stress to predict the deformation effects upon multicomponent adsorption. As a practically important example, the process of the displacement of methane by carbon dioxide from microporous carbons is considered. This process is the foundation of secondary gas recovery from shales and coalbeds associated with carbon dioxide sequestration. Theoretical predictions are correlated with the original experimental data on CO2 and CH4 individual and binary adsorption on coal samples coupled with in situ strain measurements. With the model parametrized and verified against the experimental data at ambient temperature, the projections are made for the adsorption deformation at geological conditions of elevated pressure and temperature, which increase with the depth of the reservoir. The proposed approach may have multifaceted applications in modeling the behavior of hydrocarbon mixtures in nanoporous geomaterials, gas separations, and energy storage on flexible adsorbents.

   @article{doi:10.1021/acs.jpcc.1c07363,
     author = {Corrente, Nicholas J. and Zarȩbska, Katarzyna and Neimark, Alexander V.},
     title = {Deformation of Nanoporous Materials in the Process of Binary Adsorption: Methane Displacement by Carbon Dioxide from Coal},
     journal = {The Journal of Physical Chemistry C},
     volume = {125},
     number = {38},
     pages = {21310-21316},
     year = {2021},
     doi = {10.1021/acs.jpcc.1c07363},
     url = {https://doi.org/10.1021/acs.jpcc.1c07363},
     eprint = {https://doi.org/10.1021/acs.jpcc.1c07363}
   }

2020

1. Compressibility of a Simple Fluid in Cylindrical Confinement: Molecular Simulation and Equation of State Modeling

   Christopher D. Dobrzanski, Nicholas J. Corrente, and Gennady Y. Gor

   Industrial & Engineering Chemistry Research, 2020

   Abs DOI Bib

   Fluids confined in nanoporous materials exhibit thermodynamic properties that differ from the same fluid in bulk. Recent experiments and molecular simulations suggested that the isothermal compressibility is among these properties. The compressibility determines the elastic response of a fluid to mechanical impact, and in particular, the speed of acoustic wave propagation through it. Knowledge of the compressibility of fluids confined in nanopores is needed for understanding the elastic wave propagation in fluid-saturated nanoporous media, such as hydrocarbon-bearing shales. Molecular simulations allow for the prediction of the elastic properties of a confined fluid but require computationally expensive calculations for each system and pore size. Therefore, there is interest for a more straightforward model that can predict the elastic properties of a confined fluid as a function of the external pressure and confining pore size. Such models can be based on an equation of state (EOS) for a confined system. Here, we explore a possibility for a generalized van der Waals EOS for confined fluids to predict the compressibility. We also calculate the elastic properties of argon confined in silica nanopores from grand canonical Monte Carlo simulations. We obtain comparable adsorption isotherm predictions of the EOS and simulations at various pore sizes and temperatures without changing any other parameters. We then see how the predictions of the elastic properties from simulations compare to the EOS and find reasonable agreement. Additionally, we vary the solid–fluid interaction parameters in both the EOS and molecular simulations to represent solids other than silica and see how the elastic moduli depend on the other properties of confining pores related to the interaction strength. This work is a step toward a quantitative description of wave propagation in fluid-saturated nanoporous media.

   @article{doi:10.1021/acs.iecr.0c00693,
     author = {Dobrzanski, Christopher D. and Corrente, Nicholas J. and Gor, Gennady Y.},
     title = {Compressibility of a Simple Fluid in Cylindrical Confinement: Molecular Simulation and Equation of State Modeling},
     journal = {Industrial \& Engineering Chemistry Research},
     volume = {59},
     number = {17},
     pages = {8393-8402},
     year = {2020},
     doi = {10.1021/acs.iecr.0c00693},
     url = {https://doi.org/10.1021/acs.iecr.0c00693},
     eprint = {https://doi.org/10.1021/acs.iecr.0c00693}
   }

2. Compressibility of Supercritical Methane in Nanopores: A Molecular Simulation Study

   Nicholas J. Corrente, Christopher D. Dobrzanski, and Gennady Y. Gor

   Energy & Fuels, 2020

   Abs DOI Bib

   Unmineable coalbeds are a promising source of natural gas and can act as a receptacle for CO2 sequestration. This is because they are composed of extensive nanoporous systems, which allow for significant amounts of methane or CO2 to be trapped in the adsorbed state. The amount of the fluid confined in the coal seams can be determined from seismic wave propagation using the Gassmann equation. However, to accurately apply the Gassmann theory to coalbed methane, the effects of confinement on methane in these nanoporous systems must be taken into account. In this work, we investigate these effects of confinement on supercritical methane in model carbon nanopores. Using Monte Carlo and molecular dynamics simulations, we calculated the isothermal elastic modulus of confined methane. We showed that the effects of confinement on the elastic modulus of supercritical methane are similar to the effects on subcritical fluids: (1) the elastic modulus of the confined fluid is higher than in bulk; (2) for a given pore size, the modulus monotonically increases with pressure; and (3) at a given pressure, the modulus monotonically increases with the reciprocal pore size. However, these effects appeared much more pronounced than for subcritical fluids, showing up to seven-fold increases of the modulus in 2 nm pores. Such a significant increase should be taken into account when predicting wave propagation in methane-saturated porous media.

   @article{doi:10.1021/acs.energyfuels.9b03592,
     author = {Corrente, Nicholas J. and Dobrzanski, Christopher D. and Gor, Gennady Y.},
     title = {Compressibility of Supercritical Methane in Nanopores: A Molecular Simulation Study},
     journal = {Energy \& Fuels},
     volume = {34},
     number = {2},
     pages = {1506-1513},
     year = {2020},
     doi = {10.1021/acs.energyfuels.9b03592},
     url = {https://doi.org/10.1021/acs.energyfuels.9b03592},
     eprint = {https://doi.org/10.1021/acs.energyfuels.9b03592}
   }