Selective Adsorption of CO 2 over N 2 on Graphene: Insights from First-Principles Calculations
Abstract
The potential of graphene for selective CO 2 adsorption is contingent upon a deep understanding of the adsorption energies and the dynamics of molecular cluster formation and stability. In this investigation we employed density functional theory with dispersion corrections (DFT-D3) to examine the adsorption energies as well as formation and stability of CO 2 and N 2 molecular clusters on graphene. The results indicate that CO 2 exhibits a higher adsorption energy (−0.168 eV) than N 2 (−0.120 eV), suggesting selective CO 2 adsorption on graphene in mixed gas environments. Furthermore, CO 2 shows strong intermolecular attraction, resulting in substantial interaction energies and the formation of stable clusters on the graphene surface. Ab initio molecular dynamics simulations further demonstrate the stability of CO 2 clusters at 100 and 300 K, with desorption occurring at 600 K. In contrast, N 2 clusters destabilize at 300 K. This first-principles investigation provides key insights into the selective adsorption behavior of CO 2 and N 2 on graphene, underscoring the potential of graphene for CO 2 separation from CO 2 /N 2 mixtures.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Cites
Generalized Gradient Approximation Made Simple
Perdew, J. P., Burke, K., & Ernzerhof, M. (1996) · Physical Review Letters · doi:10.1103/physrevlett.77.3865 · Cited by 215,824 · see citing works
Projector augmented-wave method
Blöchl, P. E. (1994) · Physical Review B · doi:10.1103/physrevb.50.17953 · Cited by 92,732 · see citing works
From ultrasoft pseudopotentials to the projector augmented-wave method
Kresse, G., & Joubert, D. (1999) · Physical Review B · doi:10.1103/physrevb.59.1758 · Cited by 85,307 · see citing works
Special points for Brillouin-zone integrations
Monkhorst, H. J., & Pack, J. D. (1976) · Physical Review B · doi:10.1103/physrevb.13.5188 · Cited by 71,721 · see citing works
Grimme, S., Antony, J., Ehrlich, S., & Krieg, H. (2010) · The Journal of Chemical Physics · doi:10.1063/1.3382344 · Cited by 59,686 · see citing works
Ab initio molecular dynamics for liquid metals
Kresse, G., & Häfner, J. (1993) · Physical review. B, Condensed matter · doi:10.1103/physrevb.47.558 · Cited by 45,654 · see citing works
Effect of the damping function in dispersion corrected density functional theory
Grimme, S., Ehrlich, S., & Goerigk, L. (2011) · Journal of Computational Chemistry · doi:10.1002/jcc.21759 · Cited by 28,221 · see citing works
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
Momma, K., & Izumi, F. (2011) · Journal of Applied Crystallography · doi:10.1107/s0021889811038970 · Cited by 26,123 · see citing works
Stephens, P. J., Devlin, F. J., Chabalowski, C. F., & Frisch, M. J. (1994) · The Journal of Physical Chemistry · doi:10.1021/j100096a001 · Cited by 23,329 · see citing works
Toward reliable density functional methods without adjustable parameters: The PBE0 model
Adamo, C., & Barone, V. (1999) · The Journal of Chemical Physics · doi:10.1063/1.478522 · Cited by 19,137 · see citing works
Visualization and analysis of atomistic simulation data with OVITO–the Open Visualization Tool
Stukowski, A. (2009) · Modelling and Simulation in Materials Science and Engineering · doi:10.1088/0965-0393/18/1/015012 · Cited by 16,689 · see citing works
Rationale for mixing exact exchange with density functional approximations
Perdew, J. P., Ernzerhof, M., & Burke, K. (1996) · The Journal of Chemical Physics · doi:10.1063/1.472933 · Cited by 6,600 · see citing works
Assessment of the Perdew–Burke–Ernzerhof exchange-correlation functional
Ernzerhof, M., & Scuseria, G. E. (1999) · The Journal of Chemical Physics · doi:10.1063/1.478401 · Cited by 5,490 · see citing works
Goerigk, L., & Grimme, S. (2011) · Physical Chemistry Chemical Physics · doi:10.1039/c0cp02984j · Cited by 2,012 · see citing works
Progress in adsorption-based CO 2 capture by metal–organic frameworks
Liu, J., Thallapally, P. K., McGrail, B. P., Brown, D. R., & Liu, J. (2011) · Chemical Society Reviews · doi:10.1039/c1cs15221a · Cited by 1,340 · see citing works
ABCluster: the artificial bee colony algorithm for cluster global optimization
Zhang, J., & Dolg, M. (2015) · Physical Chemistry Chemical Physics · doi:10.1039/c5cp04060d · Cited by 780 · see citing works
Potentials of physical adsorption
Vidali, G., Ihm, G., Kim, H. Y., & Cole, M. W. (1991) · Surface Science Reports · doi:10.1016/0167-5729(91)90012-m · Cited by 628 · see citing works
Interaction site models for carbon dioxide
Murthy, C. S. N., Singer, K., & McDonald, I. R. (1981) · Molecular Physics · doi:10.1080/00268978100102331 · Cited by 257 · see citing works
Electrostatic interactions in molecular crystals
Murthy, C. S., O’Shea, S. F., & McDonald, I. R. (1983) · Molecular Physics · doi:10.1080/00268978300102531 · Cited by 220 · see citing works
Pulsed molecular beam infrared absorption spectroscopy of CO2 dimer
Walsh, M. A., England, T. H., Dyke, T. R., & Howard, B. J. (1987) · Chemical Physics Letters · doi:10.1016/0009-2614(87)80935-1 · Cited by 155 · see citing works
Density functional study of Al-doped graphene nanostructure towards adsorption of CO, CO2 and H2O
Rad, A. S., & Foukolaei, V. P. (2015) · Synthetic Metals · doi:10.1016/j.synthmet.2015.09.026 · Cited by 125 · see citing works
Adsorption of CO <sub>2</sub> on Graphene: A Combined TPD, XPS, and vdW-DF Study
Takeuchi, K., Yamamoto, S., Hamamoto, Y., Shiozawa, Y., Tashima, K., Fukidome, H., Koitaya, T., Mukai, K., Yoshimoto, S., Suemitsu, M., et al. (2017) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.6b11373 · Cited by 116 · see citing works
Aquilanti, V., Bartolomei, M., Cappelletti, D., Carmona‐Novillo, E., & Pirani, F. (2002) · The Journal of Chemical Physics · doi:10.1063/1.1482696 · Cited by 96 · see citing works
Effective Separation of CO2 Using Metal‐Incorporated rGO Membranes
Jin, X., Foller, T., Wen, X., Ghasemian, M. B., Wang, F., Zhang, M., Bustamante, H., Sahajwalla, V., Kumar, P. V., Kim, H., et al. (2020) · Advanced Materials · doi:10.1002/adma.201907580 · Cited by 94 · see citing works
Shee, J., Loipersberger, M., Rettig, A., Lee, J., & Head‐Gordon, M. (2021) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.1c03468 · Cited by 86 · see citing works
Cappelletti, D., Pirani, F., Bussery‐Honvault, B., Gomez, L., & Bartolomei, M. (2008) · Physical Chemistry Chemical Physics · doi:10.1039/b803961e · Cited by 83 · see citing works
Geometric isomerism in clusters: High resolution infrared spectroscopy of a noncyclic CO2 trimer
Weida, M. J., & Nesbitt, D. J. (1996) · The Journal of Chemical Physics · doi:10.1063/1.472930 · Cited by 73 · see citing works
An ab initio and DFT study of (N2)2 dimers
Couronne, O., & Ellinger, Y. (1999) · Chemical Physics Letters · doi:10.1016/s0009-2614(99)00431-5 · Cited by 65 · see citing works
On the structure of the carbon dioxide dimer
Barton, A. E., Chablo, A., & Howard, B. J. (1979) · Chemical Physics Letters · doi:10.1016/0009-2614(79)80600-4 · Cited by 65 · see citing works
DFT study of CO2 adsorption properties on pristine, vacancy and doped graphenes
Wang, C., Fang, Y., Duan, H., Liang, G., Li, W., Chen, D., & Long, M. (2021) · Solid State Communications · doi:10.1016/j.ssc.2021.114436 · Cited by 60 · see citing works
DFT study of the CO2 and CH4 assisted adsorption on the surface of graphene
Osouleddini, N., & Rastegar, S. F. (2018) · Journal of Electron Spectroscopy and Related Phenomena · doi:10.1016/j.elspec.2018.11.006 · Cited by 56 · see citing works
CO2 Cluster Ion Beam, an Alternative Projectile for Secondary Ion Mass Spectrometry
Tian, H., Maciążek, D., Postawa, Z., Garrison, B. J., & Winograd, N. (2016) · Journal of the American Society for Mass Spectrometry · doi:10.1007/s13361-016-1423-z · Cited by 55 · see citing works
DFT studies of Ni cluster on graphene surface: effect of CO 2 activation
He, X. C., Chu, W., Sun, W., Jiang, C., & Liu, Z. (2016) · RSC Advances · doi:10.1039/c6ra14009b · Cited by 53 · see citing works
High resolution infrared spectroscopy of carbon dioxide clusters up to (CO2)13
Oliaee, J. N., Dehghany, M., McKellar, A. R. W., & Moazzen‐Ahmadi, N. (2011) · The Journal of Chemical Physics · doi:10.1063/1.3615543 · Cited by 52 · see citing works
Synergetic effect of carbon nanopore size and surface oxidation on CO2 capture from CO2/CH4 mixtures
Furmaniak, S., Kowalczyk, P., Terzyk, A. P., Gauden, P. A., & Harris, P. J. F. (2013) · Journal of Colloid and Interface Science · doi:10.1016/j.jcis.2013.01.044 · Cited by 52 · see citing works
Cabria, I., López, M. J., & Alonso, J. A. (2017) · The Journal of Chemical Physics · doi:10.1063/1.4984106 · Cited by 52 · see citing works
Ab initio MO studies of van der Waals molecule (N2)2: Potential energy surface and internal motion
Wada, A., Kanamori, H., & Iwata, S. (1998) · The Journal of Chemical Physics · doi:10.1063/1.477605 · Cited by 49 · see citing works
Cong, S., Li, H., Shen, X., Wang, J., Zhu, J., Liu, J., Zhang, Y., & der Bruggen, B. V. (2018) · Journal of Materials Chemistry A · doi:10.1039/c8ta05774e · Cited by 49 · see citing works
Bartolomei, M., Carmona‐Novillo, E., Hernández, M. I., Campos-Martı́nez, J., & Hernández‐Lamoneda, R. (2010) · Journal of Computational Chemistry · doi:10.1002/jcc.21619 · Cited by 48 · see citing works
High-resolution infrared spectroscopy of carbon dioxide dimers, trimers, and larger clusters
Dehghany, M., McKellar, A. R. W., Afshari, M., & Moazzen‐Ahmadi, N. (2010) · Molecular Physics · doi:10.1080/00268976.2010.496742 · Cited by 41 · see citing works
Reactive molecular dynamic simulations on the gas separation performance of porous graphene membrane
Esfandiarpoor, S., Fazli, M., & Ganji, M. D. (2017) · Scientific Reports · doi:10.1038/s41598-017-14297-w · Cited by 41 · see citing works
Adsorption-induced clustering of CO 2 on graphene
Meconi, G. M., & Zangi, R. (2020) · Physical Chemistry Chemical Physics · doi:10.1039/d0cp03482g · Cited by 37 · see citing works
Lemke, K. H., & Seward, T. M. (2013) · Chemical Physics Letters · doi:10.1016/j.cplett.2013.04.044 · Cited by 34 · see citing works
Hong, Q., Sun, Q., Bartolomei, M., Pirani, F., & Coletti, C. (2020) · Physical Chemistry Chemical Physics · doi:10.1039/d0cp00364f · Cited by 31 · see citing works
Adsorption of small gas molecules on pure and Al-doped graphene sheet: a quantum mechanical study
Singh, D., Kumar, A., & Kumar, D. (2017) · Bulletin of Materials Science · doi:10.1007/s12034-017-1478-x · Cited by 29 · see citing works
Physisorption of N 2 on graphene platelets: An Ab initio study
Zhechkov, L., Heine, T., & Seifert, G. (2005) · International Journal of Quantum Chemistry · doi:10.1002/qua.20895 · Cited by 26 · see citing works
Prasetyo, L., Tan, S. J., Meng, F., Do, D. D., & Nicholson, D. (2017) · The Journal of Chemical Physics · doi:10.1063/1.4982926 · Cited by 20 · see citing works
First-Principles-Based Machine Learning Models for Phase Behavior and Transport Properties of CO2
Mathur, R., Muniz, M. C., Yue, S., Car, R., & Panagiotopoulos, A. Z. (2023) · The Journal of Physical Chemistry B · doi:10.1021/acs.jpcb.3c00610 · Cited by 20 · see citing works
CO2 Capture on Functionalized Calixarenes: A Computational Study
Hymel, J. H., Townsend, J., & Vogiatzis, K. D. (2019) · The Journal of Physical Chemistry A · doi:10.1021/acs.jpca.9b08670 · Cited by 18 · see citing works
Rojas, W. Y., Winter, A. D., Grote, J. G., Kim, S. S., Naik, R. R., Williams, A. D., Weiland, C. R., Principe, E., Fischer, D. A., Banerjee, S., et al. (2017) · Langmuir · doi:10.1021/acs.langmuir.7b03260 · Cited by 17 · see citing works
Desorption Kinetics of Carbon Dioxide from a Graphene-Covered Pt(111) Surface
Smith, R. S., & Kay, B. D. (2019) · The Journal of Physical Chemistry A · doi:10.1021/acs.jpca.9b00674 · Cited by 16 · see citing works
Unraveling H2 chemisorption and physisorption on metal decorated graphene using quantum Monte Carlo
Al-Hamdani, Y. S., Zen, A., & Alfè, D. (2023) · The Journal of Chemical Physics · doi:10.1063/5.0174232 · Cited by 16 · see citing works
Sode, O., & Cherry, J. N. (2017) · Journal of Computational Chemistry · doi:10.1002/jcc.25053 · Cited by 15 · see citing works
C-O Bond Dissociation and Induced Chemical Ionization Using High Energy (CO2)n+ Gas Cluster Ion Beam
Tian, H., Maciążek, D., Postawa, Z., Garrison, B. J., & Winograd, N. (2018) · Journal of the American Society for Mass Spectrometry · doi:10.1007/s13361-018-2102-z · Cited by 15 · see citing works
CO <sub>2</sub> on Graphene: Benchmarking Computational Approaches to Noncovalent Interactions
Ehlert, C., Piras, A., & Gryn’ova, G. (2023) · ACS Omega · doi:10.1021/acsomega.3c03251 · Cited by 15 · see citing works
Five intermolecular vibrations of the CO2 dimer observed via infrared combination bands
Oliaee, J. N., Dehghany, M., Rezaei, M., McKellar, A. R. W., & Moazzen‐Ahmadi, N. (2016) · The Journal of Chemical Physics · doi:10.1063/1.4966146 · Cited by 14 · see citing works
Tiwari, A., Bahadursha, N., Chakraborty, S., & Kanungo, S. (2023) · Physica Scripta · doi:10.1088/1402-4896/ad1378 · Cited by 12 · see citing works
Ab initio and DFT studies of the weakly bound nitrogen molecule complexes (N2) (n=3–6)
Li, Q., Yin, P., Liu, Y., Tang, A., Zhang, H., & Sun, Y.-B. (2003) · Chemical Physics Letters · doi:10.1016/s0009-2614(03)00891-1 · Cited by 9 · see citing works
Wang, Y., Sun, G., Guan, J., Li, Y., Yang, Y., Zhao, M., Li, W., & Qu, Y. (2024) · ACS Applied Nano Materials · doi:10.1021/acsanm.4c05366 · Cited by 8 · see citing works
Rayón, V. M., & Cabria, I. (2022) · Journal of Computational Chemistry · doi:10.1002/jcc.26945 · Cited by 7 · see citing works
Fioccola, S., Pirani, F., Bartolomei, M., & Coletti, C. (2017) · Lecture notes in computer science · doi:10.1007/978-3-319-62404-4_21 · Cited by 6 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Enhanced CO2 reduction on transition metal-doped AlN and GaN quantum dots: A DFT study
Wang, Z., Teleb, N. H., Sakr, M. A. S., Abd-Elkader, O. H., Abdelsalam, H., & Zhang, Q. (2025) · Chemical Physics · doi:10.1016/j.chemphys.2025.112723 · Cited by 4 · see citing works
Newar, R., Sultana, N., & Baruah, A. (2025) · Journal of Solid State Chemistry · doi:10.1016/j.jssc.2025.125733 · Cited by 3 · see citing works
Campbell, J. W., DeRegis, A. P., Laub, J. A., Sholl, D. S., & Vogiatzis, K. D. (2025) · Macromolecular Rapid Communications · doi:10.1002/marc.202500490 · Cited by 2 · see citing works
Zhang, Y., He, Z., Almutairi, Z. A., Zhang, X., Lu, Y., Xue, X., Qin, N., & Zhao, P. Z. (2025) · International Journal of Hydrogen Energy · doi:10.1016/j.ijhydene.2025.05.288
Eno, E. A., Ogbogu, M. N., Ajayi, M. A., Mafimisebi, M., Ochepo, J. E., Oyebanji, O. M., Phoebe, C. C., & Irilochuwe, G. E. (2025) · RSC Advances · doi:10.1039/d5ra04777c
Zhang, B., Xing, K., Sun, Z., Zhang, B., Zhang, B., Luo, N., Bala, H., & Wang, Y. (2025) · Microchimica Acta · doi:10.1007/s00604-025-07695-9
Absor, M. A. U., Lukmantoro, A., Sari, F. D., Hamidah, N. L., & Darmawan, A. (2025) · Surfaces and Interfaces · doi:10.1016/j.surfin.2025.108296
Zheng, Q., Lu, X., Li, J., & Yang, C. (2026) · Advanced Theory and Simulations · doi:10.1002/adts.70355
Adsorption Capacity and Selectivity of Bicontinuous Nanoporous Graphene for CO 2 /N 2 Separation
Yang, L., & Branicio, P. S. (2026) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.5c08446
Self-citationCo single atom and cluster loaded heteroatom-doped graphene electrocatalysts for CO2 to CO or HCOOH
叶子燕, Tao, L., Su, Y., Dastan, D., Li, L., & An, B. (2026) · Computational and Theoretical Chemistry · doi:10.1016/j.comptc.2026.115871
Azeez, B. H., Kzar, M. K., Ajeel, F. N., & Farhood, A. K. (2026) · Applied Physics A · doi:10.1007/s00339-026-10051-0
Han, C., Zhu, Y., Ma, Q., & Chen, Z. (2026) · Chemical Physics · doi:10.1016/j.chemphys.2026.113467
Prasad, G., Tamang, S., Biswas, J., Jha, S. K., & Bhattacharyya, N. K. (2026) · Next Materials · doi:10.1016/j.nxmate.2026.103285
Jalali, T., Davani, T., & Maftoon-Azad, L. (2026) · Diamond and Related Materials · doi:10.1016/j.diamond.2026.114188
Carbon dioxide adsorption enthalpies of atomically precise Ag15, Ag9Cu6, and Au7Ag8 nanoclusters
Compton, D., Ahamed, S. S., Yoshida, W. Y., Li, Y., Sun, R., & Jensen, C. M. (2026) · Journal of Materials Chemistry A · doi:10.1039/d6ta06206g
Gultom, N. S., Qulsum, K., Budi, C. S., Widakdo, J., Rahmatunnisa, C., Chaerun, R. I., Januar, M., Zeleke, M. A., & Hidayat, S. (2026) · Sustainable Chemistry for Climate Action · doi:10.1016/j.scca.2026.100242
Scanning Probe Microscopy of Graphene Sensors Before and After Nitrogen Exposure
Sobola, D. S., Kaspar, P., Papěž, N., Al-Anber, M. A., Mousa, M. S., & Macků, R. (2026) · Microscopy Research and Technique · doi:10.1002/jemt.70190
- Authors
- Faghihnasiri, M., & Branicio, P. S.
- Affiliations
- University of Southern California (US)
- Corresponding author
- Branicio, Paulo S.
- Venue
- The Journal of Physical Chemistry C
- Publisher
- American Chemical Society (ACS)
- Published
- 2025-01-28
- Volume
- 129
- Issue
- 5
- Pages
- 2851-2864
- ISSN
- 1932-7447 (ISSN-L)
- 1932-7455
- OpenAlex
- W4406891608
- Cited by
- 17
- References
- 61
- Citations by year
- 2026: 10 · 2025: 7
- FWCI
- 4.94
- Type
- journal article
- Language
- en
- Open access
- closed
- Licence
- Locations
- The Journal of Physical Chemistry C (publishedVersion)
- Funders
- Ershaghi Center for Energy Transition (E-CET)
- Topics
- Physical Sciences › Engineering › Mechanical Engineering › Carbon Dioxide Capture Technologies
- Physical Sciences › Materials Science › Materials Chemistry › Graphene research and applications
- Physical Sciences › Chemistry › Spectroscopy › Adsorption, diffusion, and thermodynamic properties of materials
- Keywords
- CO2 adsorption, nitrogen adsorption, graphene, selective gas separation, CO2/N2 separation, molecular clusters, cluster stability, adsorption energy, intermolecular interactions, desorption temperature, mixed gas adsorption
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review