Adsorption-based direct air capture using hierarchical porous composites prepared via confined-space crystallization

del Valle-Pérez, Gabriela C.; Muñoz-Senmache, Juan Carlos; Espiña-Santiago, Sebastián; Mendez-Rios, Erick M.; Kisslinger, Kim; Hernández-Maldonado, Arturo J.

doi:10.1016/j.cej.2026.173627

Title: Adsorption-based direct air capture using hierarchical porous composites prepared via confined-space crystallization

Journal Article · Fri Jan 30 00:00:00 UTC 2026 · Chemical Engineering Journal

DOI: https://doi.org/10.1016/j.cej.2026.173627 · OSTI ID:3030625

^[1];

^[1]; Espiña-Santiago, Sebastián ^[1]; Mendez-Rios, Erick M. ^[1];

^[2];

^[1]

University of Puerto Rico Mayagüez Campus, PR (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

Capturing CO₂ at trace concentration remains a critical challenge in sustainable carbon management via adsorption, as conventional adsorbents suffer from low CO₂ selectivity, poor moisture tolerance, and energy-intensive regeneration requirements. Here, we report a hierarchical Ba²⁺-exchanged silicoaluminophosphate (Ba²⁺-CSAPO-34) composite synthesized via confined-space crystallization within an activated carbon matrix. Comprehensive characterization revealed a confined nucleation mechanism and the successful incorporation of Ba²⁺ active sites within the SAPO-34 framework, achieved via a two-step liquid ion-exchange protocol. The core-shell architecture combines the selective CO₂ binding of Ba²⁺-functionalized SAPO-34 with the hydrophobic protection of the carbon shell. Fixed-bed adsorption tests demonstrated strong CO₂ binding (at 500-2500 ppm), no roll-up, and effective suppression of water affinity, while maintaining high selectivity even at 90% relative humidity. A phenomenological adsorption model, validated against dynamic breakthrough data, accurately predicted dynamic adsorption behavior under real-world operating conditions, enabling rational process design for direct air capture (DAC) and closed-loop life support systems. Furthermore, these results establish Ba²⁺-CSAPO-34 as a scalable, moisture-resistant adsorbent that addresses key limitations in trace CO₂ capture, advancing practical implementation of carbon removal technologies.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); US National Aeronautics and Space Administration (NASA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704

OSTI ID:: 3030625

Report Number(s):: BNL-229676-2026-JAAM

Journal Information:: Chemical Engineering Journal, Journal Name: Chemical Engineering Journal Journal Issue: 2 Vol. 530; ISSN 1385-8947

Publisher:: Elsevier BVCopyright Statement

Country of Publication:: United States

Language:: English

References (66)

Crystallization in Confinement Meldrum, Fiona C.; O'Shaughnessy, Cedrick Advanced Materials, Vol. 32, Issue 31 https://doi.org/10.1002/adma.202001068	journal	June 2020
The Challenge of Water Competition in Physical Adsorption of CO₂ by Porous Solids for Carbon Capture Applications – A Short Perspective Rajendran, Arvind; Shimizu, George K. H.; Woo, Tom K. Advanced Materials, Vol. 36, Issue 12 https://doi.org/10.1002/adma.202301730	journal	July 2023
Corrected Horváth-Kawazoe equations for pore-size distribution Rege, Salil U.; Yang, Ralph T. AIChE Journal, Vol. 46, Issue 4 https://doi.org/10.1002/aic.690460408	journal	April 2000
Direct Air Capture of CO ₂ by Physisorbent Materials Kumar, Amrit; Madden, David G.; Lusi, Matteo Angewandte Chemie International Edition, Vol. 54, Issue 48 https://doi.org/10.1002/anie.201506952	journal	October 2015
Study of Water Adsorption on Activated Carbons with Different Degrees of Surface Oxidation Salame, Issa I.; Bandosz, Teresa J. Journal of Colloid and Interface Science, Vol. 210, Issue 2 https://doi.org/10.1006/jcis.1998.5918	journal	February 1999
Cation site location in hydrated chabazites. Crystal structure of potassium- and silver- exchanged chabazites Calligaris, M.; Nardin, G.; Randaccio, L. Zeolites, Vol. 3, Issue 3 https://doi.org/10.1016/0144-2449(83)90008-8	journal	July 1983
XPS spectra of Ca, Sr, Ba and their oxides Van Doveren, H.; Verhoeven, J. A. T. H. Journal of Electron Spectroscopy and Related Phenomena, Vol. 21, Issue 3 https://doi.org/10.1016/0368-2048(80)85055-9	journal	January 1980
Accumulation and spatial distribution of CO2 in the astronaut's crew quarters on the International Space Station Georgescu, Matei Razvan; Meslem, Amina; Nastase, Ilinca Building and Environment, Vol. 185 https://doi.org/10.1016/j.buildenv.2020.107278	journal	November 2020
Location and valence state of strontium cations on the framework of a carbon dioxide selective porous silicoaluminophosphate Zhang, Li; Rivera-Ramos, Milton E.; Hernández-Maldonado, Arturo J. Chemical Engineering Journal, Vol. 209 https://doi.org/10.1016/j.cej.2012.07.134	journal	October 2012
Reuse of Phoenix canariensis palm frond mulch as biosorbent and as precursor of activated carbons for the adsorption of Imazalil in aqueous phase Martín-González, M. A.; González-Díaz, O.; Susial, P. Chemical Engineering Journal, Vol. 245 https://doi.org/10.1016/j.cej.2014.02.050	journal	June 2014
Modeling of fixed-bed columns for gas physical adsorption Gutiérrez Ortiz, Francisco Javier; Barragán Rodríguez, Manuel; Yang, Ralph T. Chemical Engineering Journal, Vol. 378 https://doi.org/10.1016/j.cej.2019.121985	journal	December 2019
Experimental comparison of regeneration methods for CO2 concentration from air using amine-based adsorbent Elfving, Jere; Kauppinen, Juho; Jegoroff, Mikko Chemical Engineering Journal, Vol. 404 https://doi.org/10.1016/j.cej.2020.126337	journal	January 2021
Unveiling the power of defect engineering in MOF-808 to enhance efficient carbon dioxide adsorption and separation by harnessing the potential of DFT analysis Kazemi, Amir; Pordsari, Mahyar Ashourzadeh; Tamtaji, Mohsen Chemical Engineering Journal, Vol. 494 https://doi.org/10.1016/j.cej.2024.153049	journal	August 2024
Active metal cation exchanged in ZSM-5 for enhanced direct air capture of CO2 Kim, Do Yeong; Ryu, Kyeong-Hun; Bae, Wo Bin Chemical Engineering Journal, Vol. 503 https://doi.org/10.1016/j.cej.2024.158380	journal	January 2025
Environmentally friendly synthesis and morphology engineering of mixed-metal MOF for outstanding CO2 capture efficiency Kazemi, Amir; Pordsari, Mahyar Ashourzadeh; Tamtaji, Mohsen Chemical Engineering Journal, Vol. 505 https://doi.org/10.1016/j.cej.2024.158951	journal	February 2025
Water adsorption on carbon - A review Liu, Lumeng; Tan, Shiliang (Johnathan); Horikawa, Toshihide Advances in Colloid and Interface Science, Vol. 250 https://doi.org/10.1016/j.cis.2017.10.002	journal	December 2017
Direct air capture of CO2: an industrial perspective Nisbet, Tim M.; van der Made, Alexander W. Current Opinion in Chemical Engineering, Vol. 50 https://doi.org/10.1016/j.coche.2025.101190	journal	December 2025
Ab initio study of the water adsorption on hydroxylated graphite surfaces Collignon, B.; Hoang, P. N. M.; Picaud, S. Chemical Physics Letters, Vol. 406, Issue 4-6 https://doi.org/10.1016/j.cplett.2005.03.026	journal	May 2005
A review on progress made in direct air capture of CO2 Sodiq, Ahmed; Abdullatif, Yasser; Aissa, Brahim Environmental Technology & Innovation, Vol. 29 https://doi.org/10.1016/j.eti.2022.102991	journal	February 2023
Current status and pillars of direct air capture technologies Ozkan, Mihrimah; Nayak, Saswat Priyadarshi; Ruiz, Anthony D. iScience, Vol. 25, Issue 4 https://doi.org/10.1016/j.isci.2022.103990	journal	April 2022
Engineering a hierarchical carbon supported magnetite nanoparticles composite from metal organic framework and graphene oxide for lithium-ion storage Jia, Ruixin; Zhang, Rui; Yu, Longbiao Journal of Colloid and Interface Science, Vol. 630 https://doi.org/10.1016/j.jcis.2022.10.088	journal	January 2023
A comparative energy and costs assessment and optimization for direct air capture technologies Sabatino, Francesco; Grimm, Alexa; Gallucci, Fausto Joule, Vol. 5, Issue 8 https://doi.org/10.1016/j.joule.2021.05.023	journal	August 2021
Separation of CO2 from light gas mixtures using nanoporous silicoaluminophosphate sorbents: Effect of multiple-step ion exchange and adsorption mechanism via computational studies Arévalo-Hidalgo, Ana G.; Santana, Juan A.; Fu, Riqiang Microporous and Mesoporous Materials, Vol. 130, Issue 1-3 https://doi.org/10.1016/j.micromeso.2009.10.025	journal	May 2010
Enhancement of catalytic lifetime of nanostructured SAPO-34 in conversion of biomethanol to light olefins Aghaei, Erfan; Haghighi, Mohammad Microporous and Mesoporous Materials, Vol. 196 https://doi.org/10.1016/j.micromeso.2014.05.011	journal	September 2014
CO2 adsorption in 13X zeolite modified by alkaline earth cation exchange Barbalho, Vanessa R. C. M.; Badolato, Paulo V. S.; Detoni, Chaline Microporous and Mesoporous Materials, Vol. 398 https://doi.org/10.1016/j.micromeso.2025.113806	journal	December 2025
Impact of nanoconfinement on the physical state and conductivity mechanisms of a 2-picolinium ionic liquid crystal F. M. Santos, Andreia; Teresa Viciosa, M.; Matos, Inês Journal of Molecular Liquids, Vol. 403 https://doi.org/10.1016/j.molliq.2024.124830	journal	June 2024
CoNi nanoalloy-Co-N4 composite active sites embedded in hierarchical porous carbon as bi-functional catalysts for flexible Zn-air battery Liu, Yisi; Chen, Zhicheng; Li, Zongxu Nano Energy, Vol. 99 https://doi.org/10.1016/j.nanoen.2022.107325	journal	August 2022
Preferred crystallographic orientation of nanocrystals embedded inside nanopores Bishara, Hanna; Berger, Shlomo Progress in Crystal Growth and Characterization of Materials, Vol. 65, Issue 4 https://doi.org/10.1016/j.pcrysgrow.2019.100464	journal	November 2019
Sorption direct air capture with CO2 utilization Jiang, L.; Liu, W.; Wang, R. Q. Progress in Energy and Combustion Science, Vol. 95 https://doi.org/10.1016/j.pecs.2022.101069	journal	March 2023
Segregation effects in adsorption of CO2-containing mixtures and their consequences for separation selectivities in cage-type zeolites Krishna, R.; van Baten, J. M. Separation and Purification Technology, Vol. 61, Issue 3 https://doi.org/10.1016/j.seppur.2007.12.003	journal	July 2008
Comparative analysis of amine-functionalized silica for direct air capture (DAC): Material characterization, performance, and thermodynamic efficiency Surkatti, Riham; Abdullatif, Yasser M.; Muhammad, Raeesh Separation and Purification Technology, Vol. 354 https://doi.org/10.1016/j.seppur.2024.128641	journal	February 2025
Eco-Friendly Synthesis and Morphology Control of MOF-74 for Exceptional CO2 Capture Performance with DFT Validation Kazemi, Amir; Pordsari, Mahyar Ashourzadeh; Tamtaji, Mohsen Separation and Purification Technology, Vol. 361 https://doi.org/10.1016/j.seppur.2024.131328	journal	July 2025
Hierarchically Porous MOFs Synthesized by Soft-Template Strategies Li, Ke; Yang, Jian; Gu, Jinlou Accounts of Chemical Research, Vol. 55, Issue 16 https://doi.org/10.1021/acs.accounts.2c00262	journal	July 2022
Monolithic Covalent Organic Frameworks with Hierarchical Architecture: Attractive Platform for Contaminant Remediation Huang, Lijin; Yang, Juan; Zhao, Yingji Chemistry of Materials, Vol. 35, Issue 7 https://doi.org/10.1021/acs.chemmater.2c03282	journal	March 2023
Understanding the Effect of Water on CO ₂ Adsorption Kolle, Joel M.; Fayaz, Mohammadreza; Sayari, Abdelhamid Chemical Reviews, Vol. 121, Issue 13 https://doi.org/10.1021/acs.chemrev.0c00762	journal	May 2021
Metal–Organic Framework-Based Hierarchically Porous Materials: Synthesis and Applications Cai, Guorui; Yan, Peng; Zhang, Liangliang Chemical Reviews, Vol. 121, Issue 20 https://doi.org/10.1021/acs.chemrev.1c00243	journal	July 2021
A Review on the Recent Scientific and Commercial Progress on the Direct Air Capture Technology to Manage Atmospheric CO₂ Concentrations and Future Perspectives Chowdhury, Satyajit; Kumar, Yogendra; Shrivastava, Saket Energy & Fuels, Vol. 37, Issue 15 https://doi.org/10.1021/acs.energyfuels.2c03971	journal	June 2023
Applicability of Adsorbents in Direct Air Capture (DAC): Recent Progress and Future Perspectives Chuah, Chong Yang; Ho, Yin Liang; Syed, Abdul Moiz Hashmi Industrial & Engineering Chemistry Research, Vol. 64, Issue 8 https://doi.org/10.1021/acs.iecr.4c03265	journal	February 2025
Limitations of Breakthrough Curve Analysis in Fixed-Bed Adsorption Knox, James C.; Ebner, Armin D.; LeVan, M. Douglas Industrial & Engineering Chemistry Research, Vol. 55, Issue 16 https://doi.org/10.1021/acs.iecr.6b00516	journal	April 2016
Sorption Equilibria and Kinetics of CO₂, N₂, and H₂O on KOH-Treated Activated Carbon Liu, Lei; Jin, Seongmin; Park, Yongha Industrial & Engineering Chemistry Research, Vol. 57, Issue 50 https://doi.org/10.1021/acs.iecr.8b03862	journal	November 2018
Relationship Between Electronegativity of the Extra-Framework Cations and Adsorption Capacity for CO₂ Gas on Mordenite Framework Lee, Soojin; Lee, Hyunseung; Hwang, Huijeong Inorganic Chemistry, Vol. 64, Issue 2 https://doi.org/10.1021/acs.inorgchem.4c04062	journal	December 2024
Zeolites as Selective Adsorbents for CO₂ Separation Boer, Dina G.; Langerak, Jort; Pescarmona, Paolo P. ACS Applied Energy Materials, Vol. 6, Issue 5 https://doi.org/10.1021/acsaem.2c03605	journal	February 2023
Carbon Dioxide Removal from Humid Atmosphere by a Porous Hierarchical Silicoaluminophosphate/Carbon Composite Adsorbent del Valle-Pérez, Gabriela C.; Muñoz-Senmache, Juan C.; Cruz-Tato, Perla E. ACS Applied Engineering Materials, Vol. 1, Issue 2 https://doi.org/10.1021/acsaenm.2c00208	journal	February 2023
Using Helium Pycnometry to Study the Apparent Densities of Metal–Organic Frameworks Decker, Gerald E.; Bloch, Eric D. ACS Applied Materials & Interfaces, Vol. 13, Issue 44 https://doi.org/10.1021/acsami.1c07304	journal	June 2021
Material Exhibiting Efficient CO₂ Adsorption at Room Temperature for Concentrations Lower Than 1000 ppm: Elucidation of the State of Barium Ion Exchanged in an MFI-Type Zeolite Itadani, Atsushi; Oda, Akira; Torigoe, Hiroe ACS Applied Materials & Interfaces, Vol. 8, Issue 13 https://doi.org/10.1021/acsami.6b00909	journal	March 2016
CO ₂ Capture from the Atmosphere and Simultaneous Concentration Using Zeolites and Amine-Grafted SBA-15 Stuckert, Nicholas R.; Yang, Ralph T. Environmental Science & Technology, Vol. 45, Issue 23 https://doi.org/10.1021/es202647a	journal	December 2011
The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms Barrett, Elliott P.; Joyner, Leslie G.; Halenda, Paul P. Journal of the American Chemical Society, Vol. 73, Issue 1 https://doi.org/10.1021/ja01145a126	journal	January 1951
Hydrothermal Synthesis of Zeolites with Three-Dimensionally Ordered Mesoporous-Imprinted Structure Chen, Huiyong; Wydra, James; Zhang, Xueyi Journal of the American Chemical Society, Vol. 133, Issue 32 https://doi.org/10.1021/ja2046815	journal	August 2011
A Fine-Tuned Fluorinated MOF Addresses the Needs for Trace CO ₂ Removal and Air Capture Using Physisorption Bhatt, Prashant M.; Belmabkhout, Youssef; Cadiau, Amandine Journal of the American Chemical Society, Vol. 138, Issue 29 https://doi.org/10.1021/jacs.6b05345	journal	July 2016
Selective Adsorption of Water from Mixtures with 1-Alcohols by Exploitation of Molecular Packing Effects in CuBTC Gutiérrez-Sevillano, Juan José; Calero, Sofia; Krishna, Rajamani The Journal of Physical Chemistry C, Vol. 119, Issue 7 https://doi.org/10.1021/jp512853w	journal	February 2015
NIH Image to ImageJ: 25 years of image analysis Schneider, Caroline A.; Rasband, Wayne S.; Eliceiri, Kevin W. Nature Methods, Vol. 9, Issue 7 https://doi.org/10.1038/nmeth.2089	journal	June 2012
Oxidation-stable amine-containing adsorbents for carbon dioxide capture Min, Kyungmin; Choi, Woosung; Kim, Chaehoon Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03123-0	journal	February 2018
Environmental trade-offs of direct air capture technologies in climate change mitigation toward 2100 Qiu, Yang; Lamers, Patrick; Daioglou, Vassilis Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-31146-1	journal	June 2022
Porous materials for carbon dioxide separations Siegelman, Rebecca L.; Kim, Eugene J.; Long, Jeffrey R. Nature Materials, Vol. 20, Issue 8 https://doi.org/10.1038/s41563-021-01054-8	journal	July 2021
Water clusters and density fluctuations in liquid water based on extended hierarchical clustering methods Gao, Yitian; Fang, Hongwei; Ni, Ke Scientific Reports, Vol. 12, Issue 1 https://doi.org/10.1038/s41598-022-11947-6	journal	May 2022
Perspective on distributed direct air capture: what, why, and how? Chen, Yuanke; Wu, Ronghui; Hsu, Po-Chun npj Materials Sustainability, Vol. 3, Issue 1 https://doi.org/10.1038/s44296-025-00056-w	journal	May 2025
Cation-exchanged SAPO-34 for adsorption-based hydrocarbon separations: predictions from dispersion-corrected DFT calculations Fischer, Michael; Bell, Robert G. Phys. Chem. Chem. Phys., Vol. 16, Issue 39 https://doi.org/10.1039/C4CP01049C	journal	January 2014
Screening metal–organic frameworks for mixture separations in fixed-bed adsorbers using a combined selectivity/capacity metric Krishna, Rajamani RSC Advances, Vol. 7, Issue 57 https://doi.org/10.1039/C7RA07363A	journal	January 2017
Synthesis of core–shell Co@S-doped carbon@ mesoporous N-doped carbon nanosheets with a hierarchically porous structure for strong electromagnetic wave absorption Wen, Bo; Yang, Haibo; Lin, Ying Journal of Materials Chemistry A, Vol. 9, Issue 6 https://doi.org/10.1039/D0TA09393A	journal	January 2021
Direct air capture: process technology, techno-economic and socio-political challenges Erans, María; Sanz-Pérez, Eloy S.; Hanak, Dawid P. Energy & Environmental Science, Vol. 15, Issue 4 https://doi.org/10.1039/D1EE03523A	journal	January 2022
Carbon dioxide capture with zeotype materials Fu, Donglong; Davis, Mark E. Chemical Society Reviews, Vol. 51, Issue 22 https://doi.org/10.1039/D2CS00508E	journal	January 2022
An ecosystem of carbon dioxide removal reviews – part 1: direct air CO ₂ capture and storage van der Spek, Mijndert; Bardow, André; Baum, Chad M. Energy & Environmental Science, Vol. 18, Issue 22 https://doi.org/10.1039/D5EE01732G	journal	January 2025
A review of direct air capture (DAC): scaling up commercial technologies and innovating for the future McQueen, Noah; Gomes, Katherine Vaz; McCormick, Colin Progress in Energy, Vol. 3, Issue 3 https://doi.org/10.1088/2516-1083/abf1ce	journal	April 2021
Trace CO 2 capture by an ultramicroporous physisorbent with low water affinity Mukherjee, Soumya; Sikdar, Nivedita; O’Nolan, Daniel Science Advances, Vol. 5, Issue 11 https://doi.org/10.1126/sciadv.aax9171	journal	November 2019
Classical and Nonclassical Nucleation and Growth Mechanisms for Nanoparticle Formation Jun, Young-Shin; Zhu, Yaguang; Wang, Ying Annual Review of Physical Chemistry, Vol. 73, Issue 1 https://doi.org/10.1146/annurev-physchem-082720-100947	journal	April 2022
A Comparative Study of Different Sorbents in the Context of Direct Air Capture (DAC): Evaluation of Key Performance Indicators and Comparisons Leonzio, Grazia; Fennell, Paul S.; Shah, Nilay Applied Sciences, Vol. 12, Issue 5 https://doi.org/10.3390/app12052618	journal	March 2022

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Title: Adsorption-based direct air capture using hierarchical porous composites prepared via confined-space crystallization

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