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oai:figshare.com:article/34028056 2026-09-29T22:05:13Z category_1 category_4 category_146 category_13 category_15 category_24 category_272 category_873 category_134 category_135 portal_63 item_type_6 month_year_09_2026

Role of Aromatic Topology in Hyper-Crosslinked Polymers on CO₂ Adsorption and CO₂/N₂ Selectivity Rahulbhai Parmar (16505068) Sagnik Mukherjee (725412) Harshal Kulkarni (16505065) Prayag Gajera (16505062) Rajaram K. Nagarale (1404919) Govind Sethia (1817692) Biophysics Biochemistry Space Science Genetics Neuroscience Evolutionary Biology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Virology Computational Biology remained poorly understood including henry ’ enhanced energetic interaction accessible ultra micropores law constants (< key structural parameter molecular discrimination arise 2 </ sub tuning gas adsorption confined aromatic framework carbon dioxide adsorption 3 </ sup 109 mmol g 0 kj mol aromatic precursor topology >< sub >< framework architecture comprehensive structural aromatic topology aromatic precursors adsorption (< >< b molecular recognition ></ sub systematic variation suppressed n ring geometry rigid fused possible contribution micropore generation isosteric heats Despite extensive studies of hyper-crosslinked polymers (HCPs) for carbon dioxide adsorption and separation, the fundamental role of aromatic precursor topology in governing localized gas confinement and molecular recognition has remained poorly understood. Herein, we demonstrate that the geometric topology of aromatic precursors, spanning isolated aromatic rings, rigid fused polycyclic frameworks, and rotationally flexible biaryl linkages, directly controls framework packing and micropore generation. Systematic variation of precursor topology reveals distinct relationships between porosity, adsorption affinity, and molecular selectivity. Comprehensive structural, thermodynamic, and adsorption analyses, including Henry’s law constants (<i><b>K</b></i>_{<i><b>H</b></i>}), isotherm model fitting, and isosteric heats of adsorption (<i><b>Q</b></i>_{<i><b>st</b></i>}), reveal that topology-controlled confinement may promote cooperative multi-body interactions. Benzene-derived HCP, with the most accessible ultra micropores, delivers the highest CO₂ uptake (74.0 cm³ g^–1 at 273 K and 1 bar) and <i><b>K</b></i>_{<i><b>H</b></i>} (109 mmol g^–1 bar^–1). Anthracene-derived HCP, with its rigid fused-ring geometry, instead achieves the highest CO₂/N₂ selectivity (557 at 273 K and 0.01 bar) and <i><b>Q</b></i>_{<i><b>st</b></i>} (32.0 kJ mol^–1), suggesting a possible contribution from cooperative multi-body interactions between CO₂ and the confined aromatic framework. This enhanced energetic interaction is accompanied by suppressed N₂ adsorption, rather than by increased CO₂ capacity. Overall, these results demonstrate that CO₂ uptake and CO₂/N₂ molecular discrimination arise from distinct aspects of framework architecture, highlighting aromatic precursor topology as a key structural parameter for tuning gas adsorption and separation in HCPs. 2026-09-29T00:00:00Z Text Journal contribution 10.1021/acsapm.6c02933.s001 https://figshare.com/articles/journal_contribution/Role_of_Aromatic_Topology_in_Hyper-Crosslinked_Polymers_on_CO_sub_2_sub_Adsorption_and_CO_sub_2_sub_N_sub_2_sub_Selectivity/34028056 CC BY-NC 4.0