Enhanced ammonia adsorption on functionalized nanoporous carbons

• Polymer derived functionalized micro and mesoporous carbons were synthesized.
• Ammonia adsorption on the carbons was measured up to 9.5 bar.
• Carbon derived from PFA-PEG polymer blends showed superior adsorption capacity.
• Surface composition and chemistry were studied using XPS and FTIR.
• Highest reversible adsorption at room temperature and 1 bar was 14 mmol/g.

Nanoporous carbons were synthesized and treated with nitric acid after which the change in their propensities for ammonia adsorption was determined. The adsorbents had mean pore sizes ranging from 0.5 to 12 nm and they included polyfurfuryl alcohol (PFA)-derived carbons, commercial activated carbons, and both soft and hard-templated mesoporous carbons. The carbons were treated with concentrated nitric acid at elevated temperatures (e.g. 90 °C) and for time spans between 15 and 240 min. The textural properties of carbons, before and after nitric acid treatment, were determined using CO2 adsorption at 0 °C. Ammonia adsorption uptakes were measured at 25 °C and at pressures up to 9.5 bar. The highest total uptake of ammonia on the native carbons, that is prior to nitric acid treatment, was ∼10 mmol/g at 1 bar and 25 °C; this was obtained on a microporous carbon derived from the pyrolysis of polyfurfuryl alcohol and polyethylene glycol blends followed by CO2 oxidation. Nitric acid treatment of this carbon significantly increased its total uptake of ammonia to 17 mmol/g. This sample provided a reversible uptake of 14 mmol/g after it was outgassed at 160 °C and 10−5 bar under dynamic vacuum. This is 2 mmol/g higher than state-of-the-art ammonia adsorbents such as COF-10. An x-ray photoelectron spectrum (XPS) showed that the oxygen content of the carbon increased from 3 at.% to 16.4 at.% after the nitric acid treatment. Heats of adsorption profiles, calculated from adsorption isotherms, started from 165 kJ/mol and quickly dropped to 40 kJ/mol with ammonia loading. This showed that the isosteric heat of adsorption on the remaining surface was still higher than the native carbon sample resulting in high reversible adsorption uptake, even after excluding the irreversible adsorption on the very high energy sites.

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