Functionalization effects on HKUST-1 and HKUST-1/graphene oxide hybrid adsorbents for hydrogen sulfide removal

Nidhika Bhoria; Georgia Basina; Jeewan Pokhrel; K Suresh Kumar Reddy; Stavroula Anastasiou; Vaithilingam V Balasubramanian; Yasser Fowad AlWahedi; Georgios N Karanikolos

doi:10.1016/j.jhazmat.2020.122565

Functionalization effects on HKUST-1 and HKUST-1/graphene oxide hybrid adsorbents for hydrogen sulfide removal

J Hazard Mater. 2020 Jul 15:394:122565. doi: 10.1016/j.jhazmat.2020.122565. Epub 2020 Mar 19.

Authors

Nidhika Bhoria¹, Georgia Basina², Jeewan Pokhrel³, K Suresh Kumar Reddy², Stavroula Anastasiou², Vaithilingam V Balasubramanian⁴, Yasser Fowad AlWahedi⁵, Georgios N Karanikolos⁶

Affiliations

¹ Department of Chemical Engineering, Khalifa University, P.O. Box 127788, Abu Dhabi, United Arab Emirates; Department of Chemical and Petroleum Engineering, University of Calgary, Calgary, AB T2N 1N4, Canada.
² Department of Chemical Engineering, Khalifa University, P.O. Box 127788, Abu Dhabi, United Arab Emirates.
³ Department of Chemical Engineering, Khalifa University, P.O. Box 127788, Abu Dhabi, United Arab Emirates; Department of Chemical and Biomolecular Engineering, Tulane University, New Orleans, LA 70118, USA.
⁴ ADNOC Refining Innovation Center, PO Box 3593, Abu Dhabi, United Arab Emirates; Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, MN 55455, USA.
⁵ Department of Chemical Engineering, Khalifa University, P.O. Box 127788, Abu Dhabi, United Arab Emirates; Center for Catalysis and Separations (CeCaS), Khalifa University, P.O. Box 127788, Abu Dhabi, United Arab Emirates.
⁶ Department of Chemical Engineering, Khalifa University, P.O. Box 127788, Abu Dhabi, United Arab Emirates; Center for Catalysis and Separations (CeCaS), Khalifa University, P.O. Box 127788, Abu Dhabi, United Arab Emirates; Research and Innovation Center on CO(2) and H(2) (RICH), Khalifa University, P.O. Box 127788, Abu Dhabi, United Arab Emirates. Electronic address: georgios.karanikolos@ku.ac.ae.

PMID: 32272328
DOI: 10.1016/j.jhazmat.2020.122565

Abstract

HKUST-1, a Cu-based metalorganic framework (MOF), was synthesized solvothermally, functionalized with polyethyleneimine (PEI), and hybridized with graphene oxide (GO) and functionalized GO for H₂S removal. MOF synthesis approach, molecular weight of amines, and the content of GO in the hybrid adsorbents were systematically varied. The adsorbent materials were characterized by XRD, FTIR, SEM, elemental analysis, liquid N₂ adsorption-desorption, water vapor and oxygen sorption, and subsequently tested for H₂S adsorption in a breakthrough column. The MOF in the composite adsorbents consisting of in-situ grown HKUST-1 on GO that was pre-functionalized with low molecular weight PEI exhibited the highest H₂S adsorption uptake at ambient conditions (0.9 mmol S g^-1 MOF) in comparison to 0.5 mmol S g^-1 MOF for the parent HKUST-1, thus showing an 80 % increase in uptake, while this material also exhibited significantly enhanced sorption kinetics. H₂S adsorption at higher temperature (150 °C) was also performed, and at this temperature a HKUST/GO hybrid adsorbent resulted in the highest MOF capacity, i.e. 2.1 mmol S g^-1 MOF, which is 27 % higher than that of the parent MOF at the same conditions. Formation of hybrid adsorbents with GO coupled to tunable functionalization of both GO support and the MOF crystallites can contribute in optimizing H₂S capture performance of MOFs.

Keywords: Acid gas; Adsorption; Amines; Breakthrough; Functionalization; Gas sweetening; Graphene oxide; H(2)S; Hydrogen sulfide; MOF; MOF/GO; Metal organic frameworks; PEI.