Computational Investigation of Adsorptive Removal of Pb2+ from Water by the UiO-66 Metal–Organic Framework: Comparison of Adsorption Sites on Defects and Functionalised Linkers

Claudia S. Cox; Valeria Cossich Galicia; Martina Lessio

doi:10.1071/CH21139

RESEARCH ARTICLE (Open Access)

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Computational Investigation of Adsorptive Removal of Pb²⁺ from Water by the UiO-66 Metal–Organic Framework: Comparison of Adsorption Sites on Defects and Functionalised Linkers

Claudia S. Cox ^A , Valeria Cossich Galicia ^B and Martina Lessio

^A ^C

+ Author Affiliations

- Author Affiliations

^A School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia.

^B Columbia College, Columbia University, New York, NY 10027, USA.

^C Corresponding author. Email: martina.lessio@unsw.edu.au

Dr Martina Lessio obtained her undergraduate degree in chemistry from the University of Torino (Italy). She was awarded a Ph.D. in chemistry in 2017 from Princeton University (USA), working under the mentorship of Professor Emily Carter on computational modelling of catalysts for CO₂ conversion. After her Ph.D., Martina became a Columbia Science Fellow at Columbia University (USA), where she was a Lecturer and Research Fellow collaborating with the group of Professor David Reichman. In 2019, Martina was awarded a University of Sydney Fellowship by the University of Sydney (Australia) to investigate metal-organic frameworks for water purification applications. In 2020, Martina established her own research group in the School of Chemistry at UNSW (Australia) as a Scientia Lecturer. Her group uses computational methods to investigate molecules and materials for sustainability applications.

Australian Journal of Chemistry 75(2) 142-154 https://doi.org/10.1071/CH21139
Submitted: 10 June 2021 Accepted: 5 August 2021 Published: 3 September 2021

Journal Compilation © CSIRO 2022 Open Access CC BY

Abstract

Adsorption using metal–organic frameworks (MOFs) such as UiO-66 has shown great promise in remediating water sources contaminated with toxic heavy metals such as Pb²⁺, but detailed information about the adsorption process remains limited. In this article, we gained mechanistic insights into Pb²⁺ adsorption using both functionalised and defective UiO-66 by performing density functional theory calculations using cluster models. Our benchmarked approach led to a computational model of solvated Pb²⁺ (a hemidirected Pb(H₂O)₆²⁺ complex) fully consistent with experimental reports. The analysis of Pb²⁺ adsorption using functionalised UiO-66 determined that factors such as electrostatic attraction, chelation, and limited constraints on the Pb²⁺ coordination geometry lead to enhanced binding affinity. For these reasons, UiO-66-COO^– was identified as the most promising functionalised MOF, consistent with experimental literature. We additionally explored a novel aspect of Pb²⁺ adsorption by UiO-66: the role of missing linker defects that often characterise this MOF. We found that the defects expected to form in an aqueous environment can act as excellent adsorption sites for Pb²⁺ and the preferred adsorption geometry is again determined by electrostatic attraction, chelation, and constraints on the Pb²⁺ coordination geometry. Overall, we conclude that functional groups and defect sites can both contribute to Pb²⁺ adsorption and our study provides crucial design principles for improving the UiO-66 MOF performance in toxic Pb²⁺ removal from water.

Keywords: lead, adsorption, water purification, UiO-66, metal–organic frameworks, computational chemistry, heavy metals, defects.

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