Cardiff University | Prifysgol Caerdydd ORCA
Online Research @ Cardiff 
WelshClear Cookie - decide language by browser settings

Synthesis optimization, adsorption properties and spectroscopic investigation of an NH 2 -tagged Cu-based MOF with open metal sites †

Boudjema, Lotfi, Dahiya, Anil Kumar, da Silva, Ivan, Gianolio, Diego, Nduka, Izuchika, Schuster, Manfred Erwin, Theodora van de Kerkhof, Gea, Kalinowska, Paulina, Borrego-Marin, Emilio, Navarro, Jorge A. R., Colombo, Valentina, McCorquodale, June, Grinter, David C., Ferrer, Pilar, Held, Georg, Catlow, C. Richard A. ORCID: https://orcid.org/0000-0002-1341-1541 and Arrigo, Rosa 2025. Synthesis optimization, adsorption properties and spectroscopic investigation of an NH 2 -tagged Cu-based MOF with open metal sites †. Materials Advances 10.1039/d5ma00666j

[thumbnail of D5MA00666J.pdf] PDF - Published Version
Available under License Creative Commons Attribution.

Download (2MB)
License URL: https://creativecommons.org/licenses/by/3.0/
License Start date: 25 June 2025

Abstract

We report the rapid microwave-assisted solvothermal synthesis of a Cu-MOF (metal–organic framework) with open metal sites, focusing on understanding its CO2 capture properties in relation to phase purity and stability. A combined experimental and theoretical approach is used to identify the MOF's structural features involved in the adsorption process. Specifically, Cu(i) defects are found to play an important role in the CO2 adsorption process, with the Cu-1 sample, synthesized using an optimized ligand/Cu precursor ratio for the highest phase purity, exhibiting more abundant Cu(i) defects as well as the highest adsorption capacity. Grand canonical Monte Carlo simulations show that the Cu(i) sites exhibit a greater affinity for CO2 adsorption compared to the Cu(ii) sites. In situ soft and hard X-ray absorption fine structure spectroscopic techniques confirm the conversion of Cu(i) to Cu(ii) upon CO2 chemisorption, with this conversion being more pronounced in the core of the particles. The simulations are used to estimate the fraction of Cu(i) defects and Cu(ii) sites present within the Cu-1 and to validate the experimental isotherm. Overall, this study provides insights into the CO2 capture properties of this type of Cu-MOF and highlights the importance of phase purity and the role of defects in achieving high adsorption performance.

Item Type: Article
Date Type: Published Online
Status: Published
Schools: Schools > Chemistry
Additional Information: License information from Publisher: LICENSE 1: URL: https://creativecommons.org/licenses/by/3.0/, Start Date: 2025-06-25
Publisher: Royal Society of Chemistry
Date of First Compliant Deposit: 6 August 2025
Date of Acceptance: 25 June 2025
Last Modified: 06 Aug 2025 08:15
URI: https://orca.cardiff.ac.uk/id/eprint/180283

Actions (repository staff only)

Edit Item Edit Item

Downloads

Downloads per month over past year

View more statistics