Issue 27, 2024

Tunable optical properties of isoreticular UiO-67 MOFs for photocatalysis: a theoretical study

Abstract

A theoretical study of the reported photocatalytic systems based on Zr-based MOF (UiO-67) with biphenyl-4,4′-dicarboxylic acid (bpdc) and 2,2′-bipyridine-5,5′-dicarboxylic acid (bpydc) as linkers was performed. Quantum chemical calculations were carried out to understand the optical properties of the materials and to facilitate the rational design of new UiO-67 derivatives with potentially improved features as photocatalysts under ambient conditions. Hence, the effect of the structural modifications on the optical properties was studied considering different designs based on the nature of the linkers: in 1 only the bpdc linker was considered, or the mixture 1 : 1 between bpdc and bpydc linkers (labeled as 1A). Also, substituents R, –NH2, and –SH, were included in the 1A MOF only over the bpdc linker (labeled as 1A-bpdc-R) and on both bpdc and bpydc linkers (labeled as 1A-R). Thus a family of six isoreticular UiO-67 derivatives was theoretically characterized using Density Functional Theory (DFT) calculations on the ground singlet (S0) and first excited states (singlet and triplet) using Time-Dependent Density Functional Theory (TD-DFT), multiconfigurational post-Hartree–Fock method via Complete Active Space Self-Consistent Field (CASSCF). In addition, the use of periodic DFT calculations suggest that the energy transfer (ET) channel between bpdc and bpydc linkers might generate more luminescence quenching of 1A when compare to 1. Besides, the results suggest that the 1A-R (R: –SH and NH2) can be used under ambient conditions; however, the ET exhibited by 1A, cannot take place in the same magnitude in these systems. These ET can favor the photocatalytic reduction of a potential metal ion, that can coordinate with the bpydc ligand, via LMCT transition. Consequently, the MOF might be photocatalytically active against molecules of interest (such as H2, N2, CO2, among others) with photo-reduced metal ions. These theoretical results serve as a useful tool to guide experimental efforts in the design of new photocatalytic MOF-based systems.

Graphical abstract: Tunable optical properties of isoreticular UiO-67 MOFs for photocatalysis: a theoretical study

Supplementary files

Article information

Article type
Paper
Submitted
07 Apr 2024
Accepted
05 Jun 2024
First published
13 Jun 2024
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2024,53, 11310-11325

Tunable optical properties of isoreticular UiO-67 MOFs for photocatalysis: a theoretical study

M. A. Treto-Suárez, Y. Hidalgo-Rosa, M. Saavedra-Torres, B. D. Koivisto, K. Mena Ulecia, D. Páez-Hernández, X. Zarate and E. Schott, Dalton Trans., 2024, 53, 11310 DOI: 10.1039/D4DT01017E

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