Confinement Effects on the RhIIICp* / Polyoxometalate System in Photochemical CO2 Reduction Reactions: Porous Organic Polymer Versus Metal–Organic Framework

Ranscht A, Solé-Daura A, Robinson TC, Ghosh AC, Benseghir Y, Alkhurisi MH, Reber R, Chaigne-Tarlotin E, Bredy P, Quadrelli EA, Lesage A, Canivet J, Mellot-Draznieks C, Wisser FM (2026)

Publication Type: Journal article

Publication year: 2026

Journal

ChemCatChem Wiley-VCH Verlag

Book Volume: 18

Article Number: e01650

Journal Issue: 5

DOI: 10.1002/cctc.202501650

Abstract

The incorporation of polyoxometalates (POMs) into transition metal-based photosystems has emerged as an effective strategy to boost photocatalytic performances for CO2 and water reduction into renewable energy vectors. Despite significant progress in designing {POM, porous host} composites containing isolated catalytically active metal complexes, the atomic-level understanding of their structure-function relationship remains limited. Here, we investigate the effect of encapsulated [PW12O40]3− POMs on the photocatalytic CO2 reduction (CRR) performance of a Rh-catalyst, namely the pentamethylcyclopentadienyl rhodium(III) (RhIIICp*), immobilized in porous organic polymers (POPs) and compare it with the RhIIICp*-functionalized UiO-67 MOF. While the incorporated POM enhances overall activity in both systems, (POM,RhIIICp*)@POPs show a stronger shift in selectivity toward the hydrogen evolution reaction (HER). By combining the high sensitivity of dynamic nuclear polarization enhanced NMR spectroscopy with atomistic computational modelling techniques, we elucidate the POMs’ location, speciation and host-guest interactions within the amorphous POP matrices. The results reveal that in presence of solvent, electrostatic anchoring of POMs to the POP's backbone promotes the accumulation of HTEOA+ proton donors near Rh active sites, favoring selectively HER up to 240% of the initial activity of catalysts without POM incorporated. The latter contrasts with the confinement of the POM within the narrower pores of UiO-67, limiting POM···HTEOA+ interactions, thus enhancing both CRR and HER activity.

Authors with CRIS profile

Rebecca Reber Collaborative Research Centre 1452/1 Catalysis at Liquid Interfaces (CLINT)

Involved external institutions

Université Claude Bernard Lyon 1 (UCB) FR France (FR) Collège de France FR France (FR) Universität Regensburg DE Germany (DE)

How to cite

APA:

Ranscht, A., Solé-Daura, A., Robinson, T.C., Ghosh, A.C., Benseghir, Y., Alkhurisi, M.H.,... Wisser, F.M. (2026). Confinement Effects on the RhIIICp* / Polyoxometalate System in Photochemical CO2 Reduction Reactions: Porous Organic Polymer Versus Metal–Organic Framework. ChemCatChem, 18(5). https://doi.org/10.1002/cctc.202501650

MLA:

Ranscht, Alisa, et al. "Confinement Effects on the RhIIICp* / Polyoxometalate System in Photochemical CO2 Reduction Reactions: Porous Organic Polymer Versus Metal–Organic Framework." ChemCatChem 18.5 (2026).

BibTeX: Download