CO₂ as a Redox Shuttle Enables Photocatalytic Dehydrogenative Decarbonylation of Biomass-Derived Alcohols to Light Alkanes

Title data

Hu, Jun ; Su, Wenhao ; Zeng, Chaoqin ; Rodrigues, Bruno Vinicius Manzolli ; Rockstroh, Nils ; Monti, Susanna ; Barcaro, Giovanni ; Kuśtrowski, Piotr ; Jaworski, Aleksander ; Rabeah, Jabor ; Slabon, Adam ; Das, Shoubhik:
CO₂ as a Redox Shuttle Enables Photocatalytic Dehydrogenative Decarbonylation of Biomass-Derived Alcohols to Light Alkanes.
In: Angewandte Chemie International Edition. (24 July 2026) . - e9277722.
ISSN 1521-3773
DOI: https://doi.org/10.1002/anie.9277722

Official URL:

Abstract in another language

The use of CO2 as a redox shuttle offers an emerging strategy to regulate electron and hydrogen transfer in catalytic transformations, yet its potential remains largely unexplored. In particular, dehydrogenative decarbonylation of alcohols possesses a long-standing challenge, as it requires the controlled coupling of oxidative alcohol activation with reductive C─C bond cleavage, two intrinsically competing processes that are difficult to balance within a single catalytic system. Considering these, we demonstrate that CO2 can resolve this mismatch by functioning as a dynamic redox shuttle in a heterogeneous photocatalytic platform. Under visible-light irradiation, the photocatalyst promotes sequential dehydrogenation of primary alcohols to aldehydes, followed by C─C bond scission and selective formation of alkanes. Mechanistic studies, including isotope labeling, radical trapping, atmosphere-dependent reactivity, and advanced quantum mechanical calculations reveal that CO2 is not incorporated into the products but instead transiently interacts with reduced iron sites to facilitate catalyst turnover, suppress unproductive H2 evolution, and direct hydrogen equivalents toward C─H bond formation. This redox-shuttling function enables the integration of oxidative and reductive steps within a single photocatalytic cycle, thus opening new opportunities for steering complex redox transformations in photocatalysis.

Further data

Item Type:	Article in a journal
Refereed:	Yes
Keywords:	biomass alcohol; CO2 as redox shuttle; dehydrogenative decarbonylation; heterogeneous photocatalyst
Institutions of the University:	Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Organic Chemistry I - Photo- und Elektrokatalyse für Nachhaltigkeit > Chair Organic Chemistry I - Photo- und Elektrokatalyse für Nachhaltigkeit - Univ.-Prof. Dr. Shoubhik Das
Result of work at the UBT:	Yes
DDC Subjects:	500 Science > 540 Chemistry
Date Deposited:	27 Jul 2026 06:25
Last Modified:	27 Jul 2026 06:25
URI:	https://eref.uni-bayreuth.de/id/eprint/99112