Insights into Pathway Selectivity during Anodic Formic Acid Oxidation over La1–x Sr x CoO3

We report insights into the mechanism and pathway selectivity of anodic oxidation of HCOOH over La1–x Sr x CoO3, which finds application in direct formic acid fuel cells, developed using density functional theory calculations. We analyzed three reaction routes for trans-HCOOH oxidation, viz., format...

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Bibliographic Details
Published in:Industrial & engineering chemistry research 2022-04, Vol.61 (14), p.4784-4793
Main Authors: Pentyala, Phanikumar, Deshpande, Parag A
Format: Article
Language:English
Subjects:
Kinetics, Catalysis, and Reaction Engineering
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Summary:We report insights into the mechanism and pathway selectivity of anodic oxidation of HCOOH over La1–x Sr x CoO3, which finds application in direct formic acid fuel cells, developed using density functional theory calculations. We analyzed three reaction routes for trans-HCOOH oxidation, viz., formate-mediated direct oxidation, carboxyl-mediated direct oxidation, and the indirect oxidation route. For cis-HCOOH, only one route, direct oxidation via dehydrogenation, was observed. Our results conclusively indicate that the indirect reaction route, which involves the formation of poisonous CO, is suppressed by highly stable surface intermediates; hence, this pathway is not feasible. The reaction takes place predominantly via surface isomerization of trans- to cis-HCOOH.
ISSN:0888-5885
1520-5045
DOI:10.1021/acs.iecr.1c04898