Reaction Mechanism of Vapor-Phase Formic Acid Decomposition over Platinum Catalysts: DFT, Reaction Kinetics Experiments, and Microkinetic Modeling

Bhandari, Saurabh; Rangarajan, Srinivas; Maravelias, Christos T.; Dumesic, James A.; Mavrikakis, Manos

doi:10.1021/acscatal.9b05424

Title: Reaction Mechanism of Vapor-Phase Formic Acid Decomposition over Platinum Catalysts: DFT, Reaction Kinetics Experiments, and Microkinetic Modeling

Journal Article · Wed Mar 04 00:00:00 EST 2020 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.9b05424· OSTI ID:1764508

Bhandari, Saurabh ^[1];

^[1];

^[1]

Univ. of Wisconsin, Madison, WI (United States)

A combination of periodic density functional theory (DFT, PW91-GGA) calculations, reaction kinetics experiments, and mean-field microkinetic modeling is used to derive insights on the reaction mechanism and determine the nature of the active site under reaction conditions for the vapor-phase decomposition of formic acid (FA, HCOOH) over Pt/C catalysts. Microkinetic models formulated using DFT energetics derived on the clean Pt(100) and Pt(111) required large parameter adjustments to reproduce the experimentally measured apparent activation energies and reaction orders. Further, these models predicted high surface coverage of adsorbed carbon monoxide (CO*), inconsistent with the environment of the active site in the DFT calculations on the clean surfaces. Consequently, we reperformed DFT calculations for the entire reaction network on partially CO*-covered (4/9 monolayer, ML) Pt(111) and Pt(100). The resultant microkinetic models, with thermochemistry and kinetics explicitly dependent on CO* coverage, were able to reproduce the experimentally determined activation energies and reaction orders, in addition to being self-consistent in CO* coverage. Our results suggest that Pt(100) is likely poisoned by CO* under typical reaction conditions and does not contribute significantly to the experimentally observed reactivity. Instead, we find that Pt(111) better represents the active site for FA decomposition reaction on Pt/C catalysts. The optimized model on 4/9 ML CO*-covered Pt(111) suggests that the reaction occurs via the carboxyl (COOH*) intermediate and that the spectator CO*-assisted pathways play a significant role under reaction conditions. Lastly, this study underscores the importance of spectator species on the energetics and the mechanism of a catalytic reaction and their key role in developing a model that better addresses the nature of the active site under realistic catalytic reaction conditions.

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Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-05ER15731; AC02-05CH11231

OSTI ID:: 1764508

Journal Information:: ACS Catalysis, Vol. 10, Issue 7; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Formic acid
density functional theory
reaction kinetics experiments
microkinetic modeling
coverage self-consistency
renewable hydrogen production
platinum catalyst
coverage effects
activation energy
organic reactions
dehydration
catalystsl chemical reactions

Title: Reaction Mechanism of Vapor-Phase Formic Acid Decomposition over Platinum Catalysts: DFT, Reaction Kinetics Experiments, and Microkinetic Modeling

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