Resonance-Promoted Formic Acid Oxidation via Dynamic Electrocatalytic Modulation

Gopeesingh, Joshua; Ardagh, M. Alexander; Shetty, Manish; Burke, Sean T.; Dauenhauer, Paul J.; Abdelrahman, Omar A.

doi:10.1021/acscatal.0c02201

Resonance-Promoted Formic Acid Oxidation via Dynamic Electrocatalytic Modulation

Journal Article · Mon Jul 13 00:00:00 EDT 2020 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c02201· OSTI ID:1801381

Gopeesingh, Joshua ^[1]; ^[2]; ^[3]; Burke, Sean T. ^[4]; ^[2]; ^[5]

Univ. of Massachusetts, Amherst, MA (United States); OSTI
Univ. of Minnesota, Minneapolis, MN (United States); Univ. of Delaware, Newark, DE (United States)
Univ. of Minnesota, Minneapolis, MN (United States)
Univ. of Massachusetts, Amherst, MA (United States)
Univ. of Massachusetts, Amherst, MA (United States); Univ. of Delaware, Newark, DE (United States)

It is a truth universally acknowledged that faster catalysts enable more efficient transformation of molecules to useful products and enhance the utilization of natural resources. However, the limit of static catalyst performance defined by the Sabatier principle has motivated a dynamic approach to catalyst design, whereby catalysts oscillate between varying energetic states. In this work, the concept of dynamic catalytic resonance was experimentally demonstrated via the electrocatalytic oxidation of formic acid over Pt. Oscillation of the electrodynamic potential between 0 and 0.8 V NHE via a square waveform at varying frequency (10^–3 < f < 10³ Hz) increased the turnover frequency to ~20 s^–1 at 100 Hz, over one order of magnitude (20×) faster than optimal potentiostatic conditions. We attribute the accelerated dynamic catalysis to nonfaradaic formic acid dehydration to surface-bound carbon monoxide at low potentials, followed by surface oxidation and desorption to carbon dioxide at high potentials.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Delaware, Newark, DE (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0001004

OSTI ID:: 1801381

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 17 Vol. 10; 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
catalytic resonance
chemistry
dynamic catalysis
formic acid
inorganic carbon compounds
organic acids
oscillation
oxidation
oxides
platinum
potentiodynamic

Resonance-Promoted Formic Acid Oxidation via Dynamic Electrocatalytic Modulation

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