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Title: Coverage-Dependent Rate-Driving Force Relationships: Hydrogen Transfer from Cerium Oxide Nanoparticle Colloids
Abstract. Rate-driving force relationships, known as Brønsted-Evans Polanyi (BEP) relations, are central to many methods for predicting the performance of heterogeneous catalysts and electrocatalysts. Methods such as Tafel plots and ‘volcano’ analyses often assume the effect of adsorbate coverage on reaction rate across different materials is constant and known. Here we use UV-visible spectroscopy to test these assumptions, by measuring rates of net hydrogen atom transfer from colloidal cerium oxide nanoparticles (nanoceria) to organic reagents at varying surface CeO–H bond strengths and surface coverages. The resulting rate constants follow a linear BEP relationship, ∆log(k)=[alpha]∆log(Keq), across two sizes of nanoceria, two organic reagents, and a ~10 kcal mol-1 range of CeO–H bond strengths. Interestingly, the Brønsted slope is only 0.2, demonstrating that the rate constants are far less insensitive to CeO–H bond strength, than would commonly be assumed for a heterogeneous nanomaterial. Furthermore, we observe a Brønsted slope >1 when altering the reaction driving force via the organic reagent bond strength instead of that of CeO–H. The implications of these Brønsted slopes for either concerted or stepwise mechanisms are discussed. To our knowledge, these are the first solution-phase measurements of BEP relationships for hydrogen coverage on a (nano)material.  more » « less
Award ID(s):
1904813
PAR ID:
10472380
Author(s) / Creator(s):
;
Publisher / Repository:
American Chemical Society
Date Published:
Journal Name:
Journal of the American Chemical Society
Volume:
144
Issue:
45
ISSN:
0002-7863
Page Range / eLocation ID:
20699 to 20709
Subject(s) / Keyword(s):
nanocrystals nanoparticles nanochemistry nanoparticle reactivity nanoparticle reactivity hydrogen atom transfer proton coupled electron transfer kinetic-thermodynamic relationships BEP relationships liinear free energy relationships
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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