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Unveiling Synergistic Effects of Interstitial Boron in Palladium-Based Nanocatalysts for Ethanol Oxidation Electrocatalysis
journal contribution
posted on 2020-08-05, 18:33 authored by Lizhi Sun, Hao Lv, Yaru Wang, Dongdong Xu, Ben LiuAlloying
is one of the most promising routes for tuning the physicochemical
properties of noble metal-based nanocatalysts and thus improving their
(electro)catalytic performance. Despites numerous achievements, bimetallic
and trimetallic nanoalloys have still been thoroughly studied for
the past two decades. In this study, metalloid boron (B) was alloyed
within palladium (Pd)-based nanocatalysts to promote the electrochemical
ethanol oxidation reaction (EOR) in alkaline media. The optimum PdCuB
nanocatalyst exhibited remarkable electrochemical EOR activity (5.83
A mgPd–1) and good operation stability
(both cycling and chronoamperometric studies). Mechanistic studies
in both pure KOH and a KOH/ethanol mixture attributed superior EOR
performance to positive synergistic effects of B in Pd-based nanocatalysts
that kinetically accelerated the removal of poisoning ethoxy intermediates
(the rate-determining step of EOR). They included (i) an electronic
effect that changed the electronic structure of Pd and thus weakened
the adsorption of poisoning ethoxy intermediates, (ii) a bifunctional
effect that facilitated the adsorption of OHads and thus
kinetically accelerated the further oxidation of poisoning intermediates,
and (iii) a structural effect in which smaller B interstitially inserted
into Pd-based nanocrystals and thus suppressed the physical Ostwald
ripening processes.
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Palladium-Based NanocatalystsEthanol Oxidation Electrocatalysis ...Pd-based nanocatalystsmetal-based nanocatalystsB interstitiallyInterstitial Boronpoisoning intermediatesPdCuB nanocatalystMechanistic studiesEOR performancepoisoning ethoxy intermediatesrate-determining stepbifunctional effectoperation stabilitymetalloid borontrimetallic nanoalloysPd-based nanocrystalselectrochemical ethanol oxidation r...OH adsKOHphysicochemical propertiesSynergistic Effectskineticallyadsorptionchronoamperometric studies
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