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Published on: June 21, 2017
Engineering all-organic electrocatalysts with asymmetric dual-active sites for uncommon oxygen-evolving pathway
Li-Hong Yu1, Li-Ming Cao2, Xue-Feng Zhang1
1Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials, Jiangxi Normal University, Nanchang, China.
None:
The performance of electrocatalytic oxygen evolution reaction is governed by molecular evolution pathways, yet their regulation remains a significant experimental and theoretical hurdle. Herein, we propose the construction of asymmetric non-metallic dual-active sites through engineering hydroxyl groups in an all-organic electrocatalyst, thereby triggering an uncommon asymmetric oxide pathway mechanism. This reaction pathway reduces the requirement of strict equilibrium on adsorption energies at dual-active sites for traditional oxide pathway mechanism, and also avoids the limitation of the linear scaling relationship for adsorbate evolution mechanism. Therefore, the proposed metal-free electrocatalyst shows competitive oxygen evolution reaction performance with an overpotential of 364.3 ± 4.5 mV at 1.0 A·cm-2. Combining operando spectroscopic/mass spectrometry and theoretical calculations unveils that the asymmetric oxide pathway mechanism undergoes the critical step of *OH intramolecular nucleophilic attack to neighboring *O, forming *OOH with drastically reducing energy barriers. This work shows the diversity of oxygen evolution pathways in all-organic electrocatalysts and offers a viewpoint for optimizing the electrocatalytic performances of metal-free solids.
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