<p>This work reports the successful synthesis of a highly stable and durable non-PGM catalyst Co<sub>3</sub>O<sub>4</sub>/Co<sub>x</sub>Ce<sub>1−x</sub>O<sub>2−δ</sub>/C via a simple solvothermal process. The electrocatalytic ability of Co<sub>3</sub>O<sub>4</sub>/C, CeO<sub>2</sub>/C and Co<sub>3</sub>O<sub>4</sub>/Co<sub>x</sub>Ce<sub>1−x</sub>O<sub>2−δ</sub>/C are tested for oxygen reduction and oxygen evolution reaction (ORR, OER). Under identical conditions, the electrochemical studies of the catalysts reveal enhanced performance of the Co<sub>3</sub>O<sub>4</sub>/Co<sub>x</sub>Ce<sub>1−x</sub>O<sub>2−δ</sub>/C. It shows the highest geometric current density (j<sub>geo</sub> = ̶ 4.1 mAcm<sup>−2</sup> ) at 0.33&#xa0;V vs. RHE. Moreover, Co<sub>3</sub>O<sub>4</sub>/Co<sub>x</sub>Ce<sub>1−x</sub>O<sub>2−δ</sub>/C has the earliest onset for OER with a bifunctionality index of ΔE = 1.05&#xa0;V and has the highest turnover frequency. The catalyst was compared with benchmarks like 20 wt% Pt/C for ORR and RuO<sub>2</sub> for OER. Chronoamperometry studies (CA) reveals superior performance of Co<sub>3</sub>O<sub>4</sub>/Co<sub>x</sub>Ce<sub>1−x</sub>O<sub>2−δ</sub>/C over Pt/C for ORR and accelerated durability test (ADT) shows no observable shift of half-wave potential (E<sub>1/2</sub>). This enhancement of electrocatalytic ability of Co<sub>3</sub>O<sub>4</sub>/Co<sub>x</sub>Ce<sub>1−x</sub>O<sub>2−δ</sub>/C are attributed to (1) higher degree of Co<sup>2+</sup>:Co<sup>3+</sup> ratio (3.6) in Co<sub>3</sub>O<sub>4</sub>/Co<sub>x</sub>Ce<sub>1−x</sub>O<sub>2−δ</sub>/C than in Co<sub>3</sub>O<sub>4</sub>/C (0.8) as revealed from XPS. This is a result of doping of cobalt into CeO<sub>2</sub>, and (2) presence of crystalline-amorphous interfaces as observed from HRTEM.</p>

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A Robust Bifunctional Electrocatalyst with Crystalline-Amorphous Interfaces toward Oxygen Reduction/Evolution Reactions

  • Suranjana Patowary,
  • Bhugendra Chutia,
  • Pragya Moni Gogoi,
  • Pankaj Bharali

摘要

This work reports the successful synthesis of a highly stable and durable non-PGM catalyst Co3O4/CoxCe1−xO2−δ/C via a simple solvothermal process. The electrocatalytic ability of Co3O4/C, CeO2/C and Co3O4/CoxCe1−xO2−δ/C are tested for oxygen reduction and oxygen evolution reaction (ORR, OER). Under identical conditions, the electrochemical studies of the catalysts reveal enhanced performance of the Co3O4/CoxCe1−xO2−δ/C. It shows the highest geometric current density (jgeo = ̶ 4.1 mAcm−2 ) at 0.33 V vs. RHE. Moreover, Co3O4/CoxCe1−xO2−δ/C has the earliest onset for OER with a bifunctionality index of ΔE = 1.05 V and has the highest turnover frequency. The catalyst was compared with benchmarks like 20 wt% Pt/C for ORR and RuO2 for OER. Chronoamperometry studies (CA) reveals superior performance of Co3O4/CoxCe1−xO2−δ/C over Pt/C for ORR and accelerated durability test (ADT) shows no observable shift of half-wave potential (E1/2). This enhancement of electrocatalytic ability of Co3O4/CoxCe1−xO2−δ/C are attributed to (1) higher degree of Co2+:Co3+ ratio (3.6) in Co3O4/CoxCe1−xO2−δ/C than in Co3O4/C (0.8) as revealed from XPS. This is a result of doping of cobalt into CeO2, and (2) presence of crystalline-amorphous interfaces as observed from HRTEM.