Tuning the Intermolecular Electron Transfer of Low-Dimensional and Metal-Free BCN/C60 Electrocatalysts via Interfacial Defects for Efficient Hydrogen and Oxygen Electrochemistry

Md Ariful Ahsan; Tianwei He; Kamel Eid; Aboubakr M Abdullah; Michael L Curry; Aijun Du; Alain R Puente Santiago; Luis Echegoyen; Juan C Noveron

doi:10.1021/jacs.0c12386

Tuning the Intermolecular Electron Transfer of Low-Dimensional and Metal-Free BCN/C₆₀ Electrocatalysts via Interfacial Defects for Efficient Hydrogen and Oxygen Electrochemistry

J Am Chem Soc. 2021 Jan 20;143(2):1203-1215. doi: 10.1021/jacs.0c12386. Epub 2021 Jan 5.

Authors

Md Ariful Ahsan^{1

2}, Tianwei He^{3

4}, Kamel Eid⁵, Aboubakr M Abdullah⁶, Michael L Curry⁷, Aijun Du^{3

4}, Alain R Puente Santiago¹, Luis Echegoyen¹, Juan C Noveron^{1

2}

Affiliations

¹ Department of Chemistry and Biochemistry, University of Texas at El Paso, El Paso, Texas 79968, United States.
² Nanosystems Engineering Research Center for Nanotechnology-Enabled Water Treatment, Houston, Texas 77005, United States.
³ Centre for Materials Science, Queensland University of Technology, Gardens Point Campus, Brisbane, QLD 4000, Australia.
⁴ School of Chemistry and Physics, Science and Engineering Faculty, Queensland University of Technology, Gardens Point Campus, Brisbane, QLD 4000, Australia.
⁵ Gas Processing Center, College of Engineering, Qatar University, Doha 2713, Qatar.
⁶ Center for Advanced Materials, Qatar University, Doha 2713, Qatar.
⁷ Department of Chemistry, Tuskegee University, Tuskegee, Alabama 36088, United States.

PMID: 33401899
DOI: 10.1021/jacs.0c12386

Abstract

The development of low-dimensional (LD) supramolecular materials with multifunctional electrocatalytic properties has sparked the attention of the catalysis community. Herein, we report the synthesis of a new class of 0D-2D heterostructures composed of boron carbon nitride nanosheets (BCN NSs) and fullerene molecules (C₆₀/F) that exhibit multifunctional electrocatalytic properties for the hydrogen evolution/oxidation reactions (HER/HOR) and the oxygen evolution/reduction reactions (OER/ORR). The electrocatalytic properties were studied with varying F:BCN weight ratios to optimize the intermolecular electron transfer (ET) from the BCN NSs to the electron-accepting C₆₀ molecules. The nanohybrid supramolecular material with 10 wt % F in BCN NSs (10% F/BCN) exhibited the largest Raman and C 1s binding energy shifts, which were associated with greater cooperativity interactions and enhanced ET processes at the F/BCN interface. This synergistic interfacial phenomenon resulted in highly active catalytic sites that markedly boosted electrocatalytic activity of the material. The 10% F/BCN showed the highest tetrafunctional catalytic performance, outperforming the OER catalytic activity of commercial RuO₂ catalysts with a η₁₀ of 390 mV and very competitive onset potential values of -0.042 and 0.92 V vs RHE for HER and ORR, respectively, and a current density value of 1.47 mA cm^-2 at 0.1 V vs RHE with an ultralow ΔG_H* value of -0.03 eV toward the HOR process. Additionally, the 10% F/BCN catalyst was also used as both cathode and anode in a water splitting device, delivering a cell potential of 1.61 V to reach a current density of 10 mA cm^-2.