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

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 (C 60 /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 C 60 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 RuO 2 catalysts with a η 10 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 .

Low-dimensional heterostructures for advanced electrocatalysis: an experimental and computational perspective

“…25 Our group has launched a very innovative strategy to regulate the electrocatalytic properties of 2D-BCN layers for hydrogen and oxygen electrochemistry. 26 To achieve this goal, fullerenes (C 60 ) were non-covalently attached on the top of BCN nanosheets using a facile sonication strategy (Fig. 2H).…”

Recent advances in non-precious group metal-based catalysts for water electrolysis and beyond

“…In addition, faster electron transfer during the HER/OER process in acidic/alkaline media is considered a desirable feature. 7,27,28 The surface phase stability is also an important factor since the elemental dissolution and surface structure degradation are easily observed under elevated potentials. 29,30 To date, the development of new designs and viable model electrocatalysts has represented a breakthrough in replacing PGMs.…”

Efforts at Enhancing Bifunctional Electrocatalysis and Related Events for Rechargeable Zinc‐Air Batteries

“…Noble metals (e. g., Pt, Pd, Ru, and Ir) and their oxides respectively are the most active ORR and OER electrocatalysts. [53][54][55][56] For instance, Pt/C electrocatalyst shows excellent ORR activity at 284 mV, whereas RuO 2 displays great OER performance at 250 mV in 0.1 M KOH. [57] However, due to their scarcity, high cost, and self-poisoning, these materials are economically undesirable for the large-scale manufacturing of RZABs.…”