Tuning the Active Oxygen Species of Two-Dimensional Borophene Oxide toward Advanced Metal-Free Catalysis

Tuning the Active Oxygen Species of Two-Dimensional Borophene Oxide toward Advanced Metal-Free Catalysis

Abstract

Two-dimensional (2D) borophene materials are predicted to be ideal catalytic materials due to their structural analogy to graphene. However, the lack of chemical functionalization of borophene hinders its practical application in catalysis. Herein, we reported a massive production of freestanding few-layer 2D borophene oxide (BO) sheets with tunable active oxygen species by a moderate oxidation-assisted exfoliation method. State-of-the-art characterizations demonstrated the evolution of active oxygen species from surface B–O species at the initial stage to the intermediate BxOy (1.5 < x/y < 3) species and eventually to bulk B2O3 with an increasing oxidation duration. As a result, the 2D BO sheet with enhanced B–O species exhibited a strikingly high catalytic activity for the aerobic oxidation of benzylamine into N-benzylidenebenzylamine. The formation rate of imine reaches as high as 29.7 mmol gcatal–1 h–1 under mild reaction conditions, higher than that of pristine borophene, boron oxides, graphene oxide, and other metal/metal-free catalysts in the reported literature. Density functional theory calculations further revealed the critical role of surface B–O species, which favor the adsorption and N–H activation of benzylamine for high activity and suppress the deep dehydrogenation, yielding an outstanding imine selectivity (>90%). This work paves the route for a moderate and scalable synthesis of few-layer BO sheets with highly active B–O species toward advanced metal-free catalysis beyond graphene.

Summary for Non-Scientists

Researchers are developing new materials called borophene oxide (BO) sheets, which are two-dimensional (2D) and similar to graphene, to improve their use in catalysis. Catalysis is a process that speeds up chemical reactions, and these materials have great potential due to their structure.

Here's a simplified summary:

  • They created thin layers of borophene oxide by using a method that involves oxidation (adding oxygen) and exfoliation (peeling off layers).
  • They studied how these layers change over time, starting with surface B–O species and progressing to more complex forms as more oxygen is added.
  • These BO sheets showed very high catalytic activity, especially in converting benzylamine into N-benzylidenebenzylamine (a chemical reaction).
  • They found that the high activity is due to the B–O species on the surface, which help in the adsorption and activation of benzylamine while preventing unwanted reactions.
  • The BO sheets outperformed other materials like pristine borophene, boron oxides, and graphene oxide in these reactions.

Overall, this research shows that borophene oxide sheets are very promising for use in advanced catalysis, potentially surpassing graphene in certain applications.

Source :
ACS Nano
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