Boron-Functionalized Graphitic Carbon Nitride Materials for Photocatalytic Applications: Effects on Chemical,...

Graphitic carbon nitride (gC₃N₄, or CN herein) is widely studied as a photocatalyst owing to its ease of synthesis, high stability, and optoelectronic properties. However, its photocatalytic performance often remains limited, and a common approach to tune its function and enhance its performance is by doping. Boron (B) functionalization of CN has showed a potential benefit on photocatalytic performance for several reactions. However, the reason for this improvement and the links between synthesis method, exact B chemical environment, and performance remain unclear. Here, we present a fundamental study that elucidates the influence of (i) B functionalization, (ii) B content, and (iii) choice of B precursor on the physicochemical, adsorptive, optoelectronic, and photocatalytic properties of bulk B-CN. We synthesized two sets of B-CN materials (0.5-11 at% B), using either elemental boron or boric acid as precursors. The samples were characterized using several imaging and spectroscopic techniques, which confirm the integration of B into the material through B-O bonding and the creation of B clusters in the case of the boron precursor, with density functional theory (DFT) calculations supporting our analyses. The distribution of B atoms within B-CN particles remained heterogeneous. Compared to CN, B-functionalized materials show enhanced porosity and CO₂ uptake, with similar degrees of light absorption and deeper energy band positions. Transient absorption spectroscopy (TAS) measurements showed that charge carrier populations, lifetimes, and kinetics were not significantly affected by B functionalization; however, at 5 at% B doping, an increase in the concentration of charge carriers was seen. Higher B content enhances the photocatalytic NO _x removal under UVA irradiation (almost two-fold) and the selectivity to NO₃ ^- from NO _x photooxidation, but has no significant effect on CO₂ photoreduction, compared to pristine CN. Overall, this study provides fundamental insights to build on and more rationally produce better-performing B-CN photocatalysts.