Porous boron nitride (BN), a combination of hexagonal, turbostratic and amorphous BN, has emerged as a new platform photocatalyst. Yet, this material lacks photoactivity under visible light. Theoretical studies predict that tuning the oxygen content in oxygen-doped BN (BNO) could lower the band gap. This is yet to be verified experimentally. We present herein a systematic experimental route to simultaneously tune BNO's chemical, magnetic and optoelectronic properties using a multivariate synthesis parameter space. We report deep visible range band gaps (1.50-2.90 eV) and tuning of the oxygen (2-14 at.%) and specific paramagnetic OB 3 contents (7-294 a.u. g À 1 ). Through designing a response surface via a design of experiments (DOE) process, we have identified synthesis parameters influencing BNO's chemical, magnetic and optoelectronic properties. We also present model prediction equations relating these properties to the synthesis parameter space that we have validated experimentally. This methodology can help tailor and optimise BN materials for heterogeneous photocatalysis.

<p>Developing robust, multifunctional photocatalysts that can facilitate both hydrogen evolution via photoreforming of water and gas phase CO2 photoreduction is highly desirable with the long-term vision of integrated photocatalytic setups. Here, we present a new addition to the boron nitride (BN) photocatalyst material platform, boron-doped boron oxynitride (B-BNO), capable of fulfilling this goal. Detailed EPR studies revealed hyperfine interactions between free charges located on discrete OB3 sites, exhibiting an out-of-plane symmetry, and the nuclei of neighbouring boron atoms. This material resolves two long-standing bottlenecks associated to BN-based materials concomitantly: instability in water and lack of photo activity under visible light. We show that B-BNO maintains prolonged stability in water for at least three straight days and can facilitate both liquid phase H2 evolution and gas phase CO2 photoreduction, using UV-Vis and deep visible irradiation (λ > 550 nm), without any cocatalysts. The evolution rates, apparent quantum yields, and selectivities observed for both reactions with B-BNO exceed those of its porous BNO counterpart, P25 TiO2 and bulk g-C3N4. This work provides scope to expand the BN photocatalyst platform to a wider range of reactions.</p>

<p>Developing robust, multifunctional photocatalysts that can facilitate both hydrogen evolution <i>via</i> photoreforming of water and gas phase CO₂ photoreduction is highly desirable with the long-term vision of integrated photocatalytic setups. Here, we present a step-change in the family of boron oxynitride materials by introducing the first example of a B-doped boron oxynitride (B-BNO). This material resolves an on-going bottleneck associated with BN-based materials, i.e. the lack of photoactivity under visible light. Detailed EPR studies revealed distinct hyperfine interactions between the free oxygen radicals and 3 neighbouring boron nuclei. This confirmed isolated OB₃sites, which contribute to band gap narrowing, as the radical species and origin of paramagnetism in BNO materials. We show that B-BNO can facilitate both liquid phase H₂evolution and gas phase CO₂ photoreduction, using UV-Vis and deep visible irradiation (λ > 550 nm), without any co-catalysts. The evolution rates, quantum efficiencies, and selectivities observed for both reactions with B-BNO exceed those of its porous BNO counterpart, P25 TiO₂ and bulk g-C₃N₄.</p>

A family of boron nitride (BN)-based photocatalysts for solar fuel syntheses have recently emerged. Studies have shown that oxygen doping, leading to boron oxynitride (BNO), can extend light absorption to the visible range. However, the fundamental question surrounding the origin of enhanced light harvesting and the role of specific chemical states of oxygen in BNO photochemistry remains unanswered. Here, using an integrated experimental and first-principles-based computational approach, we demonstrate that paramagnetic isolated OB 3 states are paramount to inducing prominent red-shifted light absorption. Conversely, we highlight the diamagnetic nature of O−B−O states, which are shown to cause undesired larger band gaps and impaired photochemistry. This study elucidates the importance of paramagnetism in BNO semiconductors and provides fundamental insight into its photophysics. The work herein paves the way for tailoring of its optoelectronic and photochemical properties for solar fuel synthesis.

<p>Developing robust, multifunctional photocatalysts that can facilitate both hydrogen evolution via photoreforming of water and gas phase CO2 photoreduction is highly desirable with the long-term vision of integrated photocatalytic setups. Here, we present a new addition to the boron nitride (BN) photocatalyst material platform, boron-doped boron oxynitride (B-BNO), capable of fulfilling this goal. Detailed EPR studies revealed hyperfine interactions between free charges located on discrete OB3 sites, exhibiting an out-of-plane symmetry, and the nuclei of neighbouring boron atoms. This material resolves two long-standing bottlenecks associated to BN-based materials concomitantly: instability in water and lack of photo activity under visible light. We show that B-BNO maintains prolonged stability in water for at least three straight days and can facilitate both liquid phase H2 evolution and gas phase CO2 photoreduction, using UV-Vis and deep visible irradiation (λ > 550 nm), without any cocatalysts. The evolution rates, apparent quantum yields, and selectivities observed for both reactions with B-BNO exceed those of its porous BNO counterpart, P25 TiO2 and bulk g-C3N4. This work provides scope to expand the BN photocatalyst platform to a wider range of reactions.</p>