ABSTRACT
Bismuth molybdate (BMO) is a promising visible-driven photocatalyst and constructing heterojunctions in BMO-based materials is an effective way to enhance photocatalytic performance. In this study, boron-doped graphene quantum dots (BGQDs) were synthesized by one-step pyrolysis and carbonization, followed by the preparation of bismuth molybdate/boron-doped graphene quantum dots (BGQDs/BMO) heterojunction photocatalysts using in-situ growth method. The introduction of BGQDs significantly improved the photocatalytic nitrogen fixation activity under the irradiation of visible light and without scavengers. The highest NH3 yield was achieved with BGQDs/BMO-10, which was 3.48 times higher than pure phase BMO. This improvement was due to the formation of Z-scheme heterojunctions between BGQDs and BMO with the synergistic mechanism of interfacial charge transport and the generation of more protons. This study provides useful guidance for enhancing the visible-light nitrogen fixation performance of BMO materials.
ABSTRACT
Nitrogen activation with low-cost, visible-light-driven photocatalysts continues to be a major challenge. Since the discovery of biological nitrogen fixation, multi-component systems have achieved higher efficiency due to the synergistic effects, thus one of the challenges has been distinguishing the active sites in multi-component catalysts. In this study, we report the photocatalysts of In/In2O3@C with plume-blossom-like junction structure obtained by one-step roasting of MIL-68-In. The "branch" is carbon for supporting and protecting the structure, and the "blossom" is In/In2O3 for the activation and reduction of N2, which form an efficient photocatalyst for nitrogen fixation reaction with the performance of 51.83 µmol h-1 g-1. Experimental studies and DFT calculations revealed the active site of the catalyst for nitrogen fixation reaction is the In3+ around the oxygen vacancy in In2O3. More importantly, the elemental In forms the Schottky barrier with In2O3 in the catalyst, which can generate a built-in electric field to form charge transfer channels during the photocatalytic activity, not only broadens the light absorption range of the material, but also exhibits excellent metal conductivity.
Subject(s)
Prunus domestica , Catalytic Domain , Nitrogen Fixation , Carbon , OxygenABSTRACT
Defect engineering is one of the effective strategies to regulate and control catalyst properties. Constructing appropriate catalytically active centers effectively tunes the electronic and surface properties of the catalyst to achieve further enrichment of photogenerated electrons, enhances the electronic feedback of the catalytically active center to the anti-bonding orbitals of the nitrogen molecule, and enhances N2 adsorption while weakening the NîN bond. In this study, titanium vacancy (VTi)-rich undoped anatase p-TiO2 was successfully synthesized to investigate the effect of its metal vacancies on photocatalytic nitrogen reduction reaction (NRR) performance. The cation vacancies of VTi-rich p-TiO2 lead to local charge defects that enhance carrier separation and transport while trapping electrons to activate N2, allowing effective reduction of the excited electrons to NH3. This work provides a viable strategy for driving the efficiency of photocatalytic nitrogen fixation processes by altering the structural properties of semiconductors through cationic vacancies, offering new opportunities and challenges for the design and preparation of titanium dioxide-based materials.
