Lattice Distortion Engineering over Ultrathin Monoclinic BiVO₄ Nanoflakes Triggering AQE up to 69.4% in Visible‐Light‐Driven Water Oxidation

Abstract

An efficient water oxidation photocatalyst is imperative for the realization of artificial photosynthesis. Herein, a cooperative strategy is represented that enables 2D structure tailoring and lattice distortion engineering simultaneously over a BiVO4 photocatalyst for efficient visible‐light‐driven oxygen evolution reaction (OER). Specifically, the lattice distortion engineering is achieved through the introduction of a sodium (Na+) additive during the ion exchange process. Structural characterizations suggest the formation of ultrathin 2D monoclinic BiVO4 nanoflakes with shrank VO and elongated BiO bonds. Mechanistic investigations reveal the advantages of ultrathin 2D features for exposing more (010) active facets and shortening the required migration distance for charge carriers to reach the catalytic surface. More importantly, the lattice distortion effect is found to crucially govern the charge carrier dynamics and catalytic surface behavior of BiVO4 photocatalyst, endowing the optimized sample with an outstanding photocatalytic OER performance triggering up to 69.4% apparent quantum efficiency over Fe3+ sacrificial solution. These findings highlight the functional application of morphology and dimensional modification, as well as lattice distortion engineering in synthesizing superior monoclinic BiVO4 photocatalyst for efficient visible‐light‐driven water oxidation.

Unraveling the Site-Selective Doping Mechanism in Single-Crystalline BiVO4 Thin Films for Photoelectrochemical Water Splitting

“…To avoid the formation of unstable threefold coordinated V centers, oxygen vacancies are generated via the formation of bridging V–O–V bonds . Thus, the PEC performance can be enhanced under the effect of oxygen vacancies in optimizing carrier transport …”

Simultaneous Morphology and Band Structure Manipulation of BiOBr by Te Doping for Enhanced Photocatalytic Oxygen Evolution

“…Photocatalytic water splitting has drawn great attention owing to its environmental compatibility, abundant solar sources, and simple operation. − Enhancing the solar-to-energy conversion efficiency remains the biggest challenge for practical applications, particularly for the half-reaction of oxygen evolution, which is the rate-determining step that requires four electrons to realize the overall water splitting. − Bismuth oxybromide (BiOBr), a kind of oxyhalide, is regarded as a promising photocatalyst due to its suitable band structure and remarkable optical and electronic properties, whose feasibility of oxygen evolution under light irradiation has been widely studied. BiOBr possesses a layered structure with alternately [Bi 2 O 2 ] 2+ and [Br 2 ] 2– stacking slabs connected through weak van der Waals force.…”

“FeV-cofactor”-inspired bionic Fe-doped BiVO4photocatalyst decorated with few-layer 2D black phosphorus for efficient nitrogen reduction

“…The monoclinic form of BiVO 4 possesses a suitable band gap (2.3-2.4 eV) and an ideal electronic structure. 16,17 It has been reported that BiVO 4 exhibits notable photocatalytic nitrogen fixation performance, 18,19 and it is one of the ideal candidates for FeV-based bionic nitrogen-fixing photocatalysts. Furthermore, black phosphorus (BP), an emerging low-cost and highly efficient metal-free co-catalyst, has shown excellent assistant effects in photocatalytic nitrogen reduction, [20][21][22] due to its excellent optical/electronic properties such as broadspectrum light capture capability, high carrier mobility (∼1000 cm 2 V −1 s −1 ) and tunable band gap (0.3-2.0 eV).…”