Hydrogen Bonds and In situ Photoinduced Metallic Bi0/Ni0 Accelerating Z-Scheme Charge Transfer of BiOBr@NiFe-LDH for Highly Efficient Photocatalysis

Abstract

For heterojunction system, the lack of stable interfacial driving force and definite charge transfer channel makes the charge separation and transfer efficiency unsatisfactory. The photoreaction mechanism occurring at the interface also receives less attention. Herein, a 2D/2D Z-scheme junction BiOBr@NiFe-LDH with large-area contact featured by short interface hydrogen bonds and strong interfacial electric field (IEF) is synthesized, and in situ photoinduced metallic species assisting charge transfer mechanism is demonstrated. The hydrogen bonds between O atoms from BiOBr and H atoms from NiFe-LDH induce a significant interfacial charge redistribution, establishing a robust IEF. Notably, during photocatalytic reaction, Bi⁰ and Ni⁰ are in situ performed in heterojunction, which separately act as electron transport mediator and electron trap to further accelerate charge transfer efficiency up to 71.2 %. Theoretical calculations further demonstrate that the existence of Bi⁰ strengthens the IEF. Therefore, high-speed spatial charge separation is realized in Bi⁰/BiOBr@Ni⁰/NiFe-LDH, leading to a prominent photocatalytic activity with a tetracycline removal ratio of 88.3 % within 7 min under visible-light irradiation and the presence of persulfate, far exceeding majority of photocatalysts reported previously. This study provides valid insights for designing hydrogen bonding heterojunction systems, and advances mechanistic understanding on in situ photoreaction at interfaces.