Investigating the Third‐Order NLO Performance of a Three‐Phase Core‐Shell PANI@MIL‐101(Cr)@CeO2 with Internal and External Synergies

Combining metal–organic frameworks (MOFs) with other functional materials can effectively improve the third‐order nonlinear optical (NLO) performances of MOFs. In this study, two distinct functional materials are selected and a PANI@MIL‐101(Cr)@CeO2 composite is successfully synthesized. The test results of third‐order NLO indicate that introducing PANI regulates the distribution of π electron clouds within the structure of the composite. Additionally, the core@shell structure formed by PANI@MIL‐101(Cr) and CeO2 promotes charge transfer and improves charge transfer efficiency under the weak heterojunction interaction, thereby enhancing nonlinear absorption and refractive signals. Under the double synergistic action of interior and exterior, a new charge transfer occurs between the components of the composite, resulting in excellent third‐order NLO performances. This study indicates that encapsulating polymer and loading metal oxides can effectively improve the NLO response of MOFs, which offers a new idea for more research on multiphase NLO materials. Based on the excellent chemical stability and modifiable pores of MOFs, two different types of functional materials are combined with MOFs through heterojunctions to form a three‐phase core@shell composite. The effective synergistic effect between the components changes the distribution of electron clouds and improves charge transfer efficiency, thus exhibiting excellent third‐order nonlinear optical properties.