Low-Energy Photons Dual Harvest for Photocatalytic Hydrogen Evolution: Bimodal Surface Plasma Resonance Related Synergism of Upconversion and Pyroelectricity

Small. 2023 May;19(18):e2207467. doi: 10.1002/smll.202207467. Epub 2023 Jan 12.

Abstract

Utilization of low-energy photons for efficient photocatalysis remains a challenging pursuit. Herein, a strategy is reported to boost the photocatalytic performance, by promoting low-energy photons dual harvest through bimodal surface plasmon resonance (SPR)-enhanced synergistically upconversion and pyroelectricity. It is achieved by introducing triplet-triplet annihilation upconversion (TTA-UC) materials and plasmonic material (Au nanorods, AuNRs) into composite fibers composed of pyroelectric substrate (poly(vinylidene fluoride)) and photocatalyst Cd0.5 Zn0.5 S. Interestingly, the dual combination of TTA-UC and AuNRs SPR in the presence of polyvinylidene fluoride substrate with pyroelectric property promotes the photocatalytic hydrogen evolution performance by 2.88 folds with the highest average apparent quantum yield of 7.0% under the low-energy light (λ > 475 nm), which far outweighs the role of separate application of TTA-UC (34%) and AuNRs SPR (76%). The presence of pyroelectricity plays an important role in the built-in electric field as well as the accordingly photogenerated carrier behavior in the composite photocatalytic materials, and the pyroelectricity can be affected by AuNRs with different morphologies, which is proved by the Kelvin probe force microscopy and photocurrent data. This work provides a new avenue for fully utilizing low-energy photons in the solar spectrum for improving photocatalytic performance.

Keywords: photo-thermal conversion; photocatalysis; pyroelectricity; surface plasmon resonance; triplet-triplet annihilation upconversion.