研究目的
Investigating the photocatalytic effects of fluorene and dibenzo[b,d]thiophene sulfone conjugated microporous and linear polymers on hydrogen production from water under sacrificial conditions.
研究成果
The introduction of 9,9′-spirobifluorene linkers in S-CMP3 results in a microporous material with a hydrogen evolution rate that is more than three times higher than its linear non-porous analog under visible irradiation. This study suggests that conjugated microporous polymers can outperform their linear analogs in photocatalytic hydrogen evolution, provided that the materials are designed with suitable linkers that do not limit charge-transport and can be wetted by water.
研究不足
The study is limited to sacrificial conditions using TEA as a hole scavenger, and the performance under overall water splitting conditions is not explored. The role of residual palladium as a co-catalyst complicates the interpretation of the intrinsic photocatalytic activity of the polymers.
1：Experimental Design and Method Selection:
The study involved the synthesis of three series of conjugated microporous polymers (CMPs) and their linear analogs using Pd(0)-catalyzed Suzuki-Miyaura polycondensation. The photocatalytic activity was evaluated under both broad-spectrum irradiation (λ > 295 nm) and visible light (λ > 420 nm) using triethylamine (TEA) as the sacrificial hole scavenger.
2：Sample Selection and Data Sources:
The materials were characterized by FT-IR spectroscopy, elemental analysis, thermogravimetric analysis, scanning electron microscopy (SEM), powder X-ray diffraction, nitrogen sorption isotherms, UV/Visible absorption spectra, and time-correlated single photon counting for excited state life-time estimation.
3：List of Experimental Equipment and Materials:
Instruments used include SEM, TEM, UV-Vis spectrophotometer, and quasi-elastic neutron scattering (QENS) for studying water dynamics within the pores.
4：Experimental Procedures and Operational Workflow:
The photocatalytic activity was measured by suspending the polymer in a water/methanol/TEA mixture and irradiating with a 300 W Xe lamp. Hydrogen evolution rates were quantified.
5：Data Analysis Methods:
The data were analyzed to correlate the structure of the polymers with their photocatalytic performance, including the effect of porosity, wettability, and excited state life-time.
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