Polymeric carbon
nitride (CN) is a fascinating metal-free photocatalyst
for active solar energy conversion via water splitting. However, the
photocatalytic activity of CN is significantly restricted by the intrinsic
drawbacks of fast charge recombination because of incomplete polymerization.
Herein, an in situ ionothermal molten salt strategy has been developed
to construct polytriazine/heptazine based CN isotype heterojunctions
from low cost and earth-abundant urea as the single-source precursor,
with the purpose of greatly promoting the charge transfer and separation.
The engineering of crystallinity and phase structure of CN has been
attempted through facile tailoring of the condensation conditions
in a molten salt medium. Increasing the synthetic temperature and
eutectic salts/urea molar ratio leads to the formation of CN from
bulk heptazine phase to crystalline polytriazine imide (PTI) phase,
while CN isotype heterojunctions are in situ created at moderate synthetic
temperature and salt amount. As evidenced by the measurements of UV–vis
DRS and Mott–Schottky plots, the conduction band potentials
can be tuned in a wide range from −1.51 to −0.96 V by
controlling the synthetic temperature and salt amount, and the apparent
band gap energies are reduced accordingly. The difference in band
positions between PTI and heptazine phase CN enables the formation
of CN heterojunctions, greatly promoting the separation of charge
carriers. These metal-free CN heterojunctions demonstrate a well ordered
needle-like morphology, and the optimal sample yields a remarkable
hydrogen evolution rate (4813.2 μmol h–1 g–1), improved by a factor of 12 over that of bulk heptazine-based
CN and a factor of 4 over that of PTI. The enhanced photocatalytic
performance can be directly ascribed to the synergistic effect of
the improved crystallinity with reduced structural defects, the decreased
band gap energy with tunable band positions, and the efficient separation
of charge carriers induced by the formation of heterostructures.
Photocatalytic water splitting by solar light is an environmentfriendly means for generating hydrogen as energy resources. For practical use, photocatalysts with higher activity are desired.Recently it was found that the photocatalytic activity of SrTiO 3 is remarkably improved by Na-doping. However, why Nadoping enhances the activity has not been well understood. In this work, we found that Na-doping in SrTiO 3 introduces new mid-gap states. Transient absorption measurements revealed that photoexcited electrons were trapped into these states within~20 ps after excitation. These trapped electrons have longer lifetime than those in undoped SrTiO 3 , and number of surviving electrons in microseconds increased~15 times. These electrons are trapped at the mid-gap states, but still keep reactivity with reactant molecules. Furthermore, they were effectively captured by H 2 -evolution cocatalyst, indicating that they can participate in steady-state reactions. This work emphasizes the important role of electron-trapping states introduced by doping on photocatalytic activity.[a] Dr.
An efficient composite photocatalyst fabricated by dispersing ultrafine Fe2O3 nanocrystals onto g-C3N4 nanosheets via a facile deposition-precipitation method shows significantly enhanced photocatalytic performance under visible light irradiation.
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