title: Boosting Hot-Electron Generation: Exciton Dissociation at the Order-Disorder Interfaces in Polymeric Photocatalysts.
abstract: Excitonic effects, arising from the Coulomb interactions between photogenerated electrons and holes, dominate the optical excitation properties of semiconductors, whereas their influences on photocatalytic processes have seldom been discussed. In view of the competitive generation of excitons and hot carriers, exciton dissociation is proposed as an alternative strategy for hot-carrier harvesting in photocatalysts. Herein, by taking heptazine-based melon as an example, we verified that enhanced hot-carrier generation could be obtained in semicrystalline polymeric photocatalysts, which is ascribed to the accelerated exciton dissociation at the abundant order-disorder interfaces. Moreover, driven by the accompanying electron injection toward ordered chains and hole blocking in disordered chains, semicrystalline heptazine-based melon showed an ∼7-fold promotion in electron concentration with respect to its pristine counterpart. Benefiting from these, the semicrystalline sample exhibited dramatic enhancements in electron-involved photocatalytic processes, such as superoxide radical production and selective alcohol oxidation. This work brightens excitonic aspects for the design of advanced photocatalysts.
authors.affiliation: Hefei National Laboratory for Physical Science at the Microscale, Collaborative Innovation Center of Chemistry for Energy Materials, University of Science and Technology of China , Hefei, Anhui 230026, People's Republic of China.
authors.forename: Hui
authors.initials: H
authors.lastname: Wang
authors.affiliation: Hefei National Laboratory for Physical Science at the Microscale, Collaborative Innovation Center of Chemistry for Energy Materials, University of Science and Technology of China , Hefei, Anhui 230026, People's Republic of China.
authors.forename: Xianshun
authors.initials: X
authors.lastname: Sun
authors.affiliation: Department of Chemistry, Anhui University , Hefei, Anhui 230039, People's Republic of China.
authors.forename: Dandan
authors.initials: D
authors.lastname: Li
authors.affiliation: Hefei National Laboratory for Physical Science at the Microscale, Collaborative Innovation Center of Chemistry for Energy Materials, University of Science and Technology of China , Hefei, Anhui 230026, People's Republic of China.
authors.forename: Xiaodong
authors.identifier: 0000-0002-8288-035X
authors.initials: X
authors.lastname: Zhang
authors.affiliation: Hefei National Laboratory for Physical Science at the Microscale, Collaborative Innovation Center of Chemistry for Energy Materials, University of Science and Technology of China , Hefei, Anhui 230026, People's Republic of China.
authors.forename: Shichuan
authors.initials: S
authors.lastname: Chen
authors.affiliation: Hefei National Laboratory for Physical Science at the Microscale, Collaborative Innovation Center of Chemistry for Energy Materials, University of Science and Technology of China , Hefei, Anhui 230026, People's Republic of China.
authors.forename: Wei
authors.initials: W
authors.lastname: Shao
authors.affiliation: Department of Chemistry, Anhui University , Hefei, Anhui 230039, People's Republic of China.
authors.forename: Yupeng
authors.initials: Y
authors.lastname: Tian
authors.affiliation: Hefei National Laboratory for Physical Science at the Microscale, Collaborative Innovation Center of Chemistry for Energy Materials, University of Science and Technology of China , Hefei, Anhui 230026, People's Republic of China.
authors.forename: Yi
authors.identifier: 0000-0002-1416-5557
authors.initials: Y
authors.lastname: Xie