Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Her...Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Herein,with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern,the electronic structure is theoretically illustrated by the first-principles density functional theory calculations,suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI.It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal orbital Hamiltonian group analysis.The calculations of reaction free energy changes indicate that the oxygen evolution reaction should follow the reaction pathway of H_(2)O→^(*)OH→^(*)O→^(*)OOH→^(*)O_(2)with an overpotential of 0.81 V.Through an in-depth theoretical computational analysis in the atomic and electronic structures,the origin of photocatalytic oxygen evolution activity for PDI is well illustrated,which would help the rational design and modification of polymeric photocatalysts for efficient oxygen evolution.展开更多
High-temperature piezoelectric vibration sensors are the preferred choice for structural health monitoring in harsh environments such as high temperatures and complex vibrations.Bismuth layer-structured CaBi_(4)Ti_(4)...High-temperature piezoelectric vibration sensors are the preferred choice for structural health monitoring in harsh environments such as high temperatures and complex vibrations.Bismuth layer-structured CaBi_(4)Ti_(4)O_(15)(CBT)high-temperature piezoelectric ceramics,with high Curie temperature(TC),are the key components for piezoelectric vibration sensors operating at temperatures exceeding 500℃.However,their low piezoelectric coefficient(d_(33))greatly limits their high-temperature applications.In this work,a novel Bi^(3+)self-doping strategy was employed to enhance the piezoelectric performance of CBT ceramics.The enhancement is attributed to an increase in the number of grain boundaries,providing more sites for space charge accumulation and promoting formation of space charge polarization.Furthermore,given that space charge polarization predominantly occurs at low frequencies,dielectric temperature spectra at different frequencies were used to elucidate the mechanism by which space charge polarization enhances piezoelectric properties of CBT ceramics.Excellent overall performance was achieved for the CBT-based high-temperature piezoelectric ceramics.Among them,TC reached 778℃,d_(33) increased by more than 30%,reaching 20.1 pC/N,and the electrical resistivity improved by one order of magnitude(reaching 6.33×10^(6)Ω·cm at 500℃).These advancements provide a key functional material with excellent performance for practical applications of piezoelectric vibration sensors at 500℃and above.展开更多
基金supported by National Natural Science Foundation of China(No.523B2070,No.52225606).
文摘Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Herein,with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern,the electronic structure is theoretically illustrated by the first-principles density functional theory calculations,suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI.It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal orbital Hamiltonian group analysis.The calculations of reaction free energy changes indicate that the oxygen evolution reaction should follow the reaction pathway of H_(2)O→^(*)OH→^(*)O→^(*)OOH→^(*)O_(2)with an overpotential of 0.81 V.Through an in-depth theoretical computational analysis in the atomic and electronic structures,the origin of photocatalytic oxygen evolution activity for PDI is well illustrated,which would help the rational design and modification of polymeric photocatalysts for efficient oxygen evolution.
基金National Natural Science Foundation of China (51932010)。
文摘High-temperature piezoelectric vibration sensors are the preferred choice for structural health monitoring in harsh environments such as high temperatures and complex vibrations.Bismuth layer-structured CaBi_(4)Ti_(4)O_(15)(CBT)high-temperature piezoelectric ceramics,with high Curie temperature(TC),are the key components for piezoelectric vibration sensors operating at temperatures exceeding 500℃.However,their low piezoelectric coefficient(d_(33))greatly limits their high-temperature applications.In this work,a novel Bi^(3+)self-doping strategy was employed to enhance the piezoelectric performance of CBT ceramics.The enhancement is attributed to an increase in the number of grain boundaries,providing more sites for space charge accumulation and promoting formation of space charge polarization.Furthermore,given that space charge polarization predominantly occurs at low frequencies,dielectric temperature spectra at different frequencies were used to elucidate the mechanism by which space charge polarization enhances piezoelectric properties of CBT ceramics.Excellent overall performance was achieved for the CBT-based high-temperature piezoelectric ceramics.Among them,TC reached 778℃,d_(33) increased by more than 30%,reaching 20.1 pC/N,and the electrical resistivity improved by one order of magnitude(reaching 6.33×10^(6)Ω·cm at 500℃).These advancements provide a key functional material with excellent performance for practical applications of piezoelectric vibration sensors at 500℃and above.
