Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilita...Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilitate the in-plane photogenerated charge transfer,but the precise ordered alignment is limited due to the non-covalentπ-stacking of COF layers,accordingly hindering out-of-plane transfer kinetics.Herein,we address a chiral induction method to construct a parallelly superimposed stacking chiral COF ultrathin shell on the support of SiO_(2) microsphere.Compared to the achiral COF analogues,the chiral COF shell with the parallel AA-stacking structure is more conducive to enhance the built-in electric field and accumulates photogenerated electrons for the rapid migration,thereby affording superior photocatalytic performance in hydrogen evolution from water splitting.Taking the simplest ketoenamine-linked chiral COF as a shell of SiO_(2) particle,the resulting composite exhibits an impressive hydrogen evolution rate of 107.1 mmol g^(-1)h^(-1)along with the apparent quantum efficiency of 14.31% at 475 nm.Furthermore,the composite photocatalysts could be fabricated into a film device,displaying a remarkable photocatalytic performance of 178.0 mmol m^(-2)h^(-1)for hydrogen evolution.Our work underpins the surface engineering of organic photocatalysts and illustrates the significance of COF stacking structures in regulating electronic properties.展开更多
Porous graphitic carbon nitride（pg-C3N4） nanosheets have been prepared through a one-step ammonia thermopolymerization method.The effects of synthetic temperature on the structural,optical and photocatalytic propert...Porous graphitic carbon nitride（pg-C3N4） nanosheets have been prepared through a one-step ammonia thermopolymerization method.The effects of synthetic temperature on the structural,optical and photocatalytic properties of the samples have been investigated.Characterization results show that the heptazine-based conjugate heterocyclic structure was formed over 500℃,which is attributed to the inhibitory effect of ammonia from the decomposition of NH4SCN.Precise nanosheet morphology and an increased pore distribution with an enlarged surface area are observed for the samples obtained under high temperatures.Optical analysis results show that the bandgap of the samples widens and photoluminescene intensity is gradually quenched as the treating temperature is increased.The results demonstrate that a higher polymerization temperature improves the nanolayer structure,porosity and migration rate of the photo-induced carriers of the samples.The pg-C3N4 nanosheets prepared at 600℃ presents the highest photocatalytic activity for hydrogen evolution from water under visible-light irradiation.This study demonstrates a novel strategy for the synthesis and optimization of polymer semiconductor nanosheets with gratifying photocatalytic performance.展开更多
The hydrogen plasma degradation of transparent conduction oxides （TCO） is studied for hydrogenated microcrystalline Si（μc-Si：H）prepared by plasma enhanced chemical vapor deposition （PECVD）. TCO films such as S...The hydrogen plasma degradation of transparent conduction oxides （TCO） is studied for hydrogenated microcrystalline Si（μc-Si：H）prepared by plasma enhanced chemical vapor deposition （PECVD）. TCO films such as SnO2 and SnO2/ZnO bi-layer films were exposed to atomic H at various substrate temperatures and for various treatment times. A decrease in the transmittance due to reduction by atomic H was scarcely observed for SnO2 / ZnO bi-layer,while a decrease for SnO2 was found to depend strongly on the substrate temperature. The resistivity of SnO2 films decreases significantly when substrate temperature exceeds 150℃in H-plasma. However, H-plasma treatment has little impact on the resistivity of SnO2/ZnO bi-layer film. The reason for the decrease in the transmittance is the appearance of metallic Sn on the surface, and under this condition no μc-Si： H film is deposited. SnO2/ZnO bi-layer is very effective for the suppression of the reduction of TCO during μc-Si：H deposition. The performance of microcrystalline silicon solar cells fabricated on ZnO/SnO2/glass is also investigated.展开更多
文摘Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilitate the in-plane photogenerated charge transfer,but the precise ordered alignment is limited due to the non-covalentπ-stacking of COF layers,accordingly hindering out-of-plane transfer kinetics.Herein,we address a chiral induction method to construct a parallelly superimposed stacking chiral COF ultrathin shell on the support of SiO_(2) microsphere.Compared to the achiral COF analogues,the chiral COF shell with the parallel AA-stacking structure is more conducive to enhance the built-in electric field and accumulates photogenerated electrons for the rapid migration,thereby affording superior photocatalytic performance in hydrogen evolution from water splitting.Taking the simplest ketoenamine-linked chiral COF as a shell of SiO_(2) particle,the resulting composite exhibits an impressive hydrogen evolution rate of 107.1 mmol g^(-1)h^(-1)along with the apparent quantum efficiency of 14.31% at 475 nm.Furthermore,the composite photocatalysts could be fabricated into a film device,displaying a remarkable photocatalytic performance of 178.0 mmol m^(-2)h^(-1)for hydrogen evolution.Our work underpins the surface engineering of organic photocatalysts and illustrates the significance of COF stacking structures in regulating electronic properties.
基金supported by the National Natural Science Foundation of China(21503096)the Natural Science Foundation of Jiangsu Province(BK20140507)~~
文摘Porous graphitic carbon nitride（pg-C3N4） nanosheets have been prepared through a one-step ammonia thermopolymerization method.The effects of synthetic temperature on the structural,optical and photocatalytic properties of the samples have been investigated.Characterization results show that the heptazine-based conjugate heterocyclic structure was formed over 500℃,which is attributed to the inhibitory effect of ammonia from the decomposition of NH4SCN.Precise nanosheet morphology and an increased pore distribution with an enlarged surface area are observed for the samples obtained under high temperatures.Optical analysis results show that the bandgap of the samples widens and photoluminescene intensity is gradually quenched as the treating temperature is increased.The results demonstrate that a higher polymerization temperature improves the nanolayer structure,porosity and migration rate of the photo-induced carriers of the samples.The pg-C3N4 nanosheets prepared at 600℃ presents the highest photocatalytic activity for hydrogen evolution from water under visible-light irradiation.This study demonstrates a novel strategy for the synthesis and optimization of polymer semiconductor nanosheets with gratifying photocatalytic performance.
文摘The hydrogen plasma degradation of transparent conduction oxides （TCO） is studied for hydrogenated microcrystalline Si（μc-Si：H）prepared by plasma enhanced chemical vapor deposition （PECVD）. TCO films such as SnO2 and SnO2/ZnO bi-layer films were exposed to atomic H at various substrate temperatures and for various treatment times. A decrease in the transmittance due to reduction by atomic H was scarcely observed for SnO2 / ZnO bi-layer,while a decrease for SnO2 was found to depend strongly on the substrate temperature. The resistivity of SnO2 films decreases significantly when substrate temperature exceeds 150℃in H-plasma. However, H-plasma treatment has little impact on the resistivity of SnO2/ZnO bi-layer film. The reason for the decrease in the transmittance is the appearance of metallic Sn on the surface, and under this condition no μc-Si： H film is deposited. SnO2/ZnO bi-layer is very effective for the suppression of the reduction of TCO during μc-Si：H deposition. The performance of microcrystalline silicon solar cells fabricated on ZnO/SnO2/glass is also investigated.
