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Jia Liu, Shen-long Jiang, Qun Zhang. Doping Copper Ions in a Metal–Organic Framework (UiO-66-NH2): Location Effect Examined by Ultrafast Spectroscopy[J]. Chinese Journal of Chemical Physics .
Citation: Jia Liu, Shen-long Jiang, Qun Zhang. Doping Copper Ions in a Metal–Organic Framework (UiO-66-NH2): Location Effect Examined by Ultrafast Spectroscopy[J]. Chinese Journal of Chemical Physics .

Doping Copper Ions in a Metal–Organic Framework (UiO-66-NH2): Location Effect Examined by Ultrafast Spectroscopy

  • Accepted Date: 2020-07-02
  • We constructed two types of copper-doped metal–organic framework (MOF), i.e., Cu@UiO-66-NH2 and Cu-UiO-66-NH2. In the former, Cu2+ ions are impregnated in the pore space of the amine-functionalized, Zr-based UiO-66-NH2; while in the latter, Cu2+ ions are incorporated to form a bimetal-center MOF with Zr4+ being partially replaced by Cu2+ in the Zr–O oxo-clusters. Ultrafast spectroscopy revealed that the photoinduced relaxation kinetics associated with the ligand-to-cluster charge-transfer state are promoted for both Cu-doped MOFs relative to undoped one, but in a sequence of Cu-UiO-66-NH2 > Cu@UiO-66-NH2 > UiO-66-NH2. Such a sequence turned to be in line with the trend observed in the visible-light photocatalytic hydrogen evolution activity tests on the three MOFs. These findings highlighted the subtle effect of copper-doping location in this Zr-based MOF system, further suggesting that rational engineering of the specific metal-doping location in alike MOF systems to promote the photoinduced charge separation and hence suppress the detrimental charge recombination therein is beneficial for achieving improved performances in MOF-based photocatalysis.
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通讯作者: 陈斌, bchen63@163.com
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    沈阳化工大学材料科学与工程学院 沈阳 110142

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Doping Copper Ions in a Metal–Organic Framework (UiO-66-NH2): Location Effect Examined by Ultrafast Spectroscopy

Abstract: We constructed two types of copper-doped metal–organic framework (MOF), i.e., Cu@UiO-66-NH2 and Cu-UiO-66-NH2. In the former, Cu2+ ions are impregnated in the pore space of the amine-functionalized, Zr-based UiO-66-NH2; while in the latter, Cu2+ ions are incorporated to form a bimetal-center MOF with Zr4+ being partially replaced by Cu2+ in the Zr–O oxo-clusters. Ultrafast spectroscopy revealed that the photoinduced relaxation kinetics associated with the ligand-to-cluster charge-transfer state are promoted for both Cu-doped MOFs relative to undoped one, but in a sequence of Cu-UiO-66-NH2 > Cu@UiO-66-NH2 > UiO-66-NH2. Such a sequence turned to be in line with the trend observed in the visible-light photocatalytic hydrogen evolution activity tests on the three MOFs. These findings highlighted the subtle effect of copper-doping location in this Zr-based MOF system, further suggesting that rational engineering of the specific metal-doping location in alike MOF systems to promote the photoinduced charge separation and hence suppress the detrimental charge recombination therein is beneficial for achieving improved performances in MOF-based photocatalysis.

Jia Liu, Shen-long Jiang, Qun Zhang. Doping Copper Ions in a Metal–Organic Framework (UiO-66-NH2): Location Effect Examined by Ultrafast Spectroscopy[J]. Chinese Journal of Chemical Physics .
Citation: Jia Liu, Shen-long Jiang, Qun Zhang. Doping Copper Ions in a Metal–Organic Framework (UiO-66-NH2): Location Effect Examined by Ultrafast Spectroscopy[J]. Chinese Journal of Chemical Physics .

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