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...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,Cu^2+ions are incorporated to form a bimetal-center MOF,with Zr^4+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 is promoted for both Cudoped 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.展开更多
Optical properties and ultrafast exciton relaxation dynamics in PbS and core/shell PbS/CdS quantum dots(QDs) have been studied using UV-vis absorption and fluorescence spectroscopy as well as femtosecond(fs) transient...Optical properties and ultrafast exciton relaxation dynamics in PbS and core/shell PbS/CdS quantum dots(QDs) have been studied using UV-vis absorption and fluorescence spectroscopy as well as femtosecond(fs) transient absorption spectroscopy.The electronic absorption spectrum of the PbS QDs features broad absorption in the entire near IR-vis-UV region with a monotonic increase in intensity towards shorter wavelength.Relative to PbS,the absorption of the core/shell PbS/CdS QDs shows a slight blue shift in the 600?800 nm region,due to the decrease of the PbS crystal size caused by the synthetic process of the core/shell structure,and increased absorption near 400 nm due to the CdS shell.The PL of the PbS/CdS QDs was ~2.6 times more intense than that of the PbS QDs,due to surface passivation of PbS by CdS,and blue-shifted,attributable to smaller PbS size and thereby stronger quantum confinement in the core/shell QDs.Fs transient absorption measurements of both systems showed a strong transient absorption feature from 600 to 750 nm following excitation at 750 nm.The transient absorption decays can be fit to a biexponential with time constants of 8 and 100 ps for PbS and 6 and 80 ps for PbS/CdS.The amplitude and lifetime of the fast component were excitation intensity dependent,with the amplitude increasing more than linearly with increasing excitation intensity and the lifetime decreasing with increasing intensity.The fast decay is attributed to exciton-exciton annihilation and it occurs more readily for the PbS/CdS than the PbS QDs,which is attributed to a lower density of trap states in the core/shell QDs,as supported by their stronger PL.展开更多
基金the National Key Research and Development Program on Nano Science and Technology of the Ministry of Science and Technology of China(No.2016YFA0200602 and No.2018YFA0208702)the National Natural Science Foundation of China(No.21573211 and No.21633007)the Anhui Initiative in Quantum Information Technologies(No.AHY090200)。
文摘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,Cu^2+ions are incorporated to form a bimetal-center MOF,with Zr^4+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 is promoted for both Cudoped 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.
基金supported by the Basic Energy Sciences Division of the US DOE (DE-FG02-ER46232)
文摘Optical properties and ultrafast exciton relaxation dynamics in PbS and core/shell PbS/CdS quantum dots(QDs) have been studied using UV-vis absorption and fluorescence spectroscopy as well as femtosecond(fs) transient absorption spectroscopy.The electronic absorption spectrum of the PbS QDs features broad absorption in the entire near IR-vis-UV region with a monotonic increase in intensity towards shorter wavelength.Relative to PbS,the absorption of the core/shell PbS/CdS QDs shows a slight blue shift in the 600?800 nm region,due to the decrease of the PbS crystal size caused by the synthetic process of the core/shell structure,and increased absorption near 400 nm due to the CdS shell.The PL of the PbS/CdS QDs was ~2.6 times more intense than that of the PbS QDs,due to surface passivation of PbS by CdS,and blue-shifted,attributable to smaller PbS size and thereby stronger quantum confinement in the core/shell QDs.Fs transient absorption measurements of both systems showed a strong transient absorption feature from 600 to 750 nm following excitation at 750 nm.The transient absorption decays can be fit to a biexponential with time constants of 8 and 100 ps for PbS and 6 and 80 ps for PbS/CdS.The amplitude and lifetime of the fast component were excitation intensity dependent,with the amplitude increasing more than linearly with increasing excitation intensity and the lifetime decreasing with increasing intensity.The fast decay is attributed to exciton-exciton annihilation and it occurs more readily for the PbS/CdS than the PbS QDs,which is attributed to a lower density of trap states in the core/shell QDs,as supported by their stronger PL.
