Noble metal cocatalysts have shown great potential in boosting the performance of CdS in photocatalytic water splitting.However,the mechanism and kinetics of electron transfer in noble-metal-decorated CdS during pract...Noble metal cocatalysts have shown great potential in boosting the performance of CdS in photocatalytic water splitting.However,the mechanism and kinetics of electron transfer in noble-metal-decorated CdS during practical hydrogen evolution is not clearly elucidated.Herein,Pt-nanoparticle-decorated CdS nanorods(CdS/Pt)are utilized as the model system to analyze the electron transfer kinetics in CdS/Pt heterojunction.Through femtosecond transient absorption spectroscopy,three dominating exciton quenching pathways are observed and assigned to the trapping of photogenerated electrons at shallow states,recombination of free electrons and trapped holes,and radiative recombination of locally photogenerated electron-hole pairs.The introduction of Pt cocatalyst can release the electrons trapped at the shallow states and construct an ultrafast electron transfer tunnel at the CdS/Pt interface.When CdS/Pt is dispersed in acetonitrile,the lifetime and rate for interfacial electron transfer are respectively calculated to be~5.5 ps and~3.5×10^(10) s^(−1).The CdS/Pt is again dispersed in water to simulate photocatalytic water splitting.The lifetime of the interfacial electron transfer decreases to~5.1 ps and the electron transfer rate increases to~4.9×10^(10) s^(−1),confirming that Pt nanoparticles serve as the main active sites of hydrogen evolution.This work reveals the role of Pt cocatalysts in enhancing the photocatalytic performance of CdS from the perspective of electron transfer kinetics.展开更多
The ultrafast photoisomerization and excited-state dynamics of trans-4-methoxyazobenzene (trans-4-MAB) in solutions were investigated by femtosecond transient absorption spectroscopy and quantum chemistry calculations...The ultrafast photoisomerization and excited-state dynamics of trans-4-methoxyazobenzene (trans-4-MAB) in solutions were investigated by femtosecond transient absorption spectroscopy and quantum chemistry calculations. After being excited to the S2 state, the two-dimensional transient absorptions spectra show that cis-4-MAB is produced and witnessed by the permanent positive absorption in 400-480 nm. Three decay components are determined to be 0.11, 1.4 and 2.9 ps in ethanol, and 0.16, 1.5 and 7.5 ps in ethylene glycol, respectively. The fast component is assigned to the internal conversion from the S2 to S1 state. The other relaxation pathways are correlated with the decay of the S1 state via internal conversion and isomerization, and the vibrational cooling of the hot S0 state of the cis-isomer. Comparing of the dynamics in different solvents, it is demonstrated that the photoisomerization pathway undergoes the inversion mechanism rather than the rotation mechanism.展开更多
The excited-state double proton transfer(ESDPT)properties of 1,5-dihydroxyanthraquinone(1,5-DHAQ)in various solvents were investigated using femtosecond transient absorption spectroscopy and the DFT/TDDFT method.The s...The excited-state double proton transfer(ESDPT)properties of 1,5-dihydroxyanthraquinone(1,5-DHAQ)in various solvents were investigated using femtosecond transient absorption spectroscopy and the DFT/TDDFT method.The steady-state fluorescence spectra in toluene,tetrahydrofuran(THF)and acetonitrile(ACN)solvents presented that the solvent polarity has an effect on the position of the ESDPT fluorescence emission peak for the 1,5-DHAQ system.Transient absorption spectra show that the increasing polarity of the solvent accelerates the rate of excited state dynamics.Calculated potential energy curves analysis further verified the experimental results.The ESDPT barrier decreases gradually with the increase of solvent polarity from toluene,THF to ACN solvent.It is convinced that the increase of solvent polarity can promote the occurrence of the ESDPT dynamic processes for the 1,5-DHAQ system.This work clarifies the mechanism of the influence of solvent polarity on the ESDPT process of 1,5-DHAQ,which provides novel ideas for design and synthesis of new hydroxyanthraquinone derivatives.展开更多
文摘Noble metal cocatalysts have shown great potential in boosting the performance of CdS in photocatalytic water splitting.However,the mechanism and kinetics of electron transfer in noble-metal-decorated CdS during practical hydrogen evolution is not clearly elucidated.Herein,Pt-nanoparticle-decorated CdS nanorods(CdS/Pt)are utilized as the model system to analyze the electron transfer kinetics in CdS/Pt heterojunction.Through femtosecond transient absorption spectroscopy,three dominating exciton quenching pathways are observed and assigned to the trapping of photogenerated electrons at shallow states,recombination of free electrons and trapped holes,and radiative recombination of locally photogenerated electron-hole pairs.The introduction of Pt cocatalyst can release the electrons trapped at the shallow states and construct an ultrafast electron transfer tunnel at the CdS/Pt interface.When CdS/Pt is dispersed in acetonitrile,the lifetime and rate for interfacial electron transfer are respectively calculated to be~5.5 ps and~3.5×10^(10) s^(−1).The CdS/Pt is again dispersed in water to simulate photocatalytic water splitting.The lifetime of the interfacial electron transfer decreases to~5.1 ps and the electron transfer rate increases to~4.9×10^(10) s^(−1),confirming that Pt nanoparticles serve as the main active sites of hydrogen evolution.This work reveals the role of Pt cocatalysts in enhancing the photocatalytic performance of CdS from the perspective of electron transfer kinetics.
基金supported by the National Natural Science Foundation of China(No.21603049,No.11674355,No.11705043,No.21327804,No.11364043)the Fundamental Research Funds for the Central Universities(No.JZ2015HGBZ0532)+1 种基金the Industry-UniversityResearch Fund of Hefei University of Technology Xuancheng Campus(No.XC2016JZBZ11)the Natural Science Foundation of Xinjiang Uygur Autonomous Region(No.2016D01A058)
文摘The ultrafast photoisomerization and excited-state dynamics of trans-4-methoxyazobenzene (trans-4-MAB) in solutions were investigated by femtosecond transient absorption spectroscopy and quantum chemistry calculations. After being excited to the S2 state, the two-dimensional transient absorptions spectra show that cis-4-MAB is produced and witnessed by the permanent positive absorption in 400-480 nm. Three decay components are determined to be 0.11, 1.4 and 2.9 ps in ethanol, and 0.16, 1.5 and 7.5 ps in ethylene glycol, respectively. The fast component is assigned to the internal conversion from the S2 to S1 state. The other relaxation pathways are correlated with the decay of the S1 state via internal conversion and isomerization, and the vibrational cooling of the hot S0 state of the cis-isomer. Comparing of the dynamics in different solvents, it is demonstrated that the photoisomerization pathway undergoes the inversion mechanism rather than the rotation mechanism.
基金supported by the National Basic Research Program of China(No.2019YFA0307701)the National Natural Science Foundation of China(No.11874180)the Young and Middle-aged Scientific and Technological Innovation leaders and Team Projects in Jilin Province(No.20200301020RQ)。
文摘The excited-state double proton transfer(ESDPT)properties of 1,5-dihydroxyanthraquinone(1,5-DHAQ)in various solvents were investigated using femtosecond transient absorption spectroscopy and the DFT/TDDFT method.The steady-state fluorescence spectra in toluene,tetrahydrofuran(THF)and acetonitrile(ACN)solvents presented that the solvent polarity has an effect on the position of the ESDPT fluorescence emission peak for the 1,5-DHAQ system.Transient absorption spectra show that the increasing polarity of the solvent accelerates the rate of excited state dynamics.Calculated potential energy curves analysis further verified the experimental results.The ESDPT barrier decreases gradually with the increase of solvent polarity from toluene,THF to ACN solvent.It is convinced that the increase of solvent polarity can promote the occurrence of the ESDPT dynamic processes for the 1,5-DHAQ system.This work clarifies the mechanism of the influence of solvent polarity on the ESDPT process of 1,5-DHAQ,which provides novel ideas for design and synthesis of new hydroxyanthraquinone derivatives.
