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
Sliced velocity mapping ion imaging technique was employed to investigate the dynamics of the hydroxyl elimination channel in the photodissociaiton of nitric acid in the ultraviolet region. The OH product was detected...Sliced velocity mapping ion imaging technique was employed to investigate the dynamics of the hydroxyl elimination channel in the photodissociaiton of nitric acid in the ultraviolet region. The OH product was detected by （2＋1） resonance enhanced multiphoton ionization via the D^2∑^- electronic state. The total kinetic energy spectra of the OH＋NO2 channel from the photolysis of HONO2 show that both ：NO2（X2A1） and NO2（A2B2） channels are present, suggesting that both 1^1A″ and 2^1A″ excited electronic states of HONO2 are involved in the excitation. The parallel angular distributions suggest that the dissociation of the nitric acid is a fast process in comparison with the rotational period of the HNO3 molecule. The anisotropy parameter β for the hydroxyl elimination channel is found to be dependent on the OH product rotational state as well as the photolysis energy.展开更多
Recent progress in ultrafast lasers,ultrafast X-rays and ultrafast electron beams has made it possible to watch the motion of atoms in real time through pumpprobe technique.In this review,we focus on how the molecular...Recent progress in ultrafast lasers,ultrafast X-rays and ultrafast electron beams has made it possible to watch the motion of atoms in real time through pumpprobe technique.In this review,we focus on how the molecular dynamics can be studied with ultrafast electron diffraction where the dynamics is initiated by a pumping laser and then probed by pulsed electron beams.This technique allows one to track the molecular dynamics with femtosecond time resolution and Angstr6m spatial resolution.We present the basic physics and latest development of this technique.Representative applications of ultrafast electron diffraction in studies of laser-induced molecular dynamics are also discussed.This table-top technique is complementary to X-ray free-electron laser and we expect it to have a strong impact in studies of chemical dynamics.展开更多
The photodissociation of Br2 was investigated within the near-visible UV absorption band. Based on the potential curves for the ground and low-lying excited states, the optical cross-sections for the discrete transiti...The photodissociation of Br2 was investigated within the near-visible UV absorption band. Based on the potential curves for the ground and low-lying excited states, the optical cross-sections for the discrete transitions of C1^Пu,B^3Пou^＋, A^3П1u←X^1∑g＋ and their total energy absorption spectrum are derived, and the quantum yield of （Br＋Br6＊） channel are determined correspondingly. The one-dimensional Landau-Zener model is used to evaluate the behavior of curve crossing during photodissociation. The results indicate that the influence of nonadiabatic mechanism, which may be caused by the electronic-vibrational interplay between the 13 and C states, is negligibly small for the （Br＋Br^＊） channel. From the Landau-Zener modeling of the observed product recoil parameter β（Br＋Br）, the best-fit value of the coupling matrix elenment or coupling strength between the diabatic B and C state potentials is obtained.展开更多
The photodissociation dynamics of IC1 has been studied near 304 and 280 nm on a simple miniature time of flight (mini-TOF) photofragment translational spectrometer with a short pulse of a weak acceleration field. An i...The photodissociation dynamics of IC1 has been studied near 304 and 280 nm on a simple miniature time of flight (mini-TOF) photofragment translational spectrometer with a short pulse of a weak acceleration field. An intense hot band effect was ob- served. Many small peaks were resolved in each photofragment translational spectrum (PTS). Based on simulations, the principal peaks were assigned not only to the different photodissociation channels (1) I + C1, (2) I + CI*, (3) I* + C1, or (4) I* + CI*, but also to the different chlorine isotopes (35C1 and 37C1). Moreover, some extra peaks showed the existence of an intense hot band effect from vibrationally excited ICI molecules, though only a few percent of ICI molecules remained in the vibrationally excited states in our supersonic molecular beam. Based on the spectra near 304nm, the quantum yield Φ of each channel, the curve crossing, and the branching fraction a from each transition state were determined.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Ⅴ. ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China, the Ministry of Sciences and Technology, and the Chinese Academy of Sciences.
文摘Sliced velocity mapping ion imaging technique was employed to investigate the dynamics of the hydroxyl elimination channel in the photodissociaiton of nitric acid in the ultraviolet region. The OH product was detected by （2＋1） resonance enhanced multiphoton ionization via the D^2∑^- electronic state. The total kinetic energy spectra of the OH＋NO2 channel from the photolysis of HONO2 show that both ：NO2（X2A1） and NO2（A2B2） channels are present, suggesting that both 1^1A″ and 2^1A″ excited electronic states of HONO2 are involved in the excitation. The parallel angular distributions suggest that the dissociation of the nitric acid is a fast process in comparison with the rotational period of the HNO3 molecule. The anisotropy parameter β for the hydroxyl elimination channel is found to be dependent on the OH product rotational state as well as the photolysis energy.
基金The work was supported by the National Natural Science Foundation of China(No.11925505).
文摘Recent progress in ultrafast lasers,ultrafast X-rays and ultrafast electron beams has made it possible to watch the motion of atoms in real time through pumpprobe technique.In this review,we focus on how the molecular dynamics can be studied with ultrafast electron diffraction where the dynamics is initiated by a pumping laser and then probed by pulsed electron beams.This technique allows one to track the molecular dynamics with femtosecond time resolution and Angstr6m spatial resolution.We present the basic physics and latest development of this technique.Representative applications of ultrafast electron diffraction in studies of laser-induced molecular dynamics are also discussed.This table-top technique is complementary to X-ray free-electron laser and we expect it to have a strong impact in studies of chemical dynamics.
基金ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China （No.10534010 and No.20673140）.
文摘The photodissociation of Br2 was investigated within the near-visible UV absorption band. Based on the potential curves for the ground and low-lying excited states, the optical cross-sections for the discrete transitions of C1^Пu,B^3Пou^＋, A^3П1u←X^1∑g＋ and their total energy absorption spectrum are derived, and the quantum yield of （Br＋Br6＊） channel are determined correspondingly. The one-dimensional Landau-Zener model is used to evaluate the behavior of curve crossing during photodissociation. The results indicate that the influence of nonadiabatic mechanism, which may be caused by the electronic-vibrational interplay between the 13 and C states, is negligibly small for the （Br＋Br^＊） channel. From the Landau-Zener modeling of the observed product recoil parameter β（Br＋Br）, the best-fit value of the coupling matrix elenment or coupling strength between the diabatic B and C state potentials is obtained.
基金supported by the National Natural Science Foundation of China (20433080)
文摘The photodissociation dynamics of IC1 has been studied near 304 and 280 nm on a simple miniature time of flight (mini-TOF) photofragment translational spectrometer with a short pulse of a weak acceleration field. An intense hot band effect was ob- served. Many small peaks were resolved in each photofragment translational spectrum (PTS). Based on simulations, the principal peaks were assigned not only to the different photodissociation channels (1) I + C1, (2) I + CI*, (3) I* + C1, or (4) I* + CI*, but also to the different chlorine isotopes (35C1 and 37C1). Moreover, some extra peaks showed the existence of an intense hot band effect from vibrationally excited ICI molecules, though only a few percent of ICI molecules remained in the vibrationally excited states in our supersonic molecular beam. Based on the spectra near 304nm, the quantum yield Φ of each channel, the curve crossing, and the branching fraction a from each transition state were determined.
