- 标题
- 摘要
- 关键词
- 实验方案
- 产品
-
Visible Light Driven Hydrogen Evolution by Molecular Nickel Catalysts with Time-Resolved Spectroscopic and DFT Insights
摘要： Hydrogen (H2) is a clean fuel that can potentially be a future solution for the storage of intermittent renewable energy. However, current H2 production is mainly dominated by the energy intensive steam reforming reaction, which consumes a fossil fuel, methane, and emits copious amounts of carbon dioxide as one of the byproducts. To address this challenge, we report a molecular catalyst that produces H2 from aqueous solutions, is composed of affordable, earth-abundant elements such as nickel, and has been incorporated into a system driven by visible light. Under optimized conditions, we observe a turnover number of 3880, among the best for photocatalytic H2 evolution with nickel complexes from water?methanol solutions. Through nanosecond transient absorption, electron paramagnetic resonance, and UV?vis spectroscopic measurements, and supported by density functional theory calculations, we report a detailed study of this photocatalytic H2 evolution cycle. We demonstrate that a one-electron reduced, predominantly ligand-centered, reactive Ni intermediate can be accessed under visible light irradiation using triethylamine as the sacrificial electron donor and reductive quencher of the initial photosensitizer excited state. In addition, the computational calculations suggest that the second coordination sphere ether arms can enhance the catalytic activity by promoting proton relay, similar to the mechanism among [FeFe] hydrogenases in nature. Our study can form the basis for future development of H2 evolution molecular catalysts that incorporate both ligand redox noninnocence and alternative second coordination sphere effects in artificial photosynthetic systems driven by visible light.
关键词： Proton relay,Second coordination sphere,DFT calculations,Time-resolved spectroscopy,Visible light photocatalysis,Hydrogen evolution,Molecular nickel catalysts
更新于2025-09-23 15:23:52
-
Ultrafast dynamics of solvated electrons at anatase TiO<sub>2</sub>/H<sub>2</sub>O interface
摘要： Solvated electrons are known to be the lowest energy charge transfer pathways at oxide/aqueous interface and the understanding of the electron transfer dynamics at the interface is fundamental for photochemical and photocatalytic processes. Taking anatase TiO2/H2O interface as a prototypical system, we perform time-dependent ab initio nonadiabatic molecular dynamics (NAMD) calculations to study the charge transfer dynamics of solvated electrons. For the static electronic properties, we find that the dangling H atoms can stabilize solvated electrons. A solvated electron band can be formed with one monolayer H2O adsorption. The energies of the solvated electron band minimum decrease when H2O adsorbs dissociatively. Moreover, the surface oxygen vacancies are also helpful for stabilizing the solvated electron band. For the dynamics behaviour, we find that the ultrafast charge transfer from solvated electron band minimum to anatase TiO2(101) surface at 100 K is mainly contributed by nonadiabatic mechanism. Comparing with rutile TiO2(110) surface, the lifetime of solvated electron on anatase TiO2 (101) surface is longer, suggesting a better photocatalytic properties. Our results provide essential insights into the understanding of the charge transfer dynamics and the possible photocatalytic mechanism at oxide/aqueous interface.
关键词： nonadiabatic molecular dynamics,solvated electron,oxide/aqueous interface
更新于2025-09-23 15:23:52
-
A thermo-sensitive fluorescent agent based method for excitation light leakage rejection for fluorescence molecular tomography
摘要： Fluorescence molecular tomography (FMT) is widely used in preclinical oncology research. FMT is the only imaging technique able to provide three-dimensional distribution of fluorescent probes within thick highly scattering media. However, its integration into clinical medicine has been hampered by its low spatial resolution caused by the undetermined and ill-posed nature of its reconstruction algorithm. Another major factor degrading the quality of FMT images is the large backscattered excitation light component leaking through the rejection filters and coinciding with the weak fluorescent signal arising from a low tissue fluorescence concentration. In this paper, we present a new method based on the use of a novel thermo-sensitive fluorescence probe. In fact, the excitation light leakage is accurately estimated from a set of measurements performed at different temperatures and then is corrected for in the tomographic data. The obtained results show a considerable improvement in both spatial resolution and quantitative accuracy of FMT images due to the proper correction of fluorescent signals.
关键词： Excitation Light Leakage,Biomedical Imaging,Fluorescence Molecular Tomography
更新于2025-09-23 15:23:52
-
Dynamical distortions of structural signatures in molecular high-order harmonic spectroscopy
摘要： We study the signature of two-center interferences in molecular high-order harmonic spectra, with an emphasis on the spectral phase. With the help of both ab initio computations based on the time-dependent Schr?dinger equation and the molecular strong-field approximation (SFA) as developed by Chiril? et al. [Phys. Rev. A 73, 023410 (2006)] and Faria [Phys. Rev. A 76, 043407 (2007)], we observe that the phase behavior is radically different for the short and the long trajectory contributions. By means of Taylor expansions of the molecular SFA, we link this effect to the dynamics of the electron in the continuum. More precisely, we find that the value of the electric field at recombination time plays a crucial role in the shape of the destructive interference phase jump.
关键词： molecular spectroscopy,spectral phase,strong-field approximation,two-center interferences,time-dependent Schr?dinger equation,high-order harmonic generation
更新于2025-09-23 15:23:52
-
Microscopic Control and Detection of Ultracold Strontium in Optical-Tweezer Arrays
摘要： Optical tweezers provide a versatile platform for the manipulation and detection of single atoms. Here, we use optical tweezers to demonstrate a set of tools for the microscopic control of atomic strontium, which has two valence electrons. Compared to the single-valence-electron atoms typically used with tweezers, strontium has a more complex internal state structure with a variety of transition wavelengths and linewidths. We report single-atom loading into an array of subwavelength scale optical tweezers and light-shift-free control of a narrow-linewidth optical transition. We use this transition to perform three-dimensional ground-state cooling and to enable high-fidelity nondestructive imaging of single atoms on subwavelength spatial scales. These capabilities, combined with the rich internal structure of strontium, open new possibilities including tweezer-based metrology, new quantum computing architectures, and new paths to low-entropy many-body physics.
关键词： Quantum Information,Atomic and Molecular Physics,Quantum Physics
更新于2025-09-23 15:23:52
-
Alkaline-Earth Atoms in Optical Tweezers
摘要： We demonstrate single-shot imaging and narrow-line cooling of individual alkaline-earth atoms in optical tweezers; specifically, strontium trapped in 515.2-nm light. Our approach enables high-fidelity detection of single atoms by imaging photons from the broad singlet transition while cooling on the narrow intercombination line, and we extend this technique to highly uniform two-dimensional tweezer arrays with 121 sites. Cooling during imaging is based on a previously unobserved narrow-line Sisyphus mechanism, which we predict to be applicable in a wide variety of experimental situations. Further, we demonstrate optically resolved sideband cooling of a single atom to near the motional ground state of a tweezer, which is tuned to a magic-trapping configuration achieved by elliptical polarization. Finally, we present calculations, in agreement with our experimental results, that predict a linear-polarization and polarization-independent magic crossing at 520(2) nm and 500.65(50) nm, respectively. Our results pave the way for a wide range of novel experimental avenues based on individually controlled alkaline-earth atoms in tweezers—from fundamental experiments in atomic physics to quantum computing, simulation, and metrology.
关键词： Quantum Information,Atomic and Molecular Physics,Quantum Physics
更新于2025-09-23 15:23:52
-
[IEEE 2018 IEEE International Conference on Electrical Engineering and Photonics (EExPolytech) - Saint Petersburg, Russia (2018.10.22-2018.10.23)] 2018 IEEE International Conference on Electrical Engineering and Photonics (EExPolytech) - Study of Oxyfluoride Glasses with Silver Molecular Clusters for Application in Sensoric and Optoelectronics
摘要： Temperature sensitivity of Oxyfluoride glasses with molecular silver clusters and samarium ions were studied. The experimental procedure for obtaining luminescence spectra at various temperatures is described. The perspective of using oxyfluoride glasses in fiber-optic temperature sensors is considered.
关键词： sensitive element,luminescence,Fiber-optical temperature sensor,oxyfluoride glass,spectrum,molecular clusters of silver
更新于2025-09-23 15:23:52
-
Wetting Transition from the Cassie–Baxter State to the Wenzel State on Regularly Nanostructured Surfaces Induced by an Electric Field
摘要： When droplets are placed on hydrophobic textured surfaces, different wetting state Cassie-Baxter (CB) state or Wenzel (W) state may occur depending on materials and structures of surfaces, types and sizes of droplets, thermal fluctuations, and external stimuli. The wetting transition from the CB to the W state and the opposite process have attracted a great deal of attention due to their primary importance for designing and fabricating textured surfaces. In this work, molecular dynamics (MD) simulations are employed to understand the mechanism behind the CB-to-W transition for a nanoscale water film placed on a surface decorated with a single nanogroove when an external electric field is applied. The free energy variation during the transition process is computed on the basis of the restrained MD simulations. Water intrusion into the groove is observed by simulation snapshots, which provides a direct evidence for the electric-field-induced CB-to-W transition. In the previous experiments, however, only a sharp reduction in the apparent contact angle is employed to judge whether the transition takes place. The free energy curves reveal that there are two energy barriers separating the CB and W states (?E1) as well as separating the W and CB states (?E2). Owing to the presence of ?E1, although the CB state has a higher free energy than the W state, it cannot spontaneously convert to the W state. When the external energy input exceeds ?E1, the CB-to-W transition can be triggered, otherwise the transition will stop, and the water film will return to the CB state. Moreover, it is found that the maximum of free energy always occurs after the film touches the groove bottom. Thus, the requirement of the film touching the groove bottom is responsible for the presence of the energy barrier ?E1. Finally, the dependences of the two energy barriers on the electric field strength, groove aspect ratio, and intrinsic contact angle of the groove are also discussed.
关键词： Cassie-Baxter state,wetting transition,Wenzel state,energy barrier,free energy,molecular dynamics simulations.
更新于2025-09-23 15:23:52
-
Efficient separation of photo-generated charges in a ferroelectric molecular wire: nonadiabatic dynamics study on 3,5-dicyano-1,7-dimethylopyrrolo[3,2-f]indole trimer
摘要： In this work we propose and verify computationally a novel idea of spontaneous separation of charges photo-generated in a highly polar molecular 'wire'. The nuclear and electronic structure of the investigated system, so as the evolution of charge carriers, are characterized at the semi-empirical OM2/MRCI level of theory. Results point to the conclusion that 90% of optically prepared excitons break into charge carriers (holes and electrons) localized on the opposite monomeric units of the trimer on the time scale of 30 fs. Our findings can be helpful in design of photoactive and conducting components for molecular photovoltaic applications.
关键词： ferroelectric polymers,nonadiabatic molecular dynamics,molecular photovoltaics,photo-generated charge separation,molecular wire
更新于2025-09-23 15:22:29
-
Structure/Function/Dynamics of Photosystem II Plastoquinone Binding Sites
摘要： Photosystem II (PSII) continuously attracts the attention of researchers aiming to unravel the riddle of its functioning and efficiency fundamental for all life on Earth. Besides, an increasing number of biotechnological applications have been envisaged exploiting and mimicking the unique properties of this macromolecular pigment-protein complex. The PSII organization and working principles have inspired the design of electrochemical water splitting schemes and charge separating triads in energy storage systems as well as biochips and sensors for environmental, agricultural and industrial screening of toxic compounds. An intriguing opportunity is the development of sensor devices, exploiting native or manipulated PSII complexes or ad hoc synthesized polypeptides mimicking the PSII reaction centre proteins as biosensing elements. This review offers a concise overview of the recent improvements in the understanding of structure and function of PSII donor side, with focus on the interactions of the plastoquinone cofactors with the surrounding environment and operational features. Furthermore, studies focused on photosynthetic proteins structure/function/dynamics and computational analyses aimed at rational design of high-quality bio-recognition elements in biosensor devices are discussed.
关键词： plastoquinone binding site,molecular dynamics simulations,plastoquinone,Molecular docking,protein dynamics,Photosystem II
更新于2025-09-23 15:22:29