Ultrafast Desorption Research Articles

Light-induced MOF synthesis enabling composite photothermal materials

Metal-organic frameworks (MOFs) are a class of porous materials known for their large surface areas. Thus, over the past few decades the development of MOFs and their applications has been a major topic of interest throughout the scientific community. However, many current conventional syntheses of MOFs are lengthy solvothermal processes carried out at elevated temperatures. Herein, we developed a rapid light-induced synthesis of MOFs by harnessing the plasmonic photothermal abilities of bipyramidal gold nanoparticles (AuBPs). The generality of the photo-induced method was demonstrated by synthesizing four different MOFs utilizing three different wavelengths (520 nm, 660 nm and 850 nm). Furthermore, by regulating light exposure, AuBPs could be embedded in the MOF or maintained in the supernatant. Notably, the AuBPs-embedded MOF (AuBP@UIO-66) retained its plasmonic properties along with the extraordinary surface area typical to MOFs. The photothermal AuBP@UIO-66 demonstrated a significant light-induced heating response that was utilized for ultrafast desorption and MOF activation.

Robust functionalized cellulose-based porous composite for efficient capture and ultra-fast desorption of aqueous heavy metal pollution

The heavy metal pollution control industry requires convenient and cost-effective solutions to address complex aqueous environment. Adsorption method can be an effective strategy to realize these goals. Considering the importance of environmental and sustainable development strategies, there is an urgent need to develop efficient, green and non-toxic heavy metal adsorbents. In this work, a robust aminated cellulose-based porous adsorbent (PGPW) was developed from delignified wood and amino-rich polymer using a solvent-free, mild, simple and efficient preparation method. Such adsorbent exhibited excellent adsorption capacity (188.68 mg g−1) for Cu(II), and its adsorption behavior was consistent with pseudo-second order kinetic and Langmuir isotherm models. Notably, PGPW with superior compressibility could be squeezed to achieve rapid desorption and reach equilibrium within 5 min, while still retaining 87 % adsorption efficiency after 50 cycles. In addition, PGPW showed remarkable selectivity towards various coexisting ionic systems and demonstrated a considerable adsorption capacity in natural water applications. The adsorption mechanism of heavy metal ions on porous adsorption material was elucidated. This approach provides a simple, gentle and sustainable strategy for preparing functionalized wood-based composites with efficient adsorption and ultra-fast desorption of heavy metal ions.

Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111)

We report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate-adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probability increases roughly two orders magnitude, and (ii) the adsorbate-substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate-substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, ηel, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of ηel largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors.

Towards instantaneous cellular level bio diagnosis: laser extraction and imaging of biological entities with conserved integrity and activity

The prospect for spatial imaging with mass spectroscopy at the level of the cell requires new means of cell extraction to conserve molecular structure. To this aim, we demonstrate a new laser extraction process capable of extracting intact biological entities with conserved biological function. The method is based on the recently developed picosecond infrared laser (PIRL), designed specifically to provide matrix-free extraction by selectively exciting the water vibrational modes under the condition of ultrafast desorption by impulsive vibrational excitation (DIVE). The basic concept is to extract the constituent protein structures on the fastest impulsive limit for ablation to avoid excessive thermal heating of the proteins and to use strongly resonant 1-photon conditions to avoid multiphoton ionization and degradation of the sample integrity. With various microscope imaging and biochemical analysis methods, nanoscale single protein molecules, viruses, and cells in the ablation plume are found to be morphologically and functionally identical with their corresponding controls. This method provides a new means to resolve chemical activity within cells and is amenable to subcellular imaging with near-field approaches. The most important finding is the conserved nature of the extracted biological material within the laser ablation plume, which is fully consistent with in vivo structures and characteristics.

Ultrafast desorption of colloidal particles from fluid interfaces

The self-assembly of solid particles at fluid-fluid interfaces is widely exploited to stabilize emulsions and foams, and in materials synthesis. The self-assembly mechanism is very robust owing to the large capillary energy associated with particle adsorption, of the order of millions of times the thermal energy for micrometer-sized colloids. The microstructure of the interfacial colloid monolayer can also favor stability, for instance in the case of particle-stabilized bubbles, which can be indefinitely stable against dissolution due to jamming of the colloid monolayer. As a result, significant challenges arise when destabilization and particle removal are a requirement. Here we demonstrate ultrafast desorption of colloid monolayers from the interface of particle-stabilized bubbles. We drive the bubbles into periodic compression-expansion using ultrasound waves, causing significant deformation and microstructural changes in the particle monolayer. Using high-speed microscopy we uncover different particle expulsion scenarios depending on the mode of bubble deformation, including highly directional patterns of particle release during shape oscillations. Complete removal of colloid monolayers from bubbles is achieved in under a millisecond. Our method should find a broad range of applications, from nanoparticle recycling in sustainable processes to programmable particle delivery in lab-on-a-chip applications.

A new technology for applanation free corneal trephination: the picosecond infrared laser (PIRL).

The impact of using a Femtosecond laser on final functional results of penetrating keratoplasty is low. The corneal incisions presented here result from laser ablations with ultrafast desorption by impulsive vibrational excitation (DIVE). The results of the current study are based on the first proof-of-principle experiments using a mobile, newly introduced picosecond infrared laser system, and indicate that wavelengths in the mid-infrared range centered at 3 μm are efficient for obtaining applanation-free deep cuts on porcine corneas.

Ultrafast desorption of molecular ions by XUV-photons, passing through dielectric hollow tip

Pulsed desorption of organic conducting polymer by XUV-photons, formed by a thin capillary collimator, has been investigated. Short-wavelength radiation has been resulted from a metal target irradiated by a sharply focused Ti:Sa laser beam (0.8 μm, 40 fs, 3 mJ∕pulse) and has been filtered by Mylar-gold substrate. Single shot and 1-kHz pulses regimes of driving femtosecond laser have been compared using a time-of-flight mass spectrometer. A stepwise function of photoion signal vs laser pulse energy has been observed.

Quantum Dynamical Simulations of the Femtosecond‐Laser‐Induced Ultrafast Desorption of H2 and D2 from Ru(0001)

We investigate the recombinative desorption of hydrogen and deuterium from a Ru(0001) surface initiated by femtosecond laser pulses. We adopt a quantum mechanical two-state model including three molecular degrees of freedom to describe the dynamics within the desorption induced by electronic transition (DIET) limit. The energy distributions as well as the state-resolved and ensemble properties of the desorbed molecules are analyzed in detail by using the time-energy method. Our results shed light on the experimentally observed 1) large isotopic effects regarding desorption yields and translational energies and 2) the nonequal energy partitioning into internal and translational modes. In particular, it is shown that a single temperature is sufficient to characterize the energy distributions for all degrees of freedom. Further, we confirm that quantization effects play an important role in the determination of the energy partitioning.

Femtosecond pump-probe investigation of ultrafast silver nanoparticle deformation in a glass matrix

Single-color femtosecond pump-probe experiments were performed to investigate the time dependence of laser-induced ultrafast desorption and deformation processes of silver nanoparticles in glass. After laser excitation at wavelengths close to the surface plasmon resonance, transient extinction changes were found to exhibit dynamics on quite different time scales ranging from sub-picoseconds to some hundred ps. The slowest observed decay component is identified as characteristic for the deformation/desorption processes. Possible mechanisms for these processes are discussed.

Time-resolved femtosecond laser-induced desorption from magnesium oxide and lithium fluoride single crystals

We have used the pump–probe technique to measure the photostimulated positive-ion yield, as a function of time delay, between two ultraviolet laser pulses. We find that the ion yield from 265 nm femtosecond-irradiated MgO and LiF depends critically on the laser pulse delay in two-pulse correlation experiments. For example, single-pulse excitation of MgO produces a variety of ions including Mg +, MgO + and H +. If the femtosecond laser pulse is split into two sub-threshold beams and then recombined with a variable time delay, the Mg + desorption yield displays three distinct time regimes and persists for laser delays of over 100 ps. A pulse delay of only 500 fs nearly eliminates ion desorption except for Mg +. In contrast, the Li + desorption yield from LiF decays more rapidly, largely within the femtosecond pulse duration. A weak but measurable decay component of approximately 2 ps is indicated, however. We hypothesize that non-resonant excitation contributes to the ultrafast desorption mechanism, possibly through the creation of surface electron–hole pairs and allows direct observation of the surface dynamics.

Femtosecond time-resolved laser-induced desorption of positive ions from MgO

We have used the pump-probe technique to measure the photostimulated positive ion yield as a function of time delay between two sub-threshold femtosecond laser pulses. We find that the ion yield from UV femtosecond irradiated MgO depends critically on the laser pulse delay, Δt, in two-pulse experiments. In single-pulse experiments, excitation of MgO produces a variety of ions including Mg+, MgO+, and a significant yield of H+. In contrast, if the femtosecond laser pulse is split into two sub-threshold beams and then recombined with a variable time delay, the ion yield may be drastically altered depending on the delay between pulses. The Mg+ desorption yield displays three distinct lifetimes and persists for laser delays of over 100 ps. A pulse delay of only Δt=500 fs nearly eliminates ion desorption except for Mg+. The use of a pair of delayed femtosecond laser pulses can thus control the species of the desorbed ion. The mechanism for femtosecond laser desorption is clearly different from nanosecond laser desorption. We hypothesize that the creation of electron-hole pairs by nonresonant two-photon excitation contributes to the ultrafast desorption mechanism.