Pulsed laser interference patterning of transition-metal carbides for stable alkaline water electrolysis kinetics

We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed laser ablation of Co,Fe,Ti,and Mo metals in acetone.The interaction between carbon s-p-orbitals and metal d-orbitals causes a redistribution of valence structure through charge transfer,leading to the formation of surface defects as observed by X-ray photoelectron spectroscopy.These defects influence the evolved TMCs,making them effective for hydrogen and oxygen evolution reactions(HER and OER)in an alkaline medium.Co_(3)C with more oxygen affinity promoted CoO(OH)intermediates,and the electrochemical surface oxidation to Co_(3)O_(4)was captured via in situ/operando electrochemical Raman probes,increasing the number of active sites for OER activity.MoC with more d-vacancies exhibits strong hydrogen binding,promoting HER kinetics,whereas Fe_(3)C and TiC with more defect states to trap charge carriers may hinder both OER and HER activities.The results show that the assembled membrane-less electrolyzer with Co_(3)C∥Co_(3)C and MoC∥MoC electrodes requires~2.01 and 1.99 V,respectively,to deliver a 10 mA cm−2 with excellent electrochemical and structural stability.In addition,the ascertained pulsed laser synthesis mechanism and unit-cell packing relations will open up sustainable pathways for obtaining highly stable electrocatalysts for electrolyzers.

A New Synthetical Model of High-Power Pulsed Laser Ablation

We develop a new synthetical model of high-power pulsed laser ablation,which considers the dynamicabsorptance,vaporization,and plasma shielding.And the corresponding heat conduction equations with the initial andboundary conditions are given.The numerical solutions are obtained under the reasonable technical parameter condi-tions by taking YBa_2Cu_3O_7 target for example.The space-dependence and time-dependence of temperature in targetat a certain laser fluence are presented,then,the transmitted intensity through plasma plume,space-dependence oftemperature and ablation rate for different laser fluences are significantly analyzed.As a result,the satisfactorily goodagreement between our numerical results and experimental results indicates that the influences of the dynamic absorp-tance,vaporization,and plasma shielding cannot be neglected.Taking all the three mechanisms above simultaneouslyinto account for the first time,we cause the present model to be more practical.

Pulsed laser ablation in liquid of sp-carbon chains:Status and recent advances

This review provides a discussion of the current state of research on sp-carbon chains synthesized by pulsed laser ablation in liquid.In recent years,pulsed laser ablation in liquid(PLAL)has been widely employed for polyynes synthesis thanks to its flexibility with varying laser parameters,solvents,and targets.This allows the control of sp-carbon chains properties as yield,length,termination and stability.Although many reviews related to PLAL have been published,a comprehensive work reporting the current status and advances related to the synthesis of sp-carbon chains by PLAL is still missing.Here we first review the principle of PLAL and the mechanisms of formation of sp-carbon chains.Then we discuss the role of laser fluence(i.e.energy density),solvent,and target for sp-carbon chains synthesis.Lastly,we report the progress related to the prolonged stability of sp-carbon chains by PLAL encapsulated in polymeric matrices.This review will be a helpful guide for researchers interested in synthesizing sp-carbon chains by PLAL.

Synthesis of Metal/Poly(diphenylsilylenemethylene) Nanocomposite Thin Films by Pulsed Laser Ablation

A new technique to synthesize poly（diphenylsilylenemethylene） （PDPhSM） matrix nanocomposite thin films containing metal nanoparticles such as Ni, AI, Zn, and W produced by pulsed laser ablation has been developed. First, 1,1,3,3-tetra- phenyl-1,3-disilacyclobutane （TPDC） films were deposited on 4 cm2 silicon substrates cut from c-Si wafers by conventional vacuum evaporation under a pressure of 4.0×10^-3 Pa; then metal nanoparticles were deposited onto the TPDC films by pulsed laser ablation; finally the TPDC films with metal nanoparticles were heated in an electric furnace in an air atmosphere at 553 K for 10 rain to induce ring-opening polymerization of TPDC. The results indicate that it is easy to synthesize metal/ PDPhSM nanocomposite thin films by pulsed laser ablation. The morphologies and size of metal nanoparticles are closely related to the kinds of metal. Also, the polymerization efficiency depends on the kinds of metal nanoparticles deposited on the TPDC monomer films by pulsed laser ablation. In addition, The laser ablated metal nanoparticles penetrate into the TPDC monomer films during pulsed laser ablation while the DC sputtered metal nanoparticles just lay on the surface of TPDC films.

Study on Ultra-Short Laser Pulse Ablation of Metals by Molecular Dynamics Simulation

The dynamical progresses involved in ultra-short laser pulse ablation of face-centered cubic metals under stress confinement condition are described completely using molecular dynamics method. The laser beam absorption and thermal energy turning into kinetics energy of. atoms are taken into account to give a detailed picture of laser metal interaction. Superheating phenomenon is observed, and the phase change from solid to liquid is characterized by a destroyed atom configuration and a decreased number density. The steep velocity gradients are found in the systems of Cu and Ni after pulse in consequence of located heating and exponential decrease of fluences following the Lambert-Beer expression. The shock wave velocities are predicted to be about 5 000 m/s in Cu and 7 200 m/s in Ni. The higher ablation rates are obtained from simulations compared with experimental data as a result of a well-defined crystalline surface irradiated by a single pulse. Simulation results show that the main mechanisms of ablation are evaporation and thermoelastic stress due to located heating.

Silicon micro-hemispheres with periodic nanoscale rings produced by the laser ablation of single crystalline silicon

We describe the fabrication of silicon micro-hemispheres by adopting the conventional laser ablation of single crystalline silicon in the vacuum condition without using any catalysts or additives. The highly oriented structures of silicon micro-hemispheres exhibit many periodic nanoscale rings along their outer surfaces. We consider that the self-organized growth of silicon micro-structures is highly dependent on the laser intensity and background air medium. The difference between these surface modifications is attributed to the amount of laser energy deposited in the silicon material and the consequent cooling velocity.

Highly Defective Dark TiO_(2) Modified with Pt: Effects of Precursor Nature and Preparation Method on Photocatalytic Properties

The study focused on the modification with platinum of dark defective titania obtained via pulsed laser ablation. Both the method of Pt introduction and the nature of the Pt precursor were varied. All samples exhibited similar phase compositions, specific surface areas, and Pt contents. High-resolution transmission electron microscopy coupled with pulsed CO adsorption revealed increased dispersity when photoreduction and the hydroxonitrate complex (Me _(4) N) _(2) [Pt _(2) (OH) _(2) (NO _(3) ) _(8) ] were used. The sample featured a high content of single-atom species and subnano-sized Pt clusters. The X-ray photoelectron spectroscopy results showed that the photoreduction method facilitated the appearance of a larger number of Pt ^(2+) states, which appeared owing to the strong metal-support interaction (SMSI) eff ect of the transfer of electron density from the electron-saturated defects on the TiO _(2) surface to Pt ^(4+) . In the hydrogen evolution reaction, samples with a significant fraction of the Pt ^(2+) ionic component, capable of generating short-lived Pt^(0) single-atom sites under irradiation due to the SMSI eff ect, exhibited the highest photocatalytic activity. The 0.5Pt(C)/TiO_(2) -Ph sample exhibited the highest hydrogen yield with a quantum efficiency of 0.53, retaining its activity even after 8 h of operation.

Sustainable Furfural Biomass Feedstocks Electrooxidation toward Value-Added Furoic Acid with Energy-Saving H_(2) Fuel Production Using Pt-Decorated Co_(3)O_(4) Nanospheres

Here,furfural oxidation was performed to replace the kinetically sluggish O_(2)evolution reaction(OER).Pt-Co_(3)O_(4)nanospheres were developed via pulsed laser ablation in liquid(PLAL)in a single step for the paired electrocatalysis of an H_(2)evolution reaction(HER)and furfural oxidation reaction(FOR).The FOR afforded a high furfural conversion(44.2%)with a major product of 2-furoic acid after a 2-h electrolysis at 1.55 V versus reversible hydrogen electrode in a 1.0-M KOH/50-mM furfural electrolyte.The Pt-Co_(3)O_(4)electrode exhibited a small overpotential of 290 mV at 10 mA cm^(-2).As an anode and cathode in an electrolyzer system,the Pt-Co_(3)O_(4)electrocatalyst required only a small applied cell voltage of~1.83 V to deliver 10 mA cm^(-2),compared with that of the pure water electrolyzer(OER||HER,~1.99 V).This study simultaneously realized the integrated production of energy-saving H_(2)fuel at the cathode and 2-furoic acid at the anode.

Manifolding active sites and in situ/operando electrochemical-Raman spectroscopic studies of single-metal nanoparticle-decorated CuO nanorods in furfural biomass valorization to H_(2) and 2-furoic acid

Here,CuO nanorods fabricated via pulsed laser ablation in liquids were decorated with Ir,Pd,and Ru NPs(loading~7 wt%) through pulsed laser irradiation in the liquids process.The resulting NPs-decorated CuO nanorods were characterized spectroscopically and employed as multifunctional electrocatalysts in OER,HER,and the furfural oxidation reactions(FOR).Ir-CuO nanorods afford the lowest overpotential of~345 mV(HER) and 414 mV(OER) at 10 mA cm^(-2),provide the highest 2-furoic acid yield(~10.85 mM) with 64.9% selectivity,and the best Faradaic efficiency~72.7% in 2 h of FOR at 1.58 V(vs.RHE).In situ electrochemical-Raman analysis of the Ir-CuO detects the formation of the crucial intermediates,such as Cu(Ⅲ)-oxide,Cu(OH)_(2),and Ir_x(OH)_y,on the electrode-electrolyte surface,which act as a promoter for HER and OER.The Ir-CuO ‖ Ir-CuO in a coupled HER and FOR-electrolyzer operates at~200 mV lower voltage,compared with the conventional electrolyzer and embodies the dual advantage of energy-saving H_(2) and 2-furoic acid production.

Control of Deposition Processes and Structures of Fibroin Nanofilms by IR Pulsed Laser Ablation

1 Results Protein thin films gather increasing interests in various biomedical-related materials including surface treatment of implants and bio-tips.Processes via colloid chemical routes such as simple adsorption,dip-or spin coating enable formation of protein thin films on various substrates.Related methods are facile andconvenient without sophisticated instrumentation but not without restriction.Typical drawbacks are limited solubility of the film-forming species and wettability determined by the com...

Numerical model and experimental demonstration of high precision ablation of pulse CO_2 laser

To reveal the physical mechanism of laser ablation and establish the prediction model for figuring the surface of fused silica, a multi-physical transient numerical model coupled with heat transfer and fluid flow was developed under pulsed CO2laser irradiation. The model employed various heat transfer and hydrodynamic boundary and thermomechanical properties for assisting the understanding of the contributions of Marangoni convention,gravitational force, vaporization recoil pressure, and capillary force in the process of laser ablation and better prediction of laser processing. Simulation results indicated that the vaporization recoil pressure dominated the formation of the final ablation profile. The ablation depth increased exponentially with pulse duration and linearly with laser energy after homogenous evaporation. The model was validated by experimental data of pulse CO2laser ablation of fused silica. To further investigate laser beam figuring, local ablation by varying the overlap rate and laser energy was conducted, achieving down to 4 nm homogenous ablation depth.

Femtosecond laser ablation of Au film around single pulse threshold

Ablation process of 1-kHz femtosecond lasers （pulse duration of 148 fs, wavelength of 775 nm） of Au film on silica substrates is studied. The thresholds for single and multi pulses can be obtained directly from the relation between the squared diameter D^2 of the ablated craters and the laser fluence Ф0. From the plot of the accumulated laser fluence NCth（N） and the number of laser pulses N, incubation coefficient of Au film is obtained to be 0.765. Some experimental data obtained around the single pulse threshold are in good agreement with the theoretical calculation.

Laser-generated high entropy metallic glass nanoparticles as bifunctional electrocatalysts

High entropy metallic glass nanoparticles(HEMG NPs)are very promising materials for energy conversion due to the wide tuning possibilities of electrochemical potentials offered by their multimetallic character combined with an amorphous structure.Up until now,the generation of these HEMG NPs involved tedious synthesis procedures where the generated particles were only available on highly specialized supports,which limited their widespread use.Hence,more flexible synthetic approaches to obtain colloidal HEMG NPs for applications in energy conversion and storage are highly desirable.We utilized pulsed laser ablation of bulk high entropy alloy targets in acetonitrile to generate colloidal carbon-coated CrCoFeNiMn and CrCoFeNiMnMo HEMG NPs.An in-depth analysis of the structure and elemental distribution of the obtained nanoparticles down to single-particle levels using advanced transmission electron microscopy(TEM),energy-dispersive X-ray spectroscopy(EDX),X-ray diffraction(XRD),and Xray photoelectron spectroscopy(XPS)methods revealed amorphous quinary and senary alloy phases with slight manganese oxide/hydroxide surface segregation,which were stabilized within graphitic shells.Studies on the catalytic activity of the corresponding carbon-HEMG NPs during oxygen evolution and oxygen reduction reactions revealed an elevated activity upon the incorporation of moderate amounts of Mo into the amorphous alloy,probably due to the defect generation by atomic size mismatch.Furthermore,we demonstrate the superiority of these carbon-HEMG NPs over their crystalline analogies and highlight the suitability of these amorphous multi-elemental NPs in electrocatalytic energy conversion.

Enhanced photocatalytic degradation of lindane using metal–semiconductor Zn@ZnO and ZnO/Ag nanostructures

To achieve enhanced photocatalytic activity for the degradation of lindane, we prepared metal–semiconductor composite nanoparticles（NPs）. Zn@ZnO core–shell（CS） nanocomposites, calcined ZnO, and Ag-doped ZnO（ZnO/Ag） nanostructures were prepared using pulsed laser ablation in liquid, calcination, and photodeposition methods, respectively, without using surfactants or catalysts. The as-prepared catalysts were characterized by using X-ray diffraction（XRD）, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, ultraviolet–visible（UV–vis） spectroscopy, and photoluminescence spectroscopy. In addition, elemental analysis was performed by energy dispersive X-ray spectroscopy. The obtained XRD and morphology results indicated good dispersion of Zn and Ag NPs on the surface of the ZnO nanostructures. Investigation of the photocatalytic degradation of lindane under UV–vis irradiation showed that Zn@ZnO CS nanocomposites exhibit higher photocatalytic activity than the other prepared samples. The maximum degradation rate of lindane was 99.5% in 40 min using Zn@ZnO CS nanocomposites. The radical trapping experiments verified that the hydroxyl radical（·OH） was the main reactive species for the degradation of lindane.

Temperature and electron density of soil plasma generated by LA-FPDPS

Electron temperature and electron number density are important parameters in the characterization of plasma. In this paper the electron temperature and electron number density of soil plasma generated by laser ablation combined with nanosecond discharge spark at different discharge voltages have been studied. Saha-Boltzmann plot and Stark broadening are used to determine the temper- ature and electron number density. It is proved that local thermal equilibrium is fulfilled in the nanosecond spark enhanced plasma. The enhanced optical emission, signal to noise ratio and the stability in term of the relative standard deviation of signal intensity at different spark voltages were investigated in detail. A relative stable discharge process was observed with use of a 10 kV discharge voltage under the carried experimental configuration.

Droplet Evaporation to Boiling in Van Der Waals Fluid

Superheated droplets vaporized in a vacuum or vapor chamber was studied using smoothed particle hydrodynamics method.The two-phase fluids of vapor and liquid with a diffused interface were modeled by Navier-Stokes-Korteweg equations,with the van der Waals equation of state.The liquid-vapor separation was processed with different initial temperature and density.Simulation was firstly validated by the proper equilibrium states with analytical data from the binodal line of Maxwell construction,as well as the droplet surface tension compared with experimental and other groups’numerical data in a good agreement.Droplet morphology,density,temperature and entropy increment were then carefully examined during the dynamic process from evaporation to boiling.Four phase transitions patterns were concluded,namely from surface evaporation,internal bubble,fragment and explosion,to flash boiling with increasing equivalent superheat degree that is defined by the non-dimensional superheat temperature over surface tension.Results showed that droplet temperature and density decreased slightly at surface evaporation when equivalent superheat degree was lower than 1/3.Above this criterion,the internal bubble could be sustained.Growth of new liquid nucleates and connected secondary liquid ring were calculated by domain growth theory.We found that droplet continuous to expand at high superheat but withdrawn at equivalent superheat degree equal to or lower than 0.52.At equivalent superheat degree higher than 1,the growth and expansion of droplet resulted in liquid fragment and explosion to many small secondary droplets.Mean mass and diameter of these droplets were found to have power-law dependency on the expansion rate.Finally,fast flash boiling occurred at equivalent superheat degree higher than 3.The vapor pressure in the chamber showed a negative linear correlation between the overpressure and the atmospheric pressure.We also found out that comparing to increase the pressure value,dense gas had better efficiency on retarding the propagation of shock wave.

PEG-PLGA electrospun nanofibrous membranes loaded with Au@Fe2O3 nanoparticles for drug delivery applications

A PEGylated-PLGA random nanofibrous membrane loaded with gold and iron oxide nanoparticles and with silibinin was prepared by electrospinning deposition. The nanofibrous membrane can be remotely controlled and activated by a laser light or magnetic field to release biological agents on demand. The nanosystems were characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and thermogravimetric analyses. The drug loading efficiency and drug content percentages were determined by UV-vis optical absorption spectroscopy. The nanofibrous membrane irradiated by a relatively low-intensity laser or stimulated by a magnetic field showed sustained silibinin release for at least 60 h, without the burst effect. The proposed low-cost electrospinning procedure is capable of assembling, via a one-step procedure, a stimuli-responsive drug-loaded nanosystem with metallic nanoparticles to be externally activated for controlled drug delivery.