Liquid vortexes and flows induced by femtosecond laser ablation in liquid governing formation of circular and crisscross LIPSS

Orientations of laser induced periodic surface structures(LIPSS)are usually considered to be governed by the laser polarization state.In this work,we unveil that fluid dynamics induced by femtosecond(fs)laser ablation in liquid(fs-LAL)can easily break this polarization restriction to produce irregular circular-LIPSS(CLIPPS)and crisscross-LIPSS(CCLIPSS).Fs laser ablation of silicon in water shows formation of diverse LIPSS depending on ablation conditions.At a high power of 700 mW(repetition rate of 100 kHz,pulse duration of 457 fs and wavelength of 1045 nm),single/twin CLIPSS are produced at the bottom of macropores of several microns in diameter due to the formation of strong liquid vortexes and occurrence of the vortex shedding effect.Theoretical simulations validate our speculation about the formation of liquid vortex with an ultrahigh static pressure,which can induce the microstructure trenches and cracks at the sidewalls for fs-LAL of Si and tungsten(W)in water,respectively.At a low power of 50 mW,weak liquid vortexes are produced,which only give birth to curved LIPSS in the valleys of grooves.Consequently,it is deduced that liquid vortex plays a crucial role in the formation of macropores.Mountain-like microstructures induce complex fluid dynamics which can cause the formation of CCLIPSS on them.It is believed that liquid vortexes and fluid dynamics presented in this work open up new possibilities to diversify the morphologies of LIPSS formed by fs-LAL.

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.

Up/down-conversion luminescence of monoclinic Gd_(2)O_(3):Er^(3+)nanoparticles prepared by laser ablation in liquid

Multifunctional luminescent materials are attracting attention nowadays.In this work,monoclinic Gd_(2)O_(3):Er^(3+)nanoparticles,which possess up-conversion luminescence and down-conversion luminescence properties,were successfully synthesized by laser ablation in liquid(LAL)technique.Up-conversion luminescence and down-conversion luminescence of monoclinic Gd_(2)O_(3):Er^(3+)nanoparticles were got under the excitation of 980 nm and 379 nm,respectively.In addition,tunable luminescence was got.Furthermore,the cytotoxicity of the nanoparticles is low and the fluorescence of the nanoparticles in cell is also strong enough.The results indicate that the Gd_(2)O_(3):Er^(3+)nanoparticles synthesized by LAL technique are promising candidates for bio-imaging or other fields that require controllable fluorescence.

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.

Diverse nanomaterials synthesized by laser ablation of pure metals in liquids

Diverse nanomaterials, in the forms of carbides, sulfides, oxides, metals, hydroxides, etc., have been synthesized by laser ablation in liquids(LAL) with metal targets as the dominant educts. Many advantages of LAL technique itself and its products have been revealed since 1983 when the first report about LAL was released. Different from traditional wet-chemical synthesis,one unique feature of LAL is its resultant extreme high-temperature and high-pressure local environment for the nucleation and growth of nanomaterials, despite being performed at room temperature. This extreme condition can induce the atomization and ionization of the target materials and liquid molecules to incur different chemical reactions. The laser, liquid, liquid additive, and target can significantly alter the local environment in a broad range. Thus, different phases and shapes of nanomaterials are producible even from the same target. Through directly comparing the products of LAL of 13 kinds of chosen representative metals synthesized under different conditions, this review presents and discusses current understandings, challenging issues, and perspectives related to the diversity of LAL-products, which is willing to promote a deeper investigation and discussion on a clear clarification of the chemical reactions and particle nucleation/growth processes.

Quantitative evaluation of LAL productivity of colloidal nanomaterials:Which laser pulse width is more productive,ergonomic,and economic?

Near-IR(wavelength≈1μm)laser ablation of bulk,chemically-inert gold in water was compared for different laser pulse width in broad the range of 300 fs–100 ns,comparing a number of key ablation characteristics:mass loss,singleshot crater volume and extinction coefficient of the generated colloidal solutions taken in the spectral ranges of interband transitions and localized plasmon resonance.Comparing to related air-based ablation results,at the given fluences laser ablation in the liquid resulted in the maximum ablation yield per unit energy and maximum NP yield per pulse and per unit energy for the picosecond lasers,occurring at subcritical peak pulse powers for laser self-focusing.The self-focusing effect was demonstrated to yield in incomplete,effectively weaker focusing in the water filaments of ultrashort laser pulses with supercritical peak powers,comparing to linear(geometrical)focusing at sub-critical peak powers.At the other,nanosecondpulse extreme the high ablation yield per pulse,but low ablation yield per unit energy and low NP yield per pulse and per unit energy were related to strong ablation plasma screening,providing mass removal according to the well-established scaling relationships for plasma.Illustrative comparison of the ablation and nanoparticle generation efficiency versus the broad fs–ns laser pulse width range was enabled in terms of productivity,economicity,and ergonomicity,using the proposed universal quantitative criteria.

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.