Femtosecond laser-induced nanoparticle implantation into flexible substrate for sensitive and reusable microfluidics SERS detection

Surface-enhanced Raman spectroscopy(SERS)microfluidic system,which enables rapid detection of chemical and biological analytes,offers an effective platform to monitor various food contaminants and disease diagnoses.The efficacy of SERS microfluidic systems is greatly dependent on the sensitivity and reusability of SERS detection substrates to ensure repeated use for prolonged periods.This study proposed a novel process of femtosecond laser nanoparticle array(NPA)implantation to achieve homogeneous forward transfer of gold NPA on a flexible polymer film and accurately integrated it within microfluidic chips for SERS detection.The implanted Au-NPA strips show a remarkable electromagnetic field enhancement with the factor of 9×108 during SERS detection of malachite green(MG)solution,achieving a detection limit lower than 10 ppt,far better than most laser-prepared SERS substrates.Furthermore,Au-NPA strips show excellent reusability after several physical and chemical cleaning,because of the robust embedment of laser-implanted NPA in flexible substrates.To demonstrate the performance of Au-NPA,a SERS microfluidic system is built to monitor the online oxidation reaction between MG/NaClO reactants,which helps infer the reaction path.The proposed method of nanoparticle implantation is more effective than the direct laser structuring technique.It provides better performance for SERS detection,robustness of detection,and substrate flexibility and has a wider range of applications for microfluidic systems without any negative impact.

P-induced electron transfer interaction for enhanced selective hydrogenation rearrangement of furfural to cyclopentanone

Optimizing the intrinsic activity of non-noble metal by precisely tailoring electronic structure offers an appealing way to construct cost-effective catalysts for selective biomass valorization.Herein,we reported a P-doping bifunctional catalyst(Ni-P/mSiO_(2))that achieved 96.6%yield for the hydrogenation rearrangement of furfural to cyclopentanone at mild conditions(1 MPaH_(2),150°C).The turnover frequency of Ni-P/mSiO_(2)was 411.9 h^(-1),which was 3.2-fold than that of Ni/mSiO_(2)(127.2 h^(-1)).Detailed characterizations and differential charge density calculations revealed that the electron-deficient Niδ+species were generated by the electron transfer from Ni to P,which promoted the ring rearrangement reaction.Density functional theory calculations illustrated that the presence of P atoms endowed furfural tilted adsorb on the Ni surface by the C=O group and facilitated the desorption of cyclopentanone.This work unraveled the connection between the localized electronic structures and the catalytic properties,so as to provide a promising reference for designing advanced catalysts for biomass valorization.

Analysis of the electron transfer pathway in small laccase by EPR and UV-vis spectroscopy coupled with redox titration

Bacterial small laccases(SLAC) are promising industrial biocatalysts due to their ability to oxidize a broad range of substrates with exceptional thermostability and tolerance for alkaline p H. Electron transfer between substrate, copper centers, and O2is one of the key steps in the catalytic turnover of SLAC. However, limited research has been conducted on the electron transfer pathway of SLAC and SLAC-catalyzed reactions, hindering further engineering of SLAC to produce tunable biocatalysts for novel applications. Herein, the combinational use of electron paramagnetic resonance(EPR) and ultraviolet-visible(UV-vis) spectroscopic methods coupled with redox titration were employed to monitor the electron transfer processes and obtain further insights into the electron transfer pathway in SLAC. The reduction potentials for type 1 copper(T1Cu), type 2 copper(T2Cu) and type 3copper(T3Cu) were determined to be 367 ± 2 mV, 378 ± 5 m V and 403 ± 2 mV,respectively. Moreover, the reduction potential of a selected substrate of SLAC, hydroquinone(HQ), was determined to be 288 mV using cyclic voltammetry(CV). In this way, an electron transfer pathway was identified based on the reduction potentials. Specifically,electrons are transferred from HQ to T1Cu, then to T2Cu and T3Cu, and finally to O2.Furthermore, superhyperfine splitting observed via EPR during redox titration indicated a modification in the covalency of T2Cu upon electron uptake, suggesting a conformational alteration in the protein environment surrounding the copper sites, which could potentially influence the reduction potential of the copper sites during catalytic processes. The results presented here not only provide a comprehensive method for analyzing the electron transfer pathway in metalloenzymes through reduction potential measurements, but also offer valuable insights for further engineering and directed evolution studies of SLAC in the aim for biotechnological and industrial applications.

Balancing electron transfer and intermediate adsorption ability of metallic Ni-Fe-RE-P bifunctional catalysts via 4f-2p-3d electron interaction for enhanced water splitting

Balancing electron transfer and intermediate adsorption ability of bifunctional catalysts via tailoring electronic structures is crucial for green hydrogen production,while it still remains challenging due to lacking efficient strategies.Herein,one efficient and universal strategy is developed to greatly regulate electronic structures of the metallic Ni-Fe-P catalysts via in-situ introducing the rare earth(RE)atoms(Ni-Fe-RE-P,RE=La,Ce,Pr,and Nd).Accordingly,the as-prepared optimal Ni-Fe-Ce-P/CC self-supported bifunctional electrodes exhibited superior electrocatalytic activity and excellent stability with the low overpotentials of 247 and 331 mV at 100 mA cm^(-2) for HER and OER,respectively.In the assembled electrolyzer,the Ni-Fe-Ce-P/CC as bifunctional electrodes displayed low operation potential of 1.49 V to achieve a current density of 10 mA cm^(-2),and the catalytic performance can be maintained for 100 h.Experimental results combined with density functional theory(DFT)calculation reveal that Ce doping leads to electron decentralization and crystal structure distortion,which can tailor the band structures and d-band center of Ni-Fe-P,further increasing conductivity and optimizing intermediate adsorption energy.Our work not only proposes a valuable strategy to regulate the electron transfer and intermediate adsorption of electrocatalysts via RE atoms doping,but also provides a deep under-standing of regulation mechanism of metallic electrocatalysts for enhanced water splitting.

An active learning workflow for predicting hydrogen atom adsorption energies on binary oxides based on local electronic transfer features

Machine learning combined with density functional theory(DFT)enables rapid exploration of catalyst descriptors space such as adsorption energy,facilitating rapid and effective catalyst screening.However,there is still a lack of models for predicting adsorption energies on oxides,due to the complexity of elemental species and the ambiguous coordination environment.This work proposes an active learning workflow(LeNN)founded on local electronic transfer features(e)and the principle of coordinate rotation invariance.By accurately characterizing the electron transfer to adsorption site atoms and their surrounding geometric structures,LeNN mitigates abrupt feature changes due to different element types and clarifies coordination environments.As a result,it enables the prediction of^(*)H adsorption energy on binary oxide surfaces with a mean absolute error(MAE)below 0.18 eV.Moreover,we incorporate local coverage(θ_(l))and leverage neutral network ensemble to establish an active learning workflow,attaining a prediction MAE below 0.2 eV for 5419 multi-^(*)H adsorption structures.These findings validate the universality and capability of the proposed features in predicting^(*)H adsorption energy on binary oxide surfaces.

Fe-lnduced Electronic Transfer and Structural Evolution of Lotus Pod-Like CoNiFeP_(x)@P,N-C Heterostructure for Sustainable Oxygen Evolution

Transition metal phosphides with metallic properties are a promising candidate for electrocatalytic water oxidation,and developing highly active and stable metal phosphide-based oxygen evolution reaction catalysts is still challenging.Herein,we present a facile ion exchange and phosphating processes to transform intestine-like CoNiP_(x)@P,N-C into lotus pod-like CoNiFeP_(x)@P,N-C heterostructure in which numerous P,N-codoped carboncoated CoNiFeP_(x)nanoparticles tightly anchors on the 2D carbon matrix.Meanwhile,the as-prepared CoNiFeP_(x)@P,N-C enables a core-shell structure,high specific surface area,and hierarchical pore structure,which present abundant heterointerfaces and fully exposed active sites.Notably,the incorporation of Fe can also induce electron transfer in CoNiP_(x)@P,IM-C,thereby promoting the oxygen evolution reaction.Consequently,CoNiFeP_(x)@P,IM-C delivers a low overpotential of 278 mV(vs RHE)at a current density of10 mA cm^(-1)and inherits excellent long-term stability with no observable current density decay after 30 h of chronoamperometry test.This work not only highlights heteroatom induction to tune the electronic structure but also provides a facile approach for developing advanced and stable oxygen evolution reaction electrocatalysts with abundant heterointerfaces.

The surface electron transfer strategy promotes the hole of PDI release and enhances emerging organic pollutant degradation

In semiconductor photocatalysts,the easy recombination of photogenerated carriers seriously affects the application of photocatalytic materials in water treatment.To solve the serious problem of electron−hole pair recombination in perylene diimide(PDI)organic semiconductors,we loaded ferric hydroxyl oxide(FeOOH)on PDI materials,successfully prepared novel FeOOH@PDI photocatalytic materials,and constructed a photo-Fenton system.The system was able to achieve highly efficient degradation of BPA under visible light,with a degradation rate of 0.112 min^(−1)that was 20 times higher than the PDI system,and it also showed universal degradation performances for a variety of emerging organic pollutants and anti-interference ability.The mechanism research revealed that the FeOOH has the electron trapping property,which can capture the photogenerated electrons on the surface of PDI,effectively reducing the compounding rate of photogenerated carriers of PDI and accelerating the iron cycling and H2O2 activation on the surface of FeOOH at the same time.This work provides new insights and methods for solving the problem of easy recombination of carriers in semiconductor photocatalysts and degrading emerging organic pollutants.

The recent progress of laser-induced graphene based device applications

Laser writing is a fast and efficient technology that can produce graphene with a high surface area,whereas laser-induced graphene(LIG)has been widely used in both physics and chemical device application.It is necessary to update this important progress because it may provide a clue to consider the current challenges and possible future directions.In this review,the basic principles of LIG fabrication are first briefly described for a detailed understanding of the lasing process.Sub-sequently,we summarize the physical device applications of LIGs and describe their advantages,including flexible electronics and energy harvesting.Then,chemical device applications are categorized into chemical sensors,supercapacitors,batteries,and electrocatalysis,and a detailed interpretation is provided.Finally,we present our vision of future developments and challenges in this exciting research field.

Coupling ferromagnetic ordering electron transfer channels and surface reconstructed active species for spintronic electrocatalysis of water oxidation

Sluggish reaction kinetics of oxygen evolution reaction(OER), resulting from multistep proton-coupled electron transfer and spin constriction, limits overall efficiency for most reported catalysts. Herein, using modeled ZnFe_(2-x)Ni_xO_(4)(0 ≤ x ≤ 0.4) spinel oxides, we aim to develop better OER electrocatalyst through combining the construction of ferromagnetic(FM) ordering channels and generation of highly active reconstructed species. The number of symmetry-breaking Fe–O–Ni structure links to the formation of FM ordering electron transfer channels. Meanwhile, as the number of Ni^(3+)increases, more ligand holes are formed, beneficial for redirecting surface reconstruction. The electro-activated ZnFe_(1.6)Ni_(0.4)O_(4) shows the highest specific activity, which is 13 and 2.5 times higher than that of ZnFe_(2)O_(4) and unactivated ZnFe_(1.6)Ni_(0.4)O_(4), and even superior to the benchmark IrO_(2) under the overpotential of 350 mV. Applying external magnetic field can make electron spin more aligned, and the activity can be further improved to 39 times of ZnFe_(2)O_(4). We propose that intriguing FM exchange-field interaction at FM/paramagnetic interfaces can penetrate FM ordering channels into reconstructed oxyhydroxide layers, thereby activating oxyhydroxide layers as spin-filter to accelerate spin-selective electron transfer. This work provides a new guideline to develop highly efficient spintronic catalysts for water oxidation and other spin-forbidden reactions.

Promoting and controlling electron transfer of furfural oxidation efficiently harvest electricity,furoic acid,hydrogen gas and hydrogen peroxide

Conventional chemical oxidation of aldehydes such as furfural to corresponding acids by molecular oxygen usually needs high pressure to increase the solubility of oxygen in aqueous phase,while electrochemical oxidation needs input of external electric energy.Herein,we developed a liquid flow fuel cell(LFFC)system to achieve oxidation of furfural in anode for furoic acid production with co-production of hydrogen gas.By controlling the electron transfer in cathode for reduction of oxygen,efficient generation of electricity or production of H_(2)O_(2)were achieved.Metal oxides especially Ag_(2)O have been screened as the efficient catalyst to promote the oxidation of aldehydes,while liquid redox couples were used for promoting the kinetics of oxygen reduction.A novel alkaline-acidic asymmetric design was also used for anolyte and catholyte,respectively,to promote the efficiency of electron transfer.Such an LFFC system achieves efficient conversion of chemical energy of aldehyde oxidation to electric energy and makes full use the transferred electrons for high-value added products without input of external energy.With(VO_(2))_(2)SO_(4)as the electron carrier in catholyte for four-electron reduction of oxygen,the peak output power density(Pmax)at room temperature reached 261 mW/cm^(2)with furoic acid and H_(2)yields of 90%and 0.10 mol/mol furfural,respectively.With anthraquinone-2-sulfonate(AQS)as the cathodic electron carrier,Pmaxof 60 mW/cm^(2)and furoic acid,H_(2)and H_(2)O_(2)yields of 0.88,0.15 and 0.41 mol/mol furfural were achieved,respectively.A new reaction mechanism on furfural oxidation on Ag_(2)O anode was proposed,referring to one-electron and two-electron reaction pathways depending on the fate of adsorbed hydrogen atom transferred from furfural aldehyde group.

Activating coordinative conjugated polymer via interfacial electron transfer for efficient CO_(2) electroreduction

With tunable local electronic environment,high mass density of MN4sites,and ease of preparation,metal-organic conjugated coordinative polymer(CCP) with inherent electronic conductivity provides a promising alternative to the well-known M-N-C electrocatalysts.Herein,the coordination reaction between Cu^(2+)and 1,2,4,5-tetraaminobenzene(TAB) was conducted on the surface of metallic Cu nanowires,forming a thin layer of CuN4-based CCP(Cu-TAB) on the Cu nanowire.More importantly,interfacial transfer of electrons from Cu core to the CuN4-based CCP nanoshell was observed within the resulting CuTAB@Cu,which was found to enrich the local electronic density of the CuN4sites.As such,the CuTAB@Cu demonstrates much improved affinity to the*COOH intermediate formed from the rate determining step;the energy barrier for C-C coupling,which is critical to convert CO_(2)into C2products,is also decreased.Accordingly,it delivers a current density of-9.1 mA cm^(-2)at a potential as high as 0.558 V(vs.RHE) in H-type cell and a Faraday efficiency of 46.4% for ethanol.This work emphasizes the profound role of interfacial interaction in tuning the local electronic structure and activating the CuN4-based CCPs for efficient electroreduction of CO_(2).

Nanodot array deposition via single shot laser interference pattern using laser-induced forward transfer

Laser-induced forward transfer(LIFT)is a direct-writing technique capable of depositing a single dot smaller than the laser wavelength at small shot energy through the laser-induced dot transfer(LIDT)technique.To deposit a single nanodot in a single shot of laser irradiation,a liquid nanodrop is transferred from donor to receiver and finally solidified via a solid–liquid–solid(SLS)process.In conventional LIDT experiments,multi-shots with step scanning have been used to form array structures.However,interference laser processing can achieve an arrayed process and generate a periodic structure in a single shot.In this study,a femtosecond laser interference pattern was first applied to LIDT,and an array of nanodots was successfully deposited in a single shot,producing the following unit structures:a single dot,adjoining dots,and stacking dots.The diameter of the smallest nanodot was 355 nm,and the narrowest gap between two adjoining nanodots was 17.2 nm.The LIDT technique produces high-purity,catalyst-free that do not require post-cleaning or alignment processes.Given these significant advantages,LIDT can expand the usability of nanodots in a wide range of fields.

A comprehensive review on microchannel heat sinks for electronics cooling

The heat generation of electronic devices is increasing dramatically,which causes a serious bottleneck in the thermal management of electronics,and overheating will result in performance deterioration and even device damage.With the development of micro-machining technologies,the microchannel heat sink(MCHS)has become one of the best ways to remove the considerable amount of heat generated by high-power electronics.It has the advantages of large specific surface area,small size,coolant saving and high heat transfer coefficient.This paper comprehensively takes an overview of the research progress in MCHSs and generalizes the hotspots and bottlenecks of this area.The heat transfer mechanisms and performances of different channel structures,coolants,channel materials and some other influencing factors are reviewed.Additionally,this paper classifies the heat transfer enhancement technology and reviews the related studies on both the single-phase and phase-change flow and heat transfer.The comprehensive review is expected to provide a theoretical reference and technical guidance for further research and application of MCHSs in the future.

Radio-frequency compressed electron pulse-width characterization by cross-correlation between electron bunches and laser-induced plasma

A method is proposed to determine the temporal width of high-brightness radio-frequency compressed electron pulses based on cross-correlation technique involving electron bunches and laser-induced plasma. The temporal evolution of 2-dimensional transverse profile of ultrafast electron bunches repelled by the formed transient electric field of laser-induced plasma on a silver needle is investigated, and the pulse-width can be obtained by analyzing these time-dependent images.This approach can characterize radio-frequency compressed ultrafast electron bunches with picosecond or sub-picosecond timescale and up to 105 electron numbers.

Experimental study on microdeposition of the copper thin film by femtosecond laser-induced forward transfer

The morphologies of the deposited dots on the 40 nm-thick copper film by the femtosecond laser-induced forward transfer that depend on the irradiated laser fluence have been studied, and the variations of orderliness of the diameter of deposited dots on the quartz substrate and forward ablated dot on the donor substrate with increasing pulse fluence have been obtained experimentally. The experimental results show that a thinner copper film would generate larger-sized ablated dot and deposited dot at the threshold fluence for transfer. By x-ray diffraction measurement, it is demonstrated that the crystal form of the transferred copper films is unaltered and the size of the crystallites is diminished.

Laser-induced quadrupole-quadrupole collisional energy transfer in Xe-Kr

By considering the relative velocity distribution function and multipole expansion interaction Hamiltonian, a three-state model for calculating the cross section of laser-induced quadrupole-quadrupole collisional energy transfer is presented. Calculated results in Xe-Kr system show that in the present system, the laser-induced collision process occurs for -4 ps, which is much shorter than the dipole-dipole laser-induced collisional energy transfer （LICET） process. The spectrum of laser-induced quadrupole quadrupole collisional energy transfer in Xe-Kr system has wider tunable range in an order of magnitude than the dipole-dipole LICET spectra. The peak cross section decreases and moves to the quasi-static wing with increasing temperature and the full width at half peak of the profile becomes larger as the system temperature increases.

Laser-induced forward transferred silver nanomembrane with controllable light absorption

Laser processing provides highly-controlled modification and on-demand fabrication of plasmon metal nanostructures for light absorption and photothermal convention.We present the laser-induced forward tansfer(LIFT)fabrication of silver nanomembranes in control of light absorption.By varying the hatch distance,different morphologies of randomly distributed plasmon silver nanostructures were produced,leading to well-controlled light absorption levels from 11%to 81%over broadband.The anti-reflection features were maintained below 17%.Equilibrated and plain absorptions were obtained throughout all absorption levels with a maximum intensity fluctuation of±8.5%for the 225μJ cases.The 45μJ pulse energy can offer a highly equilibrated absorption at a 60%absorption level with an intensity fluctuation of±1%.Pattern transfer was also achieved on a thin tape surface.The laser-transferred characters and patterns demonstrate a localized temperature rise.A rapid temperature rising of roughly 15℃can be achieved within 1 s.The LIFT process is highly efficiently fabricated with a typical speed value of 10^(3)to 10^(5)cm^(2)/h.The results indicated that LIFT is a well-controlled and efficient method for the production of optical films with specific absorption levels.

Laser-induced collisional energy transfer in Sr-Li system

A four-state model considering the relative velocity distribution function for calculating the cross section of laserinduced collisional energy transfer in a Sr Li system is presented and profiles of laser-induced collision cross section are obtained. The resulting spectra obtained from different intermediate states are strongly asymmetrical in an opposite asymmetry. Both of the two intermediate states have contributions to the final state, and none of the intermediate states should be neglected. The peak of the laser-induced collisional energy transfer （LICET） profile shifts toward the red and the FWHM becomes narrower obviously with laser field intensity increasing. A cross section of 1.2 × 10^-12 cm2 at a laser field intensity of 2.17 ×107 V/m is obtained, which indicates that this collision process can be an effective way to transfer energy selectively from a storage state to a target state. The existence of saturation for cross section with the increase of the laser intensity shows that the high-intensity redistribution of transition probabilities is an important feature of this process, which is not accounted for in a two-state treatment.

Four-level model of ion-ion laser-induced collisional energy transfer and numerical calculations for Ca^+-Sr^+ system

The four-level model of laser-induced collisional energy transfer （LICET） for the ion-ion collision system is established based on the time-dependent SchrSdinger equation for the electron dynamics, through which the equations of motion of the probability amplitudes and cross section of the collision system are obtained. Numerical calculations are performed for the Ca＋ Sr＋ system, with the results showing that the peak of the LICET spectrum appears at a resonant frequency of the transfer laser. The magnitude of the obtained collision cross section is in the order of 10-16 cm2, and is comparable to that obtained in atomic systems, which indicates the validity of the established four-level model.

Influence of dye molecular structure on electron transfer in 2,9,16,23-tetracarboxy zinc phthalocyanine sensitized solar cell

2, 9, 16, 23-tetracarboxy zinc phthalocyanine （ZnTCPc） is synthesized and characterized by physicochemical and theoretical methods and it is used as a photosensitizer in dye-sensitized solar cells （DSSC）. The excited lifetime, band gap and frontier orbital distribution of ZnTCPc are investigated by fluorescence spectra, cyclic voltammetry and quantum calculation. The results show that the excited lifetime and band gap are 0. 1 ns and 1.81 eV, respectively. Moreover, it is found that the highest occupied molecular orbital （HOMO） location is not shared by both the zinc metal and the isoindoline ligands, and the lowest unoccupied molecular orbital（LUMO） location does not strengthen the interaction coupling between ZnTCPc and TiO：. As a result, the ZnTCPc-DSSC gains a short-circuit current density of 0. 147 mA/cm2, an open-circuit photovoltage of 277 mV, a fill factor of 0. 51 and an overall conversion efficiency of 0. 021%.