There remain a number of unsolved problems about chemical reactions, and it is significant to explore new detection methods because they always offer some unique information about reactions from new points of view. Fo...There remain a number of unsolved problems about chemical reactions, and it is significant to explore new detection methods because they always offer some unique information about reactions from new points of view. For the first time, the solidification course of a modified two-component acrylic structural adhesive is measured by using reed-vibration mechanical spectroscopy for liquids (RMS-L) in this work, and results show that there are four sequential processes of mechanical spectra with time. The in-depth analyses indicate that RMS-L can detect in real-time the generation and disappearance of active free radicals, as well as the chemical cross-link processes in the adhesive. This kind of real-time detection will undoubtedly facilitate the study of the chemical reaction dynamics controlled by free radicals.展开更多
The melting of crystals is one of the most common and general phase transition phenomena.However, the mechanism of crystal melting is not well understood, and more experimental measurements and explorations are still ...The melting of crystals is one of the most common and general phase transition phenomena.However, the mechanism of crystal melting is not well understood, and more experimental measurements and explorations are still needed.The mechanical spectra of propylene carbonate and 1,3-propanediol during the crystal melting processes are measured by the reed vibration mechanical spectroscopy for liquids(RMS-L) for the first time.The experimental results show that as the temperature increases, the real part of the complex Young modulus first decreases slowly, and then quickly drops to zero;meanwhile, its imaginary part increases slowly at first, then goes up and drops quickly to zero, showing a peak of internal friction.Preliminary analyses indicate that both the real and imaginary parts can present some characteristics of the melting process, such as the transition from the disconnected liquid regions to the connected liquid regions, that from the connected crystal regions to the disconnected crystal regions, and so on.In addition, the results show that the melting rate per unit volume of crystalline phase versus temperature satisfies the Arrhenius relation at the initial stage of melting, and deviates from this relation as the temperature increases to a certain value.Therefore, the RMS-L will provide an effective supplement for the further study of melting.展开更多
Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely use...Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely used to study the reaction mechanism of the hydrogen evolution reaction(HER),but the calculation results need to be supported by experimental results and direct evidence to confirm the mechanistic insights.In this review,we discuss the fundamental principles of the in situ spectroscopic strategy and a theoretical model for a mechanistic understanding of the HER.In addition,we investigate recent studies by in situ Fourier transform infrared(FTIR),Raman spectroscopy,and X-ray absorption spectroscopy(XAS) and cover new findings that occur at the catalyst-electrolyte interface during HER.These spectroscopic strategies provide practical ways to elucidate catalyst phase,reaction intermediate,catalyst-electrolyte interface,intermediate binding energy,metal valency state,and coordination environment during HER.展开更多
In this study,the microstructures,mechanical properties,corrosion behaviors,and biocompatibility of extruded magnesium-zirconiumstrontium-holmium(Mg-Zr-Sr-Ho)alloys were comprehensively investigated.The effect of diff...In this study,the microstructures,mechanical properties,corrosion behaviors,and biocompatibility of extruded magnesium-zirconiumstrontium-holmium(Mg-Zr-Sr-Ho)alloys were comprehensively investigated.The effect of different concentrations of Ho on the microstructural characteristics,tensile and compressive properties,corrosion resistance,and biocompatibility were investigated.The microstructures of the extruded Mg-1Zr-0.5Sr-xHo(x=0.5,1.5,and 4 wt.%)alloys consisted ofα-Mg matrix,fineα-Zr particles,and intermetallic phase particles of Mg_(17)Sr_(2) and Ho_(2)Mg mainly distributed at the grain boundaries.Extensive{1012}tensile twins were observed in the partially recrystallized samples of Mg-1Zr-0.5Sr-0.5Ho and Mg-1Zr-0.5Sr-1.5Ho.Further addition of Ho to 4 wt.%resulted in a complete recrystallization due to activation of the particle stimulated nucleation around the Mg_(17)Sr_(2) particles.The evolution of a rare earth(RE)texture was observed with the Ho addition,which resulted in the weakened basal and prismatic textures.Furthermore,a drastic increase of 200%in tensile elongation and 89%in compressive strain was observed with Ho addition increased from 0.5 to 4 wt%,respectively.The tension-compression yield asymmetry was significantly decreased from 0.62 for Mg-1Zr-0.5Sr-0.5Ho to 0.98 for Mg-1Zr-0.5Sr-4Ho due to the weakening of textures.Corrosion analysis of the extruded Mg-Zr-Sr-Ho alloys revealed the presence of pitting corrosion.A minimum corrosion rate of 4.98 mm y^(−1) was observed in Mg-1Zr-0.5Sr-0.5Ho alloy.The enhanced corrosion resistance is observed due to the presence of Ho_(2)O_(3) in the surface film which reduced galvanic effect.The formation of a stabilized surface film due to the Ho_(2)O_(3) was confirmed through the electrical impedance spectroscopy and XPS analysis.An in vitro cytotoxicity assessment revealed good biocompatibility and cell adhesion in relation to SaOS2 cells.展开更多
The pursuit of high-performance electrode materials is highly desired to meet the demand of batteries with high energy and power density.However,a deep understanding of the charge storage mechanism is always challengi...The pursuit of high-performance electrode materials is highly desired to meet the demand of batteries with high energy and power density.However,a deep understanding of the charge storage mechanism is always challenging,which limits the development of advanced electrode materials.Herein,high-resolution mass spectroscopy(HR-MS)is employed to detect the evolution of organic electrode materials during the redox process and reveal the charge storage mechanism,by using small molecular oxamides as an example,which have ortho-carbonyls and are therefore potential electrochemical active materials for batteries.The HR-MS results adequately proved that the oxamides could reversibly store lithium ions in the voltage window of 1.5–3.8 V.Upon deeper reduction,the oxamides would decompose due to the cleavage of the C–N bonds in oxamide structures,which could be proved by the fragments detected by HR-MS,^(1)H NMR,and the generation of NH_(3)after the reduction of oxamide by Li.This work provides a strategy to deeply understand the charge storage mechanism of organic electrode materials and will stimulate the further development of characterization techniques to reveal the charge storage mechanism for developing high-performance electrode materials.展开更多
PEO-based all-solid-state electrolytes are extensively utilized and researched owing to their exceptional safety,low-mass-density,and cost-effectiveness.However,the low oxidation potential of PEO makes the interface p...PEO-based all-solid-state electrolytes are extensively utilized and researched owing to their exceptional safety,low-mass-density,and cost-effectiveness.However,the low oxidation potential of PEO makes the interface problem with the high-voltage cathode extremely severe.In this work,the impedance of PEO-based all-solid-state batteries with high-voltage cathode(NCM811)was studied at different potentials.The Nyquist plots displayed a gyrate arc at low-frequencies for NCM811/PEO interface.Based on the kinetic modeling,it was deduced that there is a decomposition reaction of PEO-matrix in addition to de-embedded reaction of NCM811,and the PEO intermediate product(dehydra-PEO)adsorbed on the electrode surface leading to low-frequency inductive arcs.Furthermore,the distribution of relaxation time shows the dehydra-PEO results in the kinetic tardiness of the charge transfer process in the temporal dimension.Hence,an artificial interface layer(CEI_(x))was modified on the surface of NCM811 to regulate the potential of cathode/electrolyte interface to prevent the high-voltage deterioration of PEO.NCM/CEI_(x)/PEO batteries exhibit capacity retentions of 96.0%,84.6%,and 76.8%after undergoing 100 cycles at cut-off voltages of 4.1,4.2,and 4.3 V,respectively.Therefore,here the failure mechanism of high-voltage PEO electrolyte is investigated by EIS and a proposed solving strategy is presented.展开更多
The conversion of acetone derived from biomass to isobutene has attracted extensive attentions.In comparison with Brønsted acidic catalyst,Lewis acidic catalyst could exhibit a better catalytic performance with a...The conversion of acetone derived from biomass to isobutene has attracted extensive attentions.In comparison with Brønsted acidic catalyst,Lewis acidic catalyst could exhibit a better catalytic performance with a higher isobutene selectivity.However,the catalyst stability remains a key problem for the long-running acetone conversion and the reasons for catalyst deactivation are poorly understood up to now.Herein,the deactivation mechanism of Lewis acidic Y/Beta catalyst during the acetone to isobutene conversion was investigated by various characterization techniques,including acetone-temperature-programmed surface reaction,gas chromatography-mass spectrometry,in situ ultraviolet-visible,and ^(13)C cross polarization magic angle spinning nuclear magnetic resonance spectroscopy.A successive aldol condensation and cyclization were observed as the main side-reactions during the acetone conversion at Lewis acidic Y sites.In comparison with the low reaction temperature,a rapid formation and accumulation of the larger cyclic unsaturated aldehydes/ketones and aromatics could be observed,and which could strongly adsorb on the Lewis acidic sites,and thus cause the catalyst deactivation eventually.After a simple calcination,the coke deposits could be easily removed and the catalytic activity could be well restored.展开更多
In the field of dual-pulse laser-induced breakdown spectroscopy(DP-LIBS)research,the pursuit of methods for determining pulse intervals and other parameters quickly and conveniently in order to achieve optimal spectra...In the field of dual-pulse laser-induced breakdown spectroscopy(DP-LIBS)research,the pursuit of methods for determining pulse intervals and other parameters quickly and conveniently in order to achieve optimal spectral signal enhancement is paramount.To aid researchers in identification of optimal signal enhancement conditions and more accurate interpretation of the underlying signal enhancement mechanisms,theoretical simulations of the spatiotemporal processes of coaxial DP-LIBS-induced plasma have been established in this work.Using a model based on laser ablation and two-dimensional axisymmetric fluid dynamics,plasma evolutions during aluminum–magnesium alloy laser ablation under single-pulse and coaxial dualpulse excitations have been simulated.The influences of factors,such as delay time,laser fluence,plasma temperature,and particle number density,on the DP-LIBS spectral signals are investigated.Under pulse intervals ranging from 50 to 1500 ns,the time evolutions of spectral line intensity,dual-pulse emission enhancement relative to the single-pulse results,laser irradiance,spatial distribution of plasma temperature and species number density,as well as laser irradiance shielded by plasma have been obtained.The study indicates that the main reason behind the radiation signal enhancement in coaxial DP-LIBS-induced plasma is attributed to the increased species number density and plasma temperature caused by the second laser,and it is inferred that the shielding effect of the plasma mainly occurs in the boundary layer of the stagnation point flow over the target surface.This research provides a theoretical basis for experimental research,parameter optimization,and signal enhancement tracing in DP-LIBS.展开更多
Transition metal ditellurides(TMTDs)have versatile physical properties,including non-trivial topology,Weyl semimetal states and unique spin texture.Controlled growth of high-quality and large-scale monolayer TMTDs wit...Transition metal ditellurides(TMTDs)have versatile physical properties,including non-trivial topology,Weyl semimetal states and unique spin texture.Controlled growth of high-quality and large-scale monolayer TMTDs with preferred crystal phases is crucial for their applications.Here,we demonstrate the epitaxial growth of 1T'-MoTe_(2) on Au(111)and graphitized silicon carbide(Gr/SiC)by molecular beam epitaxy(MBE).We investigate the morphology of the grown1T'-MoTe_(2) at the atomic level by scanning tunnelling microscopy(STM)and reveal the corresponding microscopic growth mechanism.It is found that the unique ordered Te structures preferentially deposited on Au(111)regulate the growth of monolayer single crystal 1T'-MoTe_(2),while the Mo clusters were preferentially deposited on the Gr/SiC substrate,which impedes the ordered growth of monolayer MoTe_(2).We confirm that the size of single crystal 1T'-MoTe_(2) grown on Au(111)is nearly two orders of magnitude larger than that on Gr/SiC.By scanning tunnelling spectroscopy(STS),we observe that the STS spectrum of the monolayer 1T'-MoTe_(2) nano-island at the edge is different from that at the interior,which exhibits enhanced conductivity.展开更多
Air-dry density,modulus of rupture(MOR),modulus of elasticity(MOE),compressive strength parallel to grain,and hardness of Catalpa bungei clones were investigated in this study with feasibility of predicting these prop...Air-dry density,modulus of rupture(MOR),modulus of elasticity(MOE),compressive strength parallel to grain,and hardness of Catalpa bungei clones were investigated in this study with feasibility of predicting these properties by near infrared(NIR)spectroscopy.The best candidate Luoqiu 3'has been selected from three clones based on wood physical and mechanical property indices.Lower values of wood physical and mechanical properties have been found in the corewood compared to the outerwood.There were significant positive correlations between the air-dry density and mechanical properties.Information from Cross section for air dry density,compressive strength parallel to grain,and hardness yielded prediction models with better effects,along with the best MOR and MOE modeling effects resulted from average sections'spectra collection.Multiplicative scatter correction(MSC)+Savitzky-Golay(S-G)smoothing method has been proved to be the most applicable way.In addition,the predictions from five point sampling method were slightly better than three point one.Overall,results suggest NIR spectroscopy was viable to predict the physical and mechanical properties of C bungei dones with methods developed in this study proved effective in preliminary screening.展开更多
The effects of Fe2O3 content on the microstructure and mechanical properties of the CaO-Al2O3-SiO2 system were investigated by differential thermal analysis(DTA), X-ray diffraction(XRD), scanning electron microsc...The effects of Fe2O3 content on the microstructure and mechanical properties of the CaO-Al2O3-SiO2 system were investigated by differential thermal analysis(DTA), X-ray diffraction(XRD), scanning electron microscopy(SEM), electron spin resonance(ESR), and Mssbauer spectroscopy. The results show that the addition of Fe2O3 does not affect the main crystalline phase in the prepared glasses, but it reduces the crystallisation peak temperature, increases the crystallisation activation energy, and reduces the crystal granularity. The ESR results indicate that Fe2O3 can promote crystallization, as it leads to the phase separation of the CaO-Al2O3-SiO2 system due to axial distortion. Moreover, Fe2O3 alters the network structure of the CaO-Al2O3-SiO2 system, allowing Fe3+ to enter octahedral sites that exhibit higher symmetry than tetrahedral sites. All of these factors are favourable to increasing the bending strength. The Mssbauer results reveal that there are two types of coordination for both Fe3+ and Fe2+ and the bending strength of the CaO-Al2O3-SiO2 system increases with the amount of six-coordinate Fe3+. The increasing interaction between Fe3+ and Fe2+ can also enhance the bending strength of the CaO-Al2O3-SiO2 system. The microhardness of the CaO-Al2O3-SiO2 system was determined to be HV 896.9 and the bending strength to be 217 MPa under the heat treatment conditions of nucleation temperature of 700 °C and nucleation time of 2 h, crystallization temperature of 910 °C and crystallization time of 3 h.展开更多
Metal Ti and its alloys have been widely utilized in the fields of aviation, medical science, and micro-electromechanical systems, for its excellent specific strength, resistance to corrosion, and biological compatibi...Metal Ti and its alloys have been widely utilized in the fields of aviation, medical science, and micro-electromechanical systems, for its excellent specific strength, resistance to corrosion, and biological compatibility. As the application of Ti moves to the micro or nano scale, however, traditional methods of planarization have shown their short slabs.Thus, we introduce the method of chemical mechanical polishing(CMP) to provide a new way for the nano-scale planarization method of Ti alloys. We obtain a mirror-like surface, whose flatness is of nano-scale, via the CMP method. We test the basic mechanical behavior of Ti–6Al–4V(Ti64) in the CMP process, and optimize the composition of CMP slurry.Furthermore, the possible reactions that may take place in the CMP process have been studied by electrochemical methods combined with x-ray photoelectron spectroscopy(XPS). An equivalent circuit has been built to interpret the dynamic of oxidation. Finally, a model has been established to explain the synergy of chemical and mechanical effects in the CMP of Ti–6Al–4V.展开更多
Mechanical properties of micro-structured porous silicon film (PS) were studied combining X-ray diffraction with micro-Raman spectroscopy. The micro-structured porous silicon samples with different porosities rangin...Mechanical properties of micro-structured porous silicon film (PS) were studied combining X-ray diffraction with micro-Raman spectroscopy. The micro-structured porous silicon samples with different porosities ranging from 30.7700 to 96.2500 were obtained by chemical etching. Lattice parameters of the samples were measured using X-ray diffraction and its maximal change is up to (1.000.) This lattice mismatch with the bulk silicon substrate may introduce residual stress to the porous film. The residual stress measurement by micro-Raman spectroscopy reveals that the maximum of tensile residual stress has reached GPa level in the porous film. Moreover, the lattice mismatch and its corresponding residual stress are increasing with the porosity of PS, but average (elastic) modulus is about 14.5 GPa, one order of magnitude lower than that of substrate Si. The mechanical properties of PS have a close relation with its micro-pore structure.展开更多
Four FeCrNiMnMo_(x)(x=0,0.1,0.3,0.5,in molar ratio)high-entropy alloys(HEAs)were synthesized by vacuum arc melting to explore the potential impact of Mo on the microstructure,mechanical properties,and passivation and ...Four FeCrNiMnMo_(x)(x=0,0.1,0.3,0.5,in molar ratio)high-entropy alloys(HEAs)were synthesized by vacuum arc melting to explore the potential impact of Mo on the microstructure,mechanical properties,and passivation and electrochemical behaviors in 0.5 M H_(2)SO_(4)solution.The results display that the FeCrNiMn alloy exhibits a single face-centered cubic(FCC)structure while the microstructures of the FeCrNiMnMo_(0.1),FeCrNiMnMo_(0.3),and FeCrNiMnMo_(0.5)alloys consist of the FCC andσphase.The appear of theσphase ascribed to the addition of Mo enhances the hardness and yield strength with the sacrifice of plasticity.The FeCrNiMnMox HEAs achieve the maximum hardness of 414 HV_(0.2)and the highest compressive yield strength of 830 MPa when x=0.5,but compressive fracture strain is lowered to 10.8%.X-ray photoelectron spectroscopy(XPS)and electrochemical analysis show that the passivation film in FeCrNiMnMox alloy mainly consists of chromium oxides and molybdenum oxides.Mo has a beneficial effect on the corrosion resistance of the FeCrNiMnMox HEAs in a 0.5 M H_(2)SO_(4)solution by increasing the corrosion potential(E_(corr))and decreasing the corrosion current density(I_(corr))and passivation current density(I_(pass)).The FeCrNiMnMo_(0.1)alloy shows the best corrosion resistance,mainly due to its passivation film consisting of a large proportion of chromium oxide(Cr_(2)O_(3)).More Mo additions promote the formation of the precipitate ofσphase and the matrix regions depleted Cr and Mo elements adverse to the resistance to preferential localized corrosion.展开更多
We propose a scheme that can generate tunable double optomechanically induced transparency in a hybrid optomechanical cavity system.In this system, the mechanical resonator of the optomechanical cavity is coupled with...We propose a scheme that can generate tunable double optomechanically induced transparency in a hybrid optomechanical cavity system.In this system, the mechanical resonator of the optomechanical cavity is coupled with an additional mechanical resonator and the additional mechanical resonator can be driven by a weak external coherently mechanical driving field.We show that both the intensity and the phase of the external mechanical driving field can control the propagation of the probe field, including changing the transmission spectrum from double windows to a single-window.Our study also provides an effective way to generate intensity-controllable, narrow-bandwidth transmission spectra, with the probe field modulated from excessive opacity to remarkable amplification.展开更多
Thermal barrier coatings (TBCs) were developed to protect metallic blades and vanes working in turbo-engines. The two-layered structure TBCs, consisting of NiCoCrAlY bond coat and yttria stabilized zirconia (YSZ),...Thermal barrier coatings (TBCs) were developed to protect metallic blades and vanes working in turbo-engines. The two-layered structure TBCs, consisting of NiCoCrAlY bond coat and yttria stabilized zirconia (YSZ), were deposited on a cylinder of superalloy substrate by the electron beam-physical vapor deposition (EB-PVD). The failure mechanism of the TBCs was investigated with a thermo-mechanical fatigue testing system under the service condition similar to that for turbine blades. Non-destructive evaluation of the coated specimens was conducted through the impedance spectroscopy. It is found that the crack initiation mainly takes place on the top coat at the edge of the heated zones.展开更多
Cadmium zinc telluride (CdZnTe) semiconductor has applications in the detection of X-rays and gamma-rays at room temperature without having to use a cooling system. Chemical etching and chemo-mechanical polishing are ...Cadmium zinc telluride (CdZnTe) semiconductor has applications in the detection of X-rays and gamma-rays at room temperature without having to use a cooling system. Chemical etching and chemo-mechanical polishing are processes used to smoothen CdZnTe wafer during detector device fabrication. These processes reduce surface damages left after polishing the wafers. In this paper, we compare the effects of etching and chemo-mechanical polishing on CdZnTe nuclear detectors, using a solution of hydrogen bromide in hydrogen peroxide and ethylene glycol mixture. X-ray photoelectron spectroscopy (XPS) was used to monitor TeO2 on the wafer surfaces. Current-voltage and detector-response measurements were made to study the electrical properties and energy resolution. XPS results showed that the chemical etching process resulted in the formation of more TeO2 on the detector surfaces compared to chemo-mechanical polishing. The electrical resistivity of the detector is of the order of 1010 Ω-cm. The chemo-mechanical polishing process increased the leakage current more that chemical etching. For freshly treated surfaces, the etching process is more detrimental to the energy resolution compared to chemo-mechanically polishing.展开更多
This work is realized in the context of valorizing natural and local resources, in particular, luffa plant fruit (luffa sponge). The raw fibers of the luffa sponge have a short lifetime. Hence, when they are chemicall...This work is realized in the context of valorizing natural and local resources, in particular, luffa plant fruit (luffa sponge). The raw fibers of the luffa sponge have a short lifetime. Hence, when they are chemically treated, it constitutes a solution is prepared to limit their degradation in the long term and to improve their mechanical characteristics. Therefore, this paper studies the effect of the chemical treatment on the mechanical properties of the luffa sponge’s fibers (fibers of luffa Sponge). The chemical process consists of dipping a brunch of luffa in various concentrations of sodium hydroxide (NaOH) at different time intervals and at different temperature conditions. The luffa sponge’s fibers were mechanical. Characterized before and after the treatment, mechanically (micro traction test). It has been shown that an optimum of 61% increase in mechanical properties (tensile strength) has been reached in the following conditions: treatment with 1% concentration for 90 min at 50°C.展开更多
基金supported by the Natural Science Foundations of Xinjiang Automatic Region, China (Grant Nos. 200821104, 2009211B16, and 2010211B16)the Support Program of Science and Technology of Xinjiang Automatic Region, China (Grant No. 201091112)the West-Light Foundation of the Chinese Academy of Sciences (Grant No. RCPY200906)
文摘There remain a number of unsolved problems about chemical reactions, and it is significant to explore new detection methods because they always offer some unique information about reactions from new points of view. For the first time, the solidification course of a modified two-component acrylic structural adhesive is measured by using reed-vibration mechanical spectroscopy for liquids (RMS-L) in this work, and results show that there are four sequential processes of mechanical spectra with time. The in-depth analyses indicate that RMS-L can detect in real-time the generation and disappearance of active free radicals, as well as the chemical cross-link processes in the adhesive. This kind of real-time detection will undoubtedly facilitate the study of the chemical reaction dynamics controlled by free radicals.
基金Project supported by the National Natural Science Foundation of China(Grant No.11664042)
文摘The melting of crystals is one of the most common and general phase transition phenomena.However, the mechanism of crystal melting is not well understood, and more experimental measurements and explorations are still needed.The mechanical spectra of propylene carbonate and 1,3-propanediol during the crystal melting processes are measured by the reed vibration mechanical spectroscopy for liquids(RMS-L) for the first time.The experimental results show that as the temperature increases, the real part of the complex Young modulus first decreases slowly, and then quickly drops to zero;meanwhile, its imaginary part increases slowly at first, then goes up and drops quickly to zero, showing a peak of internal friction.Preliminary analyses indicate that both the real and imaginary parts can present some characteristics of the melting process, such as the transition from the disconnected liquid regions to the connected liquid regions, that from the connected crystal regions to the disconnected crystal regions, and so on.In addition, the results show that the melting rate per unit volume of crystalline phase versus temperature satisfies the Arrhenius relation at the initial stage of melting, and deviates from this relation as the temperature increases to a certain value.Therefore, the RMS-L will provide an effective supplement for the further study of melting.
基金the immense support provided by the National Research Foundation of Korea(NRF)Grant funded by the Korean Government(MSIT)(RS-2023–00210114)the National R&D Program through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(2021M3D1A2051636)。
文摘Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely used to study the reaction mechanism of the hydrogen evolution reaction(HER),but the calculation results need to be supported by experimental results and direct evidence to confirm the mechanistic insights.In this review,we discuss the fundamental principles of the in situ spectroscopic strategy and a theoretical model for a mechanistic understanding of the HER.In addition,we investigate recent studies by in situ Fourier transform infrared(FTIR),Raman spectroscopy,and X-ray absorption spectroscopy(XAS) and cover new findings that occur at the catalyst-electrolyte interface during HER.These spectroscopic strategies provide practical ways to elucidate catalyst phase,reaction intermediate,catalyst-electrolyte interface,intermediate binding energy,metal valency state,and coordination environment during HER.
基金the financial support for this research by the Australian Research Council(ARC)through the Future Fellowship(FT160100252)the Discovery Project(DP170102557)。
文摘In this study,the microstructures,mechanical properties,corrosion behaviors,and biocompatibility of extruded magnesium-zirconiumstrontium-holmium(Mg-Zr-Sr-Ho)alloys were comprehensively investigated.The effect of different concentrations of Ho on the microstructural characteristics,tensile and compressive properties,corrosion resistance,and biocompatibility were investigated.The microstructures of the extruded Mg-1Zr-0.5Sr-xHo(x=0.5,1.5,and 4 wt.%)alloys consisted ofα-Mg matrix,fineα-Zr particles,and intermetallic phase particles of Mg_(17)Sr_(2) and Ho_(2)Mg mainly distributed at the grain boundaries.Extensive{1012}tensile twins were observed in the partially recrystallized samples of Mg-1Zr-0.5Sr-0.5Ho and Mg-1Zr-0.5Sr-1.5Ho.Further addition of Ho to 4 wt.%resulted in a complete recrystallization due to activation of the particle stimulated nucleation around the Mg_(17)Sr_(2) particles.The evolution of a rare earth(RE)texture was observed with the Ho addition,which resulted in the weakened basal and prismatic textures.Furthermore,a drastic increase of 200%in tensile elongation and 89%in compressive strain was observed with Ho addition increased from 0.5 to 4 wt%,respectively.The tension-compression yield asymmetry was significantly decreased from 0.62 for Mg-1Zr-0.5Sr-0.5Ho to 0.98 for Mg-1Zr-0.5Sr-4Ho due to the weakening of textures.Corrosion analysis of the extruded Mg-Zr-Sr-Ho alloys revealed the presence of pitting corrosion.A minimum corrosion rate of 4.98 mm y^(−1) was observed in Mg-1Zr-0.5Sr-0.5Ho alloy.The enhanced corrosion resistance is observed due to the presence of Ho_(2)O_(3) in the surface film which reduced galvanic effect.The formation of a stabilized surface film due to the Ho_(2)O_(3) was confirmed through the electrical impedance spectroscopy and XPS analysis.An in vitro cytotoxicity assessment revealed good biocompatibility and cell adhesion in relation to SaOS2 cells.
基金financialy supported by the National Natural Science Foundation of China(52173163,22279038,and 22205069)the National 1000-Talents Program,the Innovation Fund of WNLO,the Open Fund of the State Key Laboratory of Integrated Optoelectronics(IOSKL2020KF02)+1 种基金Wenzhou Science&Technology Bureau(ZG2022020,G20220022,and G20220026)the China Postdoctoral Science Foundation(2021TQ0115,2021 M701302,and 2020 M672323)
文摘The pursuit of high-performance electrode materials is highly desired to meet the demand of batteries with high energy and power density.However,a deep understanding of the charge storage mechanism is always challenging,which limits the development of advanced electrode materials.Herein,high-resolution mass spectroscopy(HR-MS)is employed to detect the evolution of organic electrode materials during the redox process and reveal the charge storage mechanism,by using small molecular oxamides as an example,which have ortho-carbonyls and are therefore potential electrochemical active materials for batteries.The HR-MS results adequately proved that the oxamides could reversibly store lithium ions in the voltage window of 1.5–3.8 V.Upon deeper reduction,the oxamides would decompose due to the cleavage of the C–N bonds in oxamide structures,which could be proved by the fragments detected by HR-MS,^(1)H NMR,and the generation of NH_(3)after the reduction of oxamide by Li.This work provides a strategy to deeply understand the charge storage mechanism of organic electrode materials and will stimulate the further development of characterization techniques to reveal the charge storage mechanism for developing high-performance electrode materials.
基金financially supported by the National Natural Science Foundation of China (Nos. 51972023, 11210304)
文摘PEO-based all-solid-state electrolytes are extensively utilized and researched owing to their exceptional safety,low-mass-density,and cost-effectiveness.However,the low oxidation potential of PEO makes the interface problem with the high-voltage cathode extremely severe.In this work,the impedance of PEO-based all-solid-state batteries with high-voltage cathode(NCM811)was studied at different potentials.The Nyquist plots displayed a gyrate arc at low-frequencies for NCM811/PEO interface.Based on the kinetic modeling,it was deduced that there is a decomposition reaction of PEO-matrix in addition to de-embedded reaction of NCM811,and the PEO intermediate product(dehydra-PEO)adsorbed on the electrode surface leading to low-frequency inductive arcs.Furthermore,the distribution of relaxation time shows the dehydra-PEO results in the kinetic tardiness of the charge transfer process in the temporal dimension.Hence,an artificial interface layer(CEI_(x))was modified on the surface of NCM811 to regulate the potential of cathode/electrolyte interface to prevent the high-voltage deterioration of PEO.NCM/CEI_(x)/PEO batteries exhibit capacity retentions of 96.0%,84.6%,and 76.8%after undergoing 100 cycles at cut-off voltages of 4.1,4.2,and 4.3 V,respectively.Therefore,here the failure mechanism of high-voltage PEO electrolyte is investigated by EIS and a proposed solving strategy is presented.
文摘The conversion of acetone derived from biomass to isobutene has attracted extensive attentions.In comparison with Brønsted acidic catalyst,Lewis acidic catalyst could exhibit a better catalytic performance with a higher isobutene selectivity.However,the catalyst stability remains a key problem for the long-running acetone conversion and the reasons for catalyst deactivation are poorly understood up to now.Herein,the deactivation mechanism of Lewis acidic Y/Beta catalyst during the acetone to isobutene conversion was investigated by various characterization techniques,including acetone-temperature-programmed surface reaction,gas chromatography-mass spectrometry,in situ ultraviolet-visible,and ^(13)C cross polarization magic angle spinning nuclear magnetic resonance spectroscopy.A successive aldol condensation and cyclization were observed as the main side-reactions during the acetone conversion at Lewis acidic Y sites.In comparison with the low reaction temperature,a rapid formation and accumulation of the larger cyclic unsaturated aldehydes/ketones and aromatics could be observed,and which could strongly adsorb on the Lewis acidic sites,and thus cause the catalyst deactivation eventually.After a simple calcination,the coke deposits could be easily removed and the catalytic activity could be well restored.
基金supported by the National Key R&D Program of China (No. 2017YFA0304203)the National Energy R&D Center of Petroleum Refining Technology (RIPP, SINOPEC)+3 种基金Changjiang Scholars and Innovative Research Team at the University of the Ministry of Education of China (No. IRT_17R70)National Natural Science Foundation of China (NSFC) (Nos. 61975103, 61875108 and 627010407)111 Project (No. D18001)Fund for Shanxi (No. 1331KSC)
文摘In the field of dual-pulse laser-induced breakdown spectroscopy(DP-LIBS)research,the pursuit of methods for determining pulse intervals and other parameters quickly and conveniently in order to achieve optimal spectral signal enhancement is paramount.To aid researchers in identification of optimal signal enhancement conditions and more accurate interpretation of the underlying signal enhancement mechanisms,theoretical simulations of the spatiotemporal processes of coaxial DP-LIBS-induced plasma have been established in this work.Using a model based on laser ablation and two-dimensional axisymmetric fluid dynamics,plasma evolutions during aluminum–magnesium alloy laser ablation under single-pulse and coaxial dualpulse excitations have been simulated.The influences of factors,such as delay time,laser fluence,plasma temperature,and particle number density,on the DP-LIBS spectral signals are investigated.Under pulse intervals ranging from 50 to 1500 ns,the time evolutions of spectral line intensity,dual-pulse emission enhancement relative to the single-pulse results,laser irradiance,spatial distribution of plasma temperature and species number density,as well as laser irradiance shielded by plasma have been obtained.The study indicates that the main reason behind the radiation signal enhancement in coaxial DP-LIBS-induced plasma is attributed to the increased species number density and plasma temperature caused by the second laser,and it is inferred that the shielding effect of the plasma mainly occurs in the boundary layer of the stagnation point flow over the target surface.This research provides a theoretical basis for experimental research,parameter optimization,and signal enhancement tracing in DP-LIBS.
基金Project supported by the National Key R&D Program of China (Grant No.2022YFA1204302)the National Natural Science Foundation of China (Grant Nos.52022029,52221001,92263107,U23A20570,62090035,U19A2090,and 12174098)+1 种基金the Hunan Provincial Natural Science Foundation of China (Grant Nos.2022JJ30142 and 2019XK2001)in part supported by the State Key Laboratory of Powder Metallurgy,Central South University。
文摘Transition metal ditellurides(TMTDs)have versatile physical properties,including non-trivial topology,Weyl semimetal states and unique spin texture.Controlled growth of high-quality and large-scale monolayer TMTDs with preferred crystal phases is crucial for their applications.Here,we demonstrate the epitaxial growth of 1T'-MoTe_(2) on Au(111)and graphitized silicon carbide(Gr/SiC)by molecular beam epitaxy(MBE).We investigate the morphology of the grown1T'-MoTe_(2) at the atomic level by scanning tunnelling microscopy(STM)and reveal the corresponding microscopic growth mechanism.It is found that the unique ordered Te structures preferentially deposited on Au(111)regulate the growth of monolayer single crystal 1T'-MoTe_(2),while the Mo clusters were preferentially deposited on the Gr/SiC substrate,which impedes the ordered growth of monolayer MoTe_(2).We confirm that the size of single crystal 1T'-MoTe_(2) grown on Au(111)is nearly two orders of magnitude larger than that on Gr/SiC.By scanning tunnelling spectroscopy(STS),we observe that the STS spectrum of the monolayer 1T'-MoTe_(2) nano-island at the edge is different from that at the interior,which exhibits enhanced conductivity.
基金This study was supported by the National Key Research and Development Program of China(2017YFD0600201)the Central Public Interest Scientific Institution Basal Research Fund(CAFYBB2018GD001,CAFYBB2018ZB001-5).
文摘Air-dry density,modulus of rupture(MOR),modulus of elasticity(MOE),compressive strength parallel to grain,and hardness of Catalpa bungei clones were investigated in this study with feasibility of predicting these properties by near infrared(NIR)spectroscopy.The best candidate Luoqiu 3'has been selected from three clones based on wood physical and mechanical property indices.Lower values of wood physical and mechanical properties have been found in the corewood compared to the outerwood.There were significant positive correlations between the air-dry density and mechanical properties.Information from Cross section for air dry density,compressive strength parallel to grain,and hardness yielded prediction models with better effects,along with the best MOR and MOE modeling effects resulted from average sections'spectra collection.Multiplicative scatter correction(MSC)+Savitzky-Golay(S-G)smoothing method has been proved to be the most applicable way.In addition,the predictions from five point sampling method were slightly better than three point one.Overall,results suggest NIR spectroscopy was viable to predict the physical and mechanical properties of C bungei dones with methods developed in this study proved effective in preliminary screening.
基金Project(50974090)supported by the National Natural Science Foundation of ChinaProjects(JCYJ20140418182819155,JCYJ20130329113849606)supported by the Shenzhen Dedicated Funding of Strategic Emerging Industry Development Program,China
文摘The effects of Fe2O3 content on the microstructure and mechanical properties of the CaO-Al2O3-SiO2 system were investigated by differential thermal analysis(DTA), X-ray diffraction(XRD), scanning electron microscopy(SEM), electron spin resonance(ESR), and Mssbauer spectroscopy. The results show that the addition of Fe2O3 does not affect the main crystalline phase in the prepared glasses, but it reduces the crystallisation peak temperature, increases the crystallisation activation energy, and reduces the crystal granularity. The ESR results indicate that Fe2O3 can promote crystallization, as it leads to the phase separation of the CaO-Al2O3-SiO2 system due to axial distortion. Moreover, Fe2O3 alters the network structure of the CaO-Al2O3-SiO2 system, allowing Fe3+ to enter octahedral sites that exhibit higher symmetry than tetrahedral sites. All of these factors are favourable to increasing the bending strength. The Mssbauer results reveal that there are two types of coordination for both Fe3+ and Fe2+ and the bending strength of the CaO-Al2O3-SiO2 system increases with the amount of six-coordinate Fe3+. The increasing interaction between Fe3+ and Fe2+ can also enhance the bending strength of the CaO-Al2O3-SiO2 system. The microhardness of the CaO-Al2O3-SiO2 system was determined to be HV 896.9 and the bending strength to be 217 MPa under the heat treatment conditions of nucleation temperature of 700 °C and nucleation time of 2 h, crystallization temperature of 910 °C and crystallization time of 3 h.
基金Project supported by the National Major Scientific and Technological Special Project during the Twelfth Five-year Plan Period of China(Grant No.2009ZX02030-1)the National Natural Science Foundation of China(Grant No.51205387)+1 种基金the Support by Science and Technology Commission of Shanghai City,China(Grant No.11nm0500300)the Science and Technology Commission of Shanghai City,China(Grant No.14XD1425300)
文摘Metal Ti and its alloys have been widely utilized in the fields of aviation, medical science, and micro-electromechanical systems, for its excellent specific strength, resistance to corrosion, and biological compatibility. As the application of Ti moves to the micro or nano scale, however, traditional methods of planarization have shown their short slabs.Thus, we introduce the method of chemical mechanical polishing(CMP) to provide a new way for the nano-scale planarization method of Ti alloys. We obtain a mirror-like surface, whose flatness is of nano-scale, via the CMP method. We test the basic mechanical behavior of Ti–6Al–4V(Ti64) in the CMP process, and optimize the composition of CMP slurry.Furthermore, the possible reactions that may take place in the CMP process have been studied by electrochemical methods combined with x-ray photoelectron spectroscopy(XPS). An equivalent circuit has been built to interpret the dynamic of oxidation. Finally, a model has been established to explain the synergy of chemical and mechanical effects in the CMP of Ti–6Al–4V.
文摘Mechanical properties of micro-structured porous silicon film (PS) were studied combining X-ray diffraction with micro-Raman spectroscopy. The micro-structured porous silicon samples with different porosities ranging from 30.7700 to 96.2500 were obtained by chemical etching. Lattice parameters of the samples were measured using X-ray diffraction and its maximal change is up to (1.000.) This lattice mismatch with the bulk silicon substrate may introduce residual stress to the porous film. The residual stress measurement by micro-Raman spectroscopy reveals that the maximum of tensile residual stress has reached GPa level in the porous film. Moreover, the lattice mismatch and its corresponding residual stress are increasing with the porosity of PS, but average (elastic) modulus is about 14.5 GPa, one order of magnitude lower than that of substrate Si. The mechanical properties of PS have a close relation with its micro-pore structure.
文摘Four FeCrNiMnMo_(x)(x=0,0.1,0.3,0.5,in molar ratio)high-entropy alloys(HEAs)were synthesized by vacuum arc melting to explore the potential impact of Mo on the microstructure,mechanical properties,and passivation and electrochemical behaviors in 0.5 M H_(2)SO_(4)solution.The results display that the FeCrNiMn alloy exhibits a single face-centered cubic(FCC)structure while the microstructures of the FeCrNiMnMo_(0.1),FeCrNiMnMo_(0.3),and FeCrNiMnMo_(0.5)alloys consist of the FCC andσphase.The appear of theσphase ascribed to the addition of Mo enhances the hardness and yield strength with the sacrifice of plasticity.The FeCrNiMnMox HEAs achieve the maximum hardness of 414 HV_(0.2)and the highest compressive yield strength of 830 MPa when x=0.5,but compressive fracture strain is lowered to 10.8%.X-ray photoelectron spectroscopy(XPS)and electrochemical analysis show that the passivation film in FeCrNiMnMox alloy mainly consists of chromium oxides and molybdenum oxides.Mo has a beneficial effect on the corrosion resistance of the FeCrNiMnMox HEAs in a 0.5 M H_(2)SO_(4)solution by increasing the corrosion potential(E_(corr))and decreasing the corrosion current density(I_(corr))and passivation current density(I_(pass)).The FeCrNiMnMo_(0.1)alloy shows the best corrosion resistance,mainly due to its passivation film consisting of a large proportion of chromium oxide(Cr_(2)O_(3)).More Mo additions promote the formation of the precipitate ofσphase and the matrix regions depleted Cr and Mo elements adverse to the resistance to preferential localized corrosion.
基金Project supported by the Strategic Priority Research Program of China(Grant No.XDB01010200)the National Natural Science Foundation of China(Grant Nos.61605225,11674337,and 11547035)Natural Science Foundation of Shanghai,China(Grant No.16ZR1448400)
文摘We propose a scheme that can generate tunable double optomechanically induced transparency in a hybrid optomechanical cavity system.In this system, the mechanical resonator of the optomechanical cavity is coupled with an additional mechanical resonator and the additional mechanical resonator can be driven by a weak external coherently mechanical driving field.We show that both the intensity and the phase of the external mechanical driving field can control the propagation of the probe field, including changing the transmission spectrum from double windows to a single-window.Our study also provides an effective way to generate intensity-controllable, narrow-bandwidth transmission spectra, with the probe field modulated from excessive opacity to remarkable amplification.
基金National Natural Science Foundation of China (50571005)
文摘Thermal barrier coatings (TBCs) were developed to protect metallic blades and vanes working in turbo-engines. The two-layered structure TBCs, consisting of NiCoCrAlY bond coat and yttria stabilized zirconia (YSZ), were deposited on a cylinder of superalloy substrate by the electron beam-physical vapor deposition (EB-PVD). The failure mechanism of the TBCs was investigated with a thermo-mechanical fatigue testing system under the service condition similar to that for turbine blades. Non-destructive evaluation of the coated specimens was conducted through the impedance spectroscopy. It is found that the crack initiation mainly takes place on the top coat at the edge of the heated zones.
文摘Cadmium zinc telluride (CdZnTe) semiconductor has applications in the detection of X-rays and gamma-rays at room temperature without having to use a cooling system. Chemical etching and chemo-mechanical polishing are processes used to smoothen CdZnTe wafer during detector device fabrication. These processes reduce surface damages left after polishing the wafers. In this paper, we compare the effects of etching and chemo-mechanical polishing on CdZnTe nuclear detectors, using a solution of hydrogen bromide in hydrogen peroxide and ethylene glycol mixture. X-ray photoelectron spectroscopy (XPS) was used to monitor TeO2 on the wafer surfaces. Current-voltage and detector-response measurements were made to study the electrical properties and energy resolution. XPS results showed that the chemical etching process resulted in the formation of more TeO2 on the detector surfaces compared to chemo-mechanical polishing. The electrical resistivity of the detector is of the order of 1010 Ω-cm. The chemo-mechanical polishing process increased the leakage current more that chemical etching. For freshly treated surfaces, the etching process is more detrimental to the energy resolution compared to chemo-mechanically polishing.
文摘This work is realized in the context of valorizing natural and local resources, in particular, luffa plant fruit (luffa sponge). The raw fibers of the luffa sponge have a short lifetime. Hence, when they are chemically treated, it constitutes a solution is prepared to limit their degradation in the long term and to improve their mechanical characteristics. Therefore, this paper studies the effect of the chemical treatment on the mechanical properties of the luffa sponge’s fibers (fibers of luffa Sponge). The chemical process consists of dipping a brunch of luffa in various concentrations of sodium hydroxide (NaOH) at different time intervals and at different temperature conditions. The luffa sponge’s fibers were mechanical. Characterized before and after the treatment, mechanically (micro traction test). It has been shown that an optimum of 61% increase in mechanical properties (tensile strength) has been reached in the following conditions: treatment with 1% concentration for 90 min at 50°C.