This study demonstrates the electrochemical reduction of carbon monoxide(COR)at high current densities in a zero-gap electrolyzer cell and cell stack.By systematically optimizing both the commercially available membra...This study demonstrates the electrochemical reduction of carbon monoxide(COR)at high current densities in a zero-gap electrolyzer cell and cell stack.By systematically optimizing both the commercially available membrane electrode assembly components(including binder content and gas diffusion layer)and the operating conditions,we could perform COR at current densities up to 1.4 A cm^(-2)with a maximum C2+selectivity of 90%.We demonstrated the scale-up to a 3×100 cm^(2)electrolyzer stack that can sustain stable operation at 1 A cm^(-2)for several hours without significant performance decay and with a total C2+selectivity of~80%and an ethylene selectivity of~40%.We provide critical insights into the holistic optimization of key system parameters,without using special catalysts or surface additives,which can pave the way for scalable and industrially viable COR processes.展开更多
Density(p),speed of sound(u),viscosity(η),and refractive index(n_(D))were measured for pure acetonitrile,trichloroethene,and tetrachloroethene,as well as their binary mixtures at temperatures T=(293.15,298.15,303.15)...Density(p),speed of sound(u),viscosity(η),and refractive index(n_(D))were measured for pure acetonitrile,trichloroethene,and tetrachloroethene,as well as their binary mixtures at temperatures T=(293.15,298.15,303.15)K and at ambient pressure(81.5 kPa).From the experimental data,excess molar volume(V_(m)~E),thermal expansion coefficients(α),deviations in isentropic compressibility(Δκ_(S)),viscosity(Δ_η),and refractive index(Δn_(D))were calculated.These values were then correlated using the Redlich-Kister polynomial equation,with fitting coefficients and standard deviations determined.Additionally,the Prigogine-Flory-Patterson(PFP)theory and the Extended Real Associated Solution(ERAS)model were employed to correlate the excess molar volume,while the Perturbed Chain Statistical Associating Fluid Theory(PC-SAFT)was used to predict the density of mixtures.展开更多
Composite microcrystals of the nitramines(NAs)viz.,RDX,HMX,BCHMX,and CL-20 with electrically conductive polyaniline(PANi)are a charge transfer complexes in coagglomerated composite crystals(CACs).The activation energi...Composite microcrystals of the nitramines(NAs)viz.,RDX,HMX,BCHMX,and CL-20 with electrically conductive polyaniline(PANi)are a charge transfer complexes in coagglomerated composite crystals(CACs).The activation energies of thermolysis,E_(a),of the pure NAs and their PANi-CACs were determined using the Kissinger method,and decomposition processes are discussed.Except for the RDX/PANi CACs,all the other CACs show higher E_(a) values for decomposition compared to their pure NA counterparts.For all CACs,relationships are specified between the E_(a) values,on the one hand,and the squares of the detonation velocities,enthalpies of formation,spark energy and impact sensitivities,on the other.The relationships between their low-temperature heats of decomposition,ΔH,from DSC,and their enthalpy of formation,logarithm of impact sensitivity,electric spark energy,as well as detonation energy,are described.The PANi favorably influences the density of the corresponding CACs;surprisingly close linear correlations were found,and explained,between these densities and the E_(a) values.This presence of PANi strongly increased the electrical spark sensitivity of the CACs in comparison to the base NAs.Based on the results obtained,it can be noted in particular the exceptional desensitization of HMX to impact and the increased sensitivity to electrical spark by coating its crystals with polyaniline.展开更多
The development of actuators based on ionic polymers as soft robotics,artificial muscles,and sensors is currently considered one of the most urgent topics.They are lightweight materials,in addition to their high effic...The development of actuators based on ionic polymers as soft robotics,artificial muscles,and sensors is currently considered one of the most urgent topics.They are lightweight materials,in addition to their high efficiency,and they can be controlled by a low power source.Nevertheless,the most popular ionic polymers are derived from fossil-based resources.Hence,it is now deemed crucial to produce these actuators using sustainable materials.In this review,the use of ionic polymeric materials as actuators is reviewed through the emphasis on their role in the domain of renewablematerials.The reviewencompasses recent advancements inmaterial formulation and performance enhancement,alongside a comparative analysis with conventional actuator systems.It was found that renewable polymeric actuators based on ionic gels and conductive polymers are easier to prepare compared to ionic polymermetal composites.In addition,the proportion of actuator manufacturing utilizing renewable materials rose to 90%,particularly for ion gel actuators,which was related to the possibility of using renewable polymers as ionic or conductive substances.Moreover,the possible improvements in biopolymeric actuators will experience an annual rise of at least 10%over the next decade,correlating with the growth of their market,which aligns with the worldwide goal of reducing global warming.Additionally,compared to fossil-derived polymers,the decomposition rate of renewable materials reaches 100%,while biodegradable fossil-based substances can exceed 60%within several weeks.Ultimately,this review aims to elucidate the potential of ionic polymeric materials as a viable and sustainable solution for future actuator technologies.展开更多
Kinetics of the gas-phase reactions of•OH radicals with a series of fluoroesters were studied for the first time at 298±3 K and atmospheric pressure.Relative rate coefficients were determined by in situ FTIR spec...Kinetics of the gas-phase reactions of•OH radicals with a series of fluoroesters were studied for the first time at 298±3 K and atmospheric pressure.Relative rate coefficients were determined by in situ FTIR spectroscopy in nitrogen and GC-FID in air to monitor the decay of reactants and references.The following coefficient values(in 10^(−12)cm^(3)/(molecule•sec))were obtained for ethyl fluoroacetate(EFA),ethyl 4,4,4-trifluorobutyrate(ETB),and butyl fluoroacetate(BFA),respectively:k_(1)(EFA+OH)=1.15±0.25 by FTIR and 1.34±0.23 by GC-FID;k_(2)(ETB+OH)=1.61±0.36 by FTIR and 2.02±0.30 by GC-FID;k_(3)(BFA+OH)=2.24±0.37 by FTIR.Reactivity trends were developed and correlated with the number of CH_(3)and F substituents in the fluoroester,and structure-activity relationships(SARs)calculations were performed.In addition,the tropospheric lifetimes of EFA,ETB,and BFA upon degradation by OH radicals were calculated to be 9,6,and 5 days,respectively,indicating that these fluorinated compounds could have a possible regional effect from the emission source.Relatively small photochemical ozone creation potentials of 9,7,and 19 were estimated for EFA,ETB,and BFA,respectively.The GlobalWarming Potentials(GWPs)for EFA,ETB,and BFA were calculated for different time horizons.For a 20-year time horizon,the GWPs were 1.393,0.063,and 0.062,respectively.In the case of a 100-year time horizon,the GWPs were 0.379,0.017,and 0.017,and for a 500-year time horizon,the GWPs were 0.108,0.005,and 0.005 for EFA,ETB,and BFA.展开更多
The selection of carbon sources and the biosynthesis of polyhydroxybutyrate(PHB)by the Azotobacter vinelandii N-15 strain using renewable raw materials were investigated.Among the tested substrates(starch,sucrose,mola...The selection of carbon sources and the biosynthesis of polyhydroxybutyrate(PHB)by the Azotobacter vinelandii N-15 strain using renewable raw materials were investigated.Among the tested substrates(starch,sucrose,molasses,bran),molasses as the carbon source yielded the highest PHB production.The maximum polymer yield(26%of dry biomass)was achieved at a molasses concentration of 40 g/L.PHB formation was confirmed via thinlayer chromatography,gas chromatography and Fourier transform infrared spectroscopy.Composite films based on PHB,polylactic acid(PLA),and their blends were fabricated using the solvent casting.The biodegradation of these films was studied with bacteria isolated from plastic-contaminated soil.These bacteria utilized the biopolymers as their sole carbon source,with the biodegradation process lasting three months.Structural and chemical changes in the films were analyzed using FTIR spectroscopy,differential scanning calorimetry,and thermogravimetry.Among the microorganisms used to study the biodegradation of PHB,PLA,and their blends,Streptomyces sp.K2 and Streptomyces sp.K4 exhibited the highest biodegradation efficiency.PHB-containing films demonstrated significant advantages over other biodegradable polymers,as they degrade under aerobic conditions via enzymatic hydrolysis using microbial depolymerases.展开更多
As a promising optical and piezoelectric crystal,efficient growth of LGN single crystal is crucial for its practical applications.Herein,a langanite(La_(3)Ga_(5.5)Nb_(0.5)O_(14),LGN)crystal with high quality was succe...As a promising optical and piezoelectric crystal,efficient growth of LGN single crystal is crucial for its practical applications.Herein,a langanite(La_(3)Ga_(5.5)Nb_(0.5)O_(14),LGN)crystal with high quality was successfully grown by the Bridgman method along the Z direction.In order to prepare high-purity polycrystalline precursors for LGN crystal growth,the sintering conditions of LGN polycrystalline precursors were studied in detail.The melting point of LGN was also measured to provide a reference for the crystal growth temperature.For the[001]oriented wafer,the full width at half maximum(EWHM)value of the nigh-resolution X-ray diffraction(HRXRD)analysis is 38.52",demonstrating that the LGN crystal exhibits excellent crystalline quality.In addition,we also measured the thermal properties and transmission spectrum of the as-grown LGN crystal.It is found that the absorption peak at 1.85μm of the LGN crystal grown in air using the Bridgman method disappears compared with previous reports(grown in N_(2+)(1-3)vol%O_(2)atmosphere),which is attributed to the oxygen-enriched growth environment.Similar phenomenon also occurs in other LGS-type disordered crystals.It is believed that these findings may expand the potential applications of LGS series crystals at 1.85μm.展开更多
Hydrophilicity is critical in Nafion membranes during fuel cell operation as insufficient membrane hydration leads to brittle behavior and a drop in proton conductivity.The incorporation of APTS(3-(aminopro pyl)trieth...Hydrophilicity is critical in Nafion membranes during fuel cell operation as insufficient membrane hydration leads to brittle behavior and a drop in proton conductivity.The incorporation of APTS(3-(aminopro pyl)triethoxysilane)into exfoliated graphene oxide(EGO)by covalent functionalization to be used as filler into Nafion membranes allows higher hydrophilicity for these membranes.This is associated with promoting hydroxyl,carbonyl,siloxane,silane,and amine groups within the EGO-APTS matrix.The incorporation of these materials as Fuel Cell MEAs leads to a significant reduction of the ohmic resistance measured at high frequency resistance(HFR)in electrochemical impedance spectroscopy(EIS)experiments and achieves maximum power densities of 1.33 W cm^(-2)at 60℃ at 100%RH(APTS-EGO,0.2 wt%)and1.33 W cm^(-2)at 60℃ at 70%RH(APTS-EGO,0.3 wt%),which represents an improvement of 190%compared to the commercial Nafion 212 when utilizing low humidification conditions(70%).Moreover,the as-synthesized membrane utilizes lower Nafion ionomer mass,which,in conjunction with the excellent cell performance,has the potential to decrease the cost of the membrane from 87 to 80￡/W as well as a reduction of fluorinated compounds within the membrane.展开更多
The therapeutic efficacy of cuproptosis,ferroptosis,and apoptosis is hindered by inadequate intracellular copper and iron levels,hypoxia,and elevated glutathione(GSH)expression in tumor cells.Thermoelectric technology...The therapeutic efficacy of cuproptosis,ferroptosis,and apoptosis is hindered by inadequate intracellular copper and iron levels,hypoxia,and elevated glutathione(GSH)expression in tumor cells.Thermoelectric technology is an emerging frontier in medical therapy that aims to achieve efficient thermal and electrical transport characteristics within a narrow thermal range for biological systems.Here,we systematically constructed biodegradable Cu_(2)MnS_(3-x)-PEG/glucose oxidase(MCPG)with sulfur vacancies(S_(V))using photothermoelectric catalysis(PTEC),photothermal-enhanced enzyme catalysis,and starvation therapy.This triggers GSH consumption and disrupts intracellular redox homeostasis,leading to immunogenic cell death.Under 1064 nm laser irradiation,MCPG enriched with S_(V),owing to doping,generates a local temperature gradient that activates PTEC and produces toxic reactive oxygen species(ROS).Hydroxyl radicals and oxygen are generated through peroxide and catalase-like processes.Increased oxygen levels alleviate tumor hypoxia,whereas hydrogen peroxide production from glycometabolism provides sufficient ROS for a cascade catalytic reaction,establishing a self-reinforcing positive mechanism.Density functional theory calculations demonstrated that vacancy defects effectively enhanced enzyme catalytic activity.Multimodal imaging-guided synergistic therapy not only damages tumor cells,but also elicits an antitumor immune response to inhibit tumor metastasis.This study offers novel insights into the cuproptosis/ferroptosis/apoptosis pathways of Cu-based PTEC nanozymes.展开更多
A silver microelectrode with a diameter of 30μm in an aqueous K_(2)SO_(4) electrolyte was irradiated with 55 fs and 213 fs laser pulses.This caused the emission of electrons which transiently charged the electrochemi...A silver microelectrode with a diameter of 30μm in an aqueous K_(2)SO_(4) electrolyte was irradiated with 55 fs and 213 fs laser pulses.This caused the emission of electrons which transiently charged the electrochemical double layer.The two applied pulse durations were significantly shorter than the electron-phonon relaxation time.The laser pulse durations had negligible impact on the emitted charge,which is incompatible with multiphoton emission.On the other hand,the ob-served dependence of emitted charge on laser fluence and electrode potential supports the thermionic emission mechanism.展开更多
Salt stress is one of the most harmful environmental stresses in recent times and represents a significant threat to food security. Soil salinization is caused by spontaneous natural processes of mineral dissolution a...Salt stress is one of the most harmful environmental stresses in recent times and represents a significant threat to food security. Soil salinization is caused by spontaneous natural processes of mineral dissolution and human activities such as inappropriate irrigation practices. Natural geological progressions like weathering of rocks, arid climate, and higher evaporation, as well as anthropogenic activities, including the use of brackish water for irrigation, and poor tillage operations, are the foremost causes of soil salinization. Typical characteristics of saline soils are salt stress, high pH, and lack of organic carbon, as well as low availability of nutrients. Disruption of precipitation patterns as well as high average annual temperatures due to climate change additionally negatively affects the process of soil salinization. Productivity and ability to support crop growth are reduced on saline soil. Salinity-induced stress reduces plant growth by modulating the antioxidative system and nutrient orchestration. The aim of this work is to show that the mentioned problems can be alleviated in several ways such as the addition of biochar, exogenous application of several elicitors, seed priming, etc. Research has shown that the addition of biochar can significantly improve the recovery of saline soil. The addition of biochar has no significant effect on soil pH, while the cation exchange capacity of the soil increased by 17%, and the electrical conductivity of the saturated paste extract decreased by 13.2% (depends on the initial salinity and the type of biochar raw material). Moreover, biochar enriched with silicon increases the resistance of bananas to salt stress. In addition, exogenous application of several elicitors helps plants to alleviate stress by inducing stress-related physicochemical and molecular changes (selenium, sulfur, silicon, salicylic acid). Finally, seed priming showed positive effects on metabolomics, proteomics and growth of plants subjected to abiotic stress. Priming usually involves immersing the seed in a solution for a period of time to induce physiological and metabolic progression prior to germination.展开更多
The electric field-induced irreversible domain wall motion results in a ferroelectric(FE) hysteresis. In antiferroelectrics(AFEs), the irreversible phase transition is the main reason for the hysteresis effects, which...The electric field-induced irreversible domain wall motion results in a ferroelectric(FE) hysteresis. In antiferroelectrics(AFEs), the irreversible phase transition is the main reason for the hysteresis effects, which plays an important role in energy storage performance. Compared to the well-demonstrated FE hysteresis,the structural mechanism of the hysteresis in AFE is not well understood. In this work, the underlying correlation between structure and the hysteresis effect is unveiled in Pb(Zr,Sn,Ti)O_(3) AFE system by using in-situ electrical biasing synchrotron X-ray diffraction. It is found that the AFE with a canting dipole configuration, which shows a continuous polarization rotation under the electric field, tends to have a small hysteresis effect. It presents a negligible phase transition, a small axis ratio, and electric field-induced lattice changing, small domain switching. All these features together lead to a slim hysteresis loop and a high energy storage efficiency. These results offer a deep insight into the structure-hysteresis relationship of AFEs and are helpful for the design of energy storage material.展开更多
Microplastics are persistent anthropogenic pollutants that have become a global concern due to their widespread distribution and unfamiliar threat to the environment and living organisms. Conventional technologies are...Microplastics are persistent anthropogenic pollutants that have become a global concern due to their widespread distribution and unfamiliar threat to the environment and living organisms. Conventional technologies are unable to fully decompose and mineralize plastic waste. Therefore, there is a need to develop an environmentally friendly, innovative and sustainable photocatalytic process that can destroy these wastes with much less energy and chemical consumption. In photocatalysis, various nanomaterials based on wide energy band gap semiconductors such as TiO2 and ZnO are used for the conversion of plastic contaminants into environmentally friendly compounds. In this work, the removal of plastic fragments by photocatalytic reactions using newly developed photocatalytic composites and the mechanism of photocatalytic degradation of microplastics are systematically investigated. In these degradation processes, sunlight or an artificial light source is used to activate the photocatalyst in the presence of oxygen.展开更多
To avoid carbonate precipitation for CO_(2) electrolysis,developing CO_(2) conversion in an acid electrolyte is viewed as an ultimately challenging technology.In Nature,Xia et al.recently explored a proton-exchange me...To avoid carbonate precipitation for CO_(2) electrolysis,developing CO_(2) conversion in an acid electrolyte is viewed as an ultimately challenging technology.In Nature,Xia et al.recently explored a proton-exchange membrane system for reducing CO_(2) to formic acid with a Pb±Pb SO_(4) composite catalyst derived from waste lead-acid batteries based on the lattice carbon activation mechanism.Up to 93%Faradaic efficiency was realized when formic acid was produced by this technology.展开更多
The selective oxidative esterification of aldehydes with alcohols to the corresponding esters has been one of the hot spots in scientific research and industrial synthesis.However,the application of precious metal cat...The selective oxidative esterification of aldehydes with alcohols to the corresponding esters has been one of the hot spots in scientific research and industrial synthesis.However,the application of precious metal catalytic systems is limited by their complicated synthetic steps and high cost.Thus a highly efficient,green,recyclable selective synthesis method of esters catalyzed by polyoxovanadate(POV)-based molecu-lar catalysts has been developed in this paper.The results show that supramolecular interaction between POV and 1,3-dibenzylimidazolium bromide(Act_(2)Im)can efficiently convert alcohols and aldehydes to the corresponding esters in high yield under much milder conditions.Mechanistic insight is also provided based on the control experiments,single crystal X-ray diffraction and cyclic voltammetry studies.展开更多
Relaxor ferroic dielectrics have garnered increasing attention in the past decade as promising materials for energy storage.Among them,relaxor antiferroelectrics(AFEs)and relaxor ferroelectrics(FEs)have shown great pr...Relaxor ferroic dielectrics have garnered increasing attention in the past decade as promising materials for energy storage.Among them,relaxor antiferroelectrics(AFEs)and relaxor ferroelectrics(FEs)have shown great promise in term of high energy storage density and efficiency,respectively.In this study,a unique phase transition from relaxor AFE to relaxor FE was achieved for the first time by introducing strong-ferroelectricity BaTiO_(3)into NaNbO_(3)-BiFeO_(3)system,leading to an evolution from AFE R hierarchical nanodomains to FE polar nanoregions.A novel medium state,consisting of relaxor AFE and relaxor FE,was identified in the crossover of 0.88NaNbO_(3)–0.07BiFeO_(3)–0.05BaTiO_(3)ceramic,exhibiting a distinctive core-shell grain structure due to the composition segregation.By harnessing the advantages of high energy storage density from relaxor AFE and large efficiency from relaxor FE,the ceramic showcased excellent overall energy storage properties.It achieved a substantial recoverable energy storage density W_(rec)~13.1 J/cm^(3)and an ultrahigh efficiencyη~88.9%.These remarkable values shattered the trade-off relationship typically observed in most dielectric capacitors between W_(rec)andη.The findings of this study provide valuable insights for the design of ceramic capacitors with enhanced performance,specifically targeting the development of next generation pulse power devices.展开更多
Green synthesis of silver nanoparticles (AgNPs) using aqueous extracts of orange and lemon peels, as a reducing agent, and silver nitrate salts as a source of silver ions is a promising field of research due to the ve...Green synthesis of silver nanoparticles (AgNPs) using aqueous extracts of orange and lemon peels, as a reducing agent, and silver nitrate salts as a source of silver ions is a promising field of research due to the versatility of biomedical applications of metal nanoparticles. In this paper, AgNPs were synthetized at different reaction parameters such as the type and concentration of the extracts, metal salt concentration, temperature, speed stirring, and pH. The antibacterial properties of the obtained silver nanoparticles against E. coli, as well as the physical and chemical characteristics of the synthesized silver nanoparticles, were investigated. UV-Vis spectroscopy was used to confirm the formation of AgNPs. In addition to green biogenic synthesis, chemical synthesis of silver nanoparticles was also carried out. The optimal temperature for extraction was 65˚C, while for the synthesis of AgNPs was 35˚C. The synthesis is carried out in an acidic environment (pH = 4.7 orange and pH = 3.8 lemon), neutral (pH = 7) and alkaline (pH = 10), then for different concentrations of silver nitrate solution (0.5 mM - 1 mM), optimal time duration of the reaction was 60 min and optimal stirring speed rotation was 250 rpm on the magnetic stirrer. The physical properties of the synthesized silver nanoparticles (conductivity, density and refractive index) were also studied, and the passage of laser light through the obtained solution and distilled water was compared. Positive inhibitory effect on the growth of new Escherichia coli colonies have shown AgNPs synthesized at a basic pH value and at a 0.1 mM AgNO<sub>3</sub> using orange or lemon peel extract, while for a 0.5 mM AgNO<sub>3 </sub>using lemon peel extract.展开更多
A new nanothermite system,composed of titanium and tungsten trioxide is reported.Initial investigations show that it has low-average sensitivity to mechanical stimuli(friction,impact),but that its sensitivity to laser...A new nanothermite system,composed of titanium and tungsten trioxide is reported.Initial investigations show that it has low-average sensitivity to mechanical stimuli(friction,impact),but that its sensitivity to laser irradiation can be controlled in a moderately wide range.The combustion of this nanothermite system takes place at a very high apparent temperature(>3695 K)and it follows the key predictions of the established reactive sintering mechanism,as supported by SEM-EDS and XRD analyses.展开更多
The extensive research and development in perovskite solar cells (PSCs) have rekindled the hopes of converting solar energy into electricity.An elusive understanding of underlying mechanisms is required for the develo...The extensive research and development in perovskite solar cells (PSCs) have rekindled the hopes of converting solar energy into electricity.An elusive understanding of underlying mechanisms is required for the development of efficient PSCs.Over the years,Impedance Spectroscopy (IS) characterization,along with complementary techniques,has proven to be an effective way to understand and analyze the charge transport and recombination at interface and bulk of PSCs.The IS of PSCs have been analyzed,interpreted,and improvised continuously,revealing intricate details about the work.However,there is a lack of centralized source of these details,which make it tougher to account for the generalized approach to understand the device properties.The present work is focused on compiling the research done on various PSC device architectures via IS to construct a comprehensive foundation of information on impedance plots,equivalent circuits,and associated processes.展开更多
基金Nemzeti Kutatási Fejlesztésiés Innovációs Hivatal,Grant/Award Number:RRF-2.3.1-21-2022-00009Horizon 2020 Framework Programme,Grant/Award Number:862453。
文摘This study demonstrates the electrochemical reduction of carbon monoxide(COR)at high current densities in a zero-gap electrolyzer cell and cell stack.By systematically optimizing both the commercially available membrane electrode assembly components(including binder content and gas diffusion layer)and the operating conditions,we could perform COR at current densities up to 1.4 A cm^(-2)with a maximum C2+selectivity of 90%.We demonstrated the scale-up to a 3×100 cm^(2)electrolyzer stack that can sustain stable operation at 1 A cm^(-2)for several hours without significant performance decay and with a total C2+selectivity of~80%and an ethylene selectivity of~40%.We provide critical insights into the holistic optimization of key system parameters,without using special catalysts or surface additives,which can pave the way for scalable and industrially viable COR processes.
基金Bu-Ali Sina University for providing financial support for conducting this study。
文摘Density(p),speed of sound(u),viscosity(η),and refractive index(n_(D))were measured for pure acetonitrile,trichloroethene,and tetrachloroethene,as well as their binary mixtures at temperatures T=(293.15,298.15,303.15)K and at ambient pressure(81.5 kPa).From the experimental data,excess molar volume(V_(m)~E),thermal expansion coefficients(α),deviations in isentropic compressibility(Δκ_(S)),viscosity(Δ_η),and refractive index(Δn_(D))were calculated.These values were then correlated using the Redlich-Kister polynomial equation,with fitting coefficients and standard deviations determined.Additionally,the Prigogine-Flory-Patterson(PFP)theory and the Extended Real Associated Solution(ERAS)model were employed to correlate the excess molar volume,while the Perturbed Chain Statistical Associating Fluid Theory(PC-SAFT)was used to predict the density of mixtures.
基金funding from the Student Grant Project no.SGS_2022_003 of the Faculty of Chemical Technology at the University of Pardubice Czechia.
文摘Composite microcrystals of the nitramines(NAs)viz.,RDX,HMX,BCHMX,and CL-20 with electrically conductive polyaniline(PANi)are a charge transfer complexes in coagglomerated composite crystals(CACs).The activation energies of thermolysis,E_(a),of the pure NAs and their PANi-CACs were determined using the Kissinger method,and decomposition processes are discussed.Except for the RDX/PANi CACs,all the other CACs show higher E_(a) values for decomposition compared to their pure NA counterparts.For all CACs,relationships are specified between the E_(a) values,on the one hand,and the squares of the detonation velocities,enthalpies of formation,spark energy and impact sensitivities,on the other.The relationships between their low-temperature heats of decomposition,ΔH,from DSC,and their enthalpy of formation,logarithm of impact sensitivity,electric spark energy,as well as detonation energy,are described.The PANi favorably influences the density of the corresponding CACs;surprisingly close linear correlations were found,and explained,between these densities and the E_(a) values.This presence of PANi strongly increased the electrical spark sensitivity of the CACs in comparison to the base NAs.Based on the results obtained,it can be noted in particular the exceptional desensitization of HMX to impact and the increased sensitivity to electrical spark by coating its crystals with polyaniline.
基金funded by the Russian Science Foundation(RSF),grantNo.24-23-00558,https://rscf.ru/en/project/24-23-00558/(accessed on 04 February 2025).
文摘The development of actuators based on ionic polymers as soft robotics,artificial muscles,and sensors is currently considered one of the most urgent topics.They are lightweight materials,in addition to their high efficiency,and they can be controlled by a low power source.Nevertheless,the most popular ionic polymers are derived from fossil-based resources.Hence,it is now deemed crucial to produce these actuators using sustainable materials.In this review,the use of ionic polymeric materials as actuators is reviewed through the emphasis on their role in the domain of renewablematerials.The reviewencompasses recent advancements inmaterial formulation and performance enhancement,alongside a comparative analysis with conventional actuator systems.It was found that renewable polymeric actuators based on ionic gels and conductive polymers are easier to prepare compared to ionic polymermetal composites.In addition,the proportion of actuator manufacturing utilizing renewable materials rose to 90%,particularly for ion gel actuators,which was related to the possibility of using renewable polymers as ionic or conductive substances.Moreover,the possible improvements in biopolymeric actuators will experience an annual rise of at least 10%over the next decade,correlating with the growth of their market,which aligns with the worldwide goal of reducing global warming.Additionally,compared to fossil-derived polymers,the decomposition rate of renewable materials reaches 100%,while biodegradable fossil-based substances can exceed 60%within several weeks.Ultimately,this review aims to elucidate the potential of ionic polymeric materials as a viable and sustainable solution for future actuator technologies.
文摘Kinetics of the gas-phase reactions of•OH radicals with a series of fluoroesters were studied for the first time at 298±3 K and atmospheric pressure.Relative rate coefficients were determined by in situ FTIR spectroscopy in nitrogen and GC-FID in air to monitor the decay of reactants and references.The following coefficient values(in 10^(−12)cm^(3)/(molecule•sec))were obtained for ethyl fluoroacetate(EFA),ethyl 4,4,4-trifluorobutyrate(ETB),and butyl fluoroacetate(BFA),respectively:k_(1)(EFA+OH)=1.15±0.25 by FTIR and 1.34±0.23 by GC-FID;k_(2)(ETB+OH)=1.61±0.36 by FTIR and 2.02±0.30 by GC-FID;k_(3)(BFA+OH)=2.24±0.37 by FTIR.Reactivity trends were developed and correlated with the number of CH_(3)and F substituents in the fluoroester,and structure-activity relationships(SARs)calculations were performed.In addition,the tropospheric lifetimes of EFA,ETB,and BFA upon degradation by OH radicals were calculated to be 9,6,and 5 days,respectively,indicating that these fluorinated compounds could have a possible regional effect from the emission source.Relatively small photochemical ozone creation potentials of 9,7,and 19 were estimated for EFA,ETB,and BFA,respectively.The GlobalWarming Potentials(GWPs)for EFA,ETB,and BFA were calculated for different time horizons.For a 20-year time horizon,the GWPs were 1.393,0.063,and 0.062,respectively.In the case of a 100-year time horizon,the GWPs were 0.379,0.017,and 0.017,and for a 500-year time horizon,the GWPs were 0.108,0.005,and 0.005 for EFA,ETB,and BFA.
基金financial support of this paper by the Ministry of Education and Science of Ukraine under grant(Biotherm/0124U000789).
文摘The selection of carbon sources and the biosynthesis of polyhydroxybutyrate(PHB)by the Azotobacter vinelandii N-15 strain using renewable raw materials were investigated.Among the tested substrates(starch,sucrose,molasses,bran),molasses as the carbon source yielded the highest PHB production.The maximum polymer yield(26%of dry biomass)was achieved at a molasses concentration of 40 g/L.PHB formation was confirmed via thinlayer chromatography,gas chromatography and Fourier transform infrared spectroscopy.Composite films based on PHB,polylactic acid(PLA),and their blends were fabricated using the solvent casting.The biodegradation of these films was studied with bacteria isolated from plastic-contaminated soil.These bacteria utilized the biopolymers as their sole carbon source,with the biodegradation process lasting three months.Structural and chemical changes in the films were analyzed using FTIR spectroscopy,differential scanning calorimetry,and thermogravimetry.Among the microorganisms used to study the biodegradation of PHB,PLA,and their blends,Streptomyces sp.K2 and Streptomyces sp.K4 exhibited the highest biodegradation efficiency.PHB-containing films demonstrated significant advantages over other biodegradable polymers,as they degrade under aerobic conditions via enzymatic hydrolysis using microbial depolymerases.
基金Project supported by the National Key R&D Program of China(2022YFB3204000)National Natural Science Foundation of China(51832009)。
文摘As a promising optical and piezoelectric crystal,efficient growth of LGN single crystal is crucial for its practical applications.Herein,a langanite(La_(3)Ga_(5.5)Nb_(0.5)O_(14),LGN)crystal with high quality was successfully grown by the Bridgman method along the Z direction.In order to prepare high-purity polycrystalline precursors for LGN crystal growth,the sintering conditions of LGN polycrystalline precursors were studied in detail.The melting point of LGN was also measured to provide a reference for the crystal growth temperature.For the[001]oriented wafer,the full width at half maximum(EWHM)value of the nigh-resolution X-ray diffraction(HRXRD)analysis is 38.52",demonstrating that the LGN crystal exhibits excellent crystalline quality.In addition,we also measured the thermal properties and transmission spectrum of the as-grown LGN crystal.It is found that the absorption peak at 1.85μm of the LGN crystal grown in air using the Bridgman method disappears compared with previous reports(grown in N_(2+)(1-3)vol%O_(2)atmosphere),which is attributed to the oxygen-enriched growth environment.Similar phenomenon also occurs in other LGS-type disordered crystals.It is believed that these findings may expand the potential applications of LGS series crystals at 1.85μm.
基金financially supported by the UK Research Council EPRSC EP/W03395X/1the Program grant SynHiSel EP/V047078/1the Hydrogen and Fuel Cells Hub(H_(2)FC SUPERGEN)EP/P024807/1。
文摘Hydrophilicity is critical in Nafion membranes during fuel cell operation as insufficient membrane hydration leads to brittle behavior and a drop in proton conductivity.The incorporation of APTS(3-(aminopro pyl)triethoxysilane)into exfoliated graphene oxide(EGO)by covalent functionalization to be used as filler into Nafion membranes allows higher hydrophilicity for these membranes.This is associated with promoting hydroxyl,carbonyl,siloxane,silane,and amine groups within the EGO-APTS matrix.The incorporation of these materials as Fuel Cell MEAs leads to a significant reduction of the ohmic resistance measured at high frequency resistance(HFR)in electrochemical impedance spectroscopy(EIS)experiments and achieves maximum power densities of 1.33 W cm^(-2)at 60℃ at 100%RH(APTS-EGO,0.2 wt%)and1.33 W cm^(-2)at 60℃ at 70%RH(APTS-EGO,0.3 wt%),which represents an improvement of 190%compared to the commercial Nafion 212 when utilizing low humidification conditions(70%).Moreover,the as-synthesized membrane utilizes lower Nafion ionomer mass,which,in conjunction with the excellent cell performance,has the potential to decrease the cost of the membrane from 87 to 80￡/W as well as a reduction of fluorinated compounds within the membrane.
基金supported by the National Natural Science Foundation of China(NSFC 52002091,U22A20347,and 52102344)Heilongjiang Natural Science Foundation Project of Outstanding Youth Project(YQ2023B005)+1 种基金China Postdoctoral Science Foundation(2023T160154)the Fundamental Research Funds for the Central Universities。
文摘The therapeutic efficacy of cuproptosis,ferroptosis,and apoptosis is hindered by inadequate intracellular copper and iron levels,hypoxia,and elevated glutathione(GSH)expression in tumor cells.Thermoelectric technology is an emerging frontier in medical therapy that aims to achieve efficient thermal and electrical transport characteristics within a narrow thermal range for biological systems.Here,we systematically constructed biodegradable Cu_(2)MnS_(3-x)-PEG/glucose oxidase(MCPG)with sulfur vacancies(S_(V))using photothermoelectric catalysis(PTEC),photothermal-enhanced enzyme catalysis,and starvation therapy.This triggers GSH consumption and disrupts intracellular redox homeostasis,leading to immunogenic cell death.Under 1064 nm laser irradiation,MCPG enriched with S_(V),owing to doping,generates a local temperature gradient that activates PTEC and produces toxic reactive oxygen species(ROS).Hydroxyl radicals and oxygen are generated through peroxide and catalase-like processes.Increased oxygen levels alleviate tumor hypoxia,whereas hydrogen peroxide production from glycometabolism provides sufficient ROS for a cascade catalytic reaction,establishing a self-reinforcing positive mechanism.Density functional theory calculations demonstrated that vacancy defects effectively enhanced enzyme catalytic activity.Multimodal imaging-guided synergistic therapy not only damages tumor cells,but also elicits an antitumor immune response to inhibit tumor metastasis.This study offers novel insights into the cuproptosis/ferroptosis/apoptosis pathways of Cu-based PTEC nanozymes.
文摘A silver microelectrode with a diameter of 30μm in an aqueous K_(2)SO_(4) electrolyte was irradiated with 55 fs and 213 fs laser pulses.This caused the emission of electrons which transiently charged the electrochemical double layer.The two applied pulse durations were significantly shorter than the electron-phonon relaxation time.The laser pulse durations had negligible impact on the emitted charge,which is incompatible with multiphoton emission.On the other hand,the ob-served dependence of emitted charge on laser fluence and electrode potential supports the thermionic emission mechanism.
文摘Salt stress is one of the most harmful environmental stresses in recent times and represents a significant threat to food security. Soil salinization is caused by spontaneous natural processes of mineral dissolution and human activities such as inappropriate irrigation practices. Natural geological progressions like weathering of rocks, arid climate, and higher evaporation, as well as anthropogenic activities, including the use of brackish water for irrigation, and poor tillage operations, are the foremost causes of soil salinization. Typical characteristics of saline soils are salt stress, high pH, and lack of organic carbon, as well as low availability of nutrients. Disruption of precipitation patterns as well as high average annual temperatures due to climate change additionally negatively affects the process of soil salinization. Productivity and ability to support crop growth are reduced on saline soil. Salinity-induced stress reduces plant growth by modulating the antioxidative system and nutrient orchestration. The aim of this work is to show that the mentioned problems can be alleviated in several ways such as the addition of biochar, exogenous application of several elicitors, seed priming, etc. Research has shown that the addition of biochar can significantly improve the recovery of saline soil. The addition of biochar has no significant effect on soil pH, while the cation exchange capacity of the soil increased by 17%, and the electrical conductivity of the saturated paste extract decreased by 13.2% (depends on the initial salinity and the type of biochar raw material). Moreover, biochar enriched with silicon increases the resistance of bananas to salt stress. In addition, exogenous application of several elicitors helps plants to alleviate stress by inducing stress-related physicochemical and molecular changes (selenium, sulfur, silicon, salicylic acid). Finally, seed priming showed positive effects on metabolomics, proteomics and growth of plants subjected to abiotic stress. Priming usually involves immersing the seed in a solution for a period of time to induce physiological and metabolic progression prior to germination.
基金supported by the National Natural Science Foundation of China (Nos.22235002, 21825102 and 12004032)the Advanced Photon Source at Argonne National Laboratory was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No.DEAC02–06CH11357。
文摘The electric field-induced irreversible domain wall motion results in a ferroelectric(FE) hysteresis. In antiferroelectrics(AFEs), the irreversible phase transition is the main reason for the hysteresis effects, which plays an important role in energy storage performance. Compared to the well-demonstrated FE hysteresis,the structural mechanism of the hysteresis in AFE is not well understood. In this work, the underlying correlation between structure and the hysteresis effect is unveiled in Pb(Zr,Sn,Ti)O_(3) AFE system by using in-situ electrical biasing synchrotron X-ray diffraction. It is found that the AFE with a canting dipole configuration, which shows a continuous polarization rotation under the electric field, tends to have a small hysteresis effect. It presents a negligible phase transition, a small axis ratio, and electric field-induced lattice changing, small domain switching. All these features together lead to a slim hysteresis loop and a high energy storage efficiency. These results offer a deep insight into the structure-hysteresis relationship of AFEs and are helpful for the design of energy storage material.
文摘Microplastics are persistent anthropogenic pollutants that have become a global concern due to their widespread distribution and unfamiliar threat to the environment and living organisms. Conventional technologies are unable to fully decompose and mineralize plastic waste. Therefore, there is a need to develop an environmentally friendly, innovative and sustainable photocatalytic process that can destroy these wastes with much less energy and chemical consumption. In photocatalysis, various nanomaterials based on wide energy band gap semiconductors such as TiO2 and ZnO are used for the conversion of plastic contaminants into environmentally friendly compounds. In this work, the removal of plastic fragments by photocatalytic reactions using newly developed photocatalytic composites and the mechanism of photocatalytic degradation of microplastics are systematically investigated. In these degradation processes, sunlight or an artificial light source is used to activate the photocatalyst in the presence of oxygen.
基金supported by the Natural Science Foundation of China (No. 22268003)。
文摘To avoid carbonate precipitation for CO_(2) electrolysis,developing CO_(2) conversion in an acid electrolyte is viewed as an ultimately challenging technology.In Nature,Xia et al.recently explored a proton-exchange membrane system for reducing CO_(2) to formic acid with a Pb±Pb SO_(4) composite catalyst derived from waste lead-acid batteries based on the lattice carbon activation mechanism.Up to 93%Faradaic efficiency was realized when formic acid was produced by this technology.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.22371158,21801153,21225103)2021-2023 Intergovernmental S&T Cooperation Project No.1 between China and Serbia,Tsinghua University Initiative Foundation Research Program(No.20131089204)the State Key Laboratory of Natural and Biomimetic Drugs(No.K202008).
文摘The selective oxidative esterification of aldehydes with alcohols to the corresponding esters has been one of the hot spots in scientific research and industrial synthesis.However,the application of precious metal catalytic systems is limited by their complicated synthetic steps and high cost.Thus a highly efficient,green,recyclable selective synthesis method of esters catalyzed by polyoxovanadate(POV)-based molecu-lar catalysts has been developed in this paper.The results show that supramolecular interaction between POV and 1,3-dibenzylimidazolium bromide(Act_(2)Im)can efficiently convert alcohols and aldehydes to the corresponding esters in high yield under much milder conditions.Mechanistic insight is also provided based on the control experiments,single crystal X-ray diffraction and cyclic voltammetry studies.
基金financially supported by the National Natural Science Foundation of China(Nos.52172181,22105017)Interdisciplinary Research Project for Young Teachers of USTB(No.FRFIDRY-21–002)。
文摘Relaxor ferroic dielectrics have garnered increasing attention in the past decade as promising materials for energy storage.Among them,relaxor antiferroelectrics(AFEs)and relaxor ferroelectrics(FEs)have shown great promise in term of high energy storage density and efficiency,respectively.In this study,a unique phase transition from relaxor AFE to relaxor FE was achieved for the first time by introducing strong-ferroelectricity BaTiO_(3)into NaNbO_(3)-BiFeO_(3)system,leading to an evolution from AFE R hierarchical nanodomains to FE polar nanoregions.A novel medium state,consisting of relaxor AFE and relaxor FE,was identified in the crossover of 0.88NaNbO_(3)–0.07BiFeO_(3)–0.05BaTiO_(3)ceramic,exhibiting a distinctive core-shell grain structure due to the composition segregation.By harnessing the advantages of high energy storage density from relaxor AFE and large efficiency from relaxor FE,the ceramic showcased excellent overall energy storage properties.It achieved a substantial recoverable energy storage density W_(rec)~13.1 J/cm^(3)and an ultrahigh efficiencyη~88.9%.These remarkable values shattered the trade-off relationship typically observed in most dielectric capacitors between W_(rec)andη.The findings of this study provide valuable insights for the design of ceramic capacitors with enhanced performance,specifically targeting the development of next generation pulse power devices.
文摘Green synthesis of silver nanoparticles (AgNPs) using aqueous extracts of orange and lemon peels, as a reducing agent, and silver nitrate salts as a source of silver ions is a promising field of research due to the versatility of biomedical applications of metal nanoparticles. In this paper, AgNPs were synthetized at different reaction parameters such as the type and concentration of the extracts, metal salt concentration, temperature, speed stirring, and pH. The antibacterial properties of the obtained silver nanoparticles against E. coli, as well as the physical and chemical characteristics of the synthesized silver nanoparticles, were investigated. UV-Vis spectroscopy was used to confirm the formation of AgNPs. In addition to green biogenic synthesis, chemical synthesis of silver nanoparticles was also carried out. The optimal temperature for extraction was 65˚C, while for the synthesis of AgNPs was 35˚C. The synthesis is carried out in an acidic environment (pH = 4.7 orange and pH = 3.8 lemon), neutral (pH = 7) and alkaline (pH = 10), then for different concentrations of silver nitrate solution (0.5 mM - 1 mM), optimal time duration of the reaction was 60 min and optimal stirring speed rotation was 250 rpm on the magnetic stirrer. The physical properties of the synthesized silver nanoparticles (conductivity, density and refractive index) were also studied, and the passage of laser light through the obtained solution and distilled water was compared. Positive inhibitory effect on the growth of new Escherichia coli colonies have shown AgNPs synthesized at a basic pH value and at a 0.1 mM AgNO<sub>3</sub> using orange or lemon peel extract, while for a 0.5 mM AgNO<sub>3 </sub>using lemon peel extract.
基金the scientific and innovative merit Grant No.04/040/RGJ24/0275 of the Rector of the Silesian University of Technologythe scientific and innovative merit grant no.04/040/RGJ24/0278 of the Rector of the Silesian University of Technologythe support of the MERA.NET 3 Room temperature hydrogen sensors based on polycarbazole and its derivatives,"Hydro Sens"project(Grant No.9150,M-ERA.NET3/2021/93/HYDROSENS/2022。
文摘A new nanothermite system,composed of titanium and tungsten trioxide is reported.Initial investigations show that it has low-average sensitivity to mechanical stimuli(friction,impact),but that its sensitivity to laser irradiation can be controlled in a moderately wide range.The combustion of this nanothermite system takes place at a very high apparent temperature(>3695 K)and it follows the key predictions of the established reactive sintering mechanism,as supported by SEM-EDS and XRD analyses.
基金the ORSP of Pandit Deendayal Energy University and DST SERB(IPA/2021/96)for the financial support.
文摘The extensive research and development in perovskite solar cells (PSCs) have rekindled the hopes of converting solar energy into electricity.An elusive understanding of underlying mechanisms is required for the development of efficient PSCs.Over the years,Impedance Spectroscopy (IS) characterization,along with complementary techniques,has proven to be an effective way to understand and analyze the charge transport and recombination at interface and bulk of PSCs.The IS of PSCs have been analyzed,interpreted,and improvised continuously,revealing intricate details about the work.However,there is a lack of centralized source of these details,which make it tougher to account for the generalized approach to understand the device properties.The present work is focused on compiling the research done on various PSC device architectures via IS to construct a comprehensive foundation of information on impedance plots,equivalent circuits,and associated processes.
