An improved method is proposed for the extraction of the symmetry energy coefficient relative to the temperature,a_(sym)/T,in the heavy-ion reactions near the Fermi energy region,based on the modified Fisher Model.Thi...An improved method is proposed for the extraction of the symmetry energy coefficient relative to the temperature,a_(sym)/T,in the heavy-ion reactions near the Fermi energy region,based on the modified Fisher Model.This method is applied to the primary fragments of antisymmetrized molecular dynamics(AMD)simulations for ^(46)Fe+^(46)Fe,^(40)Ca+^(40)Ca and ^(48)Ca+^(48)Ca at 35 MeV/nucleon,in order to make direct comparison to the results from the K(N,Z)method of Ono et al.In our improved method,the extracted values of a_(sym)/T increase as the size of isotopes increases whereas,in the K(N,Z)method,the results show rather constant behavior.This increase in our result is attributed to the surface contribution of the symmetry energy in finite nuclei.In order to evaluate the surface contribution,the relation a_(sym)/T=[a_(sym)^((V))(1-k_(S/V) A^(-1/3))]/T is applied and k_(S/V)=1.20~1.25 was extracted.This value is smaller than those extracted from the mass table,reflecting the weakened surface contribution at higher temperature regime.Δμ/T,the difference of the neutron-proton chemical potentials relative to the temperature,is also extracted in this method at the same time.The average values of the extractedΔμ/T,Δμ/T show a linear dependence on the proton-neutron a_(sym)metry parameter of the system,δ_(sys),andΔμ/T=(15.1±0.2)δ_(sys)-(0.5±0.1)is obtained.展开更多
A theoretical study on the reaction of aluminum with water in the gas phase was performed using the hybrid density functional B3LYP and QCISD（T） methods with the 6-311＋G（d,p） and the 6-311＋＋G（d,p） basis sets....A theoretical study on the reaction of aluminum with water in the gas phase was performed using the hybrid density functional B3LYP and QCISD（T） methods with the 6-311＋G（d,p） and the 6-311＋＋G（d,p） basis sets. The results show that there are three possible reaction pathways that involve four isomers, seven transition structures, and two possible products for the reaction of aluminum with water. The two most favorable reaction pathways were found, whose intermediates and products agreed quite well with experimental results. The enthalpy and Gibbs free energy change of the reaction between A1 and H2O at 298 and 2000 K were calculated. Some results are also in good agreement with the previous calculations or experimental results.展开更多
Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this s...Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.展开更多
Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal int...Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.展开更多
Paclitaxel is one of the commonly used drugs in postoperative chemotherapy for ovarian cancer patients. However, affected by drug dosage and individual differences in the course of medication, patients will have diffe...Paclitaxel is one of the commonly used drugs in postoperative chemotherapy for ovarian cancer patients. However, affected by drug dosage and individual differences in the course of medication, patients will have different degrees of adverse reactions, which will cause damage to the patient’s body once they occur. This paper retrospectively analyzed the clinical data of patients with severe allergic reactions such as fecal incontinence and numbness of hands and feet caused by the use of paclitaxel liposome during postoperative chemotherapy in a case of ovarian cancer admitted to our hospital. The causes and corresponding treatment measures were analyzed, in order to provide the reference for medical staff to take effective countermeasures in advance in the future.展开更多
This paper, an addendum to “Dialectical Thermodynamics’ solution to the conceptual imbroglio that is the reversible path”, this journal, 10, 775-799, was written in response to the requests of several readers to pr...This paper, an addendum to “Dialectical Thermodynamics’ solution to the conceptual imbroglio that is the reversible path”, this journal, 10, 775-799, was written in response to the requests of several readers to provide further evidence of the said “imbroglio”. The evidence here presented relates to the incompatibility existing between the total-entropy and the Gibbs energy prescriptions for the reversible path. The previously published proof of the negentropic nature of the transformation of heat into work is here included to validate out conclusions about the Gibbs energy perspective.展开更多
One of the primary objectives in molecular nano-spintronics is to manipulate the electronic configurations of organic molecules with a d-electron center by suitable external means.Here,we demonstrate the tuning of the...One of the primary objectives in molecular nano-spintronics is to manipulate the electronic configurations of organic molecules with a d-electron center by suitable external means.Here,we demonstrate the tuning of the electronic configuration of tetrakis(pentafluorophenyl)porphyrin(FeF20TPP)molecules on the Au(111)surface through a thermally induced intramolecular quadrauplicate cyclization reaction.During the reaction,the electronic configuration of a FeF20TPP molecule on the Au(111)surface changes from(d_(z)^(1)2d_(π)^(2))to(d_(z)^(2)2d_(π)^(2)).We attribute this change to significant difference in the adsorption height and variations in coupling between the orbitals of central metal atoms and the Au(111)surface.To further validate this mechanism,we substituted the central Fe ion with a Mn ion,predicting that an electronic configuration transition would not occur in MnF_(20)TPP and its product.Low-temperature scanning tunneling microscopy(STM)revealed that the FeF20TPP on Au(111)exhibits no Kondo resonance,while its cyclization product exhibits Kondo dip near the Fermi level(E_(F)).In contrast,both the MnF_(20)TPP and its product show pronounced Kondo dip at E_(F).Our work marks a significant step forward in controlling molecular electronic configuration through on-surface chemical reactions,paving the way for advanced molecular spintronics.展开更多
The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these c...The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.展开更多
The ability to unlock the interplay between the activity and stability of oxygen reduction reaction(ORR)represents an important endeavor toward creating robust ORR catalysts for efficient fuel cells.Herein,we report a...The ability to unlock the interplay between the activity and stability of oxygen reduction reaction(ORR)represents an important endeavor toward creating robust ORR catalysts for efficient fuel cells.Herein,we report an effective strategy to concurrent enhance the activity and stability of ORR catalysts via constructing atomically dispersed Fe-Mn dualmetal sites on N-doped carbon(denoted(FeMn-DA)-N-C)for both anion-exchange membrane fuel cells(AEMFC)and proton exchange membrane fuel cells(PEMFC).The(FeMn-DA)-N-C catalysts possess ample dual-metal atoms consisting of adjacent Fe-N_(4)and Mn-N_(4)sites on the carbon surface,yielded via a facile doping-adsorption-pyrolysis route.The introduction of Mn carries several advantageous attributes:increasing the number of active sites,effectively anchoring Fe due to effective electron transfer to Mn(revealed by X-ray absorption spectroscopy and density-functional theory(DFT),thus preventing the aggregation of Fe),and effectively circumventing the occurrence of Fenton reaction,thus reducing the consumption of Fe.The(FeMn-DA)-N-C catalysts showcase half-wave potentials of 0.92 and 0.82 V in 0.1 M KOH and 0.1 M HClO_(4),respectively,as well as outstanding stability.As manifested by DFT calculations,the introduction of Mn affects the electronic structure of Fe,down-shifts the d-band Fe active center,accelerates the desorption of OH groups,and creates higher limiting potentials.The AEMFC and PEMFC with(FeMn-DA)-N-C as the cathode catalyst display high power densities of 1060 and 746 mW cm^(-2),respectively,underscoring their promising potential for practical applications.Our study highlights the robustness of designing Fe-containing dual-atom ORR catalysts to promote both activity and stability for energy conversion and storage materials and devices.展开更多
Based on the Skyrme energy density functional and reaction Q-value,this study proposed an effective nucleus-nucleus poten-tial for describing the capture barrier in heavy-ion fusion processes.The 443 extracted barrier...Based on the Skyrme energy density functional and reaction Q-value,this study proposed an effective nucleus-nucleus poten-tial for describing the capture barrier in heavy-ion fusion processes.The 443 extracted barrier heights were well reproduced with a root-mean-square(RMS)error of 1.53 MeV,and the RMS deviations with respect to 144 time-dependent Hartree-Fock capture barrier heights were only 1.05 MeV.Coupled with the Siwek-Wilczyński formula,wherein three parameters were determined by the proposed effective potentials,the measured capture cross sections at energies around the barriers were reasonably well reproduced for several fusion reactions induced by nearly spherical nuclei as well as by nuclei with large deformations,such as^(154)Sm and^(238)U.The shallow capture pockets and small values of the average barrier radii resulted in the reduction of the capture cross sections for 52,54Cr-and 64 Ni-induced reactions,which were related to the synthesis of new super-heavy nuclei.展开更多
Designing highly active and stable electrocatalysts of oxygen evolution reaction(OER)is one of the crucial challenges.In this study,a novel OER electrocatalyst,NiFe-MIL-53 modified with ultra-low rhodium(Rh@NiFe-MIL-5...Designing highly active and stable electrocatalysts of oxygen evolution reaction(OER)is one of the crucial challenges.In this study,a novel OER electrocatalyst,NiFe-MIL-53 modified with ultra-low rhodium(Rh@NiFe-MIL-53),is successfully prepared via the hydrothermal method.In-situ Raman spectroscopy and electrochemical impedance spectroscopy reveal that the doped Rh accelerates the phase transformation of NiFe-MIL-53 and the in-situ formed Rh@NiFeOOH is the actual active species.More importantly,the enhanced reversibility of electrochemical reconstruction between NiFeOOH and NiFe(OH)_(2)after doping Rh is beneficial for improving the electrochemical stability of the catalyst.X-ray photoelectron spectroscopy spectra show the strong electronic interaction between single-atom Rh and Ni/Fe in Rh@NiFeOOH.Furthermore,theoretical calculations confirm that the integration of single-atom Rh into the NiFeOOH successfully reduces the band gap,regulates the d-band center(εd),accelerates the charge transfer,and optimizes the adsorption behavior of oxygen-containing intermediates,thereby lowering the energy barrier of rate-determining steps.Consequently,the optimized Rh@NiFe-MIL-53 exhibits excellent OER activity(240 mV)with a small Tafel slope of 48.2 mV dec^(-1)and long-term durability(over1270 h at 10 m A cm^(-2)and 110 h at 200 mA cm^(-2)).This work presents a new perspective on designing highly efficient OER electrocatalysts.展开更多
Methyl methoxyacetate(MMAc)and methyl formate(MF)can be produced directly by heterogeneous zeolite-catalyzed carbonylation and disproportionation of dimethoxymethane(DMM),with near 100%selectivity for each process.Des...Methyl methoxyacetate(MMAc)and methyl formate(MF)can be produced directly by heterogeneous zeolite-catalyzed carbonylation and disproportionation of dimethoxymethane(DMM),with near 100%selectivity for each process.Despite continuous research efforts,the insight into the reaction mechanism and kinetics theory are still in their nascent stage.In this study,ZEO-1 material,a zeolite with up to now the largest cages comprising 16×16-MRs,16×12-MRs,and 12×12-MRs,was explored for DMM carbonylation and disproportionation reactions.The rate of MMAc formation based on accessible Brönsted acid sites is 2.5 times higher for ZEO-1(Si/Al=21)relative to the previously investigated FAU(Si/Al=15),indicating the positive effect of spatial separation of active sites in ZEO-1 on catalytic activity.A higher MF formation rate is also observed over ZEO-1 with lower activation energy(79.94 vs.95.19 kJ/mol)compared with FAU(Si/Al=30).Two types of active sites are proposed within ZEO-1 zeolite:Site 1 located in large cages formed by 16×16-MRs and 16×12-MRs,which is active predominantly for MMAc formation,and Site 2 located in smaller cages for methyl formate/dimethyl ether formation.Kinetics investigation of DMM carbonylation over ZEO-1 exhibit a first-order dependence on CO partial pressure and a slightly inverse-order dependence on DMM partial pressure.The DMM disproportionation is nearly first-order dependence on DMM partial pressure,while it reveals a strongly inverse dependence with increasing CO partial pressure.Furthermore,ZEO-1 exhibits good catalytic stability,and almost no deactivation is observed during the more than 70 h test with high carbonylation selectivity of above 89%,due to the well-enhanced diffusion property demonstrated by intelligent-gravimetric analysis.展开更多
Uncontrolled dendrite growth,sluggish reaction kinetics,and drastic side reactions on the anodeelectrolyte interface are the main obstacles that restrict the application prospect of aqueous zinc-ion batteries.Traditio...Uncontrolled dendrite growth,sluggish reaction kinetics,and drastic side reactions on the anodeelectrolyte interface are the main obstacles that restrict the application prospect of aqueous zinc-ion batteries.Traditional glass fiber(GF)separator with chemical inertness is almost ineffective in restricting these challenges.Herein,inspired by the ionic enrichment behavior of seaweed plants,a facile biomass species,anionic sodium alginate(SA),is purposely decorated on the commercial GF separator to tackle these issues towards Zn anode.Benefiting from the abundant zincophilic functional groups and superior mechanical strength properties,the as-obtained SA@GF separator could act as ion pump to boost the Zn^(2+)transference number(0.68),reduce the de-solvation energy barrier of hydrated Zn^(2+),and eliminate the undesired concentration polarization effect,which are verified by experimental tests,theoretical calculations,and finite element simulation,respectively.Based on these efficient modulation mechanisms,the SA@GF separator can synchronously achieve well-aligned Zn deposition and the suppression of parasitic side-reactions.Therefore,the Zn‖Zn coin cell integrated with SA@GF separator could yield a prolonged calendar lifespan over 1230 h(1 mA cm^(-2)and 1 mAh cm^(-2)),exhibiting favorable competitiveness with previously reported separator modification strategies.Impressively,the Zn-MnO_(2)full and pouch cell assembled with the SA@GF separator also delivered superior cycling stability and rate performance,further verifying its practical application effect.This work provides a new design philosophy to stabilize the Zn anode from the aspect of separator.展开更多
The Fenton-like reaction between Cu^(2+)and H_(2)O_(2)was employed in chemical mechanical polishing to achieve efficient and high-quality processing of tungsten.The microstructure evolution and material removal rate o...The Fenton-like reaction between Cu^(2+)and H_(2)O_(2)was employed in chemical mechanical polishing to achieve efficient and high-quality processing of tungsten.The microstructure evolution and material removal rate of tungsten during polishing process were investigated via scanning electron microscopy,X-ray photoelectron spectroscopy,ultraviolet−visible spectrophotometry,and electrochemical experiments.The passivation behavior and material removal mechanism were discussed.Results show that the use of mixed H_(2)O_(2)+Cu(NO_(3))_(2)oxidant can achieve higher polishing efficiency and surface quality compared with the single oxidant Cu(NO_(3))_(2)or H_(2)O_(2).The increase in material removal rate is attributed to the rapid oxidation of W into WO_(3)via the chemical reaction between the substrate and hydroxyl radicals produced by the Fenton-like reaction.In addition,material removal rate and static etch rate exhibit significantly different dependencies on the concentration of Cu(NO_(3))_(2),while the superior oxidant for achieving the balance between polishing efficiency and surface quality is 0.5 wt.%H_(2)O_(2)+1.0 wt.%Cu(NO_(3))_(2).展开更多
Transition metal carbides,known as MXenes,particularly Ti_(3)C_(2)T_(x),have been extensively explored as promising materials for electrochemical reactions.However,transition metal carbonitride MXenes with high nitrog...Transition metal carbides,known as MXenes,particularly Ti_(3)C_(2)T_(x),have been extensively explored as promising materials for electrochemical reactions.However,transition metal carbonitride MXenes with high nitrogen content for electrochemical reactions are rarely reported.In this work,transition metal carbonitride MXenes incorporated with Pt-based electrocatalysts,ranging from single atoms to sub-nanometer dimensions,are explored for hydrogen evolution reaction(HER).The fabricated Pt clusters/MXene catalyst exhibits superior HER performance compared to the single-atom-incorporated MXene and commercial Pt/C catalyst in both acidic and alkaline electrolytes.The optimized sample shows low overpotentials of 28,65,and 154 mV at a current densities of 10,100,and 500 m A cm^(-2),a small Tafel slope of 29 m V dec^(-1),a high mass activity of 1203 mA mgPt^(-1)and an excellent turnover frequency of 6.1 s^(-1)in the acidic electrolyte.Density functional theory calculations indicate that this high performance can be attributed to the enhanced active sites,increased surface functional groups,faster charge transfer dynamics,and stronger electronic interaction between Pt and MXene,resulting in optimized hydrogen absorption/desorption toward better HER.This work demonstrates that MXenes with a high content of nitrogen may be promising candidates for various catalytic reactions by incorporating single atoms or clusters.展开更多
Semiconductor-cocatalyst interfacial electron transfer has widely been considered as a fast step occurring on picosecond-microsecond timescale in photocatalytic reaction.However,the formed potential barriers severely ...Semiconductor-cocatalyst interfacial electron transfer has widely been considered as a fast step occurring on picosecond-microsecond timescale in photocatalytic reaction.However,the formed potential barriers severely slow this interfacial electronic process by thermionic emission.Although trap-assisted charge recombination can transfer electrons from semiconductor to cocatalyst and can even be evident under weak illumination,the parallel connection with thermionic emission makes the photocatalytic photon utilization encounter a minimum along the variation of light intensity.By this cognition,the light-intensity-dependent photocatalytic behaviors can be predicted by simulating the photoinduced semiconductor-cocatalyst interfacial electron transfer that mainly determines the reaction rate.We then propose a(photo)electrochemical method to evaluate the time constants for occurring this interfacial electronic process in actual photocatalytic reaction without relying on extremely high photon flux that is required to generate discernible optical signal in common instrumental methods based on ultrafast pulse laser.The evaluated decisecond-second timescale can accurately guide us to develop certain strategies to facilitate this rate-determining step to improve photon utilization.展开更多
Oxygen release and electrolyte decomposition under high voltage endlessly exacerbate interfacial ramifications and structu ral degradation of high energy-density Li-rich layered oxide(LLO),leading to voltage and capac...Oxygen release and electrolyte decomposition under high voltage endlessly exacerbate interfacial ramifications and structu ral degradation of high energy-density Li-rich layered oxide(LLO),leading to voltage and capacity fading.Herein,the dual-strategy of Cr,B complex coating and local gradient doping is simultaneously achieved on LLO surface by a one-step wet chemical reaction at room temperature.Density functional theory(DFT)calculations prove that stable B-O and Cr-O bonds through the local gradient doping can significantly reduce the high-energy O 2p states of interfacial lattice O,which is also effective for the near-surface lattice O,thus greatly stabilizing the LLO surface,Besides,differential electrochemical mass spectrometry(DEMS)indicates that the Cr_(x)B complex coating can adequately inhibit oxygen release and prevents the migration or dissolution of transition metal ions,including allowing speedy Li^(+)migration,The voltage and capacity fading of the modified cathode(LLO-C_(r)B)are adequately suppressed,which are benefited from the uniformly dense cathode electrolyte interface(CEI)composed of balanced organic/inorganic composition.Therefore,the specific capacity of LLO-CrB after 200 cycles at 1C is 209.3 mA h g^(-1)(with a retention rate of 95.1%).This dual-strategy through a one-step wet chemical reaction is expected to be applied in the design and development of other anionic redox cathode materials.展开更多
The development of highly active and cost-effective catalysts for the full pH range of the hydrogen evolution reaction(HER)to meet the industrial application demands is an urgent challenge.In this work,the performance...The development of highly active and cost-effective catalysts for the full pH range of the hydrogen evolution reaction(HER)to meet the industrial application demands is an urgent challenge.In this work,the performance and structure–activityrelationships of CuIr alloys prepared by the pulsed laser ablation in liquid technique as full pH range HER catalysts wereinvestigated.Results indicated that Ir is doped into the Cu matrix as single atoms in CuIr-0.1,and CuIr-0.1 single-atom alloys(SAAs)exhibit superior HER performance and stability across the full pH range,with overpotentials of 135,203,and 172 mVat the current density of 10 mA/cm^(2)in acidic,neutral,and alkaline electrolytes,respectively.The enhanced performance ofCuIr-0.1 SAAs can be attributed to the abundant active sites and accelerated reaction kinetics brought about by the electroniceffects.This work successfully alloyed two immiscible metals to improve the catalytic performance,providing an avenue forthe development of highly efficient and versatile HER catalysts for industrial applications.展开更多
MXene is an emerging class of two-dimensional(2D)layered transition metal carbides or nitrides.Due to the highly tunable components and surface functional groups,it holds great potential in electrocatalytic hydrogen e...MXene is an emerging class of two-dimensional(2D)layered transition metal carbides or nitrides.Due to the highly tunable components and surface functional groups,it holds great potential in electrocatalytic hydrogen evolution reaction(HER).However,MXene nanosheet suffers from a strong tendency to restack and a lack of active edge sites.In this work,the porous Ti_(3)C_(2)T_(x)was synthesized by an oxidation and etching two-step strategy and then characterized by a series of spectroscopic techniques.The obtained porous Ti_(3)C_(2)T_(x)possesses a large number of in-plane pores.This not only creates abundant active edge sites but also enhances the mass transfer and increases the accessibility of the active sites.Compared with Ti_(3)C_(2)T_(x),in a 0.5 mol/L H_(2)SO_(4)electrolyte,the porous Ti_(3)C_(2)T_(x)shows a 65.6%higher electrochemical surface area(ECSA)(440 mF/cm^(2)),a 95.2%lower charge transfer resistance(12.8Ω),and a 69.8%lower Tafel slope(144 mV/dec),and thus exhibits lower overpotential with good stability at a current density of 10 mA/cm^(2).At the same time,the HER performance of the porous Ti_(3)C_(2)T_(x)can be further enhanced by near-infrared laser irradiation based on the localized surface plasmon resonance effect.展开更多
文摘An improved method is proposed for the extraction of the symmetry energy coefficient relative to the temperature,a_(sym)/T,in the heavy-ion reactions near the Fermi energy region,based on the modified Fisher Model.This method is applied to the primary fragments of antisymmetrized molecular dynamics(AMD)simulations for ^(46)Fe+^(46)Fe,^(40)Ca+^(40)Ca and ^(48)Ca+^(48)Ca at 35 MeV/nucleon,in order to make direct comparison to the results from the K(N,Z)method of Ono et al.In our improved method,the extracted values of a_(sym)/T increase as the size of isotopes increases whereas,in the K(N,Z)method,the results show rather constant behavior.This increase in our result is attributed to the surface contribution of the symmetry energy in finite nuclei.In order to evaluate the surface contribution,the relation a_(sym)/T=[a_(sym)^((V))(1-k_(S/V) A^(-1/3))]/T is applied and k_(S/V)=1.20~1.25 was extracted.This value is smaller than those extracted from the mass table,reflecting the weakened surface contribution at higher temperature regime.Δμ/T,the difference of the neutron-proton chemical potentials relative to the temperature,is also extracted in this method at the same time.The average values of the extractedΔμ/T,Δμ/T show a linear dependence on the proton-neutron a_(sym)metry parameter of the system,δ_(sys),andΔμ/T=(15.1±0.2)δ_(sys)-(0.5±0.1)is obtained.
基金This work was supported by the National Natural Science Foundation of China （No.50476025）.
文摘A theoretical study on the reaction of aluminum with water in the gas phase was performed using the hybrid density functional B3LYP and QCISD（T） methods with the 6-311＋G（d,p） and the 6-311＋＋G（d,p） basis sets. The results show that there are three possible reaction pathways that involve four isomers, seven transition structures, and two possible products for the reaction of aluminum with water. The two most favorable reaction pathways were found, whose intermediates and products agreed quite well with experimental results. The enthalpy and Gibbs free energy change of the reaction between A1 and H2O at 298 and 2000 K were calculated. Some results are also in good agreement with the previous calculations or experimental results.
基金financially supported by the National Natural Science Foundation of China(No.5217042069)the Young Elite Scientist Sponsorship Program by China Association for Science and Technology(CAST)(No.YESS20200103)the Fundamental Research Funds for the Central Universities(No.265QZ2022004)。
文摘Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.
基金financially supported by the National Natural Science Foundation of China(22309137,22279095)Open subject project State Key Laboratory of New Textile Materials and Advanced Processing Technologies(FZ2023001).
文摘Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.
文摘Paclitaxel is one of the commonly used drugs in postoperative chemotherapy for ovarian cancer patients. However, affected by drug dosage and individual differences in the course of medication, patients will have different degrees of adverse reactions, which will cause damage to the patient’s body once they occur. This paper retrospectively analyzed the clinical data of patients with severe allergic reactions such as fecal incontinence and numbness of hands and feet caused by the use of paclitaxel liposome during postoperative chemotherapy in a case of ovarian cancer admitted to our hospital. The causes and corresponding treatment measures were analyzed, in order to provide the reference for medical staff to take effective countermeasures in advance in the future.
文摘This paper, an addendum to “Dialectical Thermodynamics’ solution to the conceptual imbroglio that is the reversible path”, this journal, 10, 775-799, was written in response to the requests of several readers to provide further evidence of the said “imbroglio”. The evidence here presented relates to the incompatibility existing between the total-entropy and the Gibbs energy prescriptions for the reversible path. The previously published proof of the negentropic nature of the transformation of heat into work is here included to validate out conclusions about the Gibbs energy perspective.
基金supported by the National Natural Science Foundation of China(Grant Nos.52350322,52201231,and 62488201)the National Key Research and Development Projects of China(Grant No.2022YFA1204100)+1 种基金the CAS Project for Young Scientists in Basic Research(Grant Nos.YSBR-003 and YSBR053)the Fundamental Research Funds for the Central Universities(Grant No.FRF-TP-24-055A)。
文摘One of the primary objectives in molecular nano-spintronics is to manipulate the electronic configurations of organic molecules with a d-electron center by suitable external means.Here,we demonstrate the tuning of the electronic configuration of tetrakis(pentafluorophenyl)porphyrin(FeF20TPP)molecules on the Au(111)surface through a thermally induced intramolecular quadrauplicate cyclization reaction.During the reaction,the electronic configuration of a FeF20TPP molecule on the Au(111)surface changes from(d_(z)^(1)2d_(π)^(2))to(d_(z)^(2)2d_(π)^(2)).We attribute this change to significant difference in the adsorption height and variations in coupling between the orbitals of central metal atoms and the Au(111)surface.To further validate this mechanism,we substituted the central Fe ion with a Mn ion,predicting that an electronic configuration transition would not occur in MnF_(20)TPP and its product.Low-temperature scanning tunneling microscopy(STM)revealed that the FeF20TPP on Au(111)exhibits no Kondo resonance,while its cyclization product exhibits Kondo dip near the Fermi level(E_(F)).In contrast,both the MnF_(20)TPP and its product show pronounced Kondo dip at E_(F).Our work marks a significant step forward in controlling molecular electronic configuration through on-surface chemical reactions,paving the way for advanced molecular spintronics.
基金supported by Shanxi Province Science Foundation for Youths(202203021212300)Taiyuan University of Science and Technology Scientific Research Initial Funding(20212064)Outstanding Doctoral Award Fund in Shanxi Province(20222060).
文摘The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.
基金supported by the National Key R&D Program of China (2021YFF0500504)National Natural Science Foundation of China (No. 51976169)the financial supports from the Fundamental Research Funds for the Central Universities。
文摘The ability to unlock the interplay between the activity and stability of oxygen reduction reaction(ORR)represents an important endeavor toward creating robust ORR catalysts for efficient fuel cells.Herein,we report an effective strategy to concurrent enhance the activity and stability of ORR catalysts via constructing atomically dispersed Fe-Mn dualmetal sites on N-doped carbon(denoted(FeMn-DA)-N-C)for both anion-exchange membrane fuel cells(AEMFC)and proton exchange membrane fuel cells(PEMFC).The(FeMn-DA)-N-C catalysts possess ample dual-metal atoms consisting of adjacent Fe-N_(4)and Mn-N_(4)sites on the carbon surface,yielded via a facile doping-adsorption-pyrolysis route.The introduction of Mn carries several advantageous attributes:increasing the number of active sites,effectively anchoring Fe due to effective electron transfer to Mn(revealed by X-ray absorption spectroscopy and density-functional theory(DFT),thus preventing the aggregation of Fe),and effectively circumventing the occurrence of Fenton reaction,thus reducing the consumption of Fe.The(FeMn-DA)-N-C catalysts showcase half-wave potentials of 0.92 and 0.82 V in 0.1 M KOH and 0.1 M HClO_(4),respectively,as well as outstanding stability.As manifested by DFT calculations,the introduction of Mn affects the electronic structure of Fe,down-shifts the d-band Fe active center,accelerates the desorption of OH groups,and creates higher limiting potentials.The AEMFC and PEMFC with(FeMn-DA)-N-C as the cathode catalyst display high power densities of 1060 and 746 mW cm^(-2),respectively,underscoring their promising potential for practical applications.Our study highlights the robustness of designing Fe-containing dual-atom ORR catalysts to promote both activity and stability for energy conversion and storage materials and devices.
基金supported by the National Natural Science Foundation of China(Nos.12265006,12375129,U1867212)the Innovation Project of Guangxi Graduate Education(No.YCSWYCSW2022176)the Guangxi Natural Science Foundation(2017GXNSFGA198001).
文摘Based on the Skyrme energy density functional and reaction Q-value,this study proposed an effective nucleus-nucleus poten-tial for describing the capture barrier in heavy-ion fusion processes.The 443 extracted barrier heights were well reproduced with a root-mean-square(RMS)error of 1.53 MeV,and the RMS deviations with respect to 144 time-dependent Hartree-Fock capture barrier heights were only 1.05 MeV.Coupled with the Siwek-Wilczyński formula,wherein three parameters were determined by the proposed effective potentials,the measured capture cross sections at energies around the barriers were reasonably well reproduced for several fusion reactions induced by nearly spherical nuclei as well as by nuclei with large deformations,such as^(154)Sm and^(238)U.The shallow capture pockets and small values of the average barrier radii resulted in the reduction of the capture cross sections for 52,54Cr-and 64 Ni-induced reactions,which were related to the synthesis of new super-heavy nuclei.
基金Natural Science Foundation of China(Grant No.NSFC-22072062,22202098)。
文摘Designing highly active and stable electrocatalysts of oxygen evolution reaction(OER)is one of the crucial challenges.In this study,a novel OER electrocatalyst,NiFe-MIL-53 modified with ultra-low rhodium(Rh@NiFe-MIL-53),is successfully prepared via the hydrothermal method.In-situ Raman spectroscopy and electrochemical impedance spectroscopy reveal that the doped Rh accelerates the phase transformation of NiFe-MIL-53 and the in-situ formed Rh@NiFeOOH is the actual active species.More importantly,the enhanced reversibility of electrochemical reconstruction between NiFeOOH and NiFe(OH)_(2)after doping Rh is beneficial for improving the electrochemical stability of the catalyst.X-ray photoelectron spectroscopy spectra show the strong electronic interaction between single-atom Rh and Ni/Fe in Rh@NiFeOOH.Furthermore,theoretical calculations confirm that the integration of single-atom Rh into the NiFeOOH successfully reduces the band gap,regulates the d-band center(εd),accelerates the charge transfer,and optimizes the adsorption behavior of oxygen-containing intermediates,thereby lowering the energy barrier of rate-determining steps.Consequently,the optimized Rh@NiFe-MIL-53 exhibits excellent OER activity(240 mV)with a small Tafel slope of 48.2 mV dec^(-1)and long-term durability(over1270 h at 10 m A cm^(-2)and 110 h at 200 mA cm^(-2)).This work presents a new perspective on designing highly efficient OER electrocatalysts.
文摘Methyl methoxyacetate(MMAc)and methyl formate(MF)can be produced directly by heterogeneous zeolite-catalyzed carbonylation and disproportionation of dimethoxymethane(DMM),with near 100%selectivity for each process.Despite continuous research efforts,the insight into the reaction mechanism and kinetics theory are still in their nascent stage.In this study,ZEO-1 material,a zeolite with up to now the largest cages comprising 16×16-MRs,16×12-MRs,and 12×12-MRs,was explored for DMM carbonylation and disproportionation reactions.The rate of MMAc formation based on accessible Brönsted acid sites is 2.5 times higher for ZEO-1(Si/Al=21)relative to the previously investigated FAU(Si/Al=15),indicating the positive effect of spatial separation of active sites in ZEO-1 on catalytic activity.A higher MF formation rate is also observed over ZEO-1 with lower activation energy(79.94 vs.95.19 kJ/mol)compared with FAU(Si/Al=30).Two types of active sites are proposed within ZEO-1 zeolite:Site 1 located in large cages formed by 16×16-MRs and 16×12-MRs,which is active predominantly for MMAc formation,and Site 2 located in smaller cages for methyl formate/dimethyl ether formation.Kinetics investigation of DMM carbonylation over ZEO-1 exhibit a first-order dependence on CO partial pressure and a slightly inverse-order dependence on DMM partial pressure.The DMM disproportionation is nearly first-order dependence on DMM partial pressure,while it reveals a strongly inverse dependence with increasing CO partial pressure.Furthermore,ZEO-1 exhibits good catalytic stability,and almost no deactivation is observed during the more than 70 h test with high carbonylation selectivity of above 89%,due to the well-enhanced diffusion property demonstrated by intelligent-gravimetric analysis.
基金supported by research grants from the National Natural Science Foundation of China(52173235,22008193,52106110)the Key Research and Development Project of Hainan Province(ZDYF2024SHFZ038)+2 种基金Venture&Innovation Support Program for Chongqing Overseas Returnees(CX2021018)Research Foundation of Chongqing University of Science and Technology(ckrc2021071)Numerical computations were performed on Hefei Advanced Computing Center.
文摘Uncontrolled dendrite growth,sluggish reaction kinetics,and drastic side reactions on the anodeelectrolyte interface are the main obstacles that restrict the application prospect of aqueous zinc-ion batteries.Traditional glass fiber(GF)separator with chemical inertness is almost ineffective in restricting these challenges.Herein,inspired by the ionic enrichment behavior of seaweed plants,a facile biomass species,anionic sodium alginate(SA),is purposely decorated on the commercial GF separator to tackle these issues towards Zn anode.Benefiting from the abundant zincophilic functional groups and superior mechanical strength properties,the as-obtained SA@GF separator could act as ion pump to boost the Zn^(2+)transference number(0.68),reduce the de-solvation energy barrier of hydrated Zn^(2+),and eliminate the undesired concentration polarization effect,which are verified by experimental tests,theoretical calculations,and finite element simulation,respectively.Based on these efficient modulation mechanisms,the SA@GF separator can synchronously achieve well-aligned Zn deposition and the suppression of parasitic side-reactions.Therefore,the Zn‖Zn coin cell integrated with SA@GF separator could yield a prolonged calendar lifespan over 1230 h(1 mA cm^(-2)and 1 mAh cm^(-2)),exhibiting favorable competitiveness with previously reported separator modification strategies.Impressively,the Zn-MnO_(2)full and pouch cell assembled with the SA@GF separator also delivered superior cycling stability and rate performance,further verifying its practical application effect.This work provides a new design philosophy to stabilize the Zn anode from the aspect of separator.
文摘The Fenton-like reaction between Cu^(2+)and H_(2)O_(2)was employed in chemical mechanical polishing to achieve efficient and high-quality processing of tungsten.The microstructure evolution and material removal rate of tungsten during polishing process were investigated via scanning electron microscopy,X-ray photoelectron spectroscopy,ultraviolet−visible spectrophotometry,and electrochemical experiments.The passivation behavior and material removal mechanism were discussed.Results show that the use of mixed H_(2)O_(2)+Cu(NO_(3))_(2)oxidant can achieve higher polishing efficiency and surface quality compared with the single oxidant Cu(NO_(3))_(2)or H_(2)O_(2).The increase in material removal rate is attributed to the rapid oxidation of W into WO_(3)via the chemical reaction between the substrate and hydroxyl radicals produced by the Fenton-like reaction.In addition,material removal rate and static etch rate exhibit significantly different dependencies on the concentration of Cu(NO_(3))_(2),while the superior oxidant for achieving the balance between polishing efficiency and surface quality is 0.5 wt.%H_(2)O_(2)+1.0 wt.%Cu(NO_(3))_(2).
基金the final support of ARC DP220103045the startup support of KFUPMPrince Sultan University for their support。
文摘Transition metal carbides,known as MXenes,particularly Ti_(3)C_(2)T_(x),have been extensively explored as promising materials for electrochemical reactions.However,transition metal carbonitride MXenes with high nitrogen content for electrochemical reactions are rarely reported.In this work,transition metal carbonitride MXenes incorporated with Pt-based electrocatalysts,ranging from single atoms to sub-nanometer dimensions,are explored for hydrogen evolution reaction(HER).The fabricated Pt clusters/MXene catalyst exhibits superior HER performance compared to the single-atom-incorporated MXene and commercial Pt/C catalyst in both acidic and alkaline electrolytes.The optimized sample shows low overpotentials of 28,65,and 154 mV at a current densities of 10,100,and 500 m A cm^(-2),a small Tafel slope of 29 m V dec^(-1),a high mass activity of 1203 mA mgPt^(-1)and an excellent turnover frequency of 6.1 s^(-1)in the acidic electrolyte.Density functional theory calculations indicate that this high performance can be attributed to the enhanced active sites,increased surface functional groups,faster charge transfer dynamics,and stronger electronic interaction between Pt and MXene,resulting in optimized hydrogen absorption/desorption toward better HER.This work demonstrates that MXenes with a high content of nitrogen may be promising candidates for various catalytic reactions by incorporating single atoms or clusters.
文摘Semiconductor-cocatalyst interfacial electron transfer has widely been considered as a fast step occurring on picosecond-microsecond timescale in photocatalytic reaction.However,the formed potential barriers severely slow this interfacial electronic process by thermionic emission.Although trap-assisted charge recombination can transfer electrons from semiconductor to cocatalyst and can even be evident under weak illumination,the parallel connection with thermionic emission makes the photocatalytic photon utilization encounter a minimum along the variation of light intensity.By this cognition,the light-intensity-dependent photocatalytic behaviors can be predicted by simulating the photoinduced semiconductor-cocatalyst interfacial electron transfer that mainly determines the reaction rate.We then propose a(photo)electrochemical method to evaluate the time constants for occurring this interfacial electronic process in actual photocatalytic reaction without relying on extremely high photon flux that is required to generate discernible optical signal in common instrumental methods based on ultrafast pulse laser.The evaluated decisecond-second timescale can accurately guide us to develop certain strategies to facilitate this rate-determining step to improve photon utilization.
基金financially supported by the National Natural Science Foundation of China(No.12304077)the Natural Science Foundation of Science and Technology Department of Sichuan Province(No.23NSFSC6224)+3 种基金Sichuan Science and Technology Program(No.2024NSFSC0989)the Key Laboratory of Computational Physics of Sichuan Province(No.YBUJSWL-YB-2022-03)the Material Corrosion and Protection Key Laboratory of Sichuan Province(No.2023CL14 and No.2023CL01)the National Innovation Practice Project(No.202411079005S).
文摘Oxygen release and electrolyte decomposition under high voltage endlessly exacerbate interfacial ramifications and structu ral degradation of high energy-density Li-rich layered oxide(LLO),leading to voltage and capacity fading.Herein,the dual-strategy of Cr,B complex coating and local gradient doping is simultaneously achieved on LLO surface by a one-step wet chemical reaction at room temperature.Density functional theory(DFT)calculations prove that stable B-O and Cr-O bonds through the local gradient doping can significantly reduce the high-energy O 2p states of interfacial lattice O,which is also effective for the near-surface lattice O,thus greatly stabilizing the LLO surface,Besides,differential electrochemical mass spectrometry(DEMS)indicates that the Cr_(x)B complex coating can adequately inhibit oxygen release and prevents the migration or dissolution of transition metal ions,including allowing speedy Li^(+)migration,The voltage and capacity fading of the modified cathode(LLO-C_(r)B)are adequately suppressed,which are benefited from the uniformly dense cathode electrolyte interface(CEI)composed of balanced organic/inorganic composition.Therefore,the specific capacity of LLO-CrB after 200 cycles at 1C is 209.3 mA h g^(-1)(with a retention rate of 95.1%).This dual-strategy through a one-step wet chemical reaction is expected to be applied in the design and development of other anionic redox cathode materials.
基金supported by the Natural Science Foundation of China(Nos.52022064 and 51971154).
文摘The development of highly active and cost-effective catalysts for the full pH range of the hydrogen evolution reaction(HER)to meet the industrial application demands is an urgent challenge.In this work,the performance and structure–activityrelationships of CuIr alloys prepared by the pulsed laser ablation in liquid technique as full pH range HER catalysts wereinvestigated.Results indicated that Ir is doped into the Cu matrix as single atoms in CuIr-0.1,and CuIr-0.1 single-atom alloys(SAAs)exhibit superior HER performance and stability across the full pH range,with overpotentials of 135,203,and 172 mVat the current density of 10 mA/cm^(2)in acidic,neutral,and alkaline electrolytes,respectively.The enhanced performance ofCuIr-0.1 SAAs can be attributed to the abundant active sites and accelerated reaction kinetics brought about by the electroniceffects.This work successfully alloyed two immiscible metals to improve the catalytic performance,providing an avenue forthe development of highly efficient and versatile HER catalysts for industrial applications.
文摘MXene is an emerging class of two-dimensional(2D)layered transition metal carbides or nitrides.Due to the highly tunable components and surface functional groups,it holds great potential in electrocatalytic hydrogen evolution reaction(HER).However,MXene nanosheet suffers from a strong tendency to restack and a lack of active edge sites.In this work,the porous Ti_(3)C_(2)T_(x)was synthesized by an oxidation and etching two-step strategy and then characterized by a series of spectroscopic techniques.The obtained porous Ti_(3)C_(2)T_(x)possesses a large number of in-plane pores.This not only creates abundant active edge sites but also enhances the mass transfer and increases the accessibility of the active sites.Compared with Ti_(3)C_(2)T_(x),in a 0.5 mol/L H_(2)SO_(4)electrolyte,the porous Ti_(3)C_(2)T_(x)shows a 65.6%higher electrochemical surface area(ECSA)(440 mF/cm^(2)),a 95.2%lower charge transfer resistance(12.8Ω),and a 69.8%lower Tafel slope(144 mV/dec),and thus exhibits lower overpotential with good stability at a current density of 10 mA/cm^(2).At the same time,the HER performance of the porous Ti_(3)C_(2)T_(x)can be further enhanced by near-infrared laser irradiation based on the localized surface plasmon resonance effect.
