This study presents a fully coupled thermo-hydro-mechanical (THM) constitutive model for clay rocks. The model is formulated within the elastic-viscoplasticity framework, which considers nonlinearity and softening aft...This study presents a fully coupled thermo-hydro-mechanical (THM) constitutive model for clay rocks. The model is formulated within the elastic-viscoplasticity framework, which considers nonlinearity and softening after peak strength, anisotropy of stiffness and strength, as well as permeability variation due to damage. In addition, the mechanical properties are coupled with thermal phenomena and accumulated plastic strains. The adopted nonlocal and viscoplastic approaches enhance numerical efficiency and provide the possibility to simulate localization phenomena. The model is validated against experimental data from laboratory tests conducted on Callovo-Oxfordian (COx) claystone samples that are initially unsaturated and under suction. The tests include a thermal phase where the COx specimens are subjected to different temperature increases. A good agreement with experimental data is obtained. In addition, parametric analyses are carried out to investigate the influence of the hydraulic boundary conditions (B.C.) and post-failure behavior models on the THM behavior evolution. It is shown that different drainage conditions affect the thermally induced pore pressures that, in turn, influence the onset of softening. The constitutive model presented constitutes a promising approach for simulating the most important features of the THM behavior of clay rocks. It is a tool with a high potential for application to several relevant case studies, such as thermal fracturing analysis of nuclear waste disposal systems.展开更多
Green and atom-economic depolymerization of lignin remains a great challenge due toits complex non-repetitive structure and the inert property for chemo-digestion. A redoxneutrallignin depolymerization system without ...Green and atom-economic depolymerization of lignin remains a great challenge due toits complex non-repetitive structure and the inert property for chemo-digestion. A redoxneutrallignin depolymerization system without the use of extra oxidant and/or reductantover a Co-NC catalyst has been developed in this work, providing the first non-noble metalheterogeneous catalytic system for redox-neutral valorization of lignin. Mechanistic studiesbased on control reactions and deuterium labeling experiments suggest that the reactionproceeds via ametal-catalyzed dehydrogenation of C_(α)-OH to afford a carbonyl intermediate,followed by C_(β)-O bond cleavage (via hydrogenolysis) to afford monophenols and aromaticketone products. The hydrogen used for the cleavage of the C_(β)-O bond originates from thealcoholmoiety in the substrate, and the cascade dehydrogenation and hydrogenolysis stepsare highly coupled, rendering it an efficient and atom-economic process.展开更多
The effect of prenatal exposure to ambient particulate matter(PM)on birth weight varies considerably across studies,and the findings remain inconclusive.In this study,we conducted a meta-analysis to assess the associa...The effect of prenatal exposure to ambient particulate matter(PM)on birth weight varies considerably across studies,and the findings remain inconclusive.In this study,we conducted a meta-analysis to assess the associations between exposure to PM_(2.5) and PM10 and birth weight.A total of 74 studies were identified through searches in Web of Science,PubMed,Embase,and Ovid Medline,as well as manual searches,up to October 2024.We found that for each 10μg/m^(3) increase in PM_(2.5),the risk of low birth weight(LBW)increased significantly during the entire pregnancy(odds ratio[OR]=2.41,95%confidence interval[CI]:1.99–2.91)and in all trimesters.Similarly,for every 10μg/m^(3) increase in PM10 concentration,the risk of LBW increased significantly during the entire pregnancy(OR=1.46,95%CI:1.16–1.84).Subgroup analysis by maternal age for PM_(2.5) showed that mothers aged 30 and above had a significantly higher risk of LBW(OR=3.69,95%CI:2.81–4.84),compared with those under 30.In conclusion,maternal exposure to PM_(2.5) and PM_(10) is associated with an increased risk of LBW across all trimesters.Additionally,mothers aged 30 and above are at a higher risk of LBW,compared with younger mothers.Further research is needed to clarify the biological mechanisms by which PM pollution may contribute to LBW.展开更多
The seepage of groundwater and the strain-softening of rock mass in a submarine tunnel expand the plastic region of rock,thereby affecting its overall stability.It is therefore essential to study the stress and strain...The seepage of groundwater and the strain-softening of rock mass in a submarine tunnel expand the plastic region of rock,thereby affecting its overall stability.It is therefore essential to study the stress and strain fields in the rocks surrounding the submarine tunnel by considering the coupled effect of strainsoftening and seepage.However,the evolution equation for the hydro-mechanical parameters in the existing fully coupled solution is a uniform equation that is unable to reproduce the characteristics of rock mass in practice.In this study,an updated numerical procedure for the submarine tunnel is derived by coupling strain-softening and seepage effect based on the experimental results.According to the hydro-mechanical coupling theory,the hydro-mechanical parameters such as elastic modulus,Poisson's ratio,Biot's coefficient and permeability coefficient of rocks are characterized by the fitting equations derived from the experimental data.Then,the updated numerical procedure is deduced with the governing equations,boundary conditions,seepage equations and fitting equations.The updated numerical procedure is verified accurately compared with the previous analytical solution.By utilizing the updated numerical procedure,the characteristics of stress field and the influences of initial pore water pressure,Biot's coefficient,and permeability coefficient on the stress,displacement and water-inflow of the surrounding rocks are discussed.Regardless of the variations in hydro-mechanical parameters,the stress distribution has a similar trend.The initial permeability coefficient exerts the most significant influence on the stress field.With the increases in initial pore water pressure and Biot's coefficient,the plastic region expands,and the water-inflow and displacement increase accordingly.Given the fact that the stability of the tunnel is more sensitive to the seepage force controlled by the hydraulic parameters,it is suggested to dewater the ground above the submarine tunnel to control the initial pore water pressure.展开更多
N-participated lignin depolymerization is of great importance for the transformation of waste lignin into value-added chemicals.The vast majority of developed strategies employ organic amines as nitrogen source,and co...N-participated lignin depolymerization is of great importance for the transformation of waste lignin into value-added chemicals.The vast majority of developed strategies employ organic amines as nitrogen source,and considerablemethods rely on excessive use of strong base,which suffers severe environmental issues.Herein,benzonitrile derivatives are synthesized from oxidized ligninβ-O-4 model compounds in the presence of solid nitrogen source(NH_(4))_(2)CO_(3)under mild,base-free conditions over commercially available copper catalyst.Mechanism studies suggest the transformation undergoes a one-pot,highly coupled cascade reaction path involving oxidative C-C bond cleavage and in-situ formation of C≡N bond.Of which,Cu(OAc)2 catalyzes the transfer of hydrogen from C_(β)(C_(β)-H)to C_(α),leading to the cleavage of C_(α)-C_(β)bonds to offer benzaldehyde derivative,this intermediate then reacts in-situ with(NH_(4))_(2)CO_(3)to afford the targeted aromatic nitrile product.Tetrabutylammonium iodide(TBAI),acting as a promoter,plays a key role in breaking the C_(α)-C_(β)bonds to form the intermediate benzaldehyde derivative.With this protocol,the feasibility of the production of value-added syringonitrile from birchwood lignin has been demonstrated.This transformation provides a sustainable approach to benzonitrile chemicals from renewable source of lignin.展开更多
The pioneering works have demonstrated that the method of single collisions in crossed molecular beams is an important technique for achieving kinetic cooling of atoms or molecules in specific rotational states.In thi...The pioneering works have demonstrated that the method of single collisions in crossed molecular beams is an important technique for achieving kinetic cooling of atoms or molecules in specific rotational states.In this study,we investigated the elastic and inelastic collisions between Al(^(2)P_(1/2))metal atoms and O_(2)molecules at high collision energies in the range of 6.4-14.8 kcal/mol,utilizing the laser-ablation crossed beams in conjunction with time-sliced ion velocity map imaging technique.We observed kinetic cooling of Al(^(2)P_(1/2))atoms with an upper-limit laboratory-frame root-mean-square velocity of 24±3 m/s,corresponding to a translational temperature of 0.9±0.2 K in the laboratory frame,facilitated by the vibrational excitation of O_(2)(v′=1)in inelastic collisions.The translational cooling of Al atoms in the lab frame enhanced detection probability in the transformation of density-to-flux,as evidenced by the scattering images obtained during the experiments.展开更多
We report the design of a wide-range energy material beamline(E-line) with multiple experimental techniques at the Shanghai Synchrotron Radiation Facility.The undulators consisted of an elliptically polarizing undulat...We report the design of a wide-range energy material beamline(E-line) with multiple experimental techniques at the Shanghai Synchrotron Radiation Facility.The undulators consisted of an elliptically polarizing undulator and in-vacuum undulator that generate the soft and hard X-rays, respectively. The beamline covered a wide energy range from 130 to 18 ke V with both a high photon flux([ 10^(12) phs/s with exit silt 30 lm in soft X-ray and [ 5 9 10^(12) phs/s in hard X-ray within 0.1%BW bandwidth) and promising resolving power(maximum E/DE [ 15,000 in soft X-ray with exit silt 30 lm and [6000 in hard X-ray). Moreover, the beam spots from the soft and hard X-rays were focused to the same sample position with a high overlap ratio, so that the surfaces, interfaces, and bulk properties were characterized in situ by changing the probing depth.展开更多
Our previous study revealed that intragastric administration of naringin improved remyelination in rats with spinal cord injury and promoted the recovery of neurological function of the injured spinal cord.This study ...Our previous study revealed that intragastric administration of naringin improved remyelination in rats with spinal cord injury and promoted the recovery of neurological function of the injured spinal cord.This study sought to reveal the mechanisms by which naringin improves oligodendrocyte precursor cell differentiation and maturation,and promotes remyelination.Spinal cord injury was induced in rats by the weight-drop method.Naringin was intragastrically administered daily（20,40 mg/kg） for 4 weeks after spinal cord injury induction.Behavioral assessment,histopathological staining,immunofluorescence spectroscopy,ultrastructural analysis and biochemical assays were employed.Naringin treatment remarkably mitigated demyelination in the white matter,increased the quality of myelinated nerve fibers and myelin sheath thickness,promoted oligodendrocyte precursor cell differentiation by upregulating the expression of NKx2.2 and 2′3′-cyclic nucleotide 3′-phosphodiesterase,and inhibited β-catenin expression and glycogen synthase kinase-3β（GSK-3β） phosphorylation.These findings indicate that naringin treatment regulates oligodendrocyte precursor cell differentiation and promotes remyelination after spinal cord injury through the β-catenin/GSK-3β signaling pathway.展开更多
The speciation and atomic structures of corrosion products in Ni-based alloys could provide basic information for understanding the Te corrosion mechanism.In this paper,two-dimensional synchrotron-radiation-induced gr...The speciation and atomic structures of corrosion products in Ni-based alloys could provide basic information for understanding the Te corrosion mechanism.In this paper,two-dimensional synchrotron-radiation-induced grazing incidence X-ray diffraction was used to characterize the corrosion products of a Ni–18%Cr binary alloy at temperatures from 600 to 1000℃.The results showed that a film of CrTe is preferentially formed when Te reacts with the Ni-based alloy at low temperatures(below 900℃),while CrTe and Ni3Te2 are formed at 900℃.Moreover,at a temperature of 1000℃,a solid solution is formed without any changes in the Ni–Cr substrate lattice parameters.Furthermore,X-ray absorption fine structure and wavelet transform analyses were used to investigate the atomic local structure of Te.The investigation indicated that Te atoms diffuse into the Ni–Cr substrate to form a substitutional Ni–Cr–Te solid solution at 1000℃.Notably,based on a discussion of the thermodynamics of the chemical reaction process,CrTe is considered to be the most stable and prevalent corrosion product due to its comparatively lower Gibbs free energy of formation.These results demonstrate that the Ni–18%Cr alloy is capable of resisting the diffusion of Te atoms.展开更多
The quantitative understanding of how atomic-level catalyst structural changes affect the reactivity of the electrochemical CO_(2)reduction reaction is challenging.Due to the complexity of catalytic systems,convention...The quantitative understanding of how atomic-level catalyst structural changes affect the reactivity of the electrochemical CO_(2)reduction reaction is challenging.Due to the complexity of catalytic systems,conventional in situ X-ray spectroscopy plays a limited role in tracing the underlying dynamic structural changes in catalysts active sites.Herein,operando high-energy resolution fluorescence-detected X-ray absorption spectroscopy was used to precisely identify the dynamic structural transformation of well-defined active sites of a representative model copper(Ⅱ)phthalocyanine catalyst which is of guiding significance in studying single-atom catalysis system.Comprehensive X-ray spectroscopy analyses,including surface sensitive△μspectra which isolates the surface changes by subtracting the disturb of bulk base and X-ray absorption near-edge structure spectroscopy simulation,were used to discover that Cu species aggregated with increasing applied potential,which is responsible for the observed evolution of C_(2)H_(4).The approach developed in this work,characterizing the active-site geometry and dynamic structural change,is a novel and powerful technique to elucidate complex catalytic mechanisms and is expected to con tribute to the rational design of highly effective catalysts.展开更多
基金funded by the European Union's Horizon 2020 research and innovation programme under a grant agreement (Grant No.847593)partially supported by the Fundamental Research Funds for the Central Universities (Grant No.22120240029).
文摘This study presents a fully coupled thermo-hydro-mechanical (THM) constitutive model for clay rocks. The model is formulated within the elastic-viscoplasticity framework, which considers nonlinearity and softening after peak strength, anisotropy of stiffness and strength, as well as permeability variation due to damage. In addition, the mechanical properties are coupled with thermal phenomena and accumulated plastic strains. The adopted nonlocal and viscoplastic approaches enhance numerical efficiency and provide the possibility to simulate localization phenomena. The model is validated against experimental data from laboratory tests conducted on Callovo-Oxfordian (COx) claystone samples that are initially unsaturated and under suction. The tests include a thermal phase where the COx specimens are subjected to different temperature increases. A good agreement with experimental data is obtained. In addition, parametric analyses are carried out to investigate the influence of the hydraulic boundary conditions (B.C.) and post-failure behavior models on the THM behavior evolution. It is shown that different drainage conditions affect the thermally induced pore pressures that, in turn, influence the onset of softening. The constitutive model presented constitutes a promising approach for simulating the most important features of the THM behavior of clay rocks. It is a tool with a high potential for application to several relevant case studies, such as thermal fracturing analysis of nuclear waste disposal systems.
基金supported by the National Key R&D Program of China(No.2023YFA1507902)the Science and Technology Bureau of Dalian City(No.2021RT04)+3 种基金the Shaanxi Provincial Science and Technology Department(Nos.2024JC-YBQN-0100 and QCYRCXM-2023-079)the Youth innovation team project of Shaanxi Province Education Department(No.23JP199)the Science and Technology Plan Project of Yulin Government(No.2023-CXY-137)the Initial Scientific Research Fund of High Level Talents in Yulin University(No.2023GK44).
文摘Green and atom-economic depolymerization of lignin remains a great challenge due toits complex non-repetitive structure and the inert property for chemo-digestion. A redoxneutrallignin depolymerization system without the use of extra oxidant and/or reductantover a Co-NC catalyst has been developed in this work, providing the first non-noble metalheterogeneous catalytic system for redox-neutral valorization of lignin. Mechanistic studiesbased on control reactions and deuterium labeling experiments suggest that the reactionproceeds via ametal-catalyzed dehydrogenation of C_(α)-OH to afford a carbonyl intermediate,followed by C_(β)-O bond cleavage (via hydrogenolysis) to afford monophenols and aromaticketone products. The hydrogen used for the cleavage of the C_(β)-O bond originates from thealcoholmoiety in the substrate, and the cascade dehydrogenation and hydrogenolysis stepsare highly coupled, rendering it an efficient and atom-economic process.
文摘The effect of prenatal exposure to ambient particulate matter(PM)on birth weight varies considerably across studies,and the findings remain inconclusive.In this study,we conducted a meta-analysis to assess the associations between exposure to PM_(2.5) and PM10 and birth weight.A total of 74 studies were identified through searches in Web of Science,PubMed,Embase,and Ovid Medline,as well as manual searches,up to October 2024.We found that for each 10μg/m^(3) increase in PM_(2.5),the risk of low birth weight(LBW)increased significantly during the entire pregnancy(odds ratio[OR]=2.41,95%confidence interval[CI]:1.99–2.91)and in all trimesters.Similarly,for every 10μg/m^(3) increase in PM10 concentration,the risk of LBW increased significantly during the entire pregnancy(OR=1.46,95%CI:1.16–1.84).Subgroup analysis by maternal age for PM_(2.5) showed that mothers aged 30 and above had a significantly higher risk of LBW(OR=3.69,95%CI:2.81–4.84),compared with those under 30.In conclusion,maternal exposure to PM_(2.5) and PM_(10) is associated with an increased risk of LBW across all trimesters.Additionally,mothers aged 30 and above are at a higher risk of LBW,compared with younger mothers.Further research is needed to clarify the biological mechanisms by which PM pollution may contribute to LBW.
基金supported by the National Natural Science Foundation of China(Grant Nos.52279118 and U21A20159)Sub-project of National Key Research and Development(Grant No.2023YFC3007403).
文摘The seepage of groundwater and the strain-softening of rock mass in a submarine tunnel expand the plastic region of rock,thereby affecting its overall stability.It is therefore essential to study the stress and strain fields in the rocks surrounding the submarine tunnel by considering the coupled effect of strainsoftening and seepage.However,the evolution equation for the hydro-mechanical parameters in the existing fully coupled solution is a uniform equation that is unable to reproduce the characteristics of rock mass in practice.In this study,an updated numerical procedure for the submarine tunnel is derived by coupling strain-softening and seepage effect based on the experimental results.According to the hydro-mechanical coupling theory,the hydro-mechanical parameters such as elastic modulus,Poisson's ratio,Biot's coefficient and permeability coefficient of rocks are characterized by the fitting equations derived from the experimental data.Then,the updated numerical procedure is deduced with the governing equations,boundary conditions,seepage equations and fitting equations.The updated numerical procedure is verified accurately compared with the previous analytical solution.By utilizing the updated numerical procedure,the characteristics of stress field and the influences of initial pore water pressure,Biot's coefficient,and permeability coefficient on the stress,displacement and water-inflow of the surrounding rocks are discussed.Regardless of the variations in hydro-mechanical parameters,the stress distribution has a similar trend.The initial permeability coefficient exerts the most significant influence on the stress field.With the increases in initial pore water pressure and Biot's coefficient,the plastic region expands,and the water-inflow and displacement increase accordingly.Given the fact that the stability of the tunnel is more sensitive to the seepage force controlled by the hydraulic parameters,it is suggested to dewater the ground above the submarine tunnel to control the initial pore water pressure.
基金supported by the National Key R&D Program of China(No.2023YFA1507902)the National Natural Science Foundation of China(Nos.21721004 and 21878288)+1 种基金the science and technology bureau of Dalian city(No.2021RT04)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB17020100).
文摘N-participated lignin depolymerization is of great importance for the transformation of waste lignin into value-added chemicals.The vast majority of developed strategies employ organic amines as nitrogen source,and considerablemethods rely on excessive use of strong base,which suffers severe environmental issues.Herein,benzonitrile derivatives are synthesized from oxidized ligninβ-O-4 model compounds in the presence of solid nitrogen source(NH_(4))_(2)CO_(3)under mild,base-free conditions over commercially available copper catalyst.Mechanism studies suggest the transformation undergoes a one-pot,highly coupled cascade reaction path involving oxidative C-C bond cleavage and in-situ formation of C≡N bond.Of which,Cu(OAc)2 catalyzes the transfer of hydrogen from C_(β)(C_(β)-H)to C_(α),leading to the cleavage of C_(α)-C_(β)bonds to offer benzaldehyde derivative,this intermediate then reacts in-situ with(NH_(4))_(2)CO_(3)to afford the targeted aromatic nitrile product.Tetrabutylammonium iodide(TBAI),acting as a promoter,plays a key role in breaking the C_(α)-C_(β)bonds to form the intermediate benzaldehyde derivative.With this protocol,the feasibility of the production of value-added syringonitrile from birchwood lignin has been demonstrated.This transformation provides a sustainable approach to benzonitrile chemicals from renewable source of lignin.
基金supported by the National Natural Science Foundation of China(Nos.22473029,21327901,and 22073019)the Science and Technology Commission of Shanghai Municipality(No.2024ZDSYS02)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning.
文摘The pioneering works have demonstrated that the method of single collisions in crossed molecular beams is an important technique for achieving kinetic cooling of atoms or molecules in specific rotational states.In this study,we investigated the elastic and inelastic collisions between Al(^(2)P_(1/2))metal atoms and O_(2)molecules at high collision energies in the range of 6.4-14.8 kcal/mol,utilizing the laser-ablation crossed beams in conjunction with time-sliced ion velocity map imaging technique.We observed kinetic cooling of Al(^(2)P_(1/2))atoms with an upper-limit laboratory-frame root-mean-square velocity of 24±3 m/s,corresponding to a translational temperature of 0.9±0.2 K in the laboratory frame,facilitated by the vibrational excitation of O_(2)(v′=1)in inelastic collisions.The translational cooling of Al atoms in the lab frame enhanced detection probability in the transformation of density-to-flux,as evidenced by the scattering images obtained during the experiments.
基金supported by the National Development and Reform Commission(NDRC) of Chinathe National Natural Science Foundation of China(No.11505280)+1 种基金the Shanghai Youth Foundation(No.14YF1407500)the National Science Foundation of China(Nos.11475251,11225527)
文摘We report the design of a wide-range energy material beamline(E-line) with multiple experimental techniques at the Shanghai Synchrotron Radiation Facility.The undulators consisted of an elliptically polarizing undulator and in-vacuum undulator that generate the soft and hard X-rays, respectively. The beamline covered a wide energy range from 130 to 18 ke V with both a high photon flux([ 10^(12) phs/s with exit silt 30 lm in soft X-ray and [ 5 9 10^(12) phs/s in hard X-ray within 0.1%BW bandwidth) and promising resolving power(maximum E/DE [ 15,000 in soft X-ray with exit silt 30 lm and [6000 in hard X-ray). Moreover, the beam spots from the soft and hard X-rays were focused to the same sample position with a high overlap ratio, so that the surfaces, interfaces, and bulk properties were characterized in situ by changing the probing depth.
基金supported by the Natural Science Foundation of Beijing of China,No.7164317the Beijing Tsinghua Changgung Hospital Fund,No.12015C1028the National Natural Science Foundation of China,No.31400717
文摘Our previous study revealed that intragastric administration of naringin improved remyelination in rats with spinal cord injury and promoted the recovery of neurological function of the injured spinal cord.This study sought to reveal the mechanisms by which naringin improves oligodendrocyte precursor cell differentiation and maturation,and promotes remyelination.Spinal cord injury was induced in rats by the weight-drop method.Naringin was intragastrically administered daily（20,40 mg/kg） for 4 weeks after spinal cord injury induction.Behavioral assessment,histopathological staining,immunofluorescence spectroscopy,ultrastructural analysis and biochemical assays were employed.Naringin treatment remarkably mitigated demyelination in the white matter,increased the quality of myelinated nerve fibers and myelin sheath thickness,promoted oligodendrocyte precursor cell differentiation by upregulating the expression of NKx2.2 and 2′3′-cyclic nucleotide 3′-phosphodiesterase,and inhibited β-catenin expression and glycogen synthase kinase-3β（GSK-3β） phosphorylation.These findings indicate that naringin treatment regulates oligodendrocyte precursor cell differentiation and promotes remyelination after spinal cord injury through the β-catenin/GSK-3β signaling pathway.
基金supported by the National Key Research and Development Program of China(No.2016YFB0700404)National Natural Science Foundation of China(No.U1732267)+2 种基金National Natural Science Foundation of China(Nos.51671122 and 51671154)Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA02004210)Talent Development Fund of Shanghai(No.201650)
文摘The speciation and atomic structures of corrosion products in Ni-based alloys could provide basic information for understanding the Te corrosion mechanism.In this paper,two-dimensional synchrotron-radiation-induced grazing incidence X-ray diffraction was used to characterize the corrosion products of a Ni–18%Cr binary alloy at temperatures from 600 to 1000℃.The results showed that a film of CrTe is preferentially formed when Te reacts with the Ni-based alloy at low temperatures(below 900℃),while CrTe and Ni3Te2 are formed at 900℃.Moreover,at a temperature of 1000℃,a solid solution is formed without any changes in the Ni–Cr substrate lattice parameters.Furthermore,X-ray absorption fine structure and wavelet transform analyses were used to investigate the atomic local structure of Te.The investigation indicated that Te atoms diffuse into the Ni–Cr substrate to form a substitutional Ni–Cr–Te solid solution at 1000℃.Notably,based on a discussion of the thermodynamics of the chemical reaction process,CrTe is considered to be the most stable and prevalent corrosion product due to its comparatively lower Gibbs free energy of formation.These results demonstrate that the Ni–18%Cr alloy is capable of resisting the diffusion of Te atoms.
基金supported by the National Natural Science Foundation of China,grant number:U1732267.
文摘The quantitative understanding of how atomic-level catalyst structural changes affect the reactivity of the electrochemical CO_(2)reduction reaction is challenging.Due to the complexity of catalytic systems,conventional in situ X-ray spectroscopy plays a limited role in tracing the underlying dynamic structural changes in catalysts active sites.Herein,operando high-energy resolution fluorescence-detected X-ray absorption spectroscopy was used to precisely identify the dynamic structural transformation of well-defined active sites of a representative model copper(Ⅱ)phthalocyanine catalyst which is of guiding significance in studying single-atom catalysis system.Comprehensive X-ray spectroscopy analyses,including surface sensitive△μspectra which isolates the surface changes by subtracting the disturb of bulk base and X-ray absorption near-edge structure spectroscopy simulation,were used to discover that Cu species aggregated with increasing applied potential,which is responsible for the observed evolution of C_(2)H_(4).The approach developed in this work,characterizing the active-site geometry and dynamic structural change,is a novel and powerful technique to elucidate complex catalytic mechanisms and is expected to con tribute to the rational design of highly effective catalysts.
