By combination of the transient Raman spectroscopic measurement and the density functional theoretical calculations,the structural evolution and stability of TATB under shock compression was investigated.Due to the im...By combination of the transient Raman spectroscopic measurement and the density functional theoretical calculations,the structural evolution and stability of TATB under shock compression was investigated.Due to the improvement in synchronization control between two-stage light gas gun and the transient Raman spectra acquisition,as well as the sample preparation,the Raman peak of the N-O mode of TATB was firstly observed under shock pressure up to 13.6 GPa,noticeably higher than the upper limit of 8.5 GPa reported in available literatures.By taking into account of the continuous shift of the main peak and other observed Raman peaks,we did not distinguish any structural transition or any new species.Moreover,both the present Raman spectra and the time-resolved radiation of TATB during shock loading showed that TATB exhibits higher chemical stability than previous declaration.To reveal the detailed structural response and evolution of TATB under compression,the density functional theoretical calculations were conducted,and it was found that the pressure make N-O bond lengths shorter,nitro bond angles larger,and intermolecular and intra-molecular hydrogen bond interactions enhanced.The observed red shift of Raman peak was ascribed to the abnormal enhancement of H-bound effect on the scissor vibration mode of the nitro group.展开更多
The presence of oxygen functional groups is detrimental to the capacitive performance of porous carbon electrode in organic electrolyte. In this regards, hydrogen thermal reduction has been demonstrated effective appr...The presence of oxygen functional groups is detrimental to the capacitive performance of porous carbon electrode in organic electrolyte. In this regards, hydrogen thermal reduction has been demonstrated effective approach in removing the unstable surface oxygen while maintaining the high porosity of carbon matrix. However, the exact evolution mechanism of various oxygen species during this process, as well as the correlation with electrochemical properties, is still under development. Herein, biomass-based porous carbon is adopted as the model material to trace its structure evolution of oxygen removal under hydrogen thermal reduction process with the temperature range of 400–800 °C. The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700°C. XPS, TPRMS and Boehm titration results indicate that the oxygen elimination undergoes three distinctive stages(intermolecular dehydration, hydrogenation and decomposition reactions). The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700 °C. Benefiting from the stable electrochemical interface and the optimized porous structure, the as-obtained HAC-700 exhibit significantly suppressed self-discharge and leak current, with improved cycling stability, which is attributable to the stabilization of electrochemical interface between carbon surface and electrolyte. The result provides insights for rational design of surface chemistry for high-performance carbon electrode towards advanced energy storage.展开更多
Lithium ion batteries are important electrochemical energy storage devices for consumer electronics and the most promising candidates for electrical/hybrid vehicles. The surface chemistry influences the performance of...Lithium ion batteries are important electrochemical energy storage devices for consumer electronics and the most promising candidates for electrical/hybrid vehicles. The surface chemistry influences the performance of the batteries significantly. In this short review, the ewlution of the surface struture of the cathode materials at different states of the pristine, storage and electrochemical reaclions are summarized. The main methods for the surface modification are also introduced.展开更多
This study aimed to investigate the mechanism of nitrogen doping,migration,and conversion during ammonia torrefaction and also explore the evolution law of the chemical structure of cellulose.The results showed that t...This study aimed to investigate the mechanism of nitrogen doping,migration,and conversion during ammonia torrefaction and also explore the evolution law of the chemical structure of cellulose.The results showed that the ammonia torrefaction pretreatment could significantly optimize the distribution of nitrogen and oxygen elements in cellulose.The carbon skeleton first captured the active nitrogenous radicals to form-NHn-N,and pyridine-N and pyrrole-N originated from the conversion of-NHn-N.The existence of C=O played a major role in the immobilization of nitrogen.The nitrogen in bio-oil exists mainly in the form of five-and six-membered heterocycles.The correlation analysis showed that the main precursors for the formation of nitrogenous heterocyclic compounds were five-membered Oheterocyclic compounds.Finally,the product distribution characteristics in the torrefaction-pyrolysis systems were summarized,and the nitrogen doping and conversion mechanisms were proposed.This study expanded the boundaries of cellulose pretreatment and the production of high-value chemicals.展开更多
The Tongnan secondary negative structure in central Sichuan Basin has controls and influences on the structural framework and petroleum geological conditions in the Gaoshiti-Moxi area.To clarify the controls and influ...The Tongnan secondary negative structure in central Sichuan Basin has controls and influences on the structural framework and petroleum geological conditions in the Gaoshiti-Moxi area.To clarify the controls and influences,the deformation characteristics,structural attributes and evolution process of the Tongnan negative structure were investigated through a series of qualitative and quantitative methods such as balanced profile restoration,area-depth-strain(ADS)analysis,and structural geometric forward numerical simulation,after comprehensive structural interpretation of high-precision 3D seismic data.The results are obtained in three aspects.First,above and below the P/AnP(Permian/pre-Permian)unconformity,the Tongnan negative structure demonstrates vertical differential structural deformation.It experiences two stages of structural stacking and reworking:extensional depression(from the Sinian Dengying Formation to the Permian),and compressional syncline deformation(after the Jurassic).The multi-phase trishear deformation of the preexisting deep normal faults dominated the extensional depression.The primary depression episodes occurred in the periods from the end of Late Proterozoic to the deposition of the 1st–2nd members of the Dengying Formation,and from the deposition of Lower Cambrian Longwangmiao Formation–Middle–Upper Cambrian until the Ordovician.Second,the multi-stage evolution process of the Tongnan negative structure controlled the oil and gas migration and adjustment and present-day differential gas and water distribution between the Tongnan negative structure and the Gaoshiti and Moxi-Longnüsi structural highs.Third,the Ordovician,which is limitedly distributed in the Tongnan negative structure and is truncated by the P/AnP unconformity on the top,has basic geological conditions for the formation of weathering karst carbonate reservoirs.It is a new petroleum target deserving attention.展开更多
Pyrolysis experiments were conducted on lacustrine organic-rich shale from Cangdong Sag in Bohai Bay Basin,China,to investigate the impact of hydrocarbon generation on shale pore structure evolution.Thermal evolution ...Pyrolysis experiments were conducted on lacustrine organic-rich shale from Cangdong Sag in Bohai Bay Basin,China,to investigate the impact of hydrocarbon generation on shale pore structure evolution.Thermal evolution is found to control the transformation of organic matter,hydrocarbon products characteristics,and pore structure changes.Furthermore,pore volume and specific surface area increase with increasing maturity.In low-mature stage,the retained oil content begins to increase,pore volumes show slight changes,and primary pores are occluded by the generated crude oil of high molecular weight and density.In the oil-window stage,the retained oil content rapidly increases and reaches maximum,and pore volumes gradually increase with increasing thermal maturity.At high mature stage,the retained oil content begins to decrease,and the pore volume increases considerably owing to the expulsion of liquid hydrocarbon.In over mature stage,natural gas content significantly increases and kerogen transforms to asphalt.Numerous organic pores are formed and the pore size gradually increases,resulting from the connection of organic pores caused the increasing thermal stress.This study lays a foundation for understanding variation of hydrocarbon products during the thermal evolution of lacustrine shales and its relationship with the evolution of shale reservoirs.展开更多
The evolution of a magnetic domain structure induced by temperature and magnetic field is reported in silicon- doped yttrium iron garnet （YIG） films with perpendicular anisotropy. During a cooling-down procedure fro...The evolution of a magnetic domain structure induced by temperature and magnetic field is reported in silicon- doped yttrium iron garnet （YIG） films with perpendicular anisotropy. During a cooling-down procedure from 300K to 7K, a 20% change in the domain width is observed, with the long tails of the stripes being shortened and the twisting stripes being straightened. Under the influence of the stray field of a barium ferrite, the garnet presents an interesting domain structure, which shows an appearance of branching protrusions. The intrinsic mechanisms in these two processes are also discussed.展开更多
We perform systematic thermal conductivity measurements on heavily hole-doped Ba1-xKxFe2As2 single crystals with 0.747 ≤ x ≤ 0.974. At x=0.747, the K0/T is negligible, indicating a nodeless superconducting gap. A sm...We perform systematic thermal conductivity measurements on heavily hole-doped Ba1-xKxFe2As2 single crystals with 0.747 ≤ x ≤ 0.974. At x=0.747, the K0/T is negligible, indicating a nodeless superconducting gap. A small residual linear term K0/T （=0.035 m W.K-2 cm-1） appears at xz0.826, and it increases slowly up to x=0.974, followed by a substantial increase of more than 20 times to of K0/T clearly shows that the nodal gap appears near x surface topology. The small values of K0/T from x=0.826 the pure KFe2As2 （x=1.0）. This doping dependence = 0.8, possibly associated with the change of Fermi to 0.974 are consistent with the Y-shaped nodal s- wave gap recently revealed by angle-resolved photoemission spectroscopy experiments at x=0.9. Furthermore, the substantial increase of K0/T from x=0.974 to 1.0 is inconsistent with a symmetry-imposed d-wave gap in KFe2 As2, and a possible nodal gap structure in KFe2As2 is discussed.展开更多
The integrability of a （2＋1）-dimensional super nonlinear evolution equation is analyzed in the framework of the fermionie covariant prolongation structure theory. We construct the prolongation structure of the mult...The integrability of a （2＋1）-dimensional super nonlinear evolution equation is analyzed in the framework of the fermionie covariant prolongation structure theory. We construct the prolongation structure of the multidimen- sional super integrable equation and investigate its Lax representation. Furthermore, the Backlund transformation is presented and we derive a solution to the super integrable equation.展开更多
The first-principles calculations are performed to examine structural,mechanical,and electronic properties at large strain for a monolayer C_(4)N_(4),which has been predicted as an anchoring promising material to atte...The first-principles calculations are performed to examine structural,mechanical,and electronic properties at large strain for a monolayer C_(4)N_(4),which has been predicted as an anchoring promising material to attenuate shuttle effect in Li–S batteries stemming from its large absorption energy and low diffusion energy barrier.Our results show that the ideal strengths of C_(4)N_(4)under tension and pure shear deformation conditions reach 13.9 GPa and 12.5 GPa when the strains are 0.07 and 0.28,respectively.The folded five-membered rings and diverse bonding modes between carbon and nitrogen atoms enhance the ability to resist plastic deformation of C_(4)N_(4).The orderly bond-rearranging behaviors under the weak tensile loading path along the[100]direction cause the impressive semiconductor–metal transition and inverse semiconductor–metal transition.The present results enrich the knowledge of the structure and electronic properties of C_(4)N_(4)under deformations and shed light on exploring other two-dimensional materials under diverse loading conditions.展开更多
With drilling and seismic data of Transtensional(strike-slip)Fault System in the Ziyang area of the central Sichuan Basin,SW China plane-section integrated structural interpretation,3-D fault framework model building,...With drilling and seismic data of Transtensional(strike-slip)Fault System in the Ziyang area of the central Sichuan Basin,SW China plane-section integrated structural interpretation,3-D fault framework model building,fault throw analyzing,and balanced profile restoration,it is pointed out that the transtensional fault system in the Ziyang 3-D seismic survey consists of the northeast-trending F_(I)19 and F_(I)20 fault zones dominated by extensional deformation,as well as 3 sets of northwest-trending en echelon normal faults experienced dextral shear deformation.Among them,the F_(I)19 and F_(I)20 fault zones cut through the Neoproterozoic to Lower Triassic Jialingjiang Formation,presenting a 3-D structure of an“S”-shaped ribbon.And before Permian and during the Early Triassic,the F_(I)19 and F_(I)20 fault zones underwent at least two periods of structural superimposition.Besides,the 3 sets of northwest-trending en echelon normal faults are composed of small normal faults arranged in pairs,with opposite dip directions and partially left-stepped arrangement.And before Permian,they had formed almost,restricting the eastward growth and propagation of the F_(I)19 fault zone.The F_(I)19 and F_(I)20 fault zones communicate multiple sets of source rocks and reservoirs from deep to shallow,and the timing of fault activity matches well with oil and gas generation peaks.If there were favorable Cambrian-Triassic sedimentary facies and reservoirs developing on the local anticlinal belts of both sides of the F_(I)19 and F_(I)20 fault zones,the major reservoirs in this area are expected to achieve breakthroughs in oil and gas exploration.展开更多
With the increase of energy consumption,the shortage of fossil resource,and the aggravation of environmental pollution,the development of cost-effective and environmental friendly bio-based energy storage devices has ...With the increase of energy consumption,the shortage of fossil resource,and the aggravation of environmental pollution,the development of cost-effective and environmental friendly bio-based energy storage devices has become an urgent need.As the second most abundant natural polymer found in nature,lignin is mainly produced as the by-product of paper pulping and bio-refining industries.It possesses several inherent advantages,such as low-cost,high carbon content,abundant functional groups,and bio-renewable,making it an attractive candidate for the rechargeable battery material.Consequently,there has been a surge of research interest in utilizing lignin or lignin-based carbon materials as the components of lithium-ion(LIBs)or sodium-ion batteries(SIBs),including the electrode,binder,separator,and electrolyte.This review provides a comprehensive overview on the research progress of lignin-derived materials used in LIBs/SIBs,especially the application of lignin-based carbons as the anodes of LIBs/SIBs.The preparation methods and properties of lignin-derived materials with different dimensions are systemically discussed,which emphasizes on the relationship between the chemical/physical structures of lignin-derived materials and the performances of LIBs/SIBs.The current challenges and future prospects of lignin-derived materials in energy storage devices are also proposed.展开更多
Electrochemical oxygen evolution reaction (OER) is a main efficiency bottleneck of water electrolysis.Commercial ruthenium oxide (RuO_(2)) catalyst displays remarkable activities but poor stability for OER.The instabi...Electrochemical oxygen evolution reaction (OER) is a main efficiency bottleneck of water electrolysis.Commercial ruthenium oxide (RuO_(2)) catalyst displays remarkable activities but poor stability for OER.The instability stems from lattice oxygen oxidation,resulting in the oxidation of Ru^(4+) to soluble Ru^(4+)(x>4) species.Herein,we redirect dynamic structural evolution of Ru-based catalysts through introducing oxidized nickel (Ni) components.By virtue of comprehensive structural characterizations,such as high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM),X-ray photoelectron spectroscopy (XPS),operando Raman and so forth,it is demonstrated that when the atomic content of Ni exceeds that of ruthenium (Ru),the Ni components can efficiently inhibit the Ru^(4+) oxidation and structural collapse.Density functional theory (DFT) calculations suggest that the introduction of Ni component hinders the formation of oxygen vacancies,and makes lattice oxygen mediated mechanism turn to adsorbate evolution mechanism,which eventually improves the stability.The optimized nickel-contained RuO_(2) catalyst delivers an effective reactivity with an overpotential of less than 215 m V to attain 10 m A cm^(-2) and remarkable stability with only 5 mV increment after 5000 potential cycles.This work provides insights into the origin of dynamic structural evolution of transition-metalmodified RuO_(2) electrocatalysts.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
In order to determine the area for oil and gas exploration in China’s north Sichuan basin,we have divided the time during which the Longmenshan foreland basin was formed into five periods,based on the sedimentary res...In order to determine the area for oil and gas exploration in China’s north Sichuan basin,we have divided the time during which the Longmenshan foreland basin was formed into five periods,based on the sedimentary response relationship of the foreland basin to structural evolution: 1) a late Triassic Noric period;2) an early-Middle Jurassic period;3) a late Jurassic to early Cretaceous period;4) a late Cretaceous to Paleogene-Neogene period and 5) the Quaternary period. As well,we analyzed the sedimentary environment and lithologic features of every basin-forming period. The results show that there are several favorable source-reservoir-cap assemblages in our study area,making it a major region for future oil and gas exploration in China’s northern Sichuan basin.展开更多
Developing bifunctional electrocatalysts with both high catalytic activity and high stability is crucial for efficient water splitting in alkaline media.Herein,a Fe-incorporated dual-metal selenide on nickel foam(Co_(...Developing bifunctional electrocatalysts with both high catalytic activity and high stability is crucial for efficient water splitting in alkaline media.Herein,a Fe-incorporated dual-metal selenide on nickel foam(Co_(0.9)Fe_(0.1)-Se/NF) is synthesized via a facile one-step electrodeposition method.As-synthesized materials could serve as self-supported bifunctional electrocatalysts with excellent catalytic activity towards oxygen evolution reaction(OER) and hydrogen evolution reaction(HER) in alkaline media.Experimental results show that delivering a 10 mA cm^(-2) water splitting current density only requires a cell voltage of 1.55 V.In addition,a very stable performance could be kept for about 36 hours,indicating their excellent working stability.Moreover,by means of phase analysis,we have identified that the evolution of the synthesized Co_(0.9)Fe_(0.1)-Se/NF experiences two entirely different processes in HER and OER,which hydroxide and oxyhydroxide are regarded as the real active sites,respectively.This work may pave the way to further understanding the relationships between the reactivity and stability of chalcogenide-based electrocatalysts and facilitating the rational design of efficient electrocatalysts for future renewable energy system applications.展开更多
We elucidate the importance of a capping layer on the structural evolution and phase change properties of carbondoped Ge2 Sb2 Te5（C-GST） films during heating in air. Both the C-GST films without and with a thin SiO2...We elucidate the importance of a capping layer on the structural evolution and phase change properties of carbondoped Ge2 Sb2 Te5（C-GST） films during heating in air. Both the C-GST films without and with a thin SiO2 capping layer（C-GST and C-GST/SiO2） are deposited for comparison. Large differences are observed between C-GST and C-GST/SiO2 films in resistance-temperature, x-ray diffraction, x-ray photoelectron spectroscopy,Raman spectra, data retention capability and optical band gap measurements. In the C-GST film, resistancetemperature measurement reveals an unusual smooth decrease in resistance above 110℃ during heating. Xray diffraction result has excluded the possibility of phase change in the C-GST film below 170℃. The x-ray photoelectron spectroscopy experimental result reveals the evolution of Te chemical valence because of the carbon oxidation during heating. Raman spectra further demonstrate that phase changes from an amorphous state to the hexagonal state occur directly during heating in the C-GST film. The quite smooth decrease in resistance is believed to be related with the formation of Te-rich GeTe4-n Gen（n = 0, 1） units above 110℃ in the C-GST film. The oxidation of carbon is harmful to the C-GST phase change properties.展开更多
Structural, electronic, and magnetic properties of AunGd （n = 6-15） small clusters are investigated by using first principles spin polarized calculations and combining with the ab-initio evolutionary structure simul...Structural, electronic, and magnetic properties of AunGd （n = 6-15） small clusters are investigated by using first principles spin polarized calculations and combining with the ab-initio evolutionary structure simulations. The calculated binding energies indicate that after doping a Gd atom AunGd cluster is obviously more stable than a pure AUn＋l cluster. Au6Gd with the quasiplanar structure has a largest magnetic moment of 7.421 gB. The Gd-4f electrons play an important role in determining the high magnetic moments of AunGd clusters, but in Au6Gd and Aul2Gd clusters the unignorable spin polarized effects from the Au-6s and Au-5d electrons further enhance their magnetism. The HOMO-LUMO （here, HOMO and LUMO stand for the highest occupied molecular orbital, and the lowest unoccupied molecular orbital, respectively） energy gaps of munGd clusters are smaller than those of pure AUn＋l clusters, indicating that AunGd clusters have potential as new catalysts with enhanced reactivity.展开更多
The pressure-induced structural evolution of apatite-type La9.33Si6026 was systematically studied using in situ syn- chrotron x-ray diffraction （XRD）. The XRD spectra indicated that a subtly reversible phase transit...The pressure-induced structural evolution of apatite-type La9.33Si6026 was systematically studied using in situ syn- chrotron x-ray diffraction （XRD）. The XRD spectra indicated that a subtly reversible phase transition from P63/m to P63 symmetry occurred at ~ 13.6 GPa because of the tilting of the SiO4 tetrahedra under compression. Furthermore, the La9.33Si6026 exhibited a higher axial compression ratio for the a-axis than the c-axis, owing to the different axial arrange- ment of the SiO4 tetrahedra. Interestingly, the high-pressure phase showed compressibility unusually higher than that of the initial phase, suggesting that the low P63 symmetry provided more degrees of freedom. Moreover, the La9.33Si6026 exhibited a lower phase transition pressure （PT） and a higher lattice compression than LaloSi6027. Comparisons between La9.33Si6026 and LaloSi6027 provided a deeper understanding of the effect of interstitial oxygen atoms on the structural evolution of apatite-type lanthanum silicates （ATLSs）.展开更多
The interdependences of preparation conditions, magnetic and crystal structures, and magnetocaloric effects （MCE） of the MnFePGe-based compounds are reviewed. Based upon those findings, a new method for the evaluati...The interdependences of preparation conditions, magnetic and crystal structures, and magnetocaloric effects （MCE） of the MnFePGe-based compounds are reviewed. Based upon those findings, a new method for the evaluation of the MCE in these compounds, based on differential scanning calorimetry （DSC）, is proposed. The MnFePGe-based compounds are a group of magnetic refrigerants with giant magnetocaloric effect （GMCE）, and as such, have drawn tremendous attention, especially due to their many advantages for practical applications. Structural evolution and phase transformation in the compounds as functions of temperature, pressure, and magnetic field are reported. Influences of preparation conditions upon the homogeneity of the compounds＇ chemical composition and microstructure, both of which play a key role in the MCE and thermal hysteresis of the compounds, are introduced. Lastly, the origin of the ＂virgin effect＂ in the MnFePGe- based compounds is discussed.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.12072299,11902276)the Natural Science Foundation of Sichuan Province(Grant No.2022NSFSC1802)+1 种基金the Basic Research Project of Southwest Jiaotong University(Grant No.2682023ZTPY009)the National Key Laboratory for Shock Wave and Detonation Physics of China(Grant No.JCKYS2019212007)。
文摘By combination of the transient Raman spectroscopic measurement and the density functional theoretical calculations,the structural evolution and stability of TATB under shock compression was investigated.Due to the improvement in synchronization control between two-stage light gas gun and the transient Raman spectra acquisition,as well as the sample preparation,the Raman peak of the N-O mode of TATB was firstly observed under shock pressure up to 13.6 GPa,noticeably higher than the upper limit of 8.5 GPa reported in available literatures.By taking into account of the continuous shift of the main peak and other observed Raman peaks,we did not distinguish any structural transition or any new species.Moreover,both the present Raman spectra and the time-resolved radiation of TATB during shock loading showed that TATB exhibits higher chemical stability than previous declaration.To reveal the detailed structural response and evolution of TATB under compression,the density functional theoretical calculations were conducted,and it was found that the pressure make N-O bond lengths shorter,nitro bond angles larger,and intermolecular and intra-molecular hydrogen bond interactions enhanced.The observed red shift of Raman peak was ascribed to the abnormal enhancement of H-bound effect on the scissor vibration mode of the nitro group.
基金National Science Foundation for Excellent Young Scholars of China (21922815)Key Research and Development (R&D) Projects of Shanxi Province (201903D121007)+3 种基金Natural Science Foundations of Shanxi Province (201801D221156)DNL Cooperation Fund of CAS (DNL180308)Science and Technology Service Network Initiative of CAS (KFJ-STS-ZDTP-068)Youth Innovation Promotion Association of CAS。
文摘The presence of oxygen functional groups is detrimental to the capacitive performance of porous carbon electrode in organic electrolyte. In this regards, hydrogen thermal reduction has been demonstrated effective approach in removing the unstable surface oxygen while maintaining the high porosity of carbon matrix. However, the exact evolution mechanism of various oxygen species during this process, as well as the correlation with electrochemical properties, is still under development. Herein, biomass-based porous carbon is adopted as the model material to trace its structure evolution of oxygen removal under hydrogen thermal reduction process with the temperature range of 400–800 °C. The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700°C. XPS, TPRMS and Boehm titration results indicate that the oxygen elimination undergoes three distinctive stages(intermolecular dehydration, hydrogenation and decomposition reactions). The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700 °C. Benefiting from the stable electrochemical interface and the optimized porous structure, the as-obtained HAC-700 exhibit significantly suppressed self-discharge and leak current, with improved cycling stability, which is attributable to the stabilization of electrochemical interface between carbon surface and electrolyte. The result provides insights for rational design of surface chemistry for high-performance carbon electrode towards advanced energy storage.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB07030200)the National Basic Research Program of China(Grant Nos.2014CB921002 and 2012CB921702)
文摘Lithium ion batteries are important electrochemical energy storage devices for consumer electronics and the most promising candidates for electrical/hybrid vehicles. The surface chemistry influences the performance of the batteries significantly. In this short review, the ewlution of the surface struture of the cathode materials at different states of the pristine, storage and electrochemical reaclions are summarized. The main methods for the surface modification are also introduced.
基金sponsored by the National Natural Science Foundation of China(52176193)the National Key Research and Development Program of China(2019YFD1100602)+1 种基金the Shandong Provincial Natural Science Foundation,China(ZR2020ME184)the SDUT & Zhangdian City Integration Development Project(2021JSCG0013)。
文摘This study aimed to investigate the mechanism of nitrogen doping,migration,and conversion during ammonia torrefaction and also explore the evolution law of the chemical structure of cellulose.The results showed that the ammonia torrefaction pretreatment could significantly optimize the distribution of nitrogen and oxygen elements in cellulose.The carbon skeleton first captured the active nitrogenous radicals to form-NHn-N,and pyridine-N and pyrrole-N originated from the conversion of-NHn-N.The existence of C=O played a major role in the immobilization of nitrogen.The nitrogen in bio-oil exists mainly in the form of five-and six-membered heterocycles.The correlation analysis showed that the main precursors for the formation of nitrogenous heterocyclic compounds were five-membered Oheterocyclic compounds.Finally,the product distribution characteristics in the torrefaction-pyrolysis systems were summarized,and the nitrogen doping and conversion mechanisms were proposed.This study expanded the boundaries of cellulose pretreatment and the production of high-value chemicals.
基金Supported by the National Natural Science Foundation of China(U19B6003-01).
文摘The Tongnan secondary negative structure in central Sichuan Basin has controls and influences on the structural framework and petroleum geological conditions in the Gaoshiti-Moxi area.To clarify the controls and influences,the deformation characteristics,structural attributes and evolution process of the Tongnan negative structure were investigated through a series of qualitative and quantitative methods such as balanced profile restoration,area-depth-strain(ADS)analysis,and structural geometric forward numerical simulation,after comprehensive structural interpretation of high-precision 3D seismic data.The results are obtained in three aspects.First,above and below the P/AnP(Permian/pre-Permian)unconformity,the Tongnan negative structure demonstrates vertical differential structural deformation.It experiences two stages of structural stacking and reworking:extensional depression(from the Sinian Dengying Formation to the Permian),and compressional syncline deformation(after the Jurassic).The multi-phase trishear deformation of the preexisting deep normal faults dominated the extensional depression.The primary depression episodes occurred in the periods from the end of Late Proterozoic to the deposition of the 1st–2nd members of the Dengying Formation,and from the deposition of Lower Cambrian Longwangmiao Formation–Middle–Upper Cambrian until the Ordovician.Second,the multi-stage evolution process of the Tongnan negative structure controlled the oil and gas migration and adjustment and present-day differential gas and water distribution between the Tongnan negative structure and the Gaoshiti and Moxi-Longnüsi structural highs.Third,the Ordovician,which is limitedly distributed in the Tongnan negative structure and is truncated by the P/AnP unconformity on the top,has basic geological conditions for the formation of weathering karst carbonate reservoirs.It is a new petroleum target deserving attention.
基金supported by the National Natural Science Foundation of China(Grant Nos.42072150,41372144)the State Science and Technology Major Project of China(Grant No.2017ZX05049001-008)
文摘Pyrolysis experiments were conducted on lacustrine organic-rich shale from Cangdong Sag in Bohai Bay Basin,China,to investigate the impact of hydrocarbon generation on shale pore structure evolution.Thermal evolution is found to control the transformation of organic matter,hydrocarbon products characteristics,and pore structure changes.Furthermore,pore volume and specific surface area increase with increasing maturity.In low-mature stage,the retained oil content begins to increase,pore volumes show slight changes,and primary pores are occluded by the generated crude oil of high molecular weight and density.In the oil-window stage,the retained oil content rapidly increases and reaches maximum,and pore volumes gradually increase with increasing thermal maturity.At high mature stage,the retained oil content begins to decrease,and the pore volume increases considerably owing to the expulsion of liquid hydrocarbon.In over mature stage,natural gas content significantly increases and kerogen transforms to asphalt.Numerous organic pores are formed and the pore size gradually increases,resulting from the connection of organic pores caused the increasing thermal stress.This study lays a foundation for understanding variation of hydrocarbon products during the thermal evolution of lacustrine shales and its relationship with the evolution of shale reservoirs.
基金Supported by the National Basic Research Program of China under Grant No 2013CB922304the National Natural Science Foundation of China under Grant No 91321310
文摘The evolution of a magnetic domain structure induced by temperature and magnetic field is reported in silicon- doped yttrium iron garnet （YIG） films with perpendicular anisotropy. During a cooling-down procedure from 300K to 7K, a 20% change in the domain width is observed, with the long tails of the stripes being shortened and the twisting stripes being straightened. Under the influence of the stray field of a barium ferrite, the garnet presents an interesting domain structure, which shows an appearance of branching protrusions. The intrinsic mechanisms in these two processes are also discussed.
基金Supported by the National Basic Research Program under Grant Nos 2012CB821402 and 2015CB921401the National Natural Science Foundation of China+1 种基金the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher LearningSTCSM of China(No 15XD1500200)
文摘We perform systematic thermal conductivity measurements on heavily hole-doped Ba1-xKxFe2As2 single crystals with 0.747 ≤ x ≤ 0.974. At x=0.747, the K0/T is negligible, indicating a nodeless superconducting gap. A small residual linear term K0/T （=0.035 m W.K-2 cm-1） appears at xz0.826, and it increases slowly up to x=0.974, followed by a substantial increase of more than 20 times to of K0/T clearly shows that the nodal gap appears near x surface topology. The small values of K0/T from x=0.826 the pure KFe2As2 （x=1.0）. This doping dependence = 0.8, possibly associated with the change of Fermi to 0.974 are consistent with the Y-shaped nodal s- wave gap recently revealed by angle-resolved photoemission spectroscopy experiments at x=0.9. Furthermore, the substantial increase of K0/T from x=0.974 to 1.0 is inconsistent with a symmetry-imposed d-wave gap in KFe2 As2, and a possible nodal gap structure in KFe2As2 is discussed.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11605096,11547101 and 11601247
文摘The integrability of a （2＋1）-dimensional super nonlinear evolution equation is analyzed in the framework of the fermionie covariant prolongation structure theory. We construct the prolongation structure of the multidimen- sional super integrable equation and investigate its Lax representation. Furthermore, the Backlund transformation is presented and we derive a solution to the super integrable equation.
基金Project support by the National Natural Science Foundation of China(Grant Nos.11704044 and 12074140)。
文摘The first-principles calculations are performed to examine structural,mechanical,and electronic properties at large strain for a monolayer C_(4)N_(4),which has been predicted as an anchoring promising material to attenuate shuttle effect in Li–S batteries stemming from its large absorption energy and low diffusion energy barrier.Our results show that the ideal strengths of C_(4)N_(4)under tension and pure shear deformation conditions reach 13.9 GPa and 12.5 GPa when the strains are 0.07 and 0.28,respectively.The folded five-membered rings and diverse bonding modes between carbon and nitrogen atoms enhance the ability to resist plastic deformation of C_(4)N_(4).The orderly bond-rearranging behaviors under the weak tensile loading path along the[100]direction cause the impressive semiconductor–metal transition and inverse semiconductor–metal transition.The present results enrich the knowledge of the structure and electronic properties of C_(4)N_(4)under deformations and shed light on exploring other two-dimensional materials under diverse loading conditions.
基金Supported by the Key Project of National Natural Science Foundation of China(42330810).
文摘With drilling and seismic data of Transtensional(strike-slip)Fault System in the Ziyang area of the central Sichuan Basin,SW China plane-section integrated structural interpretation,3-D fault framework model building,fault throw analyzing,and balanced profile restoration,it is pointed out that the transtensional fault system in the Ziyang 3-D seismic survey consists of the northeast-trending F_(I)19 and F_(I)20 fault zones dominated by extensional deformation,as well as 3 sets of northwest-trending en echelon normal faults experienced dextral shear deformation.Among them,the F_(I)19 and F_(I)20 fault zones cut through the Neoproterozoic to Lower Triassic Jialingjiang Formation,presenting a 3-D structure of an“S”-shaped ribbon.And before Permian and during the Early Triassic,the F_(I)19 and F_(I)20 fault zones underwent at least two periods of structural superimposition.Besides,the 3 sets of northwest-trending en echelon normal faults are composed of small normal faults arranged in pairs,with opposite dip directions and partially left-stepped arrangement.And before Permian,they had formed almost,restricting the eastward growth and propagation of the F_(I)19 fault zone.The F_(I)19 and F_(I)20 fault zones communicate multiple sets of source rocks and reservoirs from deep to shallow,and the timing of fault activity matches well with oil and gas generation peaks.If there were favorable Cambrian-Triassic sedimentary facies and reservoirs developing on the local anticlinal belts of both sides of the F_(I)19 and F_(I)20 fault zones,the major reservoirs in this area are expected to achieve breakthroughs in oil and gas exploration.
基金supported by the Key R&D Program of Shandong Province,China(2023CXGC010611)the State Key Project of International Cooperation Research(2023YFE0201100)the Program for Introducing Talents of Discipline to Universities(“111”plan),and the High-Level Discipline Program of Shandong Province of China.
文摘With the increase of energy consumption,the shortage of fossil resource,and the aggravation of environmental pollution,the development of cost-effective and environmental friendly bio-based energy storage devices has become an urgent need.As the second most abundant natural polymer found in nature,lignin is mainly produced as the by-product of paper pulping and bio-refining industries.It possesses several inherent advantages,such as low-cost,high carbon content,abundant functional groups,and bio-renewable,making it an attractive candidate for the rechargeable battery material.Consequently,there has been a surge of research interest in utilizing lignin or lignin-based carbon materials as the components of lithium-ion(LIBs)or sodium-ion batteries(SIBs),including the electrode,binder,separator,and electrolyte.This review provides a comprehensive overview on the research progress of lignin-derived materials used in LIBs/SIBs,especially the application of lignin-based carbons as the anodes of LIBs/SIBs.The preparation methods and properties of lignin-derived materials with different dimensions are systemically discussed,which emphasizes on the relationship between the chemical/physical structures of lignin-derived materials and the performances of LIBs/SIBs.The current challenges and future prospects of lignin-derived materials in energy storage devices are also proposed.
基金supported by the National Natural Science Foundation of China (21978278, 21838003 and 91834301)the Shanghai Scientific and Technological Innovation Project (18JC1410500 and 19JC1410400)the Fundamental Research Funds for the Central Universities (222201718002)。
文摘Electrochemical oxygen evolution reaction (OER) is a main efficiency bottleneck of water electrolysis.Commercial ruthenium oxide (RuO_(2)) catalyst displays remarkable activities but poor stability for OER.The instability stems from lattice oxygen oxidation,resulting in the oxidation of Ru^(4+) to soluble Ru^(4+)(x>4) species.Herein,we redirect dynamic structural evolution of Ru-based catalysts through introducing oxidized nickel (Ni) components.By virtue of comprehensive structural characterizations,such as high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM),X-ray photoelectron spectroscopy (XPS),operando Raman and so forth,it is demonstrated that when the atomic content of Ni exceeds that of ruthenium (Ru),the Ni components can efficiently inhibit the Ru^(4+) oxidation and structural collapse.Density functional theory (DFT) calculations suggest that the introduction of Ni component hinders the formation of oxygen vacancies,and makes lattice oxygen mediated mechanism turn to adsorbate evolution mechanism,which eventually improves the stability.The optimized nickel-contained RuO_(2) catalyst delivers an effective reactivity with an overpotential of less than 215 m V to attain 10 m A cm^(-2) and remarkable stability with only 5 mV increment after 5000 potential cycles.This work provides insights into the origin of dynamic structural evolution of transition-metalmodified RuO_(2) electrocatalysts.
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.
基金Projects 40772198 and 50678182 supported by the National Natural Science Foundation of China09-3-094 by the Research Fund for Teaching Reform in Institutes of Higher Learning,Chongqing, China
文摘In order to determine the area for oil and gas exploration in China’s north Sichuan basin,we have divided the time during which the Longmenshan foreland basin was formed into five periods,based on the sedimentary response relationship of the foreland basin to structural evolution: 1) a late Triassic Noric period;2) an early-Middle Jurassic period;3) a late Jurassic to early Cretaceous period;4) a late Cretaceous to Paleogene-Neogene period and 5) the Quaternary period. As well,we analyzed the sedimentary environment and lithologic features of every basin-forming period. The results show that there are several favorable source-reservoir-cap assemblages in our study area,making it a major region for future oil and gas exploration in China’s northern Sichuan basin.
基金financial support from the National Natural Science Foundation of China (Grant Nos. 51972191, 51722207)。
文摘Developing bifunctional electrocatalysts with both high catalytic activity and high stability is crucial for efficient water splitting in alkaline media.Herein,a Fe-incorporated dual-metal selenide on nickel foam(Co_(0.9)Fe_(0.1)-Se/NF) is synthesized via a facile one-step electrodeposition method.As-synthesized materials could serve as self-supported bifunctional electrocatalysts with excellent catalytic activity towards oxygen evolution reaction(OER) and hydrogen evolution reaction(HER) in alkaline media.Experimental results show that delivering a 10 mA cm^(-2) water splitting current density only requires a cell voltage of 1.55 V.In addition,a very stable performance could be kept for about 36 hours,indicating their excellent working stability.Moreover,by means of phase analysis,we have identified that the evolution of the synthesized Co_(0.9)Fe_(0.1)-Se/NF experiences two entirely different processes in HER and OER,which hydroxide and oxyhydroxide are regarded as the real active sites,respectively.This work may pave the way to further understanding the relationships between the reactivity and stability of chalcogenide-based electrocatalysts and facilitating the rational design of efficient electrocatalysts for future renewable energy system applications.
基金Supported by the National Natural Science Foundation of China under Grant No 11704161the Natural Science Foundation of Jiangsu Province under Grant Nos BK20170309 and BK20151172the Changzhou Science and Technology Bureau under Grant Nos CJ20159049 and CJ20160028
文摘We elucidate the importance of a capping layer on the structural evolution and phase change properties of carbondoped Ge2 Sb2 Te5（C-GST） films during heating in air. Both the C-GST films without and with a thin SiO2 capping layer（C-GST and C-GST/SiO2） are deposited for comparison. Large differences are observed between C-GST and C-GST/SiO2 films in resistance-temperature, x-ray diffraction, x-ray photoelectron spectroscopy,Raman spectra, data retention capability and optical band gap measurements. In the C-GST film, resistancetemperature measurement reveals an unusual smooth decrease in resistance above 110℃ during heating. Xray diffraction result has excluded the possibility of phase change in the C-GST film below 170℃. The x-ray photoelectron spectroscopy experimental result reveals the evolution of Te chemical valence because of the carbon oxidation during heating. Raman spectra further demonstrate that phase changes from an amorphous state to the hexagonal state occur directly during heating in the C-GST film. The quite smooth decrease in resistance is believed to be related with the formation of Te-rich GeTe4-n Gen（n = 0, 1） units above 110℃ in the C-GST film. The oxidation of carbon is harmful to the C-GST phase change properties.
基金Project supported by the National Basic Research Program of China(Grant No.2014CB643703)the National Natural Science Foundation of China(Grant Nos.11464008 and 51401060)+1 种基金the Natural Science Foundation of Guangxi Zhuang Autonomous Region,China(Grant Nos.2014GXNSFGA118001 and 2016GXNSFGA380001)the Guangxi Provincial Key Laboratory of Information Materials(Grant Nos.1210908-215-Z and 131022-Z)
文摘Structural, electronic, and magnetic properties of AunGd （n = 6-15） small clusters are investigated by using first principles spin polarized calculations and combining with the ab-initio evolutionary structure simulations. The calculated binding energies indicate that after doping a Gd atom AunGd cluster is obviously more stable than a pure AUn＋l cluster. Au6Gd with the quasiplanar structure has a largest magnetic moment of 7.421 gB. The Gd-4f electrons play an important role in determining the high magnetic moments of AunGd clusters, but in Au6Gd and Aul2Gd clusters the unignorable spin polarized effects from the Au-6s and Au-5d electrons further enhance their magnetism. The HOMO-LUMO （here, HOMO and LUMO stand for the highest occupied molecular orbital, and the lowest unoccupied molecular orbital, respectively） energy gaps of munGd clusters are smaller than those of pure AUn＋l clusters, indicating that AunGd clusters have potential as new catalysts with enhanced reactivity.
基金Project supported by the Natural Science Foundation of Shandong Province,China(Grant Nos.ZR2015AQ010 and ZR2016FB16)the Open Project Fund of State Key Laboratory of Superhard Materials of China(Grant No.201509)
文摘The pressure-induced structural evolution of apatite-type La9.33Si6026 was systematically studied using in situ syn- chrotron x-ray diffraction （XRD）. The XRD spectra indicated that a subtly reversible phase transition from P63/m to P63 symmetry occurred at ~ 13.6 GPa because of the tilting of the SiO4 tetrahedra under compression. Furthermore, the La9.33Si6026 exhibited a higher axial compression ratio for the a-axis than the c-axis, owing to the different axial arrange- ment of the SiO4 tetrahedra. Interestingly, the high-pressure phase showed compressibility unusually higher than that of the initial phase, suggesting that the low P63 symmetry provided more degrees of freedom. Moreover, the La9.33Si6026 exhibited a lower phase transition pressure （PT） and a higher lattice compression than LaloSi6027. Comparisons between La9.33Si6026 and LaloSi6027 provided a deeper understanding of the effect of interstitial oxygen atoms on the structural evolution of apatite-type lanthanum silicates （ATLSs）.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51171003,51071007,and 51401002)
文摘The interdependences of preparation conditions, magnetic and crystal structures, and magnetocaloric effects （MCE） of the MnFePGe-based compounds are reviewed. Based upon those findings, a new method for the evaluation of the MCE in these compounds, based on differential scanning calorimetry （DSC）, is proposed. The MnFePGe-based compounds are a group of magnetic refrigerants with giant magnetocaloric effect （GMCE）, and as such, have drawn tremendous attention, especially due to their many advantages for practical applications. Structural evolution and phase transformation in the compounds as functions of temperature, pressure, and magnetic field are reported. Influences of preparation conditions upon the homogeneity of the compounds＇ chemical composition and microstructure, both of which play a key role in the MCE and thermal hysteresis of the compounds, are introduced. Lastly, the origin of the ＂virgin effect＂ in the MnFePGe- based compounds is discussed.
