The Hoek-Brown （HB） strength criterion has been widely applied to the estimation of strength of intact rock and rock mass, while evolving ever since. However, negligence of the effect of the intermediate principal s...The Hoek-Brown （HB） strength criterion has been widely applied to the estimation of strength of intact rock and rock mass, while evolving ever since. However, negligence of the effect of the intermediate principal stress still remains in the criterion＇s latest version. At the same time, several three-dimensional （3D） HB strength, which can takes into account the influence of the intermediate principal stress, have already been proposed, among which the 3D HB criterion proposed by Zhang and Zhu seems to be the most reasonable one. However, the Zhang 3D HB criterion may have problems with some stress path close to triaxial extension state because of the non-convexity characteristic of its failure surface. In this paper, a new 3D HB strength criterion is presented based on a generalized form of the HB criterion, which also considers the effect of the intermediate principal stress and inherits all the merits of the original version of the HB criterion. In addition, this new criterion can remedy to some extent the shortcomings observed in the Zhang 3D HB criterion. Polyaxial tests for five different rocks from pub- lished literatures are used for evaluating this new criterion and comparing it with the Zhang 3D HB criterion. The re- sults show that this new criterion may over-predict or under- predict the polyaxial strength of rocks but the errors are rela- tively small, and similar results are also found for the Zhang 3D HB criterion, which one is better depends on the type of the rock under estimation.展开更多
OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using Mn SO4（OMS-2-SO4） and Mn（CH3COO）2（OMS-2-AC） as precursors. SO4^2--doped OMS-2-AC catalysts with different SO4^2-concentratio...OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using Mn SO4（OMS-2-SO4） and Mn（CH3COO）2（OMS-2-AC） as precursors. SO4^2--doped OMS-2-AC catalysts with different SO4^2-concentrations were prepared next by adding（NH4）2SO4solution into OMS-2-AC samples to investigate the effect of the anion SO4^2-on the OMS-2-AC catalyst. All catalysts were then tested for the catalytic oxidation of ethanol. The OMS-2-SO4 catalyst synthesized demonstrated much better activity than OMS-2-AC. The SO4^2-doping greatly influenced the activity of the OMS-2-AC catalyst, with a dramatic promotion of activity for suitable concentration of SO4^2-（SO4/catalyst = 0.5% W/W）. The samples were characterized by X-ray diffraction（XRD）, field emission scanning electron microscopy（FE-SEM）, transmission electron microscopy（TEM）, X-ray photoelectron spectroscopy（XPS）,inductively coupled plasma optical emission spectroscopy（ICP-OES）, NH3-TPD and H2-TPR techniques. The results showed that the presence of a suitable amount of SO4^2-species in the OMS-2-AC catalyst could decrease the Mn–O bond strength and also enhance the lattice oxygen and acid site concentrations, which then effectively promoted the catalytic activity of OMS-2-AC toward ethanol oxidation. Thus it was confirmed that the better catalytic performance of OMS-2-SO4 compared to OMS-2-AC is due to the presence of some residual SO4^2-species in OMS-2-SO4 samples.展开更多
The investigation of the environmental properties of minerals, i.e., environmental mineralogy, is a branch of science dealing with interactions between natural minerals and spheres of the Earth surface as well as a re...The investigation of the environmental properties of minerals, i.e., environmental mineralogy, is a branch of science dealing with interactions between natural minerals and spheres of the Earth surface as well as a reflection of global change, prevention of ecological destruction, participation in biomineralogy, and remediation of environmental pollution. Pollutant treatment by natural minerals is based on the natural law and reflects natural self-purification functions in the inorganic world, similar to that of the organic world - a biological treatment. A series of case studies related to natural self-purification, which were mostly completed by our group, are discussed in this paper. In natural cryptomelane there is a larger pseudotetragonal tunnel than that formed by [MnO6] octahedral double chains, with an aperture of 0.462-0.466 nm2, filled with K cations. Cryptomelane might be a real naturally-occurring mineral of the active octahedral molecular sieve (OMS-2). CrⅥ-bearing wastewater can be treated by natural pyrrhotite, which is used as a reductant to reduce CrⅥ and as a precipitant to precipitate CrⅢ simultaneously. Batch experiments were conducted using the CTMAB-Montmorillonite as an adsorbent for aromatic contaminants (phenol, aniline, benzene, toluene and xylenes), which are detected frequently in the leaching water from municipal waste deposits around China. The CTMAB modification has proved very effective to enhance the adsorption capacity of the sorbent. Expansion of vermiculite develops loose interior structures, such as pores or cracks, inside briquettes, and thus brings enough oxygen for combustion and the sulfation reaction. Effective combustion of the original carbon reduces the amount of dust in the fly ash.展开更多
The yield criteria of geomaterials play a crucial role in studying and designing the strength of materials and structures.The basic characteristics of yield criteria for geomaterials need to be studied under the frame...The yield criteria of geomaterials play a crucial role in studying and designing the strength of materials and structures.The basic characteristics of yield criteria for geomaterials need to be studied under the framework of continuum mechanics.These characteristics include the effects of strength difference（SD） of materials in tension and compression,normal stress,intermediate principal stress,intermediate principal shear stress,hydrostatic stress,twin-shear stresses,and the convexity of yield surface.Most of the proposed yield criteria possess only one or some of these basic characteristics.For example,the Tresca yield criterion considers only single-shear stress effect,and ignores the effect of SD,normal stress,intermediate principal stress,intermediate principal shear stress,hydrostatic stress,and twin-shear stresses.The Mohr-Coulomb yield criterion accounts for the effect of SD,normal stress,single-shear stress and hydrostatic stress,but disregards the effect of intermediate principal stress,intermediate principal shear stress,and twin-shear stresses.The basic characteristics remain to be fully addressed in the development of yield criterion.In this paper,we propose a new yield criterion with three features,that is,newly developed,better than existing criteria and ready for application.It is shown that the proposed criterion performs better than the existing ones and is ready for application.The development of mechanical models for various yield criteria and the applications of the unified strength theory to engineering are also summarized.According to a new tetragonal mechanical model,a tension-cut condition is added to the unified strength theory.The unified strength theory is extended to the tension-tension region.展开更多
The title complex, C37H34N6NiO5, has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P2（1/c） with a = 1.15244（8）, b = 1.69679（12）, c = 1.78341...The title complex, C37H34N6NiO5, has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P2（1/c） with a = 1.15244（8）, b = 1.69679（12）, c = 1.78341 （13） nm, β = 102.2320（10）°, V = 3.4082（4） nm^3, Z = 4, Mr = 701.41, F（000） = 1464, Dc = 1.367 g/cm^3 and μ（MoKα） = 0.622 mm^-1. The structure was refined to R = 0.0459 and wR = 0.1199 for 5718 observed reflections. The intramolecular hydrogen bonds in the crystal structure play important roles in the title complex＇s thermostability.展开更多
The biggest challenging issue in photocatalysis is efficient separation of the photoinduced carriers and the aggregation of photoexcited electrons on photocatalyst’s surface.In this paper,we report that double metall...The biggest challenging issue in photocatalysis is efficient separation of the photoinduced carriers and the aggregation of photoexcited electrons on photocatalyst’s surface.In this paper,we report that double metallic co-catalysts Ti3C2 MXene and metallic octahedral(1T)phase tungsten disulfide(WS2)act pathways transferring photoexcited electrons in assisting the photocatalytic H2 evolution.TiO2 nanosheets were in situ grown on highly conductive Ti3C2 MXenes and 1T-WS2 nanoparticles were then uniformly distributed on TiO2@Ti3C2 composite.Thus,a distinctive 1T-WS2@TiO2@Ti3C2 composite with double metallic co-catalysts was achieved,and the content of 1T phase reaches 73%.The photocatalytic H2 evolution performance of 1T-WS2@TiO2@Ti3C2 composite with an optimized 15 wt%WS2 ratio is nearly 50 times higher than that of TiO2 nanosheets because of conductive Ti3C2 MXene and 1T-WS2 resulting in the increase of electron transfer efficiency.Besides,the 1T-WS2 on the surface of TiO2@Ti3C2 composite enhances the Brunauer–Emmett–Teller surface area and boosts the density of active site.展开更多
The synthesis of surface composition-tunable Pt-based octahedral nanoalloys is key to unravel the structureproperty relationship in fuel cells. Herein, we report a facile route to prepare composition-tunable Pt Cu oct...The synthesis of surface composition-tunable Pt-based octahedral nanoalloys is key to unravel the structureproperty relationship in fuel cells. Herein, we report a facile route to prepare composition-tunable Pt Cu octahedral nanoalloys by using halogen ions(Br-or/and I-) as composition modulators. Among these Pt Cu octahedral nanoalloys,Pt59 Cu41 octahedron exhibits the highest catalytic activity and durability in alkaline solution. The specific activity/mass activity of Pt59 Cu41 octahedron is 20.25 m A cm^-2/3.24 A mg^-1 Pt,which is 6.64/5.3 times higher than commercial Pt black in 0.5 mol L^-1 CH3 OH, respectively. In the case of using ethanol(0.5 mol L^-1) as fuel source, Pt59 Cu41 octahedron shows much better catalytic activity, that is 34.84 m A cm^-2/5.58 A mg^-1 Pt for specific activity/mass activity, which is 9.16/7.34 times higher than commercial Pt black, respectively. In situ Fourier transform infrared spectroscopy is employed to detect the intermediate species and products for methanol/ethanol oxidation reaction and a plausible mechanism is proposed to explain the improved activity and durability of Pt59 Cu41 octahedron toward methanol/ethanol oxidation in alkaline medium.展开更多
An equivalent visco-elastic model of saturated soft clay was studied under unconsolidated undrained (UU) condition, which can be used to evaluate the stability of ocean foundation. Cyclic triaxial compression and exte...An equivalent visco-elastic model of saturated soft clay was studied under unconsolidated undrained (UU) condition, which can be used to evaluate the stability of ocean foundation. Cyclic triaxial compression and extension tests were conducted to study the parameters of the model. Results showed that the relationships of the damping ratio and the octahedral shear modulus with the octahedral cyclic shear strain were nearly unique, when the initial octahedral shear stress ratios of specimens were equal to 0.3, 0.5 and 0.7. The relationships of the damping ratio and the octahedral shear modulus with the octahedral cyclic shear strain determined from the cyclic triaxial compression tests were basically the same as those determined from the cyclic triaxial extension tests. Furthermore, the relationships were not related to the initial stress condition, the test stress state and the octahedral cyclic shear stress ratio. The relationships determined from the cyclic triaxial tests under no deviatoric stress were basically the same as those determined from the cyclic triaxial tests under deviatoric stress. The change of the octahedral cyclic accumulative strain with the number of cycles was unique under different tests stress states. An equivalent visco-elastic constitutive model of saturated soft clay under UU condition was initially established.展开更多
Several catalysts comprising Pt supported on octahedral Fe3O4（Pt/Fe3O4） were prepared by a facile method involving co-precipitation followed by thermal treatment at different temperatures. A variety of characterizat...Several catalysts comprising Pt supported on octahedral Fe3O4（Pt/Fe3O4） were prepared by a facile method involving co-precipitation followed by thermal treatment at different temperatures. A variety of characterization results revealed that this preparation process afforded highly crystalline octahedral Fe3O4 with a uniform distribution of Pt nanoparticles on its surface. The thermal-treatment temperature significantly influenced the redox properties of the Pt/Fe3O4 catalysts. All the Pt/Fe3O4 catalysts were found to be catalytically active and stable for the oxidation of low-concentration formaldehyde（HCHO） with oxygen. The catalyst prepared by thermal treatment at 80 °C（labelled Pt/Fe3O4-80） exhibited the highest catalytic activity, efficiently converting HCHO to CO2 and H2 O under ambient temperature and moisture conditions. The excellent performance of Pt/Fe3O4-80 was mainly attributed to beneficial interactions between the Pt and Fe species that result in the formation a higher density of active interface sites（e.g., Pt-O-FeO x and Pt-OH-FeO x）. The introduction of water vapor improves the catalytic activity of the Pt/Fe3O4 catalysts as it participates in a water-assisted dissociation process.展开更多
The introduction of small size non-metal elements(e.g.,oxygen)into solid solution alloys may be a promising strategy for fabricating efficient Pt-based catalysts with high activity and stability toward oxygen reductio...The introduction of small size non-metal elements(e.g.,oxygen)into solid solution alloys may be a promising strategy for fabricating efficient Pt-based catalysts with high activity and stability toward oxygen reduction reaction(ORR).Herein,oxygen interstitially inserted PtCu(O-PtCu)alloys are firstly designed by an oxygen-microalloying strategy,through ultraviolet(UV)irradiation-assisted galvanic replacement in an aqueous solution containing H_(2)PtCl_(6) and Cu_(2)O nanowires as sacrificial templates.The obtained O-PtCu alloys feature a typical face-centered cubic(FCC)structure with majority Pt,Cu atoms as building bricks and trace interstitial oxygen(1.65 wt.%)existed in the octahedral sites surrounding Cu atoms,leading to a short-range disordered structure.The alloy reaches a recorded half-wave potential of 0.96 V(vs.reversible hydrogen electrode(RHE))and mass activity of 0.48 A·mgPt^(−1),much higher than those of commercial Pt/C.During the accelerated degradation test(ADT),the mass activity lost only 4.2%after 10k cycles,while the commercial Pt/C lost 66.7%under the same conditions.Compared with pure Pt and undoped PtCu alloy,the remarkably improved performance can be attributed to the lattice distortion and energy band reconstruction caused by the interstitial oxygen atoms in form of Cu–O bonds.Moreover,the stable Cu–O bonds delay the possible place exchange between surface Pt atoms and surface-adsorbed oxygen species,thereby hindering Pt dissolution,providing a new paradigm to address Pt degradation issue.Therefore,the introduction of interstitial oxygen into Pt-based alloys may be a facile and smart strategy for the development of advanced Pt-based alloys electrocatalysts.展开更多
Submicrometer sized pure cubic phase,Eu^(3+)doped,and Yb^(3+)/Er^(3+)co-dopedα-NaYF4 particles with octahedral morphology have been prepared in acetic acid.The acetate anion plays a critical role in the formation of ...Submicrometer sized pure cubic phase,Eu^(3+)doped,and Yb^(3+)/Er^(3+)co-dopedα-NaYF4 particles with octahedral morphology have been prepared in acetic acid.The acetate anion plays a critical role in the formation of such symmetric octahedral structures through its selective adsorption on the(111)faces of the products.The size of the as-prepared octahedra can be tuned by varying the amount of sodium acetate added to the acetic acid.A possible formation mechanism for these octahedra has been proposed.The dopedα-NaYF_(4) octahedral submicrometer particles show down-conversion and up-conversion photoluminescence typical of these materials.展开更多
In this study,the truncated octahedral CeO_(2)(CeO_(2)-to)with special morphology was prepared by the solvothermal method with oleic acid(OA)and oleamine(OM)as the morphology-directing agents.High-resolution transmiss...In this study,the truncated octahedral CeO_(2)(CeO_(2)-to)with special morphology was prepared by the solvothermal method with oleic acid(OA)and oleamine(OM)as the morphology-directing agents.High-resolution transmission electron microscopy(HRTEM)results show that CeO_(2)-to exposes composite{100}and{111}facets,while CeO_(2)cubic(CeO_(2)-c)and CeO_(2)octahedral(CeO_(2)-o)only expose single crystal facets of{100}plane and{111}plane,respectively.Interestingly,this CeO_(2)-to photocatalyst exhibits remarkable photooxidation performance of gaseous acetaldehyde(CH_(3)CHO)degradation,in which CO_(2)generation value reaches 1.78 and 7.97-times greater than that of CeO_(2)-c and CeO_(2)-o,respectively.In addition,the active species trapping experiment signifies that superoxide(·O_(2)^(-))and holes(h^(+))are the main reactive substances during the CH_(3)CHO degradation process,and the electron paramagnetic resonance(EPR)spectra indicates that the former is the major contributor.Notably,the electron transfer mechanism between CeO_(2)-to{100}and{111}facets and the surface oxygen adsorption ability are revealed via density functional theory(DFT)calculations.It is also confirmed that{100}facets are more conducive to the absorption of acetaldehyde than{111}facets.Finally,a reasonable mechanism for improved photocatalytic CH_(3)CHO degradation on CeO_(2)-to is proposed based on relevant experiments and DFT calculations.This study demonstrates that the systematic development of surface homojunction structured photocatalysts can efficiently increase the degradation activity for volatile organic compounds(VOCs).It also offers additional direction for optimizing the photocatalytic activity of other ceriumbased photocatalysts.展开更多
A photocatalyst composed of TiO 2 nanotube arrays（TNTs） and octahedral Cu2 O nanoparticles was fabricated,and its performance in the photocatalytic reduction of CO2 under visible and simulated solar irradiation was ...A photocatalyst composed of TiO 2 nanotube arrays（TNTs） and octahedral Cu2 O nanoparticles was fabricated,and its performance in the photocatalytic reduction of CO2 under visible and simulated solar irradiation was studied. The average nanotube diameter and length was 100 nm and 5 μm,respectively. The different amount of octahedral Cu2 O modified TNTs were obtained by varying electrochemical deposition time. TNTs modified with an optimized amount of Cu2 O nanoparticles exhibited high efficiency in the photocatalysis,and the predominant hydrocarbon product was methane. The methane yield increased with increasing Cu2 O content of the catalyst up to a certain deposition time,and decreased with further increase in Cu2 O deposition time. Insufficient deposition time（5 min） resulted in a small amount of Cu2 O nanoparticles on the TNTs,leading to the disadvantage of harvesting light. However,excess deposition time（45 min） gave rise to entire TNT surface being most covered with Cu2 O nanoparticles with large sizes,inconvenient for the transport of photo-generated carriers. The highest methane yield under simulated solar and visible light irradiation was observed for the catalysts prepared at a Cu2 O deposition time of 15 and 30 min respectively. The morphology,crystallization,photoresponse and electrochemical properties of the catalyst were characterized to understand the mechanism of its high photocatalytic activity. The TNT structure provided abundant active sites for the adsorption of reactants,and promoted the transport of photogenerated carriers that improved charge separation. Modifying the TNTs with octahedral Cu2 O nanoparticles promoted light absorption,and prevented the hydrocarbon product from oxidation. These factors provided the Cu2O-modified TNT photocatalyst with high efficiency in the reduction of CO2,without requiring co-catalysts or sacrificial agents.展开更多
Pt-based magnetic nano catalysts are one of the most suitable cand idates for electrocatalytic materials due to their high electrochemistry activity and retrievability.Unfortunately,the inferior durability prevents th...Pt-based magnetic nano catalysts are one of the most suitable cand idates for electrocatalytic materials due to their high electrochemistry activity and retrievability.Unfortunately,the inferior durability prevents them from being scaled-up,limiting their commercial applications.Herein,an antiferromagnetic element Mn was introduced into PtCo nanostructured alloy to synthesize uniform Mn-PtCo truncated octahedral nanoparticles(TONPs)by one-pot method.Our results show that Mn can tune the blocking temperature of Mn-PtCo TONPs due to its an tiferromag netism.At low temperatures,Mn-PtCo TONPs are ferromag netic,and the coercivity in creases gradually with in creasi ng Mn contents.At room temperature,the Mn-PtCo TONPs display superparamag netic behavior,which is greatly helpful for in dustrial recycling.Mn doping can not only modify the electronic structure of PtCo TONPs but also enhanee electrocatalytic performance for methanol oxidation reaction.The maximum specific activity of Mn-PtCo-3 reaches 8.1 A`m^-2,3.6 times of commercial Pt/C(2.2 A·m^-2)and 1.4 times of PtCo TONPs(5.6 A`m^-2),respectively.The mass activity decreases by only 30%after 2,000 cycles,while it is 45%and 99%(nearly inactive)for PtCo TONPs and commercial Pt/C catalysts,respectively.展开更多
Nanomagnetic CoPt truncated octahedral nanoparticles （TONPs） were successfully synthesised through a facile one-pot strategy. These single crystal CoPt TONPs with an average size of about 8 nm exhibit excellent elec...Nanomagnetic CoPt truncated octahedral nanoparticles （TONPs） were successfully synthesised through a facile one-pot strategy. These single crystal CoPt TONPs with an average size of about 8 nm exhibit excellent electrocatalytic performance of both activity and stability for methanol oxidation reaction （MOR）. The mass and specific activities of CoPt TONPs is 8 and 6 times higher than that of standard commercial Pt/C, respectively. After accelerated durability test （ADT）, the loss of electrochemical surface area （ECSA） for CoPt TONPs is only 18.5%, which is significantly less than that of commercial Pt/C （68.2%）, indicating that CoPt TONPs possess much better stability than commercial Pt/C in the prolonged operation. The Curie temperature of CoPt TONPs down to 8 nm is as high as 350 K with weak ferromagntism at room temperature （RT）, which is greatly valuable for recycling in the eletrocatalytic applications.展开更多
Halide perovskites have attracted tremendous attention as semiconducting materials for various optoelectronic applications.The functional metal-halide octahedral units and their spatial arrangements play a key role in...Halide perovskites have attracted tremendous attention as semiconducting materials for various optoelectronic applications.The functional metal-halide octahedral units and their spatial arrangements play a key role in the optoelectronic properties of these materials.At present,most of the efforts for material exploration focus on substituting the constituent elements of functional octahedral units,whereas designing the spatial arrangement of the functional units has received relatively little consideration.In this work,via a global structure search based on density functional theory(DFT),we discovered a metastable three-dimensional honeycomb-like perovskite structure with the functional octahedral units arranged through mixed edge-and comer-sharing.We experimentally confirmed that the honeycomb-like perovskite structure can be stabilized by divalent molecular cations with suitable size and shape,such as 2,2’-bisimidazole(BIM).DFT calculations and experimental characterizations revealed that the honeycomb-like perovskite with the formula of BIMPb2l6,synthesized through a solution process,exhibits high electronic dimensionality,a direct allowed bandgap of 2.1 eV,small effective masses for both electrons and holes,and high optical absorption coefficients,which indicates a significant potential for optoelectronic applications.The employed combination of DFT and experimental study provides an exemplary approach to explore prospective optoelectronic semiconductors via spatially arranging functional units.展开更多
基金supported by Western Transportation Technology Funds of China (200731800038)the Special Fund for Basic Scientific Research of Central Colleges,Chang’an University(CHD2011JC175)
文摘The Hoek-Brown （HB） strength criterion has been widely applied to the estimation of strength of intact rock and rock mass, while evolving ever since. However, negligence of the effect of the intermediate principal stress still remains in the criterion＇s latest version. At the same time, several three-dimensional （3D） HB strength, which can takes into account the influence of the intermediate principal stress, have already been proposed, among which the 3D HB criterion proposed by Zhang and Zhu seems to be the most reasonable one. However, the Zhang 3D HB criterion may have problems with some stress path close to triaxial extension state because of the non-convexity characteristic of its failure surface. In this paper, a new 3D HB strength criterion is presented based on a generalized form of the HB criterion, which also considers the effect of the intermediate principal stress and inherits all the merits of the original version of the HB criterion. In addition, this new criterion can remedy to some extent the shortcomings observed in the Zhang 3D HB criterion. Polyaxial tests for five different rocks from pub- lished literatures are used for evaluating this new criterion and comparing it with the Zhang 3D HB criterion. The re- sults show that this new criterion may over-predict or under- predict the polyaxial strength of rocks but the errors are rela- tively small, and similar results are also found for the Zhang 3D HB criterion, which one is better depends on the type of the rock under estimation.
基金financially supported by the National Natural Science Foundation of China (No. 21422706)the Program of the Ministry of Science and Technology of China (No. 2012AA062702)
文摘OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using Mn SO4（OMS-2-SO4） and Mn（CH3COO）2（OMS-2-AC） as precursors. SO4^2--doped OMS-2-AC catalysts with different SO4^2-concentrations were prepared next by adding（NH4）2SO4solution into OMS-2-AC samples to investigate the effect of the anion SO4^2-on the OMS-2-AC catalyst. All catalysts were then tested for the catalytic oxidation of ethanol. The OMS-2-SO4 catalyst synthesized demonstrated much better activity than OMS-2-AC. The SO4^2-doping greatly influenced the activity of the OMS-2-AC catalyst, with a dramatic promotion of activity for suitable concentration of SO4^2-（SO4/catalyst = 0.5% W/W）. The samples were characterized by X-ray diffraction（XRD）, field emission scanning electron microscopy（FE-SEM）, transmission electron microscopy（TEM）, X-ray photoelectron spectroscopy（XPS）,inductively coupled plasma optical emission spectroscopy（ICP-OES）, NH3-TPD and H2-TPR techniques. The results showed that the presence of a suitable amount of SO4^2-species in the OMS-2-AC catalyst could decrease the Mn–O bond strength and also enhance the lattice oxygen and acid site concentrations, which then effectively promoted the catalytic activity of OMS-2-AC toward ethanol oxidation. Thus it was confirmed that the better catalytic performance of OMS-2-SO4 compared to OMS-2-AC is due to the presence of some residual SO4^2-species in OMS-2-SO4 samples.
基金supported by the National Key Program for Basic Research of China(No.2001CCA02400)the National Natural Science Foundation of China(Grant No.49672097,49972017 and 40172022).
文摘The investigation of the environmental properties of minerals, i.e., environmental mineralogy, is a branch of science dealing with interactions between natural minerals and spheres of the Earth surface as well as a reflection of global change, prevention of ecological destruction, participation in biomineralogy, and remediation of environmental pollution. Pollutant treatment by natural minerals is based on the natural law and reflects natural self-purification functions in the inorganic world, similar to that of the organic world - a biological treatment. A series of case studies related to natural self-purification, which were mostly completed by our group, are discussed in this paper. In natural cryptomelane there is a larger pseudotetragonal tunnel than that formed by [MnO6] octahedral double chains, with an aperture of 0.462-0.466 nm2, filled with K cations. Cryptomelane might be a real naturally-occurring mineral of the active octahedral molecular sieve (OMS-2). CrⅥ-bearing wastewater can be treated by natural pyrrhotite, which is used as a reductant to reduce CrⅥ and as a precipitant to precipitate CrⅢ simultaneously. Batch experiments were conducted using the CTMAB-Montmorillonite as an adsorbent for aromatic contaminants (phenol, aniline, benzene, toluene and xylenes), which are detected frequently in the leaching water from municipal waste deposits around China. The CTMAB modification has proved very effective to enhance the adsorption capacity of the sorbent. Expansion of vermiculite develops loose interior structures, such as pores or cracks, inside briquettes, and thus brings enough oxygen for combustion and the sulfation reaction. Effective combustion of the original carbon reduces the amount of dust in the fly ash.
基金Supported by the National Natural Science Foundation of China (59924033)
文摘The yield criteria of geomaterials play a crucial role in studying and designing the strength of materials and structures.The basic characteristics of yield criteria for geomaterials need to be studied under the framework of continuum mechanics.These characteristics include the effects of strength difference（SD） of materials in tension and compression,normal stress,intermediate principal stress,intermediate principal shear stress,hydrostatic stress,twin-shear stresses,and the convexity of yield surface.Most of the proposed yield criteria possess only one or some of these basic characteristics.For example,the Tresca yield criterion considers only single-shear stress effect,and ignores the effect of SD,normal stress,intermediate principal stress,intermediate principal shear stress,hydrostatic stress,and twin-shear stresses.The Mohr-Coulomb yield criterion accounts for the effect of SD,normal stress,single-shear stress and hydrostatic stress,but disregards the effect of intermediate principal stress,intermediate principal shear stress,and twin-shear stresses.The basic characteristics remain to be fully addressed in the development of yield criterion.In this paper,we propose a new yield criterion with three features,that is,newly developed,better than existing criteria and ready for application.It is shown that the proposed criterion performs better than the existing ones and is ready for application.The development of mechanical models for various yield criteria and the applications of the unified strength theory to engineering are also summarized.According to a new tetragonal mechanical model,a tension-cut condition is added to the unified strength theory.The unified strength theory is extended to the tension-tension region.
基金The project was supported by the Natural Science Foundation of Hubei Province (No. 00A046)
文摘The title complex, C37H34N6NiO5, has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P2（1/c） with a = 1.15244（8）, b = 1.69679（12）, c = 1.78341 （13） nm, β = 102.2320（10）°, V = 3.4082（4） nm^3, Z = 4, Mr = 701.41, F（000） = 1464, Dc = 1.367 g/cm^3 and μ（MoKα） = 0.622 mm^-1. The structure was refined to R = 0.0459 and wR = 0.1199 for 5718 observed reflections. The intramolecular hydrogen bonds in the crystal structure play important roles in the title complex＇s thermostability.
基金fundings from the National Natural Science Foundation of China (Nos. 51872173 and 51772167)Taishan Scholarship of Young Scholars (No. tsqn201812068)+2 种基金Natural Science Foundation of Shandong Province (No. ZR2017JL020)Taishan Scholarship of Climbing Plan (No. tspd20161006)Key Research and Development Program of Shandong Province (No. 2018GGX102028)
文摘The biggest challenging issue in photocatalysis is efficient separation of the photoinduced carriers and the aggregation of photoexcited electrons on photocatalyst’s surface.In this paper,we report that double metallic co-catalysts Ti3C2 MXene and metallic octahedral(1T)phase tungsten disulfide(WS2)act pathways transferring photoexcited electrons in assisting the photocatalytic H2 evolution.TiO2 nanosheets were in situ grown on highly conductive Ti3C2 MXenes and 1T-WS2 nanoparticles were then uniformly distributed on TiO2@Ti3C2 composite.Thus,a distinctive 1T-WS2@TiO2@Ti3C2 composite with double metallic co-catalysts was achieved,and the content of 1T phase reaches 73%.The photocatalytic H2 evolution performance of 1T-WS2@TiO2@Ti3C2 composite with an optimized 15 wt%WS2 ratio is nearly 50 times higher than that of TiO2 nanosheets because of conductive Ti3C2 MXene and 1T-WS2 resulting in the increase of electron transfer efficiency.Besides,the 1T-WS2 on the surface of TiO2@Ti3C2 composite enhances the Brunauer–Emmett–Teller surface area and boosts the density of active site.
基金supported by the National Natural Science Foundation of China (21571038 and 21361005)the Open Fund of the Key Lab of Organic Optoelectronics & Molecular Engineering (Tsinghua University)+1 种基金the Foundation for Excellent Young Scientific and Technological Talents of Guizhou Province (2019-5666)the Special Fund for Natural Science of Guizhou University (201801)
文摘The synthesis of surface composition-tunable Pt-based octahedral nanoalloys is key to unravel the structureproperty relationship in fuel cells. Herein, we report a facile route to prepare composition-tunable Pt Cu octahedral nanoalloys by using halogen ions(Br-or/and I-) as composition modulators. Among these Pt Cu octahedral nanoalloys,Pt59 Cu41 octahedron exhibits the highest catalytic activity and durability in alkaline solution. The specific activity/mass activity of Pt59 Cu41 octahedron is 20.25 m A cm^-2/3.24 A mg^-1 Pt,which is 6.64/5.3 times higher than commercial Pt black in 0.5 mol L^-1 CH3 OH, respectively. In the case of using ethanol(0.5 mol L^-1) as fuel source, Pt59 Cu41 octahedron shows much better catalytic activity, that is 34.84 m A cm^-2/5.58 A mg^-1 Pt for specific activity/mass activity, which is 9.16/7.34 times higher than commercial Pt black, respectively. In situ Fourier transform infrared spectroscopy is employed to detect the intermediate species and products for methanol/ethanol oxidation reaction and a plausible mechanism is proposed to explain the improved activity and durability of Pt59 Cu41 octahedron toward methanol/ethanol oxidation in alkaline medium.
基金Supported by National Natural Science Foundation of China ( No. 51179120)
文摘An equivalent visco-elastic model of saturated soft clay was studied under unconsolidated undrained (UU) condition, which can be used to evaluate the stability of ocean foundation. Cyclic triaxial compression and extension tests were conducted to study the parameters of the model. Results showed that the relationships of the damping ratio and the octahedral shear modulus with the octahedral cyclic shear strain were nearly unique, when the initial octahedral shear stress ratios of specimens were equal to 0.3, 0.5 and 0.7. The relationships of the damping ratio and the octahedral shear modulus with the octahedral cyclic shear strain determined from the cyclic triaxial compression tests were basically the same as those determined from the cyclic triaxial extension tests. Furthermore, the relationships were not related to the initial stress condition, the test stress state and the octahedral cyclic shear stress ratio. The relationships determined from the cyclic triaxial tests under no deviatoric stress were basically the same as those determined from the cyclic triaxial tests under deviatoric stress. The change of the octahedral cyclic accumulative strain with the number of cycles was unique under different tests stress states. An equivalent visco-elastic constitutive model of saturated soft clay under UU condition was initially established.
文摘Several catalysts comprising Pt supported on octahedral Fe3O4（Pt/Fe3O4） were prepared by a facile method involving co-precipitation followed by thermal treatment at different temperatures. A variety of characterization results revealed that this preparation process afforded highly crystalline octahedral Fe3O4 with a uniform distribution of Pt nanoparticles on its surface. The thermal-treatment temperature significantly influenced the redox properties of the Pt/Fe3O4 catalysts. All the Pt/Fe3O4 catalysts were found to be catalytically active and stable for the oxidation of low-concentration formaldehyde（HCHO） with oxygen. The catalyst prepared by thermal treatment at 80 °C（labelled Pt/Fe3O4-80） exhibited the highest catalytic activity, efficiently converting HCHO to CO2 and H2 O under ambient temperature and moisture conditions. The excellent performance of Pt/Fe3O4-80 was mainly attributed to beneficial interactions between the Pt and Fe species that result in the formation a higher density of active interface sites（e.g., Pt-O-FeO x and Pt-OH-FeO x）. The introduction of water vapor improves the catalytic activity of the Pt/Fe3O4 catalysts as it participates in a water-assisted dissociation process.
基金supported by the National Natural Science Foundation of China(No.22278016).
文摘The introduction of small size non-metal elements(e.g.,oxygen)into solid solution alloys may be a promising strategy for fabricating efficient Pt-based catalysts with high activity and stability toward oxygen reduction reaction(ORR).Herein,oxygen interstitially inserted PtCu(O-PtCu)alloys are firstly designed by an oxygen-microalloying strategy,through ultraviolet(UV)irradiation-assisted galvanic replacement in an aqueous solution containing H_(2)PtCl_(6) and Cu_(2)O nanowires as sacrificial templates.The obtained O-PtCu alloys feature a typical face-centered cubic(FCC)structure with majority Pt,Cu atoms as building bricks and trace interstitial oxygen(1.65 wt.%)existed in the octahedral sites surrounding Cu atoms,leading to a short-range disordered structure.The alloy reaches a recorded half-wave potential of 0.96 V(vs.reversible hydrogen electrode(RHE))and mass activity of 0.48 A·mgPt^(−1),much higher than those of commercial Pt/C.During the accelerated degradation test(ADT),the mass activity lost only 4.2%after 10k cycles,while the commercial Pt/C lost 66.7%under the same conditions.Compared with pure Pt and undoped PtCu alloy,the remarkably improved performance can be attributed to the lattice distortion and energy band reconstruction caused by the interstitial oxygen atoms in form of Cu–O bonds.Moreover,the stable Cu–O bonds delay the possible place exchange between surface Pt atoms and surface-adsorbed oxygen species,thereby hindering Pt dissolution,providing a new paradigm to address Pt degradation issue.Therefore,the introduction of interstitial oxygen into Pt-based alloys may be a facile and smart strategy for the development of advanced Pt-based alloys electrocatalysts.
基金by the National Basic Research Program of China(2007CB925101)National Science Foundation of China(20671087).
文摘Submicrometer sized pure cubic phase,Eu^(3+)doped,and Yb^(3+)/Er^(3+)co-dopedα-NaYF4 particles with octahedral morphology have been prepared in acetic acid.The acetate anion plays a critical role in the formation of such symmetric octahedral structures through its selective adsorption on the(111)faces of the products.The size of the as-prepared octahedra can be tuned by varying the amount of sodium acetate added to the acetic acid.A possible formation mechanism for these octahedra has been proposed.The dopedα-NaYF_(4) octahedral submicrometer particles show down-conversion and up-conversion photoluminescence typical of these materials.
基金supported by the National Natural Science Foundation of China(Nos.21805191 and 22205084)Project funded by China Postdoctoral Science Foundation(No.2023M741039)+3 种基金Project funded by National&Local Joint Engineering Research Center for Mineral Salt Deep Utilization(SF202303)Project Funded by Yangzhou University(137013308),Guangdong Basic and Applied Basic Research Foundation(No.2020A1515010982)Shenzhen Stable Support Project(No.20200812122947002),the Innovative Science and Technology Platform Project of Cooperation between Yangzhou City and Yangzhou UniversityPostgraduate Research&Practice Innovation Program of Jiangsu Province(Yangzhou University,No.XKYCX20_014)。
文摘In this study,the truncated octahedral CeO_(2)(CeO_(2)-to)with special morphology was prepared by the solvothermal method with oleic acid(OA)and oleamine(OM)as the morphology-directing agents.High-resolution transmission electron microscopy(HRTEM)results show that CeO_(2)-to exposes composite{100}and{111}facets,while CeO_(2)cubic(CeO_(2)-c)and CeO_(2)octahedral(CeO_(2)-o)only expose single crystal facets of{100}plane and{111}plane,respectively.Interestingly,this CeO_(2)-to photocatalyst exhibits remarkable photooxidation performance of gaseous acetaldehyde(CH_(3)CHO)degradation,in which CO_(2)generation value reaches 1.78 and 7.97-times greater than that of CeO_(2)-c and CeO_(2)-o,respectively.In addition,the active species trapping experiment signifies that superoxide(·O_(2)^(-))and holes(h^(+))are the main reactive substances during the CH_(3)CHO degradation process,and the electron paramagnetic resonance(EPR)spectra indicates that the former is the major contributor.Notably,the electron transfer mechanism between CeO_(2)-to{100}and{111}facets and the surface oxygen adsorption ability are revealed via density functional theory(DFT)calculations.It is also confirmed that{100}facets are more conducive to the absorption of acetaldehyde than{111}facets.Finally,a reasonable mechanism for improved photocatalytic CH_(3)CHO degradation on CeO_(2)-to is proposed based on relevant experiments and DFT calculations.This study demonstrates that the systematic development of surface homojunction structured photocatalysts can efficiently increase the degradation activity for volatile organic compounds(VOCs).It also offers additional direction for optimizing the photocatalytic activity of other ceriumbased photocatalysts.
基金supported by the National Natural Science Foundation of China(2137704421573085)+5 种基金the Key Project of Natural Science Foundation of Hubei Province(2015CFA037)Wuhan Planning Project of Science and Technology(2014010101010023)Self-determined Research Funds of CCNU from the Colleges’Basic Research and Operation of MOE(CCNU15ZD007CCNU15KFY005)China Postdoctoral Science Foundation(2015M572187)Hubei Provincial Department of Education(D20152702)~~
文摘A photocatalyst composed of TiO 2 nanotube arrays（TNTs） and octahedral Cu2 O nanoparticles was fabricated,and its performance in the photocatalytic reduction of CO2 under visible and simulated solar irradiation was studied. The average nanotube diameter and length was 100 nm and 5 μm,respectively. The different amount of octahedral Cu2 O modified TNTs were obtained by varying electrochemical deposition time. TNTs modified with an optimized amount of Cu2 O nanoparticles exhibited high efficiency in the photocatalysis,and the predominant hydrocarbon product was methane. The methane yield increased with increasing Cu2 O content of the catalyst up to a certain deposition time,and decreased with further increase in Cu2 O deposition time. Insufficient deposition time（5 min） resulted in a small amount of Cu2 O nanoparticles on the TNTs,leading to the disadvantage of harvesting light. However,excess deposition time（45 min） gave rise to entire TNT surface being most covered with Cu2 O nanoparticles with large sizes,inconvenient for the transport of photo-generated carriers. The highest methane yield under simulated solar and visible light irradiation was observed for the catalysts prepared at a Cu2 O deposition time of 15 and 30 min respectively. The morphology,crystallization,photoresponse and electrochemical properties of the catalyst were characterized to understand the mechanism of its high photocatalytic activity. The TNT structure provided abundant active sites for the adsorption of reactants,and promoted the transport of photogenerated carriers that improved charge separation. Modifying the TNTs with octahedral Cu2 O nanoparticles promoted light absorption,and prevented the hydrocarbon product from oxidation. These factors provided the Cu2O-modified TNT photocatalyst with high efficiency in the reduction of CO2,without requiring co-catalysts or sacrificial agents.
基金The work was supported by the National Natural Science Foundation(Nos.51625101,51431009,5180118&and 51701202)the State Key Development Program for Basic Research of China(No.2015CB921401)+3 种基金the Fundamental Research Funds for the Central University Universities of China(No.FRF-TP-16-001C2)the China Postdoctoral Science Foundation(No.2018M632792)Startup Research Fund of Zhengzhou University(No.32210815)Bejing Natural Science Foundation(No.Z180014).
文摘Pt-based magnetic nano catalysts are one of the most suitable cand idates for electrocatalytic materials due to their high electrochemistry activity and retrievability.Unfortunately,the inferior durability prevents them from being scaled-up,limiting their commercial applications.Herein,an antiferromagnetic element Mn was introduced into PtCo nanostructured alloy to synthesize uniform Mn-PtCo truncated octahedral nanoparticles(TONPs)by one-pot method.Our results show that Mn can tune the blocking temperature of Mn-PtCo TONPs due to its an tiferromag netism.At low temperatures,Mn-PtCo TONPs are ferromag netic,and the coercivity in creases gradually with in creasi ng Mn contents.At room temperature,the Mn-PtCo TONPs display superparamag netic behavior,which is greatly helpful for in dustrial recycling.Mn doping can not only modify the electronic structure of PtCo TONPs but also enhanee electrocatalytic performance for methanol oxidation reaction.The maximum specific activity of Mn-PtCo-3 reaches 8.1 A`m^-2,3.6 times of commercial Pt/C(2.2 A·m^-2)and 1.4 times of PtCo TONPs(5.6 A`m^-2),respectively.The mass activity decreases by only 30%after 2,000 cycles,while it is 45%and 99%(nearly inactive)for PtCo TONPs and commercial Pt/C catalysts,respectively.
基金supported by the National Basic Research Program of China(2015CB921401)the National Instrument Program of China(2012YQ120048)+2 种基金the National Natural Science Foundation of China(51625101,51431009,51471183,51331002,51371015,11274371 and 11674023)the Instrument Development Program of Chinese Academy of Sciences(YZ201345)the Fundamental Research Funds for the Central Universities(FRF-BR-15-009B)
文摘Nanomagnetic CoPt truncated octahedral nanoparticles （TONPs） were successfully synthesised through a facile one-pot strategy. These single crystal CoPt TONPs with an average size of about 8 nm exhibit excellent electrocatalytic performance of both activity and stability for methanol oxidation reaction （MOR）. The mass and specific activities of CoPt TONPs is 8 and 6 times higher than that of standard commercial Pt/C, respectively. After accelerated durability test （ADT）, the loss of electrochemical surface area （ECSA） for CoPt TONPs is only 18.5%, which is significantly less than that of commercial Pt/C （68.2%）, indicating that CoPt TONPs possess much better stability than commercial Pt/C in the prolonged operation. The Curie temperature of CoPt TONPs down to 8 nm is as high as 350 K with weak ferromagntism at room temperature （RT）, which is greatly valuable for recycling in the eletrocatalytic applications.
基金the National Natural Science Foundation of China (NSFC) (Grant No. 51972130)Startup Fund of Huazhong University of Science and Technology, and Director Fund of Wuhan National Laboratory for Optoelectronics.
文摘Halide perovskites have attracted tremendous attention as semiconducting materials for various optoelectronic applications.The functional metal-halide octahedral units and their spatial arrangements play a key role in the optoelectronic properties of these materials.At present,most of the efforts for material exploration focus on substituting the constituent elements of functional octahedral units,whereas designing the spatial arrangement of the functional units has received relatively little consideration.In this work,via a global structure search based on density functional theory(DFT),we discovered a metastable three-dimensional honeycomb-like perovskite structure with the functional octahedral units arranged through mixed edge-and comer-sharing.We experimentally confirmed that the honeycomb-like perovskite structure can be stabilized by divalent molecular cations with suitable size and shape,such as 2,2’-bisimidazole(BIM).DFT calculations and experimental characterizations revealed that the honeycomb-like perovskite with the formula of BIMPb2l6,synthesized through a solution process,exhibits high electronic dimensionality,a direct allowed bandgap of 2.1 eV,small effective masses for both electrons and holes,and high optical absorption coefficients,which indicates a significant potential for optoelectronic applications.The employed combination of DFT and experimental study provides an exemplary approach to explore prospective optoelectronic semiconductors via spatially arranging functional units.
