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1.
Porous spinel ferrites Mn(1-x)Zn(x)Fe(2)O(4) (0 ≤ x ≤ 0.8) are synthesized by a simple sol-gel method with egg white. All samples exhibit porous morphologies and large BET surface area (S(BET)). The substitution of Zn(2+) affects the magnetic properties of ferrites and the adsorption properties of methylene blue (MB) on ferrites, obviously. The saturation magnetization (Ms) of Mn(1-x)Zn(x)Fe(2)O(4) increases before x=0.4, and decreases with further increase of Zn(2+) substitution. This can be ascribed to the changes of the cationic distribution and the variation of spin arrangement in A-site and B-site of spinel structure. All samples show high adsorption capacity and the removal efficiencies of MB reach up to >90% within 3 h. The Zn(2+) substitution accelerates the adsorption rate and capacity of MB on Mn(1-x)Zn(x)Fe(2)O(4). The quickest adsorption occurred at x=0.2 and the largest adsorption capacity occurred at x=0.8.  相似文献   

2.
Ten compounds belonging to the series of oxygen-deficient perovskite oxides Ca(2)Fe(2-x)Mn(x)O(5) and CaSrFe(2-x)Mn(x)O(5+y), where x = 1/2, 2/3, and 1 and y ≈ 0-0.5, were synthesized and investigated with respect to the ordering of oxygen vacancies on both local and long-range length scales and the effect on crystal structure and magnetic properties. For the set with y ≈ 0 the oxygen vacancies always order in the long-range sense to form the brownmillerite structure containing alternating layers of octahedrally and tetrahedrally coordinated cations. However, there is a change in symmetry from Pnma to Icmm upon substitution of Sr for one Ca for all x, indicating local T(d) chain (vacancy) disorder. In the special case of CaSrFeMnO(5) the neutron diffraction peaks broaden, indicating only short-range structural order on a length scale of ~160 ?. This reveals a systematic progression from Ca(2)FeMnO(5) (Pnma, well-ordered tetrahedral chains) to CaSrFeMnO(5) (Icmm, disordered tetrahedral chains, overall short-range order) to Sr(2)FeMnO(5) (Pm3m, destruction of tetrahedral chains in a long-range sense). Systematic changes occur in the magnetic properties as well. While long-range antiferromagnetic order is preserved, the magnetic transition temperature, T(c), decreases for the same x when Sr substitutes for one Ca. A review of the changes in T(c) for the series Ca(2)Fe(2-x)M(x)O(5), taking into account the tetrahedral/octahedral site preferences for the various M(3+) ions, leads to a partial understanding of the origin of magnetic order in these materials in terms of a layered antiferromagnetic model. While in all cases the preferred magnetic moment direction is (010) at low temperatures, there is a cross over for x = 0.5 to (100) with increasing temperature for both the Ca(2)Fe(2-x)Mn(x)O(5) and the CaSrFe(2-x)Mn(x)O(5) series. For the y > 0 phases, while a brownmillerite ordering of oxygen vacancies is preserved for the Ca(2) phases, a disordered Pm3m cubic perovskite structure is always found when Sr is substituted for one Ca. Long-range magnetic order is also lost, giving way to spin glass or cluster-glass-like behavior below ~50 K. For the x = 0.5 phase, neutron pair distribution function (NPDF) studies show a local structure related to brownmillerite ordering of oxygen vacancies. Neutron diffraction data at 3.8 K show a broad magnetic feature, incommensurate with any multiple of the chemical lattice, and with a correlation length (magnetic domain) of 6.7(4) ?.  相似文献   

3.
M?ssbauer spectroscopy and magnetization studies of YBaCo(4-x)Fe(x)O(7+δ) (x = 0-0.8) oxidized at 0.21 and 100 atm O(2), indicate an increasing role of penta-coordinated Co(3+) states when the oxygen content approaches 8-8.5 atoms per formula unit. Strong magnetic correlations are observed in YBaCo(4-x)Fe(x)O(8.5) from 2 K up to 55-70 K, whilst the average magnetic moment of Co(3+) is lower than that for δ ≤ 0.2, in correlation with the lower (57)Fe(3+) isomer shifts determined from M?ssbauer spectra. The hypothesis on dominant five-fold coordination of cobalt cations was validated by molecular dynamics modeling of YBaCo(4)O(8.5). The iron solubility limit in YBaCo(4-x)Fe(x)O(7+δ) corresponds to approximately x ≈ 0.7. The oxygen intercalation processes in YBaCo(4)O(7+δ) at 470-700 K, analyzed by X-ray diffraction, thermogravimetry and controlled-atmosphere dilatometry, lead to unusual volume expansion opposing to the cobalt cation radius variations. This behavior is associated with increasing cobalt coordination numbers and with rising local distortions and disorder in the crystal lattice on oxidation, predicted by the computer simulations. When the oxygen partial pressure increases from 4 × 10(-5) to 1 atm, the linear strain in YBaCo(4)O(7+δ) ceramics at 598 K is as high as 0.33%.  相似文献   

4.
We investigated the Fe-site substitution effect on the structural and magnetic properties of the infinite layer iron oxide Sr(Fe(1-x)M(x))O(2) (M = Co, Mn) using synchrotron X-ray diffraction, neutron diffraction, and (57)Fe Mo?ssbauer spectroscopy. Both systems have a similar solubility limit of x ≈ 0.3, retaining the ideal infinite layer structure with a space group of P4/mmm. For the Fe-Co system, both in-plane and out-of-plane axes decrease linearly and only slightly with x, reflecting the ionic radius difference between Fe(2+) and Co(2+). For the Fe-Mn system the lattice evolution also follows Vegard's law but is anisotropic: the in-plane axis increases, while the out-of-plane decreases prominently. The magnetic properties are little influenced by Co substitution. On the contrary, Mn substitution drastically destabilizes the G-type magnetic order, featured by a significant reduction and a large distribution of the hyperfine field in the Mo?ssbauer spectra, which suggests the presence of magnetic frustration induced presumably by a ferromagnetic out-of-plane Mn-Fe interaction.  相似文献   

5.
由高温焙烧法制备层状前驱体Na_(2/3)[Mn_(1-x)M_x]O_2(M=Cr, Mg),再 经离子交换反应得到层状O2结构产物Li_y-[Mn_(1-x)M_x]。XRD表明Li_y[Mn_(1-x) M_x]O_2属六方晶系,P3ml空间群。Cr的添加量对前驱体的晶体结构有很大影响: 随着x值的增大,前驱体逐渐由层状P2结构Na_(2/3)[Mn_(1-x)Cr_x]O_2向正交结构 Na_4Mn_90_(18)转变。由SEM可以看到样品Li_y[Mn_(1-x)Cr_x]-O_2(x≤0.05)具有 六方层状结构。XPS分析结果表明样品Li_y[Mn_(0.95)Cr_(0.05)]O_2表面上的Mn和 Cr分别以Mn~(4+)存在,并且表面中Cr相对含量高于体相,而样品Li_y[Mn_(0.90) Mg_(0.10)]O_2的表面Mn和Mg分别以Mn~(4+)和Mg~(2+)存在,Mg/Mn比在表面与体相 基要一致。  相似文献   

6.
Bi(0.9)Sm(0.1)Fe(1-x)Mn(x)O(3), with x=0.00, 0.15, 0.30 have been synthesised by solid-state reaction. The structures of the materials, characterised via Rietveld analysis of high resolution powder neutron diffraction data, reveal a structural transition from R3c to orthorhombic Imma symmetry is complete for the x=0.30 sample. The antiferromagnetic ordering temperature, magnitude of the ordered magnetic moment at the B-site, and the dielectric constant all decrease as a function of increasing Mn content.  相似文献   

7.
Semimagnetic Pb(1-x)Mn(x)Se nanocrystals were synthesized by a fusion method in a glass matrix and characterized by optical absorption (OA), atomic/magnetic force microscopy (AFM/MFM), and photoluminescence techniques. MFM images strongly indicated the formation of Pb(1-x)Mn(x)Se magnetic phases in the glass system. Quantum dot size was manipulated by tuning annealing time. It was shown that Mn(2+) impurity affects nucleation, where Mn(2+)-doped samples present a redshift of the OA peak after a short annealing time and a blueshift after long annealing time compared to undoped PbSe NCs. This behavior was linked to the dependence of band-gap energy and the absorption selection rule on Mn(2+) concentration. Photoluminescence in the Pb(1-x)Mn(x)Se nanocrystals increases as the temperature rises up to a point and then decreases at higher temperatures. Anomalous increases in emission efficiency were analyzed by considering temperature induced carrier-transfer in semimagnetic Pb(1-x)Mn(x)Se quantum dots nanocrystals of different sizes.  相似文献   

8.
LiNbO(3) (LN), corundum (cor), and hexagonal (hex) phases of (In(1-x)M(x))MO(3) (x = 0.143; M = Fe(0.5)Mn(0.5)) were prepared. Their crystal structures were investigated with synchrotron X-ray powder diffraction, and their properties were studied by differential thermal analysis, magnetic measurements, and M?ssbauer spectroscopy. The LN-phase was prepared at high pressure of 6 GPa and 1770 K; it crystallizes in space group R3c with a = 5.25054(7) ?, c = 13.96084(17) ?, and has a long-range antiferromagnetic ordering near T(N) = 270 K. The cor- and hex-phases were obtained at ambient pressure by heating the LN-phase in air up to 870 and 1220 K, respectively. The cor-phase crystallizes in space group R-3c with a = 5.25047(10) ?, c = 14.0750(2) ?, and the hex-phase in space group P6(3)/mmc with a = 3.34340(18) ?, c = 11.8734(5) ?. T(N) of the cor-phase is about 200 K, and T(N) of the hex-phase is about 140 K. During irreversible transformations of LN-(In(1-x)M(x))MO(3) with the (partial) cation ordering, the In(3+), Mn(3+), and Fe(3+) cations become completely disordered in one crystallographic site of the corundum structure, and then they are (partially) ordered again in the hex-phase. LN-(In(1-x)M(x))MO(3) exhibits a reversible transformation to a perovskite GdFeO(3)-type structure (space group Pnma; a = 5.2946(3) ?, b = 7.5339(4) ?, c = 5.0739(2) ? at 10.3 GPa) at room temperature and pressure of about 5 GPa.  相似文献   

9.
The electrical and magnetic properties of Zn-doped Fe(3)O(4) at different doping concentrations of Zn have been investigated using a density functional method with generalized-gradient approximation corrected for on-site Coulombic interactions. The electronic structure calculation predicts that Zn(x)Fe(3-x)O(4) (0 ≤x≤ 0.875) is half-metallic with a full spin polarization. The hopping carrier concentration of Zn(x)Fe(3-x)O(4) decreases with increasing x, which indicates a distinct increase in the resistivity. The saturation magnetization of Zn(x)Fe(3-x)O(4) increases evidently with increasing x from x = 0 to x = 0.75 (i.e. from 4.0 to 8.3 μ(B)/f.u.) and then decreases rapidly to zero at x = 1. The robust half-metallicity, large tunability of electrical and magnetic properties of a Zn doped Fe(3)O(4) system make it a promising functional material for spintronic applications.  相似文献   

10.
合成了NdnSrFenO3n+1(n=1,2 ,3,∞ ) 系列复合氧化物 ,其中Nd3SrFe3O10 是首次合成 ,并研究了其晶体结构 ,IR谱以及 30 0~ 110 0K之间的电性质和磁性质。相对于NdSrFeO4 ,Nd2 SrFe2 O7中ab平面上的Fe O键较短而c轴方向的Fe O键较长 ;而NdFeO3中只有一种Fe O键 ,在 30 0~110 0K之间 ,NdSrFeO4 ,显反铁磁性行为 ,Nd2 SrFe2 O7表现为亚铁磁性 ,而Nd3SrFe3O10 和NdFeO3为顺磁性。随着n值的增大 ,该系列氧化物电阻率增大 ,这可能是系统四价Fe离子浓度减小的结果。  相似文献   

11.
New members of the family of complex-perovskite oxides with the formula RCu(3)(Mn(3)Fe)O(12) (R = Ce, Pr, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y) have been synthesized and characterized. Polycrystalline samples have been prepared from citrate precursors treated under moderate pressure conditions (2-3.5 GPa) and 1000 °C in the presence of KClO(4) as an oxidizing agent. All the samples have been studied by neutron powder diffraction (NPD) at 300 K and 2 K. These oxides crystallize in the cubic space group Im3[combining macron] (no. 204). Mn(4+)/Mn(3+) and Fe(3+) occupy at random the octahedral B positions of the perovskite structure. These materials have also been characterized by magnetic and magnetotransport measurements. The observed enhancement of T(C) along the RCu(3)(Mn(3)Fe)O(12) series is understood as an effect of the chemical pressure on the (Mn,Fe)-O bonds as R(3+) size decreases. The semiconducting behaviour observed in all of the samples is related with the introduction of Fe at B position. Despite the drastic change of the transport properties, significant negative magnetoresistance values are observed in the Fe-containing compounds both at 10 K and 300 K.  相似文献   

12.
The isostructural heterometallic complexes [Ln(III)(2)Mn(III)(2)O(2)(ccnm)(6)(dcnm)(2)(H(2)O)(2)] (Ln = Eu (1Eu), Gd (1Gd), Tb (1Tb), Er (1Er); ccnm = carbamoylcyanonitrosomethanide; dcnm = dicyanonitrosomethanide) have been synthesised and structurally characterised. The in situ transition metal promoted nucleophilic addition of water to dcnm, forming the derivative ligand ccnm, plays an essential role in cluster formation. The central [Ln(III)(2)Mn(III)(2)(O)(2)] moiety has a "butterfly" topology. The coordinated aqua ligands and the NH(2) group of the ccnm ligands facilitate the formation of a range of hydrogen bonds with the lattice solvent and neighbouring clusters. Magnetic measurements generally reveal weak intracluster antiferromagnetic coupling, except for the large J(MnMn) value in 1Gd. There is some evidence for single molecule magnetic (SMM) behaviour in 1Er. Comparisons of the magnetic properties are made with other recently reported butterfly-type {Ln(III)(x)M(III)(4-x) (d-block)} clusters, x = 1, 2; M = Mn, Fe.  相似文献   

13.
The reaction of [Mn(dmptacn)OH(2)](2+) and [Ni(dmptacn)OH(2)](2+) (dmptacn = 1,4-bis(2-pyridylmethyl)-1,4,7-triazacyclononane) with each cyano ligand on ferricyanide results in the assembly of heteropolynuclear cations around the cyanometalate core and reduction of Fe(III) to Fe(II). In [[Mn(dmptacn)CN](6)Fe][ClO(4)](8) x 5H(2)O (1) and [[Ni(dmptacn)CN](6)Fe][ClO(4)](8) x 7H(2)O (2), ferrocyanide is encapsulated by either six Mn(II) or Ni(II) dmptacn moieties. These same products are obtained when ferrocyanide salts are used in the synthesis instead of ferricyanide. A binuclear complex, [[Mn(dmptacn)](2)CN][ClO(4)](3) (3), has also been formed from KCN and [Mn(dmptacn)OH(2)](2+). For both Mn(II) and Ni(II), the use of the pentadentate dmptacn ligand facilitates the formation of discrete cations in preference to networks or polymeric structures. 1 crystallizes in the trigonal space group R3 macro (No. 148) with a = 30.073(3) A, c = 13.303(4) A, and Z = 3 and is composed of heptanuclear [[Mn(dmptacn)CN](6)Fe](8+) cations whose charge is balanced by perchlorate counteranions. Weak H-bonding interactions between neighboring heptanuclear cations and some perchlorate counterions generate an infinite 1D chain of alternating [[Mn(dmptacn)CN](6)Fe](8+) and ClO(4)(-) ions running along the c-axis. Complex 3 crystallizes in the orthorhombic space group Pbcn (No. 60) with a = 16.225(3) A, b = 16.320(2) A, c = 18.052(3) A, and Z = 8 and is composed of binuclear [[Mn(dmptacn)](2)CN](3+) cations in which the cyano-bridged Mn(II) centers are in a distorted trigonal prismatic geometry. Variable temperature magnetic susceptibility measurements have revealed the presence of a weak ferromagnetic interaction between the paramagnetic Mn(II) centers in 1, mediated either by the -NC-Fe-CN- bridging units or by Mn-NH...ClO(4-)...NH-Mn intercluster pathways.  相似文献   

14.
Syntheses,StructuresandPropertiesofSome NewCompositionPerovskiteCompounds:Sr_(0.6)Bi_(0.4)FeO_(2.7),Sr_(1-x)Bi_xFeO_(3-y) and Ba...  相似文献   

15.
Seven cyanide-bridged bimetallic complexes have been synthesized by the reaction of [Fe(1-CH3im)(CN)5]2- with Mn(III) Schiff base complexes. Their crystal structure and magnetic properties have been characterized. Five complexes, [Mn2(5-Brsalen)2Fe(CN)5(1-CH3im)] x H2O (1), [Mn2(5-Clsalen)2(H2O)2Fe(CN)5(1-CH3im)] x H2O (2), [Mn2(5-Clsaltn)2(H2O)2Fe(CN)5(1-CH3im)] (3), [Mn2(5-Clsaltmen)2(H2O)2Fe(CN)5(1-CH3im)] x H2O (4), and [Mn2(5-Brsaltmen)2(H2O)2Fe(CN)5(1-CH3im)] x CH3OH (5), are neutral and trinuclear with two [Mn(SB)]+ (SB2- = Schiff base ligands) and one [Fe(1-CH3im)(CN)5]2-. Complex {[Et4N][Mn(acacen)Fe(CN)5(1-CH3im)]}n x 6nH2O (6) is one-dimensional with alternate [Mn(acacen)]+ and [Fe(CN)5(1-CH3im)]2- units. The two-dimensional complex {[Mn4(saltmen)4Fe(CN)5(1-CH3im)]}n[ClO4]2n x 9nH2O (7) consists of Mn4Fe units which are further connected by the phenoxo oxygen atoms. Magnetic studies show the presence of ferromagnetic Mn(III)-Fe(III) coupling in the trinuclear compounds with the magnetic coupling constant (J) ranging from 4.5 to 6.0 cm-1, based on the Hamiltonian H = -2JSFe(SMn(1) + SMn(2)). Antiferromagnetic interaction has been observed in complex 6, whereas ferromagnetic coupling occurs in complex 7. Complexes 6 and 7 exhibit long-range magnetic ordering with a TN value of 4.0 K for 6 and Tc of 4.8 K for 7. Complex 6 shows metamagnetic behavior at 2 K, and complex 7 possesses a hysteresis loop with a coercive field of 500 Oe, typical of a soft ferromagnet.  相似文献   

16.
Mo doped Li excess transition metal oxides formulated as 0.3Li[Li(0.33)Mn(0.67)]O(2)·0.7Li[Ni(0.5-x)Co(0.2)Mn(0.3-x)Mo(2x)]O(2) were synthesized using the co-precipitation process. The effects of the substitution of Ni and Mn with Mo were investigated for the density of the states, the structure, cycling stability, rate performance and thermal stability by tools such as first principle calculations, synchrotron X-ray diffraction, field-emission SEM, solid state (7)Li MAS nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), elemental mapping by scanning TEM (STEM), inductively coupled plasma atomic emission spectrometry (ICP-AES) and a differential scanning calorimeter (DSC). It was confirmed that high valence Mo(6+) doping of the Li-excess manganese-nickel-cobalt layered oxide in the transition metal enhanced the structural stability and electrochemical performance. This increase was due to strong Mo-O hybridization inducing weak Ni-O hybridization, which may reduce O(2) evolution, and metallic behavior resulting in a diminishing cell resistance.  相似文献   

17.
The Zn(1-x)Mn(x)O (x = 0, 0.16, and 0.25) thin films were grown on fused quartz substrates by reactive magnetron cosputtering. X-ray-diffraction measurement revealed that all the films were single phase and had wurtzite structure with c-axis orientation. As Mn concentration increased in the Zn(1-x)Mn(x)O films, the c-axis lattice constant and band-gap energy increased gradually. In Raman-scattering studies, an additional Mn-related vibration mode appeared at 520 cm(-1). E(2H) phonon line of Zn(1-x)Mn(x)O alloy was broadened asymmetrically and redshifted as a result of microscopic structural disorder induced by Mn(2+) random substitution. The Zn(0.84)Mn(0.16)O film exhibited a ferromagnetic characteristic with a Curie temperature of approximately 62 K. However, with increasing Mn concentration to 25 at. %, ferromagnetism disappeared due to the enhanced antiferromagnetic superexchange interactions between neighboring Mn(2+) ions.  相似文献   

18.
Several compositions of manganese-tin-bismuth selenide solid-solution series, Mn(1-x)Sn(x)Bi(2)Se(4) (x = 0, 0.3, 0.75), were synthesized by combining high purity elements in the desired ratio at moderate temperatures. X-ray single crystal studies of a Mn-rich composition (x = 0) and a Mn-poor phase (x = 0.75) at 100 and 300 K revealed that the compounds crystallize isostructurally in the monoclinic space group C2/m (no.12) and adopt the MnSb(2)Se(4) structure type. Direct current (DC) magnetic susceptibility measurements in the temperature range from 2 to 300 K indicated that the dominant magnetic ordering within the Mn(1-x)Sn(x)Bi(2)Se(4) solid-solutions below 50 K switches from antiferromagnetic (AFM) for MnBi(2)Se(4) (x = 0), to ferromagnetic (FM) for Mn(0.7)Sn(0.3)Bi(2)Se(4) (x = 0.3), and finally to paramagnetic (PM) for Mn(0.25)Sn(0.75)Bi(2)Se(4) (x = 0.75). We show that this striking variation in the nature of magnetic ordering within the Mn(1-x)Sn(x)Bi(2)Se(4) solid-solution series can be rationalized by taking into account: (1) changes in the distribution of magnetic centers within the structure arising from the Mn to Sn substitutions, (2) the contributions of spin-polarized free charge carriers resulting from the intermixing of Mn and Sn within the same crystallographic site, and (3) a possible long-range ordering of Mn and Sn atoms within individual {M}(n)Se(4n+2) single chain leading to quasi isolated {MnSe(6)} octahedra spaced by nonmagnetic {SnSe(6)} octahedra.  相似文献   

19.
以聚乙烯吡咯烷酮(PVP)和金属盐为原料,采用静电纺丝、溶胶-凝胶技术以及随后的热处理工艺,制备了La、Co共掺杂的M型锶铁氧体Sr1-xLaxFe12-xCoxO19(x=0.12)(SLFC)纳米纤维.利用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和超导量子干涉仪(SQUID)技术对纳米纤维样品的结构、形貌和磁学性能进行了观测,系统地研究了不同温度下样品的磁性能变化.结果表明:经过950°C焙烧2h后,得到纯相的M型锶铁氧体纳米纤维,纤维呈竹节状结构,直径约55nm;室温下测得矫顽力(Hc)为498.53kA·m-1,饱和磁化强度(Ms)为70.76A·m2·kg-1,剩磁(Mr)为36.35A·m2·kg-1,这比未掺杂SrFe12O19(SF)时纳米纤维的磁性能有明显的改善,并且与在相同温度下制得的相应纳米粉体样品相比,磁性能明显提高.  相似文献   

20.
Influence of the vacancy concentration on the Li conductivity of the (Li(1-x)Na(x))(0.2)La(0.6)TiO(3) and (Li(1-x)Na(x)(0.5)La(0.5)TiO(3) perovskite series, with 0 < or = x < 1, has been investigated by neutron diffraction (ND), impedance spectroscopy (IS), nuclear magnetic resonance (NMR), and Monte Carlo simulations. In both series, Li(+) ions occupy unit cell faces, but Na(+) ions are located at A sites of the perovskite. From this fact, the amount of vacant A sites that participate in Li conductivity is given by the expression n(v) = [Li] + square, where square is the nominal vacancy concentration. Substitution of Li by Na decreases the amount of vacancies, reducing drastically the Li conductivity when n(v) approaches the percolation threshold of the perovskite conduction network. In disordered (Li(1-x)Na(x))(0.5)La(0.5)TiO(3) perovskites, the percolation threshold is 0.31; however, in ordered (Li(1-x)Na(x))(0.2)La(0.6)TiO(3) perovskites, this parameter changes to 0.26. Near the percolation threshold, the amount of mobile Li species deduced by (7)Li NMR spectroscopy is lower than that derived from structural formulas but higher than deduced from dc conductivity measurements. Conductivity values have been explained by Monte Carlo simulations, which assume a random walk for Li ions in the conduction network of the perovskite. In these simulations, distribution of vacancies conforms to structural models deduced from ND experiments.  相似文献   

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