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1.
ZrCo1−xNix (x = 0, 0.1, 0.2 and 0.3) alloys were prepared and their hydrogen storage behavior were studied. ZrCo1−xNix alloys of compositions with x = 0, 0.1, 0.2 and 0.3 prepared by arc-melting method and characterized by X-ray diffraction analysis. XRD analysis showed that the alloys of composition with x = 0, 0.1, 0.2 and 0.3 forms cubic phase similar to ZrCo with traces of ZrCo2 phase. A trace amount of an additional phase similar to ZrNi was found for the alloy with composition x = 0.3. Hydrogen desorption pressure–composition–temperature (PCT) measurements were carried out using Sievert's type volumetric apparatus and the hydrogen desorption pressure–composition isotherms (PCIs) were generated for all the alloys in the temperature range of 523–603 K. A single sloping plateau was observed for each isotherm and the plateau pressure was found to increase with increasing Ni content in ZrCo1−xNix alloys at the same experimental temperature. A van't Hoff plot was constructed using plateau pressure data of each pressure–composition isotherm and the thermodynamic parameters were calculated for desorption of hydrogen in the ZrCo1−xNix–H2 systems. The enthalpy and entropy change for desorption of hydrogen were calculated. In addition, the hydrogen absorption–desorption cyclic life studies were performed on ZrCo1−xNix alloys at 583 K up to 50 cycles. It was observed that with increasing Ni content the durability against disproportionation of alloys increases.  相似文献   

2.
Recovery of hydrogen from industrial H2S waste using spinel photocatalyst was studied. Spinel metal oxide photocatalysts (CuGa2−xFexO4 for x = 0.8, 0.6 and 0.4) were synthesized by ceramic route. They were loaded with 0.5 and 1 wt% noble metal oxide, RuO2. Their XRD pattern revealed a single phase cubic spinel crystalline structure for all the catalysts. SEM displayed small size cubic particles with the particle size decreasing with the decrease in iron content. 1 wt% RuO2 loaded CuGa1.6Fe0.4O4 decomposed H2S in aqueous 0.5 M KOH solution under visible light (λ ≥ 420 nm) irradiation and generated H2 to the tune of 10,045 μmol/h, giving rise to a high quantum efficiency of 21% at 510 nm.  相似文献   

3.
Ni, Fe2O3, and CNT were added to Mg. The content of the additives was about 20 wt % with that of Fe2O3 6 wt%. The contents of about 20 wt % additives and 6 wt% Fe2O3 are known optimum ones to improve the reaction rates of Mg with H2. Samples with compositions of 80 wt% Mg–14 wt% Ni–6 wt% Fe2O3 (named as Mg–14Ni–6Fe2O3), and 78 wt% Mg–14 wt% Ni–6 wt% Fe2O3–2 wt% CNT (named as Mg–14Ni–6Fe2O3–2CNT) were prepared by reactive mechanical grinding. The hydriding and dehydriding properties of these samples were then measured, and the effects of Ni, Fe2O3, and CNT addition on the hydriding and dehydriding rates of Mg-based alloys were investigated by comparing their hydrogen-storage properties with those of pure Mg and Mg–10 wt% Fe2O3.  相似文献   

4.
We report on the growth of Zn1−xMgxO (ZMO) thin films on quartz substrate using pulsed laser deposition (PLD) technique. The influence of varying Mg composition on structural, electrical and optical properties of ZMO films has been systematically investigated. Increase in Mg content (in the range 0.0?x?1.0), reflects the structural phase transition from wurtzite via mixed phase region to cubic one. X-ray diffraction (XRD) studies indicate the hexagonal wurtzite phase at Mg composition ranging from 0% to 30%; mixture of wurtzite and cubic phases for 40% and single cubic phase at Mg content greater than 50%. The variation of the cation-anion bond length to Mg content shows that the lattice constant of the hexagonal ZMO decreases with corresponding increase in Mg content, which result in the structure gradually deviating from the wurtzite structure. The optical measurements reveal a blue shift in absorption edge and increase in transmittance from 75% to 96% with increase in Mg content. Tuning of the band gap has been obtained from 3.41 to 6.58 eV with corresponding increase in Mg content from x=0.0 to 1.0, which demonstrates that the films are useful for window layer of solar cells that improve the overall efficiency by decreasing the absorption loss.  相似文献   

5.
Ni/xY2O3–Al2O3 (x = 5, 10, 15, 20 wt%) catalysts were prepared by sequential impregnation synthesis. The catalytic performance for the autothermal reforming of methane was evaluated and compared with Ni/γ-Al2O3 catalyst. The physicochemical properties of catalysts were characterized by X-ray diffraction (XRD), Transmission electron microscope (TEM), X-Ray Photoelectron Spectrometer (XPS), Thermo Gravimetric Analyzer (TGA) and H2-temperature programmed reduction techniques (TPR). The decrease of nickel particle size and the change of reducibility were found with Y modification. The CH4 conversion increased with elevating levels of Y2O3 from 5% to 10%, then decreased with Y content from 10% to 20%. Ni/xY2O3–Al2O3 catalysts maintained high activity after 24 h on stream, while Ni/Al2O3 had a significant deactivation. The characterization of spent catalysts indicated that the addition of Y retarded Ni sintering and decreased the amount of coke.  相似文献   

6.
ZnIn2S4/CdIn2S4 composite photocatalysts (x = 0–1) were successfully synthesized via a hydrothermal route. Compositions of ZnIn2S4/CdIn2S4 composite photocatalysts were optimized according to the photocatalytic H2 evolution rate. XRD patterns indicate the as-prepared samples are mixtures of hexagonal and cubic structures. FESEM and TEM images show that the as-prepared samples are composed of flower-like microspheres with wide distribution of diameter. There is obviously distinguishing distribution of Zn, Cd elements among the composite architectures. UV–vis absorption spectra of different compositions exhibit that absorption edges of ZnIn2S4/CdIn2S4 composites slightly move towards longer wavelengths with the increment of CdIn2S4 component. A typical time course of photocatalytic H2 evolution from an aqueous Na2SO3 and Na2S solution over unloaded and PdS-loaded ZnIn2S4/CdIn2S4 composite photocatalyst is carried out. The initial activity for H2 evolution over 0.75 wt% PdS-loaded sample is up to 780 μmol h−1. And the activity of unloaded sample also reaches 490 μmol h−1 with consistent stability.  相似文献   

7.
Cd1−xZnxS solid solutions (x = 0.05–0.3) supported on mesoporous silica SBA-16 substrate with 3D cubic structure were investigated for hydrogen production from water splitting under visible light. The influence of Zn concentration (x) in the Cd1−xZnxS solid solution and support morphology were investigated. The bare SBA-16 substrate was synthetized by the hydrothermal method whereas the Cd1−xZnxS photocatalysts were prepared by coprecipitation of metal sulfides from aqueous solutions of Cd2+ and Zn2+ using Na2S as precipitating agent. An attempt has been made to determine the photocatalyst structures using several techniques including elemental analysis, N2 adsorption–desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM), UV–Vis diffuse reflectance spectroscopy (UV–Vis DRS) and Raman spectroscopy. Surface characterization of the samples by XPS indicates that Cd1−xZnxS nanoparticles are unevenly distributed on both external surface and within the pore network. An increase of the band gap energy with increasing Zn loading up to x = 0.2 in the Cd1−xZnxS solid solution was observed. As a consequence, H2 evolution increases gradually with an increase of the Zn loading in the photocatalysts from 0.05 to 0.2 wt% being the Cd0.8Zn0.2S/SBA-16 system the most active among the catalysts studied. The highest activity of this photocatalyst was explained in terms not only of its large band gap energy but also by the enhancement of the interaction between the particles of solid solution and the SBA-16 substrate.  相似文献   

8.
The influence of titanium doping level in Ba0.6Sr0.4Co1−yTiyO3−δ (BSCT) oxides on their phase structure, electrical conductivity, thermal expansion coefficient (TEC), and single-cell performance with BSCT cathodes has been investigated. The incorporation of Ti can lead to the phase transition of Ba0.6Sr0.4CoO3−δ from hexagonal to cubic structure. The solid solution limitation of Ti in Ba0.6Sr0.4Co1−yTiyO3−δ is 0.15–0.3 under 1100 °C. BSCT shows a small polaron conduction behavior and the electrical conductivity increases steadily in the testing temperature range (300–900 °C), leading to a relatively high conductivity at high temperatures. The electrical conductivity decreases with increasing Ti content. The addition of Ti deteriorates the cathode performance of BSCT slightly but decreases the TEC significantly. The TEC of BSCT is about 14 × 10−6 K−1, which results in a good physical compatibility of BSCT with Gd0.2Ce0.8O2−δ (GDC) electrolyte. BSCT also shows excellent thermal cyclic stability of electrical conductivity and good chemical stability with GDC. These properties make BSCT a promising cathode candidate for intermediate temperature solid oxide fuel cells (IT-SOFCs).  相似文献   

9.
A series of Y2O3-promoted NiO/SBA-15 (9 wt% Ni) catalysts (Ni:Y weight ratio = 9:0, 3:1, 3:2, 1:1) were prepared using a sol–gel method. The fresh as well as the catalysts used in CO2 reforming of methane were characterized using N2-physisorption, XRD, FT-IR, XPS, UV, HRTEM, H2-TPR, O2-TPD and TG techniques. The results indicate that upon Y2O3 promotion, the Ni nanoparticles are highly dispersed on the mesoporous walls of SBA-15 via strong interaction between metal ions and the HO–Si-groups of SBA-15. The catalytic performance of the catalysts were evaluated at 700 °C during CH4/CO2 reforming at a gas hourly space velocity of 24 L gcat−1 h−1(at 25 °C and 1 atm) and CH4/CO2molar ratio of 1. The presence of Y2O3 in NiO/SBA-15 results in enhancement of initial catalytic activity. It was observed that the 9 wt% Y–NiO/SBA-15 catalyst performs the best, exhibiting excellent catalytic activity, superior stability and low carbon deposition in a time on stream of 50 h.  相似文献   

10.
In this work, differently from our previous work, MgH2 instead of Mg was used as a starting material. Ni, Ti, and LiBH4 with a high hydrogen-storage capacity of 18.4 wt% were added. A sample with a composition of MgH2–10Ni–2LiBH4–2Ti was prepared by reactive mechanical grinding. MgH2–10Ni–2LiBH4–2Ti after reactive mechanical grinding contained MgH2, Mg, Ni, TiH1.924, and MgO phases. The activation of MgH2–10Ni–2LiBH4–2Ti for hydriding and dehydriding reactions was not required. At the number of cycles, n = 2, MgH2–10Ni–2LiBH4–2Ti absorbed 4.09 wt% H for 5 min, 4.25 wt% H for 10 min, and 4.44 wt% H for 60 min at 573 K under 12 bar H2. At n = 1, MgH2–10Ni–2LiBH4–2Ti desorbed 0.13 wt% H for 10 min, 0.54 wt% H for 20 min, 1.07 wt% H for 30 min, and 1.97 wt% H for 60 min at 573 K under 1.0 bar H2. The PCT (Pressure–Composition–Temperature) curve at 593 K for MgH2–10Ni–2LiBH4–2Ti showed that its hydrogen-storage capacity was 5.10 wt%. The inverse dependence of the hydriding rate on temperature is partly due to a decrease in the pressure differential between the applied hydrogen pressure and the equilibrium plateau pressure with the increase in temperature. The rate-controlling step for the dehydriding reaction of the MgH2–10Ni–2LiBH4–2Ti at n = 1 was analyzed.  相似文献   

11.
Mg2Ni1−xMnx(x = 0, 0.125, 0.25, 0.375) electrode alloys are prepared by mechanical alloying (MA) under argon atmosphere at room temperature using a planetary high-energy ball mill. The microstructures are characterized by XRD and SEM. XRD analysis results indicate that the substitution of Mn for Ni could inhibit the formation of MgNi2 phase with the increases of x from 0 to 0.375. Replacing Ni with Mn can also promote the formation of the amorphous phase when x increases from 0 to 0.25 for the MA alloys milled for 48 h. The new phase Mg3MnNi2 is formed only when x = 0.375 after 48 h of milling. This new phase belongs to the face-centered cubic lattice (Fd-3m) with the lattice constant a being 1.1484 nm. Estimated from the peaks broadening, the crystallite size and lattice strain of Mg3MnNi2 phase are 15.6 ± 3.6 nm and 1.09 ± 0.34%, respectively. Curve fit of XRD shows that amorphous and nanocrystalline Mg2Ni coexist in the Mg2Ni1−xMnx (x = 0, 0.125, 0.25) alloys milled for 48 h. The SEM observation reveals that all the MA alloys particles are mainly flaky and show cleavage fracture morphology and these particles are agglomerates of many smaller particles, namely subparticles. Electrochemical measurements indicate that all MA alloys have excellent activation properties. The discharge capacities of MA alloys increase with the prolongation of milling time. For 16 h of milling, with the increase of Mn content, the discharge capacities of Mg2Ni1−xMnx (x = 0, 0.125, 0.25, 0.375) MA alloys monotonously decrease. For 24 h of milling, the discharge capacities of the Mg2Ni1−xMnx (x = 0, 0.125, 0.25, 0.375) alloys also show a rough tendency to decrease with the increase of Mn content except Mg2Ni0.875Mn0.125 MA alloy. On the other hand, for 48 h of milling, as the rise of Mn content from x = 0.125 to 0.375, the discharge capacities increase. Mg(OH)2 is formed during charge/discharge cycles in the KOH solution for all MA alloys. After 48 h of milling, the substitution of Mn for Ni for x = 0.25 improves the cycle stability at the expense of decreasing the discharge capacity. In contrast, Mg3MnNi2 phase is relatively stable during charge/discharge cycles and therefore can significantly enhance the cycle stability under simultaneously maintaining a high discharge capacity.  相似文献   

12.
The structural changes of pristine and ZrO2-coated LiMn0.5Ni0.5O2 cathode materials were investigated by using in situ X-ray diffraction (XRD) during charging process. An obviously solid solution phase transition from a hexagonal structure (H1) to another hexagonal structure (H2) was observed during the charging process at a constant current of 0.3 mA in the potential range of 2.5–5.7 V. The second hexagonal structure has a shorter a-axis and a longer c-axis before the crystal collapse. Before the structure collapses the c-axis length increases to maximum and then significantly decreases to 14.1 Å. The c-axis length of the pristine and ZrO2-coated LiMn0.5Ni0.5O2 increases to the maximum at the charge capacity of 119.2 and 180.9 mAh g−1, respectively. It can be concluded that the ZrO2 coating can strongly stabilize the crystal structure of the LiMn0.5Ni0.5O2 compound from the comparison of the lattice parameter variations between the pristine and the ZrO2-coated LiMn0.5Ni0.5O2 compounds upon charge. The potential fluctuation resulting from the decomposition of electrolytes starts at the charge capacity of around 200 and 260 mAh g−1 for the pristine and ZrO2-coated LiMn0.5Ni0.5O2, respectively. It suggests that the ZrO2 coating layer can impede the reaction between the cathode material and electrolyte.  相似文献   

13.
A simple co-precipitation method was employed to synthesize a series of cubic zinc-blende phase of ZnxCd1−xS photocatalysts using Na2S as the S source. Structural, morphological and optical properties of the samples have been investigated by XRD, SEM, EDS, XRF, ICP, N2 physisorption and UV–vis diffuse reflectance techniques. The ZnxCd1−xS solid solution is not a simple compound mixture of ZnS and CdS, its XRD patterns show new structural peaks instead of mixture of original peaks. The lattice parameter a measured from the XRD patterns of the ZnxCd1−xS samples exhibits a slightly nonlinear relationship with the Zn mole fraction, which is slightly inconsistent with Vegard's law, thus suggesting that a nonhomogeneous alloy structure exists in ZnxCd1−xS solid solution. The photocatalytic H2 evolution from water splitting in the sacrificial reagents of 0.25 M Na2S/0.35 M K2SO3 under visible light at 30 °C and 55 °C were also examined in the study. It is found that ZnxCd1−xS solid solution with composition x = 0.4–0.5 shows the highest photocatalytic H2 production performance. The studied ZnxCd1−xS exhibits at least 50 h stable photocatalytic activity under outdoor sunlight irradiation.  相似文献   

14.
A highly dispersed 50 wt% Ni/MgO–Al2O3 catalyst was prepared by deposition–precipitation (DP) method for the diesel pre-reforming reaction. The pH of the precursor solution was controlled from pH 9.5 to 12.0 to examine the effects on NiO crystallite size and metal dispersion. The increase of pH of the precursor solution causes an increase of specific surface area and metal dispersion, and reduces NiO crystallite size. The pre-reforming reaction was carried out using n-tetradecane as surrogate compound of diesel. The coke formation of used catalysts was examined by TGA, TEM, SEM, and Raman analysis. The 50 wt% Ni/MgO–Al2O3 catalyst prepared at pH 11.5 showed a high catalytic activity and excellent coke resistance due to high metal dispersion (8.71%), small NiO crystallite size (3.5 nm), and strong interaction between Ni and support. Furthermore, this catalyst showed a good stability in the pre-reforming reaction at S/C ratio of 3.5 and 450 °C for 88 h.  相似文献   

15.
The effect of Ni-substitution on the structure and hydrogen storage properties of Mg2Cu1−xNix (x = 0, 0.2, 0.4, 0.6, 0.8, 1) alloys prepared by a method combining electric resistance melting with isothermal evaporation casting process (IECP) has been studied. The X-ray single-crystal diffraction analysis results showed that the cell volume decreases with increasing Ni concentration, and crystal structure transforms Mg2Cu with face-centered orthorhombic into Ni-containing alloys with hexagonal structure. The Ni-substitution effects on the hydriding reaction indicated that absorption kinetics and hydrogen storage capacity increase in proportion to the concentration of the substitutional Ni. The activated Mg2Cu and Mg2Ni alloys absorbed 2.54 and 3.58 wt% H, respectively, at 573 K under 50 bar H2. After a combined high temperature and pressure activation cycle, the charged samples were composed of MgH2, MgCu2 and Mg2NiH4 while the discharged samples contained ternary alloys of Mg–Cu–Ni system with the helpful effect of rising the desorption plateau pressures compared with binary Mg–Cu and Mg–Ni alloys. With increasing nickel content, the effect of Ni is actually effective in MgH2 and Mg2NiH4 destabilization, leading to a decrease of the desorption temperature of these two phases.  相似文献   

16.
MgH2, rather than Mg, was used as a starting material in this work. A sample with a composition of MgH2–10Ni–4Ti was prepared by reactive mechanical grinding. Activation of the sample was completed after the first hydriding cycle. At n = 1, the sample desorbed 2.53 wt% H for 10 min, 3.99 wt% H for 20 min, 4.58 wt% H for 30 min, and 4.68 wt% H for 60 min at 593 K under 1.0 bar H2. At n = 2, the sample absorbed 3.59 wt% H for 5 min, 4.55 wt% H for 25 min, and 4.60 wt% H for 45 min at 593 K under 12 bar H2. The inverse dependence of the hydriding rate on the temperature in the initial stage and the normal dependence of the hydriding rate on the temperature in the later stage were discussed. The rate-controlling step for the dehydriding reaction of activated MgH2–10Ni–4Ti was analyzed as the chemical reaction at the hydride/α-solid solution interface.  相似文献   

17.
The effect of preparation method on MgO-promoted Ni–Ce0.8Zr0.2O2 catalysts was investigated in CO2 reforming of CH4. Co-precipitated Ni–MgO–Ce0.8Zr0.2O2 exhibited very high activity as well as stability (XCH4 > 95% at 800 °C for 200 h) due to high surface area, high dispersion of Ni, small Ni crystallite size, and easier reducibility. Four elements (Ni, Mg, Ce, and Zr) are located at the same position for the co-precipitated catalyst, resulting in easier reducibility.  相似文献   

18.
The aim of this study is to investigate the promotional effect of Ce on Ni/ZSM-5 catalysts in the CO2 reforming of CH4 reaction. The evaluation of the catalytic performances of the composite catalysts was conducted in a fixed-bed reactor at atmospheric pressure. The influencing factors, including temperature, Ni and Ce loadings, molar feed ratio of CO2/CH4, and time-on-stream (TOS), were investigated. The characteristics of the catalysts were checked with Brunauer-Emmett-Teller (BET) analysis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The reduction and the basic properties of the composite catalysts were elucidated by temperature-programmed reduction by H2 (H2-TPR) and temperature-programmed desorption of CO2 (CO2-TPD), respectively. The reactivity of deposited carbon was studied by sequential temperature-programmed surface reaction of CH4 (CH4-TPSR) and temperature-programmed oxidation using CO2 and O2 (CO2-TPO and O2-TPO). Results indicate that higher CH4 conversion, H2 selectivity, and desired H2/CO ratio for 5 wt% Ni & 5 wt% Ce/ZSM-5 could be achieved with CO2/CH4 feed ratio close to unity over the temperature range of 500–900 °C. Moreover, the addition of Ce could not only promote CH4 decomposition for H2 production but also the gasification of deposited carbon with CO2. The dispersion of Ni particles could be improved with Ce presence as well. A partial reduction of CeO2 to CeAlO3 was observed from XPS spectra over 5 wt% Ni & 5 wt% Ce/ZSM-5 after H2 reduction and 24 h CO2–CH4 reforming reaction. Benefiting from the introduction of 5 wt% Ce, the calculated apparent activation energies of CH4 and CO2 over the temperature range of 700–900 °C could be reduced by 30% and 40%, respectively.  相似文献   

19.
Pr2−xSrxNiO4 (PSNO, x = 0.3, 0.5 and 0.8) cathode materials for intermediate-temperature solid oxide fuel cell (IT-SOFC) were synthesized by a glycine-nitrate process using Pr6O11, Ni(NO3)2·6H2O and SrCO3 powders as raw materials. Phase structure of the synthesized powders was characterized by X-ray diffraction analysis (XRD). Microstructure of the sintered PSNO samples was observed and thermal expansion coefficient (TEC) and electrical conductivity were investigated. Electrochemical impedance spectroscopy (EIS) measurement of the PSNO materials on Sm0.2Ce0.8O1.9 (SCO) electrolyte was carried out, and single cells based on the PSNO cathodes were also assembled and their performances were tested. The results show that the synthesized PSNO powders have pure K2NiF4-type structure and the PSNO materials are chemically stable with Sm0.2Ce0.8O1.9 (SCO) electrolyte. The sintered PSNO samples have porous and fine microstructure with pore size smaller than 1 μm. Average thermal expansion coefficient of the PSNO materials is about 12–13 × 10−6 K−1 at 200–800 °C and the electrical conductivity is in the range of 70–120 Scm−1 at 800 °C. Area specific resistance (ASR) of the Pr2−xSrxNiO4 materials on SCO electrolyte is 0.407 Ωcm2, 0.126 Ωcm2 and 0.112 Ωcm2 for x = 0.3, 0.5 and 0.8 at 800 °C, respectively. Maximum open circuit voltage (OCV) and power density of the single NiO-SCO/SCO/PSNO cells are 0.75 V and 298 mWcm−2 at 700 °C, respectively, which indicates that Pr2−xSrxNiO4 may be a potential cathode material for IT-SOFC.  相似文献   

20.
Ni sulfides layers were formed on the surface of a Ti50Ni50 alloy by reacting sulfur with a Ni film deposited on the alloy, and then microstructures, transformation behavior, shape memory characteristics, superelasticity and electrochemical properties were investigated. When a Ni film deposited on a Ti50Ni50 alloy was annealed under the sulfur pressure of 100 kPa at 623 K, sulfides layers consisted of NiS and NiS2 were formed. When annealing was made at 648 K with annealing time less than 0.9 ks, sulfides layers with a mixture of NiS and NiS2 were formed, while only NiS2 was formed when it was made for 1.8 ks. When annealing was made at 673 K with annealing time longer than 0.9 ks, only NiS2 was formed. With raising annealing temperature and prolong annealing time, NiS changed into NiS2 accompanied with a morphological change from a particulate-like to a dense film-like. A Ti50Ni50 alloy with surface NiS2 layer showed the two-stage B2–R–B19′ transformation behavior, the shape memory effect and a partial superelasticity with a superelastic recovery ratio of 78%. NiS2 cathode showed a clear discharge behavior with multivoltage plateaus induced by intermediate reaction products; NiS and Ni3S2. The initial discharge capacity was 743 mA h g−1 corresponding to 85% of theoretical capacity and 65% of capacity duration is obtained at 20th discharge.  相似文献   

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