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1.
《Ceramics International》2016,42(15):16626-16632
A series of Ce3+ doped and Ce3+/Mn2+ co-doped calcium zirconium silicate CaZrSi2O7 (CZS) phosphors have been synthesized via conventional high temperature solid state reactions. The luminescence properties, energy transfer between Ce3+ and Mn2+ have been investigated systematically. Under 320 nm excitation, the phosphor CZS: 0.05Ce3+ exhibit strong blue emission ranging from 330 nm to 500 nm, attributed to the spin-allowed 5d-4f transitions of Ce3+ ions. There are two different emission centers of Ce3+ ions, Ce3+(I) and Ce3+(II). The emission spectra of Ce3+, Mn2+ co-doped phosphors shows a broad emission around 550 nm corresponding to the 4T1(4G)-6A1(6S) spin-forbidden transition of Mn2+. The energy transfer between Ce3+ and Mn2+ is detected and the transfer efficiency of Ce3+(II) to Mn2+ is faster than that of Ce3+(I) to Mn2+. The resonant type is identified via dipole-dipole mechanism. Additionally, a blue-shift emission of Ce3+ and a red-shift emission of Mn2+ have been observed following the increase of Mn2+ content in relation to the energy transfer. Thermal quenching has been investigated and the emission spectra show a blue-shift with the temperature increases, which have been discussed in details. CZS: 0.05Ce3+, yMn2+ phosphors can be tuned from blue to white and even to yellow by adjusting the Mn2+ content. All the results indicate that CZS: Ce3+, Mn2+ phosphor have a potential application for near-UV LEDs.  相似文献   

2.
Zhao  Nannan  Wang  Songbo  Cheng  Penggao  Zhang  Jianping  Zhang  Lei  Du  Wei  Tang  Na 《Catalysis Letters》2021,151(6):1810-1820

Co3?xMnxO4 is a bimetal oxide with excellent electrochemical activity in alkaline solution, has been regarded as a promising alternative in the field of ion-air batteries and proton exchange membrane fuel cell (PEMFC). Herein, we report a simple solvothermal-calcination method to fabricate Co3?xMnxO4 with tunable external Co3+/Co2+ and Mn3+/Mn2+ ratio. The tunable ratio of element valence in the bimetal results in a higher exposure of active center for oxygen redox reaction (ORR), and thus lead to a better ORR activity, which was confirmed by X-ray photoelectron spectroscopy characterizations and electrochemical measurements. Specially, Co1.8Mn1.2O4 with a Co3+/Co2+ ratio of 2.08 showed an overpotential of 0.37 V at benchmark ORR current density of 3 mA/cm2 in 0.1 M KOH, which is lower than that of pure oxide (Mn3O4 0.53 V and Co3O4 0.56 V). In addition, the as prepared Co1.8Mn1.2O4 exhibited a positive half-wave potential (0.83 V vs RHE) due to their more active sites, promotes charge transfer, adsorption and desorption of oxygen species. This work provides a strategy for the design and fabrication of earth-abundant, low-cost electrocatalysts for PEMFC in practical applications.

Graphic Abstract

Co3?xMnxO4 was fabricated by tuning external Co3+/Co2+ and Mn3+/Mn2+ ratio, and the activity initially shows a positive correlation with the ration of Co3+/Co2+ in Co3?xMnxO4.

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3.
探讨了以Ce3+/Ce4+为媒质的1,4-萘醌间接电化学合成反应。考察了液相氧化、Ce3+电解氧化过程的影响因素,并进行了萘醌的间接电合成实验。结果发现,硫酸浓度、溶液温度对铈离子的氧化能力和电化学反应活性具有重要的影响;当温度为70℃、硫酸浓度为1.0 mol·L-1时,液相氧化反应的收率最高(85.8%)。Ce3+电解氧化的最优条件为:电流密度50 mA·cm-2、硫酸浓度1.0 mol·L-1、温度为50℃,其电流效率可达90.6%;间接电合成实验过程中萘醌的平均收率达85.7%,Ce3+电解氧化的平均电流效率达87.8%,并且电解过程具有良好的稳定性,表明该技术具有良好的产业化应用前景。  相似文献   

4.
《Ceramics International》2019,45(11):13685-13691
High-performance inductive couplers require Ni-Zn ferrites of high saturation magnetization, Curie temperature, permeability and application frequency. However, for inductive couplers some of these properties run against each other in one ferrite. To balance these requirements, in this work, novel Ni-Zn ferrite ceramics co-doped by Ce3+ and Co2+ ions with chemical formula Ni0.4Zn0.5Co0.1CexFe2-xO4 (x = 0–0.06) were designed and fabricated by a molten salt method. For the acquired ferrites, both Ce3+ and Co2+ ions could come into the lattices. The initially doped Co2+ ions would cause a slightly decreased grain size and dramatically reduced the specimen densification, but the further added Ce3+ ions could effectively inhibit the density reduction, while the grain size continues to dwindle. The additional Ce3+ ions would generate a foreign CeO2 phase in the acquired specimens. The sole doping of Co2+ ions would aggrandize the saturation magnetization of ferrites, but the introduction of Ce3+ ions would cause its decrease. However, with an appropriate doping level, the Ce3+ and Co2+ ions co-doped ferrites could preserve a relatively high saturation magnetization, while the Curie temperature and cut-off frequency of the ferrites are dramatically augmented, although the permeability would be somewhat reduced. The as-acquired ferrites were simulated to apply in inductive couplers, revealing that the devices manufactured by the Ni0.4Zn0.5Co0.1CexFe2-xO4 ferrites had significantly high maximum operating frequency, compared with that of the one manufactured by pure Ni0.5Zn0.5Fe2O4 ferrite.  相似文献   

5.
Uniform orange‐to‐red spherical phosphors of Sr2P2O7:Ce3+, Mn2+ have been synthesized by the co‐precipitation method and characterized by X‐ray powder diffraction, scanning electron microscopy, and photoluminescence spectroscopy. The results indicate that the morphology, size, and photoluminescence properties of Sr2P2O7:Ce3+, Mn2+ phosphors can be effectively controlled by the reaction and the sintering temperatures. Energy transfer from Ce3+ to Mn2+ in Sr2P2O7 phosphor was observed from photoluminescence spectra of Sr2P2O7:Ce3+, Sr2P2O7:Mn2+, and Sr2P2O7:Ce3+, Mn2+. Moreover, based on a self‐assembly process, a possible formation mechanism for the spherical phosphors is proposed. The uniform phosphor spheres obtained in this work exhibit great potential for high‐resolution display devices such as light emitting diodes.  相似文献   

6.
The development of novel single-component white-emitting phosphors with high thermal stability is essential for improving the illumination quality of white light-emitting diodes. In this work, we synthesized a series of Ce3+, Tb3+, Mn2+ single- and multiple-doped Ca9La(PO4)7 (CLPO) phosphors with β-Ca3(PO4)2-type structure by the simple high-temperature solid-state reaction. The crystallization behavior, crystal structure, surface morphology, photoluminescence performance, decay lifetime and thermal stability were systematically investigated. The PL spectra and decay curves have evidenced the efficient energy transfer from Ce3+ to Tb3+ and from Ce3+ to Mn2+ in the CLPO host, and corresponding energy transfer efficiency reaches 41.8% and 54.1%, respectively. The energy transfer process of Ce3+→Tb3+ and Ce3+→Mn2+ can be deduced to the resonant type via dipole-dipole and dipole-quadrupole interaction mechanism, and corresponding critical distance were determined to be 12.23 and 14.4 Å, respectively. Based on the efficient energy transfer, the white light emission can be successfully achieved in the single-component CLPO:0.15Ce3+, 0.10Tb3+, 0.04Mn2+ phosphor, which owns CIE chromaticity coordinates of (0.3245, 0.3347), CCT of 5878 K, internal and external quantum efficiency of 84.51% and 69.32%. Especially, compared with the emission intensity at 25 °C, it still remains 98.5% at 150 °C and 92.0% at 300 °C. Based on these results, the single-component white light emission phosphor CLPO:0.15Ce3+, 0.10Tb3+, 0.04Mn2+ is a potential candidate for UV-converted white LEDs.  相似文献   

7.
Color‐tunable phosphors NaCaBO3: Ce3+, Mn2+ were synthesized by sol–gel (SG) and solid state (SS) method. SEM observation indicated that the microstructure of phosphor (SG) consisted of regular fine grains with an average size of about 5 μm. NaCaBO3: Ce3+, Mn2+ showed two emission bands: one at 425 nm for Ce3+ and another at 610 nm for Mn2+. NaCaBO3: Ce3+, Mn2+ (SG) exhibit higher energy‐transfer efficiency (90%) and higher Mn2+ quantum efficiency (80%) than SS samples, due to smooth surface, narrow size distribution, and improved homogeneity of sensitizer/activator ions. NaCaBO3: Ce3+, Mn2+ exhibits blue‐to‐red tunable color by changing Ce3+/Mn2+ ratio.  相似文献   

8.
《Ceramics International》2020,46(1):560-567
The synthesis and photo-luminescence properties of Eu2+/Eu3+ or Ce3+/Eu3+ co-doped Sr5(BO3)3F compounds are reported. Using the Sr5(BO3)3F as the host, through the solid state reaction under the reductive atmosphere, Eu2+/Eu3+ and Ce3+/Eu3+co-doped samples were prepared. These compounds exhibit good photo-luminescence properties. Under the excitation of 376 nm, an unusual red orange emission coming from the Eu2+ ions can be obtained in Eu ions doped Sr5(BO3)3F, which exhibits a broadband emission in the range of 450–800 nm with the peak at around 600 nm. At the same time, the characteristic f-f excitation and emission of Eu3+ can improve and adjust the Eu2+ emission in Eu3+/Eu2+ codoped Sr5(BO3)3F. In addition, the adjustable luminescence properties from blue to white of Sr5(BO3)3F:Ce3+, Eu3+ are investigated. The energy transfer behavior from Ce3+ to Eu3+ was confirmed. In the spectra of the co-doped samples, we can hardly observe the characteristic peak of Eu2+, because Ce4+ can oxidize Eu2+ to Eu3+, and Ce4+ itself is reduced to Ce3+. The CIE coordinates from (0.2758, 0.2420) to (0.3857, 0.3015) show Sr5(BO3)3F:3%Ce3+, x%Eu3+ (x = 1,3,5,7,9) are in the white light emission region. All results demonstrate that the Sr5(BO3)3F:Eu3+/Eu2+ and Sr5(BO3)3F:Ce3+/Eu3+ phosphors have good application prospects for LED plant growth and white LED, respectively. The bond energy method was used to explain the reason why the Eu2+/Eu3+ ion instead of only Eu2+ and Ce3+/Eu3+ instead of Ce3+/Eu3+/Eu2+ can exist in the host Sr5(BO3)3F. The theoretical analysis agree well with the experimental result.  相似文献   

9.
The catalytic effects of the silver ion on toluene oxidation by Ce4+ as well as the anodic generation of Ce4+ were investigated. The rates of toluene oxidation were first order with respect to both Ag+ and Ce4+. Argentic oxides formed on the surface of the platinum anode when Ag+ was present in the anolyte, which increased the activity of the electrode. About 3×10–3M of Ag+ was needed to obtain maximum current efficiency.  相似文献   

10.
《Ceramics International》2023,49(8):12088-12096
Mn4+ activated fluoride red phosphors, as candidate red materials in white light-emitting diodes (WLEDs), have received widespread attention. However, the poor water stability limits their application. Herein, a novel dodec-fluoride red phosphor Na3Li3In2F12:Mn4+ with good waterproof stability was successfully synthesized by solvothermal method. The crystal structure, optical property, micro-morphology, element composition, waterproof property and thermal behavior of Na3Li3In2F12:Mn4+ phosphor were analyzed. Under the 468 nm blue light excitation, the Na3Li3In2F12:Mn4+ phosphor has narrow emission bands in the area of 590–680 nm. Compared with commercial red phosphor K2SiF6:Mn4+, the Na3Li3In2F12:Mn4+ phosphor possesses better waterproof stability. When soaked in water for 360 min, the PL intensity of the Na3Li3In2F12:Mn4+ phosphor remains at initial 80%. Finally, warm WLEDs with CRI of 87 and CCT of 3386 K have been fabricated using blue InGaN chip, YAG:Ce3+ yellow phosphor and Na3Li3In2F12:Mn4+ red phosphor.  相似文献   

11.
Developing environment-friendly dual-emission phosphors of both blue–cyan and deep-red lights is desirable for the utilized indoor plant lighting research. Notably, the naked 6s and 6p Bi3+ ions are sensitive to the lattice sites, which emit from Ultraviolet (UV) to red lights in various crystal compounds. Meanwhile, the 2E → 4A2g transition of Mn4+ ions promises its deep-red light emissions, which satisfies the demand for specific wavelength lights for plants growth. Hence, a Bi3+/Mn4+ co-doped Sr2LaGaO5: Bi3+, Mn4+ (SLGO:Bi3+:Mn4+) phosphor was finally synthesized. The phase, micromorphology and luminescent properties were systematically evaluated. Upon excitation at 350 nm light, dual emissions of both blue–cyan (470 nm) and deep-red (718 nm) lights were observed. Besides, due to the pronounced photoluminescence (PL) spectral overlap between Bi3+ and Mn4+ ions, a potential energy transfer process from Bi3+ to Mn4+ ions was confirmed. The relative PL intensities between Bi3+ and Mn4+ ions can be tuned just by adjusting the Mn4+ ion concentration. Besides, Li+ co-doping has been evidenced to improve the deep-red emissions (718 nm) of SLGO:0.005Mn4+ due to charge compensation and rationally designed lattice distortion, together with the improved thermal stability. Finally, the emissions of SLGO:Bi3+, Mn4+, Li+ phosphor suit properly with the absorption of the four fundamental pigments for plant growth, indicating that the prepared phosphorescent materials may have a prospect in plant light-emitting diodes lighting.  相似文献   

12.
Persistent luminescence (PersL) phosphors are considered as promising candidates for the next generation of information storage medium. Mg4Ga4Ge3O16 (MGG) is an electron trapping material which exhibits defect luminescence, and the luminescent properties are easily tuned via doping various activated ions. In this work, undoped and Mn2+/Pr3+/Tb3+ single-doped MGG phosphors were synthesized via high temperature solid phase reactions. X-ray diffraction and scanning electron microscope results confirm that the activated ions tend to occupy Mg2+ sites. Excited at 265 nm, the MGG host exhibits a defect emission band peaked at 450 nm. Red, pink and green emissions are observed in the Mn2+/Pr3+/Tb3+ single-doped MGG samples, which are ascribed to the Mn2+: 4T1(G) → 6A1(S), Pr3+: 1D23H4 and Tb3+: 5D47F5 transitions, respectively. All the samples exhibit bright PersL for minutes after the cessation of excitation. The energy transfer, concentration quenching, luminescence decay and afterglow mechanisms are also discussed in detail. The phosphors exhibit efficient thermal and optical stimuli response, showing great potentials in the optical information storage.  相似文献   

13.
The reaction of Ce4+ with H2O2 in H2SO4 is studied as a function of pH, Ce3+, SO4= and the ionic strength. The reaction mechanism proposed assumes the existence of a Ce3+ -HO2 complex. Direct evidence for the reaction, Ce3+ + HO2 + H+ → Ce4+ + H2O2 is presented.  相似文献   

14.
Ce3+ ion doped BiPO4 phosphors were synthesized by co-precipitation method using ethylene glycol as capping agent. The prepared phosphors were characterized by XRD, SEM, FT-IR, UV-Vis, and PL spectroscopy techniques. The formation of monoclinic phase was confirmed from XRD and FT-IR studies. SEM study revealed the rice shape morphology of BiPO4:Ce3+ (7at.%). In the photoluminescence analysis, a broad emission band extending in a wide wavelengths range with maxima around 419 and 470 nm was observed under excitation at 370 and 417 nm, respectively. These emission bands are originated from the electronic transitions, viz., 5d → 2F5/2, 2F7/2 of Ce3+ ion. The emission intensity was accentuated with the increase of Ce3+ ion till 7at.% and subsequently attenuated with further increase of Ce3+ ion concentration; which is due to the concentration quenching effect. The BiPO4:Ce3+ (7at.%) sample was characterized for the feasibility of photocatalytic degradation of methylene blue under UV light irradiation and degradation of 90% of the dye was degraded within 120 minutes was observed. From the results, it is believed that the prepared BiPO4:Ce3+ may have potential applications in solid state lighting as well as in photocatalysis for the degradation of organic dyes.  相似文献   

15.
The thermal decomposition of manganese and cobalt-terephthalate Metal-Organic Framework precursors was utilized as a synthetic route for fabrication of Co3O4, Mn3O4 and Mn2O3 nanoparticles. The prepared metal oxide nanoparticles of Co3O4, Mn3O4 and Mn2O3 possess average size diameter of 40, 60 and 80 nm respectively. The findings demonstrate that spinel structure nanoparticles of Co3O4 and Mn3O4 exhibit efficient catalytic activity toward heterogeneous olefin epoxidation in the presence of tert-butyl hydroperoxide. In addition, Co3O4 and Mn3O4 nanoparticles illustrated excellent catalytic stability and reusability for nine and four cycles, respectively, toward olefin oxidation.  相似文献   

16.
The Eu2+, M‐codoped(= Ce3+, Mn2+) phosphor powders were prepared by a solid‐state reaction. The addition of Ce3+ in the Eu2+ sites in partially nitridated bredigite‐structure phosphor(CMSN) remarkably enhances the luminescent intensity by ~180% through sensitized luminescence. Dual band emission was observed for Eu, Mn‐codoped CMSN through energy transfer from Eu2+ to Mn2+. Ce3+–Eu2+ and Eu2+–Mn2+ energy‐transfer mechanism was investigated through decay profile analysis using Inokuti–Hirayama model and energy‐transfer parameters are determined. Interaction mechanism was identified as dipole–dipole interaction. In addition, phosphor in glass plates was prepared using the phosphor and its feasibility in white LED application was studied and is presented.  相似文献   

17.
The redox kinetics of VO2+/VO2 + and V3+/V2+ couples on a carbon paper (CP, HCP030 N, Shanghai Hesen, Ltd., China) electrode were investigated in terms of their standard rate constant (k 0) and reaction mechanism. The values determined for k 0 for VO2+ ?? VO2 + and V3+ ?? V2+ using the CP electrode are 1.0 × 10?3 and 1.1 × 10?3 cm s?1, respectively. The value of k 0 increases by one or two order(s) of magnitude compared with values obtained using electrodes composed of pyrolytic graphite and glassy carbon. The acceleration of the redox kinetics of vanadium ions is a result of the large surface area of the CP electrode. An inner-sphere mechanism for the reaction on the surface of the electrode is proposed. The kinetic features of vanadium redox reactions on the CP electrode reveal that CP is suitable for use as the electrodes in vanadium redox-flow batteries.  相似文献   

18.
Tetra-valent manganese (Mn4+) has been regarded as an efficient non-rare-earth red-light emitting ion, which has stimulated continued search of robust hosts and efficient synthetic methods to stabilize Mn4+ centers with strong photoluminescence. In this work, we demonstrate a facile synthetic method for Mn4+ doped glass-ceramic (GC) based on crystallization-induced oxidation state change in an oxide glass. The parent glass with a formula of LiNaGe4O9 is fabricated by melt-quenching and crystallization is induced by thermal treatment in air. Oxidation of Mn2+ in glass to Mn4+ in the GC is confirmed by both optical spectroscopy and electron paramagnetic resonance (EPR) measurements. After thermal treatment, the characteristic reddish photoluminescence (PL) of Mn2+ in the glass centered at 611 nm disappears and a strong photoluminescence peak at 660 nm attributed to Mn4+ is observed. The conversion to Mn4+ after crystallization in the examined system may have strong implications for synthesis of Mn4+ doped phosphors which always requires rigorous control of the redox equilibrium during synthesis.  相似文献   

19.
Europium (Eu3+)-doped fluorophosphate (PNCA:P2O5+NaF + CaF2+AlF3) glasses with the addition of cerium (Ce3+) ions were fabricated by the melt-quenching technique to know their ability for the bright red (615 nm) luminescence. The emission (PL) and excitation (PLE) spectra, decay curve measurements as well as energy transfer (ET) process of Ce3+→ Eu3+ were studied in detail. An excitation spectrum related to the 7F05D2 level of Eu3+ is used to estimate the phonon energy (1121 cm?1) of the title glass host. Under ultraviolet (UV) irradiation of 299 nm, the PL spectra of (Ce3+/Eu3+):PNCA glasses show intense red emission at 615 nm whereas the lifetime decrease with respect to increase of Eu3+ that could support the observed efficient ET from Ce3+ to Eu3+. The ET:Ce3+ →Eu3+ via quadrupole-quadrupole process was confirmed by Reisfeld's approximation and Dexter's ET formula. The ET efficiency (ηET) and critical distance (Rc) were also calculated. Interestingly, the (Ce3+/Eu3+):PNCA glasses showed intense red light emission with low correlated color temperatures and the corresponding color purity reached as great as 99%, indicating its potentiality as a red component for warm light sources.  相似文献   

20.
《Ceramics International》2023,49(15):24703-24711
Ce/Mn/Cr: Y3Al5O12 transparent ceramics with a pure garnet structure and a high color rendering index were prepared by a solid-state reaction method. Mn2+ and Cr3+ enhance the emission between 500 and 700 nm and expand the conventional Ce: YAG phosphors spectrum. The Ce3+ can work both, as activators and sensitizers, and the intense energy transfer from Ce3+ to Mn2+/Cr3+ is realized through the non-radiative and radiative processes. In the sample with the optimized doping concentration the high color rendering index (CRI) value of 75.3 can be achieved under a 450 nm laser diode excitation. The chromaticity coordinates can be tuned from (0.3125, 0.3232) to (0.2917,0.2851) by varying the doping concentration. With the increasing Mn2+/Cr3+ doping concentration, the lifetime of Ce3+, quantum efficiency and luminous efficiency are all gradually decreased. This work effectively offers a scheme for realizing the high color rendering performance of phosphor-converted transparent ceramics in white LEDs/LDs.  相似文献   

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