A Eu and Tb co-doped MOF-5 compound for ratiometric high temperature sensing

In this work, a new Eu and Tb co-doped luminescent compound based on MOF-5, [Zn₄O(BDC)₃], (named as compound 1) was successfully synthesized. The structure and morphology characterizations demonstrate that the initial framework of MOF-5 is retained well after co-doping Eu and Tb. The systematic investigations of photoluminescence behaviors reveal that the heat-treated compound 1 (called as compound 1a) can be utilized as a multi-channel readout luminescent thermometer in emission intensity ratio, decay time ratio, and luminescence color. It simultaneously exhibits the excellent repetitiveness and reversibility under high temperature region from 303 to 473?K. The relative sensitivity of 1.8%/K at 473?K is much higher than the best one of 1.19%/K previously reported for the mixed-lanthanide MOF Tb_0.8Eu_0.2BPDA. Until now, such a ratiometric luminescent thermometer with a high sensitivity at the temperature as high as 473?K has been rarely explored.     

An investigation on the photocatalytic activity of sub-stoichiometric TiO2-x coatings produced by suspension plasma spray

To enhance the photocatalytic activity, sub-stoichiometric TiO_2-x films were coated on stainless steel substrates by Suspension Plasma Spraying. Because the TiO₂ particles are exposed to high temperature during deposition by plasma spray, TiO_2-x coating are typically produced. To achieve different levels of oxygen vacancies, as-sprayed TiO_2-x coatings were annealed at four different temperatures for 48 h in air. In this work, the degradation of methylene blue was performed to evaluate the photocatalytic activity under visible light. The results indicated that oxygen vacancy positively affects the photocatalytic activity of TiO_2-x by introducing some energy levels into the bandgap of titania. Moreover, these energy levels could act as traps for photo-excited holes and electrons, reducing the recombination rate of charges, thus improving the photocatalytic activity under the visible lamp. Additionally, coatings were analyzed by X-ray diffraction, confocal laser microscopy, scanning electron microscopy, Raman spectroscopy, thermogravimetric analysis, Fourier-transform infrared spectroscopy, and UV–vis spectroscopy.     

Fabrication and characterization of Pr6O11-HfO2 ultra-high temperature infrared radiation coating

In this study, pure HfO₂ and Pr₆O₁₁-HfO₂ coatings were prepared by atmospheric plasma spraying. The chemical compositions, morphologies, infrared radiation performances and thermal resistances of the coatings were characterized. The results showed that doping Pr₆O₁₁ could effectively improve the infrared emittance of the HfO₂ coating. The HfO₂ coating doping with 10 wt. % Pr₆O₁₁ exhibited the highest infrared emittance, which was 0.859 at room temperature and 0.883 at 1600 °C, correspondingly. This was mainly attributed to the oxygen vacancies, which created by the substitution of Hf⁴⁺ by Pr³⁺, could introduce localized energy states within the HfO₂ band gap and increase the lattice distortion, producing lower symmetry vibrations. In addition, the Pr₆O₁₁-HfO₂ infrared radiation coating possessed high tensile adhesive strength and good thermal resistance, which could withstand a high temperature treatment at 1700 °C for at least 50 h without exfoliation, and there was only a slight reduction in emittance.     

Correlation between the radius of acceptor ion and the dielectric properties of co-doped TiO2 ceramics

There is an urgent need to seek colossal dielectric materials with better dielectric properties because of the rapid development of the electronics industry. In this work, (M_0.5Nb_0.5)_0.01Ti_0.99O₂ (M = Al, In, Eu) ceramics are synthesized by traditional solid-state reaction, and recorded as ANTO, INTO and ENTO ceramics, respectively. The effects of different radius acceptor ions on the phase structure, microstructure and dielectric properties of TiO₂ based ceramics are investigated. It is found that all samples are rutile phases without the generation of the second phase, but the difference of ion radius resulted in lattice distortion of different degrees, which affects the defect structure in the material. The dielectric properties of the materials are related to the defect structure in the material, and the ability to localize electrons in different defect structures is different. The dielectric properties of ANTO ceramics are similar to those of un-doped TiO₂; INTO ceramics have the lowest dielectric loss (0.039), the best temperature and frequency stability, and there are no dielectric loss peak near the room temperature; The ENTO ceramics has the maximum permittivity (2.01 × 10⁵).     

钒氮共掺杂纳米二氧化钛光触媒乳液的制备及性能研究

以四氯化钛、有机羧酸、稳定剂、表面活性剂、氨水、偏钒酸铵等简单易得的试剂为主要原料,采用常温络合-控制水解新技术,制备出了钒氮共掺杂的纳米二氧化钛透明乳液。采用X射线衍射(XRD)、纳米激光粒度分析仪、紫外-可见分光光度计等对样品进行了表征。结果表明:样品平均粒度在7nm左右,晶型为锐钛矿,样品最大吸收边拓展到了可见光区域。当钒氮掺杂量为0.1%,回流时间为30min时,得到钒氮共掺杂纳米TiO2水溶胶的光催化性能最好,经太阳光照射50min后,对浓度为50mg/L的酸性红3R染料溶液的降解率达到98%以上。     

铽与电气石比对Tb/电气石/TiO_2纳米管的形貌及光学性能的影响

采用溶胶凝胶法与水热法相结合的方法成功制备了Tb/电气石/TiO_2纳米管,采用SEM、TEM、XRD、XPS等研究m(Tb)/m(T)质量比对合成Tb/电气石/TiO_2粉体的形貌和光学性能的影响。实验结果表明,不同的m(Tb)/m(T)比对水热法合成Tb/电气石/TiO_2有很大影响;当掺杂量为1∶2时,Tb/电气石/TiO_2纳米管的为中空管状结构,且结构完整,形貌整齐。水热处理后生成的复合纳米管样品具有更好的光催化活性,晶型以锐钛矿型为主,结晶质量与结晶程度都有所提升,同时在TiO_2表面形成了稳定的Ti-O-Si化学键;稀土Tb的掺杂拓宽了TiO_2的光响应范围;电气石的掺杂有助于提升TiO_2的光催化性能,最佳的掺杂质量比为1∶2,掺杂过多的电气石后光催化效率却有所下降,可能是由于电气石在TiO_2表面覆盖过多导致。     

Simultaneous enhancement of electrical and mechanical properties in CaBi2Nb2O9-based ceramics

CaBi₂Nb₂O₉ (CBN) with Aurivillius phase has an enormous potential in high-temperature piezoelectric devices due to their high Curie temperature and excellent free-fatigue characteristics. Nevertheless, simultaneous enhancement of electrical and mechanical properties in CBN-based ceramics are still a great challenge because of the trade-off between the electrical and mechanical properties. Herein, a strategy, the synergy effect of lattice distortion and oxygen vacancy, is designed to realize the enhanced electrical and mechanical properties of CBN-based ceramics via the domain structure and grain size engineering. The materials can simultaneously deliver a high piezoelectric property of 17.3 pC/N, large hardness of 4.68 GPa, and intensive bending strength of 113.07 MPa, which are enhanced by 346%, 197%, and 141% over those of unmodified CBN ceramics. We believe that the founding of this research opened up a novel and efficient guideline for exploring new bismuth-layered structure ceramics with excellent electrical and mechanical properties.     

Preparation,structural and photocatalytic activity of Sn/Fe co-doped TiO2 nanoparticles by sol-gel method

Pure and Sn/Fe co-doped (0.2 at.% Sn and 0.6 at.% Fe, 0.6 at.% Sn and 0.2 at.% Fe, 1.0 at.% Sn and 1.0 at.% Fe) TiO₂ nanoparticles were synthesized via a sol-gel method and subsequently calcined at different temperatures. Furthermore, the particles were analyzed by TG-DSC, XRD, TEM, HRTEM, EDS, SAED and UV–Vis for investigating the influences of dopant and calcination temperature on the thermal effect, composition, morphology, energy band gap (E_g) and the degradation efficiency of methyl orange (MO) under various light irradiations respectively. Results indicated that Sn/Fe co-doping inhibited the crystallization transformation from anatase to rutile phase of TiO₂ and decreased the E_g. The increased calcination temperature and Sn/Fe co-doped effect brought about the abnormal grain growth of TiO₂ nanoparticles. 0.6 at.% Sn/0.2 at.% Fe and 1.0 at.% Sn/1.0 at.% Fe co-doped TiO₂ nanoparticles presented better photocatalytic performance than pure and 0.2 at.% Sn/0.6 at.% Fe co-doped TiO₂ nanoparticles under visible light irradiation mainly due to the decreased E_g. On the contrary, 0.2 at.% Sn and 0.6 at.% Fe co-doped TiO₂ nanoparticles calcined at 650 °C showed the most excellent photocatalytic performance under UV light irradiation, which was about twice as large as that of pure TiO₂ possibly due to the formed hybrid structure of anatase and rutile phase as well as the h⁺-mediated decomposition pathway.     

Facile fabrication of TiO2-SiO2-C composite with anatase/rutile heterostructure via sol-gel process and its enhanced photocatalytic activity in the presence of H2O2

Constructing anatase/rutile heterostructure in TiO₂ based materials is a quite powerful approach to enhance their photocatalytic activities. Herein, by simply annealing the sol-gel derived TiO₂-SiO₂ composite in N₂ atmosphere at 850 °C, TiO₂-SiO₂-C composite (CTS-850) with anatase/rutile heterostructure has been successfully prepared, while the counterpart prepared in air contains only anatase phase. It was proven that the residual organic groups in the sol-gel process were converted into carbon species upon N₂ annealing, during which TiO₂ in the composite was partially reduced, not only leaving lots of oxygen vacancies on its surface but also promoting the phase transformation. By turning the annealing temperature and atmosphere, a series of control products were further synthesized. Among these samples, the CTS-850 showed the best photocatalytic performance toward Rhodamine B degradation in the presence of H₂O₂, which was mainly due to its lowest band gap and the enhanced sensitization of H₂O₂ by oxygen vacancies. Moreover, the photocatalytic activity of CTS-850 remained unchanged after five cycles and a proper mechanism was also proposed.     

Corrosion resistance and infrared emissivity properties of EPDM (EPDM-g-MAH) film on low infrared emissivity PU/Cu coating

In order to improve the corrosion resistance of low infrared emissivity polyurethane (PU)/Cu coating, ethylene-propylene-diene monomer (EPDM) and maleic anhydride grafted EPDM (EPDM-g-MAH) were deposited on PU/Cu coating by spin coating, respectively. The ability of EPDM and EPDM-g-MAH to serve as corrosion protective films for PU/Cu coating was examined by evolved emissivity immersion test and potentiodynamic polarization measurements in 3.5% NaCl solution. And the chemical composition and surface morphology of PU/Cu coating before and after corrosion were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results showed that all of the coated samples present a better corrosion resistance than bare PU/Cu coating due to indissolubility of Cu by aggressive ions, and the effect of EPDM-g-MAH is better than that of EPDM.     

La／B共掺杂Ti02光催化降解苋菜红的研究

采用溶胶-凝胶法制备La/B共掺杂Ti O2催化剂和纯TiO2催化剂。以苋菜红溶液为降解目标物,研究了La/B共掺杂TiO2为催化剂的紫外光催化反应。重点考察了La/B共掺TiO2催化剂的掺杂比、催化剂的煅烧温度、光照时间、催化剂的添加量、溶液初始浓度、溶液p H值对降解率的影响。实验结果表明：单纯只靠紫外光光照或催化剂并不能快速、有效地降解苋菜红溶液。在La和B掺杂比为1：2、催化剂的煅烧温度为600℃、催化剂用量为3.0g/L、溶液p H值为5.5、溶液初始浓度为10mg/L的苋菜红溶液200m L,紫外光光照60min的条件下,La/B共掺杂的TiO2催化剂和纯TiO2催化剂光催化脱色率分别可达99.60%、86.45%,TOC的去除率为60.06%。     

Thermal radiation and cycling properties of (Ca,Fe) or (Sr,Mn) co-doped La2Ce2O7 coatings

La₂Ce₂O₇ with low thermal conductivity as a potential candidate of thermal barrier coatings (TBCs) was co-doped with (Ca, Fe) or (Sr, Mn) in order to further improve its thermal radiation at high temperatures. The microstructure, chemical composition, infrared emission properties (reflection and absorption properties) and thermal cycling lifetime of the coatings were respectively investigated. The results revealed that La_2-xCa_xCe_2-xFe_xO₇₊δ and La_2-xSr_xCe_2-xMn_xO₇₊δ coatings had defected fluorite structure and their infrared emittances were much higher than that of the parent La₂Ce₂O₇. The superior infrared emission could be ascribed to the enhancement of the intrinsic absorption (electron transition absorption), free-carrier absorption and impurity absorption as well as lattice vibration absorption. However, the thermal cycling lifetime of La₂Ce₂O₇ coatings presented a reduction after the (Ca, Fe) or (Sr, Mn) substitution, primarily due to the decrease in the fracture toughness and the increase in the thermal conductivity.     

N/B/Fe共掺杂生物质炭阴极制备及电芬顿降解对硝基酚

以玉米芯为主要原料,采用热沉积、高温焙烧法,制备N/B/Fe共掺杂生物质炭（N/B/Fe@BC）,通过X射线衍射（XRD）、扫描电子显微镜（SEM）、高分辨透射电子显微镜（HRTEM）和X射线光电子能谱仪（XPS）等手段对样品的晶格结构、形貌特征和组成等进行表征,并以对硝基酚为对象,探究N/B/Fe@BC电极的电芬顿催化性能。结果表明,N/B/Fe@BC为纳米薄片交错堆积的三维多孔结构,表面缺陷较未掺杂生物质炭显著增加,催化氧还原以两电子产H₂O₂为主。在电流强度50mA、初始pH为3的电芬顿体系中,120min时对硝基酚的去除率为97.93%±1.62%,60min内反应速率常数k为0.040min^-1,是未掺杂生物质炭电极的2.7倍。N/B/Fe@BC电极的pH适用范围较宽,受水质的影响较小,循环使用10次后120min对硝基酚的去除率仍可达到85%以上。     

A-site Ca/Sr co-doping to optimize room-temperature TCR of La0.7Ca0.3-xSrxMnO3 films

Based on the analysis of crystal structure, Mn³⁺/Mn⁴⁺ pairs, distortion of MnO₆ octahedron, and electrical transport properties of La_1-xCa_xMnO₃ and La_1-xSr_xMnO₃ materials, room-temperature coefficient of resistivity (TCR) of La_0.7Ca_0.3-xSr_xMnO₃ (LCSMO) films was optimized by Ca/Sr co-doping at the A-site. LCSMO films are successfully fabricated on LaAlO₃ (100) substrates via facile spin coating technology. The microstructure of LCSMO films is characterized by X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, atomic force microscopy and X-ray photoemission spectroscopy. Results reveal that A-site Ca/Sr co-doping significantly influenced crystal structure, formation of Mn³⁺/Mn⁴⁺ pairs, and distortion of MnO₆ octahedron. The correlation between microstructure and electrical transport properties was explained through the phenomenological percolation model, double-exchange mechanism and Jahn-Teller effect. Furthermore, the TCR reached 10.2% K^-1 at 296.1 K in La_0.7Ca_0.18Sr_0.12MnO₃ films.     

Fabrication and characterizations of (Lu,Gd)2O3:Eu scintillation ceramics

In this paper, (Lu,Gd)₂O₃:Eu ceramics were consolidated by the solid-state reaction method combined with vacuum sintering at 1820 °C for 10 h. It is found that the Gd₂O₃ incorporates well into the Lu₂O₃ lattices and forms a solid solution. Particularly, strong red emission of ⁵D₀→⁷F₂ transition of Eu³⁺ at 611 nm, matched well to the spectral sensitivity of typical CCD arrays, was observed in the photoluminescence and radioluminescence spectra. What's more, radioluminescence intensity of the 4f→4f transitions of Eu³⁺ reaches up to 10 times of bismuth germanium oxide (BGO) single crystal reference scintillator. Intensities of the radioluminescence and the integrated thermoluminescence versus temperatures, as well as the influence of annealing treatment on the thermoluminescence intensity, were also studied. We think that (Lu,Gd)₂O₃:Eu ceramic scintillators may have great potential in medical X-ray computed tomography (CT) due to their excellent properties.     

Metal organic framework derived Ni/CeO2 catalyst with highly dispersed ultra-fine Ni nanoparticles: Impregnation synthesis and the application in CO2 methanation

CO₂ methanation is a promising strategy to convert the greenhouse gas into synthetic natural gas, which is known as a clean fuel with higher energy density. Ni/CeO₂ is one of the active catalysts for CO₂ methanation reaction. However, Ni/CeO₂ with conventional metal/support structure suffers from the problem of nanocrystal coarsening during high-temperature reaction and thus decreasing catalytic activity. In this work, a Ni/CeO₂ catalyst with novel structure was designed and synthesized through impregnation of Ce-based metal organic framework (MOF) with Ni precursor followed by calcination process. Due to the confinement effect of ultra-small pores derived from the MOF, Ni/CeO₂ catalysts with ultrafine Ni nanoparticles, high dispersion and good thermostability were resulted. Among all the samples, Ni/CeO₂ calcined at 600 °C showed the best catalytic performance due to the highest amount of oxygen vacancies. This work demonstrates a facile way to synthesize a broad range of ultra-fine metal/metal oxide nanocomposite catalysts with high catalytic activity and good stability for various applications.     

Spectroscopic properties of Er/Yb co-doped glass ceramics containing nanocrystalline Bi2ZnB2O7 for broadband near-infrared emission

Er/Yb co-doped transparent glass ceramics containing nanocrystalline Bi₂ZnB₂O₇ were successfully prepared by a high-temperature melting method. X-ray diffraction analysis confirmed the structural properties of the crystal and glass phases of the glass ceramics. Scanning electron microscope images indicated that nanocrystalline Bi₂ZnB₂O₇ with an average size of 30–40 nm was uniformly distributed in the glass matrix. Infrared spectroscopy demonstrated that the glass and glass ceramics had different vibrational peaks. The absorption spectra showed the absorption peaks of the samples, and the main spectral parameters of each absorption peak were calculated using the Judd–Ofelt theory. The emission spectra of the samples showed ultra-wideband fluorescence from 1400 to 1700 nm under excitation at 980 nm, which was enhanced by precipitation of nanocrystalline Bi₂ZnB₂O₇ and the addition of Yb³⁺ ions. Our research showed that Er/Yb co-doped glass ceramics containing nanocrystalline Bi₂ZnB₂O₇ are a promising material for application in near-infrared optical amplifiers.     

Effects of Ca2+-Sr2+ doping on the infrared emissivity of LaCrO3

LaCrO₃ shows excellent thermal stability and good emissivity, and can be used as a potential thermal protection material for hypersonic vehicle. In this study, LaCrO₃ and Ca²⁺-Sr²⁺ doped LaCrO₃ were prepared by solid state reaction at 1400 °C for 2 h. The microstructures of the samples and effects of Ca²⁺-Sr²⁺ doping on the infrared emissivity of LaCrO₃ were studied by XRD, XPS, FT-IR, and UV–VIS–NIR spectrophotometer. The results show that after doping Ca²⁺ and Sr²⁺ ions, the infrared emissivity of all samples has significantly improved at 2.5–10 μm, from 0.61 (minimum value) to above 0.90. In the range of 10–14 μm, the emissivity of pure LaCrO₃ and La_0.8Ca_xSr_0.2-xCrO₃ samples shows a similar trend and all remains above 0.97. Therefore, doping Ca²⁺ and Sr²⁺ can significantly increase the emissivity of LaCrO₃ at 2.5–10 μm, which makes it have a wider application prospect in the field of high temperature thermal protection.