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Materials · 2021 ·Vol. 14 ·期 21 ·6666 · IF 3.623

Improved Non-Piezoelectric Electric Properties Based on La Modulated Ferroelectric-Ergodic Relaxor Transition in (Bi0.5Na0.5)TiO3-Ba(Ti, Zr)O3 Ceramics

Xingru Zhang,Yinan Xiao,Beining Du,Yueming Li,Yuandong Wu,Liyuan Sheng,Wenchang Tan

The characteristic transition from ferroelectric (FE) to ergodic relaxor (ER) state in (Bi0.5Na0.5)TiO3(BNT) based lead-free ceramics provides an efficient approach to bring a highly ordered phase back to a disordered one. It would be rational to utilize this transition to improve relevant non-piezoelectric properties based on domain decomposition. In this work, different La contents were introduced to 0.93(Bi0.5Na0.5)TiO3-0.07Ba(Ti0.945Zr0.055)O3ceramics (BNT-BZT-xLa) to induce evolution of ergodic degree. The results reveal that with increasing La content, both the FE-ER transition temperatureTF-Rand depolarization temperatureTdshift towards room temperature, implying a deepened ergodic degree. By modulation of ergodic degree, thermally stimulated depolarization current experiment shows a higher current density peak, and corresponding pyroelectric coefficient increases from 2.46 to 2.81 μC/(cm2∙°C) atTd. For refrigeration, the indirect measurement demonstrates the ΔTmaximum increases from 1.1 K to 1.4 K, indicating an enhanced electrocaloric effect. Moreover, the optimized energy storage effect is observed after La doping. With appearance of “slimmer”P-Eloops, both calculated recoverable energy storage densityWrecand storage efficiencyηincrease to 0.23 J/cm3and 22.8%, respectively. These results denote La doping conduces to the improvement of non-piezoelectric properties of BNT-based ceramics in a certain range. Therefore, La doping should be an adopted modification strategy for lead-free ceramics used in areas like refrigerator and pulse capacitors.Keywords:BNT-based lead-free ceramics;electric properties;ferroelectric to ergodic relaxor state transition;La doping

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Green Processing and Synthesis · 2022 ·Vol. 11 ·期 1 ·184-194 · IF 3.97

Fabrication of silicotungstic acid immobilized on Ce-based MOF and embedded in Zr-based MOF matrix for green fatty acid esterification

Qiuyun Zhang,Binbin Yang,Yuanyuan Tian,Xianju Yang,Rongfei Yu,Jialu Wang,Taoli Deng,Yutao Zhang

In the present study, a facile solvothermal method was used for the synthesis of silicotungstic acid (HSiW) immobilized on Ce-based metal organic framework (Ce-BDC) and embedded in Zr-based metal-organic framework (UiO-66(Zr)) composite catalyst, namely, Ce-BDC@HSiW@UiO-66 for the production of biodiesel through green fatty acid esterification. The obtained hybrids were characterized by various characterization technologies, including Fourier transform infrared, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N 2 physisorption, X-ray photoelectron spectroscopy, and temperature-programmed desorption of NH 3 (NH 3 -TPD) analysis. The characterization analyses showed that the hybrids have been successfully synthesized. Also, the volume and pore size of UiO-66(Zr) were changed by introducing HSiW@Ce-BDC, and the resulting Ce-BDC@HSiW@UiO-66 possessed the mesoporous structure and relatively high surface area. Simultaneously, the NH 3 -TPD analysis of Ce-BDC@HSiW@UiO-66 reveals that the acid strength was increased in comparison with HSiW@Ce-BDC. In addition, the composite Ce-BDC@HSiW@UiO-66 demonstrated high catalytic activity, and the oleic acid esterification gave 81.5% conversion at optimum conditions of 0.2 g catalysts, 1:30 oleic acid to methanol molar ratio at 130°C for 4 h. More interestingly, after six recycling cycles, the reduction in the conversion rate was only 4.6%, indicating that Ce-BDC@HSiW@UiO-66 has excellent reusability. Our study provides an effective approach to synthesize multifunctional hybrids for green biofuel production.

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KOREAN JOURNAL OF CHEMICAL ENGINEERING · 2017 ·Vol. 34 ·期 12 ·3132-3141 · IF 2.007

Deep desulfurization of model oil by photocatalytic air oxidation and adsorption using Ti(1−x)M x O2 (M=Zr, Ce)

Zhang Wei,Li Xin,Wang Hong,Song Yongji,Zhang Shenghong,Li Cuiqing

Deep desulfurization of model oil by photocatalytic air oxidation and adsorption using Ti (1− x ) M x O 2 (M=Zr, Ce) was investigated. Ti (1− x ) M x O 2 (M=Zr, Ce) was prepared by urea gelation/co-precipitation method, and characterized by N 2 adsorption, XRD and UV-vis spectra. UV irradiation greatly enhanced the adsorptive capacity and selectivity of TiO 2 -ZrO 2 for organosulfur in model oil because organosulfur compounds were first photocatalytically oxidized to sulfoxides and sulfones over TiO 2 -ZrO 2 , which were then selectively adsorbed on the bifunctional material due to much higher polarities of generated sulfoxides and sulfones. The Ti/Zr molar ratio and calcination temperature were optimized to 5 : 5 and 500 °C with the sulfur removal of 99.6% after reaction for 2 h under UV irradiation. After adding 25 wt% toluene into model oil, the sulfur removal could still reach 97.2% after reaction for 7 h. TiO 2 -ZrO 2 could be well regenrated by washing with acetonitrile followed by thermal treatment in air.

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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2021 ·Vol. 32 ·期 3 ·2685-2695 · IF 2.478

Microstructure, magnetic, and dielectric properties of Co–Zr co-doped hexagonal barium ferrites based on the sintering temperature and doping concentration

Zhang Hongbo,Fan Lining,Cao Hechun,Yu Yishi,Zhang Tianchi,Feng Qianqian,Zheng Hui,Wu Qiong,Zhang Yang

In this work, M-type hexagonal barium ferrites co-doped with Co and Zr atoms were prepared by a solid-phase method based on the sintering temperature and doping concentration. First, the influences of the sintering temperature on the crystal structure, microstructure, and magnetic properties of ferrites were studied. The crystallinity of the materials increases with the sintering temperature and obtaining high density and uniform grain size at 1300 °C, which promotes grain-boundary diffusion and suppresses grain-boundary migration. Second, the dependence of the crystal structure, microstructure, magnetic, and dielectric properties of Ba(Co x Zr x )Fe 12−2 x O 19 on the doping concentration ( x  = 0, 0.2, 0.4, 0.6) was investigated at sintering temperature of 1300 °C. The increase of the crystal parameter c with x value reveals that the ions of Co 2+ and Zr 4+ successfully replace the Fe 3+ ions. Additionally, the co-doping ions of Co 2+ –Zr 4+ promote the grain-boundary migration and result in some large size grain (> 20 mm) that appeared and increased with the doping concentration. The magnetic hysteresis loops reveal the saturation magnetization increases from 60.45 to 68.6 emu/g, and the coercivity decreases from 1800 to 190 Oe with the x increased to 0.6. The dielectric properties measurement displays the Co–Zr co-doping can improve the dielectric and reduce the dielectric loss. The highest value of the real part of permittivity ( ε ′) and the lowest value of the imaginary part of permittivity ( ε ″) can be obtained at a doping concentration of x  = 0.4.

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LANGMUIR · 2022 · IF 4.331

Environmentally Friendly Zr-Based MOF for Pesticide Delivery: Ultrahigh Loading Capacity, pH-Responsive Release, Improved Leaf Affinity, and Enhanced Antipest Activity

Saijie Song,Minghui Wan,Wenli Feng,Yu Tian,Xuefeng Jiang,Yi Luo,Jian Shen

The stimuli responsive pesticide delivery system (PDS) has drawn increasing attention in recent years, a system which can effectively improve the utilization of pesticides. In the current research, we report a pH responsive PDS by using carboxymethyl cellulose (CMC) modified Zr-based metal organic frameworks (UiO-66-NH2) as the nanocarrier for acetamiprid (ATP). UiO-66-NH2-CMC possesses a large surface area and abundant pores, which can effectively load ATP, and the loading rate is as high as 90.79%. Compared with free ATP, the ATP@UiO-66-NH2-CMC nanopesticide exhibits pH responsive controlled release behavior, and the pesticide can sustained release to the medium. In addition, it also shows improved leaf affinity, which makes it easier to wet the leaf surface and improve the utilization of pesticide. Therefore, ATP@UiO-66-NH2-CMC displays better antipest activity against aphids than free ATP does. Meanwhile, ATP@UiO-66-NH2-CMC shows no negative effects on the germination and growth of maize, showing good biosafety. Moreover, the ATP@UiO-66-NH2-CMC nanopesticide does not contain any toxic organic solvents or additives. Therefore, we hope that it can be a suitable candidate for plant protection and sustainable agriculture.

✓ 已验证 DOI PubMed 高影响因子
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FUEL PROCESSING TECHNOLOGY · 2019 · IF 4.507

Comparative study on dry reforming of methane over Co-M (M = Ce, Fe, Zr) catalysts supported on N-doped activated carbon

Yinghui Sun,Guojie Zhang,Ying Xu,Yongfa Zhang,Yongkang Lv,Riguang Zhang

A series of Co-M (M = Ce, Fe, Zr) binary oxides supported on N-doped catalysts were prepared by impregnation methods and tested for DRM reaction. Moreover, the influence of Co and Ce atomic contents in the catalysts on DRM performance was investigated. Significant enhancement of activity performance over Ce promoted 3Co-1Ce/AC-N catalyst was observed. Compared with Fe and Zr, the catalyst with 1/4 mol% of Ce showed the highest activity and was higher than the supported Co catalyst . The calcined and spent catalysts were characterized by XPS , H 2 -TPR, TEM and EDX mapping studies. The characterization results demonstrated that the increase of 3Co-1Ce/AC-N reforming reactivity was attributed to the presence of Ce in Co-based catalyst, which modified the chemical states of Co-Ce composite oxide and redox properties, and increased the presence of Co 2+ species, the content of chemisorbed oxygen and the oxygen mobility. Among the different Co/Ce ratio catalysts, the one with a Co/Ce molar ratio at 1 exhibited better catalytic performance. As the Ce content increases, the content of chemisorbed oxygen was further decreased. In addition, the introduction of N on the support could also affect the catalyst reduction property and interaction of Co-Ce bimetal, which would improve catalytic performance.

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Journal of Materials Chemistry A · 2025 · IF 9.5

A Li-enriched amorphous Zr-based oxychloride solid electrolyte for high-rate and long-cycling all-solid-state ultrahigh-nickel cathodes

Shiliang Yang,Qilin Feng,Xiaoke Liu,Changmeng Xu,Xianyi Liu,Wenxin He,Jiangmin Jiang,Tao Ma,Jipeng Fu,Yichen Yin

The Zr-based chloride solid electrolyte (SE) Li2ZrCl6 is well compatible with 4 V-class cathodes and cost-effective, yet its low conductivity (<1 mS cm−1) would restrain the capacity delivery of the electrodes especially at high rates. Herein, we further elevated the room-temperature ionic conductivity of Zr-based lithium oxychloride to 2.11 mS cm−1 in Li2.15Zr0.85In0.15Cl4O by tuning its Li content through partial substitution of Zr4+ with In3+ in the formula Li2+xZr1−xInxCl4O. Cold-pressed Li2.15Zr0.85In0.15Cl4O presents both a dense morphology arising from its amorphous phase and enhanced ionic conductivity, which is significantly higher than that of Li2ZrCl6, facilitating better solid–solid contact and improved reaction kinetics in the composite cathodes. As a result, the all-solid-state cathode coupling Li2.15Zr0.85In0.15Cl4O and LiNi0.92Co0.03Mn0.05O2 shows a capacity of 175.3 mAh g−1 at 4C and a retention of 91.44% for 450 cycles when charged to 4.3 V vs. Li+/Li. More attractively, as the charge upper limit increases to 4.8 V, Li2.15Zr0.85In0.15Cl4O also enables ultrahigh-nickel cathodes to cycle for over 250 cycles with a capacity retention of 81.86%.

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ACS Applied Materials & Interfaces · 2024 · IF 8.3

UiO-66(Zr)-2OH-Supported Pd0 NP Catalysts Accelerated a Fenton-Like Reaction: Iron Cycling and Hydrogen Peroxide Generation Achieved Simultaneously

Ying Gao,Qinqin Chen,Xinhao Shen,Shuang Yao,Zhiwen Jiang,Sanjian Ma,Hailiang Yang,Juanhong Li,Zixia Lin,Xin Liu

Both the sluggish kinetics of Fe(II) regeneration and usage restriction of H2O2 have severely hindered the scientific progress of the Fenton reaction toward practical applications. Herein, a reduction strategy of activated hydrogen, which was used to simultaneously generate H2O2 and accelerate the regeneration of ferrous in a Fenton-like reaction based on the reduction of activated hydrogen derived from H2, was proposed. Two types of composite catalysts, namely, Pd/UiO-66(Zr)-2OH and Pd@UiO-66(Zr)-2OH, were successfully prepared by loading nano-Pd particles onto the outer and inner pores of UiO-66(Zr)-2OH in different loading modes, respectively. They were used to enhance the reduction of activated hydrogen. The characterization results based on the analysis of scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy revealed that the materials were successfully prepared. By using a trace amount of ferrous iron and without adding H2O2, trimethoprim (C0 = 20 mg·L–1), as a target pollutant, could be nearly 100% degraded within 180 min in the reaction system composed of these two materials. The cycle of iron and the self-generation of H2O2 were verified by the detection of ferrous H2O2 in the system. Density functional theory calculation results further confirmed that the pore-filled Pd0 NPs, as the main catalytic site for Pd@UiO-66(Zr)-2OH, could produce H2O2 under the combined action of hydrogen and oxygen. The Pd@UiO-66(Zr)-2OH system had excellent stability after multiple applications (at least 6 cycles), all of which resulted in 100% removal of trimethoprim. The degradation efficiency of the Pd/UiO-66(Zr)-2OH system for TMP gradually decreased from 97 to 80% after six cycles. The results of electron paramagnetic resonance combined with classical radical burst experiments revealed the degradation pathways in the reaction system with hydroxyl radicals and singlet oxygen as the main reactive oxygen particles.

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MICROCHEMICAL JOURNAL · 2024 · IF 4.9

Ultrasensitive electrochemical sensing platform based on Zr-based MOF embellished single-wall carbon nanotube networks for trace analysis of methyl parathion

Jiale Han,Fang Li,Mengyuan Zhao,Meimei Guo,Yunhang Liu,Xiangxing Guo,Qiwen Ran,Zhankui Wang,Hongyuan Zhao

In this work, a novel electrochemical sensor was designed based on Zr-based metal–organic framework (UIO-66) nanoparticles embellished single-wall carbon nanotube networks (SCN) for the detection of methyl parathion (MP). The synergistic combination of SCN and UIO-66 nanoparticles could fully exert each advantage to boost the MP electrochemical sensing analysis performance. SCN with one-dimensional hollow nanostructures formed three-dimensional interconnected carbon conductive networks, which possessed excellent conductive properties and acceptable specific surface area, enabling efficient transport of electrons and ions. UIO-66 nanoparticles with Zr-OH groups contributes and porous structure to the good affinity for phosphate groups on MP molecules, which enhanced the selective recognition and enrichment capability of sensing electrode towards MP. Under the multifunctional integration of SCN and UIO-66 nanoparticles, the SCN@UIO-66/GCE sensor could present satisfactory MP electrochemical detection performance (LOD: 8.05 nM, linear MP concentration range: 0.01–10 μM). The satisfactory practical property was realized at the SCN@UIO-66/GCE sensor with satisfactory recovery rates of 98.28–101.95 % and low RSD of 1.23–3.01 % for the electrochemical detection of MP in orange juice and lettuce samples.

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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Enhancing interfacial stability in sulfide all-solid-state batteries through surface dual-doping of Zr and F in Ni-rich cathodes

Daoyan Feng,Yu Liu,Chen Zhao,Han Su,Xia Kong,Yu Zhong,Junzhang Wang,Zhou Xu,Xiuli Wang,Xingzhong Guo,Jonghee Lee,Jiangping Tu

Achieving a stable interface between sulfide solid-state electrolytes (SSEs) and high-voltage Ni-rich oxide cathodes is crucial for enhancing the electrochemical performance of all-solid-state batteries (ASSBs). However, addressing the interface challenges through surface coating modifications remains a significant hurdle. In this work, a straightforward modification approach is proposed to achieve a highly stable interface by surface dual doping of Zr and F in LiNi 0.83 Co 0.12 Mn 0.05 O 2 (NCM83) cathodes via acid washing followed by annealing. First-principle calculations demonstrate the thermodynamic stability of Zr-F doped NCM83, effectively inhibiting the formation of unfavorable interfaces with decomposition products. The modified NCM83-1% ZrF cathode exhibits exceptional long-cycle stability, retaining 85.1% of its capacity after 1000 cycles at 0.5C rate. This simple and scalable modification strategy offers a new perspective for the design of high-performance sulfide-based ASSBs.

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ANALYTICA CHIMICA ACTA · 2026 · IF 6.1

Amino-functionalized europium-doped Zr-MOF as a ratiometric fluorescent probe for ultra-sensitive visual detection of trace water in organic solvents

Tianhong Liu,Ziyi Xu,Shuiyuan Zhang,Long Yu,Junting Mo,Mingtai Sun,Suhua Wang

Background Trace water contamination in organic solvents severely hampers chemical synthesis, pharmaceutical manufacturing, and electronic device fabrication; however, existing detection methods lack portability, adequate sensitivity, or stability. While MOF-based fluorescent sensors show promise, most are limited by single-signal outputs, weak anti-interference capability, and poor solvent tolerance. Results To address these challenges, we report an amino-functionalized europium-doped zirconium MOF (Eu@MOF-NH 2 ), synthesized via a one-step solvothermal method, serving as a robust ratiometric fluorescent probe for trace water detection. The material exhibits dual emissions: ligand-based (435 nm) and Eu 3+ -centered (614 nm). Upon water exposure, strong hydrogen bonds with the ligand activate intramolecular charge transfer (ICT) to intensify the blue emission. Concurrently, high-frequency O–H vibrational coupling quenches the red emission by blocking ligand-to-metal energy transfer, causing a rapid (<30 s) pink-to-blue visual transition. The fluorescence intensity ratio (I 435 /I 614 ) demonstrates excellent linearity with water content (0–10% v/v) and achieves ultralow limits of detection in ethanol (0.1643%), THF (0.0311%), methanol (0.3355%), and acetonitrile (0.0148%). Furthermore, this probe maintains consistent sensing performance across 11 diverse organic solvents with highly varying polarities. Integrated with a smartphone-assisted RGB colorimetric platform based on the blue-to-red intensity ratio, Eu@MOF-NH 2 enables portable, on-site, and quantitative visual detection. Significance This work overcomes the traditional limitations of sensitivity and stability, providing reliable material design and sensing strategies for industrial trace water monitoring and quality control.

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MICROCHIMICA ACTA · 2025 ·Vol. 192 ·期 11 ·1-16 · IF 5.3

A simple, sensitive and reusable bifunctional ratiometric fluorescent sensing platform RhB@Zr-MOF for rapid detection of adenosine triphosphate and malachite green

Zhuang Dengke,Guo Hao,Wei Yuli,Yu Zhiguo,Peng Liping,Ma Yanyan,Hui Yingfei,Yan Yu,Yang Wu

A sensitive and accurate ratiometric fluorescent sensor (RhB@UIO-67) is constructed by simply encapsulating rhodamine B (RhB) within a zirconium-based metal–organic framework (UIO-67). Based on the inhibition effect of ligand–to-metal charge transfer, adenosine triphosphate ATP induces a significant enhancement in the MOF centre emission, but does not affect the fluorescence of RhB in the probe material at all, which are respectively employed as detection signal and reference signal to realize sensitive ratiometric fluorescence detection of ATP in human serum and urine with a detection limit (LOD) of 0.45 μM. In particular, since the introduction of the target molecules does not cause any structural degradation, the sensor can be reused. Additionally, due to fluorescence resonance energy transfer between the probe components and malachite green (MG), addition of MG results in different degrees of quenching of the fluorescence emissions of UIO-67 and RhB in the RhB@UIO-67 and thus the probe material can simultaneously serve as a sensitive ratiometric sensing platform for MG detection in aquatic products including fish and shrimp with a low LOD of 0.03 μM. Benefited from its simplicity, sensitivity, and reusability, the sensing material has a wide application potential. Graphical abstract

CAS / MDL: 10026-11-6 787-70-2
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