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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2022 ·Vol. 29 ·期 45 ·68320-68331 · IF 5.19

Efficient capture of U(VI) by magnetic Zr(IV)-ethylenediamine tetramethylene phosphonic acid inorganic-organic hybrid

Luo Qie,Cui Wenzheng,Wang Huan,Xiao Bo,Chen Lei,Wang Youqun,Zhang Zhibin,Liu Yunhai,Cao Xiaohong

The separation of magnetic adsorbents from aqueous solutions is made simple by using an external magnetic field. Herein, magnetic Zr(IV)-ethylenediamine tetramethylene phosphonic acid (EDTMPA) hybrids (MZrOP- x -T, x , and T were the different quality of Fe 3 O 4 @C and temperature in the synthesis process, respectively). A study was conducted on the uses of MZrOP- x -T in the capture of U(VI). The influences of pH, adsorption period, initial concentration, and temperature were all investigated. Furthermore, the desorption and reusability of the materials were explored. The optimal values of x and T were 0.2 g and 100 °C, respectively. At 298.15 K, the maximum adsorption capacity of MZrOP-0.2-100 was 330.30 mg·g −1 . The current research demonstrates that MZrOP-0.2-100 is a potentially effective material in removing U(VI) from radioactive solution.

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SCIENCE OF THE TOTAL ENVIRONMENT · 2022 · IF 10.753

Size- and shape-dependent cytotoxicity of nano-sized Zr-based porphyrinic metal-organic frameworks to macrophages

Fang Hao,Zhu-Ying Yan,Xiu-Ping Yan

The wide utilization of nano-sized metal-organic frameworks (NMOFs) leads to inevitable health risks to humans. Previous studies on health risks of NMOFs mainly focus on the cytotoxic tests of typical NMOFs,but lack sufficient studies on the effects of physiochemical characteristics of NMOFs on the cytotoxicity and the related mechanisms. Here, four kinds of Zr-based porphyrinic NMOFs (PCNs), including spherical 30, 90, and 180 nm PCN-224 and rod-like 90 nm PCN-222, were taken as a proof of the concept to investigate the effects of the size and shape of NMOFs on the cytotoxicity and related mechanisms to macrophages. The 30 nm spherical PCN-224 induced significant rupture of cell membrane and dissolved in lysosome, leading to the most significant cell necrosis among the studied other nano-sized PCNs. However, other studied PCNs showed insignificant membrane rupture and their dissolution in lysosome. Furthermore, the 90 nm-sized PCN-224 led to much more significant cell necrosis by inducing lysosome damage and inhibiting of autophagy flux than the rod-like 90 nm PCN-222. These findings reveal the size- and shape-dependent cytotoxicity of PCNs and the related mechanisms and are helpful to the assessment of the potential health risks of NMOFs and the safe application of NMOFs.

CAS / MDL: 68-12-2 13520-92-8
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RENEWABLE ENERGY · 2022 · IF 8.634

Natural lignocellulose welded Zr–Al bimetallic hybrids for the sustainable conversion of xylose to alkyl levulinate

Lincai Peng,Xin Huangfu,Yao Liu,Huai Liu,Junhua Zhang

The processing of C6 sugars to alkyl levulinate (AL), a versatile biomass-derived building block, can be readily implemented via the straightforward acid-catalyzed reaction in alcohol medium while it remains a challenge to produce AL from C5 sugars in the one-pot procedure over a monolithic catalyst. In this contribution, a budget and multifunctional natural lignocellulose welded Zr–Al bimetallic hybrid (ZrAl@CS-MSA) has been successfully constructed with crude corn stalk as a sustainable support. The becoming Lewis and Brønsted acid sites of ZrAl@CS-MSA catalyst guarantee a high AL yield of 54.3% from xylose via a one-pot process in a renewable n -butanol medium. Experimental findings revealed that the sulfonic group of ZrAl@CS-MSA plays a significant role in the xylose dehydration, furfuryl alcohol etherification and alcoholysis reactions while Zr species is in charge of the transfer hydrogenation of furfural. The Al species enclosed in ZrAl@CS-MSA can regulate its Brønsted and Lewis acidity, accelerating the etherification and alcoholysis reactions as well as alleviating the over hydrogenation of AL. This work opens a green, sustainable and reliable avenue for producing C5 sugar-based AL using natural lignocellulose-related multifunctional catalysts.

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Catalysts · 2023 ·Vol. 13 ·期 5 ·915 · IF 3.9

Synthesis of a Series of Methyl Benzoates through Esterification with a Zr/Ti Solid Acid Catalyst

Xiaofeng Yu,Chunjie Shi,Yueling Cheng,Yejing Zhu,Renyuan Song,Shengfei Hu

Methyl benzoate (MB) compounds are prepared by reacting various benzoic acids with methanol using an acidic catalyst. In this study, the solid acids of zirconium metal solids fixed with various substances were studied. We determined that zirconium metal catalysts with fixed Ti had the best activity. The catalytic synthesis of a series of MB compounds using titanium zirconium solid acids was studied. The direct condensation of benzoic acid and methanol using a metallic Lewis acid without other auxiliary Bronsted acids is reported for the first time.Keywords:methyl benzoate;solid acid;catalysis

CAS / MDL: 71-43-2 65-85-0
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ENERGY & FUELS · 2021 · IF 3.605

Enhanced Thermochemical Energy Storage Stability of CaO-Based Composite Pellets Incorporated with a Zr-Based Stabilizer

Yue Zhou,Zijian Zhou,Lei Liu,Xiangyao She,Ruichang Xu,Jian Sun,Minghou Xu

Calcium looping is a potential thermochemical energy storage technology applied in a high-temperature working window. However, CaCO3/CaO materials are prone to encounter severe sintering, exhibiting poor thermal energy storage/release stability. To improve the thermochemical energy storage stability, different amounts (5, 15, and 30 wt %) of a Zr-based stabilizer were incorporated into CaCO3/CaO materials. Moreover, the graphite-casting method was adopted to prepare the Zr-stabilized, CaO-based composite pellets aiming to improve the practicability. The incorporation of the Zr-based stabilizer can effectively resist the sintering of CaO-based composite powders during a high-temperature precalcination process. It is mainly attributed to the large amounts of generated, nanosized CaZrO3 grains possessing desirable antisintering ability evenly distributed within the composites. Particularly, the Zr-stabilized, CaO-based composite pellets containing 30 wt % of CaZrO3 possess a relatively high compression strength of 2.28 ± 0.87 MPa and a desirable thermal storage density of 1.15 GJ/t after 20 cycles. Additionally, the graphite-casted, Zr-stabilized, CaO-based composite pellets have potential to be applied in a large-scale thermochemical energy storage system because the graphite-casting method is easy to be scaled-up.

CAS / MDL: 5949-29-1
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2023 · IF 7.2

Enhanced room-temperature hydrogen storage by CuNi nanoparticles decorated in metal-organic framework UiO-66(Zr)

Pengxiao Liu,Yan Jia,Yao Ning,Xiaocheng Zhang,Shuhui Tian,Fan Yang,Weiyu Song,Ying Zhang

This study demonstrates the significant effect of incorporating inexpensive transition metal nanoparticles into metal-organic frameworks (MOFs) to improve their room-temperature hydrogen storage properties. Low-cost nanoparticles (Cu, Ni, and CuNi) were incorporated into UiO-66(Zr) via the double-solvent approach (DSA) plus chemical reduction processes. All composites exhibited higher hydrogen storage capacity compared to pure UiO-66 at both room temperature and 60 bar. Notably, the hydrogen spillover efficiency of CuNi nanoparticles loaded in UiO-66 was comparable to that of MOF adsorbents embedded with noble metals such as Pd and Pt. The hydrogen storage capacity of CuNi@UiO-66 was significantly increased from 0.20 wt% to 0.74 wt%. DFT calculations showed that the CuNi alloys facilitated the adsorption and dissociation of hydrogen molecules in comparison to the single metal nanoparticles , thus favoring the hydrogen spillover effect and improving the hydrogen storage performance. This work demonstrates the potential of designing MOF loaded with inexpensive metal nanoparticles for optimized room-temperature hydrogen storage.

CAS / MDL: 10026-11-6 100-21-0
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RESEARCH ON CHEMICAL INTERMEDIATES · 2022 ·Vol. 48 ·期 3 ·1181-1198 · IF 3.134

Selective production of γ-Valerolactone from ethyl levulinate by catalytic transfer hydrogenation over Zr-based catalyst

Zhang Zhongze,Liu Zonghui,Gu Zhiyuan,Wen Zhe,Xue Bing

The catalytic transfer hydrogenation (CTH) reaction of ethyl levulinate (EL) with alcohol to γ-valerolactone (GVL) has been investigated over a series of Zr-based catalysts, including ZrO 2 , ZrP, Zrβ, ZrP/Hβ and ZrO 2 /HZSM-5. It is found that the simplest ZrO 2 was the most efficient for GVL production, giving an EL conversion as high as 97% and GVL selectivity of 91% after 7 h at 170 °C using 2-propanol as the hydrogen donor and solvent. The effects of reaction temperature, time and solvent on catalytic performance were investigated. Moreover, the kinetic behavior of CTH reaction of EL was also studied over ZrO 2 catalyst. The as-prepared ZrO 2 gives an Ea value of 32.9 kJ/mol, which is much lower than other catalysts in the literatures. Furthermore, those catalysts have been, respectively, characterized by XRD, IR, BET and NH 3 -TPD techniques to reveal the physical properties and structures of these materials. Correlating the catalyst performance with its physical and chemical properties uncovers that the higher pore diameter, lower total acidity and higher Lewis acid sites of catalyst surface would be the key to the catalyst performance. Graphical abstract

CAS / MDL: 5398-29-8 108-29-2
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CERAMICS INTERNATIONAL · 2023 · IF 5.2

Multicomponent Si–Zr-based lightweight nanofiber films with a hollow structure exhibiting excellent thermal insulation properties

Fengyue Shi,Siyu Huang,Jianwen Wang,Jun Li,Yang Yang,Guangdong Zhao,Dongyu Zhao

Hollow-structured ceramic fibers with multiple components are ideal as lightweight insulation materials. In this study, tetraethyl orthosilicate , boric acid, and zirconia octahydrate were used as raw materials for fabricating SiZrBOC hollow ceramic fibers through coaxial electrospinning. These ceramic fibers exhibit a low thermal conductivity and an excellent temperature resistance. The electrospun SiZrBOC hollow ceramic fibers display a clean and compact morphology with internal folds. Fourier-transform infrared spectroscopy and thermogravimetric analysis (TGA) were used to assess the transformation process and thermal behavior of the hollow ceramic fibers. The results suggest that the incorporation of B promotes the formation of Si–O–B bonds within the system, leading to a maximum yield of 75.49 wt% for the production of the SiZrBOC hollow ceramic fibers. The phase composition and microstructure of the SiZrBOC hollow ceramic fibers were analyzed via X-ray diffraction (XRD) measurements. The pyrolysis at 1000 °C resulted in the appearance of diffraction peaks corresponding to SiO 2 and SiC in the XRD patterns of the SiZrBOC hollow ceramic fibers. Laser thermal conductivity measurements reveal that the SiZrBOC hollow ceramic fibers exhibit a thermal conductivity of only 0.06 W‧m −1 K −1  at 25 °C and 0.124 W‧m −1 K −1  at 500 °C, indicating a significantly superior thermal insulation performance compared with conventional solid SiZrBOC ceramic fibers.

CAS / MDL: 13520-92-8 9002-89-5
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FOOD CHEMISTRY · 2023 · IF 8.8

Highly sensitive ratiometric fluorescence detection of tetracycline residues in food samples based on Eu/Zr-MOF

Lei Zhang,Yuxin He,Yue Wu,Jieyuan Zhang,Siqiao Li,Zhengwei Zhang

The development of a simple, rapid, and sensitive method for monitoring antibiotic residues is crucial for maintaining food safety. Herein, a ratiometric fluorescence probe based on bimetallic organic framework (Eu/Zr-MOF) was developed for the detection of tetracycline (TC). The Eu/Zr-MOF was synthesized by the coordination of Eu 3+ and Zr 4+ with 2-APDC, which exhibited a grape-like cluster morphology and dual-emitting fluorescence at 430 nm/616 nm. Based on the internal filtering effect (IFE), significant fluorescence quenching was observed at 430 nm, whereas only slight changes occurred at 616 nm. The ratiometric sensing offered two broad linear ranges (0.5–8 μg/mL; 10–60 μg/mL) and a low detection limit (26.7 ng/mL). The proposed method was applied to the determination of TC in pork and water samples. Fluorescent sensors have the advantages of simple design, fast response, and high sensitivity, thus providing a promising means for evaluating the safety of food contaminated with TC.

CAS / MDL: 10312-55-7 10026-11-6
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CERAMICS INTERNATIONAL · 2023 · IF 5.2

High-temperature oxidation behaviors of dense TMC (TM= Ta, Nb, Ti and Zr) ceramics in air

Zhangyi Huang,Zhengwei Zhu,Mingyu Su,Yang Shi,Mao Deng,Ruichong Chen,Zhijun Wang,Zhi Zhou,Jianqi Qi,Haomin Wang

This study investigated the high-temperature oxidation behaviors of TMC ceramics. The results indicate that the high-temperature oxidation curves of the four TMC ceramics follow a parabolic law, suggesting a diffusion-controlled process. The activation energies for the oxidation of TaC, NbC, TiC, and ZrC ceramics are 105.4, 124.3, 169.3, and 78.7 kJ/mol, respectively, with oxidation rate constants at 1000 °C of 16.84, 40.45, 0.18, and 14.43 mg 2 /cm 4 ·h for each ceramic, respectively. The temperatures at which the ceramics disintegrate into fragments in high-temperature air are 800, 800, >1000, and 600 °C, respectively. The anti-oxidation performance of the four TMC ceramics ranks as follows: TiC > TaC > NbC > ZrC. In comparison to the reported high-entropy carbide ceramics, the TiC ceramic in this study demonstrates superior anti-oxidation performance due to dense TiO 2 layer formation, characterized by significantly low oxidation rates and excellent structural stability.

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JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY · 2020 ·Vol. 97 ·期 1 ·1-4 · IF 2.008

A flexible self-detoxifying Zr(OH)4-carbon fiber composite for decontamination of chemical warfare agent

Chen Wenming,Wang Haibo,Guo Xuan,Zhong Jinyi

Self-detoxifying materials for capturing and destructing chemical warfare agents (CWAs) have attracted intense attention in efficient personal protection and safe handling of contaminated materials. In this study, we reported an approach for synthesis of flexible Zr(OH) 4 -carbon fiber composite by sol–gel method. Activated carbon fibers serving as substrate carrier and adsorption conveyor could effectively make Zr(OH) 4 evenly distributed on the surface, which has excellent sorption properties and wide-ranging reactivity toward CWAs. The results demonstrated that the Zr(OH) 4 -carbon fiber composite could quickly remove (within 10 s) and 6-h degradation efficiency to 10-mg/mL sulfur mustard (HD) and O-ethyl S-(2-diisopropylamino)-ethyl methylphosphonothioate (VX) could reach 92.2 and 99.99%. In addition, it was found that Zr(OH) 4 -carbon fiber composite remained intact after adsorption, which could recollect resources and avoid Zr(OH) 4 leakage into waters. Therefore, the designed Zr(OH) 4 -carbon fiber composite will be a good potential application in precision equipment or skin decontamination equipment.

CAS / MDL: 57-13-6
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Inorganic Chemistry Frontiers · 2020 ·Vol. 7 ·期 12 ·2343-2351 · IF 5.958

SrTaO2N co-doped with La/Zr as promising photocatalysts for water reduction under visible light illumination

Ran Wang,Guoan Lin,Xiaoxiang Xu

La/Zr co-doped SrTaO2N has been investigated as visible-light-active photocatalysts for water reduction. Unlike previous aliovalent doping that leads to a decrease in light absorption, La/Zr co-doping largely preserves the visible light absorption of SrTaO2N. More importantly, the La/Zr co-doping not only helps to improve surface hydrophilicity and reduce particle sizes but also effectively inhibits defect formation (e.g. Ta4+) in SrTaO2N. These modifications are responsible for significant enhancements in photocatalytic H2 production. AQE as high as 0.84% was achieved at 420 ± 20 nm for Sr0.4La0.6Ta0.4Zr0.6O2N (x = 0.6), which also showed good durability and stability. Further analysis suggests that La/Zr co-doping negatively shifts the conduction band edge positions of SrTaO2N and contributes to better charge separation conditions.

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