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Journal of Materials Chemistry A · 2024 ·Vol. 12 ·期 10 ·5875-5884 · IF 10.7

Transport properties of the Ba(Zr,Ce,Y,Yb)O3−δ proton conductor: the real role of co-substitution of Y and Yb

Hui Guo,Yifeng Li,Lulu Jiang,Yenan Sha,Shihang Guo,Donglin Han

Proton conducting oxides are attracting increasing attention due to their promising application as electrolytes in solid-state electrochemical devices for energy conversion and chemical production, including protonic ceramic fuel cells, electrolyzers and membrane reactors. BaZrO3 and Ba(Zr,Ce)O3 substituted by acceptor dopants are currently the most promising proton conductors. In principle, replacing Zr or Ce with one kind of trivalent element (e.g., Y or Yb) can generate oxygen vacancies, which are necessary for the hydration reaction to introduce charge carriers of protons. However, it is commonly recognized that substituting Zr or Ce with Y and Yb simultaneously leads to high performance of the devices, but the reason is not clear. In this work, we studied the transport properties of four different compositional classes: BaZr0.8−xCexY0.2O3−δ (BZCY20), BaZr0.8Y0.2−xYbxO3−δ (BZYYb), BaZr0.1Ce0.7Y0.2−xYbxO3−δ (BZCYYb) and BaCe0.8Y0.2−xYbxO3−δ (BCYYb), at 600, 650 and 700 °C. For BZCY20, the ionic conductivity decreases on replacing Zr in BZY20 with x = 0.1 of Ce, increases with increasing Ce content within x = 0.1–0.5, and decreases on further increasing Ce content from x = 0.5 to 0.8. The ionic transport number increases with increasing Ce content. The ionic conductivity, partial conductivity of oxide ions and hole conductivity of BZCYYb and BCYYb increase with increasing Yb content. Since the increment of hole conductivity is larger, the ionic transport number decreases. For BZYYb, the ionic conductivity decreases and the hole conductivity increases with increasing Yb content, leading to decreasing ionic transport number. Both the high ionic conductivity and transport number are vital factors governing the performance of protonic ceramic cells (PCCs). Therefore, the improved performance of PCCs by adding both Y and Yb into the electrolyte cannot be explained from the viewpoint of electrical properties of the electrolytes. Thereby, we summarized our recent series of studies on the chemical compatibility between the electrolyte and NiO negatrode substrate, and suggested that the loss of dopant was suppressed by partly replacing Y with Yb. The high ionic conduction of the electrolyte can be maintained after co-sintering at high temperature to fabricate PCCs. This might be the real reason for the high performance of the devices using Y and Yb co-substituted electrolytes, prepared by the co-sintering method.

CAS / MDL: 12047-27-7 1314-37-0
研究领域: 材料科学 · 能源科学
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FOOD CHEMISTRY · 2025 · IF 9.8

A novel fluorescent sensor for highly sensitive detection of ascorbic acid in food based on inhibiting phosphatase-like activity of Zr-based MOF

Zhen Wu,Jinlong Wang,Xing Cheng,Yue Tang,Lian Xia,Xiaojuan Niu,Yuangen Wu

Nanozyme-based sensors for detecting ascorbic acid (AA) generally depend on the reducibility of the analyte. However, these sensors are susceptible to interference from reducing substances in food. Herein, a novel fluorescent sensor for AA detection was developed based on inhibiting the phosphatase-like activity of a Zr-based metal-organic framework (Zr-CAU-28). Hydroxyl-rich AA molecules adsorb on the surface of Zr-CAU-28 through hydrogen bonding with [Zr 6 O 4 (OH) 4 ] cluster, leading to a decrease in the relative content of terminal hydroxyl groups within the catalytic sites. The constructed sensor exhibits a wide detection range (0.08–11 μg·mL −1 ) and low detection limit of 0.025 μg·mL −1 . Potential interfering studies demonstrated the good selectivity of the sensor. Moreover, the fluorescent sensor can effectively detect AA in juices and vitamin C tablets, with the recovery rate ranging from 96.25 % to 108.50 %. This work represents the first application of phosphatase mimics for AA detection, offering a new strategy for food analysis.

研究领域: 食品科学 · 分析化学 · 纳米技术
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INORGANIC CHEMISTRY · 2024 · IF 4.3

Engineering the Activity and Stability of the Zn-MOF Catalyst via the Interaction of Doped Zr with Zn

Xue Ye,Chenxi Bai,Peipei Zhang,Fuyuan Han,Junyu Xia,Xinhua Gao,Wenlin Xu,Lisheng Guo,Jie Li

Metallic atoms within metal–organic framework (MOF) materials exhibit a distinctive and adaptable coordination structure. The three-dimensional (3D) pore configuration of MOFs enables the complete exposure of metal active sites, rendering them prevalent in various catalytic reactions. In this study, zinc (Zn) atoms within Zn-based MOF materials, characterized by an abundance of valence electrons, are utilized for the transesterification of dimethyl carbonate (DMC). Additionally, the introduction of zirconium (Zr) effectively addresses the susceptibility of the MOFs’ crystal structure to dissolution in organic solvents. The formulated catalyst, Zn-10%Zr-MOF(300), demonstrates remarkable catalytic performance with 91.5% DMC selectivity, 61.9% propylene carbonate (PC) conversion, and 56.6% DMC yield. Impressively, the catalyst maintains its high performance over five cycles. Results indicate that Zr interacts with Zn, forming new coordination bonds and enhancing the catalyst crystal structure stability. Moreover, electron transfer intensifies the alkalinity of the active Zn atoms, enhancing the overall catalyst performance. This research informs the development of transesterification heterogeneous catalysts and broadens the application scope of MOF catalysts.

CAS / MDL: 108-32-7
研究领域: 材料科学 · 催化 · 化学工程
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MICROCHEMICAL JOURNAL · 2024 · IF 4.9

Potential-resolved real-time ultrasensitive sensing of bisphenol compounds based on ionic liquid coupled Zr-MOF@GO nanosensor

Zarfashan Shahid,Bairong Fu,Saima Rehman,Zia Ahmad,Jiping Chen,Xianbo Lu

Bisphenol compounds, including BPA and BPS, are significant pollutants found in the environment, food, and daily necessities. They pose various adverse effects, including estrogenic, immunotoxic, metabolic, and reproductive toxicity, which severely threaten human health and ecological safety. Achieving simultaneous rapid detection of BPA and BPS is still very challenging due to their similar structures and co-existence in actual samples at ultratrace level. This study addresses the problem of developing an effective method for the rapid detection of BPA and BPS simultaneously. A new electrochemical nanosensor based on ionic liquid (IL) coupled Zr-MOF@GO was developed for ultrasensitive real-time detection of BPA and BPS. The Zr-MOF@GO/IL nanocomposite features a custom-built structure with an ordered framework, abundant pores, and highly coupled interfaces. The experimental findings demonstrate that the introduction of IL enhances the conductivity and dispersibility of the nanocomposite, improves the absorption capability for target bisphenols, and significantly improves the detection limit and linear range of the Zr-MOF@GO based electrochemical sensor. The sensor demonstrated wide linear ranges with detection limits of 5.5 nmol/L for BPA and 7.1 nmol/L for BPS (S/N = 3), respectively. Comparative studies revealed that the detection limits of the Zr-MOF@GO/IL-based sensor improved by an order of magnitude compared to the Zr-MOF@GO-based sensor. Additionally, the sensor exhibited superior analytical performance regarding reproducibility, stability, and selectivity. This study investigated the capability and synergy of IL coupled high-valent stable transition metal Zr IV -based MOFs in electrochemical sensing for the first time. This development sets a new benchmark in non-enzymatic electrochemical sensing, establishing the Zr-MOF@GO/IL-based sensor as a promising platform for the individual or simultaneous rapid detection of bisphenols in actual samples.

研究领域: 环境科学 · 分析化学 · 材料科学 · 纳米技术
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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.

研究领域: 分析化学 · 环境科学 · 材料科学
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FUEL · 2024 · IF 6.7

Improving the anti-coking ability in the Ni-M(M = Ce, Zr, Co)@SiO2 yolk-shell catalysts for dry reforming of methane

Xiao Yang,Zhuwei Yang,Linsen Li,Zhao Jiang,Guangxu Cheng

Dry methane reforming (DRM) represents a highly promising approach to greenhouse gas conversion (CO 2 and CH 4 ) to valuable byproducts. However, severe carbon deposition and catalyst deactivation inhibit large-scale applications. The work designed new catalysts with a yolk-shell structure using the water-in-oil microemulsion method. The catalysts were composed of a yolk-shell structure, with Ni-M as the active point and silica as the shell. The catalytic performance evaluation indicates that the Ni-M @SiO 2 catalysts show higher CH 4 and CO 2 conversion compared with the Ni@SiO 2 and conventional catalysts at 750 ℃, suggesting the yolk-shell structure and added M species enhance the DRM activity. The XRD, HRTEM, XPS, BET, H 2 -TPR, and CO 2 -TPD analysis confirmed the existence of yolk-shell configuration and evident electronic effect among Ni, M species, and SiO 2 . The long term measurements indicate that the added M species also bring higher carbon deposition tolerance for DRM, where Ni-Ce@SiO 2 and Ni-Zr@SiO 2 exhibit good structural and catalytic stability for DRM over 100 h. Through XRD, TEM, and TGA characterizations of the exhausted catalysts, it is determined that the coke deposition resistance of the catalyst is improved as a result of increased oxygen mobility and enhanced Ni dispersion on the catalytic surface, both of which are enhanced by the added Ce species. The structural analysis of the spent catalysts indicates that the tolerance of carbon deposition is improved by the yolk-shell samples. This study can offer valuable insights for the development of Ni-based catalysts with exceptional carbon deposition capability for DRM.

研究领域: 催化 · 化学工程 · 材料科学
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LWT-FOOD SCIENCE AND TECHNOLOGY · 2025 · IF 6.6

Synergizing Polydopamine-Modified Electrodes with DNA-Anchored UIO-66(Zr) MOF for Ultrasensitive Detection of Horsemeat Adulteration in Camel Meat

Jianmei Li,Yuting Yin,Haiyu Li,Zongyao Zhao,Mengqin Xiang,Yong Tang,Qi Sun

The escalating economic and ethical concerns associated with camel meat adulteration using cheaper horsemeat necessitate the development of rapid, on-site detection technologies that overcome the limitations of conventional laboratory-based methods. In this study, a portable electrochemical DNA biosensor was fabricated by integrating a polydopamine (PDA)-modified screen-printed carbon electrode (SPCE) with a nucleic acid-functionalized UIO-66(Zr) metal-organic framework (MOF). The PDA coating facilitated stable, covalent immobilization of DNA capture probes through Schiff base reactions, while the UIO-66(Zr) MOF functioned as a high-capacity signal amplifier owing to its large surface area and intrinsic redox activity. This synergistic architecture enabled ultrasensitive detection, achieving a limit of 3.57 pmol/L for horsemeat DNA and 0.5 g/kg adulteration in camel meat blends—significantly surpassing the performance of existing detection methods. The biosensor exhibited excellent specificity by distinguishing single-base mismatches, along with high reproducibility (RSD = 4.12%), operational stability over 15 days, and accurate recovery rates ranging from 91.7% to 112.4% in spiked samples. Its disposable electrode format, cost-effectiveness, and compatibility with portable potentiostats underscore its strong potential for on-site meat authentication. Overall, this work provides a practical and scalable solution to combat meat fraud in resource-limited settings and establishes a versatile MOF-electrode nanoassembly platform for advanced food safety monitoring.

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NEW JOURNAL OF CHEMISTRY · 2025 · IF 2.5

Efficient electrochemical sensing of methyl parathion residues using a PEDOT:PSS/Zr(OH)4/ZIF-90 composite

Huanjing Chen,Wanqiao Bai,Hongmei Chai,Loujun Gao

To achieve the rapid and sensitive detection of trace methyl parathion (MP) in river water and edible agricultural products, the catalytic composite material zirconium hydroxide (Zr(OH)4)/zeolite imidazolate framework-90 (ZIF-90) was prepared by a one-step synthesis method. The composite was further incorporated with a conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hydrogel to prepare a modified electrode. Then, an electrochemical sensing method based on the PEDOT:PSS/Zr(OH)4/ZIF-90 composite was successfully established for the analysis and detection of MP. The component ratio of the composite material, modification amount and pH value of the detection substrate were optimized. The electrochemical properties of the composite modified electrode were evaluated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques, and the results confirmed that it had good electrochemical properties. The electrochemical response of the established sensing method to MP showed a good linear relationship in the concentration range of 1–250 µmol L−1, and its detection limit and sensitivity reached 0.74 µmol L−1 and 0.09 µA µmol−1 L−1, respectively. The interference of common coexisting ions on the detection performance of the PEDOT:PSS/Zr(OH)4/ZIF-90 modified electrode was further investigated, and it was applied for the quantitative analysis of MP in actual river water and apple samples. The electrochemical sensing method developed in this work provides a new way for the efficient detection of MP residues in environmental water and agricultural products.

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Journal of Natural Gas Chemistry · 2012 · IF 1.348

Effects of Zr/Ti molar ratio in SO2−4/ZrO2-TiO2 calcined at different temperatures on its surface properties and glucose reactivity in near-critical methanol

Lincai Peng,Junping Zhuang,Lu Lin

Effects of Zr/Ti molar ratio in SO 2− 4 /ZrO 2 -TiO 2 solid acid catalyst calcined at different temperatures on its surface properties and catalytic activity were thoroughly investigated in this paper. The physicochemical characteristics of prepared samples were determined by N2 adsorptiondesorption, XRD, NH3-TPD and XPS techniques, respectively. It was found that the crystallization temperature of the samples increased after the combination of ZrO 2 and TiO 2 ; and phase transformations from the anatase to the rutile of TiO 2 species and the tetragonal to the monoclinic of ZrO 2 species were effectively suppressed at higher temperature. The sample with a Zr/Ti molar ratio of 3/1 calcined at 450 °C showed the highest surface area and the most acid sites among all the tested samples. The acid site densities of samples were relatively closed to each other if they were calcined at the same temperature, however, decreased with the calcination temperature. The result indicates that the sulfur content in samples is a crucial factor to control the acid site density. Calcining the sample at 650 °C and higher temperatures resulted in a significant desorption of sulfate ion on the samples. The synthesized samples were evaluated as a potential catalyst for glucose conversion under the near-critical methanol conditions (200 °C/4 MPa). The results suggested that the relatively weaker acid sites of the catalyst were more favorable for the accumulation of methyl glucosides, while the moderate acid sites were responsible for the formation of methyl levulinate. The catalytic activity for methyl levulinate production almost increases linearly with the catalyst acid site density. The catalyst deactivation is due to the loss of sulfate ion and the two catalysts with Zr/Ti molar ratios of 3/1 and 1/3 could effectively alleviate the deactivation caused by sulfate solution in the reaction medium and can be reused after calcination with the reuse rate of over 90% in terms of the methyl levulinate selectivity.

CAS / MDL: 13520-92-8
研究领域: 催化化学 · 材料科学
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JOURNAL OF MOLECULAR LIQUIDS · 2025 · IF 5.2

Preparation of Zr-doped MXene@MIL-125(Ti) composite to mediate the ultrasonic removal of organic dyes and microplastics

Fangfang Yang,Xueyan Wang,Jialu Li,Zhanfeng Li,Zonghua Wang

In recent years, the ultrasonic removal of organic pollutants has attracted a great deal of attention. In this study, a novel MOF-based sonocatalyst with bimetallic center was formed by doping Zr atoms into the MX@MIL-125(Ti), aiming to improve the ultrasonic removal performance of organic pollutants. The successfully prepared MX@MIL-125(Ti/Zr) showed a porous structure with abundant grooves and channels (average pore size of 21.8 nm, and specific surface area of 36.910 m 2 /g), and significantly had a higher quantum yield (13.24 %) than MIL-125(Ti) and MX@MIL-125(Ti), thereby producing more OH and O 2 − free radicals under ultrasonic irradiation. The experimental results showed that the MX@MIL-125(Ti/Zr) had good sonocatalytic activity and could effectively deal with small-molecule dyes and macro-molecule microplastics under ultrasonic conditions, where the removal efficiency achieved approximately 95 % for Rhodamine B (within 12 min) and approximately 90 % for micro-polyethylene (within 4 h in the presence of persulfate). In addition, a possible degradation-dominant mechanism was proposed to explain the MX@MIL-125(Ti/Zr)-mediated sonocatalytic removal, where the existence of Zr atoms could help sono-excited electrons generate and transfer onto the conductive MXene, thereby facilitating more charge carriers to create reactive free radicals. Therefore, the study would provide a green and feasible approach for the industrial treatment of organic pollutants in water bodies.

CAS / MDL: 5593-70-4 9022-96-2
研究领域: 环境科学 · 材料科学 · 化学工程 · 纳米技术
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Food Analytical Methods · 2025 · IF 3

An Ultra-Sensitive Electrochemical Sensing Platform Based on a Novel Ternary Heterostructured Ag-TiO2@Zr-TCBPE Nanocomposite for Ciprofloxacin Detection in Food

Li Congwei,Wang Beibei,Kang Kai,Wang Lanyue,Zhao Zhenzhen,Wang Yuping,Ji Xueping

To address ciprofloxacin (CIP) contamination in animal-derived foods, an ultrasensitive electrochemical sensing platform based on a novel ternary heterostructure (Ag-TiO 2 @Zr-TCBPE) was developed through interfacial engineering. The heterointerface was constructed by anchoring a metal–metal oxide electrocatalyst (Ag-TiO 2 ) onto a conductive metal–organic framework (Zr-TCBPE) with a 3D porous hexagonal prismatic structure and high conductivity. This work demonstrates for the first time that the large-scale conjugated architecture of Zr-TCBPE nanotubes enhances CIP enrichment, while the Ag-TiO 2 /Zr-TCBPE heterointerface optimizes electron transport pathways and synergistically promotes CIP oxidation via interfacial electric field-driven effects. Under acidic conditions (pH 5.0), the Ag-TiO 2 @Zr-TCBPE/GCE sensor exhibited optimal performance: a linear range spanning five orders of magnitude (2.5 nmol·L −1 to 150 μmol·L −1 ), a limit of detection (LOD) of 1.6 nmol·L −1 , surpassing most reported CIP sensors. The sensor also showed high anti-interference capability (97.1–107% signal retention), long-term stability (> 96.4% signal retention after 15 days), and satisfactory recovery rates (91.6–103%) in complex matrices (milk, eggs, and river water). This study provides fundamental insights into TCBPE-MOF heterointerface engineering and establishes a robust analytical platform for detecting trace antimicrobials in food and environmental samples.

研究领域: 分析化学 · 材料科学 · 食品安全 · 环境监测 · 电化学
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2025 · IF 6.2

Defect-Engineered Zr-TCPE Coupled with a Target-Oligonucleotide-Driven DNAzyme Motor for Ultrasensitive Patulin Detection in Apple Juice

Xiaohai Yan,Jia Li,Fudai Cai,Xuejun Zeng,Sijia Li,Kai Wang,Qinglin Sheng,Kewei Feng,Yahong Yuan,Tianli Yue

Patulin (PAT) is a mycotoxin with immunotoxicity, genotoxicity, and neurotoxicity, so effective methods are needed for its detection. Fluorescence aptasensors provide a homogeneous detection method, but their sensitivity needs to be further improved. Herein, we developed a fluorescence aptasensor based on a target-oligonucleotide-driven DNAzyme motor and defective Zr-TCPE for PAT detection. The defective Zr-TCPE achieved an enhanced fluorescence intensity (increased by ∼1.9-fold) via defect engineering. The target-oligonucleotide-driven DNAzyme motor achieved effective PAT transduction, with a signal background ratio 4.4-fold that of the competitive transduction strategy. By combining defective Zr-TCPE with a target-oligonucleotide-driven DNAzyme motor, we achieved ultrasensitive detection of PAT with a detection limit as low as 9.38 fg/mL. In addition, the proposed fluorescence aptasensor could be used for the detection of PAT in apple juice, with recoveries ranging from 95.93% to 105.71%. This fluorescence aptasensor provides reasonable guidance for trace detection of hazardous substances in food and the environment.

研究领域: 分析化学 · 生物传感器 · 食品安全 · 纳米技术 · 毒理学
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