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CHEMICAL ENGINEERING JOURNAL · 2019 · IF 8.355

Highly selective recovery of Au(III) from wastewater by thioctic acid modified Zr-MOF: Experiment and DFT calculation

Chen Wang,Guo Lin,Jiling Zhao,Shixing Wang,Libo Zhang,Yunhao Xi,Xiteng Li,Ying Ying

A novel adsorbent (UiO-66-TA) was presented by modifying metal-organic framework composites with thioctic acid. UiO-66-TA were characterized by fourier transform infrared (FT-IR), field emission scanning electron microscopy (FESEM), thermogravimetric (TG), Brunner-Emment-Teller (BET) measurement and X-ray photoelectron spectroscopy (XPS), which indicating that it had excellent morphology and specific surface area. The adsorption performances of UiO-66-TA for Au(III) were studied. The results showed that UiO-66-TA had a strong adsorption capacity under acidic conditions and the optimal pH was 2.0. Isotherm and kinetic adsorption were also conducted and found that the experimental values correspond to Langmuir model and pseudo-second-order isotherm model, indicating that the mechanism is mainly chemical adsorption on a uniform surface. Wastewater experiment showed that UiO-66-TA can be used for highly selective recovery Au(III) in actual life. The regeneration and thermodynamic experiments indicated that UiO-66-TA can be reused and were a spontaneous endothermic process. XPS analysis and the zeta potential proved that the main adsorption mechanisms were ion exchange and chelation. DFT calculation found that there are two ways to combine Au with S on UiO-66-TA and their distances are 2.38 Å and 2.39 Å, indicating that the gold and sulfur play a major role in chelation. In summary, UiO-66-TA was a hopeful adsorbent and could be used to collect gold ions from wastewater in a sustainability perspective.

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JOURNAL OF CHROMATOGRAPHY A · 2018 · IF 3.716

Zr-based metal-organic framework-modified cotton for solid phase micro-extraction of non-steroidal anti-inflammatory drugs

Wenqing Li,Rong Wang,Zilin Chen

A novel metal-organic framework UiO-66-modified cotton was prepared and applied to solid phase microextraction of non-steroidal anti-inflammatory drugs, namely ketoprofen, naproxen and flurbiprofen. UiO-66 was immobilized onto the surface of cotton by a polydopamine functionalized method. The resultant cotton@PDA@UiO-66 was characterized by Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscopy. The solid phase microextraction conditions were optimized, including sampling flow rate, formic acid content of the eluent, pH value of sample solution, NaCl content and sample volume. By combining with HPLC, this method showed high extraction efficiency (the enrichment factors of ketoprofen, naproxen and flurbiprofen were 44, 49 and 45, respectively), wide linear range (0.1–500 ng/mL), good linearity with R ≥ 0.9996 and satisfactory sensitivity (LODs ≤ 0.03 ng/mL, LOQs ≤ 0.1 ng/mL), as well as good reproducibility (RSD ≤ 4.51%). This method was also successfully applied to extraction of NSAIDs in swine muscle sample. Good recoveries were obtained, ranging from 88.54% to 95.7% with relative standard deviations less than 3.77%.

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Journal of Materials Chemistry B · 2015 ·Vol. 3 ·期 20 ·4242-4248 · IF 4.726

Zr-based metal–organic frameworks for specific and size-selective enrichment of phosphopeptides with simultaneous exclusion of proteins

Xiangyang Zhu,Jinlou Gu,Jian Yang,Zhe Wang,Yongsheng Li,Liming Zhao,Wenru Zhao,Jianlin Shi

The accurate characterization of low abundance phosphopeptides based on mass spectrometry (MS) techniques remains a challenge due to signal suppression by the large excess of interfering proteins and non-phosphopeptides. This demands better methods to effectively enrich phosphopeptides prior to MS analysis. In the current work, facilely synthesized Zr-based metal–organic frameworks (MOFs) of UiO-66 and UiO-67 have been successfully exploited as novel affinity materials for the enrichment and analysis of phosphopeptides. Thanks to their abundantly existent and naturally exposed Zr–O clusters, intrinsically large surface areas and highly ordered open cavities, UiO-66 and UiO-67 exhibited sensitive and specific enrichment of phosphopeptides with an interesting molecular sieving effect. An optimized protocol for loading, washing and elution was developed. Under these most optimized conditions, specific accumulation was demonstrated by the selective enrichment of phosphopeptides in the presence of abundant non-phosphorylated species. Meanwhile, high-abundance interfering proteins could be effectively excluded during the enrichment process. Additionally, the MOFs have also been successfully used to enrich phosphopeptides from human serum. These merits combined with their high chemical and thermal stabilities, make UiO-66 and UiO-67 highly promising for applications in phosphopeptidome research.

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TALANTA · 2015 · IF 3.545

Preparation of magnetic graphene @polydopamine @Zr-MOF material for the extraction and analysis of bisphenols in water samples

Xianying Wang,Chunhui Deng

In this work, a simple method for the extraction and analysis of bisphenols in environmental samples was presented. And the prepared zirconium-based magnetic MOFs (magG@PDA@Zr-MOF) were used as the sorbents for the magnetic solid-phase extraction. With the simple solvothermal reaction and sol–gel method, the prepared material showed great characteristics of large surface area, homogeneous pore size, good magnetic responsivity and super-hydrophilicity. The large surface area provided abundant sites to extract target compounds; the magnetic property could simplify the whole extraction procedure; and the hydrophilicity improved the dispersibility of the material in matrix. Here, various extraction parameters were optimized, including amounts of sorbents, adsorption time, species of elution solvents and desorption time. The whole extraction procedure could be accomplished in 30   min. And under the optimized conditions, method validations were also studied, such as linearity, the limit of detection and recovery. Finally, the prepared material was used in real water samples. The results showed this material had good potential as the sorbent for the extraction of targets in environmental water samples.

CAS / MDL: 10026-11-6
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POLYMERS FOR ADVANCED TECHNOLOGIES · 2024 ·Vol. 35 ·期 6 ·e6474 · IF 3.1

Effects of dopamine-modified ZnO and Ce-Zr oxides on UV resistance and thermal stability of epoxy composites

Yi Li,Ning Zhang,Yanchao Zhu,Min Cheng,Shuang Gao

In this work, surface-modified Ce-Zr oxides and ZnO nanoparticles were conveniently prepared by dopamine (Dpa) treatment and then composited with epoxy (EP) by hot pressing. Thermogravimetric analysis (TGA) and UV-shielding properties of the EP composites with surface modification with Dpa-CZ and Dpa-ZnO were measured. The TGA results showed that the modified treated fillers had no loss of heat resistance of the matrix and had an enhancement effect on the initial and maximum decomposition temperatures. In addition, the UV-shielding properties of EP composites after Dpa-CZ and Dpa-ZnO modifications both showed a significant enhancement effect compared to pure EP. The T(UVA) of the 0.5 wt% Dpa-ZnO modified composite decreased to less than 0.017%, and the T(UVB) decreased to less than 0.0059%. The T(UVA) of the 0.5 wt% Dpa-CZ modified composite decreased to less than 15.98%, and the T(UVB) decreased to below 1.14%. The composites have both excellent thermal stability and UV-shielding efficiency.

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CERAMICS INTERNATIONAL · 2024 · IF 5.1

Enhanced thermal stability of pressureless liquid-phase sintered SiC ceramics via (Hf, Zr, Ta, Nb, Ti)B2 addition

Yang Liu,Jia-Ji Liang,Wei-Ming Guo,Chao Chang,Xiao-Ming Duan,De-Chang Jia,Hua-Tay Lin

High-temperature thermal stability plays a crucial role in the structural application of pressureless liquid-phase sintered SiC (PLS-SiC) ceramics. In this paper, a PLS-SiC ceramic processed with CeO 2 –Al 2 O 3 as sintering additives with excellent high-temperature thermal stability was achieved by incorporating (Hf, Zr, Ta, Nb, Ti)B 2 (HEB) particles. Results showed that PLS-SiC ceramics with HEB-free underwent a structural change from dense to porous microstructure after annealing at 1800 °C/1 h. Conversely, PLS-SiC ceramics with the addition of 10 vol% HEB exhibited excellent thermal stability, as evidenced by the retention of their dense microstructure after exposure to annealing at 1800 °C/1 h. The possible primary reasons for this significantly different response to the thermal stability could be probably attributed to fact that HEB reacted with CeAlO 3 and SiC to form solid-phase products, subsequently inhibiting the formation of gas-phase products after decomposition of CeAlO 3 alone in a high-temperature vacuum environment. In addition, the formation of a compact protective outer layer containing Hf–Ta containing diboride in PLS-SiC ceramics during the annealing process could effectively hinder the volatilization of volatile substances at a high temperature.

CAS / MDL: 1306-38-3
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PROGRESS IN ORGANIC COATINGS · 2024 · IF 6.5

Improved ablation resistance of silicone/phenolic hybrid resin coatings with Zr-Si-O glass as anti-ablation layer

Quan Yuan,Liwei Yan,Jinfeng Tian,Yang Chen,Huawei Zou

With the development of the new generation space vehicles, traditional phenolic resin (PR)-based coatings are no longer able to meet the increasingly harsh thermal environment. There is an urgent need to develop higher performance PR to ensure the flight safety of aircraft. Therefore, in this work, a novel hyperbranched polysiloxane containing Si-O-Zr bond was synthesized and then introduced into PR to develop homogeneous silicone/phenolic hybrid resin coatings. The TG results indicate that the introduction of Si-O-Zr bonds significantly improves the heat resistance of silicone. During ablation, the hyperbranched polysiloxane will undergo a ceramization to produce SiO 2 and ZrO 2 particles, both of which will subsequently generate a highly viscous Zr-Si-O glassy phase as anti-ablation layer. With the fluidity and self-healing properties, it can fill the gaps of the carbon layer and cover the surface of the carbon layer, giving the hybrid resin excellent ablative resistance. The linear ablation rate of the hybrid resin can be as low as 0.003 mm/s, which is an 80 % decrease compared to pure PR. The synthesized hybrid resin is expected to act as superior thermal protection coatings for the next generation of spaceflight.

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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2024 · IF 8.1

Coal-based carbon quantum dots modified Ni-MOF and Co/Zr-MOF heterojunctions for efficient photocatalytic hydrogen evolution

Shiyong Xu,Mei Li,Ziyu Li,Meijuan Ding,Yijun Wang,Zhiliang Jin

NS-CQDs were synthesized by a hydrothermal method using high-sulfur lignite as the carbon source. Modification of Ni-MOF and Co/Zr-MOF using NS-CQDs to explore the performance of composite photocatalysts for hydrogen production . It was found that NS-CQDs significantly enhanced the hydrogen precipitation performance of the composite photocatalysts compared with the MOFs catalysts alone, and the highest hydrogen precipitation rate of the novel composite photocatalyst 5%NS-CQDs/NCZ2 reached 3662.68 μmol g −1  h −1 . It can be inferred from the conduction band and valence band positions of Ni-MOF, Co/Zr-MOF and NS-CQDs that a double S-type heterojunction is formed. The presence of thiophene and pyrrole nitrogen in NS-CQDs can promote electron transport , reduce the rate of electron-hole pair complexation, and improve the hydrogen evolution activity of the 5%NS-CQDs/NCZ2.

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JOURNAL OF ALLOYS AND COMPOUNDS · 2024 · IF 5.8

Construction of Bi2MoO6 sheets/NH2-UiO-66(Zr) heterojunction photocatalysts toward enhanced degradation of tetracycline under visible light

Qingqing Wang,Wei Zhou,Claudia Li,Sibudjing Kawi,Yinhui Li

The application of photocatalysts in environmental field has emerged as a prominent research topic. Nevertheless, the efficiency of photocatalysts is reduced as the recombination of photogenerated chargers significantly, restricting their extensive use in this domain. In the present study, photocatalysts composed of bismuth molybdate/NH 2 -UiO-66(Zr) (Bi 2 MoO 6 /NH 2 -UiO-66(Zr)) featuring Z-scheme heterojunctions were effectively synthesized using a two-step hydrothermal technique. These photocatalysts exhibit remarkable photocatalytic degradation under visible light conditions. Notably, the broad planar configuration of Bi 2 MoO 6 sheets improves the separation of the photogenerated charge carriers. NH 2 -UiO-66(Zr) layered atop Bi 2 MoO 6 sheets enhances the availability of catalytically active sites, reduces charge recombination, and promotes charge transfer through the interface. The kinetic rate constant for Bi 2 MoO 6 /NH 2 -UiO-66(Zr) is around 0.00329 L mg −1 min −1 , indicating the increase of 3.78 and 41.13 times compared with pure Bi 2 MoO 6 and NH 2 -UiO-66(Zr), respectively. The efficiency for photocatalytic degradation of tetracycline using Bi 2 MoO 6 /NH 2 -UiO-66(Zr) reaches 81.72 % under visible light. Importantly, this efficiency exhibits a reduction of 10 % after five recycling cycles, demonstrating notable stability. The photocatalytic mechanism involved in tetracycline degradation was uncovered through trapping experiments and EPR, indicating that it is predominantly facilitated by the active oxidation of ·O 2 - and ·OH. The intermediates of the photocatalytic process as well as the possible degradation pathways were discussed. The creation of Bi 2 MoO 6 sheets/NH 2 -UiO-66(Zr) heterojunction photocatalysts provides a fresh approach to the development of novel catalysts, which may lead to significant advancements in environmental remediation efforts.

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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
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APPLIED ORGANOMETALLIC CHEMISTRY · 2025 ·Vol. 39 ·期 3 ·e70008 · IF 0

Photocatalytic Degradation of Typical Bisphenol Compounds Using Zr-NiFe2O4@ZIF-67/ZIF-8 in Collaboration With Peroxydisulfate/Peroxymonosulfate

Yawen Wu,Xueying Hou,Ao Li,Ruijian Li,Qingqing Yang,Shaohua Jiang,Jing yu Hu,Qingliang You,Rui Guo

As the amount of tetrachlorobisphenol A (TCBPA) that causes potential adverse effects on human health in the environment is continually increasing. It is therefore important to develop new materials for the adsorption or degradation of these compounds using various techniques. In this study, two novel magnetic recyclable composite catalysts Zr–NiFe 2 O 4 @ZIF-67 and Zr–NiFe 2 O 4 @ZIF-8 were synthesized. These catalysts degraded tetrachlorobisphenol A (TCBPA) in water by activating peroxydisulfate (PDS)/peroxymonosulfate (PMS), respectively. The results show that the Zr–NiFe 2 O 4 @ZIF-67-5%/LED/(NH 4 ) 2 S 2 O 8 system can degrade 95% of TCBPA (20 mg/L) within 30 min, whereas the Zr–NiFe 2 O 4 @ZIF-8-10%/LED/KHSO 5 system degrades 90% of TCBPA within 30 min. In instances of metal leaching at low concentrations, nickel and iron ions declined to 0.008 mg·L −1 , TCBPA exhibits highly efficient and sustainable catalytic properties, maintaining over 80% efficacy across six cycles. The online infrared test experiment results showed the major functional groups disappearing within approximately 130 s. The results of electron paramagnetic resonance and free-radical-quenching experiments showed that SO 4 ˙ − , ˙OH, 1 O 2 , and O 2 ˙ − were involved in the degradation of TCBPA. The possible degradation paths are isomerization polymerization, dechlorination, hydroxylation, ring-opening by oxidation, and further transformation into small molecules of acids, aldehydes, alcohols and other compounds. Thus, in this study, a reliable technique for the degradation of halogenated bisphenol compounds is developed. Overall, the photocatalytic degradation of organic pollutants in water utilizing polymetallic composites as catalysts represents an innovative approach to water treatment, demonstrating enhanced catalytic activity and recyclability, with promising prospects for significant advancements in both theoretical research and practical applications.

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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.

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