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ADVANCED FUNCTIONAL MATERIALS · 2018 ·Vol. 28 ·期 16 ·1707356 · IF 13.325

Nanoscale Zr-Based MOFs with Tailorable Size and Introduced Mesopore for Protein Delivery

Zhe Wang,Shuanggang Hu,Jian Yang,Ajuan Liang,Yongsheng Li,Qixin Zhuang,Jinlou Gu

Introduction of large pore in the primitive microporous metal–organic frameworks (MOFs) with tailorable particle size can endow them with desired properties for potential applications in the intracellular delivery of membrane-impermeable proteins. However, no research is found to focus on this topic until now. Herein, a monocarboxylic acid (MA) and organic base comodulation strategy is developed to synthesize the hierarchically porous UiO-66 nanoparticles. MA of dodecanoic acid is utilized to control the pore size while trimethylamine (TEA) plays a key role in modulating the nucleation of crystallization to regulate the particle size. In comparison with microporous UiO-66, a model protein of cytochrome c (Cyt c) could be efficiently loaded into the mesoporous MOFs (mesoMOFs). The size-dependent cellular uptake is also evaluated, and it is verified that mesoMOFs with particle size of 90 nm could be endocytosed into living cells with highest efficiency. These outstanding merits enable the current mesoMOFs not only to exhibit efficient encapsulation of Cyt c but also facilitate the protein delivery into the cytosol and subsequent endosomal escape. Given the exceptional chemical stability, hierarchically porous structure as well as tunable particle size, the elaborated mesoUiO-66 nanoparticles might offer a promising platform for a variety of biomedical applications.

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CHEMISTRY-A EUROPEAN JOURNAL · 2018 ·Vol. 24 ·期 12 ·2962-2970 · IF 5.16

Hierarchical Porous Zr-Based MOFs Synthesized by a Facile Monocarboxylic Acid Etching Strategy

Pengfei Yang,Fangxin Mao,Yongsheng Li,Qixin Zhuang,Jinlou Gu

Graphical Etch a sketch : A simple and efficient monocarboxylic acid etching (MAE) strategy was developed to prepare hierarchical porous UiO-66, which inherits excellent stability from its parent material and the pore parameters can be controlled by adjusting the monocarboxylic acid concentration and reaction temperature. A new monocarboxylic acid etching (MAE) strategy was developed for transforming chemically stable Zr-based metal-organic frameworks (MOFs) of UiO-66 to their hierarchical porous counterpart. The key design element was based on the incomplete replacement of bridging ligands in MOFs by monocarboxylic acids (MAs), leading to the departure of partial ligands and metal clusters to create mesopores in MOFs. A series of MAs with different acidity and carbon chain length were tested, and propionic acid (PA) was screened to be the suitable choice. The textural features including pore size distribution, specific surface area, and pore volume of the obtained products can be controlled by adjusting the MA concentration and reaction temperature. The obtained hierarchical porous MOFs inherited excellent stability from their parent materials. Additionally, the MAE strategy was universal to construct hierarchical porous Zr-based MOFs, and it was expanded to etch UiO-66 derivatives. The excellent adsorption behavior of the resultant hierarchical porous Zr-based MOFs over two enzymes with different size was also successfully exemplified, demonstrating their application potentials with bulky molecules involved.

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FUEL · 2017 · IF 4.601

A metal–organic framework for oxidative desulfurization: UIO-66(Zr) as a catalyst

Xiaotian Zhang,Pengcheng Huang,Aili Liu,Mingyuan Zhu

Owing to the high prices and other shortcomings associated with the existing methods of complex catalyst preparation, we used the UIO-66(Zr) metal–organic frameworks to directly catalyze the oxidative desulfurization (ODS) reaction. The synthesized UIO-66(Zr) was characterized using nitrogen adsorption–desorption isotherm analysis, X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. Under optimal reaction conditions, the ODS conversion of dibenzothiophene (DBT) reached 100%. This excellent catalytic activity was attributed to the unsaturated coordination of Zr, which may produce beneficial Lewis acid sites.

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Scientific Reports · 2017 ·Vol. 7 ·期 1 ·1-12 · IF 4.259

Soft Zr-doped TiO2 Nanofibrous Membranes with Enhanced Photocatalytic Activity for Water Purification

Song Jun,Wang Xueqin,Yan Jianhua,Yu Jianyong,Sun Gang,Ding Bin

Self-standing photocatalytic membranes constructed from TiO 2 nanofibers hold great promise in environmental remediation; however, challenges still remained for the poor mechanical properties of polycrystalline TiO 2 nanofibers. Herein, soft Zr-doped TiO 2 (TZ) nanofibrous membranes with robust mechanical properties and enhanced photocatalytic activity were fabricated via electrospinning technique. The Zr 4+ incorporation could effectively inhibit the grain growth and reduce the surface defects and breaking point of TiO 2 nanofiber. The as-prepared TZ membranes were composed of well-interconnected nanofibers with a high aspect ratios, small grain size and pore size, which exhibited good tensile strength (1.32 MPa) and showed no obvious damage after 200 cycles of bending to a radius of 2 mm. A plausible bending deformation mechanism of the soft TZ membranes was proposed from microscopic single nanofiber to macroscopical membranes. Moreover, the resultant TZ membranes displayed better photocatalytic performance for methylene blue degradation compared to a commercial catalyst (P25), including high degradation degree of 95.4% within 30 min, good reusability in 5 cycles, and easiness of recycling. The successful preparation of such fascinating materials may open up new avenues for the design and development of soft TiO 2 -based membranes for various application.

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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2025 · IF 8.5

Synergistic adsorption mechanisms in bimetallic Zr/Fe-modified chitosan hydrogels for enhanced phosphate removal

Wentao Qu,Zhikun Wang,Jiaqi Feng,Xupeng Li,Liqiang Yang,Li Wang,Jie Guo,Huiling Su,Miantuo Li,Yu Fu,Songqing Hu

This work presents a dual-adsorbent strategy for enhanced phosphate removal via chitosan-based materials with molecular-level mechanistic elucidation. Two complementary adsorbents are designed: spherical bimetallic beads (CSQ@Zr/Fe) and a porous hydrogel (CSQ@Zr). The CSQ@Zr/Fe beads demonstrate outstanding cyclic stability, retaining 84.2 % adsorption capacity after 5 regeneration cycles, while achieving a maximum adsorption capacity of 122.51 mg/g under optimized conditions. The CSQ@Zr hydrogel exhibits superior single-cycle performance with a capacity of 126.50 mg/g and rapid uptake kinetics, reaching adsorption equilibrium within 240 min. Both materials maintain high removal efficiency over a broad pH range (3–9) and show remarkable selectivity in complex ionic environments, with phosphate removal exceeding 90 % even in the presence of competing anions (Cl − , NO 3 − , SO 4 2− ). Comprehensive characterization and simulation studies reveal a synergistic adsorption mechanism dominated by electrostatic interactions (85–92 % contribution to binding energy), complemented by outer-sphere coordination (P–O–Zr: 2.25 Å; P–O–Fe: 1.85 Å) and hydrogen bonding networks. The hydrogel exhibits stronger phosphate confinement (diffusion coefficient: 0.544 × 10 −12  m 2 /s) compared to the beads (0.685 × 10 −12  m 2 /s), which correlates with its enhanced adsorption performance. This work provides not only high-performance adsorbents but also fundamental insights into the design of chitosan-based materials for sustainable phosphate removal and recovery applications.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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MICROPOROUS AND MESOPOROUS MATERIALS · 2021 · IF 5.455

Hydrogen accelerated regeneration of FeII in Fenton reaction enhanced by Pd/MOF-808(Zr)

Yang Hu,Hai-Liang Yang,San-Jian Ma,Juan-Hong Li,Xin Liu,Yong-Jing Tian,Long Jin,Zi-Xia Lin

The promotion of Fenton process in organic wastewater treatment has been hindered by the disposal of large amounts of iron sludge derived from the excess addition of ferrous salt. The operation of the Fenton reaction could be maintained using trace level Fe II through the effective acceleration reaction of active hydrogen. However, the H 2 which is the precursor of active hydrogen is insoluble in water. Herein, the composite catalyst Pd/MOF-808(Zr) was introduced into the H 2 -Fenton system to enhance the adsorption and activation of this reducing gas. In this novel improved Fenton system called MHACF-MOF-808(Zr), the hydroxyl radical would be unceasingly produced based on the unceasingly recycling of FeII/FeIII at normal temperature and pressure. 15 mg L −1 sulfamethazine could be thoroughly degraded during 2 h reaction process in the initial condition of 60 mL min −1 H 2 , 20 μmol L −1 Fe II , pH 3, 20 mmol L −1  H 2 O 2 and 2 g L −1  Pd/MOF-808(Zr). And so did 10 mg L −1 2,4-Dichlorophenol. The activity and stability of Pd/MOF-808(Zr) could be maintained after at least 6 consecutive reaction cycles. It provides new insight for improving the inherent shortcoming of the Fenton reaction which will generate large amounts of iron sludge.

研究领域: 环境科学 · 化学工程
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JOURNAL OF NANOPARTICLE RESEARCH · 2018 ·Vol. 20 ·期 3 ·1-11 · IF 2.127

Immobilization of silver nanoparticles in Zr-based MOFs: induction of apoptosis in cancer cells

Han Congcong,Yang Jian,Gu Jinlou

Silver nanoparticles (AgNPs) are a potential class of nanomaterial for antibiosis and chemotherapeutic effects against human carcinoma cells. However, the DNA-damaging ability of free AgNPs pose the critical issues in their biomedical applications. Herein, we demonstrated a facile method to capture Ag + ions and reduce them into active AgNPs within Zr-based metal-organic frameworks (MOFs) of UiO-66 with a mild reductant of DMF (AgNPs@UiO-66(DMF)). The average diameters of UiO-66 carriers and AgNPs were facilely controlled to be 140 and 10 nm, respectively. The obtained UiO-66 nanocarriers exhibited excellent biocompatibility and could be effectively endocytosed by cancer cells. Additionally, the AgNPs@UiO-66(DMF) could rapidly release Ag + ions and efficiently inhibit the growth of cancer cells. The half maximal inhibitory concentration (IC 50 ) values of the encapsulated AgNPs were calculated to be 2.7 and 2.45 μg mL −1 for SMMC-7721 and HeLa cells, respectively, which were much lower than those of free AgNPs in the reported works. Therefore, the developed AgNPs@UiO-66(DMF) not only maintained the therapeutic effect against cancer cells but also reduced the dosage of free AgNPs in chemotherapy treatment. A mild reduction process was developed for the fabrication of AgNPs@UiO-66, which exhibited efficient induction of apoptosis in cancer cells.

研究领域: 纳米技术 · 癌症研究 · 材料科学 · 生物医学工程
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2024 · IF 4.9

Green synthesis and high-performance fluoride ion removal using lanthanum-modulated MOF-808 (Zr)

Guangqin Shi,Ting He,Haian Li,Zhao Yang,Wu Lei,Mingzhu Xia,Yu Tao

In a water solution and with a low reaction temperature of 85 °C, the green preparation of lanthanum-modulated MOF-808 (Zr) was realized, the obtained La-MOF-808 have smaller grain size, larger specific surface area, higher pore volume and larger average pore diameter. When the molar ratio of La: Zr=1:1, 1L-MOF-808 had the best fluoride ion removal performance, and its maximum adsorption capacity for F - reached 101.4 mg/g, which was higher than that of the unmodulated MOF-808 and some other reported fluorine adsorbents. Meanwhile, the regeneration experiment demonstrated that even after five cycles, 1L-MOF-808 retained 73.8 % of its initial adsorption capacity, highlighting its commendable reusability. In addition, when 1L-MOF-808 was applied to actual fluorine-containing wastewater, with the fluoride ion concentration of 25.3 mg/L and an adsorbent dosage of 0.6 g/L, 1L-MOF-808 exhibited excellent resistance to anionic interference (SO 4 2- , Cl - ), the concentration of fluoride ions in effluent was lower than 10 mg/L, meeting the stipulations of fluoride ion discharge outlined in GB39371–2020. Further adsorption mechanism investigation revealed that 1L-MOF-808's affinity for F - was attributed to electrostatic interaction and ligand exchange. Overall, the as-synthesized 1L-MOF-808 not only presents an environmentally friendly approach to producing MOF materials without organic solvents but also develops a new strategy for the design of high-performance adsorbent for effectively removing fluoride ions from wastewater.

研究领域: 环境科学 · 材料科学
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JOURNAL OF SOLID STATE CHEMISTRY · 2024 · IF 3.2

Preparation of Zr-MOF/Poly(hexamethylenediamine-tannic acid)/Attapulgite for efficient Cr(VI) removal

Yuan Zhou,Jin-Long Jiang,Xia-Ping Zhu,Wen Chen

In this study, attapulgite (ATP) was modified by Zr-based metal organic framework (UiO-66-NH 2 ) and poly(hexamethylenediamine-tannic acid) (HTA), an amino material named UiO-66-NH 2 /HTA/ATP (UHA) was prepared to efficiently remove Cr(VI). The morphology and structure of UHA were analyzed through various characterization methods. The conditions and influencing factors of UHA preparation and Cr(VI) adsorption were studied. The material had a maximum adsorption capacity of 270.3 mg/g for Cr(VI) when pH was 2.0, temperature was 298 K, adsorption time was 300 min, and ionic strength was 0.01 mol/L, which was obtained by the Langmuir fitting model. The adsorption process conforms to the pseudo-second-order kinetic and Langmuir isothermal models, indicating that the adsorption process is mainly based on the chemical adsorption of monolayers. X-ray photoelectron spectroscopy analysis shows that UHA mainly removes Cr(VI) by hydrogen bonding , electrostatic attraction, reduction, and complexation. Thermodynamic investigation suggested a disordered, endothermic and spontaneous adsorption process. After UHA treatment, the simulated wastewater containing Cr(VI) met the discharge standard, and the results of cycling experiments showed that UHA has good renewable performance and offers potential prospects for Cr(VI) removal in water.

CAS / MDL: 124-09-4
研究领域: 环境科学 · 材料科学
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2024 · IF 4.9

Preparation of superhydrophobic surface on Zr-based bulk metallic glasses with excellent photocatalytic properties

Rui Zheng,Ranfeng Wei,Chaojun Li,Hao Zhang,Wei Wang,Haipeng Wang,Qijing Sun,Jingwang Lv,Guoyang Zhang,Xiangjin Zhao,Li Liu

The dyestuff industry is one of the chemical industries that cause serious environmental pollution. To degrade pollutants, we propose a top-down anodic etching approach to prepare metal/oxide micro/nanostructured photocatalytic superhydrophobic coating on the surface of bulk amorphous alloys. Unlike common amorphous strip or powder materials, this method combines the excellent properties of amorphous alloy substrates. The metal/oxide micro/nano structure on the surface provides photocatalytic and Fenton-like performance, which can degrade organic pollutants. To further improve the catalyst ability, we modulate the sample composition. Zr 48 Cu 44 Al 8 and Zr 48 (Cu 5/6 Ag 1/6 ) 44 Al 8 bulk amorphous alloys are synthesized to be analyzed. Ultimately, the superhydrophobic Zr 48 (Cu 5/6 Ag 1/6 ) 44 Al 8 sample shows high catalytic activity with its ability to degrade methyl orange (MO) by 96.9 % within 10 minutes under UV–visible light. We also investigate the superhydrophobic and bactericidal properties of the samples, making them possible to work in harsh environmental conditions. In this way, structural-functional integrate preparation of bulk amorphous alloys is realized.

CAS / MDL: 106-51-4
研究领域: 材料科学 · 环境工程 · 表面化学 · 光催化
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CRYSTENGCOMM · 2025 · IF 2.6

Sonochemical Synthesis of Zr-based metal-organic cages and their adsorption performance towards Tartrazine

De-Sheng Wei,Jian Li,Ting-Ting Xu,Wan-Yi Lan,Nan Lv,Yu-Teng Zhang,Shuang-Bao Li

Fast ultrasound-assisted processes were utilized for the first time, to achieve the successful synthesis of two highly crystalline Zr-based metal-organic cages, namely ZrT-1 and ZrT-1-OH. Varying temperature and power level, the desired product was obtained after 5-8 minutes as crystalline particles with cubic shape (ca.2-8 μm). Furthermore, ultrasound-assisted synthesized ZrT-1 and ZrT-1-OH demonstrated exceptional performance for tartrazine adsorption. Under optimal conditions, their maximum adsorption capacities were determined to be 238.6 mg/g and 225.3 mg/g, respectively.

研究领域: 材料科学 · 环境科学 · 化学工程
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COLLOIDS AND SURFACES B-BIOINTERFACES · 2026 · IF 5.9

Zr-porphyrinic MOF PCN-224 enables sequential antibacterial and inflammation-modulating PDT for periodontitis

Qi Liu,Chenxi Tang,Jiafeng Liu,Yuan Gao,Lin Peng

Periodontitis is a chronic inflammatory disease driven by microbial dysbiosis and a dysregulated host response, leading to soft-tissue destruction and alveolar bone loss. Antibacterial photodynamic therapy (aPDT) can rapidly suppress pathogens via light-triggered reactive oxygen species (ROS). Here, we report zirconium-based porphyrinic metal–organic framework (MOF) nanoparticles, PCN-224, as a bifunctional platform that couples early antibacterial aPDT with subsequent immunomodulation within the periodontal microenvironment. PCN-224 demonstrated excellent biocompatibility in vitro and in vivo . Under 660 nm irradiation, PCN-224 effectively generated singlet oxygen ( 1 O 2 ) and reduced Porphyromonas gingivalis burden. After uptake by RAW 264.7 macrophages, PCN-224 attenuated lipopolysaccharide-induced inflammation by lowering intracellular ROS levels, restoring superoxide dismutase activity, decreasing nitric oxide release, suppressing NF-κB signaling, accompanied by reduced IL-6, IL-1β, and iNOS and partial recovery of anti-inflammatory mediators. In a ligature-induced mouse model, local PCN-224 injection combined with 660 nm illumination decreased inflammatory infiltration and alleviated alveolar bone resorption. Collectively, PCN-224 provides a time-sequenced antibacterial-to-anti-inflammatory therapeutic effect and represents a potential MOF-enabled strategy for periodontitis management.

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