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MIL-125 (Ti)
ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2023 ·Vol. 30 ·期 17 ·49301-49313 · IF 5.8

Adsorption of nitrophenol onto a novel Fe3O4-κ-carrageenan/MIL-125(Ti) composite: process optimization, isotherms, kinetics, and mechanism

Abd El-Monaem Eman M.,Eltaweil Abdelazeem S.,El-Subruiti Gehan M.,Mohy-Eldin Mohamed S.,Omer Ahmed M.

Water pollution is a dreadful affair that has incessantly aggravated, exposing our planet to danger. In particular, the persistent nitro aromatic compound like nitrophenols causes anxiety to the researchers due to their hazardous impacts, excessive usage, and removal difficulty. For this purpose, a novel multi-featured composite was constructed based on κ-Carrageenan (κ-Carr), MOF (MIL-125(Ti)), and magnetic Fe 3 O 4 for efficient adsorptive removal of o-nitrophenol (o-NP). Interestingly, BET measurements revealed the high surface area of Fe 3 O 4 -κ-Carr/MIL-125(Ti) of about 163.27 m 2 /g, while VSM showed its excellent magnetic property (20.34 emu/g). The comparison study pointed out the synergistic effect between Fe 3 O 4 , κ-Carr, and MIL-125(Ti), forming a composite with an excellent adsorption performance toward o-NP. The adsorption data obeyed pseudo-second-order kinetic model, and Freundlich isotherm model was better fitted than Langmuir and Temkin. Furthermore, Langmuir verified the supreme adsorption capacity of o-NP onto Fe 3 O 4 -κ-Carr/MIL-125(Ti) since the computed q max  reached 320.26 mg/g at pH 6 and 25 °C. Furthermore, the XPS results postulated that the adsorption mechanism pf o-NP proceeded via H-bonding, π - π interaction, and electron donor–acceptor interactions. Interestingly, Fe 3 O 4 -κ-Carr/MIL-125(Ti) composite retained good adsorption characteristics after reusing for five cycles, suggesting its viable applicability as an efficient, renewable, and easy-separable adsorbent for removing nitro aromatic pollutants.

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Catalysts · 2023 ·Vol. 13 ·期 5 ·817 · IF 3.9

Microemulsion–Assisted Synthesis of Ag2CrO4@MIL–125(Ti)–NH2 Z–Scheme Heterojunction for Visible–Light Photocatalytic Inactivation of Bacteria

Haoyu Yuan,Chao Zhang,Wenjing Chen,Yuzhou Xia,Lu Chen,Renkun Huang,Ruiru Si,Ruowen Liang

Metal–organic frameworks (MOFs) are new porous materials composed of metal centers and organic ligand bridges, which received great attention in the field of photocatalysis. In this work, Ag2CrO4@MIL–125(Ti)–NH2(denoted as AgCr@M125) Z–scheme heterojunctions were synthesized via a simple microemulsion method, by which highly dispersed nano–sized Ag2CrO4can be anchored uniformly on the surfaces of porous MIL–125(Ti)–NH2(denoted as M125). Compared with pure M125 and Ag2CrO4, the as–prepared AgCr@M125 hybrids show significant photocatalytic efficiency against inactivatedStaphylococcus aureus(S. aureus), reaching over 97% inactivation of the bacteria after 15 min of visible light irradiation. Notably, the photocatalytic activity of the obtained 20%AgCr@M125 is about 1.75 times higher than that of AgCr–M125, which was prepared via a traditional precipitation method. The enhanced photocatalytic antibacterial activity of the AgCr@M125 photocatalytic system is strongly ascribed to a direct Z–scheme mechanism, which can be carefully discussed based on energy band positions and time–dependent electron spin response (ESR) experiments. Our work highlights a simple way to enhance the antibacterial effect by coupling with Ag2CrO4and M125 via a microemulsion–assisted strategy and affords an ideal example for developing MOFs–based Z–scheme photocatalysts with excellent photoactivity.Keywords:MIL–125(Ti)–NH2;Ag2CrO4;S. aureus;Z–scheme;microemulsion method

CAS / MDL: 5593-70-4 9022-96-2
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Highly enhanced photocatalytic performance for CO2 reduction on NH2-MIL-125(Ti): The impact of (Cu, Mn) co-incorporation

Wenhao Gu,Jinxian Feng,Xingshuai Lv,Weng Fai Ip,Hui Pan

Photocatalytic CO 2 reduction has been considered as an efficient way for the carbon nuetrality. In this work, a series of (Cu, Mn) co-incorporated metal-orgnaic frameworks (MOFs) (NH 2 -MIL-125(Ti) (NML)) with different Cu 2+ /Ti 4+ and Mn 2+ /Ti 4+ molar ratios are systematically investigated to improve the efficiency for photocatalytic CO 2 reduction. The optimized sample (1 M−5C−−NML) shows a highest yield of HCOOH (116.74 μmol . g −1. h −1 ) (3.71 times higher than that of NML), and a superior apparent quantum efficiency (AQE) (6.74 % at 405 nm). The improved performance is attributed to the formed oxygen vacancy and intermediate energy level as introduced by the co-incorporation, which facilitate the charge separation and enhance the visible-light-harvesting of NML. It shows that the density of oxygen vacancies increases with the increasing amount of Cu, resulting in enhanced charge separation. However, the increasing amount of Mn leads to the short-range Mn-Mn interaction, the concentration quenching effect as well as the inhibited photocatalytic performance. This work shows that the co-incorporated MOFs can be used as an advanced photocatalyst.

CAS / MDL: 10312-55-7 68-12-2
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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
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CHEMICAL ENGINEERING JOURNAL · 2020 · IF 10.652

Enhanced moisture-resistance and excellent photocatalytic performance of synchronous N/Zn-decorated MIL-125(Ti) for vaporous acetaldehyde degradation

Zhu Gao,Jiaxing Wang,Yaseen Muhammad,Yibo Zhang,Syed Jalil Shah,Yang Hu,Zhe Chu,Zhongxing Zhao,Zhenxia Zhao

High photo-catalytic activity and stable recycling performance under high humidity are main hindering factors in practical applications of metal organic frameworks (MOFs) for volatile organic compounds (VOCs) degradation. In-situ co-doping strategy of pyrrolic N/Zn was proposed to enhance surface charge separation and cycling stability of MIL-125(Ti) for degradation of vaporous acetaldehyde under highly humid conditions. Characterizations results show that pyrrolic N/Zn co-doped MIL-125(Ti) exhibited an integrated crystal structure and high surface area (1415 m 2 /g). The constructed Ti/Zn-N/O clusters narrowed band gap (from 3.40 to 1.85 eV) of MIL-125(Ti) and boosted electron conductivity. Also, it was proved to enhance surface alkalinity and hydrophobicity of MIL-125(Ti), which would strengthen MOFs selective adsorption towards CH 3 CHO and accelerated the transfer of degradation product CO 2 from catalytic active sites in MIL-125(Ti) under high humidity. As a result, synergistic effect of N/Zn co-doping exhibited an enhanced the ability of activating oxygen and H 2 O molecules into superoxide radical ( O 2 − ) and hydroxy radical ( OH), showing 10 times faster reaction kinetics for CH 3 CHO degradation under humid air compared to MIL-125(Ti). Moreover, co-dopant of N/Zn into MIL-125(Ti) has significantly promoted the recycling stability of MIL-125(Ti) under high humidity. According to the work, co-dopant elemental strategy to modify MOF surface can provide the synergistic effect for efficient degradation of aldehyde VOCs under humid conditions.

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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

Chitosan/NH2-MIL-125 (Ti) scaffold loaded with doxorubicin for postoperative bone tumor clearance and osteogenesis: An in vitro study

Yaoxun Zeng,Jiongpeng Yuan,Zhili Ran,Xiaoguang Zhan,Xinyi Li,Huiling Ye,Jiapeng Dong,Guining Cao,Zhenxing Pan,Ying Bao,Junze Tang,Xujie Liu,Yan He

Surgical resection remains the primary treatment modality for bone tumors. However, it is prone to local bone defects and tumor recurrence. Therefore, there is an urgent need for multifunctional biomaterials that combine tumor treatment and bone repair after bone tumor surgery. Herein, a chitosan composite scaffold (CS/DOX@Ti-MOF) was designed for both tumor therapy and bone repair. Among them, the amino-functionalized Ti-based metal-organic framework (NH 2 -MIL-125 (Ti), Ti-MOF) has a high specific surface area of 1116 m 2 /g and excellent biocompatibility, and promotes osteogenic differentiation. The doxorubicin (DOX) loading capacity of Ti-MOF was 322 ± 21 mg/g, and DOX@Ti-MOF has perfect antitumor activity. Furthermore, the incorporation of DOX@Ti-MOF improved the physical and mechanical properties of the composite scaffolds, making the scaffold surface rough and favorable for cells to attach. CS/DOX@Ti-MOF retains the unique properties of each component. It responds to the release of DOX in the tumor microenvironment to remove residual tumor cells, followed by providing a site for cell attachment, proliferation, and differentiation. This promotes bone repair and achieves the sequential treatment of postoperative bone tumors. Overall, CS/DOX@Ti-MOF may be a promising substitute for postoperative bone tumor clearance and bone defect repair. It also provides a possible strategy for postoperative bone tumor treatment.

CAS / MDL: 9012-76-4
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POLYHEDRON · 2023 · IF 2.6

Combining hierarchical pores and unsaturated sites into Quasi-MIL-125(Ti) for ultra-fast and efficient adsorption of cationic dyes

Yadan Ma,Xuefen Jiang,Zhongmin Liu,Longlong Geng,Xiao lei Zhang,Ping Niu,Xiuling Zhang,Yongzheng Zhang,Dashuai Zhang,Hui Hu,Xin Li,Xiaoli Wang

Developing new adsorbents with hierarchical pore and unsaturated adsorption sites are highly demanded to achieve rapid adsorption rate and good adsorption selectivity in purifying organic wastewater. We here reported a new Quasi-MIL-125(Ti) synthesized at 340 °C under air atmosphere and considered as a high-efficiency adsorbent for capturing cationic dyes. The morphology of the material is characterized by XRD, SEM, TEM, etc. and the adsorption performance of Quasi-MIL-125(Ti) was systematically studied. Remarkably, it takes only 1 min to rapidly remove 20 mg L -1 MB or NR with 1 g L -1 Quasi-MIL-125(Ti), which is far superior to the previously reported materials. Adsorption isotherm shows that dyes adsorption on Quasi-MIL-125(Ti) follow a Langmuir adsorption isotherm model. The experimental maximum adsorption capacities were 109.3 mg g -1 for MB and 151.1 mg g -1 for NR, respectively. The hierarchical pores facilitate the diffusion and co-adsorption of different dye molecules. Adsorption mechanism reveals that the strong electrostatic attraction originated from the unsaturated Ti sites in Quasi-MIL-125(Ti) contributes to the ultra-fast adsorption behavior during cationic dyes chemisorption process. This study not only provides a promising prospect for the synthetic strategy of super-adsorbents, but also provides reference and theoretical guidance for practical dye wastewater treatment.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2022 · IF 9.965

Multi-channel charge transfer of hierarchical TiO2 nanosheets encapsulated MIL-125(Ti) hollow nanodisks sensitized by ZnSe for efficient CO2 photoreduction

Yuzhen Jiao,Yajie Chen,Wei Han,Shumei Liang,Wei Li,Guohui Tian

Metal-organic frameworks-based hybrids with desirable components, structures, and properties have been proven to be promising functional materials for photocatalysis and energy conversion applications. Herein, we proposed and prepared ZnSe sensitized hierarchical TiO 2 nanosheets encapsulated MIL-125(Ti) hollow nanodisks with sandwich-like structure (MIL-125(Ti)@TiO 2 \ZnSe HNDs) through a successive solvothermal and selenylation reaction route using the as-prepared MIL-125(Ti) nanodisks as precursor. In the ternary MIL-125(Ti)@TiO 2 \ZnSe HNDs hybrid, TiO 2 nanosheets were transformed from MIL-125(Ti) and in situ grown on both sides of the MIL-125(Ti) shell, forming sandwich-like hollow nanodisks, and the ratio of MIL-125(Ti)/TiO 2 can be tuned by changing the solvothermal time. The ternary hybrids possess the advantages of enhanced incident light utilization and abundant accessible active sites originating from bimodal pore-size distribution and hollow sandwich-like heterostructure, which can effectively promote CO 2 photoreduction reaction. Especially, the formed multi-channel charge transfer routes in the ternary heterojunctions contribute to the charge transfer/separation and extend the lifespan of charge-separated state, thus boosting CO 2 photoreduction performance. The CO (513.1 μmol g −1 h −1 ) and CH 4 (45.1 μmol g −1 h −1 ) evolution rates over the optimized ternary hybrid were greatly enhanced compared with the single-component and binary hybrid photocatalysts.

CAS / MDL: 68-12-2
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SEPARATION AND PURIFICATION TECHNOLOGY · 2021 · IF 7.312

A novel solar-triggered MIL-125(Ti)/g-C3N4/SA composite aerogel with high catalytic activity for degradation of organic contaminants

Jie Zhao,Bingzhang Li,Zongyang Liu,Danling Dai,Yuqi Li,Ronghui Shi,Hui Zhang

Sodium alginate (SA) aerogels have shown outstanding potential as regenerative adsorbent materials in the field of wastewater purification. Although SA aerogel adsorption has been demonstrated as a simple and resultful method for removing dyes, it has the limitation that it only transfers or concentrates dyes on the adsorbate, and does not actually degrade them. In this study, a three-dimensional (3D) MIL-125/g-C 3 N 4 /SA (CNTi-125@SA) composite aerogel with visible light photocatalytic activity was achieved for photocatalytic degradation of organic dyes, via in-situ growth, blending and freeze-drying strategy. The results demonstrate that CNTi-125@SA has high catalytic activity for the dyes rhodamine B (RhB), methylene blue (MB) and methyl orange (MO), and the degradation rate can reach up to 99.23%. Impressively, the composite aerogel exhibits excellent antibacterial ability, and the antibacterial rate can reach up to 100% against E. coli . In addition, the developed composite aerogel has excellent reusability and stability, and the degradation efficiency can still reach 85% after seven repeated tests. Owing to their high catalytic activity, excellent antibacterial properties and stability, the CNTi-125@SA composite aerogel can be potentially used in a wide range of dye wastewater purification.

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CELLULOSE · 2019 ·Vol. 26 ·期 17 ·9335-9348 · IF 3.917

Robust fluorine-free colorful superhydrophobic PDMS/NH2-MIL-125(Ti)@cotton fabrics for improved ultraviolet resistance and efficient oil–water separation

Yang Yingying,Huang Wei,Guo Zengpei,Zhang Shiyu,Wu Feng,Huang Jingjing,Yang Hongjun,Zhou Yingshan,Xu Weilin,Gu Shaojin

Abstract Superhydrophobic cotton fabrics with improved ultraviolet resistance were prepared via in situ growing NH 2 -MIL-125(Ti)(Ti-MOF) nanoparticles on cotton fibers and subsequently coating with polydimethylsiloxane (PDMS) under room temperature. The synergetic effect of Ti-MOFs nanoparticles and PDMS was critical and essential for obtaining a superhydrophobic coating with anti-UV property. The surface microstructure, chemical composition, and superhydrophobic property of the as-prepared fabrics were characterized by K/S value, scanning electron microscopy, X-ray photoelectron spectroscopy, energy dispersive spectroscopy, and water contact angle (WCA) measurements. The as-prepared cotton fabrics not merely exhibited desirable superhydrophobic property with a water contact angle (WCA) of 154.7 ± 0.7° and a sliding angle of 3.6°, but also displayed the considerable UV resistance. The oil–water separation, stability of UV protection and superhydrophobicity were also investigated. The superhydrophobicity, anti-ultraviolet property, and K/S value of as-prepared PDMS/Ti-MOFs@cotton fabrics were stable after 300 cycles of abrasion and 5 cycles of washing. The facile synthesis technique provided a simple method for scalable construction of multifunctional fabrics. Graphic abstract

CAS / MDL: 10312-55-7 546-68-9
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2017 · IF 9.446

Palladium-decorated hierarchical titania constructed from the metal-organic frameworks NH2-MIL-125(Ti) as a robust photocatalyst for hydrogen evolution

Baolin Yan,Lijuan Zhang,Zhiyong Tang,Mohammad Al-Mamun,Huijun Zhao,Xintai Su

Engineering metal-organic frameworks (MOFs) into hierarchical structured materials is crucial for providing a viable platform to construct efficient catalysts and broaden their applications in energy conversion and photocatalysis. Here, a simple and efficient solid-state pyrolysis of Ti-MOFs (NH 2 -MIL-125) sacrificial template combined with a photo-reduction process was developed to construct a series of hierarchical TiO 2 decorated with Pd nanoparticles. The hierarchical TiO 2 inherited the well-defined rounded rectangular submicron-tablet from NH 2 -MIL-125 precursor and was constituted of uniform anatase TiO 2 nanoparticles with an average size of 12   nm. Furthermore, the photocatalytic activity for the hydrogen production from water-methanol solution was improved by the optimization of the content of Pd as a cocatalyst, and the maximum was achieved with a Pd loading of 1.5%. The rate of H 2 evolution of 1.5% Pd decorated hierarchical TiO 2 (1.5% Pd/TiO 2 ) reached to 979.7   μmol   h −1 and 112.7   μmol   h −1 , under UV–vis light and simulated solar light, respectively. This unusual photocatalytic activity may be resulted from the positive synergetic effect of efficient light absorption, promoted separation and migration of photo-induced electron-hole carriers. The work highlights the potential of the MOFs-based hierarchical TiO 2 in the photocatalytic water splitting under solar light.

CAS / MDL: 7647-10-1 3087-37-4
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APPLIED SURFACE SCIENCE · 2017 · IF 3.387

Hydrothermal fabrication of few-layer MoS2 nanosheets within nanopores on TiO2 derived from MIL-125(Ti) for efficient photocatalytic H2 evolution

Fei Ye,Houfen Li,Hongtao Yu,Shuo Chen,Xie Quan

Protons tend to bond strongly with unsaturated-coordinate S element located at the edge of nano-MoS 2 and are consequently reduced to H 2 . Therefore, increasing the active S atoms quantity will be a feasible approach to enhance hydrogen evolution. Herein we developed a porous TiO 2 derived from metal organic frameworks (MOFs) as scaffold to restrict the growth and inhibit the aggregation of MoS 2 nanosheets. As a result, the thickness of the prepared MoS 2 nanosheets was less than 3   nm (1–4 layers), with more edges and active S atoms being exposed. This few-layer MoS 2 -porous TiO 2 exhibits a H 2 evolution rate of 897.5   μmol   h −1   g −1 , which is nearly twice as much as free-stand MoS 2 nanosheets and twenty times more than physical mixture of MoS 2 with porous TiO 2 . The high performance is attributed to that more active edge sites in few-layer MoS 2 -porous TiO 2 are exposed than pure MoS 2. This work provides a new method to construct MOFs derived porous structures for controlling MoS 2 to expose active sites for HER.

CAS / MDL: 100-21-0
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