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MIL-101
SENSORS AND ACTUATORS B-CHEMICAL · 2016 · IF 4.758

Combination of an electrodeless quartz crystal microbalance and spectrometric methods and application in monitoring adsorption kinetics of iodine on metal-organic frameworks films

Ping Zhang,Lingqiang Kong,Honghai Wang,Qi Kang,Dazhong Shen

In this work, the combination of an electrodeless quartz crystal microbalance (EL-QCM) and spectrometric techniques was designed to investigate the adsorption kinetics of iodine onto two metal-organic frameworks film, MIL-101 and ZIF-67. The concentrations of I 2 adsorbed on film and in vapor phase were monitored simultaneously in real time by the frequency of EL-QCM and the absorbance, respectively. It was shown that ZIF-67 film has a high adsorption capacity of 4.41   g/g to I 2 , which is much higher than that of MIL-101 (0.58   g/g). The 2-methylimidazole unit in ZIF-67 plays an important role for I 2 adsorption with a capacity of 3.15   g/g. For adsorption on MIL-101, the amount of I 2 adsorbed at equilibrium obeys the Henry’s law. The amounts of I 2 adsorbed on ZIF-67 film increases with increasing concentration of I 2 vapor in accelerating slope due to the condensation of I 2 vapor. The diffusion coefficients of I 2 in MIL-101 and ZIF-67 films were estimated to be 6.1   ×   10 −16 and 3.7   ×   10 −16   m 2 /min, respectively. By using the concentration-time curves, adsorption kinetic parameters were estimated based on a simplified model including reversible and irreversible adsorption states. This method offers the advantage to record simultaneously the changes in both of the amount adsorbed and the vapor concentration of a corrosive adsorbate with UV-vis absorbance.

研究领域: 材料科学 · 分析化学
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OPTICAL MATERIALS · 2025 · IF 4.2

Green removal of ethylene with composite photocatalyst MIL101(Fe)/TiO2 with different molecular structure

Hanmin Zhong,Xiaoying Ye,Xueting Xie,Xianliang Song,Shucan Luo,Wenbei Situ

With the large surface area and excellent adsorption properties of MIL-101(Fe), MIL-101(Fe)/TiO 2 photocatalysts were prepared by chemical method and physical method in this research, respectively. The photocatalysts' performance on ethylene degradation was evaluated, and the photocatalyst prepared using the chemical method (CH-MT) performed better than that by physical method (PHY-MT) under the same conditions. Moreover, the photocatalysts' molecular structure was characterized by XRD, FTIR, UV–Vis DRS, BET, and XPS. The redox process of Ti 4+ /Ti 3+ of TiO 2 and Fe 3+ /Fe 2+ effectively prevents the complexation of e − -h + pairs. In this cycle, the oxidatively active substance (∙O 2 - ) is provided, which plays a key role in the ethylene degradation of MIL-101(Fe)/TiO 2 photocatalysts. Furthermore, in the BET analysis, CH-MT's specific surface area and pore volume were smaller than PHY-MT's, which improved ethylene absorption, enhanced the transfer of photogenerated carriers, and raised the photocatalytic reaction efficiency of CH-MT. The differences between MIL-101(Fe)/TiO 2 photocatalysts prepared by various methods were investigated and discussed, providing a new approach for MOF materials' application in agricultural areas.

CAS / MDL: 100-21-0
研究领域: 环境科学 · 材料科学
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RSC Advances · 2014 ·Vol. 4 ·期 97 ·54487-54493 · IF 3.708

Palladium nanoparticles encapsulated inside the pores of a metal–organic framework as a highly active catalyst for carbon–carbon cross-coupling

Ningzhao Shang,Shutao Gao,Xin Zhou,Cheng Feng,Zhi Wang,Chun Wang

Well dispersed palladium nanoparticles were successfully encapsulated in the cages of a metal–organic framework, MIL-101, by using a “double solvents” method coupled with subsequent reduction with NaBH4. Such a fabrication method can effectively avoid the aggregation of palladium nanoparticles on the external surfaces of MIL-101. The as-prepared catalyst, Pd@MIL-101, was characterized by transmission electron microscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, N2 adsorption and inductively coupled plasma atomic emission spectroscopy. The Pd@MIL-101 composite exhibited high catalytic activity toward the Suzuki–Miyaura and Heck cross-coupling reactions. The catalyst can be readily recovered and reused in at least 5 consecutive cycles without significant loss its catalytic activity.

研究领域: 材料科学 · 催化化学
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AICHE JOURNAL · 2016 ·Vol. 62 ·期 12 ·4403-4417 · IF 2.98

Catalytic dehydration of glucose to 5-hydroxymethylfurfural with a bifunctional metal-organic framework

Ye Su,Ganggang Chang,Zhiguo Zhang,Huabin Xing,Baogen Su,Qiwei Yang,Qilong Ren,Yiwen Yang,Zongbi Bao

Glucose conversion to 5-hydroxymethylfurfural (HMF) generally undergoes catalytic isomerization reaction by Lewis acids followed by the catalytical dehydration to HMF with Brönsted acid. In this work, a sulfonic acid functionalized metal-organic framework MIL-101(Cr)-SO 3 H containing both Lewis acid and Brönsted acid sites, was examined as the catalyst for γ-valerolactone-mediated cascade reaction of glucose dehydration into HMF. Under the optimal reaction conditions, the batch heterogeneous reaction gave a HMF yield of 44.9% and selectivity of 45.8%. Reaction kinetics suggested that the glucose isomerization in GVL with 10 wt % water follows the second-order kinetics with an apparent activation energy of 100.9 kJ mol −1 . Continuous reaction in the fixed-bed reactor showed that the catalyst is highly stable and able to provide a steady HMF yield. This work presents a sustainable and green process for catalytic dehydration of biomass-derived carbohydrate to HMF with a bifunctional metal-organic framework. © 2016 American Institute of Chemical Engineers AIChE J , 62: 4403–4417, 2016

CAS / MDL: 57-48-7 108-29-2
研究领域: 化学工程 · 生物质能 · 催化科学
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Journal of Physical Chemistry C · 2026 · IF 3.4

Sensitive and Selective Detection of Purine Drugs on Au/MIL-101(Cr) by SERS

Jing-Jing Li,Can-Jun Zou,Wei Tang,Cheng-Yu Zhang,Jian-Hua Jia,Ping-Ping Fang

The detection of purine drugs has been a persistent concern among scientists in the biology and medicine fields over the past few decades. However, achieving both high sensitivity and selectivity in the detection of purine drugs sharing similar molecular structures remains a significant challenge. Herein, we achieve both high detection sensitivity and selectivity for purine drugs with similar structure on the Gold/Materials of Institut Lavoisier-101(Au/MIL-101) composite by surface-enhanced Raman scattering (SERS). In water solution, the detection sensitivity for adenine (Ade) is as low as 1 ng·mL–1. Importantly, in serum containing Ade, 6-mercaptopurine, and allopurinol, Ade can be selectively detected with a detection limit of 3 ng·mL–1, indicating excellent anti-interference capability and practical application potential. Such high detection sensitivity is attributed to the specific adsorption between the amino group of the Ade and the carboxyl groups of the Materials Institut Lavoisier-101(Cr) (MIL-101(Cr)). This work provides a strategy for detecting structurally similar drugs and illustrates the potential use of functionalized SERS substrates in pharmaceutical analysis and therapeutic drug monitoring.

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SEPARATION SCIENCE AND TECHNOLOGY · 2026 · IF 2.5

Mechanistic insights into MIL-101 composites for efficient arsenic removal in near-neutral waters

Shun Zhang,Wenqi Jiang,Pengna Huang,Xianjin Qi,Yongkui Li

The development of adsorbents that combine high capacity with strong interference resistance remains a challenge for arsenic remediation in near-neutral industrial wastewater. Herein, we designed three functionalized MIL-101(Fe) composites – Si@Fe-MOF, L@Fe-MOF, and Fe/La-MOF – using silica incorporation, layered double hydroxide (LDH) assembly, and bimetallic synergy, respectively. This multi-faceted strategy aimed to overcome the inherent limitations of pristine MOFs, such as insufficient active sites. Under near-neutral conditions (pH = 7), the bimetallic Fe/La-MOF composite exhibited an exceptional adsorption capacity of 1708 mg/g for As(V), with a removal rate of 98.6%. Systematic characterization and modeling revealed that the adsorption process on all composites is governed by chemisorption. Mechanistically, the incorporated components enhance performance through distinct pathways: Si – OH groups provide additional binding sites, while La doping and Fe-La synergy create high-affinity bimetallic centers for selective arsenic complexation. This work provides a theoretical foundation and effective strategies for designing high-performance, stable adsorbents for treating arsenic in complex aquatic environments.

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Journal of Environmental Chemical Engineering · 2025 · IF 7.2

Synergistic photocatalytic reduction of CO2 enabled by MIL-101(Cr)-TiO2-polyimide nanocomposite membranes

Lipei Ren,Shuaifei Zhao,Milad Laghaei,Han Wang,Jiaqi Zhang,Weimin Gao,Joselito M. Razal,Weilin Xu,Lingxue Kong

Converting CO 2 into valuable chemicals through photocatalytic reduction is a promising method to achieve carbon neutrality. Nonetheless, the insufficient active sites of photocatalysts lead to low CO 2 reduction efficiency and product selectivity. Taking advantage of the synergistic effect of photocatalytic heterostructures is an effective way to overcome this shortcoming. Here, metal-organic frameworks (MIL-101(Cr))-titanium dioxide (TiO 2 ) staggered gap (type II) heterojunctions were deposited on different woven polyimide (PI) substrates (MIL-101-TiO 2 PI hybrid photocatalysts) via atomic layer deposition and hydrothermal reaction for CO 2 photoreduction. The immobilized photocatalysts on the PI substrates resolved the challenge of separating powdered photocatalysts from liquid products or reactants. The prepared MIL-101(Cr)-TiO 2 PI hybrid photocatalysts displayed synergistic photocatalytic reduction performance towards CO 2 by separating the photogenerated charge carriers. The charge transfer between the heterojunctions and the substrates extended the lifetime of the excited electrons and holes, thereby generating synergy effects and promoting the CO 2 reduction yield. The rougher surface and higher specific area of the PI felt enabled higher loadings of heterojunctions compared with other woven structures of the fabric and mat. As a result, MIL-101(Cr)-TiO 2 PI felts showed multiple reduction pathways over the heterostructures and enhanced photocatalytic performance, with the main product yields of 29.6, 9.2, and 0.8 μmol g −1 h −1 for CO, CH 4 and H 2 , respectively. Meanwhile, CO selectivity of the MIL-101(Cr)-TiO 2 PI felt reached as high as 75 %. This study provides significant insights into the role of the substrate in flexible and immobilized hybrid photocatalysts with synergistic performance to achieve enhanced CO 2 reduction yield.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2026 · IF 9.7

Structural-coupling driven cobalt metalloporphyrin⊂MIL-101(Fe) hybrids for efficient photocatalytic CO2 reduction

Xin Li,Ze Lv,Tong Wu,Bolin Ji,Wei Wu,Yi Zhong,Hong Xu,Zhiping Mao,Linping Zhang

Enhancing the photocatalytic CO 2 conversion efficiency of metal-organic frameworks (MOFs) remain a central challenge in advancing carbon capture and utilization (CCU) technologies. Herein, we report a mixed-ligand strategy to construct a hybrid MOF (denoted as CTN ⊂ NM) by incorporating a Co-metalated tetrakis(4-carboxyphenyl)porphyrin (CoTCPPNa 4 , CTN) into an amine-functionalized MIL-101(Fe) framework (NH 2 -MIL-101(Fe), abbreviated as NM; MIL = Materials of Institute Lavoisier, a prototypical series of robust MOFs). The optimized catalyst with a Co/Fe molar ratio of 0.40 achieves a HCOOH production rate of 119.11 μmol g −1  h −1 under visible light in the absence of a sacrificial agent, representing a 4.2-fold increase compared with pristine NM. When a sacrificial electron donor is introduced, the rate further rises to 179.87 μmol g −1  h −1 . The markedly enhanced activity originates from the synergistic integration of CTN and NM: CTN provides strong visible-light absorption and efficient catalytic sites, while NM offers high porosity and strong CO 2 affinity. This cooperation broadens the light-absorption range, suppresses charge-carrier recombination, and accelerates CO 2 -reduction kinetics. In addition, the Co 3+ center in the metalloporphyrin macrocycle functions as an active CO 2 adsorption site, facilitating its activation and selective conversion to HCOOH. Overall, this study presents an effective mixed-ligand hybridization approach for solar-to-chemical energy conversion and provides valuable insights for the rational design of MOF-based photocatalysts toward carbon-neutral fuel production.

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VACUUM · 2025 · IF 3.9

Ti-O-Cr bond-mediated TiO2@MIL-101 heterojunctions for improved photocatalytic CO2 reduction

Zhuo Li,Huiling Du,Nan Kong,Na Cao,Kemeng Hu,Lan Yang,Xian Du

Carbon dioxide conversion represents a highly promising carbon reduction strategy, and photocatalytic conversion technology, characterized by greenness, non-toxicity, and sustainability, holds significant importance. However, enhancing CO 2 adsorption on photocatalysts and improving charge carrier separation efficiency remain substantial challenges. In this study, based on MIL-101, we designed a highly interconnected TiO 2 @MIL-101 bifunctional heterojunction by in-situ compositing TiO 2 on its surface through Ti-O-Cr bonding, aiming to achieve in-situ adsorption and conversion of carbon dioxide. This composite photocatalyst exhibits enhanced photocatalytic activity, with an average CO production rate of 35.39 μmol h −1  g −1 and a CH 4 production rate of 13.81 μmol h −1  g −1 . Compared to unmodified MIL-101 (Cr), these values are increased by 1.25-fold and 2.8-fold, respectively. Experimental results combined with DFT calculations demonstrate that the porous structure and high specific surface area of MIL-101 facilitate the diffusion of CO 2 on the photocatalyst surface and improve interfacial reaction kinetics. The synergistic effect between Ti-O-Cr bonds and the built-in electric field within the highly interconnected heterojunction accelerates the directional transfer of charge carriers at the heterointerfaces, effectively promoting the catalytic conversion of carbon dioxide.

研究领域: 材料科学 · 光催化 · 环境化学 · 二氧化碳利用
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JOURNAL OF SOLID STATE CHEMISTRY · 2025 · IF 3.5

Tailoring MIL-101 for enhanced hydrogen storage via functional group introduction and Li+ doping

Guojian Ji,Chenyu Chu,Jiahua Cheng,Linya Fei,Anqi Xu,Tianle Zhang,Zhihui Zhang,Le Chen,Qunfeng Zou,Chuan Jiang

Metal-organic frameworks (MOFs) are advantageous for hydrogen storage owing to their tunable porosity. Two independent series were constructed: (i) MIL-101(Cr) functionalized with –NH 2 or –OH, and (ii) Li + -doped MIL-101 at controlled loadings. All samples retained their framework integrity. Textural analysis reveals a concentration-dependent, non-monotonic effect of Li + : at 0.015 wt%, Li + acts as an entrance unblocking (window reopening) effect, markedly increasing S BET and V total and strengthening the 1–2 nm window population; at 0.036 wt%, an optimal balance between reopened windows and accessible microporosity yields a peak H 2 uptake of 3.00 wt% (77 K, 100 kPa), surpassing both the parent framework and the –NH 2 derivative (2.37 wt%); at 0.296 wt%, partial occupation of cages/windows reduces accessibility. GCMC density maps and isosteric-heat data further corroborate that –NH 2 enhances polarity and strengthens host-guest interactions, whereas –OH blocks ultramicropores; moderate Li + simultaneously improves pore accessibility and introduces polarized adsorption sites. Overall, H 2 storage correlates more strongly with the coupling between accessible microporosity and pore-surface polarity than with S BET alone, highlighting dopant concentration as a key lever for optimizing MOF-based hydrogen storage.

CAS / MDL: 7447-41-8
研究领域: 材料科学 · 氢能存储 · 纳米多孔材料 · 吸附
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ANALYTICAL CHEMISTRY · 2023 · IF 7.4

Highly Sensitive and Selective Detection of Pharmaceuticals on Au/MIL-101(Cr) by SERS

Yu-Fei Li,Can-Jun Zou,Xing-Biao Liu,Feng Gan,Ping-Ping Fang

The detection of pharmaceuticals has been a matter of concern among scientists and health researchers in the past few decades. However, it is still difficult to realize the sensitivity and selectivity detection of pharmaceuticals with similar structures. Herein, the pharmaceutical molecules of 2-mercaptobenzimidazole (MBI) and 2-mercaptobenzothiazole (MBT) with so similar structures can be selectively detected by surface-enhanced Raman spectroscopy (SERS) taking advantage of the fingerprint identification on Au/MIL-101(Cr), with sensitive detection limits of 0.5 ng·mL–1 for MBI and 1 ng·mL–1 for MBT. MBI is selectively enriched by Au/MIL-101(Cr) from the mixture solution and detected by SERS below 30 ng·mL–1. MBI can also be selectively detected in the serum samples with a detection limit of 10 ng·mL–1. Density functional theory calculations combined with the SERS experiments explained that the high sensitivity and selectivity are caused by the intrinsic differences in Raman intensity and different adsorption energies from the pharmaceutical molecules adsorbed on Au/MIL-101(Cr), respectively. This study provides an effective way to enrich and detect pharmaceutical molecules with similar structures.

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Molecular Catalysis · 2022 · IF 5.089

Experimental and theoretical investigations into propane dehydrogenation over MIL-101(Cr/Al) derived catalysts

Rongzhao Li,Chengtao Zhang,Shuo Li,Yupeng Du

Propane dehydrogenation is commonly operated at temperatures exceeding 600 °C due to thermodynamic requirements. However, high temperature accelerates the deactivation of catalysts because of the coke deposition. Therefore, it is quite necessary to develop catalysts with high catalytic activity and improved anti-coking ability. To this end, an Al-doped Cr 2 O 3 catalyst derived from MIL-101(Cr/Al) is prepared in this work. The preparation conditions, including the carbonization temperature of MIL-101 and the proportion of Cr/Al, are optimized via experimental studies. Meanwhile, the adsorption and dehydrogenation behaviors of propane on the catalyst are investigated using Density Functional Theory (DFT) methods. Findings indicate that the optimum carbonization temperature and Cr/Al proportion are 900 °C and 6:4, respectively. Under the reaction condition of P = 0.1 MPa, T = 580 °C and GHSV = 800 h −1 , the propane conversion and propylene selectivity on the Cr 6 /Al 4 catalyst are 19.5% and 92.0%, respectively. The activity stability of the Al-doped Cr 2 O 3 is elongated significantly due to the lower desorption energy of propene and higher energy barrier for the coke formation on the catalyst. In sum, the present work completed via experiments and DFT calculations will lead to a better understanding of the Al-doped Cr 2 O 3 catalyst and guide the rational design of anti-coking catalysts for propane dehydrogenation.

CAS / MDL: 100-21-0
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