MICROPOROUS AND MESOPOROUS MATERIALS
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2019
·
IF 4.182
Weina Shi,Yanqing Zhu,Cong Shen,Jifu Shi,Gang Xu,Xiudi Xiao,Runqiang Cao
Thermochemical heat storage based on inorganic salt hydrates is a promising approach to relieve the heat energy supply and demand conflicts, but there exist lots of defects of pure salts when applied to the thermochemical. This paper attempted to use functionalized Metal-Organic Frameworks (MOFs) as the porous matrices to improve the heat storage performance of inorganic salt hydrates. A series of MOFs/CaCl 2 composites based on MIL-101(Cr)-X (X = -NH 2 , –SO 3 H, H, –CH 3 , –F) were successfully synthesized and fully characterized by combining multiple techniques (i.e. powder X-ray diffraction, scanning electron microscopy , energy-dispersive X-ray analysis, N 2 adsorption-desorption, Fourier transform infrared spectroscopy , thermogravimetric and differential scanning calorimetry). The water sorption properties of the series of MOFs/CaCl 2 composites were studied during the hydration process, and a continuous adsorption/desorption experiment was also performed to investigate the cycle stability of the MOFs/CaCl 2 composites. The results show that the hydrophilic MOFs based composites have higher water sorption capacity (0.6 g(H 2 O)/g(sample) for MIL-101(Cr)–SO 3 H/CaCl 2 ) accompanied with higher heat storage density (1274 J/g for MIL-101(Cr)–SO 3 H/CaCl 2 ). Moreover, the series of MOFs all presented excellent cycle performance with little loss after continuous 17 adsorption/desorption cycles.
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Journal of Environmental Sciences
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2026
·
IF 6.5
Mengqi Zhong,Hongrui Ma,Chao Zhu,Tingting Qu,Wenjie Quan
● The differences in the adsorption mechanisms of MIL-101(Fe) for small molecular ligands, larger molecular ligands, and mixed-ligand complexes were investigated. ● The adsorption capacity of MIL-101(Fe) for TA-Cr(Ⅲ) was superior to that of other ligands, with a maximum adsorption amount reaching 183.15 mg/g. ● The adsorption competitive of TA-Cr(Ⅲ) is stronger than that of EDTA-Cr(Ⅲ) and TA-EDTA-Cr(Ⅲ) in the mixed solution. ● The order of binding affinities for different interactions was clarified by combining DFT calculations. The ubiquity of diverse organic-Cr(Ⅲ) complexes in industrial effluents poses a significant challenge to water remediation due to their high stability and complex competitive behaviors. In this study, MIL-101(Fe) was employed to decipher the differential adsorption behaviors and mechanisms of single and co-existing Cr(Ⅲ) complexes, specifically targeting natural (Tannic acid (TA)) and anthropogenic (EDTA) ligands. The experimental results revealed a distinct selective hierarchy as TA-Cr(Ⅲ) > free Cr(Ⅲ) > EDTA-Cr(Ⅲ) > TA-EDTA-Cr(Ⅲ), with values of 183.15, 134.05, 93.02, and 73.80 mg/g, respectively. Among them, TA-Cr(Ⅲ) demonstrated an extremely strong adsorption capacity. Kinetic and isotherm analyses confirmed a chemisorption-dominated process. Crucially, the competitive mechanism was elucidated by integrating spectroscopic characterization with Density Functional Theory (DFT) calculations. The results revealed that while electrostatic interactions drive the initial approach, the specific affinity of phenolic hydroxyl groups in TA towards the Fe-clusters of metal organic frameworks (MOFs), combined with strong π-π stacking interactions, provides an advantage for TA-complexes. The differences of organic-metal complexes were revealed through analysis of electrostatic potential, frontier molecular orbitals and binding energy. This work provides a fundamental understanding of ligand-dependent competitive adsorption, offering a theoretical basis for the selective removal of complexed heavy metals in realistic aquatic environments. Download: Download high-res image (308KB) Download: Download full-size image
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CHEMICAL ENGINEERING SCIENCE
·
2026
·
IF 5.1
Yingnan Ma,Zixuan Guo,Juan Chen,Shuyan Meng,Zijian Zhang,Jihong Tian,Yanxin Hu,Yijun Fang,Yawen Zhu,Panliang Zhang
High-temperature proton exchange membranes had attracted considerable interest for electrochemical devices such as fuel cells. However, it remained challenging to simultaneously achieve high proton conductivity, effective acid retention, and robust dimensional stability. To address the limitations of conventional filler incorporation, which was insufficient to realize both efficient acid utilization and the construction of continuous proton-conduction networks, we developed a PBI-based mixed-matrix membrane (MMMs) via the in-situ growth of MIL-101(Fe). The in-situ introduced MIL-101(Fe) not only formed a well-dispersed MOFs framework with excellent interfacial compatibility, but also reconfigured the spatial distribution and physicochemical state of phosphoric acid within the membrane, transforming it from disordered accumulation into a continuous hydrogen-bonded pathway for cooperative proton transport. As the extent of MIL-101(Fe) in-situ growth increased, the acid distribution became more uniform, the proton-conduction pathways became more interconnected, the transport resistance was significantly reduced, and the conductivity was markedly enhanced. Meanwhile, the confinement effect of the MOFs channels and their interfacial nanodomains on phosphoric acid effectively suppressed acid loss and substantially improved the dimensional stability of the membrane. This study demonstrated that in-situ grown MIL-101(Fe) not only increased acid accommodation, but more importantly enabled microenvironment regulation and reconstruction of the proton-transport network, thereby providing new insight into the design of high-performance and durable high-temperature proton exchange membranes.
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JOURNAL OF ALLOYS AND COMPOUNDS
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2026
·
IF 6.7
Jun-Chuan Wang,Peng-Liang Zhang,Wen-Bo Zhang,Tai-Sen Zhang,Zi-Yan Zhen,Tian-Yu Wang,Xiang-Xiang Jia,Gang Yu
Modulating localized electronic structures and interfacial charge-transfer pathways in metal-organic framework (MOF)-based heterogeneous catalysts remains a critical challenge for achieving efficient and durable advanced oxidation processes. Herein, a highly crystalline S-scheme NH₂-MIL-101(Fe)@DQ-TFP (NM@DT) core-shell heterojunction was constructed through a microwave-assisted MOF-first in situ growth strategy. Distinct from conventional physical assembly, the anthraquinone-based β-ketoenamine covalent organic framework (COF) shell was integrated with the amino-functionalized MOF core through chemically coupled growth and interfacial hydrogen-bonding interactions, generating a robust core-shell interface. This intimate interfacial coupling induces spontaneous electronic redistribution and charge polarization, which are verified by X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and density functional theory calculations, thereby providing the electronic basis for an internal electric field-assisted S-scheme charge-transfer pathway. The optimized NM@DT-3 heterostructure exhibits enhanced photocatalytic tetracycline degradation performance, achieving 90.70% removal efficiency within 180 min without external H₂O₂ addition. The core-shell configuration not only promotes interfacial charge separation but also creates a spatially confined catalytic microenvironment, enabling efficient oxygen activation and reactive oxygen species evolution coupled with localized H₂O₂ activation at adjacent Fe centers. Mechanistic investigations reveal that freely diffusing hydroxyl radicals (·OH) make only a minor contribution under the tested conditions, whereas superoxide radicals (·O₂⁻), photogenerated holes (h⁺), and singlet oxygen (¹O₂) participate in TC oxidation. In this reaction network, ·O₂⁻ acts as a key intermediate linking photocatalytic O₂ reduction to both H₂O₂ formation and a proposed h⁺-mediated ¹O₂ generation pathway. The reduced reliance on conventional bulk ·OH-dependent chemistry is consistent with the retained catalytic activity of NM@DT-3 under alkaline conditions, with a TC removal efficiency of 77.74% at pH 10. Meanwhile, the chemically integrated core-shell structure effectively suppresses iron leaching, with only 0.107 mg L⁻¹ Fe released during the photocatalytic process. This work provides new insights into engineering chemically coupled MOF/COF interfaces for regulating interfacial charge migration and ROS evolution, offering an effective strategy for constructing stable photo-self-Fenton catalysts for environmental remediation.
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ChemSusChem
·
2026
·Vol. 19
·期 7
·e202502250
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IF 5.9
Junjie Zhang,Jingai Shao,Liwen Fu,Zhong Lin,Xiong Zhang,Shihong Zhang,Haiping Yang,Hanping Chen
Developing biomass-based solid acid catalysts and converting biomass-derived molecules into high-value chemicals has a dual promoting effect on the high-value utilization of waste biomass. This study introduces a groundbreaking one-pot hydrothermal strategy integrating biomass with MIL-101(Cr) precursor to fabricate hierarchical carbon-based catalysts for the highly efficient and selective dehydration of xylose to furfural, achieving 67.2%–72.0% furfural yield (a 33% enhancement over conventional biomass-derived catalysts) under optimized conditions (180°C, 3 h) in a toluene/water biphasic system. The modified hydrochar exhibits an ultra-high surface area of 2119.3 m 2 /g, abundant dual Lewis/Brønsted acid sites, and dispersed Cr 3+ active centers, enabled by synergistic MOF-templated modification engineering and biomass hydrothermal carbonization. Moreover, the correlation between the physicochemical properties and catalytic performance of modified hydrochar was analyzed. Notably, biomass feedstocks with low ash content and high nitrogen content can yield modified hydrochar with more acidic active sites, which exhibits superior catalytic activity. This study provides new ideas for the high-value utilization of waste biomass.
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高影响因子
Advanced Composites and Hybrid Materials
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2022
·Vol. 5
·期 4
·2896-2905
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IF 11.806
Xu Haitao,Zu Mei,Cheng Haifeng,Liu Dongqing,Xie Wei
The thermal management of electronic devices has attracted significant research attention in the recent year. However, the commonly used thermal management materials at this stage are mainly phase change materials (PCMs), which are limited by their relatively low enthalpy. In this study, the metal–organic framework MIL-101(Cr) was synthesised by an environmentally friendly and low-cost L-malic acid as the mineralising agent. The as-prepared MIL-101(Cr) composite coating was utilised as a sorbent for a passive thermal management strategy, through a vapour sorption–desorption process. By coating the as-prepared MIL-101(Cr) powder onto a metal substrate, a temperature drop for 25 min (maximum 8.6 °C) was achieved for 0.256 g of coating at a heating power of 2.5 W. The use of latent heat has emerged as an attractive method for intermittent heat dissipation. The equivalent enthalpy of the composite coating could reach as high as 1171.9 J/g coating , indicating a significant improvement in the thermal management performance compared with the conventional PCMs. Graphical abstract
Summary: A composite coating for thermal management was obtained by silicate solution and powder MIL-101(Cr).
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CHEMICAL PAPERS
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2022
·Vol. 76
·期 7
·4379-4392
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IF 2.146
Zhang Huixian,Hu Xizhou,Xia Hong,Zhou Youxiang,Peng Lijun,Wu Jianyuan,Peng Xitian
Phenoxy carboxylic acid herbicides (PCAs) are widely used in agricultural production. However, due to their potential threat to human health, it is necessary to develop efficient analysis method for monitoring PCA concentration in environment and food samples. Based on dispersive micro-solid phase extraction (D-μ-SPE) with amine-functionalized metal–organic framework MIL-101(Fe)-NH 2 , a selective, sensitive, and cost-efficient method was proposed for the extraction of PCAs from environmental water and rice samples in this study. From the perspective of adsorption kinetics and isotherms, interaction mechanisms between MIL-101(Fe)-NH 2 and PCAs were investigated. Key parameters of D-μ-SPE procedure including adsorbent dosage, solution pH, ionic strength, eluting solution, and washing solutions were optimized. Using of small amount of MIL-101(Fe)-NH 2 could achieve desirable extraction effect due to its large surface area and multiple interactions with PCAs. Under the optimized D-μ-SPE conditions, calibration curves of 8 PCAs were linear within a concentration range of 0.05–5 ng/mL for water samples ( r 2 > 0.9898) and 0.5–50 ng/g for rice samples ( r 2 > 0.9879). Limits of detection of water and rice samples were as low as 0.004–0.008 ng/mL and 0.05–0.1 ng/g, respectively. The recoveries of 8 PCAs ranged from 83.0 to 109.3%. Both inter- and intra-day relative standard deviations were less than 10.3%. Our proposed method was successfully employed in actual environmental water and rice samples.
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NEW JOURNAL OF CHEMISTRY
·
2022
·Vol. 46
·期 38
·18418-18425
·
IF 3.925
Fangfang Li,Yan Chen,Aijia Gao,Wenjing Tong,Changchun Ji,Yong Cheng,Ying-Hua Zhou
It is highly desired yet an enormous challenge to exploit efficient catalysts for epoxide cycloaddition with carbon dioxide to achieve the goal of carbon neutrality. Herein, the novel heterogeneous catalysts of MIL-101-IL(RBr) (R = Et, Pr, Bu, and Pe) were synthesized by grafting polypyridyl-based ionic liquids (IL) into the nodes of MIL-101(Cr) through the post-synthetic modification of metal–organic frameworks (MOFs). The octahedral MIL-101-IL(BuBr) with an average size of ca. 800 nm exhibited superior activity for catalyzing epichlorohydrin–CO2 cycloaddition into chloropropene carbonate, with an yield of 92% at 110 °C under 1.0 MPa CO2 without any cocatalyst and solvent. The excellent performance could be attributed to the nucleophilic nature of grafted ionic liquids in the MOF along with the effectiveness of mass transfer afforded by the MOF porosity. Moreover, MIL-101-IL(BuBr) presented a favorable versatility toward other epoxides and a satisfactory recyclability. In addition, a possible mechanism has been proposed for the catalytic reaction of epichlorohydrin–CO2 cycloaddition over MIL-101-IL(BuBr).
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NEW JOURNAL OF CHEMISTRY
·
2022
·Vol. 46
·期 24
·11840-11850
·
IF 3.925
Dongying Zhu,Zhujun Huang,Haiyan Wang,Qiujun Lu,Guihua Ruan,Chenxi Zhao,Fuyou Du
The fabrication of sustainable and reusable photocatalyst materials is urgent and desirable for the removal of emerging pharmaceutical pollutants (EPPs) in environmental water samples. In this work, we described the fabrication of electrospun nitrogen-rich carbon nitrides/MIL-101(Fe)/poly(acrylonitrile-co-maleic acid) nanofibers (E-spun g-C3N5/MIL-101(Fe)/PANCMA NFs) by using electrospinning dispersion solutions of g-C3N5/MIL-101(Fe) and PANCMA, as well as their applications as sustainable and reusable photocatalysts toward a model EPP carbamazepine degradation under light irradiation. The E-spun g-C3N5/MIL-101(Fe)/PANCMA NFs exhibited the highest carbamazepine degradation efficiency of 94.2% within 40 min. The O2˙−, ˙OH, and h+ reactive species all participated in the photodegradation process, and some degradation byproducts of carbamazepine were identified by liquid chromatography-mass spectrometry. Importantly, the electrospun photocatalyst possessed high reusability (at least 15 consecutive runs) and wide applications in the degradation of other EPPs (such as tetracycline and ciprofloxacin), which suggested the great potential of the electrospun photocatalytical nanofibers in the EPPs removal.
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Journal of Inorganic and Organometallic Polymers and Materials
·
2021
·Vol. 31
·期 11
·4195-4208
·
IF 3.543
Wang Lulu,Zeng Xiangrui,Wang Haiyan,Wang Yujia
Abstract A series of porous confined ionic liquid phosphotungstate were synthesized by encapsulated of N-(3-sulfopropyl)morpholinium phosphotungstate ([C 3 SO 3 Hnhm] 3 -PW 12 O 40 ) into MIL-101. Then the aforementioned porous confined ionic liquid phosphotungstate as heterogeneous catalyst will be used together with H 2 O 2 for the catalytic synthesis of adipic acid from cyclohexene. During the experiment, the effect of weight content of [C 3 SO 3 Hnhm] 3 PW 12 O 40 on the catalytic performance was investigated in detail. And the chemical structure of the catalyst was also characterized by XRD, FT-IR, 1 H-NMR, SEM–EDX and N 2 adsorption–desorption isotherms. Experimental results revealed that the desired products has been successfully prepared, and the best catalytic performance (81.2% yield of the adipic acid) was obtained under the dose of [C 3 SO 3 Hnhm] 3 PW 12 O 40 was 31wt%, which was almost close to the catalytic activity of original [C 3 SO 3 Hnhm] 3 PW 12 O 40 (85.3% yield of the adipic acid), which was also proved the strategy of packaging ionic liquid phosphotungstate with MIL-101 in this research is feasible. Furthermore, recycled catalytic performance of the catalyst under repeat 6 times was evaluated and the result revealed that the yield in adipic acid was still higher than 80.0%, which also proved that the catalytic active component was stable in the catalyst. Graphic Abstract
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ACS Applied Nano Materials
·
2021
·
IF 5.097
Jianqiu Gong,Weiwei Zhang,Tapas Sen,Yichen Yu,Yuchen Liu,Jinlong Zhang,Lingzhi Wang
Photocatalysis is a promising technology to treat dilute phenol–Cr(VI) mixture, where photoinduced electrons are commonly thought of as the main active species for Cr(VI) reduction. However, it generally depends on the surface adsorption to achieve efficient electron transfer. Meanwhile, the possible contribution of reductive quinone derivatives oxidized from phenol to Cr(VI) reduction has been rarely explored. The key is to explicitly understand the relation between the phenol oxidation pathway and Cr(VI) reduction. Herein, Ag/AgCl/MIL-101(Fe) prepared by directly loading Ag nanoparticles on MIL-101(Fe) was applied to the joint treatment of phenol and Cr(VI). The role of quinone derivatives in reducing Cr(VI) was revealed by excluding the surface adsorption. During the phenol oxidation, •OH radicals were more consumed in the initial stage for the ring opening of phenol. Meanwhile, 1O2 evolved from •O2– gradually caused the accumulation of reductive quinone intermediates, which dramatically accelerated the Cr(VI) reduction afterward. This study demonstrates the significance of controlling the evolution process of active oxygen species for the joint photocatalytic treatment of phenol–Cr(VI) mixture.
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FOOD CHEMISTRY
·
2021
·
IF 7.514
Yingpan Song,Lina He,Shuai Zhang,Xiao Liu,Kun Chen,Qiaojuan Jia,Zhihong Zhang,Miao Du
Iron-based metal-organic framework, NH 2 -MIL-101(Fe), was doped with different dosages of cobalt phthalocyanine nanoparticles (CoPc) to synthesize a series of NH 2 -MIL-101(Fe)@CoPc nanocomposites. The NH 2 -MIL-101(Fe)@CoPc nanocomposites were then employed to construct novel impedimetric aptasensors for the detection of ochratoxin A (OTA). Combining the intrinsic advantages of NH 2 -MIL-101(Fe) (highly porous structure and excellently electrochemical activity) and CoPc (good physiochemical stability and strong bioaffinity), the NH 2 -MIL-101(Fe)@CoPc nanocomposites show promising properties, which are beneficial for immobilizing OTA-targeted aptamer strands. Amongst, the developed impedimetric aptasensor based on NH 2 -MIL-101(Fe)@CoPc 6:1 , prepared using the mass ratio of NH 2 -MIL-101(Fe):CoPc of 6:1, exhibits the best amplified electrochemical signal and highest sensitivity for detecting OTA. The detection limitation is 0.063 fg·mL −1 within the OTA concentration of 0.0001–100 pg·mL −1 , accompanying with high selectivity, good reproducibility and stability, acceptable regenerability, and wide applicability in diverse real samples. Consequently, the proposed sensing strategy can be applied for detecting OTA to cope with food safety.
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