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MICROCHEMICAL JOURNAL · 2024 · IF 4.9

NH2-MIL-101(Fe) anchored onto nanoporous gold microelectrode: Highly sensitive electrochemical platform for simultaneously sensing of ascorbic acid and uric acid

Yan Chen,Xiaojuan Yang,Zhonggang Liu,Guohua Liu,Zheng Guo

Resolving the issue of poor conductivity and easy aggregation of MOFs is recognized as one important factor for their successful applications in electrochemical sensors and electrocatalysis. In this work, we propose an assembly of NH 2 -MIL-101(Fe) onto a nanoporous gold (NPG) microelectrode surface. The nanoporous gold could greatly improve the conductivity and reduce the aggregation of NH 2 -MIL-101(Fe). The proposed NH 2 -MIL-101(Fe)/NPG microelectrode was developed for the electroanalysis of ascorbic acid (AA) and uric acid (UA). It exhibited excellent electrochemical performance for the individual and simultaneous sensing of AA and UA in a 0.1 M PBS solution (pH 7.4). High sensitivities (2.03 μA μM −1 cm −2 for AA; 29.30 μA μM −1 cm −2 for UA) were achieved in the simultaneous analysis process. The improved electrochemical performance was attributed to the electrocatalytic properties and large specific surface area of NH 2 -MIL-101(Fe)/NPG, as well as the electrostatic interaction between NH 2 -MIL-101(Fe) and analytes. Moreover, the NH 2 -MIL-101(Fe)/NPG microelectrode was successfully used for the simultaneous detection of AA and UA in complicated environment (human sweat and advanced DMEM). This work shows great promise for the simultaneous detection of AA and UA and extends the applications of MOFs in electrochemical devices.

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MICROCHEMICAL JOURNAL · 2024 · IF 4.9

Core-shell MIL-53(Al)–NH2@UiO-66 coated solid-phase microextraction Arrow for the selective enrichment of nine alkylphenols in milk

Peixun Yang,Senwei Jiang,Zhen Wu,Daodong Pan,Hangzhen Lan

Metal-organic frameworks (MOFs) hold significant potential for sample preparation, but single-MOF materials often face limitations in selectivity and extraction efficiency. To overcome these, a mesoporous MIL-53(Al)–NH 2 @UiO-66 composites with a core–shell structure was synthesized using an epitaxial growth strategy. This composite leverages the complementary properties of both MOFs, offering enhanced active sites and interaction forces for analytes. The structure and integration of the composite were characterized using Fourier-transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction, confirming their successful integration. To address the challenge of detecting alkylphenols (APs) in food matrices, known for their endocrine-disrupting properties and low concentrations, a new solid-phase microextraction (SPME) Arrow was fabricated using the MIL-53(Al)–NH 2 @UiO-66 composite combined with polyacrylonitrile as a binder. APs were detected using ultra-performance liquid chromatography and quadrupole time-of-flight tandem mass spectrometry (UPLC-ESI-Q-ToF/MS). The developed SPME Arrow-UPLC-ESI-Q-ToF/MS method exhibits good linearity (R 2  ≥ 0.9958), wide linear range (0.01–1000 μg L –1 ), and high sensitivity (limits of detection ranging from 0.005 to 0.01 μg L –1 ) for APs determination. This method was validated for determining nine APs in milk samples from various packing materials, with spiked recoveries ranging from 85.2 % to 115 % and relative standard deviations from 3.4 % to 13.6 %. This study demonstrates the potential of MOF-on-MOF composites in enhancing the performance of adsorbents for SPME pretreatment, offering a promising approach for improving analytical methodologies in food safety.

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COMPOSITES SCIENCE AND TECHNOLOGY · 2024 · IF 8.3

A honeycomb-inspired carboxymethyl chitosan-covalently link NH2-black phosphorene biobased cellulose green nanocomposites with tremendously enhancement fire safety and thermal conductivity

Kunxin Wang,Zhencai Qu,Hui Yang,Guoming Yuan,Xiu-e Li,Zhijun Liu,Yanhan Tao,Yang Li,Kun Wu,Jun Shi

Biobased carboxymethyl chitosan-modified black phosphorene (BP-CMC) was prepared through an amidation reaction between amino group functionalized black phosphorene (NH 2 -BP) and CMC. Density functional theory (DTF) express that the adsorption energy between urea and phosphene is −6.28 eV, indicating a strong interaction. The resulting BP-CMC was further applied to reinforce the mechanical, flame-retardant and thermal conductivity performance of honeycomb cellulose nanofiber (CNF) film via vacuum filtration. Cone calorimetry test (CCT) result exhibits that the introduction of 30 wt% BP-CMC significantly promoted the fire safety of CNF. For instance, a 98.41% reduction in smoke production rate (SPR), 92.00 % decline in CO release and a 61.31% decrease in heat release rate (HRR) were observed compared to neat CNF. Furthermore, Thermogravimetric infrared (TG-IR) indicates a significant decrease in the release of flammable gases. Raman spectra verify that the incorporation of 30 wt% BP-CMC improves the graphitization degree of residual chars, thus limiting the transfer of heat and oxygen. The improvement in fire safety is attributed to the formation of an intumescent flame-retardant system, which is rich in carbon source (CMC), acid source (BP) and gas source (amino). Simultaneously, the introduction of 30 wt% BP-CMC into CNF leads to considerable enhancement in thermal conductivity (up to 17.49 %), thermal diffusion (utmost to 43.45 %) and heat capacity (increased by 19.23 %). Moreover, the 30 wt % addition of BP-CMC into CNF possesses excellent mechanical properties with the improvement of toughness (increased by 143.50 %) and tensile strength (increased by 140.90 %). This strategy not only provides a new strategy for functionalizing BP but also upgrades the application potential of BP nanosheets in the fire safety of polymer composite films.

CAS / MDL: 25952-53-8
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INORGANIC CHEMISTRY COMMUNICATIONS · 2025 · IF 5.4

Synthesis of NH2-MIL-101(Fe)/BiOI composites with enhanced visible light response photocatalytic properties for the removal of tetracycline in water

Rui Zhang,Lingqiao Hu,Zixi Li,Jingjing Hao

The special layered structure and narrow band gap of BiOI semiconductors lead to a high recombination rate of photogenerated electrons and holes. Therefore, it is compounded with the porous structure of the metal–organic backbone NH 2 -MIL-101(Fe) to form heterojunctions and provide more active sites. In this paper, NH 2 -MIL-101(Fe)/BiOI composites were successfully prepared by solvothermal method, which has a high specific surface area and adjustable pore size, which is conducive to the effective separation and transport of photogenerated electrons and holes, thereby improving the photocatalytic efficiency. The results of XRD, SEM, XPS and other characterization experiments show that NH 2 -MIL-101(Fe)/BiOI composites have been successfully prepared. Secondly, ultraviolet diffuse reflectance spectroscopy (UV–vis DRS) was used to test the light absorption performance of the composites, which confirmed that the materials had a larger visible light range. Through PL, EIS confirmed that the efficiency of photogenerated electron and hole separation was further improved. In addition, the M–S curves of NH 2 -MIL-101(Fe) and BiOI were tested to calculate the valence and conduction band values of the material. Combined with the results of free radical trapping experiments, O 2 − and h + play a major role in the degradation of tetracyclines and can be degraded into CO 2 and H 2 O. The Z-type electron transfer mechanism of the composites is deduced, which can improve the separation rate of electrons and holes. In addition, the cyclic test verified that the composite material has good stability. When the tetracycline concentration was 30 mg/L, the degradation rate of the 10 % NH 2 -MIL-101(Fe)/BiOI composite reached 93.3 %. Its materials also have certain potential application value in environmental treatment, energy conversion and other fields, especially for the treatment of pollutants in water bodies.

CAS / MDL: 7727-43-7
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APPLIED SURFACE SCIENCE · 2024 · IF 6.3

Synergy of sulfur vacancy and piezoelectric effect to tune charge migration in Sv-ZnIn2S4/UiO-66-NH2 for efficient photocatalytic H2 evolution

Ming Fang,Zhenfei Yang,Yang Guo,Shuqin Yuan,Xinnian Xia,Shuaijun Pan

High-performance photocatalytic H 2 evolution materials require strong light absorption capability, excellent photogenerated charge separation ability and efficient charge carrier migration capability. In this study, we designed a piezoelectric photocatalytic heterojunction composed of UiO-66-NH 2 and ZnIn 2 S 4 nanosheets with sulfur vacancies. The Sv-UZ-45 heterojunction achieved piezoelectric photocatalytic H 2 evolution performance of 3886.4 μmol·g -1 ·h -1 , with a 4.6 times enhancement due to the synergistic effect of piezoelectric effect and defect engineering. The introduction of sulfur vacancies enables the heterojunction to obtain stronger light absorption, while the higher CB position of rich-sulfur vacancies ZnIn 2 S 4 is more favorable for the photocatalytic reduction reaction. In addition, the heterojunction with rich-sulfur vacancies exhibits a stronger piezoelectric effect than without vacancies, thus providing a powerful driving force for the separation of photogenerated charge carriers. Finally, ESR was used to explain the potential photocatalytic mechanism and showed that Sv-UZ-45 adheres to the Z-scheme carrier migration pathway. This work elucidates the synergistic interaction between piezoelectric effect and defect engineering, providing new insights for the further development of high-performance piezoelectric photocatalysts.

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JOURNAL OF MEMBRANE SCIENCE · 2025 · IF 9

In-situ grown NH2-ZIF-8 with optimized polymers compatibility and rigidity for enhanced CO2/CH4 separation performance in mixed matrix membranes

Zikang Li,Guangyao Fan,Muning Chen,Qin Shen,Shenzhen Cong,Roberto Castro-Muñoz,Dongyang Li,Jing Wang,Yatao Zhang

By combining the advantages of polymers and porous nano-fillers, mixed matrix membranes (MMMs) have demonstrated outstanding gas separation performance. However, the ideal matching between polymers and nano-fillers is still a challenge especially under high filler loading conditions. To address this interfacial challenge, an in-situ grown amino-functionalized ZIF-8 (NH 2 -ZIF-8) is embedded in 6FDA-DAM to prepare MMMs. Compared to ZIF-8, NH 2 -ZIF-8 not only can enhance compatibility and interfacial adhesion because of the extensive hydrogen bonding, but also effectively modulates its structural flexibility by increasing the rigidity of Zn–N bonds within the ZIF-8 framework. The enhanced framework rigidity of NH 2 -ZIF-8 successfully improves the CO 2 /CH 4 separation capability of the MMMs. Under a high filler loading of 30 wt%, the CO 2 /CH 4 selectivity of the optimized NH 2 -ZIF-8/6FDA-DAM MMMs reached 35.1 and the permeability reached 1225.9 Barrer, which increased by 25.36 %, and 8.94 % respectively compared to the ZIF-8 MMMs, exceeding the 2008 Robeson upper bound. Molecular simulations further reveal the enhanced diffusion selectivity of NH 2 -ZIF-8 and the strong interactions between surface –NH 2 groups and electron-rich O/F heteroatoms in the 6FDA-DAM polyimide matrix. These simulations quantitatively elucidated the critical role of interfacial structure in determining gas separation performance. The mechanistic insights provided in this study offer valuable theoretical guidance for the development of high-performance membrane materials for CO 2 capture and gas purification applications.

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MICROCHEMICAL JOURNAL · 2025 · IF 5.1

A novel ferrofluid based on hydrophobic deep eutectic solvent and Fe3O4@NH2-graphene oxide for the analysis of estrogens from various samples

Tiemei Li,Xin Zhang,Lichong Duan,Shuhao Cui,Yingyu Chang,Xia Zhang

A new ferrofluid based on hydrophobic deep eutectic solvent and Fe 3 O 4 @NH 2 -graphene oxide was designed, and then used as extraction medium for the extraction and analysis of estrogens in water by coupled with vortex-assisted liquid-liquid micoextraction and high performance liquid chromatography. The morphology, structure, thermal stability and magnetic property of the material were studied by scanning electron microscope (SEM), Fourier Transform-Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and vibrating sample magnetometer (VSM). Four estrogens, including estradiol (E2), ethinyl estradiol (EE2), bisphenol AP (BPAP) and hexestrol (HEX), were used as the model analytes. Key parameters related to the ferrofluid preparation and extraction conditions were optimized by single-factor and response surface method. Under the optimal conditions, good linearity (R 2  > 0.99) in the concentration ranges of 0.1–200, 0.2–200, 0.007–200 and 0.15–200 μg/L were obtained for E2, EE2, BPAP and HEX, respectively. The limits of detection for E2, EE2, BPAP and HEX were 0.030, 0.070, 0.002 and 0.05 μg/L, respectively. The established method was successfully applied for the quantification of E2, EE2, BPAP and HEX in urine, environmental water, beverage and package samples. The method was simple, rapid, sensitive and producible.

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SENSORS AND ACTUATORS B-CHEMICAL · 2025 · IF 7.7

On-Site AFB1 detection in food via dual-equipped NH2-ZIF-8@Cu2+ and core-shell UCNPs embedded in SA-PAM hydrogel

Huanhuan Li,Yu Wu,Xorlali Nunekpeku,Yuhan Yang,Jingsa Zhao,Wei Sheng,Yuexia Wang

The increasing presence of Aflatoxin B 1 (AFB 1 ) residues in food continues to raise significant public health concerns. Herein, we designed an upconversion-based sensor integrated into an alginate-polyacrylamide (SA-PAM) hydrogel for on-site AFB 1 detection in food. First, core-shell upconversion nanoparticles (CSUCNPs) with enhanced fluorescence were modified with complementary DNA (cDNA), forming signal probes known as CSUCNPs-cDNA. Simultaneously, NH 2 -ZIF-8@Cu 2+ with a high surface area and specific affinity for aptamer was synthesized using a one-pot method. This was then modified with an AFB 1 -specific aptamer, forming the capture probe Apt-ZIF-8@Cu 2+ . Using base pairing, CSUCNPs-cDNA and Apt-ZIF-8@Cu 2+ were hybridized into sensing probes (CSUCNPs-ZIF-8@Cu 2+ ), which were embedded into SA-PAM hydrogels as stable sensor carrier. Furthermore, the SA-PAM hydrogel showed a reduced swelling ratio of 1.68–1.80 in water and phosphate buffer solution(s) (PBS), which improves stability. In the presence of AFB 1 , the aptamer selectively binds the AFB 1 , increasing electrostatic repulsion between CSUCNPs-cDNA and Apt-ZIF-8@Cu 2+ . This disrupts Förster resonance energy transfer (FRET), resulting in a pronounced “signal-on” fluorescence. This sensor achieves AFB 1 diffusion through the SA-PAM hydrogel, FRET disruption and upconversion signal stabilization within 18 min, faster than traditional methods. Under optimized conditions, the sensor exhibited a clear linear correlation between fluorescence intensity and the logarithm of AFB 1 concentration ranging from 0.1 to 100 µg/kg ( R ² = 0.994), with a detection limit as low as 0.08 µg/kg. Besides, its performance was further validated through tests on spiked wheat, corn, peanut, and water, demonstrating high accuracy and reproducibility with relative standard deviation (RSD) below 3.63 % and recoveries of 85.88–98.04 %.

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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2025 · IF 3.9

Core–Shell Ag@UiO-66-NH2 with Enhanced Stability and Selective Enrichment for Sensitive SERS Detection of Cr(VI) in Environmental Water

Yiwen Gui,Ao Chen,Yiting Liu,Ning Cai,Jumei Li

A sensitive and stable substrate is crucial in Raman spectroscopic techniques for the effective detection of environmental contaminants. In this study, a novel core–shell composite, Ag@UiO-66, was developed by coating Ag nanospheres with a porous metal–organic framework (MOF), UiO-66-NH2. This composite combines high stability with selective enrichment capabilities for Cr(VI). Leveraging the unique properties of UiO-66-NH2, such as its porosity, abundant amine groups, and Zr nodes, Ag@UiO-66 effectively enriches Cr(VI) through pore-filling, electrostatic interactions, and Zr–O coordination. Direct analysis of water samples spiked with Cr(VI) showed detection limits of 6.53 × 10–8 M in pond water and 7.52 × 10–8 M in lake water. The composite also exhibited excellent signal uniformity and reproducibility, with a low relative standard deviation of 6.78% across 30 batches. Additionally, it demonstrated outstanding recyclability under simulated sunlight irradiation due to the solar photocatalytic properties of UiO-66-NH2. Ag@UiO-66 also showed superior stability compared to pristine Ag nanospheres when exposed to strong acids, bases, or oxidative environments (e.g., 1% H2O2 solution). Overall, Ag@UiO-66 shows great potential as a reliable substrate for the trace detection of chemical analytes via SERS.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2025 · IF 9.7

Atomic layer deposition of ZnO on NH2-MIL-125(Ti) for enhanced selective CO2 to CH4 conversion via S-scheme heterojunction engineering

Jiepeng Zhao,Zijian Li,Yu Zuo,Sai Huang,Zhaomin Tong,Yifei Ma,Liantuan Xiao,Suotang Jia,Xuyuan Chen,Mei Wang

NH 2 -MIL-125(Ti) (NM) is a prototypical metal–organic framework (MOF) photocatalyst with visible-light responsiveness. However, its practical application in CO 2 reduction is significantly limited by fast charge carrier recombination and poor product selectivity. Constructing heterojunctions with appropriately matched semiconductors offers an effective strategy to overcome these limitations, where coupling material selection and precise interfacial engineering are key. ZnO, a stable n-type wide-bandgap semiconductor, not only possesses excellent electron mobility but also exhibits suitable conduction band alignment with NM, enabling favorable interfacial charge transfer. Moreover, ZnO can form an interfacial Ti–O–Zn bonding bridge with NM, facilitating directional electron transport and suppressing charge recombination. In this work, we employed atomic layer deposition (ALD) to construct uniform ZnO shells on NM with sub-nanometer precision, thereby finely tuning the ZnO loading and interface structure. A series of ZnO@NH 2 -MIL-125 (ZnO@NM) composites are obtained by controlling the ZnO loading, with the optimal sample showing the highest activity, yielding 13.30 μmol h −1  g −1 of CO and 5.47 μmol h −1  g −1 of CH 4 . Notably, CH 4 selectivity is significantly improved from 16 % to 29 %, and further increases to 31 % under gas-solid conditions. In situ Fourier Transform Infrared (FTIR) spectroscopy and Density Functional Theory (DFT) calculations reveal that ZnO not only promotes directional interfacial electron transfer but also facilitates the hydrogenation of *CO to *CHO, thus enhancing CH 4 selectivity. This study demonstrates an ALD-enabled interface engineering strategy to construct MOF-semiconductor heterojunctions, offering mechanistic insights and design principles for advancing efficient and selective photocatalytic systems for carbon dioxide reduction.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2025 · IF 8.5

Constructing carboxylated cellulose nanofibers/chitosan aerogel loading with CdS/UiO-66-NH2 for wastewater treatment: Synergistic adsorption and visible light photocatalytic degradation

Ziyao Mi,Xuzhen Liu,Yue Zhang,Bo Wang,Hongyu Guo,Yufeng Chen,Yanyan Du,Xinyu Wang,Xiaojun Hu,Jingxian Jiang

The discharge of industrial effluents containing heavy metal ions and organic dyes has laid heavy burdens on ecosystem, meanwhile, drawing extensive scientific attention globally. In this work, CdS/UiO-66-NH 2 heterojunction was uniformly loading on the aerogel skeleton composed of cellulose (CNF), chitosan (CS) and montmorillonite (MMT). The fabricated composite aerogel noted as CUN-CCMA was equipped with light density, a large specific area and a robust three-dimensional interpenetrating network. The MMT not only reinforced the mechanical stability of the aerogel, but also regulated the distribution of the heterojunction. The CUN-CCMA could adsorb various organic dyes and heavy metal ions, and the maximum adsorption capacities for methylene blue (MB) and Cu 2+ were 111.5 mg/g and 45.1 mg/g, respectively. The corresponding adsorption processes were in better consistence with the pseudo-second-order kinetic model and the Freundlich isotherm. The hydrogen bonding, electrostatic interaction, π-π stacking and chelating effect might be attributed to the adsorption mechanism. Most importantly, the removal efficiency of MB with a high concentration of 300 mg/L could reach 94 % when synergistic effect of adsorption and visible light photocatalytic degradation was exerted. The active species that played vital roles during the photodegradation process were recognized as ·OH and · O 2 − . Furthermore, the CUN-CCMA demonstrated an excellent reusability. These outstanding characteristics of CUN-CCMA broadened its application prospects in complicated sewage treatment.

CAS / MDL: 148-18-5
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JOURNAL OF RARE EARTHS · 2024 · IF 5.2

CeB6 nanoparticles modified Mg(NH2)2-2LiH with superior (de)hydrogenation kinetics and reversible hydrogen storage properties: an experimental and theoretical study

Haoyuan Zheng,Yuxiao Jia,Chen Jin,Hang Che,Chia-Tse Lee,Zhenke Chen,Guang Liu,Li Wang,Shixuan He,Xinhua Wang,Haizhen Liu,Mi Yan

The Mg(NH 2 ) 2 -2LiH composite system is a promising vehicle-mounted hydrogen storage material, but its application is limited due to serious thermodynamic and kinetic barriers. Adding additives can effectively optimize their hydrogen absorption and desorption kinetics and thermodynamic performance. In this work the comprehensive hydrogen storage performance of Mg(NH 2 ) 2 -2LiH with extremely small nano rare earth borides is improved, and a series of characterization methods and density functional theory (DFT) calculation systems was combined to study its hydrogen storage improvement mechanism. The research results show that the method of adding 5 wt% molten salt to prepare nano CeB 6 (24.5 nm) can significantly reduce the initial hydrogen absorption/release temperature of Mg(NH 2 ) 2 -2LiH from 110/130 to 45/90 °C, inhibit the generation of ammonia by-products, and improve hydrogen purity. Under low-temperature hydrogen absorption conditions at 120 °C, the improved sample can absorb 2.81 wt% hydrogen gas, with a hydrogen absorption capacity more than 3.5 times of the unmodified sample. The amount of hydrogen released at 150 °C reaches 3.35 wt%, which is more than twice that of the pristine sample, demonstrating excellent hydrogen absorption and release kinetics performance. After 10 consecutive hydrogen cycles, 4.64 wt% hydrogen can still be released, and the cycle retention rate can be increased from 85% before improvement to nearly 100%, demonstrating good reversibility. Mechanism studies show that nano CeB 6 can effectively weaken the Mg–N and N–H bonds of Mg(NH 2 ) 2 and inhibit the polycrystalline transformation of the hydrogen evolution product Li 2 MgN 2 H 2 at high temperatures. It can also provide nucleation active sites for hydrogen absorption and desorption in the material, making the system possess superior hydrogen absorption and desorption performance and cycling stability. This study provides new insights into the role of rare earth borides in Mg(NH 2 ) 2 -2LiH hydrogen storage materials, both experimentally and theoretically.

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