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INORGANIC CHEMISTRY · 2025 · IF 4.7

Core–Shell MIL-125-NH2@FeOOH Nanocomposites for Highly Selective Photocatalytic Oxidation of Methane to Formaldehyde in Water Vapor

Xian-Yu Shen,Ya-Nan Wang,Ya-Ting Zheng,Ye Wang,Wen-Wen Dong,Jun Zhao,Dong-Sheng Li

Formaldehyde (HCHO), a crucial industrial chemical, finds extensive applications across diverse sectors, including household products, commercial materials, aviation, and medical supplies. Methane (CH4), as an abundant C1 resource, presents a promising feedstock for HCHO synthesis. However, the direct conversion of CH4 to HCHO remains challenging due to its inherent chemical inertness, characterized by low polarizability and high C–H bond dissociation energy (439 kJ mol–1), coupled with the high reactivity of intermediate products. The development of efficient strategies for selective CH4 oxidation to high-value HCHO under mild conditions is therefore of significant practical importance. In this study, we developed a series of MIL-125-NH2@FeOOH-x heterostructured photocatalysts (FM-x) through the controlled deposition of FeOOH nanoparticles on MIL-125-NH2 surfaces. Comprehensive characterization and photocatalytic evaluations reveal that the optimized FM-1 catalyst facilitates in situ H2O2 generation and subsequent decomposition into hydroxyl radicals (•OH), enabling efficient CH4 photooxidation. Remarkably, the FM-1 catalyst achieves an exceptional HCHO production rate of 197.79 μmol·gcat–1 with >99.99% selectivity in water vapor, significantly outperforming both pristine FeOOH and MIL-125-NH2 components. This work presents a promising photocatalytic system for selective CH4 conversion, offering new insights into the design of efficient catalysts for C1 chemistry.

研究领域: 化学工程 · 材料科学 · 环境科学
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ECS Journal of Solid State Science and Technology · 2024 ·Vol. 13 ·期 5 ·057004 · IF 1.8

Fluorescein@NH2-UiO-66 Probe for Ratiometric Fluorescence Sensing of Trace Phosphate in Water

Yu Ding,Yaru Li,Soufian Chakir,Jun Mei,Xianbiao Wang

Phosphate pollution leads to deterioration in water quality, posing a serious threat to human health. Therefore, it is important to develop a highly selective and sensitive fluorescent probe for phosphate detection. Here, we report a novel ratiometric fluorescent probe, Fluorescein@NH2-UiO-66 (denoted as Flu@NH2-UiO-66), for the trace detection of phosphate in water. Specifically, during the in situ solvothermal synthesis of Flu@NH2-UiO-66, fluorescein molecules were encapsulated into the cavities of the metal-organic framework. Furthermore, the encapsulation amount of fluorescein was controlled by adjusting the acidity of the system. The Flu@NH2-UiO-66 (60 H+) sample, prepared with a 60:1 molar ratio of acetic acid to the metal center exhibited distinct dual fluorescence signal peaks. The probe showed a highly selective fluorescence response to phosphate. Within a range of 0–20 μM phosphate concentration, the probe demonstrated excellent linear detection capability with a detection limit of 0.37 μM. Moreover, the mechanism of fluorescence enhancement can be attributed to the addition of phosphate, which greatly increases the UV absorbance of the probe. This study developed a novel ratiometric fluorescent probe capable of rapid, sensitive, and stable detection of trace phosphate, which is of great significance for environmental management.

研究领域: 环境科学 · 分析化学
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DALTON TRANSACTIONS · 2015 ·Vol. 44 ·期 41 ·18012-18018 · IF 4.197

Insights into the dehydrogenation reaction process of a K-containing Mg(NH2)2–2LiH system

Yongfeng Liu,Yaxiong Yang,Xin Zhang,You Li,Mingxia Gao,Hongge Pan

The thermal dehydrogenation process of the KOH-containing Mg(NH2)2–2LiH system was systematically investigated by identifying changes in the structure and composition of its components by XRD and FTIR. During ball milling, the added KOH reacts with Mg(NH2)2 and LiH to produce MgO, KH and Li2K(NH2)3. During the initial heating process (<120 °C), the newly formed KH and Li2K(NH2)3 react with Mg(NH2)2 and LiH to yield MgNH, LiNH2 and Li3K(NH2)4 along with hydrogen release. Raising the temperature to 185 °C results in a reaction between Mg(NH2)2, MgNH and LiH that gives Li2Mg2N3H3 as the product and further releases hydrogen. As the temperature is increased to 220 °C, Li2Mg2N3H3 reacts with LiNH2 and LiH to produce Li2MgN2H2 and H2. Meanwhile, two parallel reactions between Li2Mg2N3H3, Li3K(NH2)4 and LiH also generate additional hydrogen. Specifically, the KH and Li2K(NH2)3, formed in situ during ball milling, serve as reactants in the dehydrogenation reaction of the Mg(NH2)2–2LiH system, which is responsible for the significantly improved thermodynamics and kinetics of hydrogen storage.

研究领域: 材料科学 · 化学工程
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JOURNAL OF HAZARDOUS MATERIALS · 2024 · IF 12.2

Co-adsorption performance of iodine and NOX in iodine exhaust gas by NH2-MIL-125

Xuanhao Liang,Guangyuan Chen,Hao Zhang,Ling Zhang,Tao Duan,Lin Zhu

Ti-based MOFs exhibit ultra-high stability in radioactive waste gases containing nitrogen oxides (NO X ) and are effective in capturing radioactive iodine. In this study, NH 2 -MIL-125 was synthesized via a one-pot solvothermal method and its adsorption performance for iodine was investigated using batch adsorption experiments, the stability of materials was tested by simulating post-processing conditions. The results indicated that NH 2 -MIL-125 had a maximum iodine adsorption capacity of 1.61 g/g at 75 ℃ and reached adsorption equilibrium within 60 min, and the adsorption capacity of methyl iodine reached 776.9 mg/g. The material also exhibited excellent stability and iodine adsorption performance in the presence of NO X . After soaking in NO 2 for 24 h, its structure remained stable and the adsorption capacity for iodine remained at 231.5 mg/g. The excellent co-adsorption performance of NH 2 -MIL-125 on iodine and NO X was attributed to the synergistic effects of Ti-OH groups and amino functional groups. These findings provide a reference for the capture of radioactive iodine and also demonstrate the potential of NH 2 -MIL-125 for iodine capture during spent fuel reprocessing .

研究领域: 材料科学 · 环境科学 · 核能工程
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JOURNAL OF ALLOYS AND COMPOUNDS · 2025 · IF 6.3

New insights on how metal clusters in MIL-68-NH2 influence the photocatalytic nitrogen fixation

Qiufan Sun,Yuxiang Zhu,Yan Wang,Zhengtao Jia,Xiang Zhong,Jianfeng Yao

Three isostructural MIL-68(M)-NH 2 frameworks (M = In, Fe, or Al) featuring different metal centers were synthesized to investigate their photocatalytic activities for nitrogen fixation. The influence of the metal oxo clusters on the crystalline structures, morphologies, and optical characteristics was examined. MIL-68(In)-NH 2 (MNI) with one-dimensional microrod structures has a larger surface area than bulk MIL-68(Fe)-NH 2 (MNF) and spherical MIL-68(Al)-NH 2 (MNA), and achieves an ammonia generation rate (140.34 μmol g cat −1 h −1 ) ca . 3.4 and 1.6 times higher than those of MNF (37.25 μmol g cat −1 h −1 ) and MNA (87.5 μmol g cat −1 h −1 ), respectively. The superior performance can be attributed to its high crystallinity, strong coordination between the In−oxo clusters and ligands, and microrod morphology, which enhance electron transfer, improve mass transport, and extend visible light absorption. Moreover, MNI shows greater stability in ethanol aqueous solution than other sacrificial reagents, such as methanol, potassium sulfite, and triethanolamine. While slight surface corrosion of the microrods occurs in methanol and potassium sulfite solutions, complete collapse is observed in triethanolamine.

研究领域: 材料科学 · 环境科学 · 化学工程
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JOURNAL OF MOLECULAR LIQUIDS · 2020 · IF 5.065

Effective toluene adsorption over defective UiO-66-NH2: An experimental and computational exploration

Xiaoyu Shi,Xiaodong Zhang,Fukun Bi,Zenghui Zheng,Lijun Sheng,Jingcheng Xu,Zhong Wang,Yiqiong Yang

In this thesis, defective UiO-66-NH 2 using cetyltrimethylammonium bromide (CTAB) as a template was successfully synthesized. The toluene adsorption-desorption properties were studied using breakthrough experiments and temperature programmed desorption (TPD). Modified UiO-66-NH 2 showed a high toluene increase due to the increased specific surface area and total pore volume and extra accessible adsorption sites generated by defects. Additionally, adsorption mechanisms were discussed at micro and molecule levels in light of density functional theory (DFT) calculations. By calculation, the amino hydrogen bonding gave rise to a higher toluene adsorption over UiO-66-NH 2 . In terms of the modified UiO-66-NH 2 with the most deficiencies, synergistic effects among π-π, -NH 2 , OH-CH 3 and OH-π hydrogen bonding strength also significantly intensified toluene adsorption. Furthermore, it could be noted that the OH-π interaction was stronger than the two bonded μ 3 -OH mechanisms. Notably, TPD and binding energies (BEs) depicted that defective UiO-66-NH 2 had a weaker toluene affinity than did UiO-66-NH 2 . Thus, gas toluene was easy to desorb with defective UiO-66-NH 2 at 298 K under atmospheric pressure. Finally, the repetitive regeneration experiment showed that the reproducibility of the materials was excellent.

CAS / MDL: 57-09-0 10026-11-6
研究领域: 材料科学 · 环境科学 · 计算化学
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Journal of Environmental Chemical Engineering · 2021 · IF 5.909

Adsorption of phosphate on UiO-66-NH2 prepared by a green synthesis method

Xiaoting Zhang,Mingyu Liu,Runping Han

In this study, a zirconium-based metal organic framework (UiO-66-NH 2 ) was prepared with a green synthetic method for removal of phosphate from solution. Several characterization methods were performed and the adsorption property of UiO-66-NH 2 toward phosphate was explored in batch mode. There was a good adsorption performance for phosphate with a wide range of pH (pH = 2–11) with a slight effect of salinity . The adsorption capacity was up to 43.9 mg·g –1 at 303 K from experiments. The adsorption isotherms can be better described by Langmuir, Temkin, and Koble-Corrigan model while adsorption kinetics can be well fitted by Pseudo-second-order, Double Constant and Elovich model. The process was spontaneous and exothermic and the major mechanism of phosphate adsorption was complexation. The spent adsorbent can be well regenerated using 0.01 mol·L –1 NaOH. The study shows that UiO-66-NH 2 has the potential to remove phosphate from solution.

CAS / MDL: 10312-55-7 10026-11-6
研究领域: 环境科学 · 材料科学
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RSC Advances · 2022 ·Vol. 12 ·期 38 ·24670-24680 · IF 4.036

Postsynthetic of MIL-101-NH2 MOFs supported on PVDF membrane for REEs recovery from waste phosphor

Wei Qin,Along Yu,Xue Han,Junwei Wang,Jiayin Sun,Jianli Zhang,Yaqing Weng

With the increasing demand for rare earth elements (REEs) due to their wide application in high technology, their recovery and separation from waste sources has gradually come onto the agenda. Herein, a new kind of MIL-101-NH2 (M1N) MOF functionalized with diethanol anhydride (DGA) incorporated into a polyvinylidene fluoride (PVDF) membrane (DGA-M1N@PVDF) has been fabricated for the sorption of REEs from a simulated acid leaching solution of waste phosphor, which contains a large amount of REEs. FTIR, TGA, XRD, fluorescence spectra and XPS analysis were used to characterize the synthesized composite membrane. Batch tests were employed to determine the optimal sorption conditions for Y and Eu adsorbed on DGA-M1N@PVDF adsorbent, such as pH (1–5), content of M1N MOFs (0–40 wt%), contact time (10–180 min) and ion concentration (0–20 mg L−1). Maximum adsorption capacities for Y and Eu on DGA-M1N@PVDF reached 991.7 μg g−1 and 98.76 μg g−1 for trace REE solution, respectively. Moreover, a pseudo-second-order kinetic model accurately described the sorption process, and the plotted isothermal data indicated that the Langmuir model was more suitable than the Freundlich model for Y and Eu sorption with monolayer and chemical adsorption. Meanwhile, FTIR and XPS analyses revealed that the Y and Eu adsorption on the DGA-M1N@PVDF composite membrane was mainly caused by the N and O atoms of the –CONH or –COOH groups coordinated with metal ions. Furthermore, after five cycles, the recovery efficiency by DGA-M1N@PVDF for REEs remains above 82% and the XRD patterns were consistent with the original sample, which implied that the DGA-M1N@PVDF membrane has preferable stability, recyclability and good efficiency in REE separation from waste phosphor solutions.

研究领域: 材料科学 · 环境工程
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Catalysts · 2020 ·Vol. 11 ·期 1 ·24 · IF 3.52

The Research on the Construction and the Photocatalytic Performance of BiOI/NH2-MIL-125(Ti) Composite

Juan Du,Jiaxin Zhang,Tingyu Yang,Renming Liu,Zhiyi Li,Dandan Wang,Tong Zhou,Yucun Liu,Chunbo Liu,Guangbo Che

The BiOI/NH2-MIL-125(Ti) composite photocatalyst with excellent photocatalytic performance was prepared by the solvothermal method. For the BiOI/NH2-MIL-125(Ti) (BNMT) system, the contents of NH2-MIL-125(Ti) in BNMT-4, BNMT-5, BNMT-7, BNMT-9, and BNMT-10 were 4 wt %, 5 wt %, 7 wt %, 9 wt %, and 10 wt %, respectively. XRD, XPS, SEM, and TEM characterizations indicated that BiOI/NH2-MIL-125(Ti) was successfully prepared. Brunauer, Emmett, and Teller (BET) and UV–vis diffuse reflectance spectra photoelectrochemical analysis indicated that BNMT-9 can make the specific surface area and photo absorption region larger than BiOI. In addition, the separation efficiency of photogenerated carriers was improved, and the recombination efficiency was reduced. The degradation percentages of Rhodamine B (RhB) and p-chlorophenol (P-CP) reached 99% and 90% over BNMT-9 under visible light irradiation. Additionally, the catalysts had high stability. The results of the active spices trapping experiments test indicated that h+was the main active species. The possible degradation mechanism was proposed.Keywords:photocatalysis;BiOI;NH2-MIL-125(Ti);organic pollutants

研究领域: 材料科学 · 环境科学
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Arabian Journal of Chemistry · 2020 · IF 4.762

Adsorption behavior of Pd(II) ions from aqueous solution onto pyromellitic acid modified-UiO-66-NH2

Zhen Huang,Chen Wang,Jiling Zhao,Shixing Wang,Yang Zhou,Libo Zhang

A new adsorbent was successfully fabricated by chemically linking pyromellitic acid onto a zirconium-based metal-organic framework composite for selective adsorption of Pd(II) from an aqueous solution. The adsorbent was characterized by Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller equation and scanning electron microscope. The adsorption capacity, selectivity and repeatability of the adsorbent were tested by batch experiments. The optimum pH was 2.0, and the maximum adsorption capacity at room temperature was 226.1 mg/g. In the kinetic experiments, the adsorption process achieved equilibrium within 5 h and generally conformed to the quasi-second kinetics and Freundlich isotherm model. The N-H and O H groups on the adsorbent interacted with Pd(II) by electrostatic and coordination action. The adsorbent maintained excellent adsorption capacity after at least 5 cycles. At the same time, the selectivity of the adsorbent in aqueous solution is excellent from interfering ions. Therefore, the new adsorbent will have an obvious application prospect on the recovery of palladium.

CAS / MDL: 10312-55-7
研究领域: 化学 · 环境科学
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Journal of Environmental Chemical Engineering · 2023 · IF 7.7

Bi2Sn2O7/UiO-66-NH2 heterojunction photocatalyst simultaneously adsorbed and photodegraded tetracycline

Chengdeng Yang,Sheng Feng,Changchang Ma,Yun Zhou,Xiaojun Dai,Zhiwei Ye,Yang Wang

A series of Bi 2 Sn 2 O 7 /UiO-66-NH 2 nanoparticles were synthesized by in-situ solvothermal method as efficient adsorption and visible-light-driven photocatalysts for the removal of tetracycline(TC). Among them, the BUN16 presents excellent adsorption and degradation ability for the TC, which is more than 3.6 times that of monomers . The adsorption-enhanced degradation mechanism of BUN16 nanomaterials was revealed via BET, XPS, Zeta potential , FT-IR, EPR, EIS and kinetic analysis, meanwhile the performance of removing TC decreased slightly after five cycles. The excellent catalytic performance can be attributed to its excellent adsorption capacity and the synergistic effect of the Z-type heterojunction charge transfer mechanism. This work provides a basic principle for the scientific construction of Z-type heterojunction materials with adsorption catalytic function to remove TC in actual wastewater.

研究领域: 环境科学 · 材料科学
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INORGANIC CHEMISTRY · 2023 · IF 4.6

Synergistic Enhancement of Photocatalytic H2 Evolution over NH2-MIL-125 Modified with Dual Cocatalyst

Jun-Qing Ye,Yan-Zi Dai,Shu-Ying Xu,Pin-Xi Wang,Zhong-Hua Sun,Jun-Feng Qian,Qian Liang,Ming-Yang He,Qun Chen

The construction of efficient photocatalysts for water splitting to enable H2 evolution is pivotal to alleviate energy issues and environmental concerns. In this work, carbon dots (CDs) were prepared by employing “green solvent” ionic liquids as carbon sources and then combined with Pt/NH2-MIL-125, resulting in the emergence of a high-efficiency photocatalyst termed CDs-Pt/NH2-MIL-125 for the first time. This composite photocatalyst exhibited outstanding photocatalytic activity in H2 production under visible light irradiation. Notably, the H2 production rate of CDs100-Pt/NH2-MIL-125 reaches up to 951.4 μmol/g/h, which was 3.1 times that of Pt/NH2-MIL-125. The characterization results indicate that CDs and Pt uniformly dispersed on the surface of NH2-MIL-125 and fabricated a synergistic compact structure, providing a high BET surface area (985 m2 g–1) and a suitable band gap. Furthermore, the distinctive embeddable-dispersed CDs and Pt, as dual cocatalyst, can harvest light and facilitate the transfer of photogenerated electrons, thereby significantly augmenting the exploitation of visible light. The plausible mechanism of photocatalytic H2 evolution over the CDs-Pt/NH2-MIL-125 catalyst was also discussed. This work introduces a promising strategy for designing high-performance CDs-MOFs-based photocatalysts, an innovative step toward achieving efficient photocatalytic water splitting for H2 production.

CAS / MDL: 10312-55-7 18497-13-7
研究领域: 材料科学 · 能源化学
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