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SCIENCE OF THE TOTAL ENVIRONMENT · 2018 · IF 4.61

Enhanced Cr(VI) removal from acidic solutions using biochar modified by Fe3O4@SiO2-NH2 particles

Shunquan Shi,Jiakuan Yang,Sha Liang,Mingyang Li,Quan Gan,Keke Xiao,Jingping Hu

Fe 3 O 4 @SiO 2 -NH 2 magnetic particles with core-shell structure were attached on carboxylated biochar derived from phoenix tree leaves to synthesize a novel magnetic biochar for removing Cr(VI) ions from acidic solutions. FSEM, FTEM, XRD characterizations of the synthesized magnetic biochar revealed that the Fe 3 O 4 @SiO 2 -NH 2 magnetic particles distributed uniformly on the surface or macrospores of carboxylated biochar by strong chemical bonding. The Cr(VI) ions adsorption capacity of magnetic biochar was 27.2   mg·g −1 , surpassing original carboxylated biochar (18.2   mg·g −1 ). VSM and XPS characterizations demonstrated that the attached Fe 3 O 4 @SiO 2 -NH 2 magnetic particles not only endowed biochar with perfect magnetic property (23   emu·g −1 ) but also provided complexing sites for binding Cr(III) cations reduced from Cr(VI) anions. The Cr(VI) ions removal by magnetic biochar contained three steps: (1) adsorption of Cr(VI) anions by protonated functional groups; (2) reduction of Cr(VI) anions to Cr(III) cations by electron-donor groups; and (3) chelation of Cr(III) cations by amine groups. The adsorption recycling test showed that magnetic biochar kept 85% of its initial Cr(VI) adsorption capacity at the sixth cycle, and the Fe leakage under pH   1.0 was smaller than 0.25   mg·L −1 . The results indicated that this novel magnetic biochar was applicable for the practical treatment of Cr(VI)-containing wastewater.

研究领域: 环境科学 · 材料科学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2025 · IF 9

One-pot etching UiO-66-NH2 to format orientational deposition AgCl/Ag0 without illumination for high-efficiency photocatalytic removal of Diazinon

Xiaoxia Liang,Jiakang Duan,Yu Tian,Yue Han,Zewan Qin,Huixia Zhu,Yating Lu,Dongyu Nie,Yingna Guo,Xia Yang

AgCl/Ag 0 shows great promise for the removal of environmental pollutants, while its photocatalytic performance is still a great challenge on account of the agglomeration. Herein, orientational deposited and octahedral AgCl/Ag 0 were obtained by etching the UiO-66-NH 2 template for the first time. The 0.35:1–AgCl/Ag 0 exhibited outstanding efficiency in the degradation of Diazinon (DZN), which was closely 300 times than that of UiO-66-NH 2 and 0.35:1–AgCl@Ag 0 prepared without a template. Its bigger surface area provided more active sites to promote mass transfer efficiency and large amounts of •OH and 1 O 2 were fabricated to offense specific positions of DZN determined through Fukui function. Meanwhile, a high removal rate of 91.0 % was obtained after 5 recycles. Finally, the results of HPLC-MS, T.E.S.T., TOC and IC indicated all intermediates had less toxicity than DZN and were rapidly mineralized. Our work developed a new strategy for designing superb performance AgCl/Ag 0 photocatalysts.

CAS / MDL: 10026-11-6 10312-55-7
研究领域: 环境科学 · 材料科学
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APPLIED SURFACE SCIENCE · 2024 · IF 6.3

Significantly enhanced photocatalytic performance of the W-Zr-MOF-NH2@TpTt-COF heterostructure for tetracycline removal by defects engineering

Chunhua Li,Luqian Bao,Yubo Shi,Zhehang Tian,Yixin Ji,Mengyao Cui,Zhilei Zhao,Xianyou Wang

A hollow heterojunction of W-Zr-MOF-NH 2 @TpTt-COF (WZT) was fabricated by combining etched W-Zr-MOF-NH 2 with TpTt-COF. WZT, synthesized through acid etching and hydrothermal methods, showed better tetracycline degradation than pure W-Zr-MOF-NH 2 and pure TpTt-COF due to its larger specific surface area and more active sites. The surface of WZT contains abundant oxygen vacancies (OVs) that capture electrons, promoting the separation of photogenerated e - -h + pairs and increasing WZT’s photocatalytic activity. WZT (1:1, mass) showed 87% degradation of tetracycline under 300 W Xenon lamp irradiation. The results of cycling experiments demonstrated the high stability and reusability of WZT (1:1), making it feasible for production. The excellent photocatalytic degradation of tetracycline by WZT (1:1) originates from the formation of heterojunctions and the presence of surface OVs, which reduces the strong photogenerated e - -h + complexation efficiency. Possible photocatalytic degradation mechanisms are proposed while demonstrating the formation of Z-scheme heterojunction in WZT, which aligned with the experimental results of electron spin resonance (ESR). The tetracycline oxidative decomposition process involves the participation of •OH, 1 O 2 , • O 2 - O2- , e - , and h + as proven by ESR and radical trapping experiments. This work proposes a research idea to prepare high-performance photocatalysts with MOF@COF type, featuring OVs-rich and Z-scheme heterojunctions.

研究领域: 材料科学 · 环境科学 · 光催化技术
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Journal of Materials Chemistry A · 2025 · IF 9.5

Synthesis of a carbon nanotube-modified NH2-MIL-53(Fe) adsorbent and efficient adsorption and separation of gallium ions

Chen Li,Chuncai Zhou,David French,Ian T. Graham,Zixuan Wang,Yunfei Li,Feng Wang,Guijian Liu

As strategic emerging industries represented by clean energy technologies develop rapidly, gallium (Ga), one of the critical elements due to its use in these technologies and limited supply, has attracted worldwide attention. The discovery of appropriate materials to adsorb Ga is crucial for improving the utilization of Ga resources. With the goal to recover Ga ions more efficiently and selectively, carbon nanotubes (CNTs) and amino-functionalized MIL-53 series metal–organic skeletons were hydrothermally synthesized into CNT/NH2-MIL-53(Fe) composite adsorbents. The composite's morphology, structure, chemistry and other physicochemical features were characterized, and the adsorption conditions including pH, initial Ga concentration, along with adsorbent dosage were optimized. The outcomes suggest that 2-CNT/NH2-MIL-53(Fe) performs better than the unmodified material in adsorption, and the theoretical maximum adsorption amount of Ga is 1483.8 mg g−1. The adsorption exhibited a single layer chemisorption with an endothermic spontaneous reaction. The adsorption mechanism for Ga onto 2-CNT/NH2-MIL-53(Fe) was mainly via ion exchange and chelation, accompanied by hydrogen bond interaction. The outstanding adsorption capacity and reproducibility using CNT/NH2-MIL-53(Fe) composites provide a novel method for adsorbing Ga from aqueous solutions.

研究领域: 材料科学 · 环境科学
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APPLIED SURFACE SCIENCE · 2025 · IF 6.9

Construction of ZnWO4/UiO-66-NH2 heterostructures for efficient photocatalytic reduction of Cr(VI)

Jialin Niu,Yulong Xiang,Xiaoli Dong,Yu Wang,Nan Zheng,Pei Yu

Hexavalent chromium in industrial wastewater poses a serious threat to ecosystems. Photocatalytic technology has been seen as a promising strategy for removing heavy metal ions. Construction of heterostructures offered a promising strategy to enhance the separation efficiency of photogenerated carriers, thereby improving photocatalytic performance. Herein, ZnWO 4 /UiO-66-NH 2 heterostructures were synthesized by a two-step hydrothermal method. The synthesized samples were systematically characterized via a variety of techniques, alongside an exploration of the associated photocatalytic mechanism. ZnWO 4 /UiO-66-NH 2 -2 exhibited an exceptional photocatalytic performance, attaining a 97 % degradation of hexavalent chromium within 60 min, approximately 1.3 and 4.7 times that of UiO-66-NH 2 and ZnWO 4 , respectively. The transient photocurrent response, photoluminescence (PL), and electrochemical impedance spectroscopy (EIS) results indicate that constructing heterostructures can effectively accelerate the migration of electrons while simultaneously suppressing the recombination process of photogenerated carriers. In addition, Active species trapping experiments revealed that the photogenerated electrons were the main active substances in photoreduction reaction. This study offers an effective strategy for photocatalytic reduction of hexavalent chromium.

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JOURNAL OF SOLID STATE CHEMISTRY · 2024 · IF 3.2

Co-doped NH2-UiO-66 for fast and effective adsorption of oxytetracycline: Kinetics, thermodynamics and mechanism

Yi Wang,Tao He,Siying Lv,Jing Yang,Shihai Cui

Novel type of micro mesoporous materials Co-doped NH 2 -UiO-66 had been successfully prepared. The properties of the material were understood through a series of characterization. When the dosage of Zr:Co is 2:1, the modified material showed specific surface area of 840.02 m 2 ∙g −1 , which is larger than the material without Co. Especially, the material was transformed from microporous NH 2 -UiO-66 to micro-mesoporous Co-doped NH 2 -UiO-66 through the adjustment of metal Co. The Co-doped nanocomposite was then applied to the adsorption of oxytetracycline. The effects of initial concentration, pH, humic acid and ionic strength on the adsorption were investigated. It was found that 50 mg∙L −1 oxytetracycline can be effectively adsorbed by Co-doped NH 2 -UiO-66 in pH 7. Further research showed that adsorption was pseudo-second-order kinetics and fitted Freundlich model with the maximum adsorption capacity 223.7 mg∙g −1 . In addition, the adsorption equilibrium time was only 2 h, which is shorter than the adsorption time of most adsorbents. The mechanism of pore adsorption, π-π interaction, hydrogen bonds and electrostatic interactions was deeply discussed. In conclusion, Co-doped NH 2 -UiO-66 was a fast and effective absorbent for the removal of oxytetracycline in aqueous solution.

研究领域: 环境科学 · 材料科学
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LANGMUIR · 2025 · IF 3.9

Renewable Magnetic NH2-MIL-101(Fe) for the Efficient Removal of Bisphenol A from Aqueous Solutions

Mingyang Xiong,Yao Zeng,Ruisi Qiu,Hongxing He,Yi Zhang,Zhifeng Nie,Bing Wang

Bisphenol A (BPA) is extensively utilized as an industrial chemical in the production of certain plastics and epoxy resins. They are frequently found in environmental water and have the potential to cause risks to both the environment and human health. To efficiently remove the endocrine disruptor BPA from aqueous solutions, sea urchin-like magnetic material Fe3O4@PDA@NH2-MIL-101 (Fe) was synthesized via hydrothermal methods. Fe3O4@PDA@NH2-MIL-101 (Fe) has excellent adsorption performance, with a theoretical maximum adsorption capacity of 300.47 mg/g for BPA. The adsorption kinetics of BPA by Fe3O4@PDA@NH2-MIL-101 (Fe) followed the pseudo-second-order kinetic model and Liu’s isotherm model. Magnetic separation experiments reveal a high recovery efficiency, maintaining 94.82% of its initial adsorption capacity after five cycles. The primary adsorption mechanisms of Fe3O4@PDA@NH2-MIL-101 (Fe) on BPA included pore filling, hydrogen bonding, π–π interaction, and Lewis acid–base interaction. Additionally, the material showed excellent removal performance of BPA, with a maximum adsorbed amount of 135.27 mg/g for total organic carbon (TOC) in the shale gas fracturing flowback fluid. These findings suggest that Fe3O4@PDA@NH2-MIL-101 (Fe) holds significant potential as an adsorbent for BPA removal from actual wastewater, offering promising prospects for practical applications.

CAS / MDL: 51-61-6 7705-08-0
研究领域: 环境科学 · 材料科学
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ACS Sustainable Chemistry & Engineering · 2025 · IF 7.3

Sustainable Defect-Engineered Imprinted UiO-66-NH2 for Selective Removal of Aristolochic Acids from Medicinal Herbs

Xiaoyan Han,Shan Wang,Tingting Cui,Yumin Yang,Haixiang Li,Haiwen Zhang,Huanhuan Zhou,Xiaoxia Li

Aristolochic acid I (AA-I), a known nephrotoxin and carcinogen, is commonly found in certain medicinal plants, posing significant safety concerns. In this work, defect-engineered, molecularly imprinted UiO-66-NH2 was synthesized via a one-pot hydrothermal method using indomethacin (IND) as a green alternative template. The resulting imprinted metal–organic framework effectively mitigates matrix interference, enabling highly selective recognition and the efficient adsorption of AA-I. Structural characterization confirmed that the imprinting process and template removal did not compromise the framework integrity of UiO-66-NH2. Spectroscopic analysis revealed that AA-I recognition was governed by Zr coordination, electrostatic interactions, and spatially confined recognition sites within the porous framework. Density functional theory calculations further elucidated the interaction mechanisms involved in the adsorption process. The imprinted UiO-66-NH2 exhibited a maximum adsorption capacity of 42.74 mg/g and an imprinting factor of 2.48. In real sample analysis, the material achieved recovery rates of 96.7–103.5% and excellent selectivity in Clematis armandii extracts. The adsorption efficiency remained above 80% after five adsorption–desorption cycles, indicating good structural stability and reusability. This work offers a promising and sustainable strategy for improving herbal medicine safety through the rational design of ecofriendly MOF-based adsorbents.

CAS / MDL: 53-86-1 83-46-5
研究领域: 药用植物学 · 材料科学 · 分析化学 · 环境科学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2024 · IF 3.8

Enhanced Photocatalytic Performance of UiO-66-NH2 MOFs by Ar Plasma Modification for Reduction of Cr (VI)

Douhao Yang,Ruiting Jian,Jianjun Yan,Ao Zhang,Bowen Liu,Zhongwei Liu

Defect engineering has a great effect on the properties of metal–organic frameworks (MOFs). In this study, the defective UiO-66-NH2 MOFs are successfully prepared by a rapid Ar plasma modification method. At certain experimental conditions (15 W radio frequency input power, 20 Pa working pressure, and 120 s Ar plasma modification time), the afforded UiO-66-NH2 shows significant enhancement in photocatalytic reduction of Cr(VI), and a maximum reduction efficiency of 68.5% is obtained. Advanced characterizations show that the plasma treatment generates missing-linker defects within the UiO-66-NH2 structure, which can enhance the separation of photogenerated electrons and holes and improve the photoreduction capability. The findings not only contribute to a better understanding of the relationship between the structure and performance of MOFs but also provide a simple approach for defect engineering of MOFs.

CAS / MDL: 1260119-00-3
研究领域: 材料科学 · 环境科学
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CRYSTENGCOMM · 2025 ·Vol. 27 ·期 5 ·678-686 · IF 2.6

Ligand defect engineered NH2-MIL-88B(Fe) for efficient oxygen evolution reaction in alkaline seawater

Dongling Xie,Jianan Wang,Bo Huang,Yiyi Yang,Dunmin Lin,Chenggang Xu,Fengyu Xie

Rational design of viable routes to develop affordable and efficient oxygen evolution reaction (OER) catalysts is essential for advancing electrochemical water splitting, yet significant challenges remain, particularly in seawater. Here, we propose a ligand defect engineering strategy to modify the electronic structure of NH2-MIL-88B(Fe) using a monodentate ligand (acetic acid, AcOH), inducing ligand vacancies in NH2-MIL-88B(Fe) for oxygen evolution in an alkaline seawater electrolyte, thereby improving the performance of the electrocatalysts. The resulting defective MOFs (denoted as NH2-MIL-88B(Fe)-x) exhibited exceptionally high catalytic activity for OER, requiring low overpotentials of 313 and 329 mV at a current density of 100 mA cm−2 in 1 M KOH and simulated seawater (1 M KOH + 0.5 M NaCl) solutions, respectively. Experimental analyses revealed that the introduction of AcOH can modulate the d-band center of active sites in NH2-MIL-88B(Fe)-x and play a critical role in alleviating chloride ion (Cl−) corrosion, thereby enhancing catalytic stability in seawater. When directly used as an OER catalyst in an alkaline electrolyte, wind and solar power were harnessed to operate the NH2-MIL-88B(Fe)-x || Pt/C configuration to drive the electrolytic water reaction. Thus, the ligand defect strategy can be employed to design and prepare high-performance OER electrocatalysts, particularly for generating H2 through water electrolysis powered by renewable energy sources.

研究领域: 材料科学 · 电化学 · 能源工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2025 · IF 9

Development of an Environmentally Friendly nanofiltration membrane for efficient Lithium-Magnesium separation using ZIF-8-NH2 grafted polyamide

Hongfei Jia,Yangchen Wang,Lizi Yang,Ran Fang

Lithium metal, a pivotal element in modern electric vehicles and electronics, necessitates secure and sustainable supply chains. Extracting lithium from brines presents significant challenges, particularly when dealing with high magnesium-to-lithium ratios, due to the nearly identical ionic radii of lithium and magnesium ions. Herein, we propose an innovative strategy for the selective separation of Li + /Mg 2+ by integrating ZIF-8-NH 2 into polyamide membranes through the interfacial polymerization (IP) of polyethyleneimine (PEI) and trimesoyl chloride (TMC). The synthesized PEI@ZIF-8-NH 2  + TMC membranes exhibit an impressive permeation rate for Li + of 0.863 mol m -2 h -1 , alongside a Li + /Mg 2+ selectivity ratio of 33.06. The unique pore structure of ZIF-8-NH 2 and surface chemistry facilitate efficient Li + /Mg 2+ separation, driven by synergistic interactions such as elevated positive surface charges, subnanometer channels, and strong π-π stacking with polyamide layers. These developments are anticipated to augment both the selectivity and durability of MOF-based membranes, providing new directions for research and practical implementations in ion separation technology.

研究领域: 材料科学 · 环境工程 · 化学工程
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APPLIED CATALYSIS A-GENERAL · 2024 · IF 4.7

Fabrication of Ce-doped UiO-66-NH2 for highly efficient and selective photocatalytic reduction of CO2 to CH4

Yating Xie,Nicui Yuan,Hongyang Liu,Lukai Luo,Jun Gong,Xiping Yin,Tengfei Li,Yonghua Zhou

Defect engineering by creating oxygen vacancies (OVs) and heterogeneous frustrated Lewis acid-base pairs (FLPs) emerged as an efficient strategy to enhance the selective conversion CO 2 to CH 4 . Considering the intrinsic FLPs contained in UiO-66-NH 2 (UNH for abbreviation), in this paper, the OVs was introduced therein by fabricating the Ce-doped UNH (denoted as UNH(Ce/Zr)) via one-step solvothermal route. The as-prepared UNH(Ce/Zr) catalyst exhibited the CH 4 yield of 31.02 μmol·g −1 ·h −1 accompanied with the CH 4 selectivity of 93 % and satisfying recycling stability. The XRD, SEM, FT-IR, XPS, TG, TPD and NH 3 in situ DRIFTS and in situ FT-IR characterization results justified that the UNH(Ce/Zr) possess the obviously increased OVs sites and enhanced Lewis acidic and basic properties. Additionally, the photoelectrochemical characterization results showed that UNH(Ce/Zr)−0.014 efficiently improved photogenerated electron-hole separation efficiency and charge transfer rate. It could be concluded that it was the cooperative action of OVs and FLPs that led to the high CH 4 selectivity and CH 4 yield.

CAS / MDL: 10312-55-7 18618-55-8
研究领域: 材料科学 · 环境科学 · 化学工程
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