Journal of Materials Chemistry A
·
2025
·
IF 9.5
Ziyang Xu,Zicheng Yang,Jiale Ni,Yi Feng,Jianfeng Yao
Defective metal organic frameworks have emerged as promising catalysts for CO2 conversion owing to their tunable active sites and exceptional catalytic activities. Despite their potential, achieving high defect densities through simple and scalable methods remains a major challenge. To address this, we developed an innovative low-temperature calcination strategy (300 °C, 10 min) to introduce abundant ligand defects into MIL-101(Cr) while maintaining crystallinity, thereby exposing additional Cr3+ Lewis acid sites to participate in epoxide activation. The resulting defective MIL-101 demonstrates remarkable catalytic efficiency in CO2 cycloaddition, achieving a >99% yield under mild conditions (80 °C, 0.1 MPa) within 6 h, significantly surpassing that of pristine MIL-101 (52%). Furthermore, the catalyst exhibited outstanding recyclability, retaining full activity over multiple reaction cycles. In addition to synthetic simplicity, this work provides fundamental insights into the critical role of defects in promoting epoxide activation and ring opening, establishing a sustainable pathway for CO2 utilization under mild conditions and the energy-efficient production of cyclic carbonates.
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MICROCHIMICA ACTA
·
2025
·Vol. 192
·期 12
·860
·
IF 5.3
Yan Xu,Yuan Min,Yang Ye,Du Bingqian,Liu Yanhui,Fan Menghan,Wang Qinyi,Shen Hao Shuang,Zhang Hao,Xu Fei
A limited-domain ion-imprinted fluorescence sensor (LDIFS) was developed by integrating aptamers with ion-imprinted polymers, achieving exceptional sensitivity and selectivity. Aptamers were immobilized on silanized ZnS quantum dots, after which pre-polymerized potassium dichromate and functional monomers were introduced. The polymerization process generated selective imprinted cavities and stabilized the active conformation of aptamer. LDIFS achieves the detection within 15 min by leveraging the inner filter effect. A dual-recognition mechanism, which integrates conformational locking and imprinted cavity memory, synergistically improves the analytical performance of the sensor. The sensor achieves an ultralow detection limit of 0.43 nmol/L, exhibiting 1–3 orders of magnitude higher sensitivity than conventional approaches. A high selectivity factor of 17.9 was attained, ensuring excellent anti-interference capability. The method was successfully applied to the analysis of real squid samples, yielding recoveries ranging from 85.39% to 102.5% with RSD < 3%. This work presents a highly sensitive and selective strategy for chromium ion detection, showcasing its promising applications in environmental monitoring and food safety analysis. Graphical
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JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Yupeng Mao,Ye Cheng,Khak Ho Lim,Wen-Jun Wang,Miguel A. Bañares,Qingyue Wang
Ultratrace amounts of isoprene in exhaled breath are a well-distinguished biomarker for lung cancer, and detecting isoprene by a sensor can be a fast and non-invasive screening method. However, a significant challenge lies in sensing sensitivity, selectivity, and humidity resistance to detect ppb-level of isoprene in breath, which relies on expensive noble-metal-based materials. Herein, this work develops cost-effective In 2 O 3 -based sensors with nanoflower morphology assembled by 2D nanolaminae that facilitates the diffusion of low-concentration isoprene to attain high sensitivity. Transition metal oxides (e.g., Cr and Cu) were introduced to modulate the electronic structure by constructing a heterojunction for enhanced humidity resistance. As-prepared Cr 2 O 3 @In 2 O 3 nanolamina presents a high surface area of 71.7 m 2 ‧g -1 and active surface oxygen species of 57.9%, while the Cu doping disrupts the nanolamina structure of In 2 O 3 support due to the aliovalent interactions. Consequently, Cr 2 O 3 @In 2 O 3 nanolamina exhibits a detection limit of 10 ppb isoprene with good selectivity, and it is highly resistant to water vapor in exhaled breath, and demonstrates good stability during long-term operation. These findings demonstrate Cr 2 O 3 @In 2 O 3 nanolamina as a viable candidate for the detection of isoprene in breath, and verify the effectiveness of non-noble metal doping for applications of highly sensitive and stable gas sensors.
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CHEMICAL PHYSICS LETTERS
·
2025
·
IF 3.1
Kangyue Qiao,Songyao Du,Yue Wang,Tongxin Xiao,Guodong Hao,Chao Sui,Yihan Yan
To address the severe Cr(VI) contamination in industrial wastewater, an NH 2 -MIL-101(Fe)/g-C 3 N 4 type-II heterojunction photocatalyst was synthesized via a solvothermal one-pot method. Structural characterization using XRD, SEM, XPS, and BET confirmed successful composite formation with high specific surface area and favorable interfacial contact. Photocatalytic experiments revealed that under conditions of pH = 2, a catalyst dosage of 20 mg, and an initial concentration of 10 mg/L, NM-101(Fe)/0.2CN achieved a 99.5 % reduction efficiency within 80 min. Its reaction rate constant was 3.6 times higher than that of NM-101(Fe) used alone. This study provides new insights for developing highly efficient MOF/polymer composite photocatalysts.
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WATER SCIENCE AND TECHNOLOGY
·
2025
·Vol. 92
·期 10
·1441-1456
·
IF 2.6
Wang Wenhao,Ge Aijun,Xu Yuan,Yang Xuesong,Feng Shiying,Su Ying,Wang Weida,Xing Liqun,Hao Xiujuan
View large Download slide View large Download slide Close modal In the study, a novel Fe/Al bimetal with a high specific surface area and electron transfer capacity was synthesized through ball milling Fe and Al powder. Importantly, this synthesis process did not consume Al powder and did not generate by-products that required treatment. Compared with Fe or Al powder and the ball-milled Fe or Al powder, Fe/Al could rapidly remove Cr(VI) through adsorption–reduction under near-neutral conditions. Nevertheless, the removal efficiency of Cr(VI) by Fe/Al was influenced by the initial pH of the solution and dissolved oxygen (DO). Kinetic studies and adsorption isotherm analysis demonstrated that the pseudo-second-order adsorption kinetic model and the Freundlich model could better describe the Cr(VI) removal data, and the maximum removal amount of Cr(VI) was 6.25 mg/g. Furthermore, based on the characterization analysis of XPS, the adsorbed Cr(VI) was reduced to Cr(III). SEM-EDS analysis revealed that Cr mainly overlapped with the Fe elemental distribution on the surface of Fe/Al particles, suggesting that Fe was the main reaction site. Consequently, the results indicated that highly active Fe/Al could be prepared by solid–solid blending for pollutant removal, which provided technological concepts for the waste utilization of scrap iron and aluminum. Increasing the specific surface area of Fe/Al by ball milling of Fe and Al powder was the key to enhancing Cr(VI) removal. Cr(VI) was mainly removed by adsorption–reduction under near-neutral pH. The removal sites of Cr(VI) by Fe/Al mainly occur on the surface of Fe. The maximum adsorption capacities of Cr(VI) by Fe/Al were 6.25 mg/g.
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Macromolecular Reaction Engineering
·
2020
·Vol. 15
·期 1
·2000041
·
IF 1.33
Yi Zhou,Xuelian He,Boping Liu
Two (SiO 2 /MgR 2 /MgCl 2 )·TiCl x model catalysts are made by refluxing TiCl 4 with 0.35 wt% Cr modified silica gel/alkyl Mg adducts or silica gel/alkyl Mg adducts, which are named as Cr/Ti-based bimetallic Cat-1 and Ti-based monometallic Cat-2, respectively. The kinetics, active center counting, morphology, and polymer characterizations are studied to disclose the effect of low loading Cr active sites on the Cr/Ti-based bimetallic Cat-1 polymerization under mild conditions. The activity of Cat-1 is 120.4% higher than that of Cat-2, with a 114.1% higher [ C *]/[ M ] value. Morphology results show the Cat-1 fragmentation in the first 3 min is highly accelerated, which helps to release buried clustered Ti sites. Differential scanning calorimetry results show that low-temperature heat absorbing shoulder of polyethylene (PE) from Cat-2 demonstrates the signal of low crystallinity polymer made by Cat-2 during the first 60 s, verifying the fluffy polymer in morphology results. GPC results show PE from Cat-1 has a higher M w in the first 3 min while a lower M w in the end. The Cat-1, which release active sites faster, has a high M w in the early time. Lower M w in the 900 s attributes to the effect of relative lower M w polymer made by Cr sites, compared with Cat-2.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2021
·
IF 7.312
Feifei Zhang,Kunjie Li,Jian Chen,Xinran Zhang,Kebing Li,Hua Shang,Lei Ma,Wujie Guo,Xinlong Wu,Jiangfeng Yang,Jinping Li
Natural gas purification by economic and low-energy adsorptive separation processes is important. However, as a difficult global problem, N 2 removal from N 2 /CH 4 mixtures is challenging because of their similar physical properties. In this study, the separation of N 2 /CH 4 by Cr-metal–organic frameworks (MOFs) (MIL-100Cr, MIL-101Cr and TYUT-96Cr) with various open Cr site densities was studied. Gas sorption isotherms showed that TYUT-96Cr exhibited the highest N 2 /CH 4 uptake ratio (13.67 at 0.01 bar and 298 K) of the selected Cr-MOFs, which was consistent with the highest density of Cr (III) sites. This material provided the highest CH 4 productivity (0.716 mmol/cm 3 ) per cycle for N 2 removal from a 5:95 N 2 /CH 4 mixture to produce 99.99% pure CH 4 , as shown by the breakthrough experiments. Pressure-swing adsorption simulations indicated that, by a two-bed six-step method, pristine 95% methane was enriched to 98.9% by TYUT-96Cr. The largest CH 4 productivity, high breakthrough selectivity and thermal stability of TYUT-96Cr among the Cr-MOFs, made it a promising adsorbent in trace N 2 removal for practical industrial application.
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BIORESOURCE TECHNOLOGY
·
2017
·
IF 5.651
Xingtang Liang,Xiaoyu Fan,Runmei Li,Shirong Li,Shukun Shen,Daodao Hu
A novel chitin-based biosorbent (QCP) was synthesized by cross-linking quaternized chitin and branched polyethylenimine with the aid of epichlorohydrin for efficient removal of Cr(VI) from water. Because it possessed both quaternary ammonium groups and amino groups as well as the hierarchical pore structure, QCP presented a maximum adsorption capacity of 387.7 mg/g according to the Langmuir isotherm at 25 °C. The biosorption of QCP achieved the equilibrium within 40 min and followed the pseudo-second-order kinetic model. QCP worked well even in the solution with high pH and high content of competing anions and, it exhibited an excellent reusability. The main Cr(VI) uptake mechanism was confirmed to be electrostatic attractions between Cr(VI) anions and quaternary ammonium groups as well as the protonated amino groups, and followed by partial reduction of Cr(VI) to Cr(III) by amines and hydroxyls. This work may provide a potential for Cr(VI) removal by chitin-based biosorbents.
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CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Minzhang Li,Rajendran Ramachandran,Thangavel Sakthivel,Fei Wang,Zong-Xiang Xu
In this work, we reported the synthesis of siloxene catalysts from calcium silicide at various topotactic reaction conditions and demonstrated their photocatalytic activity for Cr(VI) reduction under visible light irradiations. The topotactic reaction time influenced the surface area, structure, and optical characteristics of the siloxene, which altered the Cr(VI) photocatalytic elimination efficiency. A large specific surface area (47.04 m 2 g −1 ) and a narrow bandgap (2.45 eV) with hydroxyl-terminated layered silicon of the S-12 h catalyst could enable more active sites for photocatalytic reaction, which results in the improved catalytic performance for Cr(VI) removal. The Density Functional Theory calculations proved the siloxene’s direct bandgap feature and narrow bandgap. The initial Cr(VI) concentration, solution pH, temperature, inert gas, and different scavenger's effects on the photocatalytic performance of the S-12 h catalyst were also investigated. The S-12 h photocatalyst exhibited the Cr(VI) reduction efficiency of 98.6% for the electroplating wastewater that demonstrates the potential application in industrial for treatment of heavy metal ions removal.
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STARCH-STARKE
·
2024
·Vol. 77
·期 2
·2400050
·
IF 2.6
Xuesheng Qin,Chengzheng Wang,Zhe Zhang,Wei Ma
Hexavalent chromium (Cr(VI)) has attracted much attention because it is a harmful pollutant. In this study, acid hydrolyzed hydrothermal double modified starch (AHS) and hydroperoxide oxidized starch (HOS) are prepared from natural starch and used for the reduction of chromium (VI) in aqueous systems. The effects of hydrothermal acidolysis and oxidative modification of starch on the reduction rate of Cr(VI) are discussed, including the changes of solubility, swelling power, particle size, content of straight-chain starch, and carbonyl/carboxylic group content. The results of response surface methodology (RSM) optimization show that the influence of reaction conditions on the reduction rate of Cr(VI) by NS is as follows: reaction time > initial pH of solution > reaction temperature > starch to Cr(VI) mass ratio; and on the reduction rate of Cr(VI) by AHS and HOS is as follows: initial pH of solution > reaction time > starch to Cr(VI) mass ratio > reaction temperature.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Siqi Xiao,Luming Ma,Wenhui An,Pengfei Shen
Catalytic ozonation for advanced treatment of industrial wastewater has proved to be effective, and the stability of the catalyst is crucial for the long-term application of the ozonation process in practical engineering. In this study, the electrochemical characteristics of four iron (Fe) shavings: alloy steels (38CrMoAl and 40Cr) and carbon steels (A3 and 45#) were investigated, and a new citric acid-optimized H 2 O 2 modification method was proposed. The low open circuit potential (OCP) of carbon steels indicated that they were more likely to be oxidized therefore required shorter modification times. The higher the OCP of alloy steels, the higher H 2 O 2 concentration was required to enhance modification efficiency. By adding citric acid, the rapid modification of alloy steel was achieved, and the catalysts exhibited lower passivation current (I p ), indicating a lower rate of substrate loss and a longer lifetime of alloy steel catalysts. Furthermore, chromium (Cr) enrichment occurred in the oxide layer of alloy steel catalysts. The Cr/Fe (atomic ratio) in oxide layer for 38CrMoAl and 40Cr increased from 0.018 to 0.040 and from 0.010 to 0.037, respectively. The presence of CrOOH and Cr 2 O 3 within the oxide layer reinforced the layer’s overall structural integrity and enhanced its protection for the internal substrate, making the catalysts more resistant to adapt to high-salinity wastewater. Through laboratory tests, it was found that among the four catalysts, 38CrMoAl showed the highest stability and good catalytic activity with low Fe loss concentration. Therefore, the pilot-scale application effect of 38CrMoAl catalyst was evaluated. In the advanced treatment of pharmaceutical wastewater, chemical oxygen demand (COD) and total organic carbon (TOC) removals were 56.3% and 32.4%, respectively. These results showed that the stability of catalyst can be improved by optimizing the selection of steel, and the introduction of citric acid achieved Cr enrichment effect and amplified the potential stability advantage of alloy steel. The research provides guidance on raw material selection for catalyst preparation to different industries' wastewater treatment, especially in high-salinity wastewater ozonation treatment, which can realize the long-term stable application of catalyst.
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Green Processing and Synthesis
·
2022
·Vol. 11
·期 1
·595-603
·
IF 3.97
Fuhua Wei,Ting Zheng,Qinhui Ren,Hongliang Chen,Junhao Peng,Yufu Ma,Zhengjun Liu,Zhao Liang,Ding Chen
Metal–organic frameworks (Sm-MOFs) were prepared using a microwave-assisted ball milling method with a water solution. The structure was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and SEM, and the thermal stability of the Sm-MOFs was tested by Thermogravimetry (TGA). The results showed that the Sm-MOF material exhibited a favorable effect on removing the organic dye Congo red (CR). When the concentration of CR was 80 ppm, adding 50 mg of Sm-MOF material achieved an adsorption capacity of 396.8 mg·g −1 . The experimental data were analyzed theoretically through dynamics, and the experimental results were consistent with the second dynamics model, with correlation coefficients ( R
2 ) all above 0.99. Comprehensive data analysis revealed that the Sm-MOF materials had great potential for future application in wastewater treatment.
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