JOURNAL OF CHROMATOGRAPHY A
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2026
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IF 4
Haonan Wu,Jia Jia,Chaoqiong Zhao,Yunli Luo,Yi Pan,Jin Luo
A uniformly functionalized UiO-66 capillary column with a continuous flow process was prepared. • The hydrophobic pore channel microenvironment (−2CH 3 ) significantly reduces the mass transfer resistance of non-polar molecules. • The polar group (−2SH) triggers specific adsorption of noble gases within the confined pores. • The GCMC simulation quantitatively revealed the thermodynamic essence of the functional group control over adsorption heat. • A structure-activity relationship was established, mapping from functional group design to chromatographic performance. To address the challenges posed by the ill-defined regulatory mechanisms of pore microenvironments in metal-organic framework (MOF) chromatographic stationary phases, this study employs continuous flow synthesis to fabricate a series of functionalized UiO-66 wall-coated open-tubular column with precisely controlled thicknesses. This approach aims to decouple physical morphological interference and systematically elucidate intrinsic separation principles. In the thermodynamic dimension, the retention of aromatic compounds is synergistically governed by framework shape selectivity and π–π interactions. Conversely, for permanent gases where size-sieving is restricted, thiol functionalization achieves successful baseline separation through physical confinement and the induction of specific dipole-quadrupole interactions. Grand Canonical Monte Carlo (GCMC) simulations quantitatively confirm a significant elevation in the isosteric heat of adsorption at the molecular scale, which corroborates the macroscopic chromatographic performance. Long-term stability tests (RSD < 0.28 %) further validate the physicochemical robustness endowed by the synergy between Zr-O coordination bonds and covalent modification groups. This work provides a definitive methodological basis for the theoretical customization and engineering-scale fabrication of high-performance MOF stationary phases.
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SEPARATION AND PURIFICATION TECHNOLOGY
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2026
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IF 9.1
Fangfang Li,Jinjin Wang,Ying-Hua Zhou
Metal-organic frameworks (MOFs) possess highly tunable structures, making them promising heterogeneous catalysts for efficient CO 2 conversion reactions. In this work, cerium-modified zirconium-based metal-organic frameworks (ZrCe-UiO-66) were engineered and post-synthetically functionalized with dicationic ionic liquid moieties, enabling the simultaneous introduction of strong Lewis acidic sites and nucleophilic ionic liquid units without the need for external co-catalysts. The resulting ZrCe 0.5 -UiO-66-DIL(n-PyRIm) ( n = 2, 3, 4; R = Et, Pr, Bu, Pe) functionalized MOFs were prepared via a modular grafting approach and exhibited remarkable catalytic performance. Among them, ZrCe 0.5 -UiO-66-DIL(2-PyBuIm) converted epichlorohydrin into the corresponding cyclic carbonate with 96% yield and 98% selectivity under solvent-free conditions at 110 °C and a CO 2 pressure of 0.1 MPa. This outstanding activity arises from a cooperative activation mechanism, in which the mixed Zr 4+ /Ce 4+ activate the epoxide substrate through Lewis acid coordination with the epoxide oxygen, thereby facilitating C O bond activation, while the bromide anions embedded in the ionic liquid moieties promote nucleophilic ring opening. In addition to high catalytic efficiency, the MOF hybrids demonstrated excellent recyclability and broad substrate tolerance. Combined CO 2 adsorption measurements and in situ infrared spectroscopy further revealed key surface intermediates, enabling a plausible mechanistic pathway for the cycloaddition process to be proposed.
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ACS Applied Polymer Materials
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2026
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IF 5.2
Ziyi Yuan,Zhihong Lin,Kejing Li,Jian Li,Viatcheslav Freger,Xuezhong He
Polymers of intrinsic microporosity (PIMs) are promising membrane materials for CO2 separation due to their high permeability; however, their limited CO2/N2 selectivity restricts practical application. Herein, mixed-matrix membranes (MMMs) were fabricated by incorporating a CO2-molecularly imprinted UiO-66-NH2 filler (MIP@U) into amidoxime-functionalized PIM-1 (AOPIM-1), followed by thermal treatment at 160 or 250 °C under vacuum to regulate the membrane microstructure. Spectroscopic and porosity analyses (FTIR, XRD, and N2 physisorption) show that thermal treatment at 160 °C promoted oxadiazole-ring formation, leading to enhanced subnanometer microporosity and improved CO2/N2 selectivity. In contrast, treatment at 250 °C partially regenerates nitrile groups and generates larger micropores, resulting in higher CO2 permeability but reduced selectivity. The MIP@U filler introduces CO2-recognition cavities and improves interfacial compatibility, enabling synergistic control of polymer microporosity and interfacial transport pathways. The optimized 3 wt % MIP@U/AOPIM-1-TR160 membrane achieves a CO2 permeability of ∼1600 Barrer and a CO2/N2 selectivity of 50.8. The membrane also demonstrates stable performance under pressures up to 12 bar and during 30 h of continuous operation at 2 bar. This study highlights a dual-approach strategy combining thermally tailored PIM chemistry with molecularly imprinted MOF fillers for designing high-performance MMMs for CO2 capture.
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BIOELECTROCHEMISTRY
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2026
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IF 4.9
Mingzhu Yang,Dujuan Li,Ao Wang,Yifan Zhang,Jiale Ouyang,Xinyi Wang,Liang Hong,Dingyi Tong,Minghua Wang,Jianhan Lin,Qiong Luo,Gaofeng Wang
Breast cancer, a globally prevalent malignancy in women, requires early diagnosis to improve patient outcomes, where ctDNA serves as a key biomarker. In the present study, an electrochemical biosensor based on CRISPR/Cas12a and Au@UiO-66 nanozyme synergistic dual amplification was developed to achieve ultrasensitive detection of breast cancer marker ctDNA. Au@UiO-66-modified ssDNA probes were anchored to the gold electrode via thiol groups. The intact ssDNA probe anchors Au@UiO-66 nanozyme to the electrode, where its peroxidase-like activity efficiently catalyzes H 2 O 2 reduction to generate amplified reduction peak currents. Target ctDNA activates Cas12a's trans-cleavage capacity by binding specifically to crRNA. Under the presence of the target, Au@UiO-66 nanozymes are released, resulting in a discernible drop in the peak current linked to H 2 O 2 reduction. Benefiting from the optimized experimental conditions, the biosensor demonstrates a broad linear detection range (from 10 fM to 10 nM) for the target ctDNA, along with an exceptionally low detection limit of 6.14 fM. Successful detection in human serum samples demonstrates its practicality. The platform's high specificity is attributed to the programmable crRNA design, enabling detection of specified DNA sequences and showcasing significant adaptability for diagnosing multiple genetic targets, highlighting its potential in clinical cancer diagnosis.
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Journal of Environmental Chemical Engineering
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2026
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IF 7.5
Shuangshuang Long,Jingwen Wang,Shuqian Meng,Yaxin Liu,Jing Zhang,Zihao Ren,Jiadi Li,Yangyang Xin,Zheng Dong,Baolu Cui,Libing Qian,Wenwu Zhou,Kai Hu,Luyao Wang,Peipei Li,Yaping Zheng,Zhiyuan Yang,Dechao Wang
Porous liquids (PLs), combine the high adsorption capacity of porous solids with the fluidity of liquids, show great promise in selective CO 2 capture. However, current studies on Type I PLs lacks systematic investigations into the regulatory role of porous host particle size and its impact on in-depth analysis of the gas sorption-separation process. Herein, we successfully fabricated PLs by grafting polyether amine oligomer chains onto the surface of size-tailored UiO-66-OH as the porous host, which endow the PLs with good thermal stability, transparency, low viscosity, and promising CO 2 /N 2 separation. UiO-66-OH-PLs were fabricated by grafting polyether amine oligomer steric solvent onto UiO-66-OH via dehydrative condensation. The effect of porous host size on CO 2 separation behavior of UiO-66-OH-PLs and the selective sorption-separation mechanism were systematically investigated using sorption isotherm and kinetic models. UiO-66-OH-PLs exhibit markedly enhanced CO 2 sorption capacity relative to the pure steric solvent, confirming the preservation of accessible cavities in porous hosts. The PLs further exhibit distinct size-dependent physicochemical and sorption properties as decreasing the particle size of UiO-66-OH porous hosts increases oligomer grafting density, reduces bulk viscosity and enhances both CO 2 sorption capacity and CO 2 /N 2 separation selectivity. CO 2 adsorption isotherms are best fitted by the SS-Langmuir-Freundlich model, indicating that CO 2 sorption by UiO-66-OH-PLs is single-component sorption on heterogeneous surfaces, integrating Langmuir monolayer sorption and Freundlich non-ideal sorption characteristics. Kinetic analysis reveals that the optimal pseudo-first-order kinetic model, demonstrating that CO 2 sorption rate is dominated by the sorption-desorption process between adsorbate molecules and adsorbent surface-active sites, rather than intraparticle or liquid film diffusion. This work opens up a promising avenue for the rational design of high-performance PLs that can be tailored to meet the demands of practical industrial chemical separation processes.
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Molecular Catalysis
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2026
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IF 4.3
Jiarui Li,Bolun Mei,Zhouxuan Zang,Yi Yu,Guoji Liu,Li Xu
A series of Cr-UiO-66 catalysts with ligand-vacancy defects was prepared for the oxidative dehydrogenation of biomass-derived 1,2-propanediol to hydroxyacetone. • A volcano-shaped trend between defect level and hydroxyacetone yield was established. • Moderate ligand vacancies balance H 2 O 2 conversion and the selective formation of hydroxyacetone. • •OH radicals were identified as key species for H 2 O 2 -driven ODH of 1,2-propanediol. The oxidative dehydrogenation (ODH) of biomass-derived 1,2-propanediol (1,2-PDO) to the high-value chemical hydroxyacetone (HA) is a meaningful route for upgrading renewable feedstocks into value-added multifunctional chemicals. In this study, Cr-UiO-66 catalysts with tunable content of ligand vacancies were synthesized for the conversion of 1,2-PDO to HA. Notably, a volcano-shaped relationship was observed between defect density and HA yield. The optimized 0.4Cr-UiO-66 catalyst achieved an HA yield approximately 3 times that of pristine UiO-66, reaching 12.9% at 45 °C after 2 h. Moreover, the catalyst sustained its ODH performance over five reaction runs. Regulating the content of ligand vacancies was shown to modulate the acidic properties of Cr-UiO-66 and H 2 O 2 activation to generate •OH radicals. A moderate level of ligand vacancies enabled a balance between H 2 O 2 activation and selective HA formation, resulting in improved performance. This study highlights ligand-vacancy engineering as an effective strategy for regulating H 2 O 2 activation over UiO-66-based catalysts. It provides meaningful insights for tailoring structural defects in UiO-66 for the ODH valorization of biomass derivatives. Download: Download high-res image (159KB) Download: Download full-size image
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CHEMICAL ENGINEERING JOURNAL
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2026
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IF 12.5
Beining Qi,Shangzhen Zhang,Qingze Shi,Zexuan Gong,Qian Yue,Zhenqi Duan,Tianyi Zhang,Yinglong Wang,Limei Zhong,Fengbin Zheng
A rapid and easily scalable solvothermal method is developed to synthesize UiO-66 with different functional groups. • UiO-66-NH 2 exhibits excellent CO 2 /N 2 separation performance. • UiO-66-NH 2 significantly enhances the adsorption interaction with CO 2 . • This solvothermal method exhibits good scalability and performance reproducibility. UiO-66 is one of the most promising metal-organic framework (MOF) materials for CO 2 adsorption due to its high specific surface area, high stability, and ease of functionalization. However, its synthesis methods often suffer from problems such as long reaction times, uneven mass and heat transfer, and limitations in equipment size. Here, we develop a rapid and easily scalable solvothermal method to prepare UiO-66 with different functional groups, denoted as UiO-66-x (x = H, NH 2 , NO 2 , F, CH 3 ), for the selective separation of CO 2 and N 2 . Adsorption experiments show that UiO-66-NH 2 exhibits excellent adsorption performance for CO 2 , reaching an adsorption capacity of 76.71 cm 3 /g at 273 K and 0.1 MPa, which is superior to some reported solid adsorbents. Dynamic breakthrough experiments show that UiO-66-NH 2 has excellent separation performance for CO 2 and N 2 under practical conditions. More importantly, UiO-66-NH 2 exhibits good reusability after 10 consecutive adsorption-desorption cycles. Theoretical calculations indicate that the introduction of amino groups enhances the adsorption interaction of UiO-66-NH 2 with CO 2 , thereby improving its selective adsorption capacity. Furthermore, the UiO-66-NH 2 prepared in gram-scale experiments exhibits high consistency with the milligram-scale samples in terms of crystal structure and CO 2 adsorption performance, indicating that this method has good scalability and performance reproducibility. Download: Download high-res image (247KB) Download: Download full-size image
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Small Science
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2026
·Vol. 6
·期 8
·e70382
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IF 7
Min Chen,Yaping Lu,Xinmin Zhang,Yixin Song,Fengtao Shao,Xuetao Gao,Zhichao Liu,Chunmei Xu,Yiting Peng,Yaping Feng,Kai Xi,Yatao Liu
Lithium–sulfur (Li–S) batteries represent promising energy storage devices by virtue of their ultrahigh theoretical energy density, yet their practical deployment is severely impeded by the polysulfide shuttle, sluggish sulfur redox kinetics, and progressive degradation of lithium anodes. Herein, we design a thiol-functionalized UiO-66 (UiO-66-SH)-coated polypropylene separator that addresses these challenges simultaneously. The UiO-66-SH combines abundant coordinatively unsaturated Zr sites and SH groups, enabling both strong chemical anchoring of lithium polysulfides and catalytic acceleration of their conversion to Li 2 S. The modified separator exhibits superior electrolyte wettability, a high Li + transference number (0.76), and enhanced ionic conductivity. Furthermore, it regulates lithium deposition to achieve a dendrite-free anode and mitigates polysulfide-induced corrosion. Consequently, Li–S cells incorporating UiO-66-SH/PP separator deliver an initial discharge capacity of 821.3 mAh g −1 at 1 C, retain 521 mAh g −1 after 500 cycles, and achieve a high-rate capacity of 590.9 mAh g −1 at 5 C. Even under a high sulfur loading of 5.05 mg cm −2 , a reversible capacity of 620.1 mAh g −1 is maintained after 200 cycles. This work offers a rational design of a multifunctional MOF-based separator that integrates polysulfide entrapment, catalytic conversion, and anode protection, paving the way toward high-performance, long-life Li–S batteries.
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Nanomaterials
·
2025
·Vol. 15
·期 12
·931
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IF 4.3
Chao Wang,Junchao Ding,Haoyu Wu,Jiaxuan Zhang,Jing Xu,Ying Zhang,Mindan Ma,Ming Zhang,Hongping Li
The effective and deep removal of unreactive sulfides to achieve ultra-low-sulfur or sulfur-free oils has recently attracted extensive attention. In this work, a series of UiO-66 based catalysts have been prepared facilely for the effective removal of unreactive sulfides. Here, the incorporation of nitro functional groups into UiO-66, along with the construction of defects, results in remarkable sulfur removal for dibenzothiophene (DBT), achieving oil with sulfur content of less than 1 ppm. The successful construction of the designed catalysts was verified through a series of characterization studies. The exposed unsaturated metal sites help provide significantly more active reaction sites. In addition, the incorporated nitro group, with its electron-withdrawing property, would help increase the Lewis acidity of the catalytic metal sites. Thus, the catalytic oxidative capability of the designed UiO-66-based catalysts would be significantly increased. The enhanced catalytic oxidative performance helps ensure acceptable sulfur removal for oils with much higher sulfur concentrations. Additionally, the catalyst developed in this work can also be used to remove the derivatives of DBT with even lower reactivity. The relatively mild reaction conditions, combined with the exceptional sulfur removal, demonstrate the practicality of this reaction system.
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ACS Catalysis
·
2024
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IF 11.3
Chong Qi,Yifu Bi,Yaolin Wang,Hong Yu,Yuanyu Tian,Peijie Zong,Qinhua Zhang,Haonan Zhang,Mingqing Wang,Tao Xing,Mingbo Wu,Xin Tu,Wenting Wu
Nonthermal plasma (NTP) offers the potential for converting CH4 with CO2 into liquid products under mild conditions, but controlling liquid selectivity and manipulating intermediate species remain significant challenges. Here, we demonstrate the effectiveness of the Cu/UiO-66-NH2 catalyst in promising the conversion of CH4 and CO2 into oxygenates within a dielectric barrier discharge NTP reactor under ambient conditions. The 10% Cu/UiO-66-NH2 catalyst achieved an impressive 53.4% overall liquid selectivity, with C2+ oxygenates accounting for ∼60.8% of the total liquid products. In situ plasma-coupled Fourier-transform infrared spectroscopy (FTIR) suggests that Cu facilitates the cleavage of surface adsorbed COOH species (*COOH), generating *CO and enabling its migration to the surface of Cu particles. This surface-bound *CO then undergoes C–C coupling and hydrogenation, leading to ethanol production. Further analysis using CO diffuse reflection FTIR and 1H nuclear magnetic resonance spectroscopy indicates that in situ generated surface *CO is more effective than gas-phase CO (g) in promoting C–C coupling and C2+ liquid formation. This work provides valuable mechanistic insights into C–C coupling and C2+ liquid production during plasma-catalytic CO2 oxidation of CH4 under ambient conditions. These findings hold broader implications for the rational design of more efficient catalysts for this reaction, paving the way for advancements in sustainable fuel and chemical production.
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MOLECULES
·
2026
·Vol. 31
·期 11
·1885
·
IF 5.1
Kunyi Li,Ziyang Wang,Lingna Meng,Minjia Meng
Artesunate (ARU), a key derivative of artemisinin (ART), exhibits excellent water solubility and antimalarial activity due to its incorporation of a succinic acid group. However, the synthesis process of ARU often leaves behind ART with a highly similar structure and properties, making traditional separation methods ineffective for efficient separation. Developing selective separation technologies holds significant importance. Based on previous studies, in work involving the preparation of bidentate MOFs with different ligands, bidentate MOFs containing thiol/amino groups have been found to exhibit outstanding adsorption capacity and selectivity for ARU molecules. Among these, -NH2forms hydrogen bonds with -COOH in ARU, while -SH interacts non-specifically with Aru, significantly enhancing the adsorption effect. This study employed a delayed inversion method to prepare a sulfhydryl-amino UiO-66/PVDF hybrid membrane (UiO-66-SH/NH2/PVDF) by adjusting the composition of the coagulation bath, which was used for efficient separation of ART/ARU. The effects of ethanol ratio in the coagulation bath on membrane structure and performance were systematically investigated. Results showed that increasing the ethanol ratio delays phase transition, promotes MOF material enrichment on membrane pore surfaces, and forms more abundant pore structures. When the ethanol-to-water volume ratio was 1:1, the UiO-66-SH/NH2/PVDF membrane exhibited optimal pore structure and highest water flux. Static permeation experiments demonstrated that the membrane achieved effective separation of ARU and ART for 8 h, maintaining stable selective adsorption performance after five cycles. This study reveals the critical role of morphology regulation in separating structural analogs, providing new materials and theoretical foundations for efficient separation of artemisinin-based compounds.
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ACS Applied Materials & Interfaces
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2019
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IF 8.456
Minghu Zhao,Zhen Huang,Shixing Wang,Libo Zhang,Yang Zhou
Mercury ions can cause a series of hazards to humans and the environment, even in trace amounts. Here, we designed a novel adsorbent (Cys-UiO-66) by functionalizing NH2-UiO-66 with l-cysteine for selective removal of Hg(II) from solution. The Cys-UiO-66 was characterized by different instruments. The adsorption property of Cys-UiO-66 was evaluated by batch methods. The maximum adsorption capacity was 350.14 mg/g at pH 5.0. Furthermore, the adsorption isotherm and kinetics models were in accord with the Langmuir and pseudo-second-order models, respectively, evidencing that the adsorption behavior was dominated by monolayer chemisorption. The Cys-UiO-66 had better affinity for Hg(II) than other coexisting ions in wastewater and could be regenerated for at least five cycles. The results prove that Cys-UiO-66 is a talented and efficient sorbent for mercury ions.
研究领域:
环境化学
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材料科学
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吸附技术
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重金属去除
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水处理
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危险品化学品经营许可证（带存储）