APPLIED SURFACE SCIENCE
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2025
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IF 6.9
WooYeon Moon,Dong Gyu Park,Younghu Son,Minyoung Yoon,Kyung Min Choi
The removal of bromide ions (Br − ) from water is critical, as these ions can generate bromate and brominated disinfection by-products that are toxic, carcinogenic, and corrosive. Previous research has not focused on the removal of Br − from water with a heavy presence of chloride ions (Cl − ). To address this research gap, we proposed a defective Zr-based metal–organic framework (MOF) to selectively remove trace Br − in environments with high concentrations of Cl − . We demonstrated that the open acidic sites on the secondary building units in a defective Zr-based MOF-808 (MOF-808-Cl) selectively removed the trace Br − in the presence of high concentration of Cl − using varying degrees of electrostatic interactions induced by their own polarizability. The Br − removal was performed with the mixed mechanism of ion-exchange and −adsorption, with contributions of approximately 70% and 30%, respectively. The Br − was successfully removed when the concentration of Cl − was 100 times higher than that of Br − . Our findings demonstrate the potential of MOF-808-Cl for industrial applications requiring trace ion removal and can provide insights for future research on selective ion removal in a competitive environment.
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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS
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2025
·Vol. 36
·期 24
·1-13
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IF 2.8
Rafiq Muhammad Nasir,Dai Zhonghua,Zheng Yuanyuan,Li Xujun,Liu Chenxi,Zhao Xin,Cong Yu,Gu Shuitao
The performance of lead-based ceramics in energy storage applications is often hindered by their low energy density and inadequate phase transition properties. The (Pb, La) (Zr, Sn, Ti)O 3 (PLZST) antiferroelectric ceramics have attracted much attention as energy storage materials. In this work, ceramics Pb 1−1.5 x La x (Zr 0.93 Sn 0.05 Ti 0.02 )O 3 at ( x = 0.015, 0.025, 0.035, and 0.045) were prepared using a solid-state method, and their dielectric and energy storage characteristics were studied. It was observed that integrating lanthanum significantly improved the perovskite structure, reducing grain size and boosting the polarization intensity. In this present study, a recoverable energy storage density ( W rec ) of 6.24 J/cm 3 was achieved under an electric field of 270 kV/cm. Moreover, these ceramics demonstrated an impressive discharge energy density ( W dis ), with 90% of the energy released within 1.29 μs. The outcomes show that PLZST is a highly effective material for advanced energy storage, pulse power applications, and paving the way for technological advancements.
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APPLIED CATALYSIS A-GENERAL
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2025
·
IF 4.8
Tinghao Han,Zhongdi Liu,Lincai Peng,Weipeng Song,Huai Liu,Wenlong Jia,Rui Zhang
The efficient production of γ-valerolactone (GVL) with high yield directly from xylose is of particular interest but remains a great challenge due to the long reaction path. We herein developed a facile catalytic system to directly convert xylose to GVL with a record-high yield of 54.3 %, employing β-zeolite supported Zr-based catalyst in 1,4-dioxane/isopropanol co-solvent. Using Zr(NO 3 ) 4 ·5 H 2 O as the Zr sources resulting in well-retained β-zeolite structure, larger surface area and pore volume and better dispersion of Zr species, as well as balanced acidic sites where higher amount of Brønsted acid sites promoted the ring-opening of furfural alcohol for this cascade reaction. Notably, the introduction of 1,4-dioxane facilitated the in situ formation of furfural (i.e. yield-determining step) by diluting the competitive adsorption behavior between isopropanol and xylose, allowing more xylose molecules to access the active center, thus promoting the sequential production of GVL with unexpectedly high yield. The present work provides a efficient and straightforward preparation of GVL from xylose, paving the pathway towards higher atom economy.
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SENSORS AND ACTUATORS B-CHEMICAL
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2025
·
IF 7.7
Qing Kang,Tong Lin,Jingbo Jiao,Yidi Liu,Yurong Guo,Chenjing Ma,Xinjun Du,Shuo Wang
Salmonella typhimurium ( S. typhimurium ) contamination has become the main source of foodborne diseases and has substantial effects on human well-being. Herein, we present a nucleic acid-responsive colorimetric biosensor for ultrasensitive detection of S. typhimurium , integrating a multifunctional Fe 3 O 4 @Zr-MOF/GOx nanoprobe with exponential amplification reaction (EXPAR). The system integrates glucose oxidase (GOx) encapsulated within a Zr-based metal-organic framework (Zr-MOF) modified with magnetic Fe 3 O 4 nanoparticles. In the presence of S. typhimurium , the EXPAR reaction is triggered, and the controlled release of GOx is achieved by DNA strand displacement. The detection mechanism leverages GOx-catalyzed glucose oxidation to generate H 2 O 2 , which oxidizes 3,3’,5,5’-tetramethylbenzidine (TMB) for colorimetric signal readout. The biosensor demonstrates high specificity for S. typhimurium , with a detection limit of 2.26 CFU mL⁻¹ , and practical applicability in spiked milk samples, achieving recoveries of 89.6–111.5 %. The strategy employing stimuli-responsive DNA/MOF composites demonstrated significant potential in food quality monitoring and analysis.
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ChemNanoMat
·
2025
·
IF 2.6
Muhammad Kashif Majeed,Arshad Hussain,Muhammad Akram,M.Umar Majeed,Muhammad Arshad,Adil Saleem,Rashid Iqbal
The precise manipulation of pore structure, organic linkers, and disposition of active and co-active sites in metal-organic frameworks (MOFs)-based materials allows for the design of materials with tailored catalytic properties. However, studies that address their kinetic, dynamic, and mechanistic roles in target reactions are scarce. The development of a new functionalization method to introduce acidity into MOFs is established for heterogeneous catalysis. Exploring the effect of ligand functionalization in MOF type UiO-66(Zr) impacts its ability to catalyze the dimerization reaction of cyclohexanone. Upon treatment with a series of linkers and the addition of HCl, chemically stable MOF structures such as UiO-66 can be protonated, resulting in an acidic group attached to aromatic terephthalate linkers in the structure. A general synthetic strategy has been developed to produce functionalized UiO-66-FG compounds [FG = NH2, NO2, Br, OH, and (OH)2]. The functionalized acidic frameworks present enhanced catalytic activity toward the self-condensation of cyclohexanone. Investigating these aspects can provide valuable insights into how the functionalization of MOFs performs in real-world self-condensation scenarios and help in optimizing their practical applications.
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CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Yujia Zhao,Xianquan Li,Jifeng Pang,Wenguang Yu,Peifang Yan,Yang Su,Lin Li,Mingyuan Zheng
Catalytic conversion of bio-ethanol (EtOH) into 1,3-butadiene (1,3-BD, ETB) represents a low-carbon technology contributing to the sustainable production of renewable 1,3-BD. However, the low selectivity towards 1,3-BD and poor stability of catalysts hinder practical applications of the ETB process. In this work, we presented a novel Zn-Zr catalyst supported on dendrite-structured mesoporous silica (DSMS). Compared to the typical meso- or micro- porous materials such as SBA-15, meso-SiO 2 and Silicate-1 supported catalysts, the Zn-Zr/DSMS catalysts exhibited outstanding catalytic performance and exceptionally high stability in the ETB reaction. Over the representative 0.5%Zn2%Zr/DSMS catalyst, selectivity of 1,3-BD > 65 % and EtOH conversions of 72 %–100 % were obtained at temperatures in a wide range of 350–400 °C. More attractively, the distinguished performance was stable in a long time on stream of 172 h, and able to be effectively restored by calcining the spent catalyst. Systematic characterizations revealed that Zn and Zr species were highly dispersed on the DSMS support nearly at an atomic level, forming abundant Lewis acid sites without Bronsted acidity. This may account for the exceptionally high activity and 1,3-BD selectivity over the 0.5%Zn2%Zr/DSMS catalyst. The unique dendritic structure of the catalyst played important roles in stabilizing the catalytic performance. Correlated to the results of in-situ spectroscopy and conditional experiments, the roles of active sites and the contribution of the catalyst structure were proposed for the ETB process over the Zn-Zr/DSMS catalysts.
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CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Qu Ai,Shi-Kuan Sun,Yu Tian,Wei-Dong Xiao,Yi Zhao,Sheng-Heng Tan,Wei-Ming Guo,Hua-Tay Lin
For the sustainable development of nuclear energy, the fabrication of durable nuclear wasteforms, especially for high-level radioactive waste, is essential. This study introduces entropy engineering into zirconolite ceramics for the first time. A series of entropy-stabilized zirconolite ceramics with the general formula Ca( Zr , Hf , Sn ) x Ti 3-x O 7 (x = 0.8–2.2) were synthesized via cold-press sintering at 1450 °C for 10 h. The influence of multi-principal cation substitution on phase assemblage, microstructure, and chemical durability was systematically investigated. The incorporation of Zr, Hf, and Sn led to refined grain sizes, attributed to entropy-induced grain boundary pinning and lattice distortion. At x = 0.8, significant secondary phases including rutile and perovskite were observed. As the substitution level increased, these impurity phases were progressively suppressed, and phase-pure zirconolite was obtained at x = 1.8 and 2.0, as confirmed by XRD, although SEM still revealed trace perovskite. At x = 2.2, the reappearance of perovskite and formation of Hf-enriched zirconolite domains indicated the limit of solid solution stability. Raman and high-resolution TEM confirmed the 2 M zirconolite structure, accompanied by pronounced lattice distortion and stacking faults. Static leaching tests conducted in 1 M HCl revealed that samples with intermediate substitution levels (x = 1.2, 1.6, and 2.0) exhibited significantly improved chemical durability, with calcium release rates of 4.54 × 10 −4 , 2.79 × 10 −4 , and 1.14 × 10 −4 g·m −2 ·d −1 , respectively—an order of magnitude lower than that of conventional zirconolite (1.4 × 10 −3 g·m −2 ·d −1 ). The leaching rates of Zr, Hf, Sn, and Ti remained within the range of 10 −6 –10 −4 g·m −2 ·d −1 across all samples. These results demonstrate that entropy stabilization enhances phase purity, structural stability, and acid resistance, making entropy-stabilized zirconolite a promising matrix material for the immobilization of high-level radioactive waste.
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ADSORPTION SCIENCE & TECHNOLOGY
·
2024
·
IF 2.8
Yinghao Zhuang,Shuai Sun,Kai Jia,Lei Shi,Xiangshan Yang
Thorium is a promising nuclear fuel; however, even a small amount in nuclear wastewater can cause significant radioactive pollution. Therefore, it is urgent to develop effective adsorbents for the efficient removal of thorium to solve this problem. Herein, the phytic acid modification of carboxylated Zirconium-based metal-organic framework materials (UiO-66-COOH-PA) has been obtained by rapid high-temperature carbonization, which exhibits excellent performance in removing thorium (IV) in acidic aqueous solutions. The maximum adsorption capacity of UiO-66-COOH-PA-2 (with 40% mass ratio of phytic acid) in solution reaches 315.5 mg/g at a pH of 4, which is more than twice that of the unmodified Zr-based metal organic framework (MOF) material. The adsorption kinetics of UiO-66-COOH-PA on thorium has been analyzed using two different isothermal adsorption models, the Langmuir and Freundlich isotherm adsorption models. It turns out that the Freundlich model is more suitable for the data. The thorium adsorption process reaches dynamic equilibrium very quickly, while the adsorption dynamics of UiO-66-COOH-PA on thorium follows the pseudo-second-order adsorption kinetic model. The excellent adsorption performance of UiO-66-COOH-PA-2 at low pH values indicates that adsorption material containing phosphorus is suitable for the removal of thorium especially in acidic systems. It also exhibits excellent selectivity (up to 90.2%) for Th(IV) adsorption in the presence of several coexisting rare-earth ions. Overall, the integration of phosphorus-modified in Zr-MOFs represents a significant advancement in thorium adsorption technology, offering a pathway toward more effective management of radioactive acidic waste liquid.
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JOURNAL OF THE ELECTROCHEMICAL SOCIETY
·
2019
·Vol. 166
·期 4
·B193
·
IF 3.12
Sheying Dong,Hao Cui,Dandan Zhang,Mengmeng Tong
Several reports reveal that high level of C-reactive protein (CRP) in serum enhances venture of diabetes. In this article, we presented a platform which blended Zr(IV)-organic framework with 2,5-thiophenedicarboxylate ligand (Zr-tdc) and ionic liquid (IL) to form a steady composite membrane on the carbon paste electrode (CPE). The platform was applied to CRP and glucose biosensors which were connected with diabetes and displayed well performances. Firstly, a sensitive immunosensor for label-free and direct detection of CRP was developed at Zr-tdc/IL modified electrode. Under optimal conditions, differential pulse voltammetry (DPV) response showed the low detection limit of CRP was 0.2 ng/mL. Secondly, the glucose biosensor immobilized glucose oxidase (GOX) was constructed and studied by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and amperometric response. The Michaelis–Menten constant (KM) of immobilized GOX was 0.16 mM, and the detection limit was 2.7 μM for glucose. Two novel biosensors displayed well selectivity, stability and lower detection limit. This work improved the performance of electrochemical sensing and expand the utilization of the material by carrying on the effective immobilization of enzyme and antibody.
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Journal of Applied Spectroscopy
·
2025
·
IF 1
Han Dan,Niu Xiaoxue,Wang Jing,Yan Zihong
Zr and Cl double-doped carbon dots (Zr/Cl-CDs) were prepared by a one-step hydrothermal method using citric acid, urea, and ZrCl 4 as precursors. Zr/Cl-CDs were characterized by ultra-violet-visible spectroscopy (UV-Vis), transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy (XPS). Experimental analysis revealed that the average size of Zr/Cl-CDs was 2–3 nm, while XPS analysis revealed the presence of C–Cl and Zr–O bonds. The fluorescence quantum yield of the final CDs was 17.5% at the excitation of 360 nm. In addition, Zr/Cl-CDs exhibited excellent performance in the detection of rutin with a concentration of 30–110 and 100–160 μmol/L, respectively. Linear correlation coefficients (R 2 ) were 0.9931 and 0.9962. The underlying mechanism was that rutin had an excellent quenching effect on the emission of the Zr/Cl-CDs as the fluorescence intensity exhibited a good linear relationship between rutin concentration and fluorescence intensity. These findings provide a new strategy for synthesizing double-doped CDs for rutin detection.
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FUEL
·
2022
·
IF 8.035
Zhaoyang Qi,Huaifang Li,Jie Chen,Changshen Ye,Ting Qiu
The carboxyl functionalized ionic liquid ([mim(CH 2 ) 3 COOH]Cl) was prepared as a linker to combine phosphotungstic acid (HPW) and Zr(IV) ion. The obtained [mim(CH 2 ) 3 COO] 3 PW-Zr composite acted as a heterogeneous catalyst for removing DBT from liquid fuel with H 2 O 2 as an oxidant. As a result, [mim(CH 2 ) 3 COO] 3 PW-Zr possessed high catalytic activity in extractive and catalytic oxidative desulfurization (ECODS). Moreover, the [mim(CH 2 ) 3 COO] 3 PW-Zr was further exploited to grow on the surface of PEI/silica gel. And the fabricated large-grained Zr-PWIL@PEI/silica gel was used in the continuous ECODS process, and the removal of DBT could still reach more than 95% after running continuously for 16 h. More importantly, the synergistic catalytic mechanism between HPW and Zr(IV) in the ECODS process has been investigated in detail by experiments and DFT calculations. As a result, a plausible mechanism has been proposed and verified, which contains two parts: the Lewis acidic center activating H 2 O 2 to form superoxide ion radicals ( OOH), and the OOH oxidizing HPW to peroxotungstate (W(O 2 ) n ), which has a high oxidizability and stability. Thus, the effective combination of Zr(IV) and HPW active sites is a very effective strategy to promote desulfurization efficiency and utilization efficiency of H 2 O 2 . Besides, we also found the distance between the corresponding active sites of catalysts plays an essential role in ECODS reaction as it strongly influences the synergistic effect between different active sites.
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ELECTROPHORESIS
·
2018
·Vol. 39
·期 20
·2619-2625
·
IF 2.569
Pingxiu Tang,Rong Wang,Zilin Chen
The high stability and other properties of Zr(IV)-based metal organic frameworks(MOFs) make it a promising choice for chromatographic separation, while the application in open-tubular capillary electrochromatography (OT-CEC) separation has not been explored yet. Herein, we report the first example of the in-situ growth of UiO-66-NH 2 onto the capillary for open-tubular capillary electrochromatography. UiO-66-NH 2 consists of ZrCl 4 and 2-amino-1,4-benzenedicarboxylic acid, which is highly porous and stable in a variety of solvents. The prepared UiO-66-NH 2 modified capillary was characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectra (FT-IR), and the results confirmed the successful growth of the UiO-66-NH 2 . The baseline separation of chlorobenzenes, phenoxyacids and two groups of phenols was achieved owing to the combined interaction of π-π interaction, hydrophobic interaction, molecular sieve effect, electrophoretic migration and hydrogen-bonding interaction etc. Besides, the prepared capillaries showed good reproducibility, with relative standard deviations (RSDs) for intra-day, inter-day and column-to-column runs in the range of 1.38–2.60%, 3.39–4.05%, and 3.47–5.03%, respectively. Our work indicates Zr(IV)-based MOFs are promising materials as stationary phase in CEC separation.
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