Inorganic Chemistry Frontiers
·
2022
·Vol. 9
·期 17
·4442-4451
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IF 7.779
Pengcheng Zhang,Hao Li,Xiaoqing Chen,Shucheng Liu,Quanzhang Wen,Canbing Li,Hanning Xiao
In this work, we prepare novel Ba7Zr2Nb4O21 and Ba8Zr3Nb4O24 ceramics with a smaller tolerance factor (for the AnBn−1O3n type hexagonal perovskite in BaO–ZrO2–Nb2O5 system) using a solid-phase reaction method, which shows good microwave dielectric properties of εr ∼ 33.5, Q × f ∼ 56 500 GHz and τf ∼ −17 ppm °C−1 (Ba7Zr2Nb4O21) and εr ∼ 32, Q × f ∼ 63 000 GHz and τf ∼ −27 ppm °C−1 (Ba8Zr3Nb4O24). Rietveld refinement of XRD and TEM shows that Ba7Zr2Nb4O21 and Ba8Zr3Nb4O24 with the BaO3 layer stacking sequence of (cccccchh) and (ccch)2 are eight-layer shifted and twinned hexagonal perovskite, respectively. As the sintering temperature increases, the εr and Q × f values of Ba7Zr2Nb4O21 and Ba8Zr3Nb4O24 exhibit a strong correlation with relative density. The relationship between the structure and properties is discussed in BaO–Zr/Sn/TiO2–Nb2O5 systems. The porosity excluded εr is mainly influenced by ion polarization, while the cell volume is also an essential factor affecting the permittivity. The variation of Q × f is related to the packing fraction in BaO–Zr/SnO2–Nb2O5 systems. The variation of τf is mainly regulated by the tolerance factor. This study shows that there is an opportunity to improve the microwave dielectric properties by adjusting the size of the B-site cation.
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NEW JOURNAL OF CHEMISTRY
·
2021
·Vol. 45
·期 41
·19432-19438
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IF 3.591
Fangyuan He,Heyi Zhang,Xiaonan Li,Jie Yang,Wenqing Ma,Hong Zhang
In this study, for the first time, we selected a size-matched polyoxometalate α-Mo8O26, and successfully prepared Mo8-UiO-66(Zr) as a catalyst with double active sites for extractive and catalytic oxidative desulfurization systems (ECODS). UiO-66(Zr) can encapsulate Mo8O26 in the cage and avoid its leaching, while the sulfur compounds can also enter the cage to approach the sites. As a result, in the presence of H2O2 as an oxidant, the catalyst exhibited extraordinary oxidative desulfurization performance towards benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT). It only takes 10 min for the desulfurization efficiency to reach 100%. The catalyst can be reused for at least 4 times without significant loss in the desulfurization activity. Also, the possible reaction mechanisms of the catalytic oxidation process have also been proposed.
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INORGANIC CHEMISTRY
·
2021
·
IF 5.165
Jie Li,Shuaiheng Zhao,Zhen Li,Dan Liu,Yingnan Chi,Changwen Hu
Catalytic transformation of levulinic acid (LA) to γ-valerolactone (γ-GVL) is an important route for biomass upgradation. Because both Bro̷nsted and Lewis acidic sites are required in the cascade reaction, herein we fabricate a series of H3PW12O40@Zr-based metal–organic framework (HPW@MOF-808) by a facile impregnation method. The synthesized HPW@MOF-808 is active for the conversion of LA to γ-GVL using isopropanol as a hydrogen donor. Interestingly, with the increase in the HPW loading amount, the yield of γ-GVL increases first and then decreases, and 14%-HPW@MOF-808 gave the highest γ-GVL yield (86%). The excellent catalytic performance was ascribed to the synergistic effect between the accessible Lewis acidic Zr4+ sites in MOF-808 and Bro̷nsted acidic HPW sites. Based on the experimental results, a plausible reaction mechanism was proposed: the Zr4+ sites catalyze the transfer hydrogenation of carbonyl groups and the HPW clusters promote the esterification of LA with isopropanol and lactonization to afford γ-GVL. Moreover, HPW@MOF-808 is resistant to leaching and can be reused for five cycles without significant loss of its catalytic activity.
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MICROCHEMICAL JOURNAL
·
2023
·
IF 4.8
Shiyi Chen,Feiyang Tian,Juan Peng,Yan Meng,Yu Wang,Xiaogang He,Qian Wang,Ganghui Chu
Chemical warfare agents, especially organophosphorus warfare agents are a variety of various chemical substances employed in warfare that can massively cause damage to the organism even death. The partial catalytic function of Universitetet i Oslo-66 (UiO-66, a zirconium-based metal–organic framework) produced via de novo synthesis is similar to calf intestinal alkaline phosphatase (CIAP, EC 3.1.3.1) and has a lower usage cost, is expected to be a mimetic enzyme for hydrolyzing organophosphorus warfare agents due to the fact that it has lattice defects. 0.1–5.6 mL of acetic acid was added as a regulator to form different lattice defects. Typically, mimetic enzyme activity tests often require expensive reagents as substrates, and the experiment processes are time-consuming and inconvenient. As a result, a novel approach based on near-infrared spectroscopy (NIRs) was developed in this research for predicting UiO-66 mimetic enzyme activity. p -Nitrophenyl phosphate disodium salt ( p NPP) was selected as a lower toxic organophosphorus warfare agent to conduct the subsequent simulant research. The absorbance of the mimetic enzyme catalytic system was evaluated using Ultraviolet–Visible (UV–Vis) spectroscopy to investigate the amount of its activity and compare it with CIAP activity. The synthesized samples’ enzyme activities ranged from 1.91 to 6.67 U/g and their catalytic costs ranged from 0.65 to 2.26 CNY. The powdered samples' near-infrared spectra were obtained. The sample’s enzyme activity data were linked with each sample’s original NIR spectra to establish the NIR model. A partial least squares (PLS) model of mimetic enzyme activity was developed by coupling spectral preprocessing with a variable screening technique. The root-mean-square error of cross-validation (RMSECV), the correlation coefficient of validation set (R) value, and the ratio of prediction to deviation (RPD) value were employed as assessment model indicators. The near-infrared spectrum model was developed by merging the best 2nd derivative spectral preprocessing with the Competitive Adaptive Reweighted Sampling (CARS) variable screening method. This model's RMSECV was 0.41 U/g, the correlation coefficient of calibration set (R_cv) value was 0.916, the root-mean-square error of prediction (RMSEP) set was 0.52 U/g, R was 0.948, and RPD was 2.51. As a result, the established model could be implemented to quantify the activity of UiO-66 quickly by including more variations of de novo -synthesized samples. The prediction method is simple, rapid, low cost and adaptable to be the theoretical and practical basis for further studying other interdisciplinary research work in biomimetic enzymology and spectroscopy.
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Journal of Natural Gas Chemistry
·
2012
·
IF 1.348
Lincai Peng,Junping Zhuang,Lu Lin
Effects of Zr/Ti molar ratio in SO 2− 4 /ZrO 2 -TiO 2 solid acid catalyst calcined at different temperatures on its surface properties and catalytic activity were thoroughly investigated in this paper. The physicochemical characteristics of prepared samples were determined by N2 adsorptiondesorption, XRD, NH3-TPD and XPS techniques, respectively. It was found that the crystallization temperature of the samples increased after the combination of ZrO 2 and TiO 2 ; and phase transformations from the anatase to the rutile of TiO 2 species and the tetragonal to the monoclinic of ZrO 2 species were effectively suppressed at higher temperature. The sample with a Zr/Ti molar ratio of 3/1 calcined at 450 °C showed the highest surface area and the most acid sites among all the tested samples. The acid site densities of samples were relatively closed to each other if they were calcined at the same temperature, however, decreased with the calcination temperature. The result indicates that the sulfur content in samples is a crucial factor to control the acid site density. Calcining the sample at 650 °C and higher temperatures resulted in a significant desorption of sulfate ion on the samples. The synthesized samples were evaluated as a potential catalyst for glucose conversion under the near-critical methanol conditions (200 °C/4 MPa). The results suggested that the relatively weaker acid sites of the catalyst were more favorable for the accumulation of methyl glucosides, while the moderate acid sites were responsible for the formation of methyl levulinate. The catalytic activity for methyl levulinate production almost increases linearly with the catalyst acid site density. The catalyst deactivation is due to the loss of sulfate ion and the two catalysts with Zr/Ti molar ratios of 3/1 and 1/3 could effectively alleviate the deactivation caused by sulfate solution in the reaction medium and can be reused after calcination with the reuse rate of over 90% in terms of the methyl levulinate selectivity.
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CHEMICAL ENGINEERING JOURNAL
·
2017
·
IF 6.216
Peng Hu,Xiaopeng Liang,Muhammad Yaseen,Xiaodan Sun,Zhangfa Tong,Zhongxing Zhao,Zhenxia Zhao
A novel mechano-chemical strategy using dopamine to modify UiO-66(Zr) by N-coordination was proposed to enhance its competitive adsorption for acetaldehyde, chlorobenzene/H 2 O, both thermodynamically and kinetically. The newly synthesized material was characterized by SEM, EDX, XPS, PXRD, FT-IR, TGA/DTG and BET techniques. Results showed that N was successfully grafted into UiO-66(Zr) frameworks through coordination interaction with Zr-O clusters resulting in M-UiO-66(Zr-N 3.0 ). The obtained M-UiO-66(Zr-N 3.0 ) exhibited a significant increase in adsorption of chlorobenzene (4.94 mmol/g) and acetaldehyde (9.42 mmol/g) compared to parent UiO-66(Zr) and UiO-66(Zr)-NH 2 . The H 2 O adsorption uptake of M-UiO-66(Zr-N 3.0 ) decreased by 20% that of UiO-66(Zr) and 47% of UiO-66(Zr)-NH 2 indicating higher hydrophobicity of the modified material. Kinetic performance indicated that diffusivity of chlorobenzene on M-UiO-66(Zr-N 3.0 ) was about 7.8 and 40 times higher than that of the parent UiO-66(Zr) and UiO-66(Zr)-NH 2 respectively and 15.4 times higher than that of H 2 O on itself. Based on the results, the current N-modification strategy can be deemed as an efficient way to improve MOFs competitive adsorption towards VOCs under humid conditions and it might play active role in industries involving adsorbent applications.
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2025
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IF 9.7
Chao Zhang,Yongsheng Gao,Haipeng Wang,Lulu Jiang,Delu Zhang,Shujun Ming,Guangying Fu,Chao Wang,Zhiguo Lv
The dry reforming of methane (DRM) could convert CH 4 and CO 2 into syngas, offering potential for greenhouse gas mitigation. However, DRM catalyst sintering and carbon deposition remain major obstacles. In this study, a highly dispersed PtNi alloy@Zr-doped 3D hollow flower-like MgAl 2 O 4 (AMO) spheres was prepared through a hydrophobic driving strategy. During a 50-hour test at 550 °C, the catalyst exhibited no significant decline in CH 4 and CO 2 conversion rates, demonstrating its excellent anti-sintering and anti-coking performance. The unique anti-coking performance can be attributed to Zr-induced oxygen vacancies, which enhance oxygen mobility and reduce carbon deposition. Besides, doped Zr increases basic active sites, enhancing CO 2 adsorption and activation, thus accelerating carbon species conversion. At 700 °C, the unique synergy between highly dispersed Pt and Ni enabled CH 4 and CO 2 conversion rates to reach 67.5 % and 73.8 %, respectively. The incorporation of Pt or Zr extends the Ni–Ni bond and partially coordinates with Ni, enhancing the stability of the Ni lattice. The reaction of CH 4 and CO 2 follows the Langmuir-Hinshelwood (L-H) mechanism, where both reactant molecules are adsorbed and activated on the metallic sites. Moreover, the effective energy barrier for the CH oxidation pathway is lower by 0.16 eV than that for the C oxidation pathway, which helps suppress the formation of carbon deposits.
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MICROCHIMICA ACTA
·
2021
·Vol. 188
·期 6
·1-11
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IF 5.833
Ma Mingxuan,Zhang Jian,Li Peipei,Du Yingxiang,Gan Jie,Yang Jiangxia,Zhang Liu
Metal-organic framework (UiO-66-NH 2 )-incorporated organic polymer monolith was prepared by thermal polymerization. By virtue of the superior physical and chemical properties, the UiO-66-NH 2 -modified organic monolith was then functionalized by chiral selector cellulase via the condensation reaction between the primary amino groups and aldehyde groups. The synthesized materials were characterized by Fourier transform infrared spectroscopy, high-resolution transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectrometry, thermogravimetric analysis, and nitrogen sorption isotherm. The cellulase@poly(glycidyl methacrylate-UiO-66-NH 2 -ethylene glycol dimethacrylate) (cellulase@poly(GMA-UiO-66-NH 2 -EDMA)) monolith was applied to enantiomerically separate the basic racemic forms of metoprolol, atenolol, esmolol, bisoprolol, and propranolol. In contrast to the cellulase@poly(GMA-co-EDMA) monolith without UiO-66-NH 2 , the cellulase@poly(GMA-UiO-66-NH 2 -EDMA) monolith reveals significantly improved enantiodiscrimination performance for metoprolol (Rs: 0 → 1.67), atenolol (Rs: 0 → 1.50), esmolol (Rs: 0 → 1.52), bisoprolol (Rs: 0 → 0.36), and propranolol (Rs: 0 → 0.44). The immobilization pH of cellulase, buffer pH, UiO-66-NH 2 concentration, and the proportion of organic modifier were evaluated in detail with enantiomerically separating chiral molecules. The intra-day, inter-day, column-to-column, and inter-batch precision have been discussed, the result was preferable, and the relative standard deviation (RSD) of separation parameters was <4.3%. Graphical abstract
Schematic representation of the preparation of a UiO-66-NH 2 -modified organic polymer monolith for enantioseparating five racemic β-blockers. UiO-66-NH 2 was synthesized and converted into a monolith as the stationary phase. Then, the modified monolith containing cellulase as the chiral selector was applied in a capillary electrochromatography system for enantioseparating chiral drugs.
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高影响因子
RSC Advances
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2022
·Vol. 12
·期 33
·21574-21581
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IF 4.036
Junfeng Zhu,Xiaorong Meng,Wen Liu,Yabing Qi,Siyi Jin,Shanshan Huo
We present an efficient and easy synthesis method for incorporating organocatalytic moieties into Zr-metal organic frameworks (Zr-MOFs). The catalytic activity and selectivity of the new chiral catalysts were improved by adjusting the aperture of the MOF cavities. The hole size of the Zr-MOF was modulated by adding acid and replacing bridge ligands during synthesis. The difunctional chiral units of amino acid–thiourea are anchored onto the Zr-MOF by a mild synthesis method from an isothiocyanate intermediate which could effectively avoid the racemization of chiral moieties in the synthesis process. By means of specific surface area measurement (BET), scanning electron microscopy (SEM) and powder X-ray Diffraction (PXRD), it was confirmed that Zr-MOFs with different pore sizes were synthesized without breaking the basic octahedral structure of the MOF. Finally, good yields (up to 83%) and ee values (up to 73%) were achieved with the new heterogeneous catalysts in 48 hours for the aldol reaction of 4-nitrobenzaldehyde with acetone. By contrast, using the catalyst support without modulating the synthesis, the yield (30%) and the ee-value (26%) were both low. Experiments have confirmed the important influence on the reaction selectivity of providing a suitable reaction environment by controlling the aperture of MOF cavities.
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JOURNAL OF ALLOYS AND COMPOUNDS
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2025
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IF 6.3
Xinwei Xie,Yaoliang Huang,Li Xu,Guangyu Luo,Haifeng Liu,Xinlong Zhang,Jinyue Yang,Junze Lei,Xiaoyuan Yu
O3-type Ni/Mn-based transition metal oxides have garnered significant interest as cathode materials for sodium-ion batteries (SIBs) due to their high specific capacity and abundant resources. However, their commercialization application has been impeded by rapid capacity fading owing to structural degradation, gas evolution, irreversible phase transitions during charge/discharge cycling. Herein, The Zr 4 + /F - dual-doped strategy is developed to boost the Na-storage performance of Ni/Mn-based O3-NaNi 0.3 Fe 0.1 Mn 0.47 Cu 0.1 Zr 0.03 O 2-x F x (NFMCZF-x) layered oxide cathode material prepared by high temperature calcination method. Structural and electrochemical analyses reveal that Zr⁴⁺ doping expands Na⁺-layer spacing and F⁻ doping strengthens transition metal-oxygen bonds. These synergistic effects of Zr 4+ /F - dual-doping is benefit to suppressing O3↔P3 phase transitions, Jahn-Teller distortion and irreversible oxygen redox. Thus, the optimized NFMCZF-0.03 cathode delivers high specific capacity (178 mAh g −1 at 0.1 C) and excellent cycling stability (72 % capacity retention after 100 cycles at 1.0 C). This study establishes dual doping as an effective strategy for developing Ni/Mn-based layered oxide as high-performance cathodes for SIBs.
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LANGMUIR
·
2025
·
IF 3.9
Shangpu Zhuang,Yilin Lei,Fan Xue,Tao Wei,Di Hao,Luming Qi,Lichun Nian,Yuyu Sun,Mifen Cui,Zhuxiu Zhang,Ruiping Wei,Jihai Tang,Xu Qiao
In heterogeneous catalysis research, a significant challenge is to elucidate how metallic copper (Cu0) and cuprous (Cu+) phases interact with their supporting materials, with a special emphasis on how oxygen vacancy (OV) sites participate in hydrogenation processes. In this work, Cu/CexZr10-x catalysts were prepared by introducing Zr-incorporated Ce-MOF, followed by copper impregnation and calcination. Characterization by TEM, XPS, EPR, H2-TPD, Py-IR spectroscopy, and in situ FTIR revealed that Zr doping enhanced the OV concentration, stabilized Cu+ species, and generated abundant Lewis acid sites. The optimal Zr content effectively balances the Cu0/Cu+ redox couples and acid sites, accelerating desired reactions, while excessive Zr incorporation leads to increased Brønsted acidity and promotes undesirable side reactions. These features synergistically enhance the adsorption of 5-HMF, activate carbonyl groups, and facilitate the sequential hydrogenation and deoxygenation processes, thereby achieving 5-HMF fully converted and achieving a 2,5-DMF selectivity of 98.2% under optimal reaction parameters. This study clarifies the cooperative mechanism among Cu active sites, OV, and acid sites in the conversion of 5-HMF and demonstrates that rational Zr incorporation in MOF-derived Cu/CexZr10-x catalysts can precisely modulate surface properties and significantly improve catalytic performance. These findings offer valuable guidance for the rational design of advanced heterogeneous catalysts aimed at biomass valorization and the production of renewable fuel.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
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IF 8.1
Chao Duan,Shasha Che,Guodong Tian,Yiyang Che,Xiaoran Nie,Lei Dai
Abundant hazardous pollutants, in particular heavy metal ions and microbes, in aqueous systems seriously threaten ecological safety and human health. Photocatalysis is deemed an appealing solution yet remains challenging to exploit more efficient, economical, and sustainable photocatalytic materials. In this study, we successfully fabricated a cellulose paper-based composite membrane, namely Zr-TCPP@PDA@FP, for photoreduction of Cr(VI) and photothermal antimicrobial. For the resultant composite membrane, the self-polymerization polydopamine (PDA)-coated cellulose fibers act as sustainable scaffolds to anchor the in-situ synthesized porphyrin-doped UiO-66-NH 2 (Zr-TCPP) nano-photocatalysts. The hypotheses are that: 1) porphyrin doping in Zr-TCPP can both reinforce the visible-light absorption and the transport of photogenerated electrons; 2) mussel-inspired PDA coating on fiber surface not only services as binder to promote the Zr-TCPP loading and dispersion, but also functions as heterojunction interface to accelerate photogenerated electron separation and transfer from Zr-TCPP; As a result, Zr-TCPP@PDA@FP exhibited significant photocatalytic reduction towards Cr(VI), achieving a removal efficiency of 93.9 % within 20 mins and cycling stability. Besides, the hybrid membrane also featured excellent photothermal antibacterial performance (over 99 % for both E. coli and S. aureus ). This work will inspire the development of economic and sustainable cellulose-based functional materials for efficient wastewater remediation.
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危险品化学品经营许可证（带存储）