RSC Advances
·
2019
·Vol. 9
·期 65
·37733-37738
·
IF 3.049
Yanghe Fu,Jieyu Wu,Rongfei Du,Ke Guo,Rui Ma,Fumin Zhang,Weidong Zhu,Maohong Fan
Defect engineering can be a promising approach to improve the photocatalytic performance of metal–organic frameworks (MOFs). Herein, a series of defective NH2-UiO-66(Zr) materials were synthesized via simply controlling the synthesis temperature, with concentrated HCl as the modulator and then these as-prepared samples were used to systematically investigate the effects of their structural defects on photocatalytic CO2 reduction. Remarkably, these MOFs with defects exhibit significantly enhanced activities in photocatalytic CO2 reduction, compared with the material without defects. The defect engineering creates active binding sites and more open frameworks in the MOF, and thus facilitates the photo-induced charge transfer and restrains the recombination of photo-generated charges efficiently. The current work provides an instructive approach to improve the photocatalytic efficiency by taking advantage of the structural defects in MOFs, and could also inspire more work on the design of advanced defective MOFs.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ELECTROCHEMISTRY
·
2018
·Vol. 86
·期 4
·153-157
·
IF 1.074
Xiyun YANG,Jianfeng ZHANG,Shenghai YANG,Niuchang OUYANG
To understand the role of water on zirconium passivation in n-butanol solutions containing Bun4NBr, composition and corrosion properties of the passive film were studied using cyclic voltammetry, X-ray photoelectron and electrochemical impedance spectroscopy. Zirconium undergoes spontaneous passivation followed by pitting corrosion as a result of passivity breakdown by the aggressive attack of bromide anions. The passive film consists mainly of ZrO2, ZrO2·2H2O and a small amount of zirconium butoxide. The pitting potential shifts positively and pitting corrosion is seriously inhibited with the addition of a small amount of water. Water improves the pitting corrosion resistance of the passive film by changing the thickness and the relative ratio of OH−/O2−. The result is helpful to electrosynthesize zirconium butoxide with high energy efficiency.
✓ 已验证
产品关联
DOI
高影响因子
DALTON TRANSACTIONS
·
2024
·
IF 3.5
Zhengyan Wang,Chenhao Yuan,Dong Yang,Mifen Cui,Jihai Tang,Zhuxiu Zhang,Xu Qiao
It is of great significance to develop catalysts for the degradation of hexachlorobenzene from the industrial thermal process. In this paper, formic acid was used as a modulator to generate defect sites in Ce/Zr-UiO-66 with intrinsic Brønsted acidity. The defective formate ligands were removed through methanol–water vapor treatment to expose additional open metal sites with Lewis acidity. The intrinsic Brønsted acid sites of the resulting Ce/Zr-UiO-66-FA-P achieved a hexachlorobenzene degradation efficiency of 99.5% at 250 °C. The generated Lewis acid sites facilitated the C–C cleavage of degradation intermediates. More than 95.0% of the final products were CO2/CO, coupled with chlorinated alkanes/alkenes, which outperformed other benchmark metal oxide catalysts. The Ce/Zr-UiO-66-FA-P catalyst maintained its catalytic activity in the model industrial flue gas and humid environment. The degradation pathway of hexachlorobenzene was tracked using in situ FT-IR spectra.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
FUEL
·
2017
·
IF 4.601
Xiaotian Zhang,Pengcheng Huang,Aili Liu,Mingyuan Zhu
Owing to the high prices and other shortcomings associated with the existing methods of complex catalyst preparation, we used the UIO-66(Zr) metal–organic frameworks to directly catalyze the oxidative desulfurization (ODS) reaction. The synthesized UIO-66(Zr) was characterized using nitrogen adsorption–desorption isotherm analysis, X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. Under optimal reaction conditions, the ODS conversion of dibenzothiophene (DBT) reached 100%. This excellent catalytic activity was attributed to the unsaturated coordination of Zr, which may produce beneficial Lewis acid sites.
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2018
·Vol. 28
·期 16
·1707356
·
IF 13.325
Zhe Wang,Shuanggang Hu,Jian Yang,Ajuan Liang,Yongsheng Li,Qixin Zhuang,Jinlou Gu
Introduction of large pore in the primitive microporous metal–organic frameworks (MOFs) with tailorable particle size can endow them with desired properties for potential applications in the intracellular delivery of membrane-impermeable proteins. However, no research is found to focus on this topic until now. Herein, a monocarboxylic acid (MA) and organic base comodulation strategy is developed to synthesize the hierarchically porous UiO-66 nanoparticles. MA of dodecanoic acid is utilized to control the pore size while trimethylamine (TEA) plays a key role in modulating the nucleation of crystallization to regulate the particle size. In comparison with microporous UiO-66, a model protein of cytochrome c (Cyt c) could be efficiently loaded into the mesoporous MOFs (mesoMOFs). The size-dependent cellular uptake is also evaluated, and it is verified that mesoMOFs with particle size of 90 nm could be endocytosed into living cells with highest efficiency. These outstanding merits enable the current mesoMOFs not only to exhibit efficient encapsulation of Cyt c but also facilitate the protein delivery into the cytosol and subsequent endosomal escape. Given the exceptional chemical stability, hierarchically porous structure as well as tunable particle size, the elaborated mesoUiO-66 nanoparticles might offer a promising platform for a variety of biomedical applications.
✓ 已验证
产品关联
DOI
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
·
2018
·Vol. 24
·期 12
·2962-2970
·
IF 5.16
Pengfei Yang,Fangxin Mao,Yongsheng Li,Qixin Zhuang,Jinlou Gu
Graphical Etch a sketch : A simple and efficient monocarboxylic acid etching (MAE) strategy was developed to prepare hierarchical porous UiO-66, which inherits excellent stability from its parent material and the pore parameters can be controlled by adjusting the monocarboxylic acid concentration and reaction temperature. A new monocarboxylic acid etching (MAE) strategy was developed for transforming chemically stable Zr-based metal-organic frameworks (MOFs) of UiO-66 to their hierarchical porous counterpart. The key design element was based on the incomplete replacement of bridging ligands in MOFs by monocarboxylic acids (MAs), leading to the departure of partial ligands and metal clusters to create mesopores in MOFs. A series of MAs with different acidity and carbon chain length were tested, and propionic acid (PA) was screened to be the suitable choice. The textural features including pore size distribution, specific surface area, and pore volume of the obtained products can be controlled by adjusting the MA concentration and reaction temperature. The obtained hierarchical porous MOFs inherited excellent stability from their parent materials. Additionally, the MAE strategy was universal to construct hierarchical porous Zr-based MOFs, and it was expanded to etch UiO-66 derivatives. The excellent adsorption behavior of the resultant hierarchical porous Zr-based MOFs over two enzymes with different size was also successfully exemplified, demonstrating their application potentials with bulky molecules involved.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2024
·
IF 4.9
Jian Feng,Wenjun Jiang,Zhenzhen Tang,Keqi Shi,Haimei Jiang,Linghao Zhang,Mi Zhou,Shuangkou Chen
The design and synthesis of effective adsorbent for extracting gold from wastewater has significant environmental and economic implications. However, the development of an adsorbent with high efficiency remains challenging. Herein, we report the synthesis of an azo-phenylthiourea functionalized metal-organic framework (MOF, azo-PT-UiO-66) and its application for the adsorption of Au(Ⅲ) from aqueous solution. The performance of azo-PT-UiO-66 was significantly improved as compared with the unmodified MOF, achieving an adsorption capacity up to 650.07 mg/g. Based on the results of kinetic, isothermal and thermodynamic studies, the adsorptive behaviour was a homogeneous and spontaneous chemisorption. Moreover, characterizations revealed that the appearance of metallic gold was caused by the reduction of Au(Ⅲ) via -NH 2 groups. The density functional theory (DFT) calculations confirmed that the chemisorption is owing to the formation of coordinate bonds between azo, S and Au(Ⅲ). This work provides a clean and sustainable method for the recovery of gold from industrial wastewater.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Can Sun,Shouxin Zhu,Jingyi Qu,Zhexiao Zhu,Yutong Chen,Xuewei Tu,Wenya Cai,Zhiqin Yu,Yibin Liu,Shijie Zhang,Hui Zheng
Photocatalytic nitrogen fixation is seen to be a potential technology for nitrogen reduction due to its eco-friendliness, low energy consumption, and environmental protection. In this study, photocatalysts with abundant oxygen vacancies (Zr-naphthalene dicarboxylic acid (Zr-NDC) and Zr-phthalic acid (Zr-BDC)) were designed using 1,4-naphthalene dicarboxylic acid (H 2 NDC) and 1,4-phthalic acid (H 2 BDC) as ligands. Since the structure of H 2 NDC includes one extra benzene ring than H 2 BDC, the charge density differential of the organic ligand is probably altered. The hypothesis is proved by density function theory (DFT) calculation. The abundant oxygen vacancies of the catalyst offer numerous active sites for nitrogen fixation. Concurrently, the process of ligand–metal charge transfer facilitates photo-electron transfer, creating an active center for nitrogen reduction. Additionally, the functionalization of ligand amplifies another pathway for charge transfer, broadening the light absorption range of Metal-organic framework (MOF) and increasing its capacity for nitrogen reduction. In contrast to H 2 BDC, the benzene ring added in H 2 NDC structure acts as an electron energy storage tank with a stronger electron density difference favorable for photogenerated electron-hole separation resulting in higher photocatalytic activity in Zr-NDC. The experimental results show that the nitrogen fixation efficiency of Zr-NDC is 163.7 µmol g −1 h −1 , which is significantly better than that of Zr-BDC (29.3 µmol g −1 h −1 ). This work utilizes cost-effective and non-toxic ingredients to design highly efficient photocatalysts, thereby significantly contributing to the practical implementation of green chemistry principles.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Scientific Reports
·
2017
·Vol. 7
·期 1
·1-12
·
IF 4.259
Song Jun,Wang Xueqin,Yan Jianhua,Yu Jianyong,Sun Gang,Ding Bin
Self-standing photocatalytic membranes constructed from TiO 2 nanofibers hold great promise in environmental remediation; however, challenges still remained for the poor mechanical properties of polycrystalline TiO 2 nanofibers. Herein, soft Zr-doped TiO 2 (TZ) nanofibrous membranes with robust mechanical properties and enhanced photocatalytic activity were fabricated via electrospinning technique. The Zr 4+ incorporation could effectively inhibit the grain growth and reduce the surface defects and breaking point of TiO 2 nanofiber. The as-prepared TZ membranes were composed of well-interconnected nanofibers with a high aspect ratios, small grain size and pore size, which exhibited good tensile strength (1.32 MPa) and showed no obvious damage after 200 cycles of bending to a radius of 2 mm. A plausible bending deformation mechanism of the soft TZ membranes was proposed from microscopic single nanofiber to macroscopical membranes. Moreover, the resultant TZ membranes displayed better photocatalytic performance for methylene blue degradation compared to a commercial catalyst (P25), including high degradation degree of 95.4% within 30 min, good reusability in 5 cycles, and easiness of recycling. The successful preparation of such fascinating materials may open up new avenues for the design and development of soft TiO 2 -based membranes for various application.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL PHYSICS LETTERS
·
2025
·
IF 3.1
Jiaying Yang,Yiman Qian,Jingqi Yan,Jiayin Li,Pengfei Liu
Advanced oxidation processes (AOPs) surpass photocatalytic methods in energy efficiency, enabling organic dye degradation under mild conditions without light activation. In this study, we crafted a highly effective Zr(WO 4 ) 2 catalyst for AOPs, rigorously characterized through SEM, TEM, TG-DTA, N 2 -sorption, XRD, and XPS analyses. The system demonstrated exceptional catalytic performance, achieving 95.62 % phenol removal (2 mg/L) within 60 min using only 0.1 g/L Zr(WO 4 ) 2 and 1 mM PMS, with singlet oxygen ( 1 O 2 ) identified as the dominant reactive species. Crucially, the synergistic redox interplay between Zr 4+ and WO 4 2− surface species emerged as the critical driver for efficient PMS activation. Beyond its catalytic prowess, the Zr(WO 4 ) 2 system exhibited remarkable reusability and versatility across multiple applications, while generating treated water with minimal toxicity, positioning it as an environmentally promising solution.
✓ 已验证
产品关联
DOI
高影响因子
Advanced Science
·
2025
·
IF 14.1
Siqi Qiu,Hao Wan,Yuechao Yao,Xiao Xu,Zhangjian Li,Yongbiao Mu,Biaolin Peng,Hongliang Wu,Jizhao Zou,Lin Zeng
Iron-nitrogen-carbon (Fe-N-C) materials are promising non-precious metal catalysts for the oxygen reduction reaction (ORR), yet their long-term stability remains a critical challenge due to the dissolution of Fe-based active sites and corrosion of the carbon support. Here, a Fe-Zr dual-atom carbon-based catalyst (Fe,Zr-NC) via a one-step solid-state synthesis method is reported. The introduction of atomically dispersed Zr–N units adjacent to Fe–N 4 centers creates a dual-metal coordination structure that modulates the local electronic environment of Fe and weakens * OH adsorption, which is the rate-limiting step in the ORR process. Density functional theory (DFT) calculations reveal that the Fe–Zr synergy positions the catalyst near the apex of the ORR activity volcano. Extended experimental EXAFS confirms a Fe–Zr distance of ≈3.30 Å, closely matching the theoretical optimum (≈3.39 Å). As a result, Fe, Zr-NC achieves a high half-wave potential (0.891 V vs reversible hydrogen electrode (RHE)) with negligible activity loss over 5000 cyclic voltammetry cycles, outperforming commercial Pt/C. In zinc–air batteries, the catalyst delivers a peak power density of 185.7 mW cm −2 and operates stably for over 453 h. This work highlights the importance of dual-atom synergy in tuning intermediate binding energies and provides design principles for next-generation ORR electrocatalysts.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
LANGMUIR
·
2024
·
IF 3.7
Zhuoxue Li,Yunlei Shi,Yimian Ding,Dazhen Xiong,Zhiyong Li,Huiyong Wang,Jikuan Qiu,Xiaopeng Xuan,Jianji Wang
A Pickering emulsion is a natural microreactor for interfacial catalysis in which an emulsifier is critical. Recently, a metal–organic framework (MOF) has attracted attention to emulsify water–organic mixtures for constructing a Pickering emulsion. However, a few stimuli-responsive Pickering emulsions based on MOFs have been reported, and the MOF emulsifiers cannot be regenerated at room temperature. Herein, the Zr-MOF with a rodlike morphology is synthesized using ionic liquid as a modulator and then modified with n-(trimethoxysilylpropyl)imidazole (C3im) to prepare a series of functionalized Zr-MOFs (MOF-C3im). It is found that MOF-C3im is an excellent emulsifier to construct stable and CO2-responsive Pickering emulsions even at low content (>0.20 wt %). Notably, the emulsification and demulsification of the emulsions can be easily and reversibly switched by bubbling of CO2 and N2 alternatively at room temperature because CO2 and imidazole molecules anchored on the Zr-MOF underwent a reversible acid–base reaction, resulting in an obvious change in the wettability of the emulsifier. As a proof of concept, the reduction reactions of nitrobenzene have been successfully carried out in these Pickering emulsions, demonstrating the efficient integration as a microreactor for chemical reaction, product separation, and emulsifier recycling under ambient conditions. This strategy provides an innovative option to develop stimulus-responsive Pickering emulsions for sustainable chemical processes.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）