鑽石舞台

題目：Fabrication and Water Purification Applications of MIL-53(Al)-based Functional Materials: a Review

作者：SUN Xuezi, WANG Chongchen*, LI Yuhang

摘要：This paper reviews the fabrication strategies, morphology regulations and application (fluorescence sensors, adsorbents and photocatalysts for detecting and eliminating pollutants from water) of MIL-53(Al), NH2-MIL-53(Al) and their composites. The fabrication approaches like hydro/solvothermal methods, microwave-assisted synthesis and homogeneous phase direct synthesis along with the reaction conditions are introduced. MIL-53(Al) and NH2-MIL-53(Al) show excellent performance in detecting pollutants in water, with the characteristics of fast response time and high sensitivity. MIL-53(Al) and NH2-MIL-53(Al) can achieve adsorptive removal toward pollutants in water due to their 『respiratory effect』, large surface area and rich active sites. The performance of MIL-53(Al) in adsorption, advanced oxidation degradation, sensing detection can be improved by compositing with other functional materials. In a word, MIL-53(Al) and NH2-MIL-53(Al), as environment-friendly environmental functional materials, show great application potential in water purification field.

期刊信息：Mater. Rep.

DOI：10. 11896/cldb.22070231

題目：Derivatives of two-dimensional MXene-MOFs heterostructure for boosting peroxymonosulfate activation: enhanced performance and synergistic mechanism

作者：Xin Guo, Hao Zhang, Yiyuan Yao, Chengming Xiao, Xin Yan, Ke Chen, Junwen Qi, Yujun Zhou, Zhigao Zhu, Xiuyun Sun, Jiansheng Li*

摘要：Integrating the merits of the substrate and active sites with the water matrix is of significant importance to design novel catalysts for peroxymonosulfate (PMS)-based advanced oxidation processes. A sandwich-like heterostructure catalyst (MCoO@Co-N-C) were fabricated via anchoring zero-dimensional metal-organic frameworks (MOFs)-derived CoO nanoparticles on two-dimensional Ti3C2TxMXene nanosheets. Benefiting from the distinctive structure, the resultant catalysts achieved excellent decontamination performance under high salinity conditions (200 mM). Nearly 100% efficiency of bisphenol A (BPA) was degraded within 10min only using 0.05 g L-1catalyst and 0.1 g L-1PMS, with exceptional high turnover frequency (TOF) value (8.64 min-1) which was 22.5 times higher than that of MOFs derived catalysts without MXene. A mediated-electron transfer mechanism is found to be conducive to the oxidation of BPA. This work provides a new approach to novel catalysts designed for removing trace organic contaminants (TrOCs) in saline water.

期刊信息：Appl. Catal. B: Environ.

DOI:10.1016/j.apcatb.2022.122136

題目：Selective rubidium recovery from seawater with metal-organic framework incorporated potassium cobalt hexacyanoferrate nanomaterial

作者：Dai Quyet Truong, Youngwoo Choo, Nawshad Akther, Sharaniya Roobavannan, Ahmad Norouzi, Vipul Gupta, Michael Blumenstein, Tien Vinh Nguyen*, Gayathri Naidu*

摘要：Rubidium (Rb) is a highly-priced metal due to its scarcity in ore form. Seawater is a promising alternate source for recovering Rb. Potassium cobalt hexacyanoferrate (KCoFC) ion exchange nanomaterial achieves high selective Rb recovery in seawater; however, its performance is impaired by high potassium concentration in seawater. To address this issue, this study modified the structure of KCoFC by grafting zeolitic imidazole frameworks (ZIF) with KCoFC to synthesize KCoFC@ZIF. Detailed physicochemical characterization showed the successful synthesis of KCoFC@ZIF. KCoFC@ZIF increased the surface area of the material but reduced its pore diameter, which was influenced by 2-methylimidazole (HMIM) concentration. Reducing HMIM composition to a ratio of KCoFC:HMIM:Zn 1:12:5 (KCoFC@ZIF(d)) achieved a reasonable balance in increasing the material surface area by 63 % to that of KCoFC while reducing the pore diameter by only 30 %. Rb uptake capacity of KCoFC@ZIF(d) (Langmuir qmax1279.35 mg/g) was 8-folds higher with accelerated kinetics compared to KCoFC (qmax143.21 mg/g). The capacity of both KCoFC and KCoFC@ZIF(d) was reduced by about 45 % in seawater due to the presence of potassium. Nevertheless, KCoFC@ZIF(d) maintained a relatively high Rb uptake of 236 mg/g in seawater due to its high Rb selective capacity; consequently, demonstrating its potential for Rb extraction from seawater. KCoFC@ZIF(d) demonstrated a similar peak structure after five consecutive operative cycles, thus, establishing its regenerative efficiency. Overall, it can be indicated that KCoFC controls the selective Rb uptake of KCoFC@ZIF. At the same time, the grafted ZIF layer acts as a catalytic layer that increases the surface area and ion dehydration of KCoFC@ZIF to enhance the Rb diffusion into the core structure of KCoFC.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2022.140107

題目：Hierarchically Porous Metal–Organic Frameworks: Synthetic Strategies and Applications

作者：Yao Yao, Xinyu Zhao, Ganggang Chang*, Xiaoyu Yang*, Banglin Chen*

摘要：Metal–organic frameworks (MOFs), assemblies comprised of metal nodes and organic ligands, have captured the interest of scientists during the past two decades. The flexible approaches developed for the custom design of framework structures and intriguing pore-containing environments formed at the molecular or atomic level have elevated the interest in MOFs to a level that is far beyond those of traditional porous solids (e.g., zeolites, activated carbon). Nevertheless, applications of MOFs, particularly in the process involving large molecules, have been restricted by narrow pore size. To overcome the restriction imposed by the micropores, a great effort has been given to related hierarchically porous MOFs (HP-MOFs), which combine high surface areas of microporous materials with the spaces of meso-/macropores that allow accessibility and diffusivity by large molecules. This review focuses on recent advances and breakthroughs in the design and synthesis of HP-MOFs that contain intrinsic pores, defective pores, and pores based on interparticle accumulation, respectively. In addition, the applications of HP-MOFs in heterogeneous catalysis, water remediation, gas storage and separation, biotechnology, energy storage, and sensing are summarized from the perspective of the relationships between synthetic strategies and applications. Finally, challenging and promising research directions in the field of HP-MOFs are discussed.

期刊信息：Small Struct.

DOI:10.1002/sstr.202200187

題目：Tight UF membranes with ultrahigh water flux prepared by in-situ growing ZIF particles in NIPS process for greatly enhanced dye removal efficiency

作者：Hang Yu, Dajian Cai, Shiyang Li, Congjie Gao, Lixin Xue*

摘要：Tight ultra-filtration (TUF) membranes with in-situ grown zeolitic imidazole framework (ZIF) particles embedded in and packed under porous polysulfone (PSF) separating layers were prepared using non-solvent induced phase separation (NIPS) processes. Imidazole ligands contained in casting solutions were released and reacted with divalent Zn2+cations pre-loaded on non-woven fabric supporting layers. The capillary filling pore size and molecular-weight-cut-off (MWCO) Stokes solute rejection pore size of the formed ZIF/PSF TUF were tuned by varying the loading levels of Zn (II), polyvinylpyrrolidone (PVP) and imidazole, as well as the NIPS reaction time. With thinned PSF separating layer (200–500 nm) and embedding water permeating short-cuts from the ZIF particles, ZIF/PSF TUF membranes showed 7 times higher water permeance (up to 250 L/(m2 h bar)) and greatly enhanced dye/salt retention selectivity, bearing high potential for applications in dye and textile waste water treatment processes.

期刊信息：J. Membr. Sci.

DOI:10.1016/j.memsci.2022.121136

題目：Synergy of dielectric barrier discharge plasma and magnetically separable MOF-derived Co@C composites for the improved degradation of norfloxacin antibiotics in water

作者：Li Huang, Xiangyu Chen, Bing Wan, Shuxia Xua*.

摘要：Norfloxacin (NOR) is a highly toxic fluoroquinolone antibiotic, which is continuously discharged into aquatic environment. Due to its poor biodegradability, it is difficult to be removed and has exerted a serious impact on environmental risk. In this paper, a coaxial double dielectric barrier discharge (DBD) device was designed and built, then was synergic with cobalt-carbon (Co@C) composites for the improved degradation of NOR in wastewater with high degradation efficiency. The Co@C composite, a porous carbon material, was synthesized by calcination of Co-metal organic frameworks (Co-MOFs), and was further characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, Brunauer-Emmett-Teller surface analyzer, Fourier transform infrared spectrometry and vibrating sample magnetometer. The combination of DBD with Co@C system has an obvious synergistic effect for the removal of NOR. The degradation rate could reach to 84.7 % within the treatment time of 15 min, which were 14.1 % higher and 10 min shorter than that of solo DBD system. The synergistic factor was estimated to be 1.12, and the energy yield of process could reach the maximum of 7.6 mg/kWh. The effects of discharge voltage, pH, NOR initial concentration and Co@C dosage on the degradation rate of NOR have been explored in detail. The experimental results indicated that the system of DBD coupled with Co@C for NOR degradation was appropriate in a wide initial pH from 3.0-11.0. Moreover, Co@C can be reused several times and convenient to be magnetically recycled. Furthermore, it was proved that O, •OH and HO were the main reactive oxygen species during the catalytic decomposition reactions of NOR, and the generated O in DBD system could be converted into •OH under the synergic catalysis of Co@C, further promoting degradation efficiencies of NOR. Furthermore, main intermediate products of NOR degradation were analyzed by liquid chromatography-mass spectrometry, and possible degradation mechanism and pathways were speculated.

期刊信息：Sep. Purif. Technol.

DOI:10.1016/j.seppur.2022.122488

題目：Ultrafast and selective adsorption of pharmaceuticals from wastewater by precisely designed metal organic framework with missing linker defects

作者：Yuhua Cao, Xiang Li*, Bo Wang

摘要：Pharmaceuticals and personal care products (PPCPs) are widely used and frequently detected in the environment. A series of novel, precisely designed metal-organic framework (MOF) materials with long-range ordered defective structure was proposed by tuning the node connectivity and missing linkers/clusters. The adsorption abilities of anti-inflammatory drugs were significantly improved (79.87 mg/g, 561.37 mg/g·min for ibuprofen (IBU)) over the defective UiO-66 (node connectivity = 7.8), which were 2.5 and 59.8 times higher than that over the defect-free one (32.16 mg/g, 9.39 mg/g • min). The adsorption rate constant of IBU was accelerated 1.12 × 10 times greater than that of the activated carbon. For the first time, the performance was evaluated under the environmentally relevant concentration (200 μg/L to 0.025 μg/L) with removal percentages ∼ 90% within 1 min. Theoretical calculations were conducted to study the mechanism. Furthermore, 15 micropollutants with various functional groups (sulfonamides, quinolones, macrolides, etc.) with high environmental risks proved our concept that electrostatic interaction could be the primary mechanism. Real wastewater in Beijing was sampled and evaluated the performance of removing the pharmaceuticals (concentration: 199.21 ± 3.65 ng/L ∼ 0.10 ± 0.01 ng/L), a complete removal can be achieved in only 3 min with concentrations below instrumental detection limits. This finding provides a promising strategy for designing materials for rapidly removing pharmaceuticals in water.

期刊：J. Mater. Chem. C

DOI:10.1016/j.jclepro.2022.135060

題目：Efficient activation of peroxydisulfate by FeNC for chloramphenicol degradation: Performance and mechanisms

作者：Huihui Wu, Yuerao Gao, Xin Xu, Xiu Li, Jun Cui, Aijun Lin*

摘要：In this study, a green Fe and FeN co-doped carbon nanocomposite catalyst (FeNC) was synthesized by a simple and economical method and applied to activate peroxodisulfate (PDS) for the efficient oxidation of chloramphenicol (CAP). Characterization analysis found that the surface of Fe and FeN nanoparticles supported on nitrogen-doped carbon was wrapped by nitrogen-doped carbon nanosheets, forming a "core-shell" structure. The FeNC@PDS system has good catalytic activity, and the CAP degradation efficiency reaches 91.2% within 60 min. FeNC@PDS system exhibits excellent catalytic degradation performance under a wide pH range (2.4–8.3) and shows good reusability. The calculated % reaction stoichiometric efficiency (RSE) reached values up to 18.86%, which exceeds than those of various reported heterogeneous Fenton-like systems. Quenching experiments and electron paramagnetic resonance characterization confirmed that both free-radicals and non-radicals were involved in the activation of PDS by FeNC. In addition, the possible mechanism of the PDS activation by FeNC was proposed. Finally, the degradation pathway of CAP was determined based on the intermediates. This work provided a novel reference for the design of efficient heterogeneous catalysts to remove organic pollutants efficiently.

期刊：J. Mater. Chem. C

DOI:10.1016/j.jclepro.2022.134981

題目：MOFFeCo/B-CN composites achieve efficient degradation of antibiotics in a non-homogeneous concurrent photocatalytic-persulfate activation system

作者：Jinyang Li, Haofu Wang, Narendra Reddy, Zhijia Zhu, Jian Zheng, Wei Wang, Baojiang Liu, Chunyan Hu*

摘要：We synthesized an MFeCoB0.4CNx%(MOF-Fe/Co nanosheets/boron-doped g-C3N4) composite catalyst for enhancing the concurrent photocatalytic-persulfate activation (CPPA) system and achieved efficient degradation of antibiotics. The role of MOF-Fe/Co is to activate persulfate, while boron-doped g-C3N4can generate photogenerated electrons for the reduction of Co3+/Fe3+to enhance the regeneration of the active center. The rate constant for Tetracycline degradation by the CPPA system was 4.74 and 7.54 times higher than the photocatalytic and persulfate-activated systems, respectively. This composite was shown to be practical and economically viable for antibiotic degradation. The degradation behavior was explored based on experiments, and molecular orbitals and Fukui functions were obtained by density functional theory calculations. Mechanisms were investigated using reactive oxygen species trapping studies and electron spin resonance, and the process was explained in terms of the charge population and electron density difference of MOF-Fe/Co nanosheets. The CPPA system is an ecologically benign technology for removing antibiotic-related risks to the environment and human health.

期刊信息：Sci. Total Environ.

DOI：10.1016/j.scitotenv.2022.159795

題目：Regulation of Porosity in MOFs: A Review on Tunable Scaffolds and Related Effects and Advances in Different Applications

作者：Wenjie Zhang, Reza Taheri-Ledari*, Mahdi Saeidirad, Fateme Sadat Qazi, Amir Kashtiaray, Fatemeh Ganjali, Ye Tian, Ali Maleki*

摘要：Metal-organic frameworks (MOFs) are a form of porous and crystalline material created by combining metal ions and organic linkers and received greater attention because of their distinctive structure and widespread uses in a variety of applications such as gas storage and separation, catalysis, enzyme immobilization, drug delivery, water capture, and sensing. Various well-designed MOF-based composites that combine MOFs with other feature materials such as nanoparticles, quantum dots, natural enzymes, or polymers with notably improved or unique capabilities have recently been described compared with single components. MOFs have been used as provision substrates for nanomaterials and sacrificial templates/precursors in the preparation of various functional nanostructures. The structural-functional relations and role of MOFs are crucial for understanding to synthesize high-performance MOF-based composites effectively and directionally for specific applications. The porosity of MOFs is regarded as one of their most promising properties, as it allows for space on the micro- and meso-scales, thus constraining and exposing their functionalities. MOF research has focused on designing MOFs with high porosity and increasing effective activation methods for conserving and gaining access to their pore space. The most recent advancement of MOFs as precursors for the synthesis of various nanostructures and their possible applications are investigated in this paper. The practical activities of MOFs are categorized and explored through several instances, which can help chemical users comprehend the structural/functional link in MOF-based composites from a new perception. Finally, a perspective on future problems and possible opportunities for high porosity MOFs in various applications is discussed.

期刊信息：J. Environ. Chem. Eng.

DOI：10.1016/j.jece.2022.108836

題目：ZIF-67 and Cobalt-based@heteroatom–doped carbon nanomaterials for hydrogen production and dyes removal via adsorption and catalytic degradation

作者：Ayat Badry Aly Abdellatif, Haitham M.El-Bery, Hani Nasser Abdelhamid*, Sahar A.El-Gyar

摘要：Metal-organic frameworks (MOFs) are promising catalysts for producing clean energy and environmental-based applications. This paper reported one-pot encapsulation of guest molecules, e.g., thiourea (TU) and D-Glucose-6-phosphate disodium salt dihydrate (G6P-Na2), into zeolitic imidazolate frameworks (ZIF-67), denoted as S@ZIF-67 and P@ZIF-67, respectively. The organic guest molecules offered the synthesis of cobalt-based materials (e.g., Co3O4, CoP, and CoS), embedded heteroatoms (P, N, and S) via carbonization. The materials were tested for hydrogen generation via sodium borohydride (NaBH4) hydrolysis. ZIF-67, S@ZIF-67, and P@ZIF-67 displayed maximum hydrogen generation rates (HGRmax) of 27,273, 24,000, and 60,000 mLH2gcat−1min−1, respectively, using 20 mg of the catalyst and 0.2 wt.% of NaBH4at 60 °C. The materials were also investigated as potential catalysts for the adsorption and catalytic degradation of water pollutants such as organic dyes, e.g., methyl orange (MO) and Congo red (CR), with degradation efficiency of 100% and 99% in a short time (30–60 min).

期刊信息：J. Environ. Chem. Eng.

DOI：10.1016/j.jece.2022.108848

題目：Enhanced water permeance and EDCs rejection using a UiO-66-NH2-predeposited polyamide membrane

作者：Bin Zhao, Min Sun, Zhiqiang Guo, Liang Wang*, Yiran Qian, Xiaojia He, Jixiang Li

摘要：Endocrine disrupting compounds (EDCs) have been increasingly detected in drinking water sources, and pose sever threat to human health. Polyamide (PA) based nanofiltration (NF) membrane has great potential for EDCs removal from water, but the removal of hydrophobic EDCs by PA-based membrane is not satisfying due to strong hydrophobic affinity. In this study, UiO-66-NH2/PA membranes were prepared by predepositing hydrophilic UiO-66-NH2onto the substrate prior to interfacial polymerization. The UiO-66-NH2aggregates increased the permeable area and strengthened the 「gutter effect」. Therefore, the pure water flux of UiO-66-NH2/PA increased by 115% compared with that of the thin-film composite (TFC) membrane, and its rejection of Na2SO4was 96%. The hydrophilicity-enhanced PA film reduced its adsorption of EDCs and decreased the driving force for EDCs diffusion. Moreover, the UiO-66-NH2-induced hydrophilic nanochannels, including the interfacial gaps between PA film and UiO-66-NH2aggregates, the gaps in UiO-66-NH2aggregates, and the inherent pores in UiO-66-NH2crystals, alleviated the hydrophobic affinity and effectively restricted EDCs diffusion. The rejection rates of methylparaben, propylparaben, bisphenol A, and benzylparaben by the optimal UiO-66-NH2/PA were 50%, 67%, 75%, and 85%, respectively, and the water/benzylparaben selectivity was 4.4 times as high as that of TFC. The results demonstrate that incorporating hydrophilic metal-organic frameworks (MOFs) can improve the membrane hydrophilicity and create hydrophilic nanochannels, and is an effective strategy to enhance EDCs removal by nanofiltration.

期刊：Chemosphere

DOI：10.1016/j.chemosphere.2022.137114

題目：Flexible Ligand-Gd Dye-Encapsulated Dual Emission Metal-Organic Framework

作者：Ya-Ru Zhang, Xiao-Zheng Xie, Xue-Bo Yin*ab Yan Xia*

摘要：Multiple emission metal-organic frameworks (MOFs) are superior for ratiometric fluorescence sensing and visible detection. Guest-encapsulated strategy is simple by integration of the open structure of MOFs and the abundant selections of emissive guests. Herein, we revealed the factors that affect the performance of host-guest multi-emission MOFs from the selection of ligands, metal nodes, and guest dyes. The size of organic dyes is often larger than 1 nm, to be incompatible to the small pores of traditional MOFs. We therefore selected a flexible ligand, 1,3,5-tris(5-methoxy-1,3-benzene dicarboxylic acid)benzene (L), to enlarge the pore size of MOF to 18 Å. Energy transfer from ligand and guest dye to the metal nodes may occur, so we selected Gd3+ion because of its high excited state level. L and Gd3+ions were used to form Gd-L MOF with the pore size of 18 Å as revealed from single crystal result. Rhodamine B (RhB), as the guest dye with the size of 15.9×11.8×5.6Å3, was encapsulated in Gd-L MOF as RhB@MOF. The matched size between RhB and MOF pore and the breathing effect of the flexible MOF effectively prevented the leakage of RhB. Dual emission was observed at 360 nm and 583 nm under the excitation of 290 nm from RhB@MOF. While Cu2+could quench the emission at 360 nm with the electron transfer procedure, Fe3+could interact to both L and RhB and thus quenched the two emissions, simultaneously. However, the other metal ions showed little effect on the two emissions. Differentiation between Cu2+and Fe3+as well as them from the other metal ions was realized with the dual-emission MOF. Thus, guest-encapsulation strategy is simple and flexible ligand is efficient to encapsulate molecular dye for dual-emission MOFs to improve the sensing performance, while flexible ligand is powerful to enhance the capacity and extend the applications of the MOFs.

期刊信息：Dalton Trans.

DOI：10.1039/D2DT03043H

題目: Magnetic MnFe2O4-MIL-53(Fe) composite as an effective adsorbent for As(V) adsorption in wastewater

作者：Guizhi Yan, Xianjin Qi* Heng Wang, Jiahao Shi

摘要：Arsenic as a significant hazardous pollutant has a severe threat to the natural system, human health, and social sustainability due to its high toxicity and carcinogenicity. Herein, an effective magnetic composite material, MF-MIL-53(Fe), was fabricated by loading magnetic composite material MF on MIL-53(Fe) for removing As(V) from wastewater. Scanning electron microscope (SEM) imaging combined with energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) were used to reveal the Physico-chemical characteristics of the composite material MF-MIL-53(Fe). The effect of four independent variables, including pH (2–9), reaction times (10–360 min), initial concentrations (30–300 mg/L), and temperatures (298–318 K), on sorption performance, were carried out. The composite material MF-MIL-53(Fe) displayed under neutral conditions a high adsorption capacity of 402 mg/g, which is twice that of any previously reported As(V) adsorbents. Bath experiments show that MF-MIL-53(Fe) exhibits high selectivity toward As(V). In addition, Pseudo-second-order, Langmuir models, and single-layer adsorption reasonably explain kinetics for As(V). Thermodynamic studies revealed that the sorption process was spontaneous and endothermic. The mechanism study indicated that static electricity and surface adsorption effects were the main mechanisms responsible for As(V) ions adsorption. Moreover, the adsorption efficiency of MF-MIL-53(Fe) is still very high at 88.04% after 5 cycles, demonstrating good adsorption and reconciliation circulation. This research provided an easy method to prepare new composite materials MF-MIL-53(Fe) for removing As(V) from wastewater.

期刊信息：Microporous Mesoporous Mater.

DOI：10.1016/j.micromeso.2022.112290

孟令輝，北京建築大學環境工程專業2021級碩士研究生，主要研究方向為金屬-有機骨架材料的設計、製備及其在水環境修復領域的應用。