鑽石舞台

題目：Immobilized N-C/Co derived from ZIF-67 as PS-AOP catalyst for effective tetracycline matrix elimination: from batch to continuous process

作者：Xiu-Wu Zhang, Ming-Yan Lan, Fei Wang, Chong-Chen Wang*, Peng Wang, Chengjun Ge, Wen Liu

摘要：The successful preparation of immobilized nitrogen-doped carbon/cobalt @ porous spherical substrate (N-C/Co@PSS) catalyst derived from ZIF-67 was reported in this work. The oxytetracycline (OTC), tetracycline (TTC), and chlortetracycline (CTC) in the simulated wastewater were decomposed via the peroxymonosulfate (PMS) activation by N-C/Co@PSS. The degradation of TCs was initially investigated by batch-type experiments, in which ca. 100% TCs with an initial concentration of 10.0 mg L-1 can be degraded over N-C/Co@PSS + PMS system within 15 min for 30 runs』 operation. In addition, detailed non-radical dominating degradation mechanism was explored by active species capture experiments, electron spin resonance (ESR) tests and electrochemical technology. Furthermore, continuous degradation of TCs antibiotics for up to 200 h in the packed N-C/Co@PSS fixed bed reactors could be accomplished. This work provides theoretical and technical support for the application of MOFs-based catalysts in large-scale wastewater remediation.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2022.138082

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題目：Multivalent Ce-MOFs as biomimetic laccase nanozyme for environmental remediation

作者：Shan Liang, Xiao-Ling Wu, Jun Xiong, Xin Yuan, Shu-Li Liu, Min-Hua Zong, Wen-Yong Lou*

摘要：Nanozyme has emerged as promising alternative to natural enzyme during recent years. Currently, laccase nanozyme is mainly limited to Cu-containing materials with catalytic Cu as active site. Noncopper laccase nanozyme, however, has not attracted extensive attention. Herein, inspired by multicopper active site and redox Cu2+/Cu+electron transfer pathway of natural laccase, a range of multivalent cerium-based metal-organic frameworks (Ce-MOFs) with considerable laccase-mimicking activity were designed, where the internal cerium redox (Ce4+/Ce3+) reactivity could mimic the active center and catalytic function of natural laccase. Compared with natural laccase, Ce-UiO-66 and Ce-MOF-808 exhibited not only better catalytic efficiency (at identical mass concentration) but also superior stability and recyclability toward the oxidation of phenolic compounds. Accordingly, they were applied for detection of mercaptan contaminants and degradation of bisphenol A, showing great potential in environmental catalysis. This work provides new deep insights for rational design of advanced nanozymes and demonstrates the huge potential of applying nanozymes for environmental remediation.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2022.138220

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題目：The chemical stability of metal-organic frameworks in water treatments: Fundamentals, effect of water matrix and judging methods

作者：Liangjie Wang，Xitong Li，Bo Yang，Ke Xiao，Huabo Duan，Huazhang Zhao*

摘要：Metal-organic frameworks (MOFs), with high surface areas and abundant active sites, have been widely studied as adsorbents and catalysts in water treatments. Although some MOFs are water stable, they do not always keep their stability in water treatments, because MOFs would face threats from not only water but also the water matrix related factors, such as pH, inorganic ions, metal ions and reactive oxygen species. Thus, it is meaningful to have insight into the relationship between MOFs stability and water matrix. However, a lot of studies have reported the excellent performances of MOFs in water treatments, but few ones have deeply revealed the instability of MOFs. In addition, overestimation of MOFs stability might occur, because the commonly used judgment methods of MOFs stability have their disadvantages. Taking the X-ray diffraction (XRD) pattern as an example, partial loss of metal ions and ligands would not result in the obvious change in the XRD pattern of MOFs. Hence, this review pays attention to the fundamentals of MOFs stability, the chemical stability of MOFs in water treatments and judging methods of MOFs stability. Overall, this review is expected to guide a comprehensive understanding of MOFs stability in water treatments, and further help to select suitable MOFs according to the application environments.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2022.138215

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題目：Cerium-Based Metal–Organic Framework with Intrinsic Haloperoxidase-Like Activity for Antibiofilm Formation

作者：Zijun Zhou, Sirong Li, Gen Wei, Wanling Liu, Yihong Zhang, Chenxin Zhu, Shujie Liu, Tong Li, Hui Wei*

摘要：Biofilms adhering to surfaces have severe impacts on both public health and industry. Environmentally friendly strategies for combating biofilms are needed due to the biosafety issues brought by traditional commercial anti-biofilm additives. Enzyme-based strategies for biofilm treatment have attracted great research interest, but there is still a major challenge ahead due to the high economic cost and limited stability of natural enzymes. Inspired by the antifouling mechanism of natural haloperoxidase (HPO) secreted by marine algae, which catalyzes the oxidative bromination of bacterial quorum sensing signaling molecules, its artificial enzyme is proposed here in response to the situation mentioned above. A cerium-based metal–organic framework (Ce-MOF) is verified to possess HPO-like activity. Based on its favorable enzyme-like activity, the Ce-MOF exhibits remarkable antibacterial and biofilm formation suppression abilities. This study not only expands the variety of HPO-like artificial enzymes but also paves the way for the application prospect of Ce-MOFs in water pipe cleaning and biofouling treatment.

期刊信息：Adv. Funct. Mater.

DOI：10.1002/adfm.202206294

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題目：Preferential Destruction of Micropollutants in Water through a Self-Purification Process with Dissolved Organic Carbon Polar Complexation

作者：Yumeng Wang, Peng Zhang, Lai Lyu, Tong Li, and Chun Hu*

摘要：Removing micropollutants in real water is a scientific challenge due to primary dissolved organic carbon (DOC) and high energy consumption of current technologies. Herein, we develop a self-purification process for the preferential destruction of various micropollutants in municipal wastewater, raw drinking water, and ultrapure water with humic acid (HA) driven by the surface microelectronic field of Fe0-FeyCz/Fex-GZIF-8-rGO without any additional input. It was verified that a strongly polar complex consisting of an electron-rich HA/DOC area and an electron-poor micropollutant area was formed between HA/DOC and micropollutants, promoting more electrons of micropollutants in the adsorbed complex to delocalizing to electron-rich Fe species area and be trapped by O2, which resulted in their surface cleavage and hydrolyzation preferentially. The higher micropollutant degradation efficiency observed in real wastewaters was due to the greater complex polarity of DOC. Moreover, the electron transfer process ensured the stability of the surface microelectronic field and continuous water purification. Our findings provide a new insight into low-energy combined-micropollution water treatment.

期刊信息：Environ. Sci. Technol.

DOI：10.1021/acs.est.2c03354

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題目：MOF-derived MnO@C with high activity for electric field-assisted catalytic oxidation of aqueous pollutants

作者：Lin-Feng Zhai*, Yue-Yue Chen, Yi Hua, Yi-Xiao Pan, Min Sun*, Jun Yu, Yan Wang, Wei Kong

摘要：The activation of oxygen (O2) under room condition is important for the utilization of air to perform oxidation. Here, we report a porous carbon-encapsulated MnO (MnO@C) derived from Mn metal-organic framework (MOF)grown in-situ on a graphite felt (GF) support. The MnO@C exhibits superior catalytic activity in an electric field-assisted catalytic oxidation system for the degradation of organic pollutants under room condition. The catalytic oxidation reaction applies a surface reaction pathway in which the surface-bound chemisorbed oxygen species are electro-oxidized and then involved in the oxidation of co-adsorbed organic pollutants. The abundant oxygen vacancies and oxygenated functional groups in MnO@C provide active sites for the chemisorption of O2, and its conductive mesoporous structure allows facile electrons and mass transfer. As a result, the MnO@C/GF catalyst displays quite high turnover frequency (TOF) value as 0.038 mg-TOC mg-MnO-1min-1, which is 6.66 times higher than that of the MnO/GF catalyst prepared by impregnation method as a comparison. With the aid of +1.0 V of positive electric field, the catalytic oxidation system exhibits extensive effectiveness in mineralizing a variety of dyes, pharmaceuticals, personal care products, and phenolic compounds under room condition with significantly enhanced biodegradability.

期刊信息：J. Hazard. Mater.

DOI：10.1016/j.jhazmat.2022.129670

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題目：Pore creation nanoarchitectonics from non-porous metal-organic framework to porous carbon for adsorptive elimination of sulfanilamide and chloroxylenol from aqueous solution

作者：Md. Mahmudul HassanMondol, Sung Hwa Jhung*

摘要：Three isomeric metal-organic frameworks (MOFs) such as MAF-5, -6, and -32 (with the same composition of [Zn(2-ethylimidazole)2]) were carbonized and, for the first time, activated further with KOH to prepare highly porous MOF-derived carbons (MDCs). Importantly, MDC-32 derived from non-porous MAF-32 had the highest porosity among the three MDCs although it has the lowest porosity when no KOH activation was done. Adsorption of sulfanilamide and chloroxylenol from water was investigated with the MDCs. Among the MDCs, MDC-32 showed the best adsorptive performance for sulfanilamide and chloroxylenol. Moreover, MDC-32, had the highest adsorption capacity (256 mg/g) for removing sulfanilamide from water, compared with any adsorbent reported so far. Based on the observed adsorption and properties of the adsorbate and adsorbent, π–π and hydrogen bonding interactions, with a slight contribution of repulsive electrostatic interaction, could be suggested as the mechanism for the sulfanilamide adsorption over the MDC-32. Moreover, the MDC-32 could be recycled easily for up to four cycles. It could be suggested that non-porous MOFs can be a good precursor for highly porous MDCs, if activated well using KOH, for example. Finally, MAF-32-derived carbon, MDC-32, might be suggested as a plausible adsorbent to eliminate organics such as sulfanilamide from water.

期刊信息：J. Hazard. Mater.

DOI：10.1016/j.jhazmat.2022.129659

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題目：MOFs-derived hollowFeCo@Cas peroxymonosulfate activator for degradation of organic pollutants: Insight into the catalytic sites by experimental and theoretical study

作者：Huanxuan Li*, Shun Lu, Junting Zheng, Ning Li, Yucheng Lou, Junhong Tang*, Jie Zhou, Huaiwei Zhang, Mingzhi Huang, Di Wang

摘要：A hollow sphere (FeCo@C) is developed and serves as a highly efficient catalyst of peroxymonosulfate (PMS) for degradation of orange G (OG) with a pseudo first-order constant of 0.119 min−1that was 5.15 and 1.43 times of Fe@C and Co@C, respectively. X-ray photoelectron spectroscopy and Density Functional Theory (DFT) calculations demonstrated that the (110) crystal plane of FeCo alloy was the most active site for activation of PMS to generate SO4•−and·OH. The quenching experiments and EPR test indicated that SO4•−,·OH, and1O2were generated in FeCo@C/PMS system and acted as the predominant reactive species. The synergistic effects between Fe and Co species were responsible for the high catalytic performance of FeCo@C. The carbon in FeCo@C act as a carrier to improve the stability with good reusability over five cycles at pH 7.0 and 9.0, as well as an electron mediator and activator to enhance the catalytic performance. Effects of PMS dosage, catalyst concentration, solution pH, and humic acids on OG removal were also investigated. Furthermore, the reduced toxicity of intermediate products was verified by quantitative structure-activity relationship (QSAR). This work demonstrates a feasible strategy for designing of high-performance and stable catalysts for the organic pollutant degradation based on PMS oxidation processes.

期刊信息：Sep. Purif. Technol.

DOI：10.1016/j.seppur.2022.121779

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題目：Zinc-based metal-organic framework nanofibers membrane ZIF-65/PAN as efficient peroxymonosulfate activator to degrade aqueous ciprofloxacin

作者：Mengjie Pu, Daqi Ye, Jinquan Wan, Bentuo Xu*, Wei Sun, Wei Li

摘要：A novel peroxymonosulfate (PMS) catalyst, zinc-based metal-organic framework electrospinning (ES) nanofibers membrane (short for ZIF-65/PAN) was firstly fabricated and used for the degradation of aqueous ciprofloxacin (CIP). Physicochemical properties, catalytic performance, stability, reusability, and the regeneration of ZIF-65/PAN was observed and conducted. Influence of various parameters including ZIF-65 loading content, reaction temperature, initial pH, and competitive organic molecules on CIP degradation was investigated. Reactive active species and degradation intermediates that involved in ZIF-65/PAN/PMS/CIP process were identified. Corresponding reaction mechanisms were speculated. The results indicate that the easy-separation ZIF-65/PAN nanofibers exhibit high efficiency for PMS activation, 89.2 % of CIP was degraded within 60 min, with up to 87.5% of PMS utilization efficiency. ZIF-65/PAN was renewable through simple layer-by-layer self-assembly, thus shows good prospect in future applications. 26.4% of surface Zn2+of ZIF-65/PAN of exists in the form of +III oxidation state after activation, indicating the role of zinc catalytic site. Through activation, oxidative active species SO4·-, ·OH, and1O2was generated, CIP was thus degraded through mainly three pathways. This study provides novel ideas for the application of MOF-based membrane on PMS based advanced oxidation processes.

期刊信息：Sep. Purif. Technol.

DOI：10.1016/j.seppur.2022.121716

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題目：Facile preparation of novelFe-BTC@PANnanofibrous aerogel membranes for highly efficient continuous flow degradation of organic dyes

作者：Guojun Jiang, Yuxin Jia, Jiajun Wang, Yutao Sun, Yicheng Zhou, Yuhao Ruan, Yuhua Xia, Tianhao Xu, Sheng Xie, Sai Zhang, Xiangyu Ye

摘要：Catalysts synthesized by immobilization of iron-based metal-organic frameworks (MOFs) on nanofibrous aerogel membranes (NFAMs) have great potential for practical applications in treatment of organic wastewaters. In this work, an ultralight Fe-BTC@polyacrylonitrile (PAN) NFAM with three-dimensional (3D) hierarchical porous structure was prepared by a green and facilein-situgrowth strategy at room temperature. It was used as a catalytic membrane in a filtrationdevice for testing the degradation of methylene blue (MB). The comprehensive characterization of the Fe-BTC@PAN NFAM confirmed thein-situgrowth of Fe-BTC on NFAM. Combining the advantages of both MOFs and NFAMs, the as-obtained Fe-BTC@PAN NFAM, as a heterogeneous Fenton-like catalyst, exhibited excellent catalytic performance towards degradation of methylene blue (over 98.3% of MB could be removed within 120 min with high reaction rate constant of 0.0284 min-1). The effects of H2O2concentration, initial pH, temperature, and MB concentration on the catalytic performance were investigated. Moreover, the removalefficiency remained up to 90% over multiple cycles with negligible iron leaching (<0.5 mg/L), which indicated catalyticstabilitywithgoodreusability. Furthermore, the plausible reaction mechanism was proposed. Hence, this study provides promising insights into the rational design of high-performance 3D MOF-based Fenton-like catalyst for treatment of organic wastewaters.

期刊信息：Sep. Purif. Technol.

DOI：10.1016/j.seppur.2022.121753

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題目：Morphological diversity effect of graphene quantum dot/MIL88A(Fe) composites on dye and pharmaceuticals (tetracycline and doxycycline) removal

作者：Bahareh Rabeie, Niyaz Mohammad Mahmoodi*, Mehrdad Mahkam*

摘要：Herein, composites with different morphologies (diamond-like, rod-like, and spindle-like) were successfully synthesized using MIL88A (Fe) and graphene quantum dots (GQDs) to remove Acid Blue 92 (AB92), pharmaceuticals (doxycycline, and tetracycline). Despite the similarity in content, chemical structure, and functional groups of the composites, interesting differences were observed in some of their physicochemical properties (BET, RAMAN, TEM, and SEM) and adsorption performance, which was the turning point of this research. Spindle-like GQDMIL88A composite with the adsorption capacity of 617 mg/g indicated the highest adsorption capacity for Acid Blue 92 (AB92) compared to 335 mg/g for rod-like composites and 114 mg/g for diamond-like composites. Also, for doxycycline removal, the spindle-like composite with the adsorption capacity of 796 mg/g, was still in the first rank, compared to 588 mg/g for rod-like and 469 mg/g for diamond-like GQDMIL88A. The tetracycline adsorption capacity for spindle-like, rod-like, and diamond-like GQDMIL88A composites was 672 mg/g, 398 mg/g, and 300 mg/g, respectively. According to the findings of this study, despite the different adsorption capacities of different GQDMIL88A composite morphologies, all three types are well compatible with the Langmuir isotherm and pseudo-second-order kinetics.

期刊信息：J. Environ. Chem. Eng.

DOI：10.1016/j.jece.2022.108321

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題目：Metal-organic frameworks as advanced sorbents for oil/water separation

作者：Mozhgan Shahmirzaee,Jafar Abdi, Abdolhossein Hemmati-Sarapardeh, Mahin Schaffie, Mohammad Ranjbar, Alireza Khataee*

摘要：The crude oil spills have direct or indirect catastrophic damage to the ecosystem and aquatic life. Metal-organic frameworks (MOFs) have gained great attention as promising candidates for cleaning up oily pollutants from water. The emphasis of this review is on the recent applications of MOFs with different morphologies and chemical compositions, e.g., different metals, for oil/water separation. The sorption by various MOFs based on the metal element is investigated to remove oily pollutants. In addition, a comparison of the MOF materials as a new hydrophobic platform and removal methods for oil sorption are presented. The other oil separation methods are briefly described, showing the potential of MOFs in cleaning up the crude oil spills. Moreover, the mechanism of sorption and efficiency enhancement strategies are highlighted and the stability of MOFs in water, as the most important feature of the sorbent, is discussed. Furthermore, the economical and practical implementation as key factors are reviewed for useful and industrial usage. The successful performance of the MOFs for the separation of oily pollutants from water is concluded to be useful for researchers to focus on it.

期刊信息：J. Mol. Liq.

DOI:10.1016/j.molliq.2022.119900

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題目：Selective Detection of Sulfasalazine Antibiotic and Controllable Photodegradation of Its into 5-Aminosalicylic acid by Visible-Light-Responsive Metal–organic Framework

作者：Han-Shu Li, Yuxuan Gong, Chen Ji, Pengyan Wu*, Bingzhuo Gao, Yufan Du, Jian Wang*

摘要：The extensive use of sulfasalazine (SSZ) antibiotics has brought potential threats to aquatic ecosystems and human health. Thus, necessary measures for removal of SSZ must be taken to prevent arbitrary antibiotic exposure in the aquatic environment. However, the rescent photocatalysts have been used for the degradation of SSZ, but they all could not achieve the controlled release of SSZ, losing their medicinal value. Herein, by utilizing an Eosin Y moiety as an efficient light-harvesting and emission site, an Eosin Y-based visible-light responsive metal–organic framework has been synthesized and characterized, which exhibits high selectivity for detecting SSZ antibiotic in water and simulated physiological conditions, with the detection limit to be below 1 μM (0.4 μg/mL). It also represents the first example of MOF-based photocatalyst for controllable degradation of SSZ into 5-aminosalicylic acid with excellent catalytic activity and recyclability.

期刊信息：Dalton Trans.

DOI: 10.1039/D2DT01270G

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題目：Bis-pyridyl-bis-amide-modulated a series of metal-organic frameworks: Formation, transformation and selectivity for the efficient detection of multiple analytes

作者：Xiao-Sa Zhang, Yan Liu, Yu Liu, Lin-jiu Xiao*, Jia-Liang Cui, Hong Xiang, Jian Luan*, Wenze Li*

摘要：The designing of luminescent metal-organic frameworks (LMOFs) as sensors for the detection of molecules and ions constitutes an active area of research. Four various three-dimensional (3D) unusual LMOFs {[Zn(3-pda)(TA)]•H2O}n(1), {[Zn(4-pda)(TA)]•2H2O}n(2), [Cd(3-pda)(TA)]n(3), and {[Cd2(4-pda)2(TA)2]•(4-fpia)•H2O}n(4), 3-pda = 1,4-bis(3-pyridylcarboxylamide)benzene, 4-pda = 1,4-bis(4-pyridylcarboxylamide)benzene, 4-fpia = N-(4-formylamino-phenyl)-isonicotinamide, TA = terephthalic acid, were successfully synthesized via hydrothermal method and characterized by single-crystal X-ray diffraction. Under the solvothermal condition, a structurally transformational 3D 3-fold interpenetrated porous MOF [Cd2(4-pda)2(TA)2(DMF)]n(4a) had been obtained, which could be further transformed to an isostructural [Cu2(4-pda)2(TA)2(DMF)]n(4b) by single-crystal to single-crystal (SCSC) transformation. The effect of the N-donor ligands, metal ions and solvents on the structures of MOFs had been discussed in detail. A series of luminescence recognition tests proved that complexes 1–4 can be served as luminescent sensors for detecting certain metal cations, oxyanions, and toxic organic solvents in an aqueous environment. Furthermore, the luminescence quenching mechanism and structure–function relationship have been studied systematically.

期刊信息：CrystEngComm

DOI: 10.1039/D2CE00915C

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賈朝庭，男，北京建築大學資源與環境專業2021級碩士研究生。研究方向：具有光催化性能的金屬-有機骨架材料衍生物的設計與合成，及其光催化處理揮發性有機污染物的應用。