鑽石舞台

01

題目：Fabrication of wide-spectra-responsive NA/NH2-MIL-125(Ti) with boosted activity for Cr(VI) reduction and antibacterial effects

作者：Yangjie Fu, Meng Tan, Zhonglu Guo, Derek Hao, Youran Xu, Hao Du, Chao Zhang, Jiayun Guo, Qiang Li, Qi Wang*

摘要：A NA/NH2-MIL-125(Ti) homojunction was prepared by grafting 1-naphthylamine (-NA, a chromophore group) on the -NH2group in part of NH2-MIL-125(Ti). In-depth investigation of the optical and structural variations was carried out. The results indicated that the lattice structure of NH2-MIL-125(Ti) was well preserved after –NA modification. Whereas NA/NH2-MIL-125(Ti) with 10% -NA ratio exhibited optimal photocurrent response and the lowest charge separation efficiency. In photocatalytic activity experiments, NA/NH2-MIL-125(Ti) showed excellent activity with more than 99% Cr(VI) reduction and 99.999% bactericidal efficiency within 60-min irradiation. Furthermore, the photocatalysts showed good stability after 5 cyclic runs. Then, a mechanism about how the bacteria were killed was proposed, which was mainly contributed by the destruction of the cell membrane by photogenerated singlet oxygen (1O2). The results of this work will open a new route to the synthesis of MOFs for multiple photocatalytic applications.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2022.139417

02

題目：Efficient adsorption of naproxen and ibuprofen by gelatin/zirconium-based metal-organic framework/sepiolite aerogels via synergistic mechanisms

作者：Lewis Kamande Njaramba, Minseok Kim, Yeonji Yea, Yeomin Yoon, Chang Min Park*

摘要：The removal of non-steroidal anti-inflammatory drugs (NSAIDs) from effluent wastewater is critical because of their adverse impacts on human health and the ecosystem. In this study, we successfully fabricated a novel biopolymer-based aerogel composite by incorporating a zirconium-based metal-organic framework, UiO-66 (MOF), and sepiolite (Sep) into gelatin (Gel) to efficiently remove naproxen (NPX) and ibuprofen (IBP). The physicochemical properties of the prepared adsorbents were comprehensively characterized, as well as batch experimental studies were carried out to probe the effect of contact time, solution pH, temperature, and coexisting ions on the adsorption process. The adsorption by the 3D mesoporous aerogel (Gel-1.0MOF-Sep) followed the pseudo-second order and the Langmuir isotherm models with maximum adsorption capacities of 8.515 and 10.23 mg/g for NPX and IBP, respectively (at 20°C and pH 7). Furthermore, central composite design (CCD) in response surface methodology (RSM) was used to assess the simultaneous interactions of independent variables, results of which suggested that the initial concentration and pH were the dominant parameters in the adsorption process. Moreover, a thermodynamic study showed that the adsorption process was exothermic (ΔH0< 0) and thermodynamically spontaneous (ΔG0< 0). Reusability studies demonstrated that the composite aerogel exhibited superior adsorption efficiencies after five successive runs, indicating its potential use in practical applications. Furthermore, the adsorption mechanisms for the pollutants were ascribed to electrostatic interactions, π–π interactions, and hydrogen bonding. The insights show that the Gel-1.0MOF-Sep aerogels are promising alternative adsorbents for the removal of NSAIDs.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2022.139426

03

題目：Piezo-photo coupling effect and extended optical absorption of piezoelectric-based hybrids for efficient bisphenol A degradation

作者：Yuying Wu, Zhangran Gao, Shulin Jiao, Gang Zhou*

摘要：The piezo-potential induced by stress or strain in piezoelectric compounds can produce an electric field, which has been demonstrated to be an effective technique for charge shifting or transfer in the domain of photocatalysis. In this study, a judicious combination of piezoelectricity and photocatalytic performance via ZIF-67N@BiFeO3@CdS composite is designed. After integrating, the intensity and scope of photo-absorption are increased. Owing to double polar electrical field in BiFeO3and CdS, photo­generated carriers separation and transfer are efficient in Z-scheme and type-II pathway simultaneously. Extraordinary bisphenol A removal ability is achieved under visible-light and near-infrared waveband over the piezo-photocatalysis process. The related mechanism has been investigated in detail by experimental and theoretical insights. With the synergistic effect of enhanced light harvesting and piezophoto coupling behavior, this work gives an innovative vision in developing new-type piezoelectric photocatalysts.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2022.139456

04

題目：Investigation of the degradation and dehalogenation properties of florfenicol by heterogeneous Fenton reaction activated with MIL-53(Al)-supported nano zero-valent iron

作者：Zhe Zhao, Wuming Xie*, Zijun Huang, Haiming Cai, Yuemeng Ji, Baocong Zhao

摘要：The antibiotic florfenicol (FF) discharged into the aquatic environment may cause serious water pollution. Therefore, an effective way to eliminate FF antibiotics from the water bodies should be proposed. Herein, MIL-53(Al)-supported nano zero-valent iron (NZVI@MIL-53(Al)) was synthesized and applied to activate hydrogen peroxide (H2O2) to spark the Fenton reaction for FF antibiotics removal. The characterization results demonstrated the successful loading and good dispersion of NZVI onto MIL-53(Al). 100% FF antibiotics degradation could be achieved under the optimal reaction conditions, including an initial FF antibiotics concentration of 20 mg L-1, initial solution pH of 3.0, NZVI@MIL-53(Al) dose of 25 mg L-1, and H2O2concentration of 0.2 mM. And after four cycles, the FF antibiotic degradation efficiency was still 81.18%. The lowest tolerance for HCO3-was observed while the degradation activity was maintained at the presence of Cl-and HA. EPR measurement and free radical quenching experiment showed that ·OH was the main reactive specie in the NZVI@MIL-53(Al)/H2O2system. FF antibiotics degradation involved hydroxylation reactions (electrophilic substitution), dehalogenation, hydrolysis, and cleavage based on the UPLC-MS/MS analysis and DFT calculation. Noteworthy, 0.247 mg L-1of F-and 1.2 mg L-1of Cl-were detected in the solution after the reaction due to the breakage of the stable C–Cl bond and C–F bond. Finally, this work revealed that the NZVI@MIL-53(Al), with high stability and recyclability, could be a potential heterogeneous catalyst for treating antibiotic wastewater.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2022.139420

05

題目：Self-Supported 3D-Printed Lattices Containing MXene/Metal–Organic Framework (MXOF) Composite as an Efficient Adsorbent for Wastewater Treatment

作者：Hossein Shahriyari Far, Mina Najafi, Mahdi Hasanzadeh*, Mahboubeh Rabbani

摘要：Metal–organic frameworks (MOFs) are well-known porous crystalline materials that have been used for the removal of organic pollutants from wastewater. To enhance the adsorption performance of these adsorbents and facilitate their recycling process, we propose a hybrid composite of an MXene/metal–organic framework (MXOF) decorated on a hierarchical and self-supported porous three-dimensional (3D) printed lattice structure (3D-MXOF). In this design, the porous MXOF composite extremely enhanced the specific surface area and synergistically promoted the dye removal efficiency of 3D-printed lattices. Scanning electron microscopy images indicated that the MXOF composite was uniformly decorated on a 3D-printed lattice structure without agglomeration. The resultant supported 3D-MXOF structures were evaluated for the adsorption of anionic dyes. The results revealed high adsorption performance (91.98% for methyl orange and 84.9% for direct red 31 dyes) and fast adsorption kinetics following a pseudo-first-order kinetic model. Moreover, the 3D-MXOF structure possesses a facile recycling process with sustainable adsorption performance after four consecutive adsorption–desorption cycles.

期刊信息：ACS Appl. Mater. Interfaces

DOI：10.1021/acsami.2c13830

06

題目：Metal–organic framework (MOF)-5/CuO@ZnIn2S4core–shell Z-scheme tandem heterojunctions for improved charge separation and enhanced photocatalytic performance

作者：Yi Yang, Zipeng Xing*, Weifeng Kong, Chunxu Wu, Hui Peng, Zhenzi Li*, Wei Zhou*

摘要：Interface engineering is regarded as an effective strategy for charge separation. Metal–organic framework (MOF)-5/CuO@ZnIn2S4core–shell Z-scheme tandem heterojunctions with a three-dimensional floral spherical shape are prepared by a two-step solvothermal and oxidative method. The flower spherical core–shell structure enhances multiple reflections and refractions of light and thus improves light utilization efficiently. In addition, this core–shell structure can supply sufficient active sites for photocatalytic reactions. Meanwhile, the composition of Z-scheme tandem heterojunctions and the photothermal effect contributed to the spatial charge separation and accelerated the photocatalytic process. The photocatalytic hydrogen production rate of MOF-5/CuO@ZnIn2S4(1938.3 μmol g-1h-1) is 18 times higher than that of pristine MOF-5, and the photocatalytic degradation efficiency of 2,4-dichlorophenol and phenol can reach up to 98.7% and 97.3%, respectively. In addition, multiple cycle experiments demonstrate high stability, which is favorable for practical applications.

期刊信息：Nanoscale

DOI：10.1039/D2NR03557J

07

題目：Statistical optimization of Mg-doped UiO-66-NH2synthesis for resource recovery from wastewater using response surface methodology

作者：Muhammad Naveed Afridi*, Jong-Oh Kim*

摘要：The response-surface-methodology (RSM) was utilized to enhance phosphate (P) removal effectiveness of a Mg-doped UiO-66-NH2nanocomposite synthesized via the solvothermal process. The RSM statistically determined the optimum parameters for evaluating and designing the P removal experiments. We investigated the effects of various operating factors of Mg-doped UiO-66-NH2nanocomposites (such as magnesium concentration, solvothermal temperature, and solvothermal time) on P removal. According to the RSM results, the optimum parameters for Mg-doped UiO-66-NH2nanocomposite fabrication consist of a magnesium concentration of 1.18 mM, solvothermal temperature of 120 °C, and solvothermal time of 12.69 h. This optimal sample demonstrates a P removal efficiency that is 1.75 times higher than that of pristine UiO-66-NH2. The adsorbent was analyzed with field emission scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and energy-dispersive X-ray spectroscopy. Adsorption kinetics and adsorption isotherms analyses reveal that the pseudo-second-order model (R2> 0.99) and the Langmuir isotherm (R2> 0.99) matched well with experimental data, implying that the P removal process was primarily based on chemical interactions. The Langmuir adsorption capacity was calculated to be 68.0 mg P/g or 208.6 mg PO4/g at an equilibrium time of 2 h. Furthermore, the adsorbed P was effectively recovered with different concentrations of sodium hydroxide.

期刊信息：Appl. Surf. Sci.

DOI：10.1016/j.apsusc.2022.154973

08

題目：Fe-metal-organic-framework/MnO2nanowire/granular activated carbon nanostructured composites for enhanced As(III) removal from aqueous solutions

作者：Wenlan Ji, Xinyu Miao, Tian C. Zhang, Yuan Wang, Shaojun Yuan*

摘要：The elimination of arsenic pollution has attracted increasing concerns due to its toxicity and severe carcinogenicity. Herein, we proposed an in-situ crystal growth strategy without surfactant to fabricate MIL-88B uniformly anchored on the surface of MnO2/GAC (MIL-88B/MnO2/GAC). Such innovative MIL-88B/MnO2/GAC nanostructured composites not only exhibited the synergetic functions of simultaneously oxidizing As(III) and adsorbing the generated As(V), but also effectively reduced the cost of metal–organic frameworks (MOFs) adsorbents. Impressively, the as-prepared sample achieved remarkably boosted As(III) removal capacity of 15.13 mg g-1compared to 4.1 mg g-1of MnO2/GAC composite and 2.1 mg g-1of sGAC, which was mainly ascribed to the synergistic effect between the excellent adsorption abilitiy of MIL-88B and oxidation property of MnO2/GAC. Owing to the unique construction and properties, the constructed MIL-88B/MnO2/GAC composites presented a desirable As(III) removal ability under a wide pH scope of 2 to 10. Moreover, the possible mechanism of the synergistic removal over MIL-88B/MnO2/GAC was elucidated by X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR) and radical trapping experiment. This work not only offers a superior bifunctional catalyst for high-efficient removal of arsenic, but also provides a new perspective for rational construction of MOF derivatives for their further applications.

期刊信息：Appl. Surf. Sci.

DOI：10.1016/j.apsusc.2022.155011

09

題目：Metal organic framework derived CuSx/C with plentiful S-vacancies for efficient heterogenous activation of peroxymonosulfate

作者：Haixian Yan, Yusong Pan*, Xiaobo Liao, Yuan Zhu, Run Huang, Chengling Pan*

摘要：Transition metal sulfides are often used as heterogeneous catalysts to activate peroxymonosulfate (PMS), but insufficient active sites on catalysts surface limited the further application. Herein, a porous carbon-based copper sulfide (CuSx/C) nanosphere with plentiful sulfur vacancies was obtained and exhibited excellent catalytic activity for degrading pollutants (97.9 % for Rhodamine B (RhB) degradation within 6 min) in PMS system, which was significantly higher than that of CuS and CuSx(7.1 % and 13.8 %). The high catalytic performance ofCuSx/Cwas mainly attributed to the existence of plentiful sulfur vacancies and the special porous morphology, thereby more Cu+/Cu2+exposed on the CuSx/C surface, and further provided more active sites for the activation of PMS. This research provides a new strategy to construct high performance transition metal sulfides catalysts with sufficient sulfur vacancies for activating PMS.

期刊信息：Appl. Surf. Sci.

DOI：10.1016/j.apsusc.2022.155009

10

題目：Nano-architecture of MOF (ZIF-67)-based Co3O4NPs@N-doped porous carbon polyhedral nanocomposites for oxidative degradation of antibiotic sulfamethoxazole from wastewater

作者：Hamed Mohtasham, Mojtaba Rostami, Behnam Gholipour, Amir Mohammad Sorouri, Hermann Ehrlich, Mohmmad Reza Ganjali, Sadegh Rostamnia*, Mehdi Rahimi-Nasrabadi*, Abdollah Salimi*, Rafael Luque

摘要：Co3O4NPs in N-doped porous carbon (Co3O4NPs@N-PC) materials were prepared by one-pot pyrolysis of a ZIF-67 powder under N2atmosphere and followed by oxidation under air atmosphere (200 °C) toward promotion catalytic activity and activation of peroxymonosulfate (PMS) to degradation sulfamethoxazole (SMZ). 2-methylimidazole was used as a nitrogen source and a competitive ligand for the synthesis of Co3O4NPs@N-PC, which in addition to affecting nucleation and growth of the crystal, promotes the production of active Co–N sites. Co3O4NPs@N-PC nano-architecture has high specific surface areas (250 m2 g-1) and is a non-toxic, effective and stable PMS activator. The effect of operating parameters including SMZ concentration, catalyst dosage, temperature and pH in the presence of Co3O4NPs@N-PC was investigated. The Co3O4NPs@N-PC composite showed superior performance in activating PMS over a wide range of pH (2-10) and different temperatures so that complete degradation of SMZ (50 μM, 100 mL) was achieved within 15 min. The role of Co2+/Co3+redox system in the mechanism before and after PMS activation was determined using XPS analysis. Surface-generated radicals led to the degradation of SMZ, in which the SMZ degradation rate attained 0.21 min-1with the mineralization of 36.8%. The feasible degradation mechanism of SMZ was studied in the presence of different scavengers and it was revealed that the degradation reaction proceeds from the radical/non-radical pathway and in this process most of the SO4·-and·OH radicals are dominant. The recoverability and reuse of Co3O4NPs@N-PC were evaluated to confirm its stability and potential for SMZ degradation and it was observed that the catalyst maintains its catalytic power for at least 5 cycles.

期刊信息：Chemosphere

DOI：10.1016/j.chemosphere.2022.136625

11

題目：Polyamidoamine dendrimers-Mil-125(Ti) MOF embedded polyethersulfone membrane for enhanced removal of heavy metal, antibiotic and dye from water

作者：Hossein Shahriyari Far, Mina Najafi, Mahdi Hasanzadeh*, Mahboubeh Rabbani

摘要：In the current study, the solvo-thermal method was used to synthesize Mil-125(Ti). Then, polyamidoamine dendrimer G.02 (PAMAM) was produced by Michael’s addition reaction and then loaded on the surface of Mil-125(Ti) to produce Mil-Den nanocomposite. The FESEM images, XRD pattern and FTIR analyses were used to investigate the physicochemical and structural features of synthesized Mil-Den. Next, the prepared Mil-Den nanocomposite was used for the fabrication of mixed matrix polyethersulfone (PES) membranes. The morphology, water flux, anti-fouling properties, hydrophilicity, and rejection of the Na2SO4salt, Lead (II) nitrates as heavy metal, cefixime antibiotic, and six different reactive dyes were assessed. The incorporation of Mil-Den nanocomposite into PES membrane led to porosity enhancement from 66.8% for the bare membrane to 87.2% for the blended ones containing 1 wt% of Mil-Den. Also, the water contact angle of membrane was reduced from 59.2° to 31.2° by use of Mil-Den. The water flux of the membrane was remarkably increased from 17.9 to 287.6 (L/m2/h) by the addition of Mil-Den. The dye rejection for the blended membrane containing 0.2 wt% of Mil-Den nanocomposite measured 99.33%, 85.18%, 98.20%, 94.67%, 82.49% and 79.05% for RG19, RB50, RB21, RY145, RY160 and RY39, respectively. In addition, the rejection of cefixime antibiotic, lead ion, and sodium sulfate solutions were measured 80.04%, 97.36%, and 65.21%, respectively. The flux recovery ratio determined > 68% for the bare PES membrane whereas that was > 90% for the modified membrane with 0.1 wt% Mil-Den nanocomposite. Consequently, this study indicated the high potential of blended Mil-Den/PES-based membranes in water treatment.

期刊信息：J. Environ. Chem. Eng.

DOI：10.1016/j.jece.2022.108644

12

題目：BiOI Nanoparticle/PCN-222 Heterojunctions for Self-Decontaminating Photocatalyst with Efficient Tetracycline Visible-Light Degradation

作者：Heyao Zhang, Qing Meng, Hujie Li, Gaigai Wu, Ke Li, Jinghan Xu, Lianlian Wang, Jie Wu*, Xiangru Meng, Hongwei Hou*

摘要：Herein, a series of crystalline Z-scheme photocatalytic heterojunctions BiOI@PCN-222 (BP-X, X donates Zr6:Bi, X = 1, 3 and 5) is constructed by highly dispersed integration of BiOI into the channel of a porphyrin-based Zr-MOFs PCN-222 through surface site engineering. BP-X exhibits stronger visible light absorption (400-800 nm) than that of PCN-222, meanwhile, remains mesoporous nature with surface area ~ 650 m2/g and large pore volume ~ 15 Å in diameter. A set of characterizations reveal the formation of internal interface electric field in the composite and the electron transfer from BiOI to PCN-222. In addition, their photocatalytic activity toward the degradation of tetracycline (TC) under visible light irradiation is investigated to illustrate the advantages of self-decontaminating photocatalyst capable of both adsorption and photodegradation. BP-X shows superior TC adsorption and photodegradation activity. Specially, the photodegradation kinetic rate constant k of BP-3 is 1.5 and 10 times than that of PCN-222 and BiOI, respectively. The improved photocatalytic performance of BP-3 is attributed to its strong TC adsorption capacity, and highly dispersed Z-scheme heterojunctions, which is beneficial to photogenerated charge separation and electron transfer. This work explored the opportunities to develope the heterojunction mesoporous materials based on MOFs for self-purification and photodegradation of organic pollutants.

期刊信息：CrystEngComm

DOI：10.1039/D2CE01109C

13

題目：A 3D/3D hetero-interpenetrated MOF with a novel (3,9)-c net and 6-c lcy net for the fluorescence detection of carbaryl

作者：Rong Shi, Ze-Ming Xu, Chen Cao, Zheng Niu*, Jian-Ping Lang*

摘要：An exceptional Zn-based MOF material with two-fold hetero-interpenetrated nets consisting of a 3D lcy network and a novel 3D (3,9)-coordinated framework has been constructed. The Zn-based MOF exhibits a rare yellow-green fluorescence, and can be used as a fluorescence sensor to detect carbaryl with a detection limit of 4.5 μM.

期刊信息：Dalton Trans.

DOI：10.1039/D2DT01893D

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