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CERAMICS INTERNATIONAL · 2023 · IF 5.2

MOFs-derived Co/C nanoparticle embedded in N, S co-doped graphene for superior electromagnetic wave absorption capacity

Lin Tan,Jing Han,Chuanwen Wang,Genwang Zhang,Huixia Feng,Nali Chen,Dan Zhao

Due to their physicochemical properties, the three-dimensional Metal-organic frameworks (MOFs) derived composites show great potential as electromagnetic wave (EMW) absorbers. However, poor impedance matching limits their actual EMW absorption performance. Composite materials that combine magnetic and dielectric losses offer a potential solution to enhance impedance match and significantly improve microwave absorption. In this work, a novel N,S-GS/Co/C composite was fabricated via a solvothermal method and a subsequent pyrolysis process to introducing nitrogen and sulfur co-doped graphene (N,S-GS) into Co-MOF. By co-doping nitrogen and sulfur, abundant defects and disordered sites were introduced on graphene, which stimulate interfacial polarization and dipole polarization. The minimum reflection loss (RL) of the sample obtained by pyrolysis at 600 °C is −68.8 dB at 9.7 GHz. Simultaneously, the thickness is 2.51 mm, and the effective absorption bandwidth (EAB) can reach 3.04 GHz. Its excellent EMW absorption performance is mainly attributed to interfacial polarization, multiple reflections, dipole polarization, magnetic resonance and eddy current loss. Accordingly, the N,S-GS/Co/C composite is convinced to be a competent candidate among EMW absorbers with high absorption intensity.

CAS / MDL: 6147-53-1 693-98-1
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Targeted accumulation and spatial confinement effect of Fe(II)-MOFs@MIP for efficiently removing low concentration dibutyl phthalate

Haiyuan Chi,Chengjun Li,Mei Huang,Jinquan Wan,Xiaoxia Zhou,Bing Yan

Sulfate radicals-based advanced oxidation processes are regarded as effective methods for removing organic contaminants. However, current removal technologies are often unable to achieve satisfactory results due to the low concentrations and high stability that are frequently characteristics for many types of organic contaminants. To improve the efficacy of using sulfate radicals to remove organic contaminants, we designed metal–organic frameworks (Fe(II)-MOFs) modified with enrichment and specific recognition of molecular imprinting layer (Fe(II)-MOFs@MIP). Using dibutyl phthalate (DBP) as the model target contaminant, the selectivity coefficient towards DBP was 7.28 for adsorption and 4.46 for catalytic degradation of Fe(II)-MOFs@MIP, which is excellent for most of the imprinted material. Additionally, we achieved the accurate recognition (169.25 μg × g −1 ) and efficient degradation (0.071 min −1 ) of DBP reducing levels to 100 μg × L -1 . UV–vis analysis confirmed that specific recognition of DBP was mainly through hydrogen bonding and π-π interaction, while in-situ Raman and radical quenching experiments showed that the imprinting layer could accurately adsorb and produce the spatial confinement effects on target contaminants, thereby reducing the transfer distance of free radicals. As a result, we show that Fe(II)-MOFs@MIP can achieve efficient targeted degradation of DBP, opening up a new avenue for the removal of this and other highly stable organic contaminants present at low concentrations in environmental systems.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2021 · IF 8.128

Carbon nanotubes interpenetrating MOFs-derived Co-Ni-S composite spheres with interconnected architecture for high performance hybrid supercapacitor

Zhenlin Ma,Rong Zheng,Yu Liu,Yulong Ying,Weidong Shi

Recently, carbon nanotubes (CNT)-based interconnected architectures exhibit promising prospects in supercapacitors due to their flexibility and high electrical conductivity. Herein, a three-dimensional (3D) interconnected network structure combined with conductive carbon nanotubes interpenetrating MOFs-derived Co-Ni-S composite spheres (Co-Ni-S/CNTs) was synthesized. Such 3D interconnected architecture significantly leads to a favorable electronic structure, fast charge-transfer capacity, and more pseudocapacitive. The Co-Ni-S/CNTs-based hybrid electrode exhibits an extraordinary specific capacitance of 540.6C g −1 at 1 A g −1 and competitive rate performance (capacity retention rate of 69.9% when the current density increases to 10 times). Subsequently, a hybrid supercapacitor is assembled using Co-Ni-S/CNTs as the positive electrode and commercial activated carbon as negative electrode. The device delivers a high energy density of 63.5 W h kg −1 at 800 W kg −1 and keeps 83.0% initial capacitance retention after 10,000 cycles. The encouraging performances demonstrate the significant contribution of the 3D interconnected architecture for the future energy storage.

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ULTRASONICS SONOCHEMISTRY · 2020 · IF 6.513

Insights into the novel application of Fe-MOFs in ultrasound-assisted heterogeneous Fenton system: Efficiency, kinetics and mechanism

Nannan Geng,Wei Chen,Hang Xu,Mingmei Ding,Tao Lin,Qiangshun Wu,Lei Zhang

In this work, as a new strategy, ultrasound/H 2 O 2 /MOF system was firstly applied by environmental-benign Fe-MOFs (MIL-53, MIL-88B and MIL-101) for tetracycline hydrochloride removal. The synthetic   Fe-MOFs were characterized by XRD, FTIR, SEM, XPS, N 2 sorption-desorption isotherms and CO-FTIR. MIL-88B demonstrated the best catalytic performance because of its highest amount of Lewis acid sites. Influencing factors, contrast experiment, and corresponding dynamics were carried out to obtain the best experimental conditions and reaction system. Under optimal conditions ([Tetracycline   hydrochloride] = 10 mg/L, [MIL-88B] = 0.3 g/L, [H 2 O 2 ] = 44 mM, [ultrasound power] = 60 W, and pH = 5.0), the-first-order kinetic rate constant k was calculated to be 0.226 min −1 , higher than the simple combination of the ultrasound system (0.004) and MIL-88B/H 2 O 2 system (0.163), indicating the importance of synergistic effect between ultrasound and Fenton reaction. EPR test and quenching experiment proved that ·OH is mainly responsible for tetracycline hydrochloride removal. The major reaction path is the adsorption and decomposition of H 2 O 2 by coordinative unsaturated iron sites on Fe-MOF, but it is not the only path. The direct decomposition of H 2 O 2 and the cavitation effect caused by ultrasound also contribute to the generation of OH.

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CHEMICAL PHYSICS · 2021 · IF 2.348

Effects of functional groups of –NH2 and –NO2 on water adsorption ability of Zr-based MOFs (UiO-66)

Xingchang Tang,Yongwei Luo,Zhijian Zhang,Wanwu Ding,Dexue Liu,Jingchuan Wang,Li Guo,Ming Wen

The high surface areas and tunable properties of Zr-based MOFs make them as attractive materials for gas capture, storage, and separation. In this work, UiO-66, one kinds of Zr-based MOFs, functionalized by single or binary –NO 2 and –NH 2 groups are synthesized. Water adsorption ability and hydrophilicity of UiO-66 and functionalized UiO-66-X were investigated. It is found that surface area of UiO-66 is decreased after introducing functional groups, while hydrophilicity of UiO-66 increased after functionalized with –NO 2 and –NH 2 . Therefore, after balance the effects of surface area and hydrophilicity, UiO-66-NH 2 shows the best water adsorption propriety.

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Catalysis Science & Technology · 2020 ·Vol. 10 ·期 6 ·1699-1707 · IF 5.721

Lewis acid sites in MOFs supports promoting the catalytic activity and selectivity for CO esterification to dimethyl carbonate

Yu-Ping Xu,Zhi-Qiao Wang,Hong-Zi Tan,Kai-Qiang Jing,Zhong-Ning Xu,Guo-Cong Guo

CO esterification to dimethyl carbonate (DMC) is an attractive route, although the catalyst is the main problem restricting the industrialization of this route. Supported palladium catalysts have been often used for this route. However, the effect of the support is not always clear. In this work, we firstly introduced three metal–organic frameworks (MOFs) materials as catalyst supports, namely UiO-66, MIL-101 and MOF-5, and studied the effect of Lewis acid sites in the MOFs supports on the catalytic activity and selectivity for CO esterification to DMC. Interestingly, the Pd(II)/UiO-66 catalyst exhibits superior catalytic performance to the other catalysts, with 87.9% CO conversion and 98.5% DMC selectivity due to the abundant Lewis acid sites in UiO-66. It was proven that UiO-66 with more defects would have a large number of Lewis acid sites, and the catalytic performance was positively correlated with the number of Lewis acid sites in MOFs supports, which can be demonstrated by characterization by NH3-TPD, pyridine-IR, XPS and in situ DRIRS. The current work not only revealed the relationship between the Lewis acidity of the support and catalytic performance, but also promotes the development of practical catalysts for CO esterification to DMC.

CAS / MDL: 10026-11-6
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MICROCHIMICA ACTA · 2020 ·Vol. 187 ·期 2 ·1-9 · IF 6.232

Cathodic electrodeposited Cu-BTC MOFs assembled from Cu(II) and trimesic acid for electrochemical determination of bisphenol A

Hu Peng,Zhu Xiaoming,Luo Xiaohui,Hu Xiaofeng,Ji Liudi

The authors describe a novel electrochemical determination method for bisphenol A (BPA) based on the electrosynthesised Cu-BTC (H 3 BTC: trimesic acid) films. Using H 3 BTC as the ligand, Cu(NO 3 ) 2 as the precursor of copper ions, and triethylamine hydrochloride (Et 3 NHCl) as the probase source, Cu-BTC films were directly deposited on glassy carbon electrode (GCE) surface via cathodic electrochemical reduction under −1.30 V. Considering the electrocatalytic activity of metal center Cu 2+ , Cu-BTC films were applied to construct the electrochemical determination platform for BPA. Chronocoulometry and electrochemical impedance spectroscopy were used to study the signal enhancement mechanism. The determination conditions were optimized. As a result, a sensitive electrochemical method was constructed for BPA. The peak currents, best measured at voltage of 0.496 V vs. SCE (KCl saturated calomel reference electrode), increase linearly in the range from 5.0 to 2000 nM. The value of determination limit is 0.72 nM. The proposed method was successfully applied to determine BPA in spiked urine, spiked waste water samples and plastic products. The results were in good agreement with those obtained for the same samples by high-performance liquid chromatography (HPLC). Schematics for the construction of electrochemical determination for bisphenol A.

CAS / MDL: 593-81-7
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JOURNAL OF HAZARDOUS MATERIALS · 2020 · IF 9.038

Enhancement of ionizing radiation-induced catalytic degradation of antibiotics using Fe/C nanomaterials derived from Fe-based MOFs

Qi Yang,Dan Chen,Libing Chu,Jianlong Wang

In present work, we studied a novel Fe/C nanomaterial fabricated using Fe-based metal organic frameworks (MOFs) as precursors through thermal pyrolysis to catalyze gamma irradiation-induced degradation of antibiotics, cephalosporin C (CEP-C) and sulfamethazine (SMT) in aqueous solution. The MOFs-derived Fe/C nanomaterials (DMOFs) had the regular octahedrons structure of MOFs and contained element C, Fe and O, while Fe° with a fraction of Fe 3 O 4 and Fe 2 O 3 were identified. Results showed that DMOFs addition could accelerate the generation of OH during gamma irradiation, while the intermediates of bonds cleavages of antibiotic molecules and OH addition were identified. DMOFs were more effective to improve the decomposition of antibiotic having the higher adsorption capacity like SMT. The degradation rate of CEP-C and SMT increased by 1.3 times and 1.8 times, and TOC reduction at 1.0 kGy reached 42 % and 51 %, respectively by gamma/DMOFs treatment, while only 20.2 % (CEP-C) and 4.5 % (SMT) of TOC reduction were obtained by γ-irradiation alone. The crystal structure, functional groups and magnetism of DMOFs changed slightly after gamma irradiation, which made it possible to be reused. DMOFs were promising to enhance the degradation of antibiotics during gamma irradiation.

CAS / MDL: 57-68-1
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Journal of Environmental Chemical Engineering · 2021 · IF 5.909

Rapid detection of orange II dyes in water with SERS imprinted sensor based on PDA-modified MOFs@Ag

Yong Xue,Jing Shao,Guoqi Sui,Yuqin Ma,Hongji Li

In this paper, a novel SERS imprinted composite material was successfully synthesized with the aid of surface enhanced Raman scattering technology and molecular imprinting technology, which could be suitable for specific detection of organic dyes in the river. The UIO-66(NH 2 ) was wrapped with a thin layer of polydopamine (PDA), after loading Ag nanoparticles on rough surface, Ag@UIO-66(NH 2 )/PDA was synthesized and applied as the SERS substrate. In order to promote the ability of selective detection property in the practical sample, the molecularly imprinted polymer (Ag@UIO-66(NH 2 )/PDA-MIPs) was proposed. When the concentrations range changed between 10 −8 mol/L and 10 −10 mol/L, the intensity of characteristic peak at 1596 cm −1 exhibited a linear relationship with OII concentrations increasing. The limit of detection was low than 10 −10 mol/L, the correlation coefficient was 0.9985. The prepared SERS substrate could be available to the practical sample detection, which expanded SERS detection fields.

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APPLIED SURFACE SCIENCE · 2021 · IF 6.707

Bimetallic CuZn-MOFs derived Cu-ZnO/C catalyst for reductive amination of nitroarenes with aromatic aldehydes tandem reaction

Wei She,Jing Wang,Xuewei Li,Jingfang Li,Guijie Mao,Weizuo Li,Guangming Li

Tuning of the metal–metal/oxide interaction is a vital route to enhance the performance of the supported catalysts. In this study, a Cu/Zn bimetallic MOFs was synthesized through a simple solvothermal method by using an adenine rigid biomolecule acted as organic linker. Furthermore, a ZnO/nitrogen-doped carbon composite supported Cu catalyst (named as Cu-ZnO/NC-BMOFs) derived from the bimetallic CuZn-MOFs was obtained via one-pot pyrolysis method. The developed Cu-ZnO/NC-BMOFs catalyst was tested for hydrogenation-amination tandem reaction. The bimetallic CuZn-MOFs with the uniformly dispersed Cu and Zn centers acted as a self-sacrificing template, which could facilitate the derived catalyst with strengthened Cu-ZnO interaction, high dispersity, and more N species. All of these advantages give the developed Cu-ZnO/NC-BMOFs catalyst with higher performance in hydrogenation-amination tandem reaction compared with traditional Cu/ZnO/NC-IWI (synthesized by incipient wetness impregnation) catalyst. The Cu-ZnO/NC-BMOFs exhibits good stability for the recycling experiments with a negligible loss in its performance. More importantly, the Cu-ZnO/NC-BMOFs catalyst could convert nitroarenes into the corresponding imines or secondary amines with excellent selectivity (>90.0%). This bimetallic MOFs-derived strategy may provide a way for fabricating NC supported catalysts in other tandem reactions.

CAS / MDL: 787-70-2 5970-45-6
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MICROCHIMICA ACTA · 2021 ·Vol. 188 ·期 8 ·1-10 · IF 5.833

A single nucleotide polymorphism electrochemical sensor based on DNA-functionalized Cd-MOFs-74 as cascade signal amplification probes

Liu Jia Li,Ma Yu Chan,Yang Tong,Hu Rong,Yang Yun Hui

An ultrasensitive electrochemical sensor has been constructed for the detection of single nucleotide polymorphisms (SNPs) based on DNA-functionalized Cd-MOFs-74 as cascade signal amplification probe under enzyme-free conditions. Interestingly, the introduction of an auxiliary probe did not disturb the detection of SNP targets, but could bind more Cd-MOFs-74 signal elements to enhance the different pulse voltammetry electrochemical signal 2~3 times as compared to sensing system without auxiliary probe, which obviously improves the sensitivity of the proposed sensor. Experimental results taking p53 tumor suppressor gene as SNP model demonstrated that the proposed method can be employed to sensitively and selectively detect target p53 gene fragment with a linear response ranging from 0.01 to 30 pmol/L (detection limit of 6.3 fmol/L) under enzyme-free conditions. Utilizing this strategy, the ultrasensitive SNP electrochemical sensor is a promising tool for the determination  of SNPs in biomedicine. Graphical Abstract

CAS / MDL: 543-90-8
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ACS ES&T Engineering · 2021 · IF 0

Trace FeCu@PC Derived from MOFs for Ultraefficient Heterogeneous Electro-Fenton Process: Enhanced Electron Transfer and Bimetallic Synergy

Xuedong Du,Wenyang Fu,Pei Su,Linlan Su,Qizhan Zhang,Jingju Cai,Minghua Zhou

A Fe0/Cu0-based bimetallic submicro-particle core with porous carbon (PC) shell hybrid rods, i.e., core–shell structured FeCu@PC-800/6, was successfully fabricated from the mixture of MIL-88B(Fe) and Cu-BDC through pyrolysis at 800 °C for 6 h and employed as novel heterogeneous electro-Fenton (Hetero-EF) catalysts to remove sulfamethazine (SMT). A trace dose catalyst (25.0 mg L–1) could achieve efficient catalytic activity (turnover frequency (TOFd), 3.92 L g–1 min–1) due to the synergy of catalytic reactivity among iron, copper, and PC, possessing the pseudo-first-order rate for SMT removal that was 3.27-foldsand 4.08-fold of the Fe@PC-800/6/Hetero-EF and Cu@PC-800/6/Hetero-EF process, respectively. According to experiments and density functional theory (DFT) calculations, Hetero-EF reactions enhanced by internal-microelectrolysis (IME) were proposed, in which Cu0 promoted the electrons transfer of Fe0 to PC while the introduced Cu+ could promote the decomposition of H2O2 and the cycle of Fe3+/Fe2+. A possible mechanism and SMT degradation pathway were suggested for this Hetero-EF process, confirming that the surface-bound hydroxyl radical played a major role. This FeCu@PC-800/6 catalyst was cost-effective and could be reused after thermal treatment in H2, demonstrating super efficiency for organic contaminants degradation by EF process.

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