Synergistic Effect of Ion Doping and Type-II Heterojunction Construction and Ciprofloxacin Degradation by MIL-68(In,Bi)-NH2@BiOBr under Visible Light.

Heterojunction structure and ion doping techniques are viable tactics in facilitating the generation and separation of photogenerated electrons and holes in photocatalysis. In the current study, a novel Bi ion-doped MIL-68(In,Bi)-NH2@BiOBr (MIBN@BOB) type-II heterojunction was first synthesized in a one-step solvothermal reaction. Doping of Bi ions not only broadened the light-sensing range but also provided reliable anchor sites for the in situ growth of BiOBr. Meanwhile, the heterostructure supplied new channels for photogenerated carriers, accelerating the transfer and inhibiting the recombination of photogenerated electron-hole. The obtained MIBN@BOB exhibited enhanced photocatalytic performance (91.1%) than MIL-68(In)-NH2 (40.8%) and BiOBr (57.5%) in ciprofloxacin (CIP) degradation under visible light, with excellent reusability. Photocatalysts were characterized in detail, and a series of photoelectrochemical tests were utilized to analyze the photoelectric properties. MIBN@BOB were deduced to conform the electron conduction mechanism of conventional type-II heterojunctions. More importantly, based on the above experiments and density functional theory (DFT) calculation, BiOBr-Bi in MIBN@BOB can serve as the major active sites of CIP enrichment, and •O2- and 1O2 generated at the BiOBr interface can react with the adsorbed CIP directly. Lastly, the possible degradation products and pathways of CIP were analyzed by liquid chromatography-tandem mass spectrometry (LC/MS/MS). This study provides a reference for the construction of ion-doping-modified metal-organic framework (MOF)-based heterojunction photocatalysts and their application in antibiotic removal.

Synthesis of mesoporous-structured MIL-68(Al)/MCM-41-NH2 for methyl orange adsorption: Optimization and Selectivity.

Here, we report a novel amino-modified mesoporous-structured aluminum-based metal-organic framework adsorbent, MIL-68(Al)/MCM-41-NH2, for dye sewage treatment. The introduction of molecular sieves overcomes the inherent defects of microporous MOFs in contaminant transfer and provides more active sites to enhance adsorption efficiency. Compared with using organic amino ligands directly, this strategy is ten times cheaper. The composite was well characterized and analyzed in terms of morphology, structure and chemical composition. Batch experiments were carried out to study the influences of essential factors on the process, such as pH and temperature. In addition, their interactions and the optimum conditions were examined using response surface methodology (RSM). The adsorption kinetics, isotherms and thermodynamics were systematically elucidated. In detail, the adsorption process conforms to pseudo-second-order kinetics and follows the Sips and Freundlich isothermal models. Moreover, the maximum adsorption capacity Qs of methyl orange (MO) was 477 mg g-1. It could be concluded that the process was spontaneous, exothermic, and entropy-reducing. Several binary dye systems have been designed for selective adsorption research. Our material has an affinity for anionic pigments. The adsorption mechanisms were discussed in depth. The electrostatic interaction might be the dominant effect. Meanwhile, hydrogen bonding, π-π stacking, and pore filling might be important driving forces. The excellent thermal stability and recyclability of the adsorbent are readily noticed. After five reuse cycles, the composite still possesses a removal efficiency of 90% for MO. Overall, the efficient and low-cost composite can be regarded as a promising adsorbent for the selective adsorption of anionic dyes from wastewater.

Copper nanowires and copper foam multifunctional bridges in zeolitic imidazolate framework-derived anode material for superior lithium storage.

Herein, a synthetic strategy for growing trimetallic zeolitic imidazolate framework (ZIF) polyhedrons on copper foam (CF) and interweaving with copper nanowires (CNWs) is proposed. Subsequently, in situ annealing under N2 atmosphere leads to the formation of multi-doped CNWs/Cu0.39Zn0.14Co2.47O4-ZnO/CF (CNWs/CZCOZ/CF). The unique structural characteristics of CNWs/CZCOZ/CF allow it to be directly assembled as a working electrode, without additional conductive additives or binders. When it's used as the lithium-ion battery (LIB) anode, this electrode exhibits a significantly high capacity of 2305 mAh g-1 at 0.1 A g-1 after 500 cycles. More importantly, kinetic analysis on the basis of cyclic voltammograms (CVs) indicates that the pseudocapacitive effect is the primary contributor to the high lithium storage capacity and also accounts for the exceptionally high rate capacity of 713 mAh g-1 even if the current density is at a maximum of 10 A g-1. Moreover, the superior battery performance originates from their advantageous structural diversity and unique compositional features, including synergistic effects among polymetallic components and two highly conductive substrates (CNWs and CF), forming unhindered paths for fast charge transfer.

Formation of N-Doped Carbon-Coated ZnO/ZnCo2 O4 /CuCo2 O4 Derived from a Polymetallic Metal-Organic Framework: Toward High-Rate and Long-Cycle-Life Lithium Storage.

Metal-organic frameworks (MOFs) are very promising self-sacrificing templates for the large-scale fabrication of new functional materials owing to their versatile functionalities and tunable porosities. Most conventional metal oxide electrodes derived from MOFs are limited by the low abundance of incorporated metal elements. This study reports a new strategy for the synthesis of multicomponent active metal oxides by the pyrolysis of polymetallic MOF precursors. A hollow N-doped carbon-coated ZnO/ZnCo2 O4 /CuCo2 O4 nanohybrid is prepared by the thermal annealing of a polymetallic MOF with ammonium bicarbonate as a pore-forming agent. This is the first report on the rational design and preparation of a hybrid composed of three active metal oxide components originating from MOF precursors. Interestingly, as a lithium-ion battery anode, the developed electrode delivers a reversible capacity of 1742 mAh g-1 after 500 cycles at a current density of 0.3 mA g-1 . Furthermore, the material shows large storage capacities (1009 and 667 mAh g-1 ), even at high current flow (3 and 10 A g-1 ). The remarkable high-rate capability and outstanding long-life cycling stability of the multidoped metal oxide benefits from the carbon-coated integrated nanostructure with a hollow interior and the three active metal oxide components.

Mesoporous MnO/C-N Nanostructures Derived from a Metal-Organic Framework as High-Performance Anode for Lithium-Ion Battery.

By application of newly designed ligand 5-(3-(pyridin-3-yl)benzamido)isophthalic acid (H2PBI) to react with Mn(NO3)2 under solvothermal conditions, a 2-fold interpenetrated Mn-based metal-organic framework (Mn-PBI) with rutile-type topology has been obtained. When treated as a precursor by pyrolysis of Mn-PBI at 500 °C, mesoporous MnO/C-N nanostructures were prepared and treated as an lithium-ion battery anode. The MnO/C-N manifests good capacity of approximately 1085 mAh g-1 after 100 cycles together with superior cyclic stability and remarkable rate capacity, which is supposed to benefit from a large accessible specific area and unique nanostructures. The remarkable performances suggest promising application as an advanced anode material.

Lithium-Ion-Battery Anode Materials with Improved Capacity from a Metal-Organic Framework.

We present a porous metal-organic framework (MOF) with remarkable thermal stability that exhibits a discharge capacity of 300 mAh g(-1) as an anode material for a lithium-ion battery. Pyrolysis of the obtained MOF gives an anode material with improved capacity (741 mAh g(-1)) and superior cyclic stability.