Metal-Organic Framework Materials for Electrochemical Supercapacitors

Exploring new materials with high stability and capacity is full of challenges in sustainable energy conversion and storage systems.Metal-organic frameworks(MOFs),as a new type of porous material,show the advantages of large specific surface area,high porosity,low density,and adjustable pore size,exhibiting a broad application prospect in the field of electrocatalytic reactions,batteries,particularly in the field of supercapacitors.This comprehensive review outlines the recent progress in synthetic methods and electrochemical performances of MOF materials,as well as their applications in supercapacitors.Additionally,the superiorities of MOFs-related materials are highlighted,while major challenges or opportunities for future research on them for electrochemical supercapacitors have been discussed and displayed,along with extensive experimental experiences.

MOF-Derived Materials Enabled Lithiophilic 3D Hosts for Lithium Metal Anode—A Review

Comprehensive Summary This work systematically reviews recent progresses in the applications of MOF-derived materials modified 3D porous conductive framework as hosts for uniform lithium deposition in LMBs.A series of commonly used lithiophilic materials and several kinds of representative MOF-derivation-modified 3D hosts as lithium metal anode(LMA)are presented.Finally,the challenges and future development of employing MOF-derived materials to modify the 3D porous conductive framework for LMA are included.

Function-regeneration of non-porous hydrolyzed-MOF-derived materials

A facile synthetic strategy based on a water-based process is developed for the preparation of metal-organic framework (MOF)-derived materials by revisiting the hydrolyzed non-porous metal-organic frameworks (h-MOF). The poor water stability of MOF has been recognized as key limitations for its commercialization and large-scale applications because the hydrolysis resulted in the complete loss of their functionalities. However, we found that the negative effect of hydrolysis on MOF can be nullified during the heat treatment. As similar to the intact MOF, h-MOF can be used as a precursor for the preparation of MOF-derived materials from porous MOF-derived carbons (MDCs) to MDC@ZnO composites. The property of h-MOF-derived materials is almost equivalent to that of MOF-derived materials. In addition, h-MOF turned the weakness of water instability to the strength of facile water-based process for hybridization. With the demonstration of the hybrid composite between h-MDC@ZnO and reduced graphene oxide (rGO) as a prototype example, it exhibited superior electrochemical performance when evaluated as an electrode material for lithium-ion batteries.

手性金属有机框架材料(MOFs)的合成及应用

手性材料一直以来都是科学工作者研究的重点,尤其是在药物和生物体中的应用方面.手性金属有机框架材料(MOFs)具有迷人的拓补结构和潜在的应用价值,受到了人们的广泛关注.主要从它的合成和应用方面做了简要的介绍.

毛细管电泳新型手性分离体系研究进展

在现代分离科学中,手性化合物的分离分析一直是研究的重点和难点。相比于高效液相色谱(HPLC)、气相色谱(GC)等传统色谱分析方法,毛细管电泳(CE)技术凭借其高效率、低消耗、分离模式多样化等诸多优势,已经发展成为手性分离研究领域最有应用前景的分析方法之一。近年来,研究人员在CE手性分析方法的构建过程中,基于毛细管电动色谱(EKC)、配体交换毛细管电泳(LECE)、毛细管电色谱(CEC)等各种基础电泳模式,不断地对传统手性分离体系进行优化和改造,构建出了许多高性能的新型手性CE分离体系。如利用各类功能化离子液体以“手性离子液体协同拆分”“手性离子液体配体交换”“离子液体手性选择剂”等模式设计出多种基于离子液体的CE手性分离体系;利用纳米材料独特的尺寸效应、多样性、可设计性等特点,直接或与传统手性选择剂有机结合构建CE手性分离体系。此外,金属有机骨架材料修饰、低共熔溶剂修饰、非连续分段式部分填充等各式新颖的CE手性分离体系也都被研究人员成功开发,并表现出较大的发展潜力。该综述将对近年来(尤其是2015~2019年)此类新型CE手性分离体系的发展状况进行梳理,并结合相应的手性识别机理研究和手性CE方法实际应用情况,对该领域存在的问题及发展前景进行分析和展望。

Solar-assisted photocatalytic water splitting using defective UiO-66 solids from modulated synthesis

Metal-organic frameworks(MOFs)are attracting increasing interests as photocatalysts for solar-driven hydrogen production from water.This paper reports on a comparative study of using either acetic acid(AA)or trifluoroacetic acid(TFA)as the representative UiO-66 organic modulators for synthesizing visible light responsive UiO-66(Zr)-X(X:NH_(2) or NO_(2))photocatalysts for water splitting.The results show that photocatalytic hydrogen generation from a water/methanol mixture can be improved by varying the nature and amount of the modulator employed to prepare the different UiO-66(Zr)-X(X:NH_(2) or NO_(2))solid derivatives.UiO-66(Zr)-NH_(2) was the most active photocatalyst,followed by UiO-66(Zr)-NO_(2),both prepared with 12 equivalents of AA with respect to the organic ligand.This UiO-66(Zr)-NH_(2) solid was more active than the parent MOF in photocatalytic overall water splitting(OWS)(H_(2) and O_(2) production of 450 and 160μmol·g^(-1),respectively,in 5 h;apparent quantum yield(AQY)at 400 nm of 0.06%)in the absence of methanol and compares favourably with analogous reports.Information on the photocatalytic activity of the most active solids of both series was obtained by means of a series of techniques,including ultraviolet-visible(UV-vis)diffuse reflectance,X-ray photoelectron spectroscopy(XPS),laser flash photolysis(LFP),electron spin resonance(ESR),photoluminescence and photoelectrochemical measurements together with density functional theory(DFT)calculations.The results showed that organic acid modulators can be used to enhance the photocatalytic activity of missing linker UiO-66 defective materials in solar-powered water splitting.

Novel strategies to tailor the photocatalytic activity of metal–organic frameworks for hydrogen generation: a mini-review

This review provides a recompilation of the most important and recent strategies employed to increase the efficiency of metal-organic framework(MOF)-based systems toward the photocatalytic hydrogen evolution(PHE)reaction through specific strategies:tailoring the photocatalytic activity of bare MOFs and guest@MOF composites,formation of heterojunctions based on MOFs and various photocatalysts,and inorganic photocatalysts derived from MOFs.According to the data reported in this mini-review,the most effective strategy to improve the PHE of MOFs relies on modifying the linkers with new secondary building units(SBUs).Although several reviews have investigated the photocatalytic activity of MOFs from a general point of view,many of these studies relate this activity to the physicochemical and catalytic properties of MOFs.However,they did not consider the interactions between the components of the photocatalytic material.This study highlights the effects of strength of the supramolecular interactions on the photocatalytic performance of bare and MOF-based materials during PHE.A thorough review and comparison of the results established that metal-nanoparticle@MOF composites have weak van der Waals forces between components,whereas heterostructures only interact with MOFs at the surface of bare materials.Regarding material derivatives from MOFs,we found that pyrolysis destroyed some beneficial properties of MOFs for PHE.Thus,we conclude that adding SBUs to organic linkers is the most efficient strategy to perform the PHE because the SBUs added to the MOFs promote synergy between the two materials through strong coordination bonds.

Two-dimensional Cu-porphyrin nanosheet membranes for nanofiltration

A kind of two-dimensional(2D)metal-organic framework(MOF)material,Cu-meso-tetrakis(4-carboxyphenyl)porphine(Cu-TCPP)nanosheets with wrinkled and flat morphologies are used as building blocks to assemble membranes by vacuum filtration(VF)and electrophoretic deposition(EPD)as energy-efficient nanofiltration(NF)membranes to remove dyes from water.Since the nanosheets with wrinkled structure can provide additional water transport channels,thereby increasing the water permeance,in the premise of a high rejection(>97.0%)for the dye brilliant blue G(BBG)(1.60 nm×1.90 nm),the water permeance of the membrane assembled by the wrinkled nanosheets(~1170 nm)is about 4 times that of the membrane assembled by the flat nanosheets(~530 nm),reaching 16.39 L·m^(−2)·h^(−1)·bar^(−1).Additionally,the use of the relatively flat nanosheets and the membrane preparation method of electrophoretic deposition is more conducive to stack nanosheets orderly and reduce defects.Therefore,the water permeance of the membrane prepared by EPD(~1170 nm)with flat nanosheets is about twice that of the membrane prepared by VF(~530 nm),achieving 9.40 L·m^(−2)·h^(−1)·bar^(−1)with similar rejection(>97.0%)of dye evans blue(EB)(3.10 nm×1.20 nm).Furthermore,these membranes still exhibit good separation performance at high pressure of 0.6 MPa.Nanosheets with diverse structures and various membrane fabrication processes provide new directions for the separation performance optimization of 2D MOF materials for water purification.

Novel metastable Bi:Co and Bi:Fe alloys nanodots@carbon as anodes for high rate K-ion batteries

Bi is a promising anode material for potassium-ion batteries(PIBs)due to its high theoretical capacity.However,severe pulverization upon cycling limits its practical applications.In this work,we propose a new approach of using metastable alloys with Bi elements.Metastable Bi:Co and Bi:Fe alloys nanodots@carbon anode materials(Bi:Co and Bi:Fe@C)are synthesized for the first time via simple annealing of their metal-organic frameworks(MOF)precursors.These prepared materials are demonstrated as ideal hosts for high-rate K-ion storage.Bi_(0.85)Co_(0.15)@C and Bi_(0.83)Fe_(0.17)@C electrodes respectively deliver superior 178 and 253 mAh·g^(−1)at 20 A·g^(−1),as well as stable cycling performance at 2 A·g^(−1).Ex situ scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),and transmission electron microscopy(TEM)studies on Bi:Co@C indicate that the elemental Co separates out during the initial potassiation and stands during the following discharge/charge cycles.In situ formed Co precipitates can act as(1)“conductive binders”as well as(2)“separators”to prevent the severe aggregation of adjacent active elemental Bi nanoparticles and(3)accelerate the potassiation/de-potassiation kinetics in elemental Bi precipitates after initial discharge/charge cycles.This work could inspire the development of metal-type anodes.