高等学校化学学报 ›› 2021, Vol. 42 ›› Issue (2): 575.doi: 10.7503/cjcu20200653
收稿日期:
2020-09-25
出版日期:
2021-02-10
发布日期:
2020-12-28
通讯作者:
赵美廷
E-mail:mtzhao@tju.edu.cn
基金资助:
WAN Yue, SONG Meina, ZHAO Meiting()
Received:
2020-09-25
Online:
2021-02-10
Published:
2020-12-28
Contact:
ZHAO Meiting
E-mail:mtzhao@tju.edu.cn
Supported by:
摘要:
二维金属有机框架(2D MOF)纳米片具有丰富且易暴露的表面活性位点、 高度有序的孔结构以及多样且可调的化学成分, 在电化学能量存储与转化中有利于降低反应电位, 提高扩散速率和反应速率. 关于2D MOF应用于电化学存储与转化的研究已有大量报道. 本文综合评述了近几年2D MOF的合成进展及其在超电容(SC)、 析氧反应(OER)、 析氢反应(HER)、 氧还原反应(ORR)和二氧化碳还原反应(CRR)的应用, 并对2D MOF作为电催化材料的研究现状和发展前景进行了总结与展望.
中图分类号:
TrendMD:
万月, 宋美娜, 赵美廷. 二维金属有机框架纳米片的合成及在超电容和电催化领域的应用. 高等学校化学学报, 2021, 42(2): 575.
WAN Yue, SONG Meina, ZHAO Meiting. Recent Progress of Two-dimensional Metal-organic Framework Nanosheets for Supercapacitor and Electrocatalysis Applications. Chem. J. Chinese Universities, 2021, 42(2): 575.
Fig.1 AFM image of [Cu2Br(IN)2]n(A)[32], crystal structure of Mn(C6H8O4)(H2O) layered(B)[33], architecture of the layered MOF precursor(C), PXRD patterns of Zn2(bim)4(D) and tapping?mode AFM topographical image of Zn2(bim)4 nanosheets on silicon wafer(E) [36](A) Insert: height profile of the nanosheets across the green line; (E) the height profile of the nanosheets along the black lines was marked in the image.(A) Copyright 2010, The Royal Society of Chemistry. (B) Copyright 2012, American Chemical Society. (C—E) Copyright 2014, American Association for the Advancement of Science.
Fig.2 Schematic illustration of the synthesis of 2D MOF nanosheets via an intercalation and chemical exfoliation approach(A), experimental PXRD patterns of Zn2(PdTCPP) before and after insertion of DPDS ligands(B), AFM image of the exfoliated MOF nanosheets with corresponding height profiles(C), high?resolution TEM image of an exfoliated multilayer MOF nanosheet(D)[45], electrochemical exfoliation of pillared?layer metal?organic framework to boost the oxygen evolution reaction(E) and the height profile of Co6O(dhbdc)2(F)[47](A—D) Copyright 2017, American Chemical Society. (E, F) Copyright 2018, Wiley?VCH.
Fig.3 Scheme of the formation of Cu?BHT film(A), SEM images of cross?section(B), upside(C) and downside surface(D) of a 200?nm?thick film[49]Copyright 2015, Macmillan Publishers Limited.
Fig.4 Traditional synthesis and surfactant‐assisted synthesis of MOF(A), STEM image of Zn‐TCPP nanosheets(B), statistical analysis of the lateral size of Zn?TCPP nanosheets measured in STEM images(C), AFM images of Zn?TCPP nanosheets(D), statistical analysis of the thickness of Zn?TCPP nanosheets measured in AFM images(E)[61], schematic illustration of the process developed to produce 2D Zr?MOF nanosheets via a surfactant?mediated method(F)[64], AFM image(G) and the corresponding height profiles(H) of the 2D Zr?BDC MOF(A—E) Copyright 2015, Wiley?VCH. (F—H) Copyright 2019, The Royal Society of Chemistry.
Fig.5 TEM images of [Cu2(BDC)2(BPY)] nanosheets prepared by adding different amounts of modulator(r=20, 30, 40 and 50, where r=[acetic acid]/[copper acetate])(A—D)[71], the crystal structure(E) and TEM image(F) of Hf6O4(OH)4?(HCO2)6(BTB)2 nanosheets[72], fcc UiO?67 viewed along the [001] direction(G) and hcp UiO?67 viewed along the [001] direction(H)[73](A—D) Copyright 2013, American Association for the Advancement of Science; (E, F) Copyright 2016, Wiley?VCH; (G, H) Copyright 2017, American Chemical Society.
Fig.6 Preparation and morphology characterization of FeCo?MNS(A), illustration of the confined growth mechanism of FeCo‐MNS adjacent to the FeCo‐ONS(B), SEM image of FeCo?ONS(C),TEM(D) and AFM(E) images of FeCo‐ONS?1.0[74], synthetic procedure for the production of ultrathin metal?organic framework nanosheets and their utilization for the oxygen evolution reaction(F) and AFM image of Ni?Fe?MOF(G)[75](A—E) Copyright 2019, Wiley?VCH. (F, G) Copyright 2019, Wiley?VCH.
Fig.7 AFM images of Ni2[CuPc(NH)8](A), specific capacitances calculated from GCD curves as a function of current density(B) and cycling stability measured at 0.4 mA/cm2 under voltage window of 0.8 V(C)[106]Copyright 2020, Wiley?VCH.
Fig.8 Molecular structur of ultrathin 2D Co?MOF nanosheets(A), magnified polarization curves of ultrathin 2D Co?MOF nanosheet, micro?nano Co?MOF and bulk Co?MOF materials at current densities of 10 mA/cm2(B), Tafel slopes of ultrathin 2D Co?MOF nanosheets, micro?nano Co?MOFs, bulk Co?MOFs and RuO2(C)[109], chemical structure of NiPc?MOF(D), pH?dependent LSV curves using the NiPc?MOF as the OER catalyst(E) and chronopotentiometry data for water oxidation at a fixed catalytic current density of 1.0 mA/cm2(F)[114](A—C) Copyright 2018, The Royal Society of Chemistry. (D—F) Copyright 2018, The Royal Society of Chemistry.
Fig.9 Comparison of the required overpotentials at 100 and 300 mA/cm2 for various electrodes(A),Tafel plots of various electrodes(B)[117], structure of TNT?Ni nanosheets(C), HER polarization plots and corresponding Tafel plot(inset) of the THT?Ni 2DSP sheet and blank glassy carbon disk electrode in 0.5?mol/L H2SO4(D)[118], structure of THAT?Co nanosheets with the MN4, MS4 and MS2N2 moieties(E) and Tafel plots of THAT?Co nanosheets(F)[119](A, B) Copyright 2020, American Chemical Society. (C, D) Copyright 2015, WILEY‐VCH. (E, F) Copyright 2017, Wiley‐VCH.
Fig.10 Perspective view of the two?dimensional layered structure of Ni3(HITP)2(A), ORR performance of Ni3(HITP)2(B)[120], schematic illustration of the preparation of the M3HITP2(C) and their LSV curves obtained in 0.1?mol/L KOH(D)[121], schematic structure of PcCu‐O8‐M(red: O, blue: carbon, white: hydrogen, brown: Cu, green: metal atoms, M=Co, Fe, Ni, Cu)(E), ORR polarization curves of PcCu‐O8‐Co/CNT at different rotating speeds(inset: corresponding K?L plots of PcCu‐O8‐Co/CNT)(F) and ORR polarization curves of PcCu‐(OH)8‐CNT, Pc‐O8‐Co/CNT, and PcCu‐O8‐Co/CNT(G)[122](A, B) Copyright 2016, Springer nature. (C, D) Copyright 2020, Wiley?VCH. (E—G) Copyright 2019, Wiley?VCH.
Fig.11 MOF Al2(OH)2TCPP?M′ integrated with a conductive substrate to achieve a functional CO2 electrochemical reduction system(A), stability of the MOF catalyst evaluated through chronoamperometric measurements in combination with faradaic efficiency measurements(B), XRD analysis indica?ting that the MOF retains its crystalline structure after chronoamperometric measurement(C), SEM images of the MOF catalyst film before(D) and after electrolysis(E) revealining the retention of the plate?like morphology[135], schematic structure of PcCu?O8?Zn(the dashed rectangular indicates the unit cell)(F), partial current(G) and faradaic efficiency(H) of CO for PcCu?O8?Zn/CNT, PcCu?O8?Cu/CNT, PcZn?O8?Zn/CNT and PcZn?O8?Cu/CNT at different potentials[138](A—E) Copyright 2015, American Chemical Society. (F—H) Copyright 2020, Springer Nature.
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