The direct pyrolysis method was adopted with graphene as the carrier, 2-methylimidazole zinc salt MAF-4(ZIF8) and urea to provide carbon and nitrogen sources, Fe as the transition metal source, to synthesize nitrogen-doped graphene(N/GO) and Fe-ZIF8(N-GO@Fe/ZIF8) composite catalyst, assembled into a zinc-air battery. The physical-chemical properties of the catalyst were characterized by using scanning electron microscope(SEM), transmission electron microscope(TEM) and rotating disk electrode. The results show that the synthesized N-GO@Fe/ZIF8-900 catalyst has excellent oxygen reduction/oxygen evolution (ORR/OER) performance. The half wave potential is 0.885 V, which is better than that of Pt/C (0.856 V). When oxygen is precipitated, the corresponding potential is 1.811 V at a current density of 10 mA/cm2, which is better than that of the noble metal Pt/C (1.968 V) and the same performance as IrO2 (1.75 V).After being assembled into a zinc air battery, the specific energy and power density reach 886.2 mW·h·g-1 and 73.44 mW/cm2 respectively, which are higher than that of Pt/C (791.04 mW·h·g-1, 57.12 mW/cm2) respectively. The catalyst has good application prospect.
FU J , CANO Z P , MOON G P , et al. Electrically rechargeable zinc-air batteries:progress, challenges, and perspectives[J]. Advanced Materials, 2017, 29 (7): 1604685.
doi: 10.1002/adma.201604685
2
GENG D S , YANG S , ZHANG Y , et al. Nitrogen doping effects on the structure of grapheme[J]. Applied Surface Science, 2011, 257 (21): 9193- 9198.
doi: 10.1016/j.apsusc.2011.05.131
QI X , CHEN X , LI B T , et al. Novel strategy for low-temperature vacuum preparation of high-quality graphene[J]. Journal of Aeronautical Materials, 2020, 40 (4): 1- 8.
4
XIA D , TANG F , YAO X , et al. Seeded growth of branched iron-nitrogen-doped carbon nanotubes as a high performance and durable non-precious fuel cell cathode[J]. Carbon, 2020, 162, 300- 307.
doi: 10.1016/j.carbon.2020.02.046
5
LIU Q , PU Z H , PU Z , et al. N-doped carbon nanotubes from functional tubular polypyrrole: a highly efficient electrocatalyst for oxygen reduction reaction[J]. Electrochemistry Communications, 2013, 36 (6): 57- 61.
6
DENG J , DENG D , BAO X H . Robust catalysis on 2D materials encapsulating metals: concept, application, and perspective[J]. Advanced Materials, 2017, 29 (43): 1606967.
doi: 10.1002/adma.201606967
7
DENG D , YU L , CHEN X , et al. Iron encapsulated within pod-like carbon nanotubes for oxygen reduction reaction[J]. Angewandte Chemie, 2013, 52 (1): 371- 375.
doi: 10.1002/anie.201204958
8
WU X , MENG G , LIU W , et al. Metal-organic framework-derived, Zn-doped porous carbon polyhedra with enhanced activity as bifunctional catalysts for rechargeable zinc-air batteries[J]. Nano Research, 2017, 11 (1): 163- 173.
9
ZHANG W , LIU X , GAO M , et al. Co-Zn-MOFs derived n-doped carbon nanotubes with crystalline Co nanoparticles embedded as effective oxygen electrocatalysts[J]. Nanomaterials, 2021, 11 (2): 261.
doi: 10.3390/nano11020261
10
YANG L , ZENG X H , WANG W C , et al. Recent progress in MOF-derived, heteroatom-doped porous carbons as highly efficient electrocatalysts for oxygen reduction reaction in fuel cells[J]. Advanced Functional Materials, 2018, 28 (7): 1704537.
doi: 10.1002/adfm.201704537
11
SU P , XIAO H , ZHAO J , et al. Nitrogen-doped carbon nanotubes derived from Zn-Fe-ZIF nanospheres and their application as efficient oxygen reduction electrocatalysts with in situ generated iron species[J]. Chemical Science, 2013, 4 (7): 2941- 2946.
doi: 10.1039/c3sc51052b
12
WANG Z H , TIAN M . Fe, Cu-coordinated ZIF-derived carbon framework for efficient oxygen reduction reaction and zinc-air batteries[J]. Advanced Functional Materials, 2018, 28 (39): 1802596.
doi: 10.1002/adfm.201802596
13
WANG S , QIN J , MENG T , et al. Metal-organic framework-induced construction of actiniae-like carbon nanotube assembly as advanced multifunctional electrocatalysts for overall water spli-tting and Zn-air batteries[J]. Nano Energy, 2017, 39, 626- 638.
doi: 10.1016/j.nanoen.2017.07.043
14
ZHAO W , LI G , TANG Z . Metal-organic frameworks as emerging platform for supporting isolated single-site catalysts[J]. Nano Today, 2019, 27, 178- 197.
doi: 10.1016/j.nantod.2019.05.007
15
ZHANG D , CHEN W , LI Z , et al. Isolated Fe and Co dual active sites on nitrogen-doped carbon for a highly efficient oxygen reduction reaction[J]. Chemical Communications, 2018, 54 (34): 4274- 4277.
doi: 10.1039/C8CC00988K
REN Z D , HAO S J , XING Y , et al. Properties of graphene oxide modified epoxy resin and its composites[J]. Journal of Aeronautical Materials, 2019, 39 (2): 29- 36.
17
QI H , FENG Y Y , CHI Z Z , et al. In situ encapsulation of Co-based nanoparticles into nitrogen-doped carbon nanotubes-modified reduced graphene oxide as an air cathode for high-perfor-mance Zn-air batteries[J]. Nanoscale, 2019, 11 (45): 21943- 21952.
doi: 10.1039/C9NR07270E
18
GUO C H , LI L , ZHANG T , et al. Space-confined iron nanoparticles in a 3D nitrogen-doped rGO-CNT framework as efficient bifunctional electrocatalysts for rechargeable zinc-air batteries[J]. Microporous and Mesoporous Materials, 2020, 298, 110100.
doi: 10.1016/j.micromeso.2020.110100
19
KUMAR M , ANDO Y . Chemical vapor deposition of carbon nanotubes: a review on growth mechanism and mass production[J]. Chem Inform, 2010, 41 (22): 3739- 3758.
20
GOHIER A , EWELS C P , MINEA T M , et al. Carbon nanotube growth mechanism switches from tip-to base-growth with decreasing catalyst particle size[J]. Carbon, 2008, 46 (10): 1331- 1338.
doi: 10.1016/j.carbon.2008.05.016
21
JIANG W J, LIN G, LI L, et al. Understanding the high activity of Fe-N-C electrocatalysts in oxygen reduction: Fe/Fe3C nano-particles boost the activity of Fe-Nx[J]. 2016, 138(10): 3570-3578.
22
MOON I K , LEE J , RUOFF R S , et al. Reduced graphene oxide by chemical graphitization[J]. Nature Communications, 2010, 1 (1): 1- 6.
23
QAZI S , RENNIE A R , COCKCROFT J K , et al. Use of wide-angle X-ray diffraction to measure shape and size of dispersed colloidal particles[J]. Journal of Colloid & Interface Science, 2009, 338 (1): 105- 110.
24
TANG C , WANG B , WANG H F , et al. Defect engineering toward atomic Co-Nx-C in hierarchical graphene for rechargeable flexible solid Zn-air batteries[J]. Advanced Materials, 2017, 29 (37): 1703185.
doi: 10.1002/adma.201703185
25
SU C Y , CHENG H , LI W , et al. Atomic modulation of FeCo-nitrogen-carbon bifunctional oxygen electrodes for rechargeable and flexible all-solid-state zinc-air battery[J]. Advanced Energy Materials, 2017, 7 (13): 1602420.
doi: 10.1002/aenm.201602420
26
LI Q , XU P , GAO W , et al. Graphene/graphene-tube nanocomposites templated from cage-containing metal-organic frameworks for oxygen reduction in Li-O2 batteries[J]. Advanced Materials, 2014, 26 (9): 1378- 1386.
doi: 10.1002/adma.201304218
2022, Vol. 50 
), 吉莹, 于沺沺, 李田成, 薛裕华
