York-shell Co@Co-N/C of bifunctional oxygen electrocatalysts

doi:10.11949/j.issn.0438-1157.20180759

Abstract

Abstract:

ZIF-67 was used as a template for producing metal and nitrogen doped carbon composite as electrocatalysts. By an in-situ polymerization of dopamine on the surface of ZIF-67, Co²⁺ ions were extracted into the polydopamine shell due to the strong chelation between them and led to the decomposition of ZIF-67, which resulted into a hollow composite of Co-PDA. Subsequently, a yolk-shell structure of metal and nitrogen doped carbon composites (Co@Co-N/C) was obtained by a high temperature pyrolysis at 900℃. The unique structure of Co@Co-N/C provided excellent bifunctional electrocatalysts for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), repetitively. For ORR, the half-wave potential was 0.81 V and the Tafel slope was 60 mV/dec. For OER, the overpotential was 390 mV at the current density of 10 mA/cm², and the Tafel slope was 71 mV/dec. More importantly, the total oxygen electrocatalytic activity was as low as 0.82 V.

Key words: electrochemistry, catalyst, nanostructure, Co-N/C composite electrocatalyst, ZIF-67

摘要：

以ZIF-67为模板，通过表面原位聚合多巴胺，与金属Co²⁺发生强烈螯合，释放出有机配体，得到中空的金属-有机结构材料（Co-PDA）。通过900℃高温处理得到类似蛋黄（yolk-shell）结构的金属氮掺杂碳材料（Co@Co-N/C）。这种特殊结构的材料具有优异的氧还原（ORR）和析氧反应（OER）电催化活性，在0.1 mol/L KOH电解液中，其ORR的半波电位为0.81 V，Tafel斜率为60 mV/dec；在电流密度为10 mA/cm²时，其OER过电位为390 mV，Tafel斜率为71 mV/dec，总的氧电极催化活性为0.82 V，是一种优良的双功能氧电极催化剂。

关键词: 电化学, 催化剂, 纳米结构, 钴氮碳掺杂氧电极, ZIF-67

CLC Number:

TQ028.8

SHUI Hengxin, PANFENG Hongkang, JIN Tian, HU Jun, LIU Honglai. York-shell Co@Co-N/C of bifunctional oxygen electrocatalysts[J]. CIESC Journal, 2018, 69(11): 4702-4712.

水恒心, 潘冯弘康, 金田, 胡军, 刘洪来. 双功能yolk-shell钴@钴氮碳掺杂氧电极催化剂[J]. 化工学报, 2018, 69(11): 4702-4712.

References 38

[1]	BU L, ZHANG N, GUO S, et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis[J]. Science, 2016, 354(6318):1410-1414.
[2]	HUANG X, ZHAO Z, CAO L, et al. High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction[J]. Science, 2015, 348(6240):1230-1234.
[3]	GAN L, CUI C, HEGGEN M, et al. Element-specific anisotropic growth of shaped platinum alloy nanocrystals[J]. Science, 2014, 346(6216):1502-1506.
[4]	ANTOLINI E. Iridium as catalyst and cocatalyst for oxygen evolution/reduction in acidic polymer electrolyte membrane electrolyzers and fuel cells[J]. ACS Catalysis, 2014, 4(5):1426-1440.
[5]	KUZUME A, HERRERO E, FELIU J M. Oxygen reduction on stepped platinum surfaces in acidic media[J]. Journal of Electroanalytical Chemistry, 2007, 599(2):333-343.
[6]	CHANG H, JOO S H, PAK C. Synthesis and characterization of mesoporous carbon for fuel cell applications[J]. Journal of Materials Chemistry, 2007, 17(30):3078-3088.
[7]	HU C, SONG L, ZHANG Z, et al. Tailored graphene systems for unconventional applications in energy conversion and storage devices[J]. Energy & Environmental Science, 2015, 8(1):31-54.
[8]	KIM J, YIN X, TSAO K C, et al. Ca2Mn2O5 as oxygen-deficient perovskite electrocatalyst for oxygen evolution reaction.[J]. Journal of the American Chemical Society, 2014, 136(42):14646-14649.
[9]	MENG Y, SONG W, HUANG H, et al. Structure-property relationship of bifunctional MnO2 nanostructures:highly efficient, ultra-stable electrochemical water oxidation and oxygen reduction reaction catalysts identified in alkaline media[J]. Journal of the American Chemical Society, 2014, 136(32):11452-11464.
[10]	ZHAO Y, NAKAMURA R, KAMIYA K, et al. Nitrogen-doped carbon nanomaterials as non-metal electrocatalysts for water oxidation[J]. Nature Communications, 2013, 4:2390.
[11]	HU C, SONG L, ZHANG Z, et al. Tailored graphene systems for unconventional applications in energy conversion and storage devices[J]. Energy & Environmental Science, 2015, 8(1):31-54.
[12]	YANG R, STEVENS K, DAHN J R. Investigation of activity of sputtered transition-metal (TM)-C-N (TM=V, Cr, Mn, Co, Ni) catalysts for oxygen reduction reaction[J]. Journal of The Electrochemical Society, 2008, 155(1):B79-B91.
[13]	EASTON E B, BONAKDARPOUR A, YANG R, et al. Magnetron sputtered Fe-C-N, Fe-C, and C-N based oxygen reduction electrocatalysts[J]. Journal of The Electrochemical Society, 2008, 155(6):B547-B557.
[14]	YANG R, BONAKDARPOUR A, EASTON E B, et al. Co-C-N oxygen reduction catalysts prepared by combinatorial magnetron sputter deposition[J]. Journal of The Electrochemical Society, 2007, 154(4):A275-A282.
[15]	KIM J H, ISHIHARA A, MITSUSHIMA S, et al. Oxygen reduction reaction of Cr-CN prepared using reactive sputtering with heat treatment[J]. Chem. Lett., 2007, 36(4):514-515.
[16]	KIM J H, ISHIHARA A, MITSUSHIMA S, et al. Oxygen reduction reaction of Ta-CN prepared by reactive sputtering with heat treatment[J]. Electrochemistry, 2007, 75(2):166-168.
[17]	ZERADJANIN A R, TOPALOV A A, VAN OVERMEERE Q, et al. Rational design of the electrode morphology for oxygen evolution-enhancing the performance for catalytic water oxidation[J]. RSC Advances, 2014, 4(19):9579-9587.
[18]	MURINZI T W, HOSTEN E, WATKINS G M. Synthesis and characterization of a cobalt-2, 6-pyridinedicarboxylate MOF with potential application in electrochemical sensing[J]. Polyhedron, 2017, 137:188-196.
[19]	MENG F, ZHONG H, BAO D, et al. In situ coupling of strung Co4N and intertwined N-C fibers toward free-standing bifunctional cathode for robust, efficient, and flexible Zn-air batteries[J]. Journal of the American Chemical Society, 2016, 138(32):10226-10231.
[20]	GUPTA S, QIAO L, ZHAO S, et al. Highly active and stable graphene tubes decorated with FeCoNi alloy nanoparticles via a template-free graphitization for bifunctional oxygen reduction and evolution[J]. Advanced Energy Materials, 2016, 6(22):1601198.
[21]	WANG Z, LU Y, YAN Y, et al. Core-shell carbon materials derived from metal-organic frameworks as an efficient oxygen bifunctional electrocatalyst[J]. Nano Energy, 2016, 30:368-378.
[22]	RAVIKUMAR A, PANNEERSELVAM P, MORAD N. A metal-polydopamine framework (MPDA) as an effective fluorescent quencher for highly sensitive detection of Hg (Ⅱ) and Ag (Ⅰ) ions through exonuclease Ⅲ activity[J]. ACS Applied Materials & Interfaces, 2018.
[23]	LIANG Y, WEI J, HU Y X, et al. Metal-polydopamine frameworks and their transformation to hollow metal/N-doped carbon particles[J]. Nanoscale, 2017, 9(16):5323-5328.
[24]	LI X, LI J, SHI Y, et al. Rational design of cobalt and nitrogen co-doped carbon hollow frameworks for efficient photocatalytic degradation of gaseous toluene[J]. Journal of Colloid and Interface Science, 2018, 528:45-52.
[25]	LI Z, SHAO M, ZHOU L, et al. Directed growth of metal-organic frameworks and their derived carbon-based network for efficient electrocatalytic oxygen reduction[J]. Advanced Materials, 2016, 28(12):2337-2344.
[26]	GONG K, DU F, XIA Z, et al. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction[J]. Science, 2009, 323(5915):760-764.
[27]	LIANG H W, ZHUANG X, BRÜLLER S, et al. Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction[J]. Nature Communications, 2014, 5:4973.
[28]	CHUNG H T, WON J H, ZELENAY P. Active and stable carbon nanotube/nanoparticle composite electrocatalyst for oxygen reduction[J]. Nature Communications, 2013, 4:1922.
[29]	QU K, ZHENG Y, DAI S, et al. Graphene oxide-polydopamine derived N, S-co doped carbon nanosheets as superior bifunctional electrocatalysts for oxygen reduction and evolution[J]. Nano Energy, 2016, 19:373-381.
[30]	AIJAZ A, MASA J, RÖSLER C, et al. Co@Co3O4 encapsulated in carbon nanotube-grafted nitrogen-doped carbon polyhedra as an advanced bifunctional oxygen electrode[J]. Angewandte Chemie International Edition, 2016, 55(12):4087-4091.
[31]	ZANG Y, ZHANG H, ZHANG X, et al. Fe/Fe2O3 nanoparticles anchored on Fe-N-doped carbon nanosheets as bifunctional oxygen electrocatalysts for rechargeable zinc-air batteries[J]. Nano Research, 2016, 9(7):2123-2137.
[32]	WANG H F, TANG C, WANG B, et al. Bifunctional transition metal hydroxysulfides:room-temperature sulfurization and their applications in Zn-air batteries[J]. Advanced Materials, 2017, 29(35):1702327.
[33]	LIU S, WANG Z, ZHOU S, et al. Metal-organic-framework-derived hybrid carbon nanocages as a bifunctional electrocatalyst for oxygen reduction and evolution[J]. Advanced Materials, 2017, 29(31):1700874.
[34]	WANG W, KUAI L, CAO W, et al. Mass-production of mesoporous MnCo2O4 spinels with manganese (Ⅳ)-and cobalt (Ⅱ)-rich surfaces for superior bifunctional oxygen electrocatalysis[J]. Angewandte Chemie, 2017, 129(47):15173-15177.
[35]	JI D, PENG S, SAFANAMA D, et al. Design of 3-dimensional hierarchical architectures of carbon and highly active transition metals (Fe, Co, Ni) as bifunctional oxygen catalysts for hybrid lithium-air batteries[J]. Chemistry of Materials, 2017, 29(4):1665-1675.
[36]	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.
[37]	CHEN P, ZHOU T, XING L, et al. Atomically dispersed iron-nitrogen species as electrocatalysts for bifunctional oxygen evolution and reduction reactions[J]. Angewandte Chemie International Edition, 2017, 56(2):610-614.
[38]	LI G, WANG X, FU J, et al. Pomegranate-inspired design of highly active and durable bifunctional electrocatalysts for rechargeable metal-air batteries[J]. Angewandte Chemie International Edition, 2016, 55(16):4977-4982.