一種高效雙功能電催化劑CoP/Co@NPC@rGO的制備

黃康; 朱梅婷; 張飛鵬; 許志龍; 王洪濤; 肖葵; 吳俊升

doi:10.13374/j.issn2095-9389.2019.07.26.002

一種高效雙功能電催化劑CoP/Co@NPC@rGO的制備

doi: 10.13374/j.issn2095-9389.2019.07.26.002

黃康^{1, 2},
朱梅婷²,
張飛鵬²,
許志龍²,
王洪濤²,
肖葵¹,
吳俊升^{1, 2, ,}

1.
北京科技大學新材料技術研究院，北京 100083
2.
北京科技大學天津學院材料科學與工程系，天津 301830

基金項目: 國家自然科學基金資助項目（51771027）；國家重點研發計劃資助項目（2017YFB0702100）

詳細信息

通訊作者:
E-mail：wujs@ustb.edu.cn

中圖分類號: O643.3
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出版歷程
- 收稿日期: 2019-07-26
- 刊出日期: 2020-01-01

Preparation of CoP/Co@NPC@rGO nanocomposites with an efficient bifunctional electrocatalyst for hydrogen evolution and oxygen evolution reaction

1.
Institute of Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China
2.
Department of Materials Science and Engineering, Tianjin College, University of Science and Technology Beijing, Tianjin 301830, China

More Information

Corresponding author: E-mail: wujs@ustb.edu.cn

摘要

摘要: 簡單的熱處理和熱處理磷化ZIF-67/氧化石墨烯（GO）前驅體得到具有典型的多孔碳結構特征的CoP/Co@NPC@rGO納米復合材料電催化劑。通過掃描電子顯微鏡（SEM）、透射電子顯微鏡（TEM）、X射線衍射（XRD）、X射線光電子能譜（XPS）、拉曼光譜（Raman）和N₂等溫吸脫附曲線等對其形貌、成分和結構進行分析和表征。采用線性掃描伏安法、電化學阻抗譜和計時電位法探討了CoP/Co@NPC@rGO納米復合電催化劑對氫氣析出反應（HER）和氧氣析出反應（OER）的電催化活性和穩定性。結果表明，CoP/Co@NPC@rGO?350在1.0 mol·L^–1 KOH溶液中達到10 mA·cm^?2電流密度的析氫過電位僅127 mV；同時，在1.0 mol·L^–1 KOH溶液中顯示出優于貴金屬RuO₂的析氧性能，達到10 mA·cm^?2電流密度的過電位為276 mV，塔菲爾斜率僅為42 mV·dec^?1。這種高析氫和析氧電催化活性主要歸因于高度石墨化的N摻雜多孔碳與N摻雜石墨烯之間的協同效應。CoP/Co@NPC@rGO是電催化全解水電催化劑的候選材料，且為基于金屬有機骨架（MOFs）/氧化石墨烯復合材料的高效電催化劑的設計開辟了一條新的途徑。
- 氧化石墨烯 /
- 電催化 /
- 氫氣析出反應 /
- 氧氣析出反應 /
- ZIF-67
Abstract: The construction of the highly active transition-metal phosphide/carbon-based electrocatalyst from metal-organic frameworks (MOFs) precursors is considered as an efficient approach. In this work, ZIF-67/GO precursors were firstly obtained by the in situ controllable growth of ZIF-67 nanocrystals on both surfaces of GO sheets. Then, a highly efficient bifunctional electrocatalyst CoP/Co@NPC@rGO nanocomposite was derived by the thermal pyrolysis of ZIF-67/GO precursors under N₂ atmosphere and a subsequent phosphatization process. The structure and elemental composition of the ZIF-67/GO, Co@NPC@rGO, and CoP/Co@NPC@rGO nanocomposites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and N₂ ad-/desorption isotherms analysis. The Co@NPC@rGO?800 nanocomposite exhibits a high Brunauer-Emmett-Teller (BET) surface area of 186.27 m²·g^?1, indicating that both micropores and mesopores existed. Subsequently, the electrocatalytic properties of the CoP/Co@NPC@rGO nanocomposites for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) were investigated by electrochemical measurements. The results suggest that the obtained CoP/Co@NPC@rGO?350 nanocomposite only requires an overpotential of 127 mV to reach a current density of 10 mA·cm^?2 for HER in 1.0 mol·L^–1 KOH solution. For OER, CoP/Co@NPC@rGO?350 nanocomposite can reach a current density of 10 mA·cm^?2 at an overpotential of 276 mV, with a Tafel slope of 42 mV·dec^?1, in the same alkaline aqueous solution, which is superior to RuO₂. In addition, for both HER and OER, CoP/Co@NPC@rGO?350 nanocomposite also shows impressive strong durability in alkaline aqueous solution. The outstanding performance can be attributed to the synergistic effect of coupled highly graphitized N-doped porous carbon and N-doped graphene. The as-prepared CoP/Co@NPC@rGO?350 electrocatalyst is a promising candidate for overall water splitting in the alkaline solution. This development offers an attractive catalyst material based on MOF/GO composites. It is expected that the presented strategy can be extended to the fabrication of other composites electrode materials for more efficient water splitting.
- graphene oxide /
- electrocatalysis /
- hydrogen evolution reaction (HER) /
- oxygen evolution reaction (OER) /
- ZIF-67

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圖 1 ZIF-67/氧化石墨烯的掃描電子顯微鏡圖片（a）和X射線衍射譜圖（b）

Figure 1. SEM image (a) and XRD pattern of ZIF-67/GO

下載: 全尺寸圖片幻燈片

圖 2 Co@NPC@GO?800的表征。（a）掃描電子顯微鏡圖片；（b）透射電子顯微鏡圖片；（c）X射線衍射譜圖；（d）拉曼光譜；（e）氮氣等溫吸脫附曲線；（f）孔徑分布

Figure 2. Characterization of Co@NPC@GO?800: (a) SEM; (b) TEM; (c) XRD; (d) Raman spectrum; (e) N₂ ad-/desorption isotherms; (f) pore size distribution

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圖 3 CoP/Co@NPC@rGO?X的X射線衍射譜圖

Figure 3. XRD patterns of CoP/Co@NPC@rGO?X

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圖 4 CoP/Co@NPC@GO?350的結構表征。（a）掃描電子顯微鏡圖片；（b）透射電子顯微鏡圖片

Figure 4. Characterization of CoP/Co@NPC@rGO?350: (a) SEM image; (b) TEM image

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圖 5 CoP/Co@NPC@rGO?350的X射線光電子能譜圖。（a）全譜圖；（b）N 1s；（c）Co 2p；（d）P 2p

Figure 5. XPS spectrum of CoP/Co@NPC@rGO?350: (a) full spectrum; (b) N 1s; (c) Co 2p; (d) P 2p

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圖 6 Co@NPC@rGO?800、CoP/Co@NPC@rGO?X和RuO₂的析氧性能。（a）線性掃描伏安曲線；（b）塔菲爾斜率；（c）電化學阻抗；（d）計時電位曲線

Figure 6. Oxygen evolution performance of Co@NPC@rGO?800, CoP/Co@NPC@rGO?X, and RuO₂: (a) Lsv curves; (b) Tafel slope; (c) EIS; (d) chronoamperometry

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圖 7 Co@NPC@rGO?800、CoP/Co@NPC@rGO?X和Pt/C的析氫性能。（a）線性掃描伏安曲線；（b）塔菲爾斜率；（c）電化學阻抗譜；（d）計時電位曲線

Figure 7. Hydrogen evolution performance of Co@NPC@rGO?800, CoP/Co@NPC@rGO?X, and Pt/C: (a) Lsv curve; (b) Tafel slope; (c) EIS; (d) chronoamperometry

下載: 全尺寸圖片幻燈片

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參考文獻(32)

[1]	Lewis N S, Nocera D G. Powering the planet: chemical challenges in solar energy utilization. Proc Natl Acad Sci USA, 2006, 103(43): 15729 doi: 10.1073/pnas.0603395103
[2]	Bard A J, Fox M A. Artificial photosynthesis: solar splitting of water to hydrogen and oxygen. Acc Chem Res, 1995, 28(3): 141 doi: 10.1021/ar00051a007
[3]	Dou S, Li X Y, Tao L, et al. Cobalt nanoparticle-embedded carbon nanotube/porous carbon hybrid derived from MOF-encapsulated Co₃O₄ for oxygen electrocatalysis. Chem Commun, 2016, 52(62): 9727 doi: 10.1039/C6CC05244D
[4]	Zhang X, Liu S W, Zang Y P, et al. Co/Co₉S₈@ S, N-doped porous graphene sheets derived from S, N dual organic ligands assembled Co-MOFs as superior electrocatalysts for full water splitting in alkaline media. Nano Energy, 2016, 30: 93 doi: 10.1016/j.nanoen.2016.09.040
[5]	Zhang J, Wang T, Pohl D, et al. Interface engineering of MoS₂/Ni₃S₂ heterostructures for highly enhanced electrochemical overall-water-splitting activity. Angew Chem Int Ed, 2016, 55(23): 6702 doi: 10.1002/anie.201602237
[6]	Fang Y H, Liu Z P. Mechanism and tafel lines of electro-oxidation of water to oxygen on RuO₂ (110). J Am Chem Soc, 2010, 132(51): 18214 doi: 10.1021/ja1069272
[7]	Jiang J, Zhang A L, Li L L, et al. Nickel-cobalt layered double hydroxide nanosheets as high-performance electrocatalyst for oxygen evolution reaction. J Power Sources, 2015, 278: 445 doi: 10.1016/j.jpowsour.2014.12.085
[8]	Reier T, Pawolek Z, Cherevko S, et al. Molecular insight in structure and activity of highly efficient, low-Ir Ir-Ni oxide catalysts for electrochemical water splitting (OER). J Am Chem Soc, 2015, 137(40): 13031 doi: 10.1021/jacs.5b07788
[9]	Song F, Hu X L. Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis. Nat Commun, 2014, 5: 4477 doi: 10.1038/ncomms5477
[10]	Nong H N, Gan L, Willinger E, et al. IrO_x core-shell nanocatalysts for cost- and energy-efficient electrochemical water splitting. Chem Sci, 2014, 5(8): 2955 doi: 10.1039/C4SC01065E
[11]	Li X Z, Fang Y Y, Lin X Q, et al. MOF derived Co₃O₄ nanoparticles embedded in N-doped mesoporous carbon layer/MWCNT hybrids: extraordinary bi-functional electrocatalysts for OER and ORR. J Mater Chem A, 2015, 3(33): 17392 doi: 10.1039/C5TA03900B
[12]	Li L L, Tian T, Jiang J, et al. Hierarchically porous Co₃O₄ architectures with honeycomb-like structures for efficient oxygen generation from electrochemical water splitting. J Power Sources, 2015, 294: 103 doi: 10.1016/j.jpowsour.2015.06.056
[13]	Jiao L, Zhou Y X, Jiang H L. Metal-organic framework-based CoP/reduced graphene oxide: high-performance bifunctional electrocatalyst for overall water splitting. Chem Sci, 2016, 7(3): 1690 doi: 10.1039/C5SC04425A
[14]	Zhao Y, Nakamura R, Kamiya K, et al. Nitrogen-doped carbon nanomaterials as non-metal electrocatalysts for water oxidation. Nat Commun, 2013, 4: 2390 doi: 10.1038/ncomms3390
[15]	Louie M W, Bell A T. An investigation of thin-film Ni?Fe oxide catalysts for the electrochemical evolution of oxygen. J Am Chem Soc, 2013, 135(33): 12329 doi: 10.1021/ja405351s
[16]	Liang Y Y, Wang H L, Zhou J G, et al. Covalent hybrid of spinel manganese?cobalt oxide and graphene as advanced oxygen reduction electrocatalysts. J Am Chem Soc, 2012, 134(7): 3517 doi: 10.1021/ja210924t
[17]	Kim J K, Yang W, Salim J, et al. Li-water battery with oxygen dissolved in water as a cathode. J Electrochem Soc, 2014, 161(3): A285
[18]	Chou N H, Ross P N, Bell A T, et al. Comparison of cobalt-based nanoparticles as electrocatalysts for water oxidation. Chem Sus Chem, 2011, 4(11): 1566 doi: 10.1002/cssc.201100075
[19]	Lee S W, Carlton C, Risch M, et al. The nature of lithium battery materials under oxygen evolution reaction conditions. J Am Chem Soc, 2012, 134(41): 16959 doi: 10.1021/ja307814j
[20]	Bajdich M, García-Mota M, Vojvodic A, et al. Theoretical investigation of the activity of cobalt oxides for the electrochemical oxidation of water. J Am Chem Soc, 2013, 135(36): 13521 doi: 10.1021/ja405997s
[21]	Zhang J T, Zhao Z H, Xia Z H, et al. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nat Nanotechnol, 2015, 10: 444 doi: 10.1038/nnano.2015.48
[22]	Yang H B, Miao J W, Hung S F, et al. Identification of catalytic sites for oxygen reduction and oxygen evolution in N-doped graphene materials: development of highly efficient metal-free bifunctional electrocatalyst. Sci Adv, 2016, 2(4): e1501122 doi: 10.1126/sciadv.1501122
[23]	Miner E M, Dinc? M. Metal-organic frameworks: Evolved oxygen evolution catalysts. Nat Energy, 2016, 1(12): 16186 doi: 10.1038/nenergy.2016.186
[24]	Zhou H C, Long J R, Yaghi O M. Introduction to metal-organic frameworks. Chem Rev, 2012, 112(2): 673 doi: 10.1021/cr300014x
[25]	Zhou H C J, Kitagawa S. Metal-organic frameworks (MOFs). Chem Soc Rev, 2014, 43(16): 5415 doi: 10.1039/C4CS90059F
[26]	Dilpazir S, He H Y, Li Z H, et al. Cobalt single atoms immobilized N-doped carbon nanotubes for enhanced bifunctional catalysis toward oxygen reduction and oxygen evolution reactions. ACS Appl Energy Mater, 2018, 1(7): 3283 doi: 10.1021/acsaem.8b00490
[27]	Liu S W, Zhang H M, Zhao Q, et al. Metal-organic framework derived nitrogen-doped porous carbon@graphene sandwich-like structured composites as bifunctional electrocatalysts for oxygen reduction and evolution reactions. Carbon, 2016, 106: 74 doi: 10.1016/j.carbon.2016.05.021
[28]	Choi C H, Park S H, Woo S I. Binary and ternary doping of nitrogen, boron, and phosphorus into carbon for enhancing electrochemical oxygen reduction activity. ACS Nano, 2012, 6(8): 7084 doi: 10.1021/nn3021234
[29]	Hou Y, Wen Z H, Cui S M, et al. An advanced nitrogen-doped graphene/cobalt-embedded porous carbon polyhedron hybrid for efficient catalysis of oxygen reduction and water splitting. Adv Funct Mater, 2015, 25(6): 872 doi: 10.1002/adfm.201403657
[30]	Nethravathi C, Rajamathi M. Chemically modified graphene sheets produced by the solvothermal reduction of colloidal dispersions of graphite oxide. Carbon, 2008, 46(14): 1994 doi: 10.1016/j.carbon.2008.08.013
[31]	Stankovich S, Dikin D A, Piner R D, et al. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Carbon, 2007, 45(7): 1558 doi: 10.1016/j.carbon.2007.02.034
[32]	Zhu Y P, Liu Y P, Ren T Z, et al. Self-supported cobalt phosphide mesoporous nanorod arrays: a flexible and bifunctional electrode for highly active electrocatalytic water reduction and oxidation. Adv Funct Mater, 2015, 25(47): 7337 doi: 10.1002/adfm.201503666