Coralloid Co2P2O7 Nanocrystals Encapsulated by Thin Carbon Shells for Enhanced Electrochemical Water Oxidation

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Jiangsu Key Laboratory of Biofunctional Materials, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, P. R. China
Key Laboratory for Organic Electronics and Information Displays, Institute of Advanced Materials, Nanjing University of Posts & Telecommunications, Nanjing 210023, P. R. China
§ State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, P. R. China
*Phone: 86-25-85891051. Fax: +86-25-85891051. E-mail: [email protected] (M.H.).
*E-mail: [email protected] (J.B.).
Cite this: ACS Appl. Mater. Interfaces 2016, 8, 34, 22534–22544
Publication Date (Web):August 8, 2016
Copyright © 2016 American Chemical Society
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Core–shell nanohybrids containing cheap inorganic nanocrystals and nanocarbon shells are promising electrocatalysts for water splitting or other renewable energy options. Despite that great progress has been achieved, biomimetic synthesis of metal [email protected] core–shell nanohybrids remains a challenge, and their use for electrocatalytic oxygen evolution reaction (OER) has not been explored. In this paper, novel nanohybrids composed of coralloid Co2P2O7 nanocrystal cores and thin porous nanocarbon shells are synthesized by combination of the structural merits of supramolecular polymer gels and a controllable thermal conversion technique, i.e., temperature programmable annealing of presynthesized supramolecular polymer gels that contain cobalt salt and phytic acid under a proper gas atmosphere. Electrocatalytic tests in alkaline solution show that such nanohybrids exhibit greatly enhanced electrocatalytic OER performance compared with that of Co2P2O7 nanostructure. At a current density of 10 mA cm–2, their overpotential is 0.397 V, which is much lower than that of Co2P2O7 nanostructures, amorphous Co-Pi nanomaterials, Co(PO3)2 nanosheets, Pt/C, and some reported OER catalysts, and close to that of commercial IrO2. Most importantly, both of their current density at the overpotential over 0.40 V and durability are superior to those of IrO2 catalyst. As revealed by a series of spectroscopic and electrochemical analyses, their enhanced electrocatalytic performance results from the presence of thin porous nanocarbon shells, which not only improve interfacial electron penetration or transfer dynamics but also vary the coordination environment and increase the number of active 5-coordinated Co2+ sites in Co2P2O7 cores.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.6b07209.

  • Other typical HRTEM images and mapping figures as well as N2 adsorption–desorption test data of CL-Co2P2O7@C nanohybrids (Figures S1 and S2), characterization of the samples obtained by annealing polymer gels at 400–900 °C in Ar and air atmospheres (Figures S3–S8), characterization of Co2P2O7 nanostructures (Figure S9), and additional electrochemical and spectroscopic data for CL-Co2P2O7@C nanohybrids (Figures S10–S12) (PDF)

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  1. Lei Chen, Jin-Tao Ren, Zhong-Yong Yuan. Insight into the Active Contribution of N-Coordinated Cobalt Phosphate Nanocrystals Coupled with Carbon Nanotubes for Oxygen Electrochemistry. ACS Sustainable Chemistry & Engineering 2021, 9 (4) , 1856-1866.
  2. Yu Bai, Long−Cheng Zhang, Qiulin Li, Yuanke Wu, Youpeng Wang, Maowen Xu, Shu−Juan Bao. Self-Supported CdP2–CDs–CoP for High-Performance OER Catalysts. ACS Sustainable Chemistry & Engineering 2021, 9 (3) , 1297-1303.
  3. Jiachen Li, Qingwen Zhou, Chenglin Zhong, Shengwen Li, Zihan Shen, Jun Pu, Jinyun Liu, Yongning Zhou, Huigang Zhang, Haixia Ma. (Co/Fe)4O4 Cubane-Containing Nanorings Fabricated by Phosphorylating Cobalt Ferrite for Highly Efficient Oxygen Evolution Reaction. ACS Catalysis 2019, 9 (5) , 3878-3887.
  4. Wen Zhou, Xue-Feng Lu, Jun-Jia Chen, Tao Zhou, Pei-Qin Liao, Mingmei Wu, Gao-Ren Li. Hierarchical Porous Prism Arrays Composed of Hybrid Ni–NiO–Carbon as Highly Efficient Electrocatalysts for Overall Water Splitting. ACS Applied Materials & Interfaces 2018, 10 (45) , 38906-38914.
  5. Yuxuan Liu, Yu Bai, Yu Han, Zhou Yu, Shimin Zhang, Guohua Wang, Junhua Wei, Qibing Wu, and Kening Sun . Self-Supported Hierarchical FeCoNi-LTH/NiCo2O4/CC Electrodes with Enhanced Bifunctional Performance for Efficient Overall Water Splitting. ACS Applied Materials & Interfaces 2017, 9 (42) , 36917-36926.
  6. Tianhua Zhou, Yonghua Du, Danping Wang, Shengming Yin, Wenguang Tu, Zhong Chen, Armando Borgna, and Rong Xu . Phosphonate-Based Metal–Organic Framework Derived Co–P–C Hybrid as an Efficient Electrocatalyst for Oxygen Evolution Reaction. ACS Catalysis 2017, 7 (9) , 6000-6007.
  7. Soumen Dutta, Chaiti Ray, Yuichi Negishi, and Tarasankar Pal . Facile Synthesis of Unique Hexagonal Nanoplates of Zn/Co Hydroxy Sulfate for Efficient Electrocatalytic Oxygen Evolution Reaction. ACS Applied Materials & Interfaces 2017, 9 (9) , 8134-8141.
  8. Lan Huang, Jing Jiang, and Lunhong Ai . Interlayer Expansion of Layered Cobalt Hydroxide Nanobelts to Highly Improve Oxygen Evolution Electrocatalysis. ACS Applied Materials & Interfaces 2017, 9 (8) , 7059-7067.
  9. Zhixiong Cai, Wei Xu, Feiming Li, Qiuhong Yao, and Xi Chen . Electropolymerization Fabrication of Co Phosphate Nanoparticles Encapsulated in N,P-Codoped Mesoporous Carbon Networks as a 3D Integrated Electrode for Full Water Splitting. ACS Sustainable Chemistry & Engineering 2017, 5 (1) , 571-579.
  10. Li-Jiao Gao, Chen-Chen Weng, Yan-Su Wang, Xian-Wei Lv, Jin-Tao Ren, Zhong-Yong Yuan. Defect-rich cobalt pyrophosphate hybrids decorated Cd0.5Zn0.5S for efficient photocatalytic hydrogen evolution: Defect and interface engineering. Journal of Colloid and Interface Science 2022, 606 , 544-555.
  11. Xiying Feng, Yali Xiao, Hai‐Hua Huang, Qiushi Wang, Jinyi Wu, Zhuofeng Ke, Yexiang Tong, Jianyong Zhang. Phytic Acid‐Based FeCo Bimetallic Metal‐Organic Gels for Electrocatalytic Oxygen Evolution Reaction. Chemistry – An Asian Journal 2021, 16 (20) , 3213-3220.
  12. Abdulmajid A. Mirghni, Kabir O. Oyedotun, Badr A. Mahmoud, Oladepo Fasakin, Delvina J. Tarimo, Ncholu Manyala. A study of Co‐Mn phosphate supported with graphene foam as promising electrode materials for future electrochemical capacitors. International Journal of Energy Research 2021, 334
  13. Ce Cui, Xiaoxu Lai, Ronghui Guo, Erhui Ren, Wenfeng Qin, Li Liu, Mi Zhou, Hongyan Xiao. Waste paper-based carbon aerogel supported ZIF-67 derived hollow NiCo phosphate nanocages for electrocatalytic oxygen evolution reaction. Electrochimica Acta 2021, 393 , 139076.
  14. . Features of the synthesis of solid solutions of divalent metal phosphates with a newberyite structure. Functional Materials 2021,,
  15. Chunfeng Zhu, Zhongyuan Yu, Tong Lin, Jintang Li, Xuetao Luo. Structural design of cobalt phosphate on nickel foam for electrocatalytic oxygen evolution. Nanotechnology 2021, 32 (30) , 305702.
  16. Abhisek Padhy, Aneeya K. Samantara, J. N. Behera. Cobalt pyrophosphate (Co 2 P 2 O 7 ) derived from an open-framework cobalt phosphite: a durable electroactive material for electrochemical energy conversion and storage application. Sustainable Energy & Fuels 2021, 5 (14) , 3729-3736.
  17. Lei Wang, Jiayao Fan, Ying Liu, Mingyu Chen, Yue Lin, Hengchang Bi, Bingxue Liu, Naien Shi, Dongdong Xu, Jianchun Bao, Min Han. Phase‐Modulation of Iron/Nickel Phosphides Nanocrystals “Armored” with Porous P‐Doped Carbon and Anchored on P‐Doped Graphene Nanohybrids for Enhanced Overall Water Splitting. Advanced Functional Materials 2021, 31 (30) , 2010912.
  18. Yibo Zhang, Yuying Zheng, Hongbo Geng, Yang Yang, Minghui Ye, Yufei Zhang, Cheng Chao Li. The Efficient K Ion Storage of M 2 P 2 O 7 /C (M=Fe, Co, Ni) Anode Derived from Organic‐Inorganic Phosphate Precursors. Chemistry – A European Journal 2021, 27 (35) , 9031-9037.
  19. Yu Cheng, Haoran Guo, Pengfei Yuan, Xinpan Li, Lirong Zheng, Rui Song. Self-supported bifunctional electrocatalysts with Ni nanoparticles encapsulated in vertical N-doped carbon nanotube for efficient overall water splitting. Chemical Engineering Journal 2021, 413 , 127531.
  20. Pawan Rekha, Sarika Yadav, Lovjeet Singh. A review on cobalt phosphate-based materials as emerging catalysts for water splitting. Ceramics International 2021, 47 (12) , 16385-16401.
  21. Yue Han, Chen Qian, Huayu Wu, Xing Chen, Xue Wu, Wei He, Hui Yan, Guisheng Li, Guowang Diao, Ming Chen. Two flowers per seed: Derivatives of [email protected]/GO with enhanced catalytic performance of overall water splitting. Journal of Energy Chemistry 2021, 54 , 761-769.
  22. Bing Li, Huan Pang, Huaiguo Xue. Fe-based phosphate nanostructures for supercapacitors. Chinese Chemical Letters 2021, 32 (2) , 885-889.
  23. Likkhasit Wannasen, Ekaphan Swatsitang, Supree Pinitsoontorn. Flexible supercapacitors based on mesoporous nanocrystalline cobalt ammonium phosphates and bacterial cellulose composite electrode. International Journal of Energy Research 2021, 45 (2) , 3075-3088.
  24. . Influence of crystal hydrate water on the process and products of heat treatment of magnesium-manganese(II) dihydrogen phosphates. Functional Materials 2020,,
  25. Pragati A. Shinde, Muhammad Farooq Khan, Malik A. Rehman, Euigeol Jung, Quang N. Pham, Yoonjin Won, Seong Chan Jun. Nitrogen-doped carbon integrated nickel–cobalt metal phosphide marigold flowers as a high capacity electrode for hybrid supercapacitors. CrystEngComm 2020, 22 (38) , 6360-6370.
  26. Hee Jo Song, Hyunseok Yoon, Bobae Ju, Dong‐Wan Kim. Sodium‐nickel pyrophosphate as a novel oxygen evolution electrocatalyst in alkaline medium. Journal of the American Ceramic Society 2020, 103 (9) , 4748-4753.
  27. Jiaxin Zhang, Peng Liu, Ranran Bu, Hao Zhang, Qi Zhang, Kang Liu, Yanru Liu, Zhenyu Xiao, Lei Wang. In situ fabrication of a rose-shaped Co 2 P 2 O 7 /C nanohybrid via a coordination polymer template for supercapacitor application. New Journal of Chemistry 2020, 44 (29) , 12514-12521.
  28. Lian-Hua Xu, Sheng-Li Zhang, Shi-Ying Guo, Xue-Ji Zhang, Serge Cosnier, Robert S. Marks, Wen-Ju Wang, Hai-Bo Zeng, Dan Shan. ATMP derived cobalt-metaphosphate complex as highly active catalyst for oxygen reduction reaction. Journal of Catalysis 2020, 387 , 129-137.
  29. Lian‐Hua Xu, Kun‐Kun Lu, Junji Li, Dan Shan. Co 2+ ‐coordinated NH 2 ‐carbon Quantum Dots Hybrid Precursor for the Rational Synthesis of Co−CoO X /Co−N−C ORR Catalyst. ChemCatChem 2020, 12 (11) , 3082-3087.
  30. Feng-Feng Li, Zheng-Hua He, Jian-Fei Gao, Ling-Bin Kong. The investigations of pyrophosphate CoNiP2O7 produced by hydrothermal process: a high-performance anode electrode material for Li-ion hybrid capacitor. Ionics 2020, 26 (6) , 2989-3001.
  31. Qi Qiu, Tao Wang, Linhai Jing, Kun Huang, Dabin Qin. Tetra-carboxylic acid based metal-organic framework as a high-performance bifunctional electrocatalyst for HER and OER. International Journal of Hydrogen Energy 2020, 45 (19) , 11077-11088.
  32. Bing Li, Rongmei Zhu, Huaiguo Xue, Qiang Xu, Huan Pang. Ultrathin cobalt pyrophosphate nanosheets with different thicknesses for Zn-air batteries. Journal of Colloid and Interface Science 2020, 563 , 328-335.
  33. Mahmoud Nasrollahzadeh, Zahra Nezafat, Nayyereh Sadat Soheili Bidgoli, Nasrin Shafiei. Recent progresses in polymer supported cobalt complexes/nanoparticles for sustainable and selective oxidation reactions. Molecular Catalysis 2020, 484 , 110775.
  34. Ni Luh Wulan Septiani, Yusuf Valentino Kaneti, Kresna Bondan Fathoni, Yanna Guo, Yusuke Ide, Brian Yuliarto, Xuchuan Jiang, Nugraha, Hermawan Kresno Dipojono, Dmitri Golberg, Yusuke Yamauchi. Tailorable nanoarchitecturing of bimetallic nickel–cobalt hydrogen phosphate via the self-weaving of nanotubes for efficient oxygen evolution. Journal of Materials Chemistry A 2020, 8 (6) , 3035-3047.
  35. Lina Jia, Chen Li, Yaru Zhao, Bitao Liu, Shixiu Cao, Dedan Mou, Tao Han, Gen Chen, Yue Lin. Interfacial engineering of Mo 2 C–Mo 3 C 2 heteronanowires for high performance hydrogen evolution reactions. Nanoscale 2019, 11 (48) , 23318-23329.
  36. Peng Guo, Zhaojie Wang, Hongyu Chen, Shaohui Ge, Chen Chen, Haowei Wang, Jinbao Zhang, Minglei Hua, Shuxian Wei, Xiaoqing Lu. In Situ Growth of MOF-Derived NaCoPO 4 @Carbon for Asymmetric Supercapacitive and Water Oxidation Electrocatalytic Performance. Nano 2019, 14 (12) , 1950148.
  37. Yueran Ni, Bowen He, Siyuan Luo, Xiaoyong Wu, Xuezhen Feng, Yi Luo, Jia Lin, Junliang Sun, Ke Fan, Yongfei Ji, Gaoke Zhang, Hong Chen. Microporous core-shell Co11(HPO3)8(OH)6/Co11(PO3)8O6 nanowires for highly efficient electrocatalytic oxygen evolution reaction. Applied Catalysis B: Environmental 2019, 259 , 118091.
  38. Eunji Pyo, Keunyoung Lee, Myeong Je Jang, In‐Hwan Ko, Chung Soo Kim, Sung Mook Choi, Seonhong Lee, Ki‐Young Kwon. Cobalt Incorporated Hydroxyapatite Catalyst for Water Oxidation. ChemCatChem 2019, 11 (22) , 5425-5429.
  39. Lian-Hua Xu, Hai-Bo Zeng, Xue-Ji Zhang, Serge Cosnier, Robert S. Marks, Dan Shan. Highly active [email protected] (M = Co and Zn) for bifunctional electrocatalysts for ORR and HER. Journal of Catalysis 2019, 377 , 20-27.
  40. Subramani Surendran, Arumugam Sivanantham, Sangaraju Shanmugam, Uk Sim, Ramakrishnan Kalai Selvan. Ni 2 P 2 O 7 microsheets as efficient Bi-functional electrocatalysts for water splitting application. Sustainable Energy & Fuels 2019, 3 (9) , 2435-2446.
  41. Nilesh R. Chodankar, Deepak P. Dubal, Su‐Hyeon Ji, Do‐Heyoung Kim. Self‐Assembled Nickel Pyrophosphate‐Decorated Amorphous Bimetal Hydroxides 2D‐on‐2D Nanostructure for High‐Energy Solid‐State Asymmetric Supercapacitor. Small 2019, 15 (19) , 1901145.
  42. Kaidi Li, Mingjing Guo, Ya Yan, Ke Zhan, Junhe Yang, Bin Zhao, Jianqiang Li. Ultrasmall Co 2 P 2 O 7 nanocrystals anchored on nitrogen-doped graphene as efficient electrocatalysts for the oxygen reduction reaction. New Journal of Chemistry 2019, 43 (17) , 6492-6499.
  43. Likkhasit Wannasen, Narong Chanlek, Santi Maensiri, Ekaphan Swatsitang. Composition effect of Co/Ni on the morphology and electrochemical properties of NH4Co1−xNixPO4·H2O nanocrystallites prepared by a facile hydrothermal method. Journal of Materials Science: Materials in Electronics 2019, 30 (8) , 7794-7807.
  44. N.M. Antraptseva, . Low-temperature synthesis of condensed zinc and cobalt (II) phosphate solid solution with the given anion structure. Functional materials 2019, 26 (1) , 58-64.
  45. Jing Yang, Donghua Guo, Shulin Zhao, Yue Lin, Rui Yang, Dongdong Xu, Naien Shi, Xiaoshu Zhang, Lingzhi Lu, Ya-Qian Lan, Jianchun Bao, Min Han. Cobalt Phosphides Nanocrystals Encapsulated by P-Doped Carbon and Married with P-Doped Graphene for Overall Water Splitting. Small 2019, 15 (10) , 1804546.
  46. Haoran Yu, Fuqiang Chu, Xiao Zhou, Junling Ji, Yang Liu, Yunfei Bu, Yong Kong, Yongxin Tao, Yongxin Li, Yong Qin. A perovskite oxide with a tunable pore-size derived from a general salt-template strategy as a highly efficient electrocatalyst for the oxygen evolution reaction. Chemical Communications 2019, 55 (17) , 2445-2448.
  47. Yuanyuan Zhang, Haohao Sun, Yunfeng Qiu, Enhao Zhang, Tiange Ma, Guang-gang Gao, Changyan Cao, Zhuo Ma, PingAn Hu. Bifunctional hydrogen evolution and oxygen evolution catalysis using CoP-embedded N-doped nanoporous carbon synthesized via TEOS-assisted method. Energy 2018, 165 , 537-548.
  48. Abdulmajid A. Mirghni, Damilola Momodu, Kabir O. Oyedotun, Julien K. Dangbegnon, Ncholu Manyala. Electrochemical analysis of Co3(PO4)2·4H2O/graphene foam composite for enhanced capacity and long cycle life hybrid asymmetric capacitors. Electrochimica Acta 2018, 283 , 374-384.
  49. Hongfang Du, Wei Ai, Zhi Liang Zhao, Yu Chen, Xin Xu, Chenji Zou, Lishu Wu, Lan Su, Kaikai Nan, Ting Yu, Chang Ming Li. Engineering Morphologies of Cobalt Pyrophosphates Nanostructures toward Greatly Enhanced Electrocatalytic Performance of Oxygen Evolution Reaction. Small 2018, 14 (31) , 1801068.
  50. Piaopiao Sun, Zhaohui Li, Lin Zhang, Cui Dong, Zhongjun Li, Hongchang Yao, Jianshe Wang, Guangheng Li. Synthesis of cobalt-nickel pyrophosphates/N-doped graphene composites with high rate capability for asymmetric supercapacitor. Journal of Alloys and Compounds 2018, 750 , 607-616.
  51. Shulin Zhao, Meng Li, Min Han, Dongdong Xu, Jing Yang, Yue Lin, Nai-En Shi, Yanan Lu, Rui Yang, Bitao Liu, Zhihui Dai, Jianchun Bao. Defect-Rich Ni 3 FeN Nanocrystals Anchored on N-Doped Graphene for Enhanced Electrocatalytic Oxygen Evolution. Advanced Functional Materials 2018, 28 (18) , 1706018.
  52. Kun Li, Tie-zhen Ren, Zhong-Yong Yuan, Teresa J. Bandosz. Electrodeposited P Co nanoparticles in deep eutectic solvents and their performance in water splitting. International Journal of Hydrogen Energy 2018, 43 (22) , 10448-10457.
  53. W.P. Wang, H. Pang, M.L. Jin, X. Shen, Y. Yao, Y.G. Wang, Y.C. Li, X.D. Li, C.Q. Jin, R.C. Yu. Studies on the structural stability of Co2P2O7 under pressure. Journal of Physics and Chemistry of Solids 2018, 116 , 113-117.
  54. Ali A. Ensafi, S.A. Sayed Afiuni, B. Rezaei. NiO nanoparticles decorated at Nile blue-modified reduced graphene oxide, new powerful electrocatalysts for water splitting. Journal of Electroanalytical Chemistry 2018, 816 , 160-170.
  55. Weikang Zhu, Rui Chen, Yan Yin, Junfeng Zhang, Qingfa Wang. Highly (110)-Oriented Co 1-x S Nanosheet Arrays on Carbon Fiber Paper as High-Performance and Binder-Free Electrodes for Oxygen Production. ChemistrySelect 2018, 3 (14) , 3970-3974.
  56. N.M. Antraptseva, . Peculiarities of thermal solid-phase transformations of hydrogenphosphates Co(II)-Mn(II). Functional materials 2018, 25 (1) , 151-157.
  57. Jun Li, Guiyu Liu, Beibei Liu, Ziyan Min, Dong Qian, Jianbo Jiang, Junhua Li. Fe-doped CoSe2 nanoparticles encapsulated in N-doped bamboo-like carbon nanotubes as an efficient electrocatalyst for oxygen evolution reaction. Electrochimica Acta 2018, 265 , 577-585.
  58. Yuanyuan Yang, Xiongyi Liang, Feng Li, Shuwen Li, Xinzhe Li, Siu-Pang Ng, Chi-Man Lawrence Wu, Rong Li. Encapsulating Co 2 [email protected] Core-Shell Nanoparticles in a Porous Carbon Sandwich as Dual-Doped Electrocatalyst for Hydrogen Evolution. ChemSusChem 2018, 11 (2) , 376-388.
  59. Pingjing Feng, Xian Cheng, Jintang Li, Xuetao Luo. Calcined Nickel-Cobalt Mixed Metal Phosphonate with Efficient Electrocatalytic Activity for Oxygen Evolution Reaction. ChemistrySelect 2018, 3 (2) , 760-764.
  60. Ziyauddin Khan, Baskar Senthilkumar, Seongdong Lim, Ravi Shanker, Youngsik Kim, Hyunhyub Ko. Redox-Additive-Enhanced High Capacitance Supercapacitors Based on Co 2 P 2 O 7 Nanosheets. Advanced Materials Interfaces 2017, 4 (12) , 1700059.
  61. Abdulmajid Abdallah Mirghni, Moshawe Jack Madito, Tshifhiwa Moureen Masikhwa, Kabir O. Oyedotun, Abdulhakeem Bello, Ncholu Manyala. Hydrothermal synthesis of manganese phosphate/graphene foam composite for electrochemical supercapacitor applications. Journal of Colloid and Interface Science 2017, 494 , 325-337.
  62. N.M. Antraptseva, . Thermal properties of solid solution of manganese (II) -cobalt (II) diphosphate. Functional Materials 2016, 23 (4) , 657-664.