SCIENCE CHINA Materials, Volume 61, Issue 10: 1305-1313(2018) https://doi.org/10.1007/s40843-018-9269-x

Constrained-volume assembly of organometal confined in polymer to fabricate multi-heteroatom doped carbon for oxygen reduction reaction

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  • ReceivedMar 5, 2018
  • AcceptedMar 31, 2018
  • PublishedApr 28, 2018


The design and preparation of non-precious metal and carbon-based nanocomposites are critical to the development of efficient catalysts for technologies ranging from water splitting to fuel cell. Here, we present a constrained-volume self-assembly process for the one-step continuous precipitation-induced formation of soft colloidal particles, in which hydrophobic organoferrous compound, (Ph3P)2Fe(CO)3, is encapsulated within poly(styrene-co-acrylonitrile) nanoparticles (NPs). The protective and confining polymer matrix ensures uniform carbonization and dispersion of (Ph3P)2Fe(CO)3 within a carbon matrix after a pyrolysis process. The obtained carbon NPs are successfully co-doped with Fe, P and N with a relatively high surface area of ~380 m2 g−1. The Fe-P-N-doped carbon catalyst exhibits high catalytic performance and stability toward oxygen reduction reaction in both alkaline and acidic electrolytes via a favorable four-electron pathway. Meanwhile, the catalytic capability of Fe-P-N-doped carbon can be tailored by the tunable nanostructures.

Funded by

the National Natural Science Foundation of China(21774095)

Shanghai Municipal Natural Science Foundation(17ZR1432200)

the Fundamental Research Funds for the Central Universities(0400219376)

and the start-up funding from Tongji University and the Young Thousand Talented Program.


This work was supported by the National Natural Science Foundation of China (21774095), Shanghai Municipal Natural Science Foundation (17ZR1432200), the Fundamental Research Funds for the Central Universities (0400219376), and the start-up funding from Tongji University and the Young Thousand Talented Program.

Interest statement

The authors declare no conflict of interest.

Contributions statement

Liu R proposed the research and guided the whole project; Li C performed the experiments and wrote the manuscript; Zhao J and Priestley RD helped analyze the data. All authors contributed to the general discussion and reviewed the manuscript.

Author information

Congling Li received his PhD degree in chemistry from East China Normal University in 2017. In the same year, she carried out her postdoctoral research at Tongji University.

Rui Liu received his PhD degree in chemistry from the University of California, Riverside in 2010. He carried out his postdoctoral research at Oak Ridge National Laboratory from 2011 to 2012. In 2012–2015, he was a postdoctoral associate at Princeton University. In 2015, he was selected in Young Thousand Talented programe and joined Tongji University as a professor. His research interests include polymer self-assembly, carbon nanoparticles and energy applications.


Supplementary information

Experimental details are available in the online version of the paper.


[1] Liu M, Zhang R, Chen W. Graphene-supported nanoelectrocatalysts for fuel cells: synthesis, properties, and applications. Chem Rev, 2014, 114: 5117-5160 CrossRef PubMed Google Scholar

[2] Jiang C, Ma J, Corre G, et al. Challenges in developing direct carbon fuel cells. Chem Soc Rev, 2017, 46: 2889-2912 CrossRef PubMed Google Scholar

[3] Zeng X, Shui J, Liu X, et al. Single-atom to single-atom grafting of Pt1 onto Fe–N4 center: Pt1@Fe–N–C multifunctional electrocatalyst with significantly enhanced properties. Adv Energy Mater, 2018, 8: 1701345 CrossRef Google Scholar

[4] Lu Y, Thia L, Fisher A, et al. Octahedral PtNi nanoparticles with controlled surface structure and composition for oxygen reduction reaction. Sci China Mater, 2017, 60: 1109-1120 CrossRef Google Scholar

[5] Shang C, Yang M, Wang Z, et al. Encapsulated MnO in N-doping carbon nanofibers as efficient ORR electrocatalysts. Sci China Mater, 2017, 60: 937-946 CrossRef Google Scholar

[6] Wu S, Zhu Y, Huo Y, et al. Bimetallic organic frameworks derived CuNi/carbon nanocomposites as efficient electrocatalysts for oxygen reduction reaction. Sci China Mater, 2017, 60: 654-663 CrossRef Google Scholar

[7] Kuang M, Wang Q, Han P, et al. Cu, Co-embedded N-enriched mesoporous carbon for efficient oxygen reduction and hydrogen evolution reactions. Adv Energy Mater, 2017, 7: 1700193 CrossRef Google Scholar

[8] Zhang G, Jin X, Li H, et al. N-doped crumpled graphene: bottom-up synthesis and its superior oxygen reduction performance. Sci China Mater, 2016, 59: 337-347 CrossRef Google Scholar

[9] Yan D, Guo L, Xie C, et al. N, P-dual doped carbon with trace Co and rich edge sites as highly efficient electrocatalyst for oxygen reduction reaction. Sci China Mater, 2018, 61: 679-685 CrossRef Google Scholar

[10] Zhu L, Liu XQ, Jiang HL, et al. Metal–organic frameworks for heterogeneous basic catalysis. Chem Rev, 2017, 117: 8129-8176 CrossRef PubMed Google Scholar

[11] Lu S, Zhuang Z. Electrocatalysts for hydrogen oxidation and evolution reactions. Sci China Mater, 2016, 59: 217-238 CrossRef Google Scholar

[12] Ding W, Wei Z, Chen S, et al. Space-confinement-induced synthesis of pyridinic- and pyrrolic-nitrogen-doped graphene for the catalysis of oxygen reduction. Angew Chem, 2013, 125: 11971-11975 CrossRef Google Scholar

[13] Wang X, Lee JS, Zhu Q, et al. Ammonia-treated ordered mesoporous carbons as catalytic materials for oxygen reduction reaction. Chem Mater, 2010, 22: 2178-2180 CrossRef Google Scholar

[14] Chen YZ, Wang C, Wu ZY, et al. From bimetallic metal-organic framework to porous carbon: high surface area and multicomponent active dopants for excellent electrocatalysis. Adv Mater, 2015, 27: 5010-5016 CrossRef PubMed Google Scholar

[15] Sun M, Zhang G, Liu H, et al. α- and γ-Fe2O3 nanoparticle/nitrogen doped carbon nanotube catalysts for high-performance oxygen reduction reaction. Sci China Mater, 2015, 58: 683-692 CrossRef Google Scholar

[16] Zhou R, Qiao SZ. An Fe/N co-doped graphitic carbon bulb for high-performance oxygen reduction reaction. Chem Commun, 2015, 51: 7516-7519 CrossRef PubMed Google Scholar

[17] Fang X, Zang J, Wang X, et al. A multiple coating route to hollow carbon spheres with foam-like shells and their applications in supercapacitor and confined catalysis. J Mater Chem A, 2014, 2: 6191-6197 CrossRef Google Scholar

[18] Wang Y, Kong B, Zhao D, et al. Strategies for developing transition metal phosphides as heterogeneous electrocatalysts for water splitting. Nano Today, 2017, 15: 26-55 CrossRef Google Scholar

[19] Wangxi Z, Jie L, Gang W. Evolution of structure and properties of PAN precursors during their conversion to carbon fibers. Carbon, 2003, 41: 2805-2812 CrossRef Google Scholar

[20] Nataraj SK, Yang KS, Aminabhavi TM. Polyacrylonitrile-based nanofibers—A state-of-the-art review. Prog Polymer Sci, 2012, 37: 487-513 CrossRef Google Scholar

[21] Kowalewski T, Tsarevsky NV, Matyjaszewski K. Nanostructured carbon arrays from block copolymers of polyacrylonitrile. J Am Chem Soc, 2002, 124: 10632-10633 CrossRef Google Scholar

[22] Zhong M, Kim EK, McGann JP, et al. Electrochemically active nitrogen-enriched nanocarbons with well-defined morphology synthesized by pyrolysis of self-assembled block copolymer. J Am Chem Soc, 2012, 134: 14846-14857 CrossRef PubMed Google Scholar

[23] Leiston-Belanger JM, Penelle J, Russell TP. Synthesis and microphase separation of poly(styrene-b-acrylonitrile) prepared by sequential anionic and ATRP techniques. Macromolecules, 2006, 39: 1766-1770 CrossRef ADS Google Scholar

[24] Lee K, Zhang J, Wang H, et al. Progress in the synthesis of carbon nanotube- and nanofiber-supported Pt electrocatalysts for PEM fuel cell catalysis. J Appl Electrochem, 2006, 36: 507-522 CrossRef Google Scholar

[25] Huang J, Wang D, Hou H, et al. Electrospun palladium nanoparticle-loaded carbon nanofibers and their electrocatalytic activities towards hydrogen peroxide and NADH. Adv Funct Mater, 2008, 18: 441-448 CrossRef Google Scholar

[26] Brunet JJ, Kindela FB, Neibecker D. Expedient synthesis of (Ph3P)2Fe(CO)3. J Organomet Chem, 1989, 368: 209-212 CrossRef Google Scholar

[27] Johnson BK, Prud'homme RK. Chemical processing and micromixing in confined impinging jets. AIChE J, 2003, 49: 2264-2282 CrossRef Google Scholar

[28] Nikoubashman A, Lee VE, Sosa C, et al. Directed assembly of soft colloids through rapid solvent exchange. ACS Nano, 2016, 10: 1425-1433 CrossRef Google Scholar

[29] He Y, Wang B, Hu X, et al. One-step constrained-volume synthesis of silver decorated polymer colloids with antimicrobial and sensing properties. Colloid Polym Sci, 2017, 295: 521-527 CrossRef Google Scholar

[30] D'Addio SM, Prud'homme RK. Controlling drug nanoparticle formation by rapid precipitation. Adv Drug Deliver Rev, 2011, 63: 417-426 CrossRef PubMed Google Scholar

[31] Saad WS, Prud’homme RK. Principles of nanoparticle formation by flash nanoprecipitation. Nano Today, 2016, 11: 212-227 CrossRef Google Scholar

[32] Hayward RC, Pochan DJ. Tailored assemblies of block copolymers in solution: it is all about the process. Macromolecules, 2010, 43: 3577-3584 CrossRef ADS Google Scholar

[33] Kumar V, Adamson DH, Prud'homme RK. Fluorescent polymeric nanoparticles: aggregation and phase behavior of pyrene and amphotericin B molecules in nanoparticle cores. Small, 2010, 6: 2907-2914 CrossRef PubMed Google Scholar

[34] Gindy ME, Panagiotopoulos AZ, Prud'homme RK. Composite block copolymer stabilized nanoparticles: simultaneous encapsulation of organic actives and inorganic nanostructures. Langmuir, 2008, 24: 83-90 CrossRef PubMed Google Scholar

[35] Johnson BK, Prud'homme RK. Flash nanoprecipitation of organic actives and block copolymers using a confined impinging jets mixer. Aust J Chem, 2003, 56: 1021-1024 CrossRef Google Scholar

[36] Akbulut M, Ginart P, Gindy ME, et al. Generic method of preparing multifunctional fluorescent nanoparticles using flash nanoprecipitation. Adv Funct Mater, 2009, 19: 718-725 CrossRef Google Scholar

[37] Zhang C, Pansare VJ, Prud'Homme RK, et al. Flash nanoprecipitation of polystyrene nanoparticles. Soft Matter, 2012, 8: 86-93 CrossRef ADS Google Scholar

[38] Sosa C, Liu R, Tang C, et al. Soft multifaced and patchy colloids by constrained volume self-assembly. Macromolecules, 2016, 49: 3580-3585 CrossRef ADS Google Scholar

[39] Liu R, Sosa C, Yeh YW, et al. A one-step and scalable production route to metal nanocatalyst supported polymer nanospheres via flash nanoprecipitation. J Mater Chem A, 2014, 2: 17286-17290 CrossRef Google Scholar

[40] Johnson BK, Prud'homme RK. Mechanism for rapid self-assembly of block copolymer nanoparticles. Phys Rev Lett, 2003, 91: 118302 CrossRef PubMed ADS Google Scholar

[41] Han J, Zhu Z, Qian H, et al. A simple confined impingement jets mixer for flash nanoprecipitation. J Pharmaceutical Sci, 2012, 101: 4018-4023 CrossRef PubMed Google Scholar

[42] Wang Y, Chen X, Lin Q, et al. Nanoporous carbon derived from a functionalized metal–organic framework as a highly efficient oxygen reduction electrocatalyst. Nanoscale, 2017, 9: 862-868 CrossRef PubMed Google Scholar

[43] Zhao L, Sui XL, Li JZ, et al. Supramolecular assembly promoted synthesis of three-dimensional nitrogen doped graphene frameworks as efficient electrocatalyst for oxygen reduction reaction and methanol electrooxidation. Appl Catal B-Environ, 2018, 231: 224-233 CrossRef Google Scholar

[44] Zhou X, Bai Z, Wu M, et al. 3-Dimensional porous N-doped graphene foam as a non-precious catalyst for the oxygen reduction reaction. J Mater Chem A, 2015, 3: 3343-3350 CrossRef Google Scholar

[45] Zhao P, Hua X, Xu W, et al. Metal–organic framework-derived hybrid of Fe3C nanorod-encapsulated, N-doped CNTs on porous carbon sheets for highly efficient oxygen reduction and water oxidation. Catal Sci Technol, 2016, 6: 6365-6371 CrossRef Google Scholar

[46] Zhao X, Mao C, Luong KT, et al. Framework cationization by preemptive coordination of open metal sites for anion-exchange encapsulation of nucleotides and coenzymes. Angew Chem Int Ed, 2016, 55: 2768-2772 CrossRef PubMed Google Scholar

[47] Jiang WJ, Gu L, Li L, et al. Understanding the high activity of Fe–N–C electrocatalysts in oxygen reduction: Fe/Fe3C nanoparticles boost the activity of Fe–Nx. J Am Chem Soc, 2016, 138: 3570-3578 CrossRef PubMed Google Scholar

[48] Zhao L, Sui XL, Li JL, et al. 3D hierarchical Pt-nitrogen-doped-graphene-carbonized commercially available sponge as a superior electrocatalyst for low-temperature fuel cells. ACS Appl Mater Interfaces, 2016, 8: 16026-16034 CrossRef Google Scholar

[49] Chen YZ, Cai G, Wang Y, et al. Palladium nanoparticles stabilized with N-doped porous carbons derived from metal–organic frameworks for selective catalysis in biofuel upgrade: the role of catalyst wettability. Green Chem, 2016, 18: 1212-1217 CrossRef Google Scholar

[50] Li C, Chen Z, Ni Y, et al. Coordination compound-derived ordered mesoporous N-free Fe–Px–C material for efficient oxygen electroreduction. J Mater Chem A, 2016, 4: 14291-14297 CrossRef Google Scholar

[51] Wang J, Li S, Zhu G, et al. Novel non-noble metal electrocatalysts synthesized by heat-treatment of iron terpyridine complexes for the oxygen reduction reaction. J Power Sources, 2013, 240: 381-389 CrossRef Google Scholar

[52] Deng C, Zhong H, Li X, et al. A highly efficient electrocatalyst for oxygen reduction reaction: phosphorus and nitrogen co-doped hierarchically ordered porous carbon derived from an iron-functionalized polymer. Nanoscale, 2016, 8: 1580-1587 CrossRef PubMed ADS Google Scholar

[53] Zhao L, Sui XL, Zhou QY, et al. 1D N-doped hierarchically porous hollow carbon tubes derived from supramolecular template as metal-free electrocatalysts for highly efficient oxygen reduction reaction. J Mater Chem A, 2018, 6: 6212-6219 CrossRef Google Scholar

[54] Li C, Chen Z, Kong A, et al. High-rate oxygen electroreduction over metal-free graphene foams embedding P–N coupled moieties in acidic media. J Mater Chem A, 2018, 6: 4145-4151 CrossRef Google Scholar

[55] Kong A, Mao C, Wang Y, et al. Hierarchically porous few-layer porphyrinic carbon nanosheets formed by a VOx-templating method for high-efficiency oxygen electroreduction. J Mater Chem A, 2016, 4: 7305-7312 CrossRef Google Scholar

  • Figure 1

    Schematic illustration of constrained-volume self-assembled (Ph3P)2Fe(CO)3@PS-c-PAN NPs and conversion into Fe-P-N-doped carbon materials.

  • Figure 2

    TEM images of (a) pure PS-c-PAN NPs; (b) (Ph3P)2Fe(CO)3@PS-c-PAN NPs. (c) STEM and elemental mapping of (Ph3P)2Fe(CO)3@PS-c-PAN NPs.

  • Figure 3

    TEM images of (a) FNP-5, (b) FNP-3 and (c) FNP-1; (d) corresponding HRTEM images of FNP-5.

  • Figure 4

    (a) Raman spectra of FNP-5 (lack line) and FNP-0 (red line); (b) N2 sorption isotherm and pore size distribution (inset) of FNP-5.

  • Figure 5

    Deconvoluted high resolution XPS of FNP-5: (a) Fe 2p, (b) N 1s and (c) P 2p; (d) a simplified model of Fe-P-N doped carbon (green ball: N; blue ball: P; red ball: Fe; black ball: C).

  • Figure 6

    CV curves of the prepared Fe-P-N-doped carbon in O2-saturated (a) 0.1 mol L−1 KOH and (d) 0.1 mol L−1 HClO4. RRDE polarization curves for Fe-P-N-doped carbon and commercial Pt/C at 1,600 rpm in O2-saturated (b) 0.1 mol L−1 KOH and (e) 0.1 mol L−1 HClO4. Calculated peroxide yields and theelectron transfer number based on the corresponding RRDE polarization curves in O2-saturated(c) 0.1 mol L−1 KOH and (f) 0.1 mol L−1 HClO4.

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