Applied Chemical Engineering

Carbon nanomaterials for metal-free electrocatalysis

Ana M.B. Honorato

Center of Advanced Science and Engineering for Carbon (Case4carbon), Department of Macromolecular Science and Engineering, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106

Mohd Khalid

Institute of Chemistry of São Carlos, University of São Paulo, POBox 780, 13560-970, São Carlos, SP

DOI: https://doi.org/10.24294/ace.v3i1.511

Keywords: Carbon Nanomaterials, Graphene, Metal-Free Electrocatalyst, Hydrogen Evolution Reaction

---

Abstract

Carbon materials are continuing in progress to accomplish the requirements of energy conversion and energy storage technologies because of their plenty in nature, high surface area, outstanding electrical properties, and readily obtained from varieties of chemical and natural sources. Recently, carbon-based electrocatalysts have been developed in the quest to replacement of noble metal based catalysts for low cost energy conversion technologies, such as fuel cell, water splitting, and metal-air batteries. Herein, we will present our short overview on recently developed carbon-based electrocatalysts for energy conversion reactions such as oxygen reduction, oxygen evolution, and hydrogen evolution reactions, along with challenges and perspectives in the emerging field of metal-free electrocatalysts.

---

References

[1] Caban-Acevedo M, Stone ML, Schmidt JR, et al. Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide. Nature Materials 2015; 14: 1245–1251.

[2] Bates MK, Jia QY, Ramaswamy N, et al. Composite Ni/NiO-Cr2O3 catalyst for alkaline hydrogen evolution reaction. The Journal of Physical Chemistry C 2015; 119: 5467–5477.

[3] Goff AL, Artero V, Jousselme B, et al. From hydrogenases to noble metal–free catalytic nanomaterials for H2 production and uptake. Science 2009; 326: 1384–1387.

[4] Liu X, Cui SS, Sun ZJ, et al. Robust and highly active copper-based electrocatalyst for hydrogen production at low overpotential in neutral water. Chemical Communication 2015; 51: 12954–12957.

[5] Liang Y, Li Y, Wang H, et al. Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. Nature Materials 2011; 10: 780–786.

[6] Sun Y, Gao S, Lei F, et al. Atomically-thin non-layered cobalt oxide porous sheets for highly efficient oxygen-evolving electrocatalysts. Chemical Science 2014; 5: 3976–3982.

[7] Smith RD, Pr_vot MS, Fagan RD, et al. Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis. Science 2013; 340: 60–63.

[8] Grimaud A, May KJ, Carlton CE, et al. Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution. Nature Communication 2013; 4: 2439.

[9] Peng Z, Jia D, Al-Enizi A, et al. Electrocatalysts: From water oxidation to reduction: homologous ni–co based nanowires as complementary water splitting electrocatalysts. Advanced Energy Materials 2015; 5: 1402031.

[10] Subbaraman R, Tripkovic D, Chang KC, et al. Trends in activity for the water electrolyser reactions on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts. Nature Materials 2012; 11: 550–557.

[11] Wee TL, Sherman BD, Gust D, et al. Photochemical synthesis of a water oxidation catalyst based on cobalt nanostructures. Journal of the American Chemical Society 2011; 133: 16742–16745.

[12] Rosen J, Hutchings GS., Jiao F. Ordered mesoporous cobalt oxide as highly efficient oxygen evolution catalyst. Journal of the American Chemical Society 2013; 135: 4516–4521.

[13] Ryu J, Jung N,Jang JH, et al. In situ transformation of hydrogen-evolving cop nanoparticles: toward efficient oxygen evolution catalysts bearing dispersed morphologies with co-oxo/hydroxo molecular units. ACS Catalysis 2015; 5: 4066–4074.

[14] Zheng YR, Gao MR, Gao Q, et al. An efficient CeO2/CoSe2 nanobelt composite for electrochemical water oxidation. Small 2015; 11: 182–188.

[15] Wu L, Li Q, Wu CH, et al. Stable cobalt nanoparticles and their monolayer array as an efficient electrocatalyst for oxygen evolution reaction. Journal of the American Chemical Society 2015; 137: 7071–7074.

[16] Koza JA, He Z, Miller A, et al. Electrodeposition of crystalline Co3O4—A catalyst for the oxygen evolution reaction. Chem. Mater. 2012; 24: 3567–3573.

[17] Hutchings GS, Zhang Y, Li J, et al. In situ formation of cobalt oxide nanocubanes as efficient oxygen evolution catalysts. Journal of the American Chemical Society 2015; 137: 4223–4229.

[18] Hamdani M, Singh R, Chartier P. Co3O4 and Co-based spinel oxides bifunctional oxygen electrodes. International Journal of Electrochemical Science 2010; 5: 556–577.

[19] Lu X, Zhao C. Highly efficient and robust oxygen evolution catalysts achieved by anchoring nanocrystalline cobalt oxides onto mildly oxidized multiwalled carbon nanotubes. Journal of Materials Chemistry A 2013; 1: 12053–12059.

[20] Zhu CZ, Wen D, Leubner S, et al. Nickel cobalt oxide hollow nanosponges as advanced electrocatalysts for the oxygen evolution reaction. Chemical Communication 2015; 51: 851–7854.

[21] Li Y, Hasin P, Wu Y. NixCo3−xO4 nanowire arrays for electrocatalytic oxygen evolution. Advanced Materials 2010; 22: 1926–1929.

[22] Chen S, Duan JJ, Jaroniec M, et al. Three-dimensional N-doped graphene hydrogel/NiCo double hydroxide electrocatalysts for highly efficient oxygen evolution. Angewandte Chemie International Edition 2013; 52: 13567–13570.

[23] Wang J, Qiu T, Chen X, et al. Hierarchical hollow urchin-like NiCo2O4 nanomaterial as electrocatalyst for oxygen evolution reaction in alkaline medium. Journal of Power Sources 2014; 268: 341–348.

[24] Trotochaud L, Ranney JK, Williams KN, et al. Solution-cast metal oxide thin film electrocatalysts for oxygen evolution. Journal of the American Chemical Society 2012; 134: 17253–17261.

[25] McCrory CCL, Jung SH, Peters JC., et al. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. Journal of the American Chemical Society 2013; 135: 16977–16987.

[26] Kanan MW., Nocera DG. In situ formation of an oxygen-evolving catalyst in neutral water containing phosphate and Co2+. Science 2008; 321: 1072–1075.

[27] Wang YC, Jiang K, Zhang H, et al. Bio-inspired leaf-mimicking nanosheet/nanotube heterostructure as a highly efficient oxygen evolution catalyst. Advanced Science 2015; 2: 1500003.

[28] Nikolov I, Darkaoui R, Zhecheva E, et al. Electrocatalytic activity of spinel related cobalties MxCo3-xO4 (M = Li, Ni, Cu) in the oxygen evolution reaction. Journal of Electroanalytical Chemistry 1997; 429: 157–168.

[29] Zhuang ZB, Sheng WC, Yan YS. Synthesis of monodispere Au@Co3O4 core-shell nanocrystals and their enhanced catalytic activity for oxygen evolution reaction. Advanced Materials 2014; 26: 3950–3955.

[30] Gong M, Zhou W, Tsai MC, et al. Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis. Nature Communication. 2014; 5: 4695.

[31] Suntivich J, May KJ, GasteigerHA, et al. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science 2011; 334: 1383–1385.

[32] Smith RDL, Prevot MS, Fagan RD, et al. Water oxidation catalysis: electrocatalytic response to metal stoichiometry in amorphous metal oxide films containing iron, cobalt, and nickel. Journal of the American Chemical Society 2013; 135: 11580–11586.

[33] Zhou W, Wu XJ., Cao X, et al. Ni3S2nanorods/Ni foam composite electrode with low overpotential for electrocatalytic oxygen evolution. Energy & Environmental Science 2013; 6: 2921–2924.

[34] Ledendecker M, Krick Calder S, Papp C, et al. The synthesis ofnanostructured Ni5P4films and their use as a non-noble bifunctional electrocatalyst for full water splitting. Angewandte Chemie International Edition 2015; 54: 12361–12365.

[35] Gao MR, Cao X, Gao Q, et al. Nitrogen-doped graphene supported CoSe2 nanobelt composite catalyst for efficient water oxidation. ACS Nano 2014; 8: 3970–3978.

[36] Merki D, Fierro S, Vrubel H, et al. Amorphous molybdenum sulfide films as catalysts for electrochemical hydrogen production in water. Chemical Science 2011; 2: 1262–1267.

[37] Li Q, Xu P, Zhang B, et al. One-step synthesis of Mn3O4/reduced graphene oxide nanocomposites for oxygen reduction in nonaqueous Li–O2 batteries. Chemical Communication 2013; 49: 10838–10840.

[38] He QG., Li Q, Khene S, et al. High-loading cobalt oxide coupled with nitrogen-doped graphene for oxygen reduction in anion-exchange-membrane alkaline fuel cells. The Journal of Physical Chemistry C 2013; 117: 8697–8707.

[39] Li Q, Xu P, Gao W, et al. One-step synthesis of Mn3O4/reduced graphene oxide nanocomposites for oxygen reduction in nonaqueous Li–O2 batteries. Advanced Materials 2014; 26: 1378– 386.

[40] Chen S, Duan JJ, Ran JR, et al. N-doped graphene film-confined nickel nanoparticles as a highly efficient three-dimensional oxygen evolution electrocatalyst. Energy & Environmental Science 2013; 6: 3693–3699.

[41] Gong M, Li YG, Wang HL, et al. An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation. Journal of the American Chemical Society 2013; 135: 8452–8455.

[42] Long X, Li JK., Xiao S, et al. A strongly coupled graphene and FeNi double hydroxide hybrid as an excellent electrocatalyst for the oxygen evolution reaction. Angewandte Chemie International Edition 2014; 53: 7584–7588.

[43] Liu X, Liu W, Ko M, et al. Metal (Ni, Co)-metal oxides/graphene nanocomposites as multifunctional electrocatalysts. Advanced Functional Materials 2015; 25: 5799–5808.

[44] Fan X, Peng Z, Ye R, et al. M3C (M: Fe, Co, Ni) nanocrystals encased in graphene nanoribbons: An active and stable bifunctional electrocatalyst for oxygen reduction and hydrogen evolution reactions. ACS Nano 2015; 9: 7407–7418.

[45] Tavakkoli M, Kallio T, Reynaud O, et al. Single-shell carbon-encapsulated iron nanoparticles: synthesis and high electrocatalytic activity for hydrogen evolution reaction. Angewandte Chemie International Edition 2015; 54: 4535–4538.

[46] Ye TN, Lv LB, Xu M, et al. Hierarchical carbon nanopapers coupled with ultrathin MoS2 nanosheets: Highly efficient large-area electrodes for hydrogen evolution. Nano Energy 2015; 15: 335–342.

[47] Gong KP, Du F, Xia ZH, et al. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 2009; 323: 760-764.

[48] Yang HB., Miao J, Hung SF, 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. Science Advances 2016; 22: e1501122.

[49] Dai L. Functionalization of graphene for efficient energy conversion and storage. Accounts of Chemical Research . 2013; 46: 31–42.

[50] Zhang J, Dai L. Heteroatom-doped graphitic carbon catalysts for efficient electrocatalysis of oxygen reduction reaction. ACS Catalysis 2015; 5: 7244 – 7253.

[51] Sun X, Song P, Zhang Y, et al. A class of high performance metal-free oxygen reduction electrocatalysts based on cheap carbon blacks. Scientific Reports 2013; 3: 2505.

[52] Liu Z, Peng F, Wang H, et al. Novel phosphorus-doped multiwalled nanotubes with high electrocatalytic activity for O2 reduction in alkaline medium. Catalysis Communications 2011; 1: 35–38.

[53] Geng D, Chen Y, Li Y, et al. High oxygen-reduction activity and durability of nitrogen-doped grapheme. Energy & Environment Science 2011; 4: 760–764.

[54] Lee RS, Kim HJ, Fischer JE, et al. Conductivity enhancement in single-walled carbon nanotube bundles doped with K and Br. Nature 1997,; 388, 255–257.

[55] Avouris P, Chen Z H, Perebeinos V. Carbon-based electronics. Nature Nanotechnology 2007; 2: 605–615.

[56] Duan JJ,Chen S, Jaroniec M, et al. Heteroatom-doped graphene-based materials for energy-relevant electrocatalytic processes. ACS Catalysis 2015; 5: 5207–5234.

[57] Xue Y, Yu D, Dai L, et al. Three-dimensional B, N-doped graphene foam as a metal-free catalyst for oxygen reduction reaction. Physical Chemistry Chemical Physics 2013; 15:12220–12226.

[58] Yu DS, Goh K, Wang H, et al. Scalable synthesis of hierarchically structured carbon nanotube-graphene fibres for capacitive energy storage. Natture Nanotechnology 2014; 9:555–562.

[59] Xue Y, Ding Y, Niu J, et al. Rationally designed graphene-nanotube 3D architectures with a seamless nodal junction for efficient energy conversion and storage. Science Advances1 2015 e1400198.

[60] Zhang J, Zhao Z, Xia Z, et al. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nature Nanotechnology 2015; 10:444–452.

[61] Zhang J, Dai L. N,P-codoped carbon networks as efficient metal-free bifunctional catalysts for oxygen reduction and hydrogen evolution reactions. Angewandte Chemie International Edition 2016; 55:2230–2234.

[62] Dai L, Xue YH, Qu LT, et al. Metal-free catalysts for oxygen reduction reaction. Chemical Reviews 2015; 115: 4823.

[63] Hu C, Dai L. Multifunctional carbon-based metal-free electrocatalysts for simultaneous oxygen reduction, oxygen evolution, and hydrogen evolution. Advanced Materials 2017; 29: 1604942.