Electrocatalytic reduction of water to molecular hydrogen via the hydrogen evolution reaction may provide a sustainable energy supply for the future, but its commercial application is hampered by the use of precious platinum catalysts. All alternatives to platinum thus far are based on nonprecious metals, and, to our knowledge, there is no report about a catalyst for electrocatalytic hydrogen evolution beyond metals. Here we couple graphitic-carbon nitride with nitrogen-doped graphene to produce a metal-free hybrid catalyst, which shows an unexpected hydrogen evolution reaction activity with comparable overpotential and Tafel slope to some of well-developed metallic catalysts. Experimental observations in combination with density functional theory calculations reveal that its unusual electrocatalytic properties originate from an intrinsic chemical and electronic coupling that synergistically promotes the proton adsorption and reduction kinetics.
Access optionsAccess options
Subscribe to Journal
Get full journal access for 1 year
We are sorry, but there is no personal subscription option available for your country.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Lewis, N. S. & Nocera, D. G. Powering the planet: chemical challenges in solar energy utilization. Proc. Natl Acad. Sci. USA 103, 15729–15735 (2007).
Turner, J. A. Sustainable hydrogen production. Science 305, 972–974 (2004).
Walter, M. G. et al. Solar water splitting cells. Chem. Rev. 110, 6446–6473 (2010).
Conway, B. E. & Tilak, B. V. Interfacial processes involving electrocatalytic evolution and oxidation of H2, and the role of chemisorbed H. Electrochim. Acta. 47, 3571–3594 (2002).
Subbaraman, R. et al. Enhancing hydrogen evolution activity in water splitting by tailoring Li+-Ni(OH)2-Pt interfaces. Science 334, 1256–1260 (2011).
Le Goff, A. et al. From hydrogenases to noble metal-free catalytic nanomaterials for H2 production and uptake. Science 326, 1384–1387 (2009).
Zhuo, J. et al. Salts of C60(OH)8 electrodeposited onto a glassy carbon electrode: surprising catalytic performance in the hydrogen evolution reaction. Angew. Chem. Int. Ed. 52, 10867–10870 (2013).
Cook, T. R. et al. Solar energy supply and storage for the legacy and nonlegacy worlds. Chem. Rev. 110, 6474–6502 (2010).
Artero, V., Chavarot-Kerlidou, M. & Fontecave, M. Splitting water with cobalt. Angew. Chem. Int. Ed. 50, 7238–7266 (2011).
DuBois, M. R. & DuBois, D. L. The roles of the first and second coordination spheres in the design of molecular catalysts for H2 production and oxidation. Chem. Soc. Rev. 38, 62–72 (2009).
Cobo, S. et al. A Janus cobalt-based catalytic material for electro-splitting of water. Nat. Mater. 11, 802–807 (2012).
Du, P. & Eisenberg, R. Catalysts made of earth-abundant elements (Co, Ni, Fe) for water splitting: recent progress and future challenges. Energy Environ. Sci. 5, 6012–6021 (2012).
Popczun, E. J. et al. Nanostructured nickel phosphide as an electrocatalyst for the hydrogen evolution reaction. J. Am. Chem. Soc. 135, 9267–9270 (2013).
Jaramillo, T. F. et al. Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 317, 100–102 (2007).
Kibsgaard, J., Chen, Z., Reinecke, B. N. & Jaramillo, T. F. Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. Nat. Mater. 11, 963–969 (2012).
Voiry, D. et al. Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution. Nat. Mater. 12, 850–855 (2013).
Najmaei, S. et al. Vapour phase growth and grain boundary structure of molybdenum disulphide atomic layers. Nat. Mater. 12, 754–759 (2013).
Laursen, A. B., Kegnæs, S., Dahla, S. & Chorkendorff, I. Molybdenum sulfides–efficient and viable materials for electro- and photoelectrocatalytic hydrogen evolution. Energy Environ. Sci. 5, 5577–5591 (2012).
Merki, D. & Hu, X. Recent developments of molybdenum and tungsten sulfides as hydrogen evolution catalysts. Energy Environ. Sci. 4, 3878–3888 (2011).
Gong, K., Du, F., Xia, Z., Durstock, M. & Dai, L. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323, 760–764 (2009).
Mirzakulova, E. et al. Electrode-assisted catalytic water oxidation by a flavin derivative. Nat. Chem. 4, 794–801 (2012).
Zhao, Y., Nakamura, R., Kamiya, K., Nakanishi, S. & Hashimoto, K. Nitrogen-doped carbon nanomaterials as non-metal electrocatalysts for water oxidation. Nat. Commun. 4, 2390 (2013).
Zheng, Y. et al. Nanoporous graphitic-C3N4@Carbon metal-free electrocatalysts for highly efficient oxygen reduction. J. Am. Chem. Soc. 133, 20116–20119 (2011).
Wang, X. et al. A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat. Mater. 8, 76–80 (2009).
Thomas, A. et al. Graphitic carbon nitride materials: variation of structure and morphology and their use as metal-free catalysts. J. Mater. Chem. 18, 4893–4908 (2008).
Suenaga, K. & Koshino, M. Atom-by-atom spectroscopy at graphene edge. Nature 468, 1088–1090 (2010).
Muller, D. A., Tzou, Y., Raj, R. & Silcox, J. Mapping sp2 and sp3 states of carbon at sub-nanometre spatial resolution. Nature 366, 725–727 (1993).
Rosenberg, R. A., Love, P. J. & Rehn, V. Polarization-dependent C(K) near-edge x-ray-absorption fine structure of graphite. Phys. Rev. B 33, 4034–4037 (1985).
Sheng, Z. et al. Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis. ACS Nano 5, 4350–4358 (2011).
Chen, Z. et al. Core-shell MoO3-MoS2 nanowires for hydrogen evolution: a functional design for electrocatalytic materials. Nano Lett. 11, 4168–4175 (2011).
Chen, W. et al. Hydrogen-evolution catalysts based on non-noble metal nickel molybdenum nitride nanosheets. Angew. Chem. Int. Ed. 51, 6131–6135 (2012).
Merki, D., Vrubel, H., Rovelli, L., Fierro, S. & Hu, X. Fe, Co, and Ni ions promote the catalytic activity of amorphous molybdenum sulfide films for hydrogen evolution. Chem. Sci. 3, 2515–2525 (2012).
Li, Y. et al. MoS2 nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction. J. Am. Chem. Soc. 133, 7296–7299 (2011).
Nørskov, J. K., Bligaard, T., Rossmeisl, J. & Christensen, C. H. Towards the computational design of solid catalysts. Nat. Chem. 1, 37–46 (2009).
Nørskov, J. K. et al. Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 152, J23–J26 (2005).
Greeley, J., Jaramillo, T. F., Bonde, J., Chorkendorff, I. & Nørskov, J. K. Computational high-throughput screening of electrocatalytic materials for hydrogen evolution. Nat. Mater. 5, 909–913 (2006).
Skulason, E. et al. Modeling the electrochemical hydrogen oxidation and evolution reactions on the basis of density functional theory calculations. J. Phys. Chem. C 114, 18182–18197 (2010).
Li, D., Muller, M. B., Gilje, S., Kaner, R. B. & Wallace, G. G. Processable aqueous dispersions of graphene nanosheets. Nat. Nanotech. 3, 101–105 (2008).
This research is financially supported by Australian Research Council (DP1095861, DP130104459). NEXAFS measurements were undertaken on the soft X-ray beamline at Australian Synchrotron. DFT calculations were undertaken on the NCI National Facility systems through the National Computational Merit Allocation Scheme.
The authors declare no competing financial interests.
About this article
Single-atoms supported (Fe, Co, Ni, Cu) on graphitic carbon nitride for CO2 adsorption and hydrogenation to formic acid: First-principles insights
Applied Surface Science (2020)
Uncovering the electrochemical mechanisms for hydrogen evolution reaction of heteroatom doped M2C MXene (M = Ti, Mo)
Applied Surface Science (2020)
Structural, electronic and photocatalytic properties of g-C3N4 with intrinsic defects: A first-principles hybrid functional investigation
Applied Surface Science (2020)
Nitrogen-rich carbon-supported ultrafine MoC nanoparticles for the hydrotreatment of oleic acid into diesel-like hydrocarbons
Chemical Engineering Journal (2020)
Engineering the HER catalytic behavior of heteroatom-doped molybdenum disulfide via versatile partial cation exchange
Journal of Energy Chemistry (2020)