Review Article | Published:

Catalysis with two-dimensional materials and their heterostructures

Nature Nanotechnology volume 11, pages 218230 (2016) | Download Citation

Abstract

Graphene and other 2D atomic crystals are of considerable interest in catalysis because of their unique structural and electronic properties. Over the past decade, the materials have been used in a variety of reactions, including the oxygen reduction reaction, water splitting and CO2 activation, and have been shown to exhibit a range of catalytic mechanisms. Here, we review recent advances in the use of graphene and other 2D materials in catalytic applications, focusing in particular on the catalytic activity of heterogeneous systems such as van der Waals heterostructures (stacks of several 2D crystals). We discuss the advantages of these materials for catalysis and the different routes available to tune their electronic states and active sites. We also explore the future opportunities of these catalytic materials and the challenges they face in terms of both fundamental understanding and the development of industrial applications.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

References

  1. 1.

    et al. Electric field effect in atomically thin carbon films. Science 306, 666–669 (2004).

  2. 2.

    Graphene as a new carbon support for low-temperature fuel cell catalysts. Appl. Catal. B 123, 52–68 (2012).

  3. 3.

    & Graphene and its application in fuel cell catalysis: a review. Asia Pac. J. Chem. Eng. 8, 218–233 (2013).

  4. 4.

    & Graphene-based photocatalytic composites. RSC Adv. 1, 1426–1434 (2011).

  5. 5.

    & Graphene-based materials for catalysis. Catal. Sci. Technol. 2, 54–75 (2012).

  6. 6.

    et al. Size effect of graphene on electrocatalytic activation of oxygen. Chem. Commun. 47, 10016–10018 (2011).

  7. 7.

    & Carbocatalysts: graphene oxide and its derivatives. Acc. Chem. Res. 46, 2275–2285 (2013).

  8. 8.

    , , & Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano 4, 1321–1326 (2010).

  9. 9.

    , , , & Oxygen reduction reaction mechanism on nitrogen-doped graphene: a density functional theory study. J. Catal. 282, 183–190 (2011).

  10. 10.

    et al. Two-dimensional atomic crystals. Proc. Natl Acad. Sci. USA 102, 10451–10453 (2005).

  11. 11.

    Nobel Lecture. Graphene: materials in the flatland. Rev. Mod. Phys. 83, 837–849 (2011).

  12. 12.

    & Van der Waals heterostructures. Nature 499, 419–425 (2013).

  13. 13.

    et al. Iron encapsulated within pod-like carbon nanotubes for oxygen reduction reaction. Angew. Chem. Int. Ed. 52, 371–375 (2013).

  14. 14.

    et al. Highly active and durable non-precious-metal catalysts encapsulated in carbon nanotubes for hydrogen evolution reaction. Energy Environ. Sci. 7, 1919–1923 (2014).

  15. 15.

    , , & Enhanced electron penetration through an ultrathin graphene layer for highly efficient catalysis of the hydrogen evolution reaction. Angew. Chem. Int. Ed. 54, 2100–2104 (2015).

  16. 16.

    et al. Podlike N-doped carbon nanotubes encapsulating FeNi alloy nanoparticles: high-performance counter electrode materials for dye-sensitized solar cells. Angew. Chem. Int. Ed. 53, 7023–7027 (2014).

  17. 17.

    et al. Visualizing chemical reactions confined under graphene. Angew. Chem. Int. Ed. 51, 4856–4859 (2012).

  18. 18.

    et al. Graphene cover-promoted metal-catalyzed reactions. Proc. Natl Acad. Sci. USA 111, 17023–17028 (2014).

  19. 19.

    & The rise of graphene. Nature Mater. 6, 183–191 (2007).

  20. 20.

    et al. A route to high surface area, porosity and inclusion of large molecules in crystals. Nature 427, 523–527 (2004).

  21. 21.

    , , & Mechanical properties of suspended graphene sheets. J. Vac. Sci. Technol. A 25, 2558–2561 (2007).

  22. 22.

    et al. Superior thermal conductivity of single-layer graphene. Nano Lett. 8, 902–907 (2008).

  23. 23.

    , , , & The electronic properties of graphene. Rev. Mod. Phys. 81, 109–162 (2009).

  24. 24.

    , , & Edge state in graphene ribbons: nanometer size effect and edge shape dependence. Phys. Rev. B 54, 17954–17961 (1996).

  25. 25.

    , & Electronic structures of graphene edges and nanographene. Int. Rev. Phys. Chem. 26, 609–645 (2007).

  26. 26.

    et al. Substrate-induced bandgap opening in epitaxial graphene. Nature Mater. 6, 916–916 (2007).

  27. 27.

    et al. Graphene at the edge: stability and dynamics. Science 323, 1705–1708 (2009).

  28. 28.

    , & Structural defects in graphene. ACS Nano 5, 26–41 (2011).

  29. 29.

    , & Defect energies of graphite: density-functional calculations. Phys. Rev. B 72, 184109 (2005).

  30. 30.

    et al. Quantitative correlation between defect density and heterogeneous electron transfer rate of single layer graphene. J. Am. Chem. Soc. 136, 16609–16617 (2014).

  31. 31.

    et al. Synthesis of large-area graphene layers on poly-nickel substrate by chemical vapor deposition: wrinkle formation. Adv. Mater. 21, 2328–2333 (2009).

  32. 32.

    , , , & Spontaneous formation of nanostructures in graphene. Nano Lett. 9, 3599–3602 (2009).

  33. 33.

    et al. Synthesis of N-doped graphene by chemical vapor deposition and its electrical properties. Nano Lett. 9, 1752–1758 (2009).

  34. 34.

    et al. Toward N-doped graphene via solvothermal synthesis. Chem. Mater. 23, 1188–1193 (2011).

  35. 35.

    et al. Synthesis, structure, and properties of boron- and nitrogen-doped graphene. Adv. Mater. 21, 4726–4730 (2009).

  36. 36.

    , & Gas adsorption on graphene doped with B, N, Al, and S: a theoretical study. Appl. Phys. Lett. 95, 232105 (2009).

  37. 37.

    et al. Phosphorus-doped graphite layers with high electrocatalytic activity for the O2 reduction in an alkaline medium. Angew. Chem. Int. Ed. 50, 3257–3261 (2011).

  38. 38.

    , , & Origin of the electrocatalytic oxygen reduction activity of graphene-based catalysts: a roadmap to achieve the best performance. J. Am. Chem. Soc. 136, 4394–4403 (2014).

  39. 39.

    et al. Sulfur-doped graphene as an efficient metal-free cathode catalyst for oxygen reduction. ACS Nano 6, 205–211 (2012).

  40. 40.

    et al. Efficient synthesis of heteroatom (N or S)-doped graphene based on ultrathin graphene oxide-porous silica sheets for oxygen reduction reactions. Adv. Funct. Mater. 22, 3634–3640 (2012).

  41. 41.

    et al. Migration and localization of metal atoms on strained graphene. Phys. Rev. Lett. 105, 196102 (2010).

  42. 42.

    et al. Doping monolayer graphene with single atom substitutions. Nano Lett. 12, 141–144 (2012).

  43. 43.

    et al. Free-standing single-atom-thick iron membranes suspended in graphene pores. Science 243, 1228–1232 (2014).

  44. 44.

    & Preparation of graphitic oxide. J. Am. Chem. Soc. 80, 1339–1339 (1958).

  45. 45.

    et al. Sulfated graphene as an efficient solid catalyst for acid-catalyzed liquid reactions. J. Mater. Chem. 22, 5495–5502 (2012).

  46. 46.

    , & Structural and electronic properties of oxidized graphene. Phys. Rev. Lett. 103, 086802 (2009).

  47. 47.

    , & Graphane: a two-dimensional hydrocarbon. Phys. Rev. B 75, 153401 (2007).

  48. 48.

    , , & Halogenation of graphene with chlorine, bromine, or iodine by exfoliation in a halogen atmosphere. Chem. Eur. J. 19, 2655–2662 (2013).

  49. 49.

    , & Light non-metallic atom (B, N, O and F)-doped graphene: a first-principles study. Nanotechnology 21, 505202 (2010).

  50. 50.

    , , , & 3D honeycomb-like structured graphene and its high efficiency as a counter-electrode catalyst for dye-sensitized solar cells. Angew. Chem. Int. Ed. 52, 9210–9214 (2013).

  51. 51.

    , & Unique chemical reactivity of a graphene nanoribbon's zigzag edge. J. Chem. Phys. 126, 134701 (2007).

  52. 52.

    , , , & Synthesis of boron doped graphene for oxygen reduction reaction in fuel cells. J. Mater. Chem. 22, 390–395 (2012).

  53. 53.

    et al. Nitrogen-doped sp2-hybridized carbon as a superior catalyst for selective oxidation. Angew. Chem. Int. Ed. 52, 2109–2113 (2013).

  54. 54.

    , , & Nitrogen and oxygen dual-doped carbon hydrogel film as a substrate-free electrode for highly efficient oxygen evolution reaction. Adv. Mater. 26, 2925–2930 (2014).

  55. 55.

    , & N-doped graphene nanosheets for Li–air fuel cells under acidic conditions. Energy Environ. Sci. 5, 6928–6932 (2012).

  56. 56.

    et al. Nitrogen doped graphene-rich catalysts derived from heteroatom polymers for oxygen reduction in nonaqueous lithium-O2 battery cathodes. ACS Nano 6, 9764–9776 (2012).

  57. 57.

    Density Functional Theory Studies on Modulating the Electronic Structures of sp2 Hybridized Carbon Materials for Oxygen Activation PhD thesis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences (2012).

  58. 58.

    , , & Mesoporous nitrogen-doped carbon for the electrocatalytic synthesis of hydrogen peroxide. J. Am. Chem. Soc. 134, 4072–4075 (2012).

  59. 59.

    , , & Investigation of hydrogen peroxide reduction reaction on graphene and nitrogen doped graphene nanoflakes in neutral solution. J. Power Sources 257, 356–363 (2014).

  60. 60.

    et al. Nitrogen-doped graphene nanosheets as metal-free catalysts for aerobic selective oxidation of benzylic alcohols. ACS Catal. 2, 622–631 (2012).

  61. 61.

    , , & A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nature Nanotech. 10, 444–452 (2015).

  62. 62.

    , , & Metal-embedded graphene: a possible catalyst with high activity. J. Phys. Chem. C 113, 20156–20160 (2009).

  63. 63.

    et al. A single iron site confined in a graphene matrix for the catalytic oxidation of benzene at room temperature. Sci. Adv. 1, e1500462 (2015).

  64. 64.

    , , & in Fifth Conference on Carbon 73–80 (Pergamon, 1962).

  65. 65.

    , & Graphene oxide: a convenient carbocatalyst for facilitating oxidation and hydration reactions. Angew. Chem. Int. Ed. 49, 6813–6816 (2010).

  66. 66.

    , , & The chemistry of graphene oxide. Chem. Soc. Rev. 39, 228–240 (2010).

  67. 67.

    , , , & Reduced graphene oxide as a catalyst for hydrogenation of nitrobenzene at room temperature. Chem. Commun. 47, 2432–2434 (2011).

  68. 68.

    , & Synthesis and characterization of nitro-functionalized electrochemically exfoliated graphene. Mater. Lett. 137, 153–155 (2014).

  69. 69.

    & Two-dimensional crystals: beyond graphene. Mater. Express 1, 10–17 (2011).

  70. 70.

    & New directions in science and technology: two-dimensional crystals. Rep. Prog. Phys. 74, 8 (2011).

  71. 71.

    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).

  72. 72.

    et al. A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nature Mater. 8, 76–80 (2009).

  73. 73.

    , & Metal-free activation CO2 by mesoporous graphitic carbon nitride. Angew. Chem. Int. Ed. 46, 2717–2720 (2007).

  74. 74.

    , , & Graphene-based carbon nitride nanosheets as efficient metal-free electrocatalysts for oxygen reduction reactions. Angew. Chem. Int. Ed. 50, 5339–5343 (2011).

  75. 75.

    et al. Hydrogen evolution by a metal-free electrocatalyst. Nature Commun. 5, 3783 (2014).

  76. 76.

    , , & Chemical synthesis of mesoporous carbon nitrides using hard templates and their use as a metal-free catalyst for Friedel–Crafts reaction of benzene. Angew. Chem. Int. Ed. 45, 4467–4471 (2006).

  77. 77.

    , , & Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. Chem. Soc. Rev. 44, 2060–2086 (2015).

  78. 78.

    , , & Advancing the electrochemistry of the hydrogen-evolution reaction through combining experiment and theory. Angew. Chem. Int. Ed. 54, 52–65 (2015).

  79. 79.

    , , & Graphitic carbon nitride nanosheet-carbon nanotube three-dimensional porous composites as high-performance oxygen evolution electrocatalysts. Angew. Chem. Int. Ed. 53, 7281–7285 (2014).

  80. 80.

    , , & Graphdiyne and graphyne: from theoretical predictions to practical construction. Chem. Soc. Rev. 43, 2572–2586 (2014).

  81. 81.

    et al. Nitrogen-doped graphdiyne as a metal-free catalyst for high-performance oxygen reduction reactions. Nanoscale 6, 11336–11343 (2014).

  82. 82.

    , , & Graphdiyne as a metal-free catalyst for low-temperature CO oxidation. Phys. Chem. Chem. Phys. 16, 5640–5648 (2014).

  83. 83.

    , , & Graphyne and graphdiyne: versatile catalysts for dehydrogenation of light metal complex hydrides. J. Phys. Chem. C 117, 21643–21650 (2013).

  84. 84.

    , , , & Atomically thin MoS2: a new direct-gap semiconductor. Phys. Rev. Lett. 105, 136805 (2010).

  85. 85.

    , , , & Physical and chemical tuning of two-dimensional transition metal dichalcogenides. Chem. Soc. Rev. 44, 2664–2680 (2015).

  86. 86.

    et al. Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 317, 100–102 (2007).

  87. 87.

    et al. Highly active and stable hybrid catalyst of cobalt-doped FeS2 nanosheets — carbon nanotubes for hydrogen evolution reaction. J. Am. Chem. Soc. 137, 1587–1592 (2015).

  88. 88.

    et al. Controllable disorder engineering in oxygen-incorporated MoS2 ultrathin nanosheets for efficient hydrogen evolution. J. Am. Chem. Soc. 135, 17881–17888 (2013).

  89. 89.

    et al. High-performance hydrogen evolution electrocatalysis by layer-controlled MoS2 nanosheets. RSC Adv. 4, 34733–34738 (2014).

  90. 90.

    et al. Layer-dependent electrocatalysis of MoS2 for hydrogen evolution. Nano Lett. 14, 553–558 (2014).

  91. 91.

    et al. Triggering the electrocatalytic hydrogen evolution activity of the inert two-dimensional MoS2 surface via single-atom metal doping. Energy Environ. Sci. 8, 1594–1601 (2015).

  92. 92.

    et al. Freestanding tin disulfide single-layers realizing efficient visible-light water splitting. Angew. Chem. Int. Ed. 51, 8727–8731 (2012).

  93. 93.

    et al. All-surface-atomic-metal chalcogenide sheets for high-efficiency visible-light photoelectrochemical water splitting. Adv. Energy Mater. 4, (2014).

  94. 94.

    et al. Oxygen vacancies confined in ultrathin indium oxide porous sheets for promoted visible-light water splitting. J. Am. Chem. Soc. 136, 6826–6829 (2014).

  95. 95.

    et al. Low overpotential in vacancy-rich ultrathin CoSe2 nanosheets for water oxidation. J. Am. Chem. Soc. 136, 15670–15675 (2014).

  96. 96.

    et al. C-oriented and {010} facets exposed BiVO4 nanowall films: template-free fabrication and their enhanced photoelectrochemical properties. Chem. Asian J. 5, 2515–2523 (2010).

  97. 97.

    et al. Pits confined in ultrathin cerium(IV) oxide for studying catalytic centers in carbon monoxide oxidation. Nature Commun. 4, 2899 (2013).

  98. 98.

    et al. Quality heterostructures from two dimensional crystals unstable in air by their assembly in inert atmosphere. Nano Lett. 15, 4914–4921 (2015).

  99. 99.

    et al. Freestanding palladium nanosheets with plasmonic and catalytic properties. Nature Nanotech. 6, 28–32 (2011).

  100. 100.

    , & C2H2 treatment as a facile method to boost the catalysis of Pd nanoparticulate catalysts. J. Am. Chem. Soc. 136, 5583–5586 (2014).

  101. 101.

    et al. Ultrathin rhodium nanosheets. Nature Commun. 5, 3093 (2014).

  102. 102.

    et al. Unique excavated rhombic dodecahedral PtCu3 alloy nanocrystals constructed with ultrathin nanosheets of high-energy {110} facets. J. Am. Chem. Soc. 136, 3748–3751 (2014).

  103. 103.

    & Metal nanoparticles at mesoporous N-doped carbons and carbon nitrides: functional Mott–Schottky heterojunctions for catalysis. Chem. Soc. Rev. 42, 6593–6604 (2013).

  104. 104.

    et al. Visualizing electronic interactions between iron and carbon by X-ray chemical imaging and spectroscopy. Chem. Sci. 6, 3262–3267 (2015).

  105. 105.

    et al. Highly active reduction of oxygen on a FeCo alloy catalyst encapsulated in pod-like carbon nanotubes with fewer walls. J. Mater. Chem. A 1, 14868–14873 (2013).

  106. 106.

    et al. Hollow spheres of iron carbide nanoparticles encased in graphitic layers as oxygen reduction catalysts. Angew. Chem. Int. Ed. 53, 3675–3679 (2014).

  107. 107.

    et al. Cobalt-embedded nitrogen-rich carbon nanotubes efficiently catalyze hydrogen evolution reaction at all pH values. Angew. Chem. Int. Ed. 53, 4372–4376 (2014).

  108. 108.

    et al. Acid-resistant catalysis without use of noble metals: carbon nitride with underlying nickel. ACS Catal. 4, 2536–2543 (2014).

  109. 109.

    et al. Boron nitride nanosheet on gold as an electrocatalyst for oxygen reduction reaction: theoretical suggestion and experimental proof. J. Am. Chem. Soc. 136, 6542–6545 (2014).

  110. 110.

    , , & Functionalization of monolayer h-BN by a metal support for the oxygen reduction reaction. J. Phys. Chem. C 117, 21359–21370 (2013).

  111. 111.

    et al. Electron tunneling through ultrathin boron nitride crystalline barriers. Nano Lett. 12, 1707–1710 (2012).

  112. 112.

    , , , & Tuning the electronic and chemical properties of monolayer MoS2 adsorbed on transition metal substrates. Nano Lett. 13, 509–514 (2013).

  113. 113.

    , , , & Single layer graphene encapsulating non-precious metals as high-performance electrocatalysts for water oxidation. Energy Environ. Sci. 9, 123–129 (2016).

  114. 114.

    , , , & Quasi-free-standing epitaxial graphene on SiC obtained by hydrogen intercalation. Phys. Rev. Lett. 103, 246804 (2009).

  115. 115.

    et al. Intercalation of metal islands and films at the interface of epitaxially grown graphene and Ru(0001) surfaces. Appl. Phys. Lett. 99, 163107 (2011).

  116. 116.

    et al. The mechanism of caesium intercalation of graphene. Nature Commun. 4, 2772 (2013).

  117. 117.

    et al. Hexagonal boron nitride cover on Pt(111): a new route to tune molecule–metal interaction and metal-catalyzed reactions. Nano Lett. 15, 3616–3623 (2015).

  118. 118.

    et al. Repeated growth and bubbling transfer of graphene with millimetre-size single-crystal grains using platinum. Nature Commun. 3, 699 (2012).

  119. 119.

    et al. Enhanced reactivity of graphene wrinkles and their function as nanosized gas inlets for reactions under graphene. Phys. Chem. Chem. Phys. 15, 19042–19048 (2013).

  120. 120.

    et al. Surface chemistry of CO on Ru(0001) under the confinement of graphene cover. J. Phys. Chem. C 118, 12391–12398 (2014).

  121. 121.

    & Catalysis on a metal surface with a graphitic cover. Chin. J. Catal. 36, 517–519 (2015).

  122. 122.

    et al. Doping mechanisms in graphene–MoS2 hybrids. Appl. Phys. Lett. 103, 251607 (2013).

  123. 123.

    et al. Atomically thin p–n junctions with van der Waals heterointerfaces. Nature Nanotech. 9, 676–681 (2014).

  124. 124.

    et al. Observation of long-lived interlayer excitons in monolayer MoSe2–WSe2 heterostructures. Nature Commun. 6, 7242 (2015).

  125. 125.

    et al. MoS2 nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction. J. Am. Chem. Soc. 133, 7296–7299 (2011).

  126. 126.

    et al. Two-dimensional hybrid nanosheets of tungsten disulfide and reduced graphene oxide as catalysts for enhanced hydrogen evolution. Angew. Chem. Int. Ed. 52, 13751–13754 (2013).

  127. 127.

    et al. Tuning the surface charge of 2D oxide nanosheets and the bulk-scale production of superlatticelike composites. J. Am. Chem. Soc. 137, 2844–2847 (2015).

  128. 128.

    et al. An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation. Nature Commun. 6, 5982 (2015).

  129. 129.

    et al. What molecular assembly can learn from catalytic chemistry. Chem. Soc. Rev. 43, 399–411 (2014).

  130. 130.

    et al. Nano-architectures by covalent assembly of molecular building blocks. Nature Nanotech. 2, 687–691 (2007).

  131. 131.

    , , , & N-doped graphene as an electron donor of iron catalysts for CO hydrogenation to light olefins. Chem. Commun. 51, 217–220 (2015).

  132. 132.

    & The global growth of graphene. Nature Nanotech. 9, 726–730 (2014).

  133. 133.

    et al. Large-scale soft colloidal template synthesis of 1.4 nm thick CdSe nanosheets. Angew. Chem. Int. Ed. 48, 6861–6864 (2009).

  134. 134.

    et al. Synthesis and structure of multi-layered WS2(CoS), MOS2(Mo) nanocapsules and single-layered WS2(W) nanoparticles. J. Mater. Sci. 40, 4287–4291 (2005).

  135. 135.

    & Transitional structures of the interface between graphene and 6H-SiC (0001). Chem. Phys. Lett. 468, 52–56 (2009).

  136. 136.

    et al. Freestanding graphene by thermal splitting of silicon carbide granules. Adv. Mater. 22, 2168–2171 (2010).

  137. 137.

    , & Carbide-derived carbons from porous networks to nanotubes and graphene. Adv. Funct. Mater. 21, 810–833 (2011).

  138. 138.

    et al. Silicon carbide-derived carbon nanocomposite as a substitute for mercury in the catalytic hydrochlorination of acetylene. Nature Commun. 5, 3688 (2014).

  139. 139.

    , , , & Nitrogen-doped carbon nanomaterials as non-metal electrocatalysts for water oxidation. Nature Commun. 4, 2390 (2013).

  140. 140.

    , , & Nitrogen-doped graphene oxide quantum dots as photocatalysts for overall water-splitting under visible light illumination. Adv. Mater. 26, 3297–3303 (2014).

  141. 141.

    et al. N-doped monolayer graphene catalyst on silicon photocathode for hydrogen production. Energy Environ. Sci. 6, 3658–3664 (2013).

  142. 142.

    et al. Nitrogen-doped graphene foams as metal-free counter electrodes in high-performance dye-sensitized solar cells. Angew. Chem. Int. Ed. 51, 12124–12127 (2012).

  143. 143.

    et al. Metal-free efficient photocatalyst for stable visible water splitting via a two-electron pathway. Science 347, 970–974 (2015).

  144. 144.

    , , , & Fe-g-C3N4-catalyzed oxidation of benzene to phenol using hydrogen peroxide and visible light. J. Am. Chem. Soc. 131, 11658–11659 (2009).

  145. 145.

    et al. mpg-C3N4-catalyzed selective oxidation of alcohols using O2 and visible light. J. Am. Chem. Soc. 132, 16299–16301 (2010).

  146. 146.

    , , , & Graphitic carbon nitride as a metal-free catalyst for NO decomposition. Chem. Commun. 46, 6965–6967 (2010).

  147. 147.

    et al. Mechanistic insight into the synthesis of higher alcohols from syngas: the role of K promotion on MoS2 catalysts. ACS Catal. 3, 1634–1637 (2013).

  148. 148.

    & Density functional theory study of CO hydrogenation on a MoS2 surface. J. Phys. Chem. C 113, 5238–5243 (2009).

  149. 149.

    et al. Determination of the local chemical structure of graphene oxide and reduced graphene oxide. Adv. Mater. 22, 4467–4472 (2010).

Download references

Acknowledgements

We thank H.B. Li for help with drawing the structural models in Figs 1 and 4a, and the National Natural Science Foundation of China (grants 21321002, 21573220 and 21303191) and the strategic Priority Research Program of the Chinese Academy of Sciences (grant no. XDA09030100) for financial support.

Author information

Affiliations

  1. State Key Laboratory of Catalysis, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023, China

    • Dehui Deng
    • , Qiang Fu
    •  & Xinhe Bao
  2. School of Physics and Astronomy, University of Manchester, Oxford Road, M13 9PL Manchester, UK

    • K. S. Novoselov
  3. State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China

    • Nanfeng Zheng
    •  & Zhongqun Tian

Authors

  1. Search for Dehui Deng in:

  2. Search for K. S. Novoselov in:

  3. Search for Qiang Fu in:

  4. Search for Nanfeng Zheng in:

  5. Search for Zhongqun Tian in:

  6. Search for Xinhe Bao in:

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to K. S. Novoselov or Zhongqun Tian or Xinhe Bao.

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nnano.2015.340

Further reading