Chinese Science Bulletin, Volume 62 , Issue 27 : 3154-3172(2017) https://doi.org/10.1360/N972016-01409

Two-dimensional materials for electrocatalytic water splitting

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  • ReceivedDec 15, 2016
  • AcceptedFeb 27, 2017
  • PublishedApr 18, 2017


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图S1 酸性溶液中电极表面析氢反应机理图

图S2 MoS2边在催化HER反应中的作用

图S3 MoS2/CoSe2催化剂在HER反应中的应用

图S4 酸性和碱性溶液中析氧反应机理图

图S5 LDHs材料在催化OER反应中的应用

本文以上补充材料见网络版csb.scichina.com. 补充材料为作者提供的原始数据, 作者对其学术质量和内容负责.


[1] Graetz J. New approaches to hydrogen storage. Chem Soc Rev, 2009, 38: 73-82 CrossRef PubMed Google Scholar

[2] Carrasco J M, Franquelo L G, Bialasiewicz J T, et al. Power-Electronic Systems for the Grid Integration of Renewable Energy Sources: A Survey. IEEE Trans Ind Electron, 2006, 53: 1002-1016 CrossRef Google Scholar

[3] Baños R, Manzano-Agugliaro F, Montoya F G, et al. Optimization methods applied to renewable and sustainable energy: A review. Renew Sustain Energ Rev, 2011, 15: 1753-1766 CrossRef Google Scholar

[4] Barton J P, Infield D G. Energy Storage and Its Use With Intermittent Renewable Energy. IEEE Trans On Energ Conv, 2004, 19: 441-448 CrossRef Google Scholar

[5] van den Berg A W C, Areán C O. Materials for hydrogenstorage: current research trends and perspectives. Chem Commun, 2008, 305: 668-681 CrossRef Google Scholar

[6] Holladay J D, Hu J, King D L, et al. An overview of hydrogen production technologies. Catal Today, 2009, 139: 244-260 CrossRef Google Scholar

[7] Turner J, Sverdrup G, Mann M K, et al. Renewable hydrogen production. Int J Energ Res, 2008, 32: 379-407 CrossRef Google Scholar

[8] Zhang J, Xia Z, Dai L. Carbon-based electrocatalysts for advanced energy conversion and storage. Sci Adv, 2015, 1: e1500564-e1500564 CrossRef PubMed ADS Google Scholar

[9] Jiao Y, Zheng Y, Jaroniec M, et al. Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. Chem Soc Rev, 2015, 44: 2060-2086 CrossRef PubMed Google Scholar

[10] Li X, Hao X, Abudula A, et al. Nanostructured catalysts for electrochemical water splitting: current state and prospects. J Mater Chem A, 2016, 4: 11973-12000 CrossRef Google Scholar

[11] Chhowalla M, Shin H S, Eda G, et al. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat Chem, 2013, 5: 263-275 CrossRef PubMed ADS Google Scholar

[12] Geim A K, Novoselov K S. The rise of graphene. Nat Mater, 2007, 6: 183-191 CrossRef PubMed ADS Google Scholar

[13] Castro Neto A H, Guinea F, Peres N M R, et al. The electronic properties of graphene. Rev Mod Phys, 2009, 81: 109-162 CrossRef ADS arXiv Google Scholar

[14] Geim A K. Graphene: Status and Prospects. Science, 2009, 324: 1530-1534 CrossRef PubMed ADS arXiv Google Scholar

[15] Zhong J H, Zhang J, Jin X, et al. Quantitative Correlation between Defect Density and Heterogeneous Electron Transfer Rate of Single Layer Graphene. J Am Chem Soc, 2014, 136: 16609-16617 CrossRef PubMed Google Scholar

[16] Li L, Reich S, Robertson J. Defect energies of graphite: Density-functional calculations. Phys Rev B, 2005, 72: 184109 CrossRef ADS Google Scholar

[17] Banhart F, Kotakoski J, Krasheninnikov A V. Structural Defects in Graphene. ACS Nano, 2011, 5: 26-41 CrossRef PubMed Google Scholar

[18] Yang S, Zhi L, Tang K, 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, 2012, 22: 3634-3640 CrossRef Google Scholar

[19] Wang H, Wang Q, Cheng Y, et al. Doping Monolayer Graphene with Single Atom Substitutions. Nano Lett, 2012, 12: 141-144 CrossRef PubMed ADS Google Scholar

[20] Liu Z W, Peng F, Wang H J, et al. Phosphorus-Doped Graphite Layers with High Electrocatalytic Activity for the O2 Reduction in an Alkaline Medium. Angew Chem Int Ed, 2011, 50: 3257-3261 CrossRef PubMed Google Scholar

[21] Yang Z, Yao Z, Li G, et al. Sulfur-Doped Graphene as an Efficient Metal-free Cathode Catalyst for Oxygen Reduction. ACS Nano, 2012, 6: 205-211 CrossRef PubMed Google Scholar

[22] Jiao Y, Zheng Y, Jaroniec M, et al. Origin of the Electrocatalytic Oxygen Reduction Activity of Graphene-Based Catalysts: A Roadmap to Achieve the Best Performance. J Am Chem Soc, 2014, 136: 4394-4403 CrossRef PubMed Google Scholar

[23] Deng D, Pan X, Yu L, et al. Toward N-Doped Graphene via Solvothermal Synthesis. Chem Mater, 2011, 23: 1188-1193 CrossRef Google Scholar

[24] Dai J, Yuan J, Giannozzi P. Gas adsorption on graphene doped with B, N, Al, and S: A theoretical study. Appl Phys Lett, 2009, 95: 232105 CrossRef ADS Google Scholar

[25] Cretu O, Krasheninnikov A V, Rodríguez-Manzo J A, et al. Migration and Localization of Metal Atoms on Strained Graphene. Phys Rev Lett, 2010, 105: 196102 CrossRef PubMed ADS Google Scholar

[26] Zhao J, Deng Q, Bachmatiuk A, et al. Free-Standing Single-Atom-Thick Iron Membranes Suspended in Graphene Pores. Science, 2014, 343: 1228-1232 CrossRef PubMed ADS Google Scholar

[27] Panchakarla L S, Subrahmanyam K S, Saha S K, et al. Synthesis, structure and properties of boron and nitrogen doped graphene. Adv Mater, 2009, 21: 4726–4730. Google Scholar

[28] Wei D, Liu Y, Wang Y, et al. Synthesis of N-Doped Graphene by Chemical Vapor Deposition and Its Electrical Properties. Nano Lett, 2009, 9: 1752-1758 CrossRef PubMed ADS Google Scholar

[29] Wu M, Cao C, Jiang J Z. Light non-metallic atom (B, N, O and F)-doped graphene: a first-principles study. Nanotechnology, 2010, 21: 505202 CrossRef PubMed ADS Google Scholar

[30] Sofo J O, Chaudhari A S, Barber G D. Graphane: A two-dimensional hydrocarbon. Phys Rev B, 2007, 75: 153401 CrossRef ADS Google Scholar

[31] Poh H L, Šimek P, Sofer Z, et al. Halogenation of Graphene with Chlorine, Bromine, or Iodine by Exfoliation in a Halogen Atmosphere. Chem Eur J, 2013, 19: 2655-2662 CrossRef PubMed Google Scholar

[32] Liu F, Sun J, Zhu L, et al. Sulfated graphene as an efficient solid catalyst for acid-catalyzed liquid reactions. J Mater Chem, 2012, 22: 5495-5502 CrossRef Google Scholar

[33] Sokolov D A, Shepperd K R, Orlando T M. Formation of Graphene Features from Direct Laser-Induced Reduction of Graphite Oxide. J Phys Chem Lett, 2010, 1: 2633-2636 CrossRef Google Scholar

[34] Ouyang Y, Ling C, Chen Q, et al. Activating Inert Basal Planes of MoS2 for Hydrogen Evolution Reaction through the Formation of Different Intrinsic Defects. Chem Mater, 2016, 28: 4390-4396 CrossRef Google Scholar

[35] Ye G, Gong Y, Lin J, et al. Defects Engineered Monolayer MoS2 for Improved Hydrogen Evolution Reaction. Nano Lett, 2016, 16: 1097-1103 CrossRef PubMed ADS Google Scholar

[36] Yin Y, Han J, Zhang Y, et al. Contributions of Phase, Sulfur Vacancies, and Edges to the Hydrogen Evolution Reaction Catalytic Activity of Porous Molybdenum Disulfide Nanosheets. J Am Chem Soc, 2016, 138: 7965-7972 CrossRef PubMed Google Scholar

[37] Zhang G, Wang J, Wu Z, et al. Shape-Dependent Defect Structures of Monolayer MoS2 Crystals Grown by Chemical Vapor Deposition. ACS Appl Mater Interfaces, 2017, 9: 763-770 CrossRef Google Scholar

[38] Zhou J, Fang G, Pan A, et al. Oxygen-Incorporated MoS2 Nanosheets with Expanded Interlayers for Hydrogen Evolution Reaction and Pseudocapacitor Applications. ACS Appl Mater Interfaces, 2016, 8: 33681-33689 CrossRef Google Scholar

[39] Chua X J, Luxa J, Eng A Y S, et al. Negative Electrocatalytic Effects of p-Doping Niobium and Tantalum on MoS2and WS2 for the Hydrogen Evolution Reaction and Oxygen Reduction Reaction. ACS Catal, 2016, 6: 5724-5734 CrossRef Google Scholar

[40] Gao G, Sun Q, Du A. Activating Catalytic Inert Basal Plane of Molybdenum Disulfide to Optimize Hydrogen Evolution Activity via Defect Doping and Strain Engineering. J Phys Chem C, 2016, 120: 16761-16766 CrossRef Google Scholar

[41] Guo J, Zhu H, Sun Y, et al. Doping MoS 2 with Graphene Quantum Dots: Structural and Electrical Engineering towards Enhanced Electrochemical Hydrogen Evolution. ElectroChim Acta, 2016, 211: 603-610 CrossRef Google Scholar

[42] Ma L, Xu L, Xu X, et al. Cobalt-doped edge-rich MoS2/nitrogenated graphene composite as an electrocatalyst for hydrogen evolution reaction. Mater Sci Eng-B, 2016, 212: 30-38 CrossRef Google Scholar

[43] Ma X, Li J, An C, et al. Ultrathin Co(Ni)-doped MoS2 nanosheets as catalytic promoters enabling efficient solar hydrogen production. Nano Res, 2016, 9: 2284-2293 CrossRef Google Scholar

[44] Pham V P, Yeom G Y. Recent Advances in Doping of Molybdenum Disulfide: Industrial Applications and Future Prospects. Adv Mater, 2016, 28: 9024-9059 CrossRef PubMed Google Scholar

[45] Oh H M, Jeong H, Han G H, et al. Modulating Electronic Properties of Monolayer MoS2via Electron-Withdrawing Functional Groups of Graphene Oxide. ACS Nano, 2016, 10: 10446-10453 CrossRef Google Scholar

[46] Tang Q, Jiang D. Stabilization and Band-Gap Tuning of the 1T-MoS2 Monolayer by Covalent Functionalization. Chem Mater, 2015, 27: 3743-3748 CrossRef Google Scholar

[47] Zhou L, He B, Yang Y, et al. Facile approach to surface functionalized MoS2 nanosheets. RSC Adv, 2014, 4: 32570-32578 CrossRef Google Scholar

[48] Voiry D, Yang J, Chhowalla M. Recent Strategies for Improving the Catalytic Activity of 2D TMD Nanosheets Toward the Hydrogen Evolution Reaction. Adv Mater, 2016, 28: 6197-6206 CrossRef PubMed Google Scholar

[49] Sathe B R, Zou X, Asefa T. Metal-free B-doped graphene with efficient electrocatalytic activity for hydrogen evolution reaction. Catal Sci Technol, 2014, 4: 2023-2030 CrossRef Google Scholar

[50] Ito Y, Cong W, Fujita T, et al. High Catalytic Activity of Nitrogen and Sulfur Co-Doped Nanoporous Graphene in the Hydrogen Evolution Reaction. Angew Chem Int Ed, 2015, 54: 2131-2136 CrossRef PubMed Google Scholar

[51] Zheng Y, Jiao Y, Li L H, et al. Toward Design of Synergistically Active Carbon-Based Catalysts for Electrocatalytic Hydrogen Evolution. ACS Nano, 2014, 8: 5290-5296 CrossRef PubMed Google Scholar

[52] Qiu H J, Ito Y, Cong W, et al. Nanoporous Graphene with Single-Atom Nickel Dopants: An Efficient and Stable Catalyst for Electrochemical Hydrogen Production. Angew Chem Int Ed, 2015, 54: 14031-14035 CrossRef PubMed Google Scholar

[53] Deng J, Ren P, Deng D, et al. Enhanced Electron Penetration through an Ultrathin Graphene Layer for Highly Efficient Catalysis of the Hydrogen Evolution Reaction. Angew Chem Int Ed, 2015, 54: 2100-2104 CrossRef PubMed Google Scholar

[54] Yang Y, Lun Z, Xia G, et al. Non-precious alloy encapsulated in nitrogen-doped graphene layers derived from MOFs as an active and durable hydrogen evolution reaction catalyst. Energ Environ Sci, 2015, 8: 3563-3571 CrossRef Google Scholar

[55] Liu Y, Yu G, Li G D, et al. Coupling Mo2 C with Nitrogen-Rich Nanocarbon Leads to Efficient Hydrogen-Evolution Electrocatalytic Sites. Angew Chem Int Ed, 2015, 54: 10752-10757 CrossRef PubMed Google Scholar

[56] Ma R, Zhou Y, Chen Y, et al. Ultrafine Molybdenum Carbide Nanoparticles Composited with Carbon as a Highly Active Hydrogen-Evolution Electrocatalyst. Angew Chem Int Ed, 2015, 54: 14723-14727 CrossRef PubMed Google Scholar

[57] Li J S, Wang Y, Liu C H, et al. Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution. Nat Commun, 2016, 7: 11204 CrossRef PubMed ADS Google Scholar

[58] Zheng Y, Jiao Y, Zhu Y, et al. Hydrogen evolution by a metal-free electrocatalyst. Nat Commun, 2014, 5: 3783. Google Scholar

[59] Duan J, Chen S, Jaroniec M, et al. Porous C3N4 Nanolayers@N-Graphene Films as Catalyst Electrodes for Highly Efficient Hydrogen Evolution. ACS Nano, 2015, 9: 931-940 CrossRef PubMed Google Scholar

[60] Zhao Y, Zhao F, Wang X, et al. Graphitic Carbon Nitride Nanoribbons: Graphene-Assisted Formation and Synergic Function for Highly Efficient Hydrogen Evolution. Angew Chem Int Ed, 2014, 53: 13934-13939 CrossRef PubMed Google Scholar

[61] Bhowmik T, Kundu M K, Barman S. Palladium Nanoparticle–Graphitic Carbon Nitride Porous Synergistic Catalyst for Hydrogen Evolution/Oxidation Reactions over a Broad Range of pH and Correlation of Its Catalytic Activity with Measured Hydrogen Binding Energy. ACS Catal, 2016, 6: 1929-1941 CrossRef Google Scholar

[62] Feng J J, Chen L X, Song P, et al. Bimetallic AuPd nanoclusters supported on graphitic carbon nitride: One-pot synthesis and enhanced electrocatalysis for oxygen reduction and hydrogen evolution. Int J Hydrogen Energ, 2016, 41: 8839-8846 CrossRef Google Scholar

[63] Kundu M K, Bhowmik T, Barman S. Gold aerogel supported on graphitic carbon nitride: an efficient electrocatalyst for oxygen reduction reaction and hydrogen evolution reaction. J Mater Chem A, 2015, 3: 23120-23135 CrossRef Google Scholar

[64] Pei Z, Zhao J, Huang Y, et al. Toward enhanced activity of a graphitic carbon nitride-based electrocatalyst in oxygen reduction and hydrogen evolution reactions via atomic sulfur doping. J Mater Chem A, 2016, 4: 12205-12211 CrossRef Google Scholar

[65] Kibsgaard J, Chen Z, Reinecke B N, et al. Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. Nat Mater, 2012, 11: 963-969 CrossRef PubMed ADS Google Scholar

[66] Xie J, Zhang H, Li S, et al. Defect-Rich MoS2 Ultrathin Nanosheets with Additional Active Edge Sites for Enhanced Electrocatalytic Hydrogen Evolution. Adv Mater, 2013, 25: 5807-5813 CrossRef PubMed Google Scholar

[67] Xie J, Zhang J, Li S, et al. Controllable Disorder Engineering in Oxygen-Incorporated MoS2 Ultrathin Nanosheets for Efficient Hydrogen Evolution. J Am Chem Soc, 2013, 135: 17881-17888 CrossRef PubMed Google Scholar

[68] Lin L, Miao N, Wen Y, et al. Sulfur-Depleted Monolayered Molybdenum Disulfide Nanocrystals for Superelectrochemical Hydrogen Evolution Reaction. ACS Nano, 2016, 10: 8929-8937 CrossRef Google Scholar

[69] Deng J, Li H, Xiao J, et al. Triggering the electrocatalytic hydrogen evolution activity of the inert two-dimensional MoS2 surface via single-atom metal doping. Energ Environ Sci, 2015, 8: 1594-1601 CrossRef Google Scholar

[70] Li Y, Wang H, Xie L, et al. MoS2 Nanoparticles Grown on Graphene: An Advanced Catalyst for the Hydrogen Evolution Reaction. J Am Chem Soc, 2011, 133: 7296-7299 CrossRef PubMed Google Scholar

[71] Gao M R, Liang J X, Zheng Y R, et al. An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation. Nat Commun, 2015, 6: 5982 CrossRef PubMed ADS Google Scholar

[72] Lukowski M A, Daniel A S, English C R, et al. Highly active hydrogen evolution catalysis from metallic WS2 nanosheets. Energ Environ Sci, 2014, 7: 2608-2613 CrossRef Google Scholar

[73] Tian J, Liu Q, Asiri A M, et al. Ultrathin Graphitic C3N4 Nanosheets/Graphene Composites: Efficient Organic Electrocatalyst for Oxygen Evolution Reaction. ChemSusChem, 2014, 7: 2125-2130 CrossRef PubMed Google Scholar

[74] Ma T Y, Dai S, Jaroniec M, et al. Graphitic Carbon Nitride Nanosheet-Carbon Nanotube Three-Dimensional Porous Composites as High-Performance Oxygen Evolution Electrocatalysts. Angew Chem Int Ed, 2014, 53: 7281-7285 CrossRef PubMed Google Scholar

[75] Ma T Y, Cao J L, Jaroniec M, et al. Interacting Carbon Nitride and Titanium Carbide Nanosheets for High-Performance Oxygen Evolution. Angew Chem Int Ed, 2016, 55: 1138-1142 CrossRef PubMed Google Scholar

[76] He B, Chen X, Lu J, et al. One-pot Synthesized Co/Co3O4 -N-Graphene Composite as Electrocatalyst for Oxygen Reduction Reaction and Oxygen Evolution Reaction. Electroanalysis, 2016, 28: 2435-2443 CrossRef Google Scholar

[77] Liu S, Zhang H, Zhao Q, et al. Metal-organic framework derived nitrogen-doped porous carbon@graphene sandwich-like structured composites as bifunctional electrocatalysts for oxygen reduction and evolution reactions. Carbon, 2016, 106: 74-83 CrossRef Google Scholar

[78] Zhao M, Li X, Song L, et al. Substrate-Assisted Deposition of Metal Oxides on Three-Dimensional Porous Reduced Graphene Oxide Networks as Bifunctional Hybrid Electrocatalysts for the Oxygen Evolution and Oxygen Reduction Reactions. ChemCatChem, 2016, 8: 2808-2816 CrossRef Google Scholar

[79] Zhang S, Yu X, Yan F, et al. N-Doped graphene-supported Co@CoO core–shell nanoparticles as high-performance bifunctional electrocatalysts for overall water splitting. J Mater Chem A, 2016, 4: 12046-12053 CrossRef Google Scholar

[80] Zou X, Goswami A, Asefa T. Efficient Noble Metal-Free (Electro)Catalysis of Water and Alcohol Oxidations by Zinc–Cobalt Layered Double Hydroxide. J Am Chem Soc, 2013, 135: 17242-17245 CrossRef PubMed Google Scholar

[81] Song F, Hu X. Ultrathin Cobalt–Manganese Layered Double Hydroxide Is an Efficient Oxygen Evolution Catalyst. J Am Chem Soc, 2014, 136: 16481-16484 CrossRef PubMed Google Scholar

[82] Ping J, Wang Y, Lu Q, et al. Self-Assembly of Single-Layer CoAl-Layered Double Hydroxide Nanosheets on 3D Graphene Network Used as Highly Efficient Electrocatalyst for Oxygen Evolution Reaction. Adv Mater, 2016, 28: 7640-7645 CrossRef PubMed Google Scholar

[83] Tang D, Liu J, Wu X, et al. Carbon Quantum Dot/NiFe Layered Double-Hydroxide Composite as a Highly Efficient Electrocatalyst for Water Oxidation. ACS Appl Mater Interfaces, 2014, 6: 7918-7925 CrossRef PubMed Google Scholar

[84] Long X, Li J, Xiao S, et al. A Strongly Coupled Graphene and FeNi Double Hydroxide Hybrid as an Excellent Electrocatalyst for the Oxygen Evolution Reaction. Angew Chem Int Ed, 2014, 53: 7584-7588 CrossRef PubMed Google Scholar

[85] Su J, Xia G, Li R, et al. Co3 ZnC/Co nano heterojunctions encapsulated in N-doped graphene layers derived from PBAs as highly efficient bi-functional OER and ORR electrocatalysts. J Mater Chem A, 2016, 4: 9204-9212 CrossRef Google Scholar

[86] Yu X Y, Feng Y, Guan B, et al. Carbon coated porous nickel phosphides nanoplates for highly efficient oxygen evolution reaction. Energ Environ Sci, 2016, 9: 1246-1250 CrossRef Google Scholar

[87] Cui X, Ren P, Deng D, et al. Single layer graphene encapsulating non-precious metals as high-performance electrocatalysts for water oxidation. Energ Environ Sci, 2016, 9: 123-129 CrossRef Google Scholar

[88] Nørskov J K, Bligaard T, Logadottir A, et al. Trends in the Exchange Current for Hydrogen Evolution. J Electrochem Soc, 2005, 152: J23 CrossRef Google Scholar

[89] Li Y, Wang J, Tian X, et al. Carbon doped molybdenum disulfide nanosheets stabilized on graphene for the hydrogen evolution reaction with high electrocatalytic ability. Nanoscale, 2016, 8: 1676-1683 CrossRef PubMed ADS Google Scholar

[90] Morales-Guio C G, Stern L A, Hu X. Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. Chem Soc Rev, 2014, 43: 6555-6569 CrossRef PubMed Google Scholar

[91] Lu Q, Hutchings G S, Yu W, et al. Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution. Nat Commun, 2015, 6: 6567 CrossRef PubMed ADS Google Scholar

[92] Conway B E, Tilak B V. Interfacial processes involving electrocatalytic evolution and oxidation of H2, and the role of chemisorbed H. ElectroChim Acta, 2002, 47: 3571-3594 CrossRef Google Scholar

[93] Zheng Y, Jiao Y, Jaroniec M, et al. Advancing the Electrochemistry of the Hydrogen-Evolution Reaction through Combining Experiment and Theory. Angew Chem Int Ed, 2015, 54: 52-65 CrossRef PubMed Google Scholar

[94] Parsons R. The rate of electrolytic hydrogen evolution and the heat of adsorption of hydrogen. Trans Faraday Soc, 1958, 54: 1053-1063 CrossRef Google Scholar

[95] Zhang J, Qu L, Shi G, et al. N,P-Codoped Carbon Networks as Efficient Metal-free Bifunctional Catalysts for Oxygen Reduction and Hydrogen Evolution Reactions. Angew Chem Int Ed, 2016, 55: 2230-2234 CrossRef PubMed Google Scholar

[96] Deng D, Novoselov K S, Fu Q, et al. Catalysis with two-dimensional materials and their heterostructures. Nat Nanotech, 2016, 11: 218-230 CrossRef PubMed ADS Google Scholar

[97] Deng D, Yu L, Chen X, et al. Iron Encapsulated within Pod-like Carbon Nanotubes for Oxygen Reduction Reaction. Angew Chem Int Ed, 2013, 52: 371-375 CrossRef PubMed Google Scholar

[98] Deng J, Ren P, Deng D, et al. Highly active and durable non-precious-metal catalysts encapsulated in carbon nanotubes for hydrogen evolution reaction. Energ Environ Sci, 2014, 7: 1919-1923 CrossRef Google Scholar

[99] Song C. An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel. Catal Today, 2003, 86: 211-263 CrossRef Google Scholar

[100] Raybaud P, Hafner J, Kresse G, et al. Structure, Energetics, and Electronic Properties of the Surface of a Promoted MoS2 Catalyst: An ab Initio Local Density Functional Study. J Catal, 2000, 190: 128-143 CrossRef Google Scholar

[101] Hinnemann B, Moses P G, Bonde J, et al. Biomimetic Hydrogen Evolution:  MoS2 Nanoparticles as Catalyst for Hydrogen Evolution. J Am Chem Soc, 2005, 127: 5308-5309 CrossRef PubMed Google Scholar

[102] Bonde J, Moses P G, Jaramillo T F, et al. Hydrogen evolution on nano-particulate transition metal sulfides. Faraday Discuss, 2009, 140: 219-231 CrossRef ADS Google Scholar

[103] Jaramillo T F, Jørgensen K P, Bonde J, et al. Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts. Science, 2007, 317: 100-102 CrossRef PubMed ADS Google Scholar

[104] Deng J, Li H, Wang S, et al. Multiscale structural and electronic control of molybdenum disulfide foam for highly efficient hydrogen production. Nat Commun, 2017, 8: 14430 CrossRef PubMed ADS Google Scholar

[105] Voiry D, Yamaguchi H, Li J, et al. Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution. Nat Mater, 2013, 12: 850-855 CrossRef PubMed ADS arXiv Google Scholar

[106] Merki D, Hu X. Recent developments of molybdenum and tungsten sulfides as hydrogen evolution catalysts. Energ Environ Sci, 2011, 4: 3878-3888 CrossRef Google Scholar

[107] Laursen A B, Kegnæs S, Dahl S, et al. Molybdenum sulfides—efficient and viable materials for electro - and photoelectrocatalytic hydrogen evolution. Energ Environ Sci, 2012, 5: 5577-5591 CrossRef Google Scholar

[108] Koper M T M. Thermodynamic theory of multi-electron transfer reactions: Implications for electrocatalysis. J ElectroAnal Chem, 2011, 660: 254-260 CrossRef Google Scholar

[109] Fabbri E, Habereder A, Waltar K, et al. Developments and perspectives of oxide-based catalysts for the oxygen evolution reaction. Catal Sci Technol, 2014, 4: 3800-3821 CrossRef Google Scholar

[110] Bajdich M, García-Mota M, Vojvodic A, et al. Theoretical Investigation of the Activity of Cobalt Oxides for the Electrochemical Oxidation of Water. J Am Chem Soc, 2013, 135: 13521-13530 CrossRef PubMed Google Scholar

[111] Suen N T, Hung S F, Quan Q, et al. Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives. Chem Soc Rev, 2017, 46: 337-365 CrossRef PubMed Google Scholar

[112] Fan G, Li F, Evans D G, et al. Catalytic applications of layered double hydroxides: recent advances and perspectives. Chem Soc Rev, 2014, 43: 7040-7066 CrossRef PubMed Google Scholar

[113] Scavetta E, Berrettoni M, Giorgetti M, et al. Electrochemical characterisation of Ni/AlX hydrotalcites and their electrocatalytic behaviour. ElectroChim Acta, 2002, 47: 2451-2461 CrossRef Google Scholar

[114] Yu X, Zhang M, Yuan W, et al. A high-performance three-dimensional Ni–Fe layered double hydroxide/graphene electrode for water oxidation. J Mater Chem A, 2015, 3: 6921-6928 CrossRef Google Scholar

[115] Yang Q, Li T, Lu Z, et al. Hierarchical construction of an ultrathin layered double hydroxide nanoarray for highly-efficient oxygen evolution reaction. Nanoscale, 2014, 6: 11789-11794 CrossRef PubMed ADS Google Scholar

[116] Vlamidis Y, Scavetta E, Gazzano M, et al. Iron vs Aluminum Based Layered Double Hydroxides as Water Splitting Catalysts. ElectroChim Acta, 2016, 188: 653-660 CrossRef Google Scholar

[117] Song F, Hu X. Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis. Nat Commun, 2014, 5: 4477. Google Scholar

[118] Lu Z, Xu W, Zhu W, et al. Three-dimensional NiFe layered double hydroxide film for high-efficiency oxygen evolution reaction. Chem Commun, 2014, 50: 6479-6482 CrossRef PubMed Google Scholar

[119] Li Z, Shao M, An H, et al. Fast electrosynthesis of Fe-containing layered double hydroxide arrays toward highly efficient electrocatalytic oxidation reactions. Chem Sci, 2015, 6: 6624-6631 CrossRef Google Scholar

[120] Jiang J, Zhang A, Li L, et al. Nickel–cobalt layered double hydroxide nanosheets as high-performance electrocatalyst for oxygen evolution reaction. J Power Sources, 2015, 278: 445-451 CrossRef ADS Google Scholar

[121] Hou Y, Lohe M R, Zhang J, et al. Vertically oriented cobalt selenide/NiFe layered-double-hydroxide nanosheets supported on exfoliated graphene foil: an efficient 3D electrode for overall water splitting. Energ Environ Sci, 2016, 9: 478-483 CrossRef Google Scholar

[122] Lu Z, Qian L, Tian Y, et al. Ternary NiFeMn layered double hydroxides as highly-efficient oxygen evolution catalysts. Chem Commun, 2016, 52: 908-911 CrossRef PubMed Google Scholar

[123] Long X, Xiao S, Wang Z, et al. Co intake mediated formation of ultrathin nanosheets of transition metal LDH—an advanced electrocatalyst for oxygen evolution reaction. Chem Commun, 2015, 51: 1120-1123 CrossRef PubMed Google Scholar

[124] Feng Y, Zhang H, Fang L, et al. Uniquely Monodispersing NiFe Alloyed Nanoparticles in Three-Dimensional Strongly Linked Sandwiched Graphitized Carbon Sheets for High-Efficiency Oxygen Evolution Reaction. ACS Catal, 2016, 6: 4477-4485 CrossRef Google Scholar

  • Figure 1

    (Color online) Schematics of graphene structures and their heterostructures (a), TMDs (b), g-C3N4 (c) and LDHs (d)

  • Figure 2

    (a) Relationship between j0 and ΔGH* under assumption of a Langmuir adsorption model. (b) Relationship between j0 and ΔGH* for HER on the surface of various metals, alloy compounds, and non-metallic materials[93]

  • Figure 3

    (Color online) (a), (b) HRTEM images of CoNi@NC, showing the graphene shells and encapsulated metal nanoparticles. (c) Schematic illustration of the CoNi@NC structure shown in (b). (d) HER polarization curves for CoNi@NC and other samples prepared at different temperatures. (e) Volcano plot of the polarized current versus ΔGH* for different samples[53]

  • Figure 4

    (Color online) TEM (a), HRTEM (b) and STEM (c) images of Mo2C@NPC/NPRGO. (d) Polarization curves of Mo2C@NPC/NPRGO and other samples[57]. Scale bars: (a) 100 nm; (b) 5 nm; (c) 50 nm

  • Figure 5

    (Color online) (a) SEM image of the inside structure of PCN@N-graphene film. (b) Polarization curves of PCN@N-graphene and other samples[59]. (c) TEM image showing the mesoporous structure of the SCN-MPC sample[64]. (d) LSV polarization curves of Pd-CNx, Pt/C, Pd/C, and g-CNx[61]

  • Figure 6

    (Color online) (a) Schematic illustration of the electrocatalytic water-splitting by S-depleted MoS1.65 NCs. (b) HRTEM image of the S-depleted MoS1.65 NCs. (c) Polarization curves of S-depleted MoS1.65NCs and other samples[68]. (d) HAADF-STEM image of Pt-MoS2 showing that the single Pt atoms uniformly disperse in the 2D MoS2 plane. (e) Magnified domain with dashed rectangle in (d) showing a honeycomb arrangement of MoS2, and the single Pt atoms occupying the exact positions of the Mo atoms (marked by arrows). (f) HER polarization curves for Pt-MoS2 in comparison with other samples[69]

  • Figure 7

    (Color online) (a) HRSTEM images of an as-exfoliated 1T-WS2 monolayer. Scale bar: 1 nm. (b) Polarization curves of as-exfoliated 1T-WS2 and other samples. (c) The variation in current density versus time of 1T-WS2 electrode operation showing that the current density remains constant over the tested period[105]. (d) HRTEM of the exfoliated 1T-WS2 nanosheets. (e) Polarization curves comparing the high-performance HER catalysis from 1T-WS2 nanosheets with other catalysts[72]

  • Figure 8

    (Color online) (a) SEM image of FeNi-GO LDHs. (b) Polarization curves of FeNi-rGO LDH and other samples[84]. (c) SEM image of NiFe-LDH NP film. Inset: cross-view SEM image and typical TEM image. Scale bar: 100 nm. (d) Polarization curves of NiFe-LDH and other catalysts[118]

  • Figure 9

    (Color online) (a) Schematic illustration of the synthesis process of M@NCs from metal-containing precursors and SBA-15. (b), (c) HRTEM images of FeNi@NC. (d) OER polarization curves for M@NCs in comparison with other samples. (e) The calculated negative overpotential against the ΔG(O*)−ΔG(HO*) on different catalysts[87]

  • 在中性及碱性条件下, 由于溶液中氢离子浓度较低,


  • Table 1   2D materials and their heterostructures for electrocatalytic water splitting




    10 mA/cm2时的过

    电势(mV vs. RHE)







    0.5 mol/L H2SO4




    N, S共掺杂三维(3D)纳米多孔


    0.5 mol/L H2SO4





    N, P共掺杂碳网络

    0.5 mol/L H2SO4/0.1 mol/L






    0.5 mol/L H2SO4






    0.1 mol/L H2SO4






    0.5 mol/L H2SO4






    0.5 mol/L H2SO4/0.1 mol/L

    磷酸缓冲液/1 mol/L KOH


    60 (0.5 mol/L





    0.5 mol/L H2SO4





    Mo2C@N, P共掺杂碳/N, P共


    0.5 mol/L H2SO4







    0.5 mol/L H2SO4






    0.5 mol/L H2SO4






    0.5 mol/L H2SO4





    Pd-CNx 复合物

    0.5 mol/L H2SO4






    0.5 mol/L H2SO4





    0.5 mol/L H2SO4






    0.5 mol/L H2SO4







    0.5 mol/L H2SO4






    0.5 mol/L H2SO4






    0.5 mol/L H2SO4






    0.5 mol/L H2SO4





    0.1 mol/L H2SO4






    0.5 mol/L H2SO4





    0.5 mol/L H2SO4







    0.5 mol/L H2SO4







    0.1 mol/L KOH






    0.1 mol/L KOH






    0.1 mol/L KOH







    0.1 mol/L NaOH






    0.1 mol/L KOH







    0.1 mol/L NaOH






    1 mol/L KOH







    0.1 mol/L KOH



    CoMn LDH

    1 mol/L KOH






    1 mol/L KOH






    1 mol/L KOH






    1 mol/L KOH







    1 mol/L KOH






    1 mol/L KOH






    1 mol/L NaOH