Highly Active 2D Layered MoS2-rGO Hybrids for Energy Conversion and Storage Applications

The development of efficient materials for the generation and storage of renewable energy is now an urgent task for future energy demand. In this report, molybdenum disulphide hollow sphere (MoS2-HS) and its reduced graphene oxide hybrid (rGO/MoS2-S) have been synthesized and explored for energy generation and storage applications. The surface morphology, crystallinity and elemental composition of the as-synthesized materials have been thoroughly analysed. Inspired by the fascinating morphology of the MoS2-HS and rGO/MoS2-S materials, the electrochemical performance towards hydrogen evolution and supercapacitor has been demonstrated. The rGO/MoS2-S shows enhanced gravimetric capacitance values (318 ± 14 Fg−1) with higher specific energy/power outputs (44.1 ± 2.1 Whkg−1 and 159.16 ± 7.0 Wkg−1) and better cyclic performances (82 ± 0.95% even after 5000 cycles). Further, a prototype of the supercapacitor in a coin cell configuration has been fabricated and demonstrated towards powering a LED. The unique balance of exposed edge site and electrical conductivity of rGO/MoS2-S shows remarkably superior HER performances with lower onset over potential (0.16 ± 0.05 V), lower Tafel slope (75 ± 4 mVdec−1), higher exchange current density (0.072 ± 0.023 mAcm−2) and higher TOF (1.47 ± 0.085 s−1) values. The dual performance of the rGO/MoS2-S substantiates the promising application for hydrogen generation and supercapacitor application of interest.

[1]  X. Lou,et al.  Defect‐Rich MoS2 Ultrathin Nanosheets with Additional Active Edge Sites for Enhanced Electrocatalytic Hydrogen Evolution , 2013, Advanced materials.

[2]  T. Jaramillo,et al.  Core-shell MoO3-MoS2 nanowires for hydrogen evolution: a functional design for electrocatalytic materials. , 2011, Nano letters.

[3]  H. Vrubel,et al.  Hydrogen evolution catalyzed by MoS3 and MoS2 particles , 2012 .

[4]  J. Baek,et al.  Graphene and molybdenum disulfide hybrids: synthesis and applications , 2015 .

[5]  Feihe Huang,et al.  Graphene-like MoS₂/graphene composites: cationic surfactant-assisted hydrothermal synthesis and electrochemical reversible storage of lithium. , 2013, Small.

[6]  Shuang Yuan,et al.  Advances and challenges for flexible energy storage and conversion devices and systems , 2014 .

[7]  Aneeya K. Samantara,et al.  Sandwiched graphene with nitrogen, sulphur co-doped CQDs: an efficient metal-free material for energy storage and conversion applications , 2015 .

[8]  Jihuai Wu,et al.  Facile one-step hydrothermal preparation of molybdenum disulfide/carbon composite for use in supercapacitor , 2015 .

[9]  Yutao Li,et al.  Facile Synthesis of MoS2/Reduced Graphene Oxide@Polyaniline for High-Performance Supercapacitors. , 2016, ACS applied materials & interfaces.

[10]  Jaesung Park,et al.  Anomalous excitonic resonance Raman effects in few-layered MoS2. , 2015, Nanoscale.

[11]  I. Chorkendorff,et al.  Biomimetic Hydrogen Evolution: MoS2 Nanoparticles as Catalyst for Hydrogen Evolution , 2005 .

[12]  Jayan Thomas,et al.  Supercapacitor electrode materials: nanostructures from 0 to 3 dimensions , 2015 .

[13]  Lei Zhang,et al.  A review of electrode materials for electrochemical supercapacitors. , 2012, Chemical Society reviews.

[14]  Guosong Hong,et al.  MoS2 nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction. , 2011, Journal of the American Chemical Society.

[15]  Kan Wang,et al.  Lattice strain effects on the optical properties of MoS2 nanosheets , 2014, Scientific Reports.

[16]  W. Ingler,et al.  Efficient Photochemical Water Splitting by a Chemically Modified n-TiO2 , 2002, Science.

[17]  A. Majumdar,et al.  Opportunities and challenges for a sustainable energy future , 2012, Nature.

[18]  W. Schreiner,et al.  Supercapacitor Electrodes Obtained by Directly Bonding 2D MoS2 on Reduced Graphene Oxide , 2014 .

[19]  Sreekumar Kurungot,et al.  Novel scalable synthesis of highly conducting and robust PEDOT paper for a high performance flexible solid supercapacitor , 2015 .

[20]  A. Okotrub,et al.  Charge Transfer in the MoS2/Carbon Nanotube Composite , 2011 .

[21]  John A. Turner,et al.  Sustainable Hydrogen Production , 2004, Science.

[22]  H. Fei,et al.  Edge‐Oriented MoS2 Nanoporous Films as Flexible Electrodes for Hydrogen Evolution Reactions and Supercapacitor Devices , 2014, Advanced materials.

[23]  Turner,et al.  A realizable renewable energy future , 1999, Science.

[24]  Xingzhong Zhao,et al.  In situ growth of double-layer MoO3/MoS2 film from MoS2 for hole-transport layers in organic solar cell , 2014 .

[25]  S. Kundu,et al.  Pt Nanoparticle Anchored Molecular Self-Assemblies of DNA: An Extremely Stable and Efficient HER Electrocatalyst with Ultralow Pt Content , 2016 .

[26]  N. Mahmood,et al.  Fabrication of zero to three dimensional nanostructured molybdenum sulfides and their electrochemical and photocatalytic applications. , 2016, Nanoscale.

[27]  Suresh Kannan Balasingam,et al.  Importance of hydrophilic pretreatment in the hydrothermal growth of amorphous molybdenum sulfide for hydrogen evolution catalysis. , 2015, Langmuir : the ACS journal of surfaces and colloids.

[28]  Liangbin Li,et al.  Molybdenum sulfide/graphene-carbon nanotube nanocomposite material for electrocatalytic applications in hydrogen evolution reactions , 2016, Nano Research.

[29]  Electrocatalytic Hydrogen Evolution Reaction on Edges of a Few Layer Molybdenum Disulfide Nanodots. , 2015, ACS applied materials & interfaces.

[30]  A. Wee,et al.  Amorphous Molybdenum Sulfide on Graphene-Carbon Nanotube Hybrids as Highly Active Hydrogen Evolution Reaction Catalysts. , 2016, ACS applied materials & interfaces.

[31]  Y. Bando,et al.  Supercapacitive energy storage performance of molybdenum disulfide nanosheets wrapped with microporous carbons , 2015 .

[32]  C. Rout,et al.  Supercapacitor electrodes based on layered tungsten disulfide-reduced graphene oxide hybrids synthesized by a facile hydrothermal method. , 2013, ACS applied materials & interfaces.

[33]  W. Xiao,et al.  Simple Synthesis of Molybdenum Disulfide/Reduced Graphene Oxide Composite Hollow Microspheres as Supercapacitor Electrode Material , 2016, Materials.

[34]  Thomas F. Jaramillo,et al.  Catalyzing the Hydrogen Evolution Reaction (HER) with Molybdenum Sulfide Nanomaterials , 2014 .

[35]  K. Krishnamoorthy,et al.  Growth, characterization and electrochemical properties of hierarchical CuO nanostructures for supercapacitor applications , 2013 .

[36]  M. Chhowalla Synthesis and Applications , 2016 .

[37]  Weitao Yang,et al.  Layer-dependent electrocatalysis of MoS2 for hydrogen evolution. , 2013, Nano letters.

[38]  Raymond J. Kopp,et al.  Energy Resources and Global Development , 2003, Science.

[39]  Li Zhang,et al.  Design of Architectures and Materials in In‐Plane Micro‐supercapacitors: Current Status and Future Challenges , 2017, Advanced materials.

[40]  Shihe Yang,et al.  Space-Confined Growth of MoS2 Nanosheets within Graphite: The Layered Hybrid of MoS2 and Graphene as an Active Catalyst for Hydrogen Evolution Reaction , 2014 .

[41]  Juanjuan Ding,et al.  High supercapacitor and adsorption behaviors of flower-like MoS2 nanostructures , 2014 .

[42]  Feng Li,et al.  Anchoring Hydrous RuO2 on Graphene Sheets for High‐Performance Electrochemical Capacitors , 2010 .

[43]  David Pech,et al.  3D RuO2 Microsupercapacitors with Remarkable Areal Energy , 2015, Advanced materials.

[44]  Z. Yin,et al.  MoS2 nanoflower-decorated reduced graphene oxide paper for high-performance hydrogen evolution reaction. , 2014, Nanoscale.

[45]  Changsheng Liu,et al.  Rapid synthesis of nitrogen-doped graphene for a lithium ion battery anode with excellent rate performance and super-long cyclic stability. , 2014, Physical chemistry chemical physics : PCCP.

[46]  Ib Chorkendorff,et al.  Molybdenum sulfides—efficient and viable materials for electro - and photoelectrocatalytic hydrogen evolution , 2012 .

[47]  Jin Wang,et al.  A Cake‐Style CoS2@MoS2/RGO Hybrid Catalyst for Efficient Hydrogen Evolution , 2017 .

[48]  Meryl D. Stoller,et al.  Review of Best Practice Methods for Determining an Electrode Material's Performance for Ultracapacitors , 2010 .

[49]  Charlie Tsai,et al.  Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies. , 2016, Nature materials.

[50]  H. Vrubel,et al.  Amorphous molybdenum sulfide films as catalysts for electrochemical hydrogen production in water , 2011 .

[51]  M. Dresselhaus,et al.  Alternative energy technologies , 2001, Nature.

[52]  W. S. Hummers,et al.  Preparation of Graphitic Oxide , 1958 .

[53]  Z. Wen,et al.  Constructing Highly Oriented Configuration by Few-Layer MoS2: Toward High-Performance Lithium-Ion Batteries and Hydrogen Evolution Reactions. , 2015, ACS nano.

[54]  Fei Meng,et al.  Enhanced hydrogen evolution catalysis from chemically exfoliated metallic MoS2 nanosheets. , 2013, Journal of the American Chemical Society.

[55]  Jakob Kibsgaard,et al.  Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. , 2012, Nature materials.

[56]  K. Ozoemena,et al.  Symmetric pseudocapacitors based on molybdenum disulfide (MoS2)-modified carbon nanospheres: correlating physicochemistry and synergistic interaction on energy storage , 2016 .

[57]  Hua Zhang,et al.  Multifunctional Architectures Constructing of PANI Nanoneedle Arrays on MoS2 Thin Nanosheets for High-Energy Supercapacitors. , 2015, Small.

[58]  Xueliang Sun,et al.  Ultrathin MoS2/Nitrogen‐Doped Graphene Nanosheets with Highly Reversible Lithium Storage , 2013 .

[59]  Jun Jin,et al.  Synthesis of Cu-MoS2/rGO hybrid as non-noble metal electrocatalysts for the hydrogen evolution reaction , 2015 .

[60]  Xinliang Feng,et al.  Hierarchical Transition‐Metal Dichalcogenide Nanosheets for Enhanced Electrocatalytic Hydrogen Evolution , 2015, Advanced materials.

[61]  Jie Yin,et al.  A Self‐Standing High‐Performance Hydrogen Evolution Electrode with Nanostructured NiCo2O4/CuS Heterostructures , 2015 .

[62]  Yongyao Xia,et al.  Electrochemical capacitors: mechanism, materials, systems, characterization and applications. , 2016, Chemical Society reviews.

[63]  Ling-Ling Wang,et al.  One-step preparation of layered molybdenum disulfide/multi-walled carbon nanotube composites for enhanced performance supercapacitor , 2014 .

[64]  R. Dryfe,et al.  Characterization of MoS2-Graphene Composites for High-Performance Coin Cell Supercapacitors. , 2015, ACS applied materials & interfaces.

[65]  Eider Goikolea,et al.  Review on supercapacitors: Technologies and materials , 2016 .

[66]  Lixia Yuan,et al.  Synthesis of hierarchical MoS2 and its electrochemical performance as an anode material for lithium-ion batteries , 2014 .

[67]  Xin Guo,et al.  A bulky and flexible electrocatalyst for efficient hydrogen evolution based on the growth of MoS2 nanoparticles on carbon nanofiber foam , 2015 .

[68]  G. Shi,et al.  Self-assembled graphene hydrogel via a one-step hydrothermal process. , 2010, ACS nano.

[69]  Koen Van Laer,et al.  Current status and future challenges , 2015 .