Liquid-Phase Exfoliated Indium-Selenide Flakes and Their Application in Hydrogen Evolution Reaction.

Single- and few-layered InSe flakes are produced by the liquid-phase exfoliation of β-InSe single crystals in 2-propanol, obtaining stable dispersions with a concentration as high as 0.11 g L-1 . Ultracentrifugation is used to tune the morphology, i.e., the lateral size and thickness of the as-produced InSe flakes. It is demonstrated that the obtained InSe flakes have maximum lateral sizes ranging from 30 nm to a few micrometers, and thicknesses ranging from 1 to 20 nm, with a maximum population centered at ≈5 nm, corresponding to 4 Se-In-In-Se quaternary layers. It is also shown that no formation of further InSe-based compounds (such as In2 Se3 ) or oxides occurs during the exfoliation process. The potential of these exfoliated-InSe few-layer flakes as a catalyst for the hydrogen evolution reaction (HER) is tested in hybrid single-walled carbon nanotubes/InSe heterostructures. The dependence of the InSe flakes' morphologies, i.e., surface area and thickness, on the HER performances is highlighted, achieving the best efficiencies with small flakes offering predominant edge effects. The theoretical model unveils the origin of the catalytic efficiency of InSe flakes, and correlates the catalytic activity to the Se vacancies at the edge of the flakes.

[1]  A. E. Del Río Castillo,et al.  Engineered MoSe2‐Based Heterostructures for Efficient Electrochemical Hydrogen Evolution Reaction , 2018, 1903.08951.

[2]  Jianxin Zhong,et al.  High‐Performance Photo‐Electrochemical Photodetector Based on Liquid‐Exfoliated Few‐Layered InSe Nanosheets with Enhanced Stability , 2018 .

[3]  Alberto Ansaldo,et al.  Exfoliation of Few-Layer Black Phosphorus in Low-Boiling-Point Solvents and Its Application in Li-Ion Batteries , 2018, 1805.02486.

[4]  L. Caputi,et al.  The Advent of Indium Selenide: Synthesis, Electronic Properties, Ambient Stability and Applications , 2017, Nanomaterials.

[5]  Omid Kavehei,et al.  A liquid metal reaction environment for the room-temperature synthesis of atomically thin metal oxides , 2017, Science.

[6]  Stefan Kaskel,et al.  Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2 , 2017, Nature Communications.

[7]  L. Gu,et al.  Two-dimensional metallic tantalum disulfide as a hydrogen evolution catalyst , 2017, Nature Communications.

[8]  Wenping Sun,et al.  Nanostructured Metal Chalcogenides for Energy Storage and Electrocatalysis , 2017 .

[9]  David H. K. Jackson,et al.  In Situ Electrochemical Activation of Atomic Layer Deposition Coated MoS2 Basal Planes for Efficient Hydrogen Evolution Reaction , 2017 .

[10]  I. Moreels,et al.  Solution-Processed Hybrid Graphene Flake/2H-MoS2 Quantum Dot Heterostructures for Efficient Electrochemical Hydrogen Evolution , 2017, 1805.01550.

[11]  J. Coleman,et al.  Enabling Flexible Heterostructures for Li-Ion Battery Anodes Based on Nanotube and Liquid-Phase Exfoliated 2D Gallium Chalcogenide Nanosheet Colloidal Solutions. , 2017, Small.

[12]  Rui Xiong,et al.  Computational mining of photocatalysts for water splitting hydrogen production: two-dimensional InSe-family monolayers , 2017 .

[13]  P. Ajayan,et al.  Electron-Doped 1T-MoS2 via Interface Engineering for Enhanced Electrocatalytic Hydrogen Evolution , 2017 .

[14]  Mengqi Zeng,et al.  Emerging two-dimensional nanomaterials for electrochemical hydrogen evolution , 2017 .

[15]  Jia Liu,et al.  The mechanism of hydrogen adsorption on transition metal dichalcogenides as hydrogen evolution reaction catalyst. , 2017, Physical chemistry chemical physics : PCCP.

[16]  S. Karmakar,et al.  Monolayer Group IV–VI Monochalcogenides: Low-Dimensional Materials for Photocatalytic Water Splitting , 2017 .

[17]  E. Kymakis,et al.  Size-Tuning of WSe2 Flakes for High Efficiency Inverted Organic Solar Cells. , 2017, ACS nano.

[18]  H. Sirringhaus,et al.  High operational and environmental stability of high-mobility conjugated polymer field-effect transistors through the use of molecular additives. , 2017, Nature materials.

[19]  Kourosh Kalantar-Zadeh,et al.  Wafer-scale two-dimensional semiconductors from printed oxide skin of liquid metals , 2017, Nature Communications.

[20]  R. Ahuja,et al.  Review of two-dimensional materials for photocatalytic water splitting from a theoretical perspective , 2017 .

[21]  Barack Obama,et al.  The irreversible momentum of clean energy , 2017, Science.

[22]  G. Armatas,et al.  Size Effects of Platinum Nanoparticles in the Photocatalytic Hydrogen Production Over 3D Mesoporous Networks of CdS and Pt Nanojunctions , 2016 .

[23]  F. Bonaccorso,et al.  Solution blending preparation of polycarbonate/graphene composite: boosting the mechanical and electrical properties , 2016, 1805.01659.

[24]  Jinhua Ye,et al.  In Situ Bond Modulation of Graphitic Carbon Nitride to Construct p–n Homojunctions for Enhanced Photocatalytic Hydrogen Production , 2016 .

[25]  Xitian Zhang,et al.  Growth of MoSe2 nanosheets with small size and expanded spaces of (002) plane on the surfaces of porous N-doped carbon nanotubes for hydrogen production. , 2016, Nanoscale.

[26]  L. Yin,et al.  Synthesis, properties and applications of 2D layered MIIIXVI (M = Ga, In; X = S, Se, Te) materials. , 2016, Nanoscale.

[27]  Xiaodong Zhuang,et al.  Engineering water dissociation sites in MoS2 nanosheets for accelerated electrocatalytic hydrogen production , 2016 .

[28]  J. Coleman,et al.  2D‐Crystal‐Based Functional Inks , 2016, Advanced materials.

[29]  P. Hu,et al.  Modulation of opto-electronic properties of InSe thin layers via phase transformation , 2016 .

[30]  Guodong Li,et al.  Overall Water Splitting Catalyzed Efficiently by an Ultrathin Nanosheet‐Built, Hollow Ni3S2‐Based Electrocatalyst , 2016 .

[31]  Qing Tang,et al.  Mechanism of Hydrogen Evolution Reaction on 1T-MoS2 from First Principles , 2016 .

[32]  Bruno Scrosati,et al.  Binder-free graphene as an advanced anode for lithium batteries , 2016 .

[33]  Guanxiong Liu,et al.  The influence of chemical reactivity of surface defects on ambient-stable InSe-based nanodevices. , 2016, Nanoscale.

[34]  C. Klinke,et al.  Solution-Processed Two-Dimensional Ultrathin InSe Nanosheets , 2016 .

[35]  Bo Chen,et al.  2D Transition‐Metal‐Dichalcogenide‐Nanosheet‐Based Composites for Photocatalytic and Electrocatalytic Hydrogen Evolution Reactions , 2016, Advanced materials.

[36]  J. Tu,et al.  Transition Metal Carbides and Nitrides in Energy Storage and Conversion , 2016, Advanced science.

[37]  J. Coleman,et al.  Thickness Dependence and Percolation Scaling of Hydrogen Production Rate in MoS2 Nanosheet and Nanosheet-Carbon Nanotube Composite Catalytic Electrodes. , 2016, ACS nano.

[38]  M. Pumera,et al.  Electrochemistry of layered GaSe and GeS: applications to ORR, OER and HER. , 2016, Physical chemistry chemical physics : PCCP.

[39]  J. Steinke,et al.  Sonochemical degradation of N-methylpyrrolidone and its influence on single walled carbon nanotube dispersion. , 2015, Chemical communications.

[40]  Y. Miao,et al.  A CNT@MoSe2 hybrid catalyst for efficient and stable hydrogen evolution. , 2015, Nanoscale.

[41]  Hongyang Zhao,et al.  Colloidally synthesized MoSe2/graphene hybrid nanostructures as efficient electrocatalysts for hydrogen evolution , 2015 .

[42]  Tatsuya Shinagawa,et al.  Insight on Tafel slopes from a microkinetic analysis of aqueous electrocatalysis for energy conversion , 2015, Scientific Reports.

[43]  Min Gyu Kim,et al.  Metal (Ni, Co)‐Metal Oxides/Graphene Nanocomposites as Multifunctional Electrocatalysts , 2015 .

[44]  Huijun Zhao,et al.  Local atomic structure modulations activate metal oxide as electrocatalyst for hydrogen evolution in acidic water , 2015, Nature Communications.

[45]  S. Lebègue,et al.  Two-Dimensional Indium Selenides Compounds: An Ab Initio Study. , 2015, The journal of physical chemistry letters.

[46]  Xiaoxin Zou,et al.  Noble metal-free hydrogen evolution catalysts for water splitting. , 2015, Chemical Society reviews.

[47]  W. Cao,et al.  Ultrahigh photo-responsivity and detectivity in multilayer InSe nanosheets phototransistors with broadband response† , 2015 .

[48]  K. Novoselov,et al.  High Broad‐Band Photoresponsivity of Mechanically Formed InSe–Graphene van der Waals Heterostructures , 2015, Advanced materials.

[49]  Hailong Yu,et al.  A strategy to synergistically increase the number of active edge sites and the conductivity of MoS2 nanosheets for hydrogen evolution. , 2015, Nanoscale.

[50]  Jonathan N. Coleman,et al.  Preparation of Gallium Sulfide Nanosheets by Liquid Exfoliation and Their Application As Hydrogen Evolution Catalysts , 2015 .

[51]  Junichiro Kono,et al.  An Atomically Layered InSe Avalanche Photodetector. , 2015, Nano letters.

[52]  M. Prato,et al.  Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems. , 2015, Nanoscale.

[53]  Ib Chorkendorff,et al.  Recent Development in Hydrogen Evolution Reaction Catalysts and Their Practical Implementation. , 2015, The journal of physical chemistry letters.

[54]  Chunming Wang,et al.  A Novel MoSe2–Reduced Graphene Oxide/Polyimide Composite Film for Applications in Electrocatalysis and Photoelectrocatalysis Hydrogen Evolution , 2015 .

[55]  Yong Zhou,et al.  State‐of‐the‐Art Progress in Diverse Heterostructured Photocatalysts toward Promoting Photocatalytic Performance , 2015 .

[56]  Benjamin J. Carey,et al.  Investigation of Two-Solvent Grinding-Assisted Liquid Phase Exfoliation of Layered MoS2 , 2015 .

[57]  S. Doğan,et al.  Structural characterizations and optical properties of InSe and InSe:Ag semiconductors grown by Bridgman/Stockbarger technique , 2014 .

[58]  W. Cao,et al.  Back Gated Multilayer InSe Transistors with Enhanced Carrier Mobilities via the Suppression of Carrier Scattering from a Dielectric Interface , 2014, Advanced materials.

[59]  Martin Pumera,et al.  Layered transition metal dichalcogenides for electrochemical energy generation and storage , 2014 .

[60]  U. Krewer,et al.  Mass-Transport Characteristics of Oxygen at Pt/Anion Exchange Ionomer Interface , 2014 .

[61]  N. Pugno,et al.  Fragmentation and exfoliation of 2-dimensional materials: a statistical approach. , 2014, Nanoscale.

[62]  V. Fal’ko,et al.  Electrons and phonons in single layers of hexagonal indium chalcogenides from ab initio calculations , 2014, 1403.4389.

[63]  B. Scrosati,et al.  An advanced lithium-ion battery based on a graphene anode and a lithium iron phosphate cathode. , 2014, Nano letters.

[64]  A. Ciesielski,et al.  Graphene via sonication assisted liquid-phase exfoliation. , 2014, Chemical Society reviews.

[65]  H. Shin,et al.  Two-dimensional hybrid nanosheets of tungsten disulfide and reduced graphene oxide as catalysts for enhanced hydrogen evolution. , 2013, Angewandte Chemie.

[66]  G. Eda,et al.  Conducting MoS₂ nanosheets as catalysts for hydrogen evolution reaction. , 2013, Nano letters.

[67]  A. Shukla,et al.  Anodic bonded 2D semiconductors: from synthesis to device fabrication , 2013, Nanotechnology.

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

[69]  S. Kocha,et al.  Enhanced Oxygen Reduction Activity on Pt/C for Nafion-free, Thin, Uniform Films in Rotating Disk Electrode Studies , 2013 .

[70]  L. Eaves,et al.  Tuning the Bandgap of Exfoliated InSe Nanosheets by Quantum Confinement , 2013, Advanced materials.

[71]  R. Hennig,et al.  Single-Layer Group-III Monochalcogenide Photocatalysts for Water Splitting , 2013 .

[72]  Hua Zhang,et al.  The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. , 2013, Nature chemistry.

[73]  A. Ferrari,et al.  Production and processing of graphene and 2d crystals , 2012 .

[74]  W. Tang,et al.  Transition Metal Oxide Work Functions: The Influence of Cation Oxidation State and Oxygen Vacancies , 2012 .

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

[76]  V. Tozzini,et al.  Prospects for hydrogen storage in graphene. , 2012, Physical chemistry chemical physics : PCCP.

[77]  D. Late,et al.  Rapid Characterization of Ultrathin Layers of Chalcogenides on SiO2/Si Substrates , 2012 .

[78]  A. Ferrari,et al.  Inkjet-printed graphene electronics. , 2011, ACS nano.

[79]  Xile Hu,et al.  Recent developments of molybdenum and tungsten sulfides as hydrogen evolution catalysts , 2011 .

[80]  Yun Wang,et al.  A review of polymer electrolyte membrane fuel cells: Technology, applications,and needs on fundamental research , 2011 .

[81]  J. Coleman,et al.  Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials , 2011, Science.

[82]  Ilie Fishtik,et al.  Kinetics of the Hydrogen Electrode Reaction , 2010 .

[83]  Francesco Bonaccorso,et al.  Brownian motion of graphene. , 2010, ACS nano.

[84]  Ramazan Sarı,et al.  Dynamics of oil price, precious metal prices, and exchange rate , 2010 .

[85]  Stefano de Gironcoli,et al.  QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials , 2009, Journal of physics. Condensed matter : an Institute of Physics journal.

[86]  S. Banerjee,et al.  Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils , 2009, Science.

[87]  R. Kandiyoti,et al.  Sample Contamination with NMP-oxidation Products and Byproduct-free NMP Removal from Sample Solutions , 2009 .

[88]  Vincenzo Barone,et al.  Role and effective treatment of dispersive forces in materials: Polyethylene and graphite crystals as test cases , 2009, J. Comput. Chem..

[89]  W. Milne,et al.  Polymer-Assisted Isolation of Single Wall Carbon Nanotubes in Organic Solvents for Optical-Quality Nanotube -Polymer Composites , 2008 .

[90]  Thomas F. Jaramillo,et al.  Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts , 2007, Science.

[91]  C. Wan,et al.  Novel method for the synthesis of hydrophobic Pt-Ru nanoparticles and its application to preparing a Nafion-free anode for the direct methanol fuel cell. , 2006, The journal of physical chemistry. B.

[92]  K. Domen,et al.  Photocatalyst releasing hydrogen from water , 2006, Nature.

[93]  Jacob Bonde,et al.  Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. , 2005, Journal of the American Chemical Society.

[94]  H. Jónsson,et al.  Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode. , 2004, The journal of physical chemistry. B.

[95]  Robert B. Moore,et al.  State of understanding of nafion. , 2004, Chemical reviews.

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

[97]  Manos Mavrikakis,et al.  Why Au and Cu Are More Selective Than Pt for Preferential Oxidation of CO at Low Temperature , 2004 .

[98]  B. V. Tilak,et al.  Interfacial processes involving electrocatalytic evolution and oxidation of H2, and the role of chemisorbed H , 2002 .

[99]  R. Schwarcz,et al.  Evolution of Raman spectra as a function of layer thickness in ultra-thin InSe films , 2002 .

[100]  Y. Kawazoe,et al.  Excitons and band structure of highly anisotropic GaTe single crystals , 2001 .

[101]  B. Sapoval,et al.  Shape-dependency of current through non-linear irregular electrodes , 2000 .

[102]  P. Fedkiw,et al.  Nafion®-based composite polymer electrolyte membranes , 1998 .

[103]  M. Eddrief,et al.  Ion Beam Modification of InSe Surfaces , 1997 .

[104]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[105]  M. Boudart,et al.  Turnover Rates in Heterogeneous Catalysis , 1995 .

[106]  T. Pajkossy,et al.  Tafel current at fractal electrodes: Connection with admittance spectra , 1990 .

[107]  C. Julien,et al.  Raman Spectra of a- and ?-In2Se3 , 1984 .

[108]  H. Monkhorst,et al.  SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS , 1976 .

[109]  S. Taylor,et al.  Abundance of chemical elements in the continental crust: A new table: Geochimica e t Cosmochimica Ac , 1964 .

[110]  P. Rüetschi Overvoltage and Catalysis , 1959 .

[111]  Shihe Yang,et al.  MoSe2 nanosheets and their graphene hybrids: synthesis, characterization and hydrogen evolution reaction studies , 2014 .

[112]  W. M. Haynes CRC Handbook of Chemistry and Physics , 1990 .

[113]  S. Jandl,et al.  Second order Raman spectrum and phase transition in InSe , 1979 .

[114]  S. Jandl,et al.  Raman spectrum of crystalline InSe , 1978 .

[115]  J. Philpot The Ultracentrifuge , 1943, Nature.

[116]  M. Muir Physical Chemistry , 1888, Nature.