Effect of dissolved LiCl on the ionic liquid–Au(111) interface: an in situ STM study

The structure of the electrolyte/electrode interface plays a significant role in electrochemical processes. To date, most studies are focusing on understanding the interfacial structure in pure ionic liquids. In this paper in situ scanning tunnelling microscopy (STM) has been employed to elucidate the structure of the charged Au(111)–ionic liquid (1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, [Py1,4]FAP) interface in the presence of 0.1 M LiCl. The addition of the Li salt to the ionic liquid has a strong influence on the interfacial structure. In the first STM scan in situ measurements reveal that Au(111) undergoes the (22×√3?>) ‘herringbone’ reconstruction in a certain potential regime, and there is strong evidence that the gold surface dissolves at negative electrode potentials in [Py1,4]FAP containing LiCl. Bulk deposition of Li is obtained at −2.9 V in the second STM scan.

[1]  Yu. I. Ustinovshchikov Diffusion phase transitions in alloys , 2014 .

[2]  R. Atkin,et al.  Effect of alkyl chain length and anion species on the interfacial nanostructure of ionic liquids at the Au(111)-ionic liquid interface as a function of potential. , 2013, Physical chemistry chemical physics : PCCP.

[3]  R. Atkin,et al.  Ionic liquid lubrication: influence of ion structure, surface potential and sliding velocity. , 2013, Physical chemistry chemical physics : PCCP.

[4]  E. Wanless,et al.  Adsorbed and near-surface structure of ionic liquids determines nanoscale friction. , 2013, Chemical communications.

[5]  Rob Atkin,et al.  Adsorbed and near surface structure of ionic liquids at a solid interface. , 2013, Physical chemistry chemical physics : PCCP.

[6]  R. Atkin,et al.  In situ STM, AFM and DTS study of the interface 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate/Au(1 1 1) , 2012 .

[7]  R. Bennewitz,et al.  Control of nanoscale friction on gold in an ionic liquid by a potential-dependent ionic lubricant layer. , 2012, Physical review letters.

[8]  Z. Tian,et al.  Adsorption of Solvent Cations on Au(111) and Au(100) in Alkylimidazolium-Based Ionic Liquids – Worm-Like versus Micelle-Like Structures , 2012 .

[9]  R. Atkin,et al.  Effect of dissolved LiCl on the ionic liquid-Au(111) electrical double layer structure. , 2012, Chemical communications.

[10]  T. Pajkossy,et al.  The interfaces of Au(111) and Au(100) in a hexaalkyl-substituted guanidinium ionic liquid: an electrochemical and in situ STM study. , 2012, Physical chemistry chemical physics : PCCP.

[11]  F. Endres,et al.  An in situ STM and DTS study of the extremely pure [EMIM]FAP/Au(111) interface. , 2012, Chemphyschem : a European journal of chemical physics and physical chemistry.

[12]  F. Endres,et al.  New insights into the interface between a single-crystalline metal electrode and an extremely pure ionic liquid: slow interfacial processes and the influence of temperature on interfacial dynamics. , 2012, Physical chemistry chemical physics : PCCP.

[13]  H. Steinrück,et al.  Interfaces of ionic liquids and transition metal surfaces-adsorption, growth, and thermal reactions of ultrathin [C1C1Im][Tf2N] films on metallic and oxidised Ni(111) surfaces. , 2012, Physical chemistry chemical physics : PCCP.

[14]  R. Atkin,et al.  The interface ionic liquid(s)/electrode(s): in situ STM and AFM measurements. , 2012, Faraday discussions.

[15]  P. Malfreyt,et al.  2D or not 2D: structural and charge ordering at the solid-liquid interface of the 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate ionic liquid. , 2012, Faraday discussions.

[16]  T. Kirchner,et al.  Molecular-scale insights into the mechanisms of ionic liquids interactions with carbon nanotubes. , 2012, Faraday discussions.

[17]  De-en Jiang,et al.  A classical density functional theory for interfacial layering of ionic liquids , 2011 .

[18]  P. Madden,et al.  Imidazolium Ionic Liquid Interfaces with Vapor and Graphite: Interfacial Tension and Capacitance from Coarse-Grained Molecular Simulations , 2011 .

[19]  Rob Atkin,et al.  An in situ STM/AFM and impedance spectroscopy study of the extremely pure 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate/Au(111) interface: potential dependent solvation layers and the herringbone reconstruction. , 2011, Physical chemistry chemical physics : PCCP.

[20]  Matthew K. Tam,et al.  Double Layer Structure of Ionic Liquids at the Au(111) Electrode Interface: An Atomic Force Microscopy Investigation , 2011 .

[21]  O. Borodin,et al.  Molecular simulations of the electric double layer structure, differential capacitance, and charging kinetics for N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide at graphite electrodes. , 2011, The journal of physical chemistry. B.

[22]  H. Steinrück,et al.  Liquid/solid interface of ultrathin ionic liquid films: [C1C1Im][Tf2N] and [C8C1Im][Tf2N] on Au(111). , 2011, Langmuir : the ACS journal of surfaces and colloids.

[23]  Sheng Dai,et al.  The importance of ion size and electrode curvature on electrical double layers in ionic liquids. , 2011, Physical chemistry chemical physics : PCCP.

[24]  A. Kornyshev,et al.  Double layer in ionic liquids: overscreening versus crowding. , 2010, Physical review letters.

[25]  A. A. Kornyshev,et al.  The anatomy of the double layer and capacitance in ionic liquids with anisotropic ions: Electrostriction vs. lattice saturation , 2010 .

[26]  Oleg Borodin,et al.  Molecular insights into the potential and temperature dependences of the differential capacitance of a room-temperature ionic liquid at graphite electrodes. , 2010, Journal of the American Chemical Society.

[27]  Dieter M. Kolb,et al.  The interface between Au(1 1 1) and an ionic liquid , 2010 .

[28]  F. Leermakers,et al.  Electrical double-layer capacitance in room temperature ionic liquids: ion-size and specific adsorption effects. , 2010, The journal of physical chemistry. B.

[29]  P. Madden,et al.  Potential-induced ordering transition of the adsorbed layer at the ionic liquid/electrified metal interface. , 2010, The journal of physical chemistry. B.

[30]  D. Macfarlane,et al.  The effect of potential bias on the formation of ionic liquid generated surface films on Mg alloys , 2010 .

[31]  Fulian Qiu,et al.  Double layer, diluent and anode effects upon the electrodeposition of aluminium from chloroaluminate based ionic liquids. , 2010, Physical chemistry chemical physics : PCCP.

[32]  A. Prowald,et al.  Do solvation layers of ionic liquids influence electrochemical reactions? , 2010, Physical chemistry chemical physics : PCCP.

[33]  R. Atkin,et al.  At the interface: solvation and designing ionic liquids. , 2010, Physical chemistry chemical physics : PCCP.

[34]  A. Kornyshev,et al.  Double layer in ionic liquids: the nature of the camel shape of capacitance , 2010 .

[35]  Zhen Cao,et al.  Molecular Dynamic Simulations of Ionic Liquids at Graphite Surface , 2010 .

[36]  F. Endres,et al.  In situ STM investigation of the lithium underpotential deposition on Au(111) in the air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide. , 2009, Physical chemistry chemical physics : PCCP.

[37]  B. Ocko,et al.  Layering of [BMIM]+-based ionic liquids at a charged sapphire interface. , 2009, The Journal of chemical physics.

[38]  R. Atkin,et al.  AFM and STM Studies on the Surface Interaction of [BMP]TFSA and [EMIm]TFSA Ionic Liquids with Au(111) , 2009 .

[39]  I. Samoylov,et al.  Molecular dynamics simulation of the electrochemical interface between a graphite surface and the ionic liquid [BMIM][PF6]. , 2009, Physical chemistry chemical physics : PCCP.

[40]  Jiawei Yan,et al.  Double layer of Au(100)/ionic liquid interface and its stability in imidazolium-based ionic liquids. , 2009, Angewandte Chemie.

[41]  R. Atkin,et al.  Pronounced structure in confined aprotic room-temperature ionic liquids. , 2009, The journal of physical chemistry. B.

[42]  R. Atkin,et al.  Influence of temperature and molecular structure on ionic liquid solvation layers. , 2009, The journal of physical chemistry. B.

[43]  Rui Qiao,et al.  Microstructure and Capacitance of the Electrical Double Layers at the Interface of Ionic Liquids and Planar Electrodes , 2009 .

[44]  Y. Ouchi,et al.  Interfacial Restructuring of Ionic Liquids Determined by Sum-Frequency Generation Spectroscopy and X-Ray Reflectivity , 2008 .

[45]  B. Ocko,et al.  Molecular Layering of Fluorinated Ionic Liquids at a Charged Sapphire (0001) Surface , 2008, Science.

[46]  A. Kornyshev,et al.  F ¨ Ur Mathematik in Den Naturwissenschaften Leipzig towards Understanding the Structure and Capacitance of Electrical Double Layer in Ionic Liquids towards Understanding the Structure and Capacitance of Electrical Double Layer in Ionic Liquids , 2022 .

[47]  A. Kornyshev,et al.  Ionic liquid near a charged wall: structure and capacitance of electrical double layer. , 2008, The journal of physical chemistry. B.

[48]  O. Fontaine,et al.  Formation of negative oxidation states of platinum and gold in redox ionic liquid: Electrochemical evidence , 2008 .

[49]  Lars Kloo,et al.  Ionic liquid electrolytes for dye-sensitized solar cells. , 2008, Dalton transactions.

[50]  Douglas R. MacFarlane,et al.  Electrodeposition from Ionic Liquids , 2008 .

[51]  K. B. Oldham A Gouy–Chapman–Stern model of the double layer at a (metal)/(ionic liquid) interface , 2008 .

[52]  S. Baldelli,et al.  A Sum Frequency Generation Study of the Room-Temperature Ionic Liquid−Titanium Dioxide Interface , 2008 .

[53]  S. Baldelli,et al.  Surface structure at the ionic liquid-electrified metal interface. , 2008, Accounts of chemical research.

[54]  Alexei A Kornyshev,et al.  Double-layer in ionic liquids: paradigm change? , 2007, The journal of physical chemistry. B.

[55]  J. Conboy,et al.  Structure and orientation of the imidazolium cation at the room-temperature ionic liquid/SiO2 interface measured by sum-frequency vibrational spectroscopy. , 2007, The journal of physical chemistry. B.

[56]  R. Atkin,et al.  Structure in Confined Room-Temperature Ionic Liquids , 2007 .

[57]  Stewart K. Reed,et al.  Electrochemical interface between an ionic liquid and a model metallic electrode. , 2007, The Journal of chemical physics.

[58]  S. Baldelli,et al.  Orientation of 1-Butyl-3-methylimidazolium Based Ionic Liquids at a Hydrophobic Quartz Interface Using Sum Frequency Generation Spectroscopy , 2007 .

[59]  F. Endres,et al.  Probing Lithium and Alumina Impurities in Air- and Water Stable Ionic Liquids by Cyclic Voltammetry and In Situ Scanning Tunneling Microscopy , 2006 .

[60]  S. Baldelli,et al.  Sum frequency generation spectroscopy and double-layer capacitance studies of the 1-butyl-3-methylimidazolium dicyanamide-platinum interface. , 2006, The journal of physical chemistry. B.

[61]  Gebo Pan,et al.  2D phase transition of PF6 adlayers at the electrified ionic liquid/Au(111) interface , 2006 .

[62]  F. Endres,et al.  In situ STM investigation of gold reconstruction and of silicon electrodeposition on Au(111) in the room temperature ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide. , 2006, The journal of physical chemistry. B.

[63]  J. Ghilane,et al.  Cathodic modifications of platinum surfaces in organic solvent: reversibility and cation type effects. , 2005, The journal of physical chemistry. B.

[64]  B. Ocko,et al.  Surface layering in ionic liquids: an X-ray reflectivity study. , 2005, Journal of the American Chemical Society.

[65]  Hiroyuki Ohno,et al.  Electrochemical Aspects of Ionic Liquids: Ohno/Electrochemical Aspects of Ionic Liquids , 2005 .

[66]  大野 弘幸,et al.  Electrochemical aspects of ionic liquids , 2005 .

[67]  J. Conboy,et al.  Structure of the Room-Temperature Ionic Liquid/SiO 2 Interface Studied by Sum-Frequency Vibrational Spectroscopy , 2004 .

[68]  J. Webster,et al.  Surface ordering of amphiphilic ionic liquids. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[69]  Jiawei Yan,et al.  An in situ STM study on the long-range surface restructuring of Au(1 1 1) in a non-chloroaluminumated ionic liquid , 2003 .

[70]  K. R. Seddon,et al.  Molecular layering and local order in thin films of 1-alkyl-3-methylimidazolium ionic liquids using X-ray reflectivity , 2001 .

[71]  J. Simonet,et al.  On the cathodic corrosion of platinum in the presence of iodides in dry aprotic solvents , 1999 .

[72]  A. Bard,et al.  Electrochemical Behavior and Standard Potential of Au- in Liquid Ammonia , 1978 .