Soft Landing Of Mass-selected Ions Research Articles

Electrochemical and Structural Characterization of Soft Landed Tungsten-Substituted Lindqvist Polyoxovanadate-Alkoxides.

Lindqvist polyoxovanadate-alkoxide (POV-alkoxide) clusters are excellent candidates for applications in energy storage and conversion due to their rich electrochemical profiles. One approach to tune the redox properties of these cluster complexes is through substitutional cationic doping within the hexavanadate core. Here, we report the synthesis of a series of tungsten-substituted POV-alkoxide clusters with one and two tungsten atoms. Soft landing of mass-selected ions was used to purify heterometal POV-alkoxides that cannot be readily separated using conventional approaches. The soft landed POV-alkoxides are characterized using infrared reflection-absorption spectroscopy and electrospray ionization mass spectrometry. The redox properties of the isolated ions are examined using an in situ electrochemical cell which enables traditional in vacuo electrochemical measurements inside of an ion soft landing instrument. Although the overall cluster core retains redox activity after tungsten doping, vanadium-based redox couples (VV /VIV ) are shifted substantially, indicating a pronounced effect of a heteroatom on the electronic structure of the core.

Directing Chemistry at Electrodes Using Precisely-Defined Electrochemical Interfaces

Molecular-level understanding of chemistry occurring at electrode-electrolyte interfaces (EEIs) during charge transfer processes as a function of electric field strength and concentration gradient is necessary to enable the rational design of more efficient electrochemical technologies for energy storage. The scientific challenge is to unravel convoluted interfacial interactions (i.e., adsorption, coordination, transport) and control the reaction pathways that lead to formation of desired products over unwanted byproducts. Ultimately the objective is to modulate the evolution of the solid-electrolyte interphase (SEI) in batteries for enhanced performance and durability. Soft landing of mass-selected ions, a versatile approach to surface modification, is ideally suited to preparation of well-defined interfaces with predetermined electrochemically active ions. The “atom-by-atom” precision of ion soft landing enables experiments that unravel the complexity associated with the multitude of interfacial processes occurring simultaneously at electrified interfaces. We present evidence for a substantial advancement in understanding such complex interfacial reactions on Mg battery electrodes employing user-defined layer-by-layer assembly of electrochemically active cations and solvated counter-ions with precisely-selected stoichiometry and concentration. As an example, ion soft landing combined with operando infrared reflection-absorption spectroscopy (IRRAS) and in-situ x-ray photoelectron spectroscopy (XPS) was used to characterize the decomposition of counter electrolyte anions and solvent molecules on Mg electrodes. Furthermore, we explored using an aliovalent doped metal (e.g., Al) on the Mg surface to control the decomposition and stabilize the SEI layer formation as a function of both concentration and potential. Our in-situ multimodal analysis enabled the capture of spectroscopic signatures from key chemical transformations of electrolyte anions and solvent molecules on reactive metal surfaces. These experimental results were correlated with the evolution of the SEI layer as predicted by theory to provide molecular-level insight into the reaction mechanism. In summary, our unique approach allowed us to acquire more delineated understanding of electrochemical transformations across length scales in operating EEIs and aids in the rational design of improved sustainable electrochemical energy technologies.

Design and Performance of a Dual-Polarity Instrument for Ion Soft Landing.

A new apparatus for ion soft landing research was developed and is reported in this contribution. The instrument includes a dual polarity high-flux electrospray ionization (ESI) interface, a tandem electrodynamic ion funnel system, a collisional flatapole, a quadrupole mass filter, and a focusing lens. The instrument enables production of ionic layers by soft landing of mass-selected ions onto surfaces with balanced or imbalanced charge conditions using either layer-by-layer (LBL) or fast polarity switching modes. We present the first evidence of using weakly coordinating stable anions to protect the ionizing protons of soft-landed cations on the surface. The observed proton retention is particularly efficient when fast polarity switching of anions and cations is employed to deposit small quantities of ions in short deposition segments. Furthermore, we observe more efficient charge retention and better ionic complexation in a charge-balanced layer prepared by fast polarity switching deposition. These findings open up new opportunities for the fabrication of novel ionic assemblies using well-defined gaseous ions as building blocks.

In-Situ Solid-State Electrochemistry of Well-Defined Electrode-Electrolyte Interfaces Using Ion Soft Landing

Molecular-level understanding of electrochemical processes at electrode-electrolyte interfaces (EEI) is key to the development of high-performance electrochemical technologies such as batteries, supercapacitors, and fuel cells. Soft landing of mass-selected ions is ideally suited for controlled preparation of well-defined surfaces necessary for understanding processes at EEI. Specifically, ion soft landing enables deposition of uniform layers of redox-active species onto electrode surfaces with precise control over the charge state, composition, and kinetic energy.(1-3) Herein, we report the development and first demonstration of the capabilities of an in-situ solid-state three electrode electrochemical cell for studying the electrochemical activity of mass- and charge- selected ionic clusters deposited onto electrode surfaces using ion soft landing. In-situ electrochemical cells were fabricated using carefully designed nanoporous ionic liquid membranes with excellent mass transfer properties compared to liquid electrolyte.(4) The in-situ electrochemical cell enables (i) characterization of both intrinsic redox and reactive processes with control over the stoichiometry and distribution of analyte species at EEIs using soft landing onto nanostructured solid-state electrolyte and (ii) understanding of the effect of diffusion of ions of interest through pores on their electrochemical activity. The in-situ electrochemical cell was fabricated by depositing a ~10 µm thick room temperature ionic liquid - polymer electrolyte membrane on a screen printed electrode. The cell showed a stable rectangular double layer capacitive behavior both in high vacuum (10-5 Torr) and reactive gaseous environments. We demonstrate the performance of the in-situ electrochemical cell for studying both the intrinsic redox activity and reactive electrochemistry of well-defined ions at EEI. Specifically, we examined the intrinsic redox activity of mixed-addenda Keggin PMoxW12-xO40 3- (x=0,1,2,3,6,9,12) polyoxometalates. Multi-electron redox activity of stable anionic Keggin POMs that enable transfer of up to 24 electrons while retaining the structure of the cluster makes them attractive systems for studies in catalysis and energy storage.(5, 6) In addition, we examined the oxygen reduction reactivity of bare Pt cluster ions ∼1 nm in diameter produced using magnetron sputtering combined with gas aggregation. Soft landing of bare metal clusters directly onto the cell eliminates the need to use stabilizing ligands or solvent and, therefore, provides a direct route for studying intrinsic electrocatalytic activity. In summary, the in-situ electrochemical cell combined with mass-selected ion deposition is a powerful approach for studying processes both at model and technologically-relevant EEIs during operating conditions.

Soft- and reactive landing of ions onto surfaces: Concepts and applications.

Soft- and reactive landing of mass-selected ions is gaining attention as a promising approach for the precisely-controlled preparation of materials on surfaces that are not amenable to deposition using conventional methods. A broad range of ionization sources and mass filters are available that make ion soft-landing a versatile tool for surface modification using beams of hyperthermal (<100 eV) ions. The ability to select the mass-to-charge ratio of the ion, its kinetic energy and charge state, along with precise control of the size, shape, and position of the ion beam on the deposition target distinguishes ion soft landing from other surface modification techniques. Soft- and reactive landing have been used to prepare interfaces for practical applications as well as precisely-defined model surfaces for fundamental investigations in chemistry, physics, and materials science. For instance, soft- and reactive landing have been applied to study the surface chemistry of ions isolated in the gas-phase, prepare arrays of proteins for high-throughput biological screening, produce novel carbon-based and polymer materials, enrich the secondary structure of peptides and the chirality of organic molecules, immobilize electrochemically-active proteins and organometallics on electrodes, create thin films of complex molecules, and immobilize catalytically active organometallics as well as ligated metal clusters. In addition, soft landing has enabled investigation of the size-dependent behavior of bare metal clusters in the critical subnanometer size regime where chemical and physical properties do not scale predictably with size. The morphology, aggregation, and immobilization of larger bare metal nanoparticles, which are directly relevant to the design of catalysts as well as improved memory and electronic devices, have also been studied using ion soft landing. This review article begins in section 1 with a brief introduction to the existing applications of ion soft- and reactive landing. Section 2 provides an overview of the ionization sources and mass filters that have been used to date for soft landing of mass-selected ions. A discussion of the competing processes that occur during ion deposition as well as the types of ions and surfaces that have been investigated follows in section 3. Section 4 discusses the physical phenomena that occur during and after ion soft landing, including retention and reduction of ionic charge along with factors that impact the efficiency of ion deposition. The influence of soft landing on the secondary structure and biological activity of complex ions is addressed in section 5. Lastly, an overview of the structure and mobility as well as the catalytic, optical, magnetic, and redox properties of bare ionic clusters and nanoparticles deposited onto surfaces is presented in section 6.

Soft landing of bare PtRu nanoparticles for electrochemical reduction of oxygen.

Magnetron sputtering of two independent Pt and Ru targets coupled with inert gas aggregation in a modified commercial source has been combined with soft landing of mass-selected ions to prepare bare 4.5 nm diameter PtRu nanoparticles on glassy carbon electrodes with controlled size and morphology for electrochemical reduction of oxygen in solution. Employing atomic force microscopy (AFM) it is shown that the nanoparticles bind randomly to the glassy carbon electrode at a relatively low coverage of 7 × 10(4) ions μm(-2) and that their average height is centered at 4.5 nm. Scanning transmission electron microscopy images obtained in the high-angle annular dark field mode (HAADF-STEM) further confirm that the soft-landed PtRu nanoparticles are uniform in size. Wide-area scans of the electrodes using X-ray photoelectron spectroscopy (XPS) reveal the presence of both Pt and Ru in atomic concentrations of ∼9% and ∼33%, respectively. Deconvolution of the high energy resolution XPS spectra in the Pt 4f and Ru 3d regions indicates the presence of both oxidized Pt and Ru. The substantially higher loading of Ru compared to Pt and enrichment of Pt at the surface of the nanoparticles is confirmed by wide-area analysis of the electrodes using time-of-flight medium energy ion scattering (TOF-MEIS) employing both 80 keV He(+) and O(+) ions. The activity of electrodes containing 7 × 10(4) ions μm(-2) of bare 4.5 nm PtRu nanoparticles toward the electrochemical reduction of oxygen was evaluated employing cyclic voltammetry (CV) in 0.1 M HClO4 and 0.5 M H2SO4 solutions. In both electrolytes a pronounced reduction peak was observed during O2 purging of the solution that was not evident during purging with Ar. Repeated electrochemical cycling of the electrodes revealed little evolution in the shape or position of the voltammograms indicating high stability of the nanoparticles supported on glassy carbon. The reproducibility of the nanoparticle synthesis and deposition was evaluated by employing the same experimental parameters to prepare nanoparticles on glassy carbon electrodes on three occasions separated by several days. Surfaces with almost identical electrochemical behavior were observed with CV, demonstrating the highly reproducible preparation of bare nanoparticles using physical synthesis in the gas-phase combined with soft landing of mass-selected ions.

Controlling the Charge State and Redox Properties of Supported Polyoxometalates via Soft Landing of Mass-Selected Ions

We investigate the controlled deposition of Keggin polyoxometalate (POM) anions, PMo12O403– and PMo12O402–, onto different self-assembled monolayer (SAM) surfaces via soft landing of mass-selected ions. Utilizing in situ infrared reflection absorption spectroscopy (IRRAS), ex situ cyclic voltammetry (CV), and electronic structure calculations, we examine the structure and charge retention of supported multiply charged POM anions and characterize the redox properties of the modified surfaces. SAMs of alkylthiol (HSAM), perfluorinated alkylthiol (FSAM), and alkylthiol terminated with NH3+ functional groups (NH3+SAM) are chosen as model substrates for soft landing to examine the factors that influence the immobilization and charge retention of multiply charged anionic molecules. The distribution of charge states of POMs on different SAM surfaces is determined by comparing the IRRAS spectra with vibrational spectra calculated using density functional theory. In contrast with the results obtained previously fo...

In situ SIMS and IR spectroscopy of well-defined surfaces prepared by soft landing of mass-selected ions.

Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of materials that are inaccessible using conventional synthesis techniques. Coupling soft landing with in situ characterization using secondary ion mass spectrometry (SIMS) and infrared reflection absorption spectroscopy (IRRAS) enables analysis of well-defined surfaces under clean vacuum conditions. The capabilities of three soft-landing instruments constructed in our laboratory are illustrated for the representative system of surface-bound organometallics prepared by soft landing of mass-selected ruthenium tris(bipyridine) dications, [Ru(bpy)3](2+) (bpy = bipyridine), onto carboxylic acid terminated self-assembled monolayer surfaces on gold (COOH-SAMs). In situ time-of-flight (TOF)-SIMS provides insight into the reactivity of the soft-landed ions. In addition, the kinetics of charge reduction, neutralization and desorption occurring on the COOH-SAM both during and after ion soft landing are studied using in situ Fourier transform ion cyclotron resonance (FT-ICR)-SIMS measurements. In situ IRRAS experiments provide insight into how the structure of organic ligands surrounding metal centers is perturbed through immobilization of organometallic ions on COOH-SAM surfaces by soft landing. Collectively, the three instruments provide complementary information about the chemical composition, reactivity and structure of well-defined species supported on surfaces.

Coverage-Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-Selected Ions

The ionic charge state of monodisperse multiply charged cationic gold clusters on surfaces may be controlled by selecting the coverage of mass-selected ions soft landed onto a substrate. Polydisperse diphosphine-capped gold clusters were synthesized in solution and introduced into the gas phase by electrospray ionization. Mass selection was employed to isolate a multiply charged cationic cluster species (Au11L53+, m/z = 1409, L = 1,3-bis(diphenylphosphino)propane) which was delivered to the surfaces of four different self-assembled monolayers on gold (SAMs) at controlled coverages of 1011 and 1012 clusters. Employing the spatial profiling capabilities of in situ time-of-flight secondary ion mass spectrometry (TOF-SIMS), it is shown that, in addition to the chemical functionality of the monolayer (as demonstrated previously: ACS Nano 2012, 6, 573), the coverage of cationic gold clusters on the surface may be used to control the relative abundance of different charge states of the soft landed multiply charg...

Charge Retention by Gold Clusters on Surfaces Prepared Using Soft Landing of Mass Selected Ions

Monodisperse gold clusters have been prepared on surfaces in different charge states through soft landing of mass-selected ions. Ligand-stabilized gold clusters were prepared in methanol solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine complex in the presence of 1,3-bis(diphenylphosphino)propane. Electrospray ionization was used to introduce the clusters into the gas phase, and mass selection was employed to isolate a single ionic cluster species (Au(11)L(5)(3+), L = 1,3-bis(diphenylphosphino)propane), which was delivered to surfaces at well-controlled kinetic energies. Using in situ time-of-flight secondary ion mass spectrometry (TOF-SIMS), it is demonstrated that the Au(11)L(5)(3+) cluster retains its 3+ charge state when soft landed onto the surface of a 1H,1H,2H,2H-perfluorodecanethiol self-assembled monolayer (FSAM) on gold. In contrast, when deposited onto 16-mercaptohexadecanoic acid (COOH-SAM) and 1-dodecanethiol (HSAM) surfaces on gold, the clusters exhibit larger relative abundances of the 2+ and 1+ charge states, respectively. The kinetics of charge reduction on the FSAM and HSAM surfaces are investigated using in situ Fourier transform ion cyclotron resonance (FT-ICR) SIMS. It is shown that an extremely slow interfacial charge reduction occurs on the FSAM surface while an almost instantaneous neutralization takes place on the surface of the HSAM. Our results demonstrate that the size and charge state of small gold clusters on surfaces, both of which exert a dramatic influence on their chemical and physical properties, may be tuned through soft landing of mass-selected ions onto carefully selected substrates.

Effect of the surface on the secondary structure of soft landed peptide ions

Ion soft landing (SL) enables highly selective modification of substrates for applications in materials science, nanotechnology and biology. Our previous study [P. Wang and J. Laskin, Angew. Chem., Int. Ed., 2008, 47, 6678-6680] showed that SL can be used for preparation of conformation-selected peptide arrays. Here we present a first study of the effect of the surface on the secondary structures of peptides soft-landed onto self-assembled monolayer surfaces (SAMs). Conformations of soft-landed peptide ions were examined using a newly constructed instrument that enables in situ infrared reflection absorption spectroscopy (IRRAS) characterization of surfaces during and after ion deposition. Polyalanine peptides, Ac-A(n)K and Ac-KA(n) (n = 7, 15), that have been extensively studied both in solution and in the gas phase were used as model systems in this study. We demonstrate that physical and chemical properties of SAM surfaces have a strong effect on the conformations of soft-landed peptide ions. For example, deposition of the α-helical [Ac-A(15)K + H](+) ion on the CH(3)-terminated (HSAM) surface results in immobilization of both the α- and 3(10)-helical conformations. In contrast, a significant fraction of Ac-A(15)K molecules are present in the β-sheet conformation on the CF(3)-(FSAM) and COOH-terminated (COOH-SAM) surfaces. We show that the kinetic energy of the polyalanine ion, the charge, and the initial conformation have only a minor effect on the conformation of deposited species suggesting that the interaction between the molecule and the surface plays a major role in determining the secondary structures of immobilized polyalanines. This study demonstrates that SL of mass-selected ions can be utilized for obtaining fundamental understanding of the intrinsic properties of biomolecules and surfaces responsible for conformational changes upon adsorption.

Covalent Immobilization of Peptides on Self-Assembled Monolayer Surfaces Using Soft-Landing of Mass-Selected Ions

Controlled immobilization of peptides onto N-hydroxysuccinimidyl ester functionalized self-assembled monolayer (SAM) surfaces using reactive landing of mass-selected ions has been demonstrated. Surface characterization using time-of-flight secondary ion mass spectrometry and grazing-incidence infrared reflection−absorption spectroscopy confirmed highly efficient covalent linkage through an amide bond formed between the SAM and the free amino group of the lysine side chain. Reactive landing opens a new way for controlled preparation of peptide arrays.

Preparing protein microarrays by soft-landing of mass-selected ions.

Intact, multiply protonated proteins of particular mass and charge were selected from ionized protein mixtures and gently landed at different positions on a surface to form a microarray. An array of cytochrome c, lysozyme, insulin, and apomyoglobin was generated, and the deposited proteins showed electrospray ionization mass spectra that matched those of the authentic compounds. Deposited lysozyme and trypsin retained their biological activity. Multiply charged ions of protein kinase A catalytic subunit and hexokinase were also soft-landed into glycerol-based liquid surfaces. These soft-landed kinases phosphorylated LRRASLG oligopeptide and D-fructose, respectively.