Ion Soft Landing Research Articles

Mobility Selective Ion Soft-Landing and Characterization Enabled Using Structures for Lossless Ion Manipulation.

While conventional ion-soft landing uses the mass-to-charge (m/z) ratio to achieve molecular selection for deposition, here we demonstrate the use of Structures for Lossless Ion Manipulation (SLIM) for mobility-based ion selection and deposition. The dynamic rerouting capabilities of SLIM were leveraged to enable the rerouting of a selected range of mobilities to a different SLIM path (rather than MS) that terminated at a deposition surface. A selected mobility range from a phosphazene ion mixture was rerouted and deposited with a current pulse (∼150 pA) resembling its mobility peak. In addition, from a mixture of tetra-alkyl ammonium (TAA) ions containing chain lengths of C5-C8, selected chains (C6, C7) were collected on a surface, reconstituted into solution-phase, and subsequently analyzed with a SLIM-qToF to obtain an IMS/MS spectrum, confirming the identity of the selected species. Further, this method was used to characterize triply charged tungsten-polyoxometalate anions, PW12O403- (WPOM). The arrival time distribution of the IMS/MS showed multiple peaks associated with the triply charged anion (PW12O403-), of which a selected ATD was deposited and imaged using TEM. Additionally, the identity of the deposited WPOM was ascertained using energy-dispersive (EDS) spectroscopy. Further, we present theory and computations that reveal ion landing energies, the ability to modulate the energies, and deposition spot sizes.

Spontaneous ligand loss by soft landed [Ni(bpy)3]2+ ions on perfluorinated self-assembled monolayer surfaces.

Transition metal (TM) complexes are widely used in catalysis, photochemical energy conversion, and sensing. Understanding factors that affect ligand loss from TM complexes at interfaces is important both for generating catalytically-active undercoordinated TM complexes and for controlling the degradation pathways of photosensitizers and photoredox catalysts. Herein, we demonstrate that well-defined TM complexes prepared on surfaces using ion soft landing undergo substantial structural rearrangements resulting in ligand loss and formation of both stable and reactive undercoordinated species. We employ nickel bipyridine (Ni-bpy) cations as a model system and explore their structural reorganization on surfaces using a combination of experimental and computational approaches. The controlled preparation of surface layers by mass-selected deposition of [Ni(bpy)3]2+ cations provides insights into the chemical reactivity of these species on surfaces. Both surface characterization using mass spectrometry and electronic structure calculations using density functional theory (DFT) indicate that [Ni(bpy)3]2+ undergoes a substantial geometry distortion on surfaces in comparison with its gas-phase structure. This distortion reduces the ligand binding energy and facilitates the formation of the undercoordinated [Ni(bpy)2]2+. Additionally, charge reduction by the soft landed [Ni(bpy)3]2+ facilitates ligand loss. We observe that ligand loss is inhibited by co-depositing [Ni(bpy)3]2+ with a stable anion such as closo-dodecaborate dianion, [B12F12]2-. The strong electrostatic interaction between [Ni(bpy)3]2+ and [B12F12]2- diminishes the distortion of the cation due to interactions with the surface. This interaction stabilizes the soft landed cation by reducing the extent of charge reduction and its structural reorganization. Overall, this study shows the intricate interplay of charge state, ion surface interactions, and stabilization by counterions on the structure and reactivity of metal complexes on surfaces. The combined experimental and computational approach used in this study offers detailed insights into factors that affect the integrity and stability of active species relevant to energy production and catalysis.

Probing fragment ion reactivity towards functional groups on coordination polymer surfaces.

Functionalization of surface-grown coordination polymer layers by ion soft-landing of highly reactive molecular fragment ions is demonstrated. The ions form covalent bonds to terminal functional groups of the polymer at the vacuum interface, opening new perspectives for controlled bond formation using reactive ions.

Electrolyte Reactivity on the MgV2O4 Cathode Surface.

Predictive understanding of the molecular interaction of electrolyte ions and solvent molecules and their chemical reactivity on electrodes has been a major challenge but is essential for addressing instabilities and surface passivation that occur at the electrode-electrolyte interface of multivalent magnesium batteries. In this work, the isolated intrinsic reactivities of prominent chemical species present in magnesium bis(trifluoromethanesulfonimide) (Mg(TFSI)2) in diglyme (G2) electrolytes, including ionic (TFSI-, [Mg(TFSI)]+, [Mg(TFSI):G2]+, and [Mg(TFSI):2G2]+) as well as neutral molecules (G2) on a well-defined magnesium vanadate cathode (MgV2O4) surface, have been studied using a combination of first-principles calculations and multimodal spectroscopy analysis. Our calculations show that nonsolvated [Mg(TFSI)]+ is the strongest adsorbing species on the MgV2O4 surface compared with all other ions while partially solvated [Mg(TFSI):G2]+ is the most reactive species. The cleavage of C-S bonds in TFSI- to form CF3- is predicted to be the most desired pathway for all ionic species, which is followed by the cleavage of C-O bonds of G2 to yield CH3+ or OCH3- species. The strong stabilization and electron transfer between ionic electrolyte species and MgV2O4 is found to significantly favor these decomposition reactions on the surface compared with intrinsic gas-phase dissociation. Experimentally, we used state-of-the-art ion soft landing to selectively deposit mass-selected TFSI-, [Mg(TFSI):G2]+, and [Mg(TFSI):2G2]+ on a MgV2O4 thin film to form a well-defined electrolyte-MgV2O4 interface. Analysis of the soft-landed interface using X-ray photoelectron, X-ray absorption near-edge structure, electron energy-loss spectroscopies, as well as transmission electron microscopy confirmed the presence of decomposition species (e.g., MgFx, carbonates) and the higher amount of MgFx with [Mg(TFSI):G2]+ formed in the interfacial region, which corroborates the theoretical observation. Overall, these results indicate that Mg2+ desolvation results in electrolyte decomposition facilitated by surface adsorption, charge transfer, and the formation of passivating fluorides on the MgV2O4 cathode surface. This work provides the first evidence of the primary mechanisms leading to electrolyte decomposition at high-voltage oxide surfaces in multivalent batteries and suggests that the design of new, anodically stable electrolytes must target systems that facilitate cation desolvation.

The rapid detection of procalcitonin in septic serum using immunoaffinity MALDI chips

BackgroundSepsis is a common worldwide health condition with high mortality. It is caused by a dysregulated immune response to the pathogen. Severe infections resulting in sepsis can be also determined by monitoring several bloodstream biomarkers, one of them being pro-hormone procalcitonin (PCT). PCT concentration in the bloodstream correlates well with sepsis and in severe cases increases up to a thousand times from the healthy physiological values in a short time. In this study, we developed a rapid technique for PCT detection by MALDI-TOF mass spectrometry, that uses in-situ enrichment directly on the specialized immuno MALDI chips that are utilized as MALDI plates. The method’s ability to detect PCT was confirmed by comparing the results with LC–MS bottom-up workflow. The new method detects intact PCT by its m/z and uncovers its alternations in septic serum.MethodsThe MALDI chips used for the detection of PCT were prepared by ambient ion soft landing of anti-PCT antibody on an ITO glass slide. The chips were used for the development of the rapid MALDI-TOF MS method. A parallel method based on affinity enrichment on magnetic beads followed by LC–MS/MS data-dependent peptide microsequencing was used to prove PCT presence in the sample. All samples were also tested by ELISA to determine PCT concentration prior to analyzing them by mass spectrometry methods.ResultsThe MALDI chip method was optimized using recombinant PCT spiked into the human serum. The PCT detection limit was 10 ng/mL. The optimized method was used to analyze 13 sera from patients suffering sepsis. The PCT results were confirmed by LC–MS/MS. The measurement of the intact PCT by the MALDI chip method revealed that sera of patients with severe sepsis have other forms of PCT present, which show post-processing of the primary sequence by cleavage of PCT, resulting in the formation of N and C termini fragments.ConclusionsProcalcitonin from human serum was successfully enriched and detected using immunoaffinity MALDI chips. The intact PCT was characterized in 13 septic patients. The method is more specific compared to non-MS-based immunoaffinity techniques and allows observation of different variants of PCT in septic patients.

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.

Coordination-Dependent Chemical Reactivity of TFSI Anions at a Mg Metal Interface

Charge transfer across the electrode-electrolyte interface is a highly complex and convoluted process involving diverse solvated species with varying structures and compositions. Despite recent advances in in situ and operando interfacial analysis, molecular specific reactivity of solvated species is inaccessible due to a lack of precise control over the interfacial constituents and/or an unclear understanding of their spectroscopic fingerprints. However, such molecular-specific understanding is critical to the rational design of energy-efficient solid-electrolyte interphase layers. We have employed ion soft landing, a versatile and highly controlled method, to prepare well-defined interfaces assembled with selected ions, either as solvated species or as bare ions, with distinguishing molecular precision. Equipped with precise control over interfacial composition, we employed in situ multimodal spectroscopic characterization to unravel the molecular specific reactivity of Mg solvated species comprising (i.e., bis(trifluoromethanesulfonyl)imide, TFSI-) anions and solvent molecules (i.e., dimethoxyethane, DME/G1) on a Mg metal surface relevant to multivalent Mg batteries. In situ multimodal spectroscopic characterization revealed higher reactivity of the undercoordinated solvated species [Mg-TFSI-G1]+ compared to the fully coordinated [Mg-TFSI-(G1)2]+ species or even the bare TFSI-. These results were corroborated by the computed reaction pathways and energy barriers for decomposition of the TFSI- within Mg solvated species relative to bare TFSI-. Finally, we evaluated the TFSI reactivity under electrochemical conditions using Mg(TFSI)2-DME-based phase-separated electrolytes representing different solvated constituents. Based on our multimodal study, we report a detailed understanding of TFSI- decomposition processes as part of coordinated solvated species at a Mg-metal anode that will aid the rational design of improved sustainable electrochemical energy technologies.

Integrated photoelectrochemical energy storage cells prepared by benchtop ion soft landing.

The exceptional photochromic and redox properties of polyoxometalate anions, PW12O403−, have been exploited to develop an integrated photoelectrochemical energy storage cell for conversion and storage of solar energy. Elimination of strongly coordinating cations using benchtop ion soft landing leads to a ∼370% increase in the maximum power output of the device. Additionally, the photocathode displayed a pronounced color change from clear to blue upon irradiation, which warrants the potential application of the IPES cell in advanced smart windows and photochromic lenses.

Role of Polysulfide Anions in Solid-Electrolyte Interphase Formation at the Lithium Metal Surface in Li-S Batteries.

Delineating intricate interactions between highly reactive Li-metal electrodes and the diverse constituents of battery electrolytes has been a long-standing scientific challenge in materials design for advanced energy storage devices. Here, we isolated lithium polysulfide anions (LiS4-) from an electrolyte solution based on their mass-to-charge ratio and deposited them on Li-metal electrodes under clean vacuum conditions using ion soft landing (ISL), a highly controlled interface preparation technique. The molecular level precision in the construction of these model interfaces with ISL, coupled with in situ X-ray photoelectron spectroscopy and ab initio theoretical calculations, allowed us to obtain unprecedented insight into the parasitic reactions of well-defined polysulfides on Li-metal electrodes. Our study revealed that the oxide-rich surface layer, which is amenable to direct electron exchange, drives multielectron sulfur oxidation (S0 → S6+) processes. Our results have substantial implications for the rational design of future Li-S batteries with improved efficiency and durability.

Insights from Adsorption and Electron Modification Studies of Polyoxometalates on Surfaces for Molecular Memory Applications.

This Account highlights recent experimental and theoretical work focusing on the development of polyoxometalates (POMs) as possible active switching units in what may be called "molecule-based memory cells". Herein, we critically discuss how multiply charged vanadium-containing POMs, which exhibit stable metal-oxo bonds and are characterized by the excellent ability to change their redox states without significant structural distortions of the central polyoxoanion core, can be immobilized best and how they may work optimally at appropriate surfaces. Furthermore, we critically discuss important issues and challenges on the long way toward POM-based nanoelectronics. This Account is divided into four sections shedding light on POM interplay in solution and on surfaces, ion soft-landing of mass-selected POMs on surfaces, electronic modification of POMs on surfaces, and computational modeling of POMs on surfaces. The sections showcase the complex nature of far-reaching POM interactions with the chemical surroundings in solution and the properties of POMs in the macroscopic environment of electrode surfaces. Section 2 describes complex relationships of POMs with their counter-cations, solvent molecules, and water impurities, which have been shown to exhibit a direct impact on the resulting surface morphology, where a concentration-dependent formation of micellar structures can be potentially observed. Section 3 gives insights into the ion soft-landing deposition of mass-selected POMs on electrode surfaces, which emerges as an appealing method because the simultaneous deposition of agglomeration-stimulating counter-cations can be avoided. Section 4 provides details of electronic properties of POMs and their modification by external electronic stimuli toward the development of multiple-state resistive (memristive) switches. Section 5 sheds light on issues of the determination of the electronic structure properties of POMs across their interfaces, which is difficult to address by experiment. The studies summarized in these four sections have employed various X-ray-scattering, microscopy, spectroscopy, and computational techniques for imaging of POM interfaces in solution and on surfaces to determine the adsorption type, agglomeration tendency, distribution, and oxidation state of deposited molecules. The presented research findings and conceptual ideas may assist experimentalists and theoreticians to advance the exploration of POM electrical conductivity as a function of metal redox and spin states and to pave the way for a realization of ("brain-inspired") POM-based memory devices, memristive POM-surface device engineering, and energy efficient nonvolatile data storage and processing technologies.

The use of a commercial ESI Z-spray source for ambient ion soft landing and microdroplet reactivity experiments

In this study, the ability of an unmodified ESI Z-spray source to carry out ambient ion soft landing (AISL) and microdroplet reactions (MR) was tested. To this aim, heme proteins were ionized and landed onto the working area of multi-walled carbon nanotubes electrodes. The voltammetric and spectroscopic analyses of the modified electrodes evidenced a strong interaction of unfolded structures of the heme proteins with the carbon nanotubes surface.Moreover, the possibility to use the ESI Z-spray source to study microdroplet reactions was attempted by exploring the accelerated acid-catalyzed decomposition of carbohydrates. The study demonstrated that a commercial ESI Z-spray source can provide successful modifications of surfaces by AISL, and represents a suitable platform for the study of accelerated microdroplet reactions.

Material and Charge Transport of Large Organic Salt Clusters and Nanoparticles in Electrospray Ion Beam Deposition.

Electrospray ion beam deposition (ES-IBD) or ion soft landing has been demonstrated as a technique suitable for processing nonvolatile molecules in vacuum under perfectly controlled conditions, an approach also desirable for the deposition of nanoparticles. Here, we present results from several approaches to generate, characterize, and deposit nanoparticle ion beams in vacuum for deposition. We focus on cluster ion beams generated by ESI of organic salt solutions. Small cluster ions of the salts appear in the mass spectra as defined peaks. In addition, we find nanoparticle-sized aggregates, appearing as a low intensity background at high m/z-ratio, and show by IBD experiments that these clusters carry the major amount of material in the ion beam. This transition from clusters to nanoparticles, and their successful deposition, shows that ES-IBD can in principle handle ion beams of very heavy and highly charged nanoparticles. In related experiments, however, we found the deposition of nanoparticles from dispersions to be of low reproducibility, due to the lack of control by mass spectrometry.

Toxicological alterations induced by subacute exposure of silver nanoparticles in Wistar rats.

Silver nanoparticles (AgNPs) have become crucial players in the field of medicine and various other industries. AgNPs have a wide array of applications, which includes production of electronic goods, cosmetics, synthesis of dyes, and printing inks, as well as targeted delivery of drugs to specialized cells inside the body. Even though humans readily come in contact with these particles, the organ-specific accumulation and resulting mechanisms of toxicity induced by inhaled AgNPs are still under investigation. The goal of this study was to determine the organ distribution of inhaled AgNPs and investigate the resulting systemic toxicity. To do this, male Wistar rats were exposed by inhalation to AgNPs for 4hr/day (200 parts per billion/day) for five consecutive days. The nanoparticles were generated using a laser ablation technique using a soft-landing ion mobility (SLIM) instrument. Inductively coupled plasma mass spectrometric (ICP-MS) analysis showed organ-specific accumulation of the nanoparticles, with the highest concentration present in the lungs, followed by the liver and kidneys. Nanoparticle distribution was characterized in the organs using scanning electron microscopy (SEM) and matrix-assisted laser desorption/ionization mass spectrometric (MALDI-MS) imaging. Bone marrow cytotoxicity assay of the cells from the femur of rats showed micronuclei formation and signs of cellular cytotoxicity. Moreover, rats displayed increased levels of circulating lactate and glutathione disulphide (GSSG), as determined by liquid chromatography-mass spectrometry (LC-MS) analysis. Collectively, our observations suggest that inhaled subacute exposure to AgNP results in accumulation of AgNPs in the lungs, liver, and kidneys, preferentially, as well as mediates induced systemic toxicity.

Direct functionalization of C−H bonds by electrophilic anions

Alkanes and [B12X12]2- (X = Cl, Br) are both stable compounds which are difficult to functionalize. Here we demonstrate the formation of a boron-carbon bond between these substances in a two-step process. Fragmentation of [B12X12]2- in the gas phase generates highly reactive [B12X11]- ions which spontaneously react with alkanes. The reaction mechanism was investigated using tandem mass spectrometry and gas-phase vibrational spectroscopy combined with electronic structure calculations. [B12X11]- reacts by an electrophilic substitution of a proton in an alkane resulting in a B-C bond formation. The product is a dianionic [B12X11CnH2n+1]2- species, to which H+ is electrostatically bound. High-flux ion soft landing was performed to codeposit [B12X11]- and complex organic molecules (phthalates) in thin layers on surfaces. Molecular structure analysis of the product films revealed that C-H functionalization by [B12X11]- occurred in the presence of other more reactive functional groups. This observation demonstrates the utility of highly reactive fragment ions for selective bond formation processes and may pave the way for the use of gas-phase ion chemistry for the generation of complex molecular structures in the condensed phase.

Metallic nanoparticle production and exposure/deposition system for toxicological research applications using zebrafish.

Metallic nanoparticles (NPs) have been accepted for various applications ranging from cosmetics to medicine. However, no method has been established in the scientific community that is capable of analyzing various metals, sizes, and levels of exposures without the concern of background chemical contaminations. We present here a system utilizing soft-landing ion mobility (SLIM) exposures of laser ablated metallic clusters capable of operating pressures of reduced vacuum (1 Torr) up to ambient (760 Torr) in the presence of a buffer gas. Clusters experience kinetic energies of less than 1 eV upon exiting the SLIM, allowing for the exposure of NPs to take place in a passive manner. While there is no mass-selection of cluster sizes in this work, it does show for the first time the creation and soft-landing of nanoclusters at ambient pressures. Factors such as area coverage and percentage distribution were studied, as well as the different effects that varying surfaces may cause in the agglomeration of the clusters. Furthermore, the system was successfully used to study the effects of silver nanoparticle exposure and determine the specific organs the NPs accumulate in using zebrafish (Danio rerio) as a model organism. This method provides a novel way to synthesize NPs and expose biological organisms for various toxicological analysis.

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.

Controlling Reactive Battery Interfaces Using Electron-Accepting Surface Layers

Understanding the reactivity of electrolyte and solvent molecules as well as electroactive species at operating battery interfaces enables the rational design of improved battery technologies. This molecular-level understanding, however, is often challenging to obtain due to the heterogeneity of electrode surfaces and the complexity of chemical transformation occurring under applied electric fields. For example, battery electrode surfaces contain various distributions of metal-oxides, -hydroxides, -carbonates, and -halides. Subsequently, redox and electron transfer properties vary widely over these heterogeneous surfaces. In this work, we provide a comprehensive outlook and delineate the reactivity of selected polysulfide electroactive ions on well-defined reactive lithium surfaces and propose an approach to modulate the surface reactivity by using electron-accepting surface layers. We used ion soft landing to deposit mass-selected lithium polysulfide ions (LiS4 - and Li5S12 -) on oxidized and fluorinated lithium surfaces. Ion soft-landing is a versatile mass spectrometry-based deposition technique that allows ionic molecules to be selectively deposited onto electrode surfaces without counter-ions and solvent molecules. The reactivity of the deposited polysulfide ions was studied using a combination of experimental and theoretical approaches. Specifically, i n-situ X-ray photoelectron and Raman spectroscopy revealed the presence of both reduced (Li2S) and oxidized (LixSOy) polysulfide species on electron-accepting lithium oxide surfaces. Ab-initio molecular dynamics calculations corroborated the formation of species observed in the experimental study. Bader charge analysis of the systems showed multi-electron transfer reactions for sulfur atoms, starting from neutral species and reacting to oxidation states ranging from +3 to -2. Calculations also indicate that a relatively thick (> 1 nm) surface oxide layer is required to promote reactivity, and that thinner layers can inhibit reaction. Our study provides fundamental insights into the complex redox chemistry and decomposition mechanism that occurs at heterogeneous lithium electrodes and will lead to rational design of efficient and stable battery interfaces.

Understanding Electrochemical Interface Using Atom-By-Atom Metal Substitution of Redox Species

Molecular-level understanding of electrochemical processes at nanostructured electrode-electrolyte interfaces (EEI) is key to the development of clean and sustainable electrochemical technologies in energy generation and storage as well as water and chemical separation and purification. Herein, we introduced a novel in situ electrochemical cell coupled with ion soft landing to study the precisely defined operating EEI. Ion soft landing is a mass spectrometry based deposition technique which enables to land uniform layers of redox-active ions onto electrode surfaces with precise control over the charge state, composition, and kinetic energy. In this work, we used ion soft landing to study (i) the multi-electron redox activity of Keggin polyoxometalate anions (POMs) to design high-performance EEIs for energy storage (ii) examined how “atom-by-atom” metal substitution affects the redox activity of well-defined mixed addenda POM anions, PMoxW12-xO40 3- (x = 0,1,2,3,6,9,12) at ionic liquid based in situ electrochemical cell. We made a striking observation in in situ experiment and well-supported by theoretical calculation, which is that substantial increase in the first reduction potential obtained by substitution of only few tungsten by molybdenum atoms in the PW12O40 3- anions. More specifically, PMo3W9O40 3- showed the highest redox activity compared to all other mixed-addenda POM anions, which making it as a “super active redox anion” for this class of redox species. This presentation will also focus how these fundamental understanding on the activity of mixed addenda POMs was translated well into achieving device-level supercapacitor performance with superior capacity and capacity retention.

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.

Corrigendum: From Isolated Ions to Multilayer Functional Materials Using Ion Soft Landing

In this Review article, a systematic shift by one in the reference numbering of the Figure captions has occurred: Figure 1 refers to Ref. [22] instead of [23] Figure 3 refers to Ref. [47] instead of [48] Figure 5 refers to Ref. [76] instead of [77] Figure 6 refers to Ref. [80] instead of [81] Figure 8 refers to Refs. [81] and [82] instead of [82] and [83]