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Soft landing eliminates counter cations from Keggin polyoxometalate-based photocathodes, resulting in a ∼370% increase in maximum power output from a novel device that simultaneously harvests and stores solar energy.
The ability to deposit intact polyatomic ions with well-defined composition, charge state, and kinetic energy onto surfaces makes preparative mass spectrometry, also called ion soft-landing, particularly attractive for preparing uniform molecular and ionic layers. Early studies characterized structures, charge states, and reactivity of sparsely distributed soft-landed species. Recent development of high-flux ionization sources has opened up new opportunities for the precisely-controlled preparation of both two-dimensional assemblies and three-dimensional multilayer architectures using ion soft-landing. Previously unknown phenomena have been uncovered following deposition of large numbers of ions onto supports thereby opening several exciting research directions in this field. Furthermore, faster ion deposition has enabled fabrication of novel functional devices. This review discusses important phenomena and highlights key developments pertaining to preparation of well-defined interfaces for studies in energy storage, catalysis, soft materials, and biology.
Soft landing spacecraft landing gear design for legged assemblies, discussing load, clearance and stability requirements
Polyoxometalates (POM) have been deposited onto carbon nanotube (CNT) electrodes using benchtop ion soft landing (SL) enabled by a vortex-confined electrohydrodynamic desolvation process. The device is based on the dry ion localization and locomotion (DRILL) mass spectrometry interface of Fedorov and co-workers. By adding electrospray emitters, heating the desolvation gas, and operating at high gas flow rates, it is possible to obtain stable ion currents up to -15 nA that are ideal for deposition. Coupled with ambient ion optics, this interface enables desolvated ions to be delivered to surfaces while excluding solvent and counterions. Electron microscopy of surfaces prepared using the device reveal discrete POM and no aggregation that degrades electrode performance. Characterization of POM-coated CNT electrodes in a supercapacitor showed an energy storage capacity similar to that achieved with SL in vacuum. For solutions that produce primarily a single ion by electrospray ionization, benchtop SL offers a simpler and less costly approach for surface modification with applications in catalysis, energy storage, and beyond.
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Computer programs for analysis and evaluation of payload and landing system structures for soft landing of instrument packages
Soft landing of mass-selected ions onto surfaces often results in partial loss of charge that may affect the structure and reactivity of deposited species. In this study, Keggin phosphotungstate anions in two selected charge states, PW12O403- (WPOM3-) and PW12O402- (WPOM2-), were soft-landed onto different self-assembled monolayer (SAM) surfaces and examined using in situ infrared reflection absorption spectroscopy (IRRAS) and density functional theory (DFT) calculations. Partial retention of the 3- charge was observed when WPOM3- was soft-landed onto the fluorinated SAM (FSAM), while the charge state distribution was dominated by the 2- charge after both WPOM3- and WPOM2- were deposited onto a hydrophilic alkylthiol SAM terminated with cationic NH3+ functional groups (NH3+SAM). We found that during the course of the soft landing of WPOM3-, the relative abundance of WPOM3- on FSAM decreased while that of WPOM2- increased. We propose that the higher stability of immobilized WPOM2- in comparison with WPOM3- makes it the preferred charge state of WPOM on both the FSAM and NH3+SAM. We also observe weaker binding of WPOM anions to SAMs in comparison with phosphomolybdate ions (MoPOM) reported previously (J. Phys. Chem. C 2014, 118, 27611–27622). The weaker binding of WPOM to SAMs is attributed to the lower reactivity of WPOM reported in the literature. This study demonstrates that both the charge retention and the reactivity of deposited anionic POM clusters on surfaces are determined by the type of addenda metal atoms in the cluster.
The secondary structures of multiply charged ubiquitin ions soft-landed onto self-assembled monolayer (SAM) surfaces were studied using in situ infrared reflection-absorption spectroscopy (IRRAS). Two charge states of ubiquitin, 5+ and 13+, were mass selected separately from a mixture of different charge states produced by electrospray ionization (ESI). The low 5+ charge state represents a native-like folded state of ubiquitin, while the high 13+ charge state assumes an extended, almost linear conformation. Each of the two charge states was soft-landed onto a CH 3- and COOH-terminated SAM of alkylthiols on gold (HSAM and COOH-SAM). HSAM is a hydrophobic surface known to stabilize helical conformations of soft-landed protonated peptides, whereas COOH-SAM is a hydrophilic surface that preferentially stabilizes β-sheet conformations. IRRAS spectra of the soft-landed ubiquitin ions were acquired as a function of time during and after ion soft-landing. Similar to smaller peptide ions, helical conformations of ubiquitin are found to be more abundant on HSAM, while the relative abundance of β-sheet conformations increases on COOH-SAM. The initial charge state of ubiquitin also has a pronounced effect on its conformation on the surface. Specifically, on both surfaces, a higher relative abundance of helical conformations and lower relative abundance of β-sheet conformations is observed for the 13+ charge state compared to the 5+ charge state. Time-resolved experiments indicate that the α-helical band in the spectrum of the 13+ charge state slowly increases with time on the HSAM surface and decreases in the spectrum of the 13+ charge state on COOH-SAM. These results further support the preference of the hydrophobic HSAM surface toward helical conformations and demonstrate that soft-landed protein ions may undergo slow conformational changes during and after deposition.
Luna-9 soft landing on moon, photographic recording, and radio transmission
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 which influence the immobilization and charge retention of multiply charged anionic molecules. The distribution of charge states of POMs on different SAM surfaces are determined by comparing the IRRAS spectra with vibrational spectra calculated using density functional theory (DFT). In contrast to the results obtained previously for multiply charged cations, soft landed anions are found to retain charge on all three SAM surfaces. This charge retention is attributed to the substantial electron binding energy of the POM anions. Investigation of redox properties by CV reveals that, while surfaces prepared by soft landing exhibit similar features to those prepared by adsorption of POM from solution, the soft landed POM2- has a pronounced shift in oxidation potential compared to POM3- for one of the redox couples. These results demonstrate that ion soft landing is uniquely suited for precisely controlled preparation of substrates with specific electronic and chemical properties that cannot be achieved using conventional deposition techniques.
Lunar and planetary soft landings by gas-filled balloons
A kinetically-limited physical synthesis method based on magnetron sputtering and gas aggregation has been coupled with size-selection and ion soft landing to prepare bare metal nanoparticles on surfaces with controlled coverage, size, composition, and morphology. Employing atomic force microscopy (AFM) and scanning electron microscopy (SEM), it is demonstrated that the size and coverage of bare nanoparticles soft landed onto flat glassy carbon and silicon as well as stepped graphite surfaces may be controlled through size-selection with a quadrupole mass filter and the length of deposition, respectively. The bare nanoparticles are observed with AFM to bind randomly to the flat glassy carbon surface when soft landed at relatively low coverage (1012 ions). In contrast, on stepped graphite surfaces at intermediate coverage (1013 ions) the soft landed nanoparticles are shown to bind preferentially along step edges forming extended linear chains of particles. At the highest coverage (5 x 1013 ions) examined in this study the nanoparticles are demonstrated with both AFM and SEM to form a continuous film on flat glassy carbon and silicon surfaces. On a graphite surface with defects, however, it is shown with SEM that the presence of localized surface imperfections results in agglomeration of nanoparticles onto these features and the formation of neighboring depletion zones that are devoid of particles. Employing high resolution scanning transmission electron microscopy in the high angular annular dark field imaging mode (STEM-HAADF) and electron energy loss spectroscopy (EELS) it is demonstrated that the magnetron sputtering/gas aggregation synthesis technique produces single metal particles with controlled morphology as well as bimetallic alloy nanoparticles with clearly defined core-shell structure. Therefore, this kinetically-limited physical synthesis technique, when combined with ion soft landing, is a versatile complementary method for preparing a wide range of bare supported nanoparticles with selected properties that are free of the solvent, organic capping agents, and residual reactants present with nanoparticles synthesized in solution.
Closed loop optimal guidance equations for soft landing
Hypothesis that Luna IX rocket exhaust during soft landing caused formation of shallow crater visible in Ranger VII lunar probe photographs
Instrumentation for analysis of Mars atmosphere after soft landing
Propellant requirements for unmanned lunar and interplanetary soft landing vehicles presented with equations that couple injection, midcourse and terminal phases
Propellant requirements for unmanned lunar and interplanetary soft landing vehicles presented with equations that couple injection, midcourse and terminal phases
We report the design and evaluation of a new high-intensity electrospray ionization source for ion soft-landing experiments. The source incorporates a dual ion funnel, which enables operation with a higher gas load through an expanded heated inlet into the additional first region of differential pumping. This capability allowed us to examine the effect of the inner diameter (ID) of the heated stainless steel inlet on the total ion current transmitted through the dual funnel interface and, more importantly, the mass-selected ion current delivered to the deposition target. The ion transmission of the dual funnel is similar to the transmission of the single funnel used in our previous soft landing studies. However, substantially higher ion currents were obtained using larger ID heated inlets and an orthogonal inlet geometry, in which the heated inlet is positioned perpendicular to the direction of ion propagation through the instrument. The highest ion currents were obtained using the orthogonal geometry and a 1.4 mm ID heated inlet. The corresponding stable deposition rate of ~1 μg of mass-selected ions per day will facilitate future studies focused on the controlled deposition of biological molecules on substrates and preparation of materials for studies in catalysis, energy storage, and self-assembly