Intraparticle ion motions are critical to the structure and properties of nanomaterials, but rarely disclosed. Herein, in situ visualization of ion motions in a single nanoparticle is presented by dark-field microscopy imaging, which shows HgCl2 -induced structural transformation of amorphous selenium nanoparticles (SeNPs) with the main composition of Se8 . Owing to the high binding affinity with selenium and coulomb interactions, Hg2+ ions can permeate into the interior of SeNPs, making the amorphous Se8 turn to polycrystalline Hg3 Se2 Cl2 . As a proof of concept, SeNPs then serve as a highly effective scavenger for selective removal of Hg2+ ions from solution. This new finding offers visual proof for the photophysical process involving intraparticle ion motion, demonstrating that tracking the ion motions is a novel strategy to comprehend the formation mechanism with the purpose of developing new nanostructures like nanoalloys and nano metal compounds.

Perovskite solar cells that incorporate small concentrations of Cs in their A-site have shown increased lifetime and improved device performance. Yet, the development of fully stable devices operating near the theoretical limit requires understanding how Cs influences perovskites\' electrical properties at the nanoscale. Here, we determine how the chemical composition of three perovskites (MAPbBr3, MAPbI3, and Cs-mixed) affects their short- and long-term voltage stabilities, with <50 nm spatial resolution. We map an anomalous irreversible electrical signature on MAPbBr3 at the mesoscale, resulting in local V oc variations of ∼400 mV, and in entire grains with negative contribution to the V oc. These measurements prove the necessity of high spatial resolution mapping to elucidate the fundamental limitations of this emerging material. Conversely, we capture the fully reversible voltage response of Cs-mixed perovskites, composed by Cs0.06(MA0.17FA0.83)0.94Pb(I0.83Br0.17)3, demonstrating that the desired electrical output persists even at the nanoscale. The Cs-mixed material presents no spatial variation in V oc, as ion motion is restricted. Our results show that the nanoscale electrical behavior of the perovskites is intimately connected to their chemical composition and macroscopic response.

Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) at the cyclotron frequency instead of the reduced cyclotron frequency has been experimentally demonstrated using narrow aperture detection electrode (NADEL) ICR cells. Here, based on the results of SIMION simulations, we provide the initial mechanistic insights into the cyclotron frequency regime generation in FT-ICR MS. The reason for cyclotron frequency regime is found to be a new type of a collective motion of ions with a certain dispersion in the initial characteristics, such as pre-excitation ion velocities, in a highly non-quadratic trapping potential as realized in NADEL ICR cells. During ion detection, ions of the same m/z move in phase for cyclotron ion motion but out of phase for magnetron (drift) ion motion destroying signals at the fundamental and high order harmonics that comprise reduced cyclotron frequency components. After an initial magnetron motion period, ion clouds distribute into a novel type of structures - ion slabs, elliptical cylinders, or star-like structures. These structures rotate at the Larmor (half-cyclotron) frequency on a plane orthogonal to the magnetic field, inducing signals at the true cyclotron frequency on each of the narrow aperture detection electrodes. To eliminate the reduced cyclotron frequency peak upon dipolar ion detection, a number of slabs or elliptical cylinders organizing a star-like configuration are formed. In a NADEL ICR cell with quadrupolar ion detection, a single slab or an elliptical cylinder is sufficient to minimize the intensity of the reduced cyclotron frequency components, particularly the second harmonic. Graphical Abstract ᅟ.

The performance of organic solar cells (OSCs) with edetate electrolytes depends on external bias, and ions are speculated to be responsible for this phenomenon. To clarify the detailed relationship between the ions of electrolytes and the bias-dependent behaviors of devices, this work introduces four edetate cathode interlayers (EDTA-X, X = nH(4-n)Na, n = 0, 1, 2, and 4) containing different kinds and number of cations into inverted OSCs. The results show that the devices initial and saturated (after external bias treatment) power conversion efficiencies (PCEs) both decrease with the increase in the number of H+. Moreover, the bias-dependent degrees increase with the increase in H+ number; with that, the PCE increment of EDTA-4H device is 53.4%, while that of the EDTA-4Na device is almost unchanged. The electrical impedance spectroscopy and capacitance-voltage tests reveal that the interfacial recombination is greatly suppressed by external bias treatment, which is not a result of the decreased density of defect states. The results indicate that the ion\'s motion, specifically the H+ motion, under external electrical field is responsible for the bias-dependent behavior, which is conducive to the design of new efficient electrolytic interlayers without bias-dependent performance.

The phenomenon of ion cyclotron resonance allows for determining mass-to-charge ratio, m/z, of an ensemble of ions by means of measurements of their cyclotron frequency, ω c . In Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), the ω c quantity is usually unavailable for direct measurements: the resonant state is located close to the reduced cyclotron frequency (ω+), whereas the ω c and the corresponding m/z values may be calculated via theoretical derivation from an experimental estimate of the ω+ quantity. Here, we describe an experimental observation of a new resonant state, which is located close to the ω c frequency and is established because of azimuthally-dependent trapping electric fields of the recently developed ICR cells with narrow aperture detection electrodes. We show that in mass spectra, peaks close to ω+ frequencies can be reduced to negligible levels relative to peaks close to ω c frequencies. Due to reduced errors with which the ω c quantity is obtained, the new resonance provides a means of cyclotron frequency measurements with precision greater than that achieved when ω+ frequency peaks are employed. The described phenomenon may be considered for a development into an FT-ICR MS technology with increased mass accuracy for applications in basic research, life, and environmental sciences. Graphical Abstract ᅟ.

Secular frequency scanning is implemented and characterized using both a benchtop linear ion trap and a miniature rectilinear ion trap mass spectrometer. Separation of tetraalkylammonium ions and those from a mass calibration mixture and from a pesticide mixture is demonstrated with peak widths approaching unit resolution for optimized conditions using the benchtop ion trap. The effects on the spectra of ion trap operating parameters, including waveform amplitude, scan direction, scan rate, and pressure are explored, and peaks at black holes corresponding to nonlinear (higher-order field) resonance points are investigated. Reverse frequency sweeps (increasing mass) on the Mini 12 are shown to result in significantly higher ion ejection efficiency and superior resolution than forward frequency sweeps that decrement mass. This result is accounted for by the asymmetry in ion energy absorption profiles as a function of AC frequency and the shift in ion secular frequency at higher amplitudes in the trap due to higher order fields. We also found that use of higher AC amplitudes in forward frequency sweeps biases ions toward ejection at points of higher order parametric resonance, despite using only dipolar excitation. Higher AC amplitudes also increase peak width and decrease sensitivity in both forward and reverse frequency sweeps. Higher sensitivity and resolution were obtained at higher trap pressures in the secular frequency scan, in contrast to conventional resonance ejection scans, which showed the opposite trend in resolution on the Mini 12. Mass range is shown to be naturally extended in secular frequency scanning when ejecting ions by sweeping the AC waveform through low frequencies, a method which is similar, but arguably superior, to the more usual method of mass range extension using low q resonance ejection. Graphical Abstract ᅟ.