Monitoring the state of charge of vanadium redox flow batteries with an EPR-on-a-Chip dipstick sensor.

The vanadium redox flow battery (VRFB) is considered a promising candidate for large-scale energy storage in the transition from fossil fuels to renewable energy sources. VRFBs store energy by electrochemical reactions of different electroactive species dissolved in electrolyte solutions. The redox couples of VRFBs are VO2+/VO2+ and V2+/V3+, the ratio of which to the total vanadium content determines the state of charge (SOC). V(IV) and V(II) are paramagnetic half-integer spin species detectable and quantifiable with electron paramagnetic resonance spectroscopy (EPR). Common commercial EPR spectrometers, however, employ microwave cavity resonators which necessitate the use of large electromagnets, limiting their application to dedicated laboratories. For an SOC monitoring device for VRFBs, a small, cost-effective submersible EPR spectrometer, preferably with a permanent magnet, is desirable. The EPR-on-a-Chip (EPRoC) spectrometer miniaturises the complete EPR spectrometer onto a single microchip by utilising the coil of a voltage-controlled oscillator as both microwave source and detector. It is capable of sweeping the frequency while the magnetic field is held constant enabling the use of small permanent magnets. This drastically reduces the experimental complexity of EPR. Hence, the EPRoC fulfils the requirements for an SOC sensor. We, therefore, evaluate the potential for utilisation of an EPRoC dipstick spectrometer as an operando and continuously online monitor for the SOC of VRFBs. Herein, we present quantitative proof-of-principle submersible EPRoC experiments on variably charged vanadium electrolyte solutions. EPR data obtained with a commercial EPR spectrometer are in good agreement with the EPRoC data.

Microwave field mapping for EPR-on-a-chip experiments.

Electron paramagnetic resonance-on-a-chip (EPRoC) devices use small voltage-controlled oscillators (VCOs) for both the excitation and detection of the EPR signal, allowing access to unique sample environments by lifting the restrictions imposed by resonator-based EPR techniques. EPRoC devices have been successfully used at multiple frequencies (7 to 360 gigahertz) and have demonstrated their utility in producing high-resolution spectra in a variety of spin centers. To enable quantitative measurements using EPRoC devices, the spatial distribution of the B1 field produced by the VCOs must be known. As an example, the field distribution of a 12-coil VCO array EPRoC operating at 14 gigahertz is described in this study. The frequency modulation-recorded EPR spectra of a "point"-like and a thin-film sample were investigated while varying the position of both samples in three directions. The results were compared to COMSOL simulations of the B1-field intensity. The EPRoC array sensitive volume was determined to be ~19 nanoliters. Implications for possible EPR applications are discussed.

Transition-Metal-Doping of CaO as Catalyst for the OCM Reaction, a Reality Check.

In this study, first-row transition metal-doped calcium oxide materials (Mn, Ni, Cr, Co., and Zn) were synthesized, characterized, and tested for the OCM reaction. Doped carbonate precursors were prepared by a co-precipitation method. The synthesis parameters were optimized to yield materials with a pure calcite phase, which was verified by XRD. EPR measurements on the doped CaO materials indicate a successful substitution of Ca2+ with transition metal ions in the CaO lattice. The materials were tested for their performance in the OCM reaction, where a beneficial effect towards selectivity and activity effect could be observed for Mn, Ni, and Zn-doped samples, where the selectivity of Co- and Cr-doped CaO was strongly reduced. The optimum doping concentration could be identified in the range of 0.04-0.10 atom%, showing the strongest decrease in the apparent activation energy, as well as the maximum increase in selectivity.

Rapid-scan electron paramagnetic resonance using an EPR-on-a-Chip sensor.

Electron paramagnetic resonance (EPR) spectroscopy is the method of choice to investigate and quantify paramagnetic species in many scientific fields, including materials science and the life sciences. Common EPR spectrometers use electromagnets and microwave (MW) resonators, limiting their application to dedicated lab environments. Here, novel aspects of voltage-controlled oscillator (VCO)-based EPR-on-a-Chip (EPRoC) detectors are discussed, which have recently gained interest in the EPR community. More specifically, it is demonstrated that with a VCO-based EPRoC detector, the amplitude-sensitive mode of detection can be used to perform very fast rapid-scan EPR experiments with a comparatively simple experimental setup to improve sensitivity compared to the continuous-wave regime. In place of a MW resonator, VCO-based EPRoC detectors use an array of injection-locked VCOs, each incorporating a miniaturized planar coil as a combined microwave source and detector. A striking advantage of the VCO-based approach is the possibility of replacing the conventionally used magnetic field sweeps with frequency sweeps with very high agility and near-constant sensitivity. Here, proof-of-concept rapid-scan EPR (RS-EPRoC) experiments are performed by sweeping the frequency of the EPRoC VCO array with up to 400 THz s-1, corresponding to a field sweep rate of 14 kT s-1. The resulting time-domain RS-EPRoC signals of a micrometer-scale BDPA sample can be transformed into the corresponding absorption EPR signals with high precision. Considering currently available technology, the frequency sweep range may be extended to 320 MHz, indicating that RS-EPRoC shows great promise for future sensitivity enhancements in the rapid-scan regime.

EPR study of NO radicals encased in modified open C60 fullerenes.

Using pulsed electron paramagnetic resonance (EPR) techniques, the low-temperature magnetic properties of the NO radical being confined in two different modified open C60-derived cages are determined. It is found that the smallest principal g value g3, being assigned to the axis of the radical, deviates strongly from the free electron value. This behaviour results from partial compensation of the spin and orbital contributions to the g3 value. The measured g3 values in the range of 0.7 yield information about the deviation of the locking potential for the encaged NO from axial symmetry. The estimated 17 meV asymmetry is quite small compared to the situation found for the same radical in polycrystalline or amorphous matrices ranging from 300 to 500 meV. The analysis of the temperature dependence of spin relaxation times resulted in an activation temperature of about 3 K, assigned to temperature-activated motion of the NO within the modified open C60-derived cages with coupled rotational and translational degrees of freedom in a complicated three-dimensional locking potential.

Complexation of copper(II)-Chelidamate: A multifrequency-pulsed electron paramagnetic resonance and electron nuclear double resonance analysis.

Multifrequency electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) techniques were used to obtain structural information about the copper(II)-chelidamate complex. Well-resolved nitrogen ENDOR spectra could be recorded from solid solution samples by using selective excitation of spin packets. Evaluation of nuclear quadrupole and dipolar hyperfine interaction of the directly ligated nitrogen allowed for an identification of the bond direction to the copper ion within the eigen frame of the copper g-matrix. Invoking two-dimensional EPR techniques, additional hyperfine interaction with a "distant" nitrogen spin, identified as resulting from the solvent dimethylformamide (DMF), was observed. The experimental data are only consistent with formation of a stable pseudoplanar copper complex with single solvent ligation via its oxygen atom.

Room temperature manipulation of long lifetime spins in metallic-like carbon nanospheres.

The time-window for processing electron spin information (spintronics) in solid-state quantum electronic devices is determined by the spin-lattice and spin-spin relaxation times of electrons. Minimizing the effects of spin-orbit coupling and the local magnetic contributions of neighbouring atoms on spin-lattice and spin-spin relaxation times at room temperature remain substantial challenges to practical spintronics. Here we report conduction electron spin-lattice and spin-spin relaxation times of 175 ns at 300 K in 37±7 nm carbon spheres, which is remarkably long for any conducting solid-state material of comparable size. Following the observation of spin polarization by electron spin resonance, we control the quantum state of the electron spin by applying short bursts of an oscillating magnetic field and observe coherent oscillations of the spin state. These results demonstrate the feasibility of operating electron spins in conducting carbon nanospheres as quantum bits at room temperature.

The effect of atomic nitrogen on the C(60) cage.

We herein report the investigation of N@C(60) exposed to laser flash excitation to exhibit the acceleration of the decay of (N@C(60))* by the encased N atom.

Comparative EPR study of Cu@C60 and N@C60 endofullerenes.

A comparative study of C60-based endohedral fullerenes was performed. From an analysis of spin relaxation times of the recently characterized Cu@C60 metallo-endofullerene, it could be shown that the encased ion occupies a well-defined off-centre position even at room temperature. Localization on the timescale of an EPR experiment is combined with charge transfer of approximately two electrons, resulting in the EPR signature of a 3d9 copper ion. This is in contrast to N@C60, for which a nearly complete decoupling from the cage is found. An upper limit for the variance of collision-induced modulation of the anisotropic nitrogen hfi is determined as (A(eff)2)(1/2) < 500 kHz by an analysis of cross peak intensities in a 2D EPR experiment. Pulsed 95 GHZ ENDOR experiments have been performed to confirm that deformation-induced hyperfine anisotropies are expected to be very small in N@C60.

High-field/high-frequency EPR of paramagnetic functional centers in Cu2+- and Fe3+-modified polycrystalline Pb[Zr(x)Ti(1-x)]O3 ferroelectrics.

Copper(II)- and iron(III)-modified Pb[Zr(x)Ti(1-x)]O3 ferroelectrics were investigated by means of high-field/high-frequency EPR. The results obtained suggest that Cu2+ and Fe3+ both substitute as acceptor centers for [Zr,Ti]4+. Whereas for the iron-doped system the charge compensating oxygen vacancies (V(O)**) lead to the formation of charged (Fe'(Ti-)V(O)**)* defect associates, no such associates have been observed for the copper-modified system. As regards the morphotropic phase boundary, the model of a mesoscopic mixing of the pure-member phases has been refined to a picture in which a nanoscale composition distribution prevails.