Current Developments in Operando Electron Paramagnetic Resonance Spectroscopy.

Electron paramagnetic resonance (EPR) spectroscopy is a powerful tool for in situ/operando tracking of catalytic reactions that involve paramagnetic species either as a catalyst (e.g. transition metal ions or defects), reaction intermediates (radicals) or poisoning agents such as coke. This article provides a summary of recent experimental examples and developments in resonator design as well as detection schemes that were carried out in our group. Opportunities for applying this technique are illustrated by examples, including studies of transition metal exchanged zeolites and metal-free zeolites as well as metal oxide catalysts. The inherent limitations of EPR applied at high temperatures are discussed, as well as strategies in reducing or lifting these restrictions are evaluated and ideas for future improvements and methodologies are discussed.

Cryogenic 35GHz pulse ENDOR probehead accommodating large sample sizes: Performance and applications.

The construction and performance of a cryogenic 35GHz pulse electron nuclear double resonance (ENDOR) probehead for large samples is presented. The resonator is based on a rectangular TE(102) cavity in which the radio frequency (rf) B(2)-field is generated by a two turn saddle ENDOR coil crossing the resonator along the sample axis with minimal distance to the sample tube. An rf power efficiency factor is used to define the B(2)-field strength per square-root of the transmitted rf power over the frequency range 2-180MHz. The distributions of the microwave B(1)- and E(1)-field, and the rf B(2)-field are investigated by electromagnetic field calculations. All dielectrics, the sample tube, and coupling elements are included in the calculations. The application range of the probehead and the advantages of using large sample sizes are demonstrated and discussed on a number of paramagnetic samples containing transition metal ions.

Cryogenic Q-band (35GHz) probehead featuring large excitation microwave fields for pulse and continuous wave electron paramagnetic resonance spectroscopy: performance and applications.

The construction and performance of a Q-band (35GHz) cryogenic probehead for pulse electron paramagnetic resonance and continuous wave electron paramagnetic resonance measurements with down-scaled loop gap resonators (LGRs) is presented. The advantage of the LGR in comparison to TE(012) resonators lies in the large B(1) microwave (mw) fields that can be generated with moderate input mw power. We demonstrated with several examples that this allows optimal performance for double-quantum electron coherence, HYSCORE, and hyperfine decoupling experiments employing matched and high turning angle mw pulses with high B(1)-fields. It is also demonstrated that with very low excitation power (i.e. 10-40 mW), B(1)-fields in LGRs are still sufficient to allow short mw pulses and thus experiments such as HYSCORE with high-spin systems to be performed with good sensitivity. A sensitivity factor Lambda(rs) of LGRs with different diameters and lengths is introduced in order to compare the sensitivity of different resonant structures. The electromagnetic field distribution, the B(1)-field homogeneity, the E(1)-field strength, and the microwave coupling between wave guide and LGRs are investigated by electromagnetic field calculations. The advantage and application range using LGRs for small sample diameters is discussed.

Direct EPR detection of transient and continuous wave signals at 2.5 GHz.

Direct detection of free induction decays and electron spin echoes, and the recording of echo-detected EPR spectra and electron spin echo envelope modulation patterns at a microwave frequency of 2.5 GHz is demonstrated. This corresponds to the measurement of the transverse magnetization in the laboratory frame, rather than in the rotating frame as usually done by down-converting the signal (homodyne detection). An oscilloscope with a 6-GHz analog bandwidth, a sampling rate of 20 GigaSamples per second, and a trigger frequency of 5 GHz for the edge trigger and 750 MHz for the advanced trigger, is used in these experiments. For signal averaging a 3-GHz microwave clock divider has been developed to synchronize the oscilloscope with the frequency of the EPR signal. Moreover, direct detection of continuous wave EPR signals at 2.5 GHz is described.