Ammonia absorption has been investigated in metal-organic frameworks (UiO-67, HKUST-1 and CPO-27-Co) using custom-built apparatus that allows simultaneous neutron powder diffraction (NPD), microwave dielectric characterisation and out-gas mass spectroscopy of solid-state materials during ammonia adsorption. Deuterated ammonia was flowed through the sample and absorption monitored using mass flow meters and mass spectroscopy. Argon gas was then flowed through the ammoniated sample to cause ammonia desorption. Changes in structure found from NPD measurements were compared to changes in dielectric characteristics to differentiate physisorbed and metal-coordinated ammonia, as well as determine decomposition of sample materials. The results of these studies allow the identification of materials with useful ammonia storage properties and provides a new metric for the measurement of gas absorption within mesoporous solids.

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Microwave cavity perturbation measurements are a useful way to analyze material properties. Temperature changes can be introduced during these measurements either intentionally or as a result of some other process. The microwave cavity itself also has a temperature-dependent response, which can affect the results. A common method to correct is to use another resonant mode separately to the measurement mode, which is not affected by the sample. Instead of using independent modes, this paper describes a method to use split degenerate TM m10 modes of cylindrical cavities. TM m10 consists of two modes with identical field patterns with a relative rotation between them and identical resonant frequencies. A strategically placed perturbation reduces the frequency of one of the TM m10 modes and affects the coupling of both modes by reconfiguring the fields. This can be used for temperature correction by placing a sample such that both modes are equally coupled. The lower frequency, the perturbed mode is used as a measurement mode. The higher mode is used as a reference for temperature correction as it is unaffected by the sample. This technique was verified by measuring the permittivity of pure water using an aluminum microwave cavity resonator at 3.96 GHz. The temperature was swept between 20 • C and 60 • C, and the results was verified against the literature.

This paper describes the design considerations for a dual mode X-band continuous wave (CW) Electron Paramagnetic Resonance (EPR) cavity, for simultaneous EPR measurement and microwave heating of the same sample. An elliptical cavity geometry is chosen to split the degeneracy of the TM110 mode, allowing for a well resolved EPR signal with the TM110,a and TM110,b modes resonating at around 10 GHz and 9.5 GHz, respectively, the latter of which is used for EPR measurements. This geometry has the benefit that the TM010 mode used for microwave heating resonates at 6.1 GHz, below the cut off frequency of the X-band waveguide used for the EPR channel, providing effective isolation between the heating and EPR channels. The use of a pair of 9 µm thick copper clad laminates as the flat cavity walls allows for sufficient penetration of the modulation field (Bmod) into the cavity, as well as maintaining a high cavity Q factor (> 5700) for sensitive EPR measurements. Locating the heating port at an angle of 135° to the EPR port provides additional space for easier coupling adjustment and for larger sample access to be accommodated. The associated decrease of EPR signal strength is fully compensated for by using a 7.2 GHz low pass filter on the heating port. EPR spectra using 1.6 mm and 4.0 mm sample tubes are shown at room temperature (298 K) and 318 K for a standard Cu(acac)2 solution, demonstrating the effectiveness of this dual-mode EPR cavity for microwave heating during EPR detection.

The industrially important para-xylene oxidation reaction, based on a Co/Mn/Br catalyst, operates in a water/acetic acid (H2O/AcOH) solvent system. The correct H2O/AcOH ratio of the solvent is crucial in controlling...