Multiscale investigation of adsorption properties of novel 3D printed UTSA-16 structures

Structuring MOF materials is a fundamental step towards their commercialization. Herein we report intensive characterization of 3D-printed UTSA-16 monoliths, facilitated by the development of a new non-aqueous ink formulation, employing hydroxypropyl cellulose and boehmite to adjust the rheology of the ink. What makes this formulation and printing process different from the printed adsorbents and catalysts published previously, is that the resulting structures in this work were not sintered. The presence of the binder matrix not only produced the physical properties for printability but also ensured a homogeneous dispersion of UTSA-16 in the structures, as well as gas adsorption characteristics. The monoliths were tested for the adsorption of different gases (N2, CH4, CO2 and H2O) in order to apply them into separation processes that contribute to defossilizing energy and fuels production. Water is strongly adsorbed in this material (~14 mol/kg at 293 K) and is competing with CO2 for adsorption sites. Breakthrough curves showed that the retention time of CO2 decreases significantly when the feed stream is saturated with water. In this study, synchrotron XRD-CT data were collected in situ, in a non-destructive way, and phase distribution maps were reconstructed to, for the first time, gain insight into the spatial and temporal evolution of the UTSA-16 containing phases in the operating 3D printed monolith during the exposure to CO2.publishedVersio

Sustainable iron-based oxygen carriers for hydrogen production : real-time operando investigation

In this work, a spray-dried Fe-based oxygen carrier with an in situ generated Mg1-xAl2-yFex+yO4-support was investigated during packed-bed chemical looping operation with methane at 900 degrees C. The evolution of the solid-state chemistry taking place in the oxygen carrier material was investigated in real-time with synchrotron X-ray diffraction while the spatial distribution of the phases was investigated using X-ray diffraction computed tomography (XRD-CT). These measurements revealed that some Fe-cations were systematically taken up and released from the spinel support. This take-up and release was shown to be strongly related with the oxidation state of the active phase. Although this take-up and release of Fe-cations decreased the amount of Fe-oxides active in the chemical looping process, the oxygen transfer capacity was still sufficiently high. The microstructure of the oxygen carriers along the length of the packed reactor bed was also investigated with scanning electron microscopy (SEM). The experiments indicate that the MgFeAlOx support with an extra Fe-based active phase is a promising material for oxygen carriers, as it forms a sustainable non-toxic, stable and green alternative to the typical Ni-based oxygen carriers, for hydrogen generation by chemical looping

3D printed Ni/Al2O3 based catalysts for CO2 methanation : a comparative and operando XRD-CT study

Ni-alumina-based catalysts were directly 3D printed into highly adaptable monolithic/multi-channel systems and evaluated for CO2 methanation. By employing emerging 3D printing technologies for catalytic reactor design such as 3D fibre deposition (also referred to as direct write or microextrusion), we developed optimised techniques for tailoring both the support's macro-and microstructure, as well as its active particle precursor distribution. A comparison was made between 3D printed commercial catalysts, Ni-alumina based catalysts and their conventional counterpart, packed beds of beads and pellet. Excellent CO2 conversions and selectivity to methane were achieved for the 3D printed commercial catalyst (95.75% and 95.63% respectively) with stability of over 100 h. The structure-activity relationship of both the commercial and in-house 3D printed catalysts was explored under typical conditions for CO2 hydrogenation to CH4, using operando 'chemical imaging', namely X-Ray Diffraction Computed Tomography (XRD-CT). The 3D printed commercial catalyst showed a more homogenous distribution of the active Ni species compared to the in-house prepared catalyst. For the first time, the results from these comparative characterisation studies gave detailed insight into the fidelity of the direct printing method, revealing the spatial variation in physico-chemical properties (such as phase and size) under operating conditions