NOx emissions are a major source of pollution, demanding ever improving performance from catalytic aftertreatment systems. However, catalyst development is often hindered by limited understanding of the catalyst at work, exacerbated by widespread use of model rather than technical catalysts, and global rather than spatially-resolved characterisation tools. Here we combine operando X-ray absorption spectroscopy with microtomography to perform 3D chemical imaging of the chemical state of copper species in a Cu-SSZ-13 washcoated monolith catalyst during NOx reduction. Gradients in copper oxidation state and coordination environment, resulting from an interplay of NOx reduction with adsorption-desorption of NH3 and mass transport phenomena, were revealed with micrometre spatial resolution while simultaneously determining catalytic performance. Crucially, direct 3D visualisation of complex reactions on nonmodel catalysts is only feasible using operando X-ray spectrotomography, which can improve our understanding of structure-activity relationships including the observation of mass and heat transport effects.Due to health and environmental concerns, there is currently a strong societal demand for improved air quality, driving strict emission limits for CO, NOx, unburnt hydrocarbons and particulates. The primary means of mitigating such pollutants is through more efficient catalytic converters. Highly effective Cu-zeolite catalysts such as Cu-SSZ-13 (chabazite) are among the prominent recent examples of active materials for selective catalytic reduction of NOx with ammonia (NH3-SCR) 1,2 .
This paper presents a deep learning algorithm for tomographic reconstruction (GANrec). The algorithm uses a generative adversarial network (GAN) to solve the inverse of the Radon transform directly. It works for independent sinograms without additional training steps. The GAN has been developed to fit the input sinogram with the model sinogram generated from the predicted reconstruction. Good quality reconstructions can be obtained during the minimization of the fitting errors. The reconstruction is a self‐training procedure based on the physics model, instead of on training data. The algorithm showed significant improvements in the reconstruction accuracy, especially for missing‐wedge tomography acquired at less than 180° rotational range. It was also validated by reconstructing a missing‐wedge X‐ray ptychographic tomography (PXCT) data set of a macroporous zeolite particle, for which only 51 projections over 70° could be collected. The GANrec recovered the 3D pore structure with reasonable quality for further analysis. This reconstruction concept can work universally for most of the ill‐posed inverse problems if the forward model is well defined, such as phase retrieval of in‐line phase‐contrast imaging.
Three-dimensional (3D) x-ray microscopy by ptychographic tomography requires elaborate numerical reconstructions. We describe a coupled ptychography-tomography reconstruction algorithm and apply it to an experimental ptychographic x-ray computed tomography data set of a catalyst particle. Compared to the traditional sequential algorithm, in which ptychographic projections are reconstructed to serve as input for subsequent tomographic reconstruction, the coupled ptychography-tomography algorithm reconstructs the 3D volume with higher spatial resolution over a larger field of view. Coupling the data from different projections improves the overall reconstruction, and the ptychographic sampling in individual projections can be coarsened beyond the point of overlap between neighboring scan points, still leading to stable reconstructions.
Two in situ `nanoreactors' for high-resolution imaging of catalysts have been designed and applied at the hard X-ray nanoprobe endstation at beamline P06 of the PETRA III synchrotron radiation source. The reactors house samples supported on commercial MEMS chips, and were applied for complementary hard X-ray ptychography (23 nm spatial resolution) and transmission electron microscopy, with additional X-ray fluorescence measurements. The reactors allow pressures of 100 kPa and temperatures of up to 1573 K, offering a wide range of conditions relevant for catalysis. Ptychographic tomography was demonstrated at limited tilting angles of at least ±35° within the reactors and ±65° on the naked sample holders. Two case studies were selected to demonstrate the functionality of the reactors: (i) annealing of hierarchical nanoporous gold up to 923 K under inert He environment and (ii) acquisition of a ptychographic projection series at ±35° of a hierarchically structured macroporous zeolite sample under ambient conditions. The reactors are shown to be a flexible and modular platform for in situ studies in catalysis and materials science which may be adapted for a range of sample and experiment types, opening new characterization pathways in correlative multimodal in situ analysis of functional materials at work. The cells will presently be made available for all interested users of beamline P06 at PETRA III.
The hierarchical pore systems of Pt/Al 2 O 3 exhaust gas aftertreatment catalysts were analyzed with a collection of correlative imaging techniques to monitor changes induced by hydrothermal aging. Synergistic imaging with laboratory X-ray microtomography, synchrotron radiation ptychographic X-ray computed nanotomography and electron tomography allowed quantitative observation of the catalyst pore architecture from cm to nm scale. Thermal aging at 750 °C in air and hydrothermal aging at 1050 °C in 10% H 2 O/air caused increasing structural degradation, which manifested as widespread sintering of Pt particles, increased volume and quantity of macropores (>20 nm), and reduction in effective surface area coupled to decreasing volume and frequency of mesopores (2-20 nm) and micropores (<2 nm). Electron tomography unraveled the 3D structure with high resolution allowing visualization of meso-and macropores, but with samples of maximum 300 nm thickness. To complement this, hard X-ray ptychographic tomography produced quantitative 3D electron density maps of 5 µm diameter samples with spatial resolution <50 nm, effectively filling the resolution gap between electron tomography and hard X-ray microtomography. The obtained 3D volumes are an essential input for future computational modelling of fluid dynamics, mass transport or diffusion properties and may readily complement bulk 1D porosimetry measurements or simulated porosity.
Structure–activity relations in heterogeneous catalysis can be revealed through in situ and operando measurements of catalysts in their active state. While hard X-ray tomography is an ideal method for non-invasive, multimodal 3D structural characterization on the micron to nm scale, performing tomography under controlled gas and temperature conditions is challenging. Here, we present a flexible sample environment for operando hard X-ray tomography at synchrotron radiation sources. The setup features are discussed, with demonstrations of operando powder X-ray diffraction tomography (XRD-CT) and energy-dispersive tomographic X-ray absorption spectroscopy (ED-XAS-CT). Catalysts for CO2 methanation and partial oxidation of methane are shown as case studies. The setup can be adapted for different hard X-ray microscopy, spectroscopy, or scattering synchrotron radiation beamlines, is compatible with absorption, diffraction, fluorescence, and phase-contrast imaging, and can operate with scanning focused beam or full-field acquisition mode. We present an accessible methodology for operando hard X-ray tomography studies, which offer a unique source of 3D spatially resolved characterization data unavailable to contemporary methods.
Many processes and materials in heterogeneous catalysis undergo dynamic structural changes depending on their chemical environment. Monitoring such dynamic changes can be challenging using conventional spectroscopic characterization tools, due to the high time resolution required. Here, a high-resolution 2D X-ray camera operating at 50 Hz full-frame rate was synchronized with a QEXAFS monochromator, enabling rapid spectro-microscopic imaging with chemical contrast over individual pixels. This was used to monitor chemical gradients within a model Pt/Al2O3 catalyst during catalytic partial oxidation of methane to synthesis gas. The transition from methane combustion (partly oxidized Pt) to combustion-reforming and partial oxidation (fully reduced Pt) was observed by a characteristic reduction front, which progressed from the end of the catalyst bed towards its beginning on the second time scale. The full-field QEXAFS imaging method applied here allows acquisition of entire XANES spectra `on the fly' in a rapid and spatially resolved manner. The combination of high spatial and temporal resolution with spectroscopic data offers new opportunities for observing dynamic processes in catalysts and other functional materials at work. The methodology is flexible and can be applied at beamlines equipped with a QEXAFS or other fast-scanning monochromators and a suitable sample environment for gas phase analytics to allow for catalytic studies at the same time.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
334 Leonard St
Brooklyn, NY 11211
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.