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Coexisting multi-states in catalytic hydrogen oxidation on rhodium.

ABSTRACT: Catalytic hydrogen oxidation on a polycrystalline rhodium foil used as a surface structure library is studied by scanning photoelectron microscopy (SPEM) in the 10^-6 mbar pressure range, yielding spatially resolved X-ray photoemission spectroscopy (XPS) measurements. Here we report an observation of a previously unknown coexistence of four different states on adjacent differently oriented domains of the same Rh sample at the exactly same conditions. A catalytically active steady state, a catalytically inactive steady state and multifrequential oscillating states are simultaneously observed. Our results thus demonstrate the general possibility of multi-states in a catalytic reaction. This highly unusual behaviour is explained on the basis of peculiarities of the formation and depletion of subsurface oxygen on differently structured Rh surfaces. The experimental findings are supported by mean-field micro-kinetic modelling. The present observations raise the interdisciplinary question of how self-organising dynamic processes in a heterogeneous system are influenced by the permeability of the borders confining the adjacent regions.

SUBMITTER: Winkler P

PROVIDER: S-EPMC8586342 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

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Coexisting multi-states in catalytic hydrogen oxidation on rhodium.

Winkler P P Zeininger J J Raab M M Suchorski Y Y Steiger-Thirsfeld A A Stöger-Pollach M M Amati M M Gregoratti L L Grönbeck H H Rupprechter G G

Nature communications 20211111 1

Catalytic hydrogen oxidation on a polycrystalline rhodium foil used as a surface structure library is studied by scanning photoelectron microscopy (SPEM) in the 10<sup>-6</sup> mbar pressure range, yielding spatially resolved X-ray photoemission spectroscopy (XPS) measurements. Here we report an observation of a previously unknown coexistence of four different states on adjacent differently oriented domains of the same Rh sample at the exactly same conditions. A catalytically active steady state ...[more]

PMID: 34764290

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Project description:Accurate and complete microkinetic models (MKMs) are powerful for anticipating the behavior of complex chemical systems at different operating conditions. In heterogeneous catalysis, they can be further used for the rapid development and screening of new catalysts. Density functional theory (DFT) is often used to calculate the parameters used in MKMs with relatively high fidelity. However, given the high cost of DFT calculations for adsorbates in heterogeneous catalysis, linear scaling relations (LSRs) and machine learning (ML) models were developed to give rapid estimates of the parameters in MKM. Regardless of the method, few studies have attempted to quantify the uncertainty in catalytic MKMs, as the uncertainties are often orders of magnitude larger than those for gas phase models. This study explores uncertainty quantification and Bayesian Parameter Estimation for thermodynamic parameters calculated by DFT, LSRs, and GemNet-OC, a ML model developed under the Open Catalyst Project. A model for catalytic partial oxidation of methane (CPOX) on Rhodium was chosen as a case study, in which the model's thermodynamic parameters and their associated uncertainties were determined using DFT, LSR, and GemNet-OC. Markov Chain Monte Carlo coupled with Ensemble Slice Sampling was used to sample the highest probability density (HPD) region of the posterior and determine the maximum of the a posteriori (MAP) for each thermodynamic parameter included. The optimized microkinetic models for each of the three estimation methods had quite similar mechanisms and agreed well with the experimental data for gas phase mole fractions. Exploration of the HPD region of the posterior further revealed that adsorbed hydroxide and oxygen likely bind on facets other than Rhodium 111. The demonstrated workflow addresses the issue of inaccuracies arising from the integration of data from multiple sources by considering both experimental and computational uncertainties, and further reveals information about the active site that would not have been discovered without considering the posterior.

Dataset Information

Coexisting multi-states in catalytic hydrogen oxidation on rhodium.

Publications

Coexisting multi-states in catalytic hydrogen oxidation on rhodium.

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