Automated Mechanism Generation Using Linear Scaling Relationships and Sensitivity Analyses Applied to Catalytic Partial Oxidation of Methane

ACS Catalysis ◽  
2021 ◽  
pp. 7114-7125
Author(s):  
Emily J. Mazeau ◽  
Priyanka Satpute ◽  
Katrín Blöndal ◽  
C. Franklin Goldsmith ◽  
Richard H. West
Keyword(s):  
Partial Oxidation ◽  
Partial Oxidation Of Methane ◽  
Sensitivity Analyses ◽  
Catalytic Partial Oxidation ◽  
Linear Scaling ◽  
Scaling Relationships ◽  
Oxidation Of Methane

scholarly journals Automated Mechanism Generation Using Linear Scaling Relationships and Sensitivity Analyses Applied to Catalytic Partial Oxidation of Methane

2021 ◽  
Author(s):  
Emily Mazeau ◽  
Priyanka Satpute ◽  
Katrin Blondal ◽  
Franklin Goldsmith ◽  
Richard West
Keyword(s):  
Rate Control ◽  
Binding Energies ◽  
Sensitivity Analyses ◽  
Catalytic Partial Oxidation ◽  
Linear Scaling ◽  
Scaling Relationships ◽  
Oxidation Of Methane ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Rate Limiting

<div>Kinetic parameters for surface reactions can be predicted using a combination of DFT calculations, scaling relations, and machine learning algorithms; however, construction of microkinetic models still requires a knowledge of all the possible, or at least reasonable, reaction pathways. The recently developed Reaction Mechanism Generator (RMG) for heterogeneous catalysis, now included in RMG version 3.0, is built upon well-established, open-source software that can provide detailed reaction mechanisms from user-supplied initial conditions without making <i>a priori</i> assumptions. RMG is now able to estimate adsorbate thermochemistry and construct detailed microkinetic models on a range of hypothetical metal surfaces using linear scaling relationships. These relationships are a simple, computationally efficient way to estimate adsorption energies by scaling the energy of a calculated surface species on one metal to any other metal. By conducting simulations with sensitivity analyses, users can not only determine the rate limiting step on each surface by plotting a "volcano surface" for the degree of rate control of each reaction as a function of elemental binding energies, but also screen novel catalysts for desirable properties. We investigated the catalytic partial oxidation of methane to demonstrate the utility of this new tool and determined that an inlet gas C/O ratio of 0.8 on a catalyst with carbon and oxygen binding energies of -6.75 eV and -5.0 eV, respectively, yields the highest amount of synthesis gas. Sensitivity analyses show that while the dissociative adsorption of O<sub>2</sub> has the highest degree of rate control, the interactions between individual reactions and reactor conditions are complex, which result in a dynamic rate-limiting step across differing metals.</div>

scholarly journals Automated Mechanism Generation Using Linear Scaling Relationships and Sensitivity Analyses Applied to Catalytic Partial Oxidation of Methane

2021 ◽  
Author(s):  
Emily Mazeau ◽  
Priyanka Satpute ◽  
Katrin Blondal ◽  
Franklin Goldsmith ◽  
Richard West
Keyword(s):  
Rate Control ◽  
Binding Energies ◽  
Sensitivity Analyses ◽  
Catalytic Partial Oxidation ◽  
Linear Scaling ◽  
Scaling Relationships ◽  
Oxidation Of Methane ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Rate Limiting

<div>Kinetic parameters for surface reactions can be predicted using a combination of DFT calculations, scaling relations, and machine learning algorithms; however, construction of microkinetic models still requires a knowledge of all the possible, or at least reasonable, reaction pathways. The recently developed Reaction Mechanism Generator (RMG) for heterogeneous catalysis, now included in RMG version 3.0, is built upon well-established, open-source software that can provide detailed reaction mechanisms from user-supplied initial conditions without making <i>a priori</i> assumptions. RMG is now able to estimate adsorbate thermochemistry and construct detailed microkinetic models on a range of hypothetical metal surfaces using linear scaling relationships. These relationships are a simple, computationally efficient way to estimate adsorption energies by scaling the energy of a calculated surface species on one metal to any other metal. By conducting simulations with sensitivity analyses, users can not only determine the rate limiting step on each surface by plotting a "volcano surface" for the degree of rate control of each reaction as a function of elemental binding energies, but also screen novel catalysts for desirable properties. We investigated the catalytic partial oxidation of methane to demonstrate the utility of this new tool and determined that an inlet gas C/O ratio of 0.8 on a catalyst with carbon and oxygen binding energies of -6.75 eV and -5.0 eV, respectively, yields the highest amount of synthesis gas. Sensitivity analyses show that while the dissociative adsorption of O<sub>2</sub> has the highest degree of rate control, the interactions between individual reactions and reactor conditions are complex, which result in a dynamic rate-limiting step across differing metals.</div>

scholarly journals Automated Mechanism Generation Using Linear Scaling Relationships and Sensitivity Analyses Applied to Catalytic Partial Oxidation of Methane

2021 ◽  
Author(s):  
Emily Mazeau ◽  
Priyanka Satpute ◽  
Katrin Blondal ◽  
Franklin Goldsmith ◽  
Richard West
Keyword(s):  
Rate Control ◽  
Binding Energies ◽  
Sensitivity Analyses ◽  
Catalytic Partial Oxidation ◽  
Linear Scaling ◽  
Scaling Relationships ◽  
Oxidation Of Methane ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Rate Limiting

<div>Kinetic parameters for surface reactions can be predicted using a combination of DFT calculations, scaling relations, and machine learning algorithms; however, construction of microkinetic models still requires a knowledge of all the possible, or at least reasonable, reaction pathways. The recently developed Reaction Mechanism Generator (RMG) for heterogeneous catalysis, now included in RMG version 3.0, is built upon well-established, open-source software that can provide detailed reaction mechanisms from user-supplied initial conditions without making <i>a priori</i> assumptions. RMG is now able to estimate adsorbate thermochemistry and construct detailed microkinetic models on a range of hypothetical metal surfaces using linear scaling relationships. These relationships are a simple, computationally efficient way to estimate adsorption energies by scaling the energy of a calculated surface species on one metal to any other metal. By conducting simulations with sensitivity analyses, users can not only determine the rate limiting step on each surface by plotting a "volcano surface" for the degree of rate control of each reaction as a function of elemental binding energies, but also screen novel catalysts for desirable properties. We investigated the catalytic partial oxidation of methane to demonstrate the utility of this new tool and determined that an inlet gas C/O ratio of 0.8 on a catalyst with carbon and oxygen binding energies of -6.75 eV and -5.0 eV, respectively, yields the highest amount of synthesis gas. Sensitivity analyses show that while the dissociative adsorption of O<sub>2</sub> has the highest degree of rate control, the interactions between individual reactions and reactor conditions are complex, which result in a dynamic rate-limiting step across differing metals.</div>

scholarly journals Oscillatory Behaviour of Ni Supported on ZrO2 in the Catalytic Partial Oxidation of Methane as Determined by Activation Procedure

Materials ◽  
2021 ◽  
Vol 14 (10) ◽  
pp. 2495
Author(s):  
Daniela Pietrogiacomi ◽  
Maria Cristina Campa ◽  
Ida Pettiti ◽  
Simonetta Tuti ◽  
Giulia Luccisano ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Partial Oxidation ◽  
Active Sites ◽  
Direct Reduction ◽  
Partial Oxidation Of Methane ◽  
Catalytic Partial Oxidation ◽  
Oxidation Of Methane ◽  
Short Contact Time ◽  
Oxidation Reduction ◽  
Ni Species

Ni/ZrO2 catalysts, active and selective for the catalytic partial oxidation of methane to syngas (CH4-CPO), were prepared by the dry impregnation of zirconium oxyhydroxide (Zhy) or monoclinic ZrO2 (Zm), calcination at 1173 K and activation by different procedures: oxidation-reduction (ox-red) or direct reduction (red). The characterization included XRD, FESEM, in situ FTIR and Raman spectroscopies, TPR, and specific surface area measurements. Catalytic activity experiments were carried out in a flow apparatus with a mixture of CH4:O2 = 2:1 in a short contact time. Compared to Zm, Zhy favoured the formation of smaller NiO particles, implying a higher number of Ni sites strongly interacting with the support. In all the activated Ni/ZrO2 catalysts, the Ni–ZrO2 interaction was strong enough to limit Ni aggregation during the catalytic runs. The catalytic activity depended on the activation procedures; the ox-red treatment yielded very active and stable catalysts, whereas the red treatment yielded catalysts with oscillating activity, ascribed to the formation of Niδ+ carbide-like species. The results suggested that Ni dispersion was not the main factor affecting the activity, and that active sites for CH4-CPO could be Ni species at the boundary of the metal particles in a specific configuration and nuclearity.

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