A Theoretical Framework for Predicting Catalytic Selectivity in CO₂ Conversion Reactions under Operando Conditions
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| Format: | Recurso digital |
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2025
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| _version_ | 1866901129937289216 |
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| author | Karimi Baghmaleki, Majid |
| author_facet | Karimi Baghmaleki, Majid |
| contents | <p>Catalytic selectivity remains one of the most fundamental and least predictable aspects of heterogeneous catalysis, particularly in complex reaction networks such as CO₂ hydrogenation, where multiple competitive pathways coexist. Conventional theoretical approaches, largely based on static density functional theory (DFT) calculations combined with fixed microkinetic parameters, implicitly assume invariant activation free energies and therefore struggle to capture experimentally observed selectivity switching under operando conditions. Here, we develop a unified theoretical framework that explicitly incorporates the influence of reaction conditions into catalytic energetics through an environment-dependent free energy functional integrated with microkinetic modeling. The framework introduces a systematic modulation of intrinsic activation free energies as a controlled expansion of the surface free energy with respect to temperature, pressure, surface coverage, and electronic perturbations. This formulation provides a direct analytical link between operando conditions and effective reaction barriers, enabling prediction of selectivity trends and inversion phenomena. The theory is analytically derived, computationally implementable, and broadly applicable to heterogeneous catalytic systems. Its relevance is illustrated through application to CO₂ hydrogenation pathways leading to methanol and methane, where experimentally observed selectivity shifts are rationalized within a single theoretical construct. The proposed framework establishes a general basis for operando-aware catalyst design beyond static energy landscapes. <br> Keywords Catalytic selectivity; CO₂ hydrogenation; microkinetic modeling; operando catalysis; theoretical catalysis; free energy modulation </p> |
| format | Recurso digital |
| id | zenodo_https___doi_org_10_5281_zenodo_18099383 |
| institution | Zenodo |
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| publishDate | 2025 |
| publisher | Zenodo |
| record_format | zenodo |
| spellingShingle | A Theoretical Framework for Predicting Catalytic Selectivity in CO₂ Conversion Reactions under Operando Conditions Karimi Baghmaleki, Majid <p>Catalytic selectivity remains one of the most fundamental and least predictable aspects of heterogeneous catalysis, particularly in complex reaction networks such as CO₂ hydrogenation, where multiple competitive pathways coexist. Conventional theoretical approaches, largely based on static density functional theory (DFT) calculations combined with fixed microkinetic parameters, implicitly assume invariant activation free energies and therefore struggle to capture experimentally observed selectivity switching under operando conditions. Here, we develop a unified theoretical framework that explicitly incorporates the influence of reaction conditions into catalytic energetics through an environment-dependent free energy functional integrated with microkinetic modeling. The framework introduces a systematic modulation of intrinsic activation free energies as a controlled expansion of the surface free energy with respect to temperature, pressure, surface coverage, and electronic perturbations. This formulation provides a direct analytical link between operando conditions and effective reaction barriers, enabling prediction of selectivity trends and inversion phenomena. The theory is analytically derived, computationally implementable, and broadly applicable to heterogeneous catalytic systems. Its relevance is illustrated through application to CO₂ hydrogenation pathways leading to methanol and methane, where experimentally observed selectivity shifts are rationalized within a single theoretical construct. The proposed framework establishes a general basis for operando-aware catalyst design beyond static energy landscapes. <br> Keywords Catalytic selectivity; CO₂ hydrogenation; microkinetic modeling; operando catalysis; theoretical catalysis; free energy modulation </p> |
| title | A Theoretical Framework for Predicting Catalytic Selectivity in CO₂ Conversion Reactions under Operando Conditions |
| url | https://doi.org/10.5281/zenodo.18099383 |