Production of acrylic acid through nickel-mediated coupling of ethylene and carbon dioxide - A DFT study
The production of acrylic acid (CH2=CHCO2H) via homogeneous nickel-mediated coupling of ethylene (CH2=CH2) and carbon dioxide (CO2) is industrially unattractive at present due to its stoichiometric, rather than catalytic, reaction profile. We utilize density functional theory (DFT) to describe the p...
| Main Authors: | , , , , , |
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| Format: | Journal Article |
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ACS Publications
2007
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| Online Access: | http://hdl.handle.net/20.500.11937/47030 |
| _version_ | 1848757723037958144 |
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| author | Graham, D. Mitchell, C. Bruce, M. Metha, G. Bowie, J. Buntine, Mark |
| author_facet | Graham, D. Mitchell, C. Bruce, M. Metha, G. Bowie, J. Buntine, Mark |
| author_sort | Graham, D. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | The production of acrylic acid (CH2=CHCO2H) via homogeneous nickel-mediated coupling of ethylene (CH2=CH2) and carbon dioxide (CO2) is industrially unattractive at present due to its stoichiometric, rather than catalytic, reaction profile. We utilize density functional theory (DFT) to describe the potential energy surface for both the nickel-mediated coupling reaction and an intramolecular deactivation reaction reported to hinder the desired catalytic activity. The calculated route for the catalytic production of acrylic acid can be divided into three main parts, none of which contain significantly large barriers that would be expected to prohibit the overall catalytic process. Investigation of the catalyst deactivation reaction reveals that the proposed product lies +102.6 kJ mol(-1) above the reactants, thereby ruling out this type of pathway as the cause of the noncatalytic activity. Instead, it is far more conceivable that the overall reaction thermodynamics are responsible for the lack of catalytic activity observed, with the solvation -corrected Gibbs free energy of the coupling reaction in question (i.e., CH2=CH2) + CO2- --> CH2=CHCO2H) calculated to be an unfavorable +42.7 kJ mol(-1). |
| first_indexed | 2025-11-14T09:32:37Z |
| format | Journal Article |
| id | curtin-20.500.11937-47030 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T09:32:37Z |
| publishDate | 2007 |
| publisher | ACS Publications |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-470302017-09-13T14:28:07Z Production of acrylic acid through nickel-mediated coupling of ethylene and carbon dioxide - A DFT study Graham, D. Mitchell, C. Bruce, M. Metha, G. Bowie, J. Buntine, Mark MOLECULAR ALCULATIONS AUGMENTED BASIS-SETS COORDINATION CHEMISTRY OXANICKELACYCLOPENTENE COMPLEX POLARIZABLE CONTINUUM MODEL TRANSITION-METAL COMPLEXES REDUCTIVE ELIMINATION HOMOGENEOUS HYDROGENATION AB-INITIO CORRELATION-ENERGY The production of acrylic acid (CH2=CHCO2H) via homogeneous nickel-mediated coupling of ethylene (CH2=CH2) and carbon dioxide (CO2) is industrially unattractive at present due to its stoichiometric, rather than catalytic, reaction profile. We utilize density functional theory (DFT) to describe the potential energy surface for both the nickel-mediated coupling reaction and an intramolecular deactivation reaction reported to hinder the desired catalytic activity. The calculated route for the catalytic production of acrylic acid can be divided into three main parts, none of which contain significantly large barriers that would be expected to prohibit the overall catalytic process. Investigation of the catalyst deactivation reaction reveals that the proposed product lies +102.6 kJ mol(-1) above the reactants, thereby ruling out this type of pathway as the cause of the noncatalytic activity. Instead, it is far more conceivable that the overall reaction thermodynamics are responsible for the lack of catalytic activity observed, with the solvation -corrected Gibbs free energy of the coupling reaction in question (i.e., CH2=CH2) + CO2- --> CH2=CHCO2H) calculated to be an unfavorable +42.7 kJ mol(-1). 2007 Journal Article http://hdl.handle.net/20.500.11937/47030 10.1021/om700592w ACS Publications restricted |
| spellingShingle | MOLECULAR ALCULATIONS AUGMENTED BASIS-SETS COORDINATION CHEMISTRY OXANICKELACYCLOPENTENE COMPLEX POLARIZABLE CONTINUUM MODEL TRANSITION-METAL COMPLEXES REDUCTIVE ELIMINATION HOMOGENEOUS HYDROGENATION AB-INITIO CORRELATION-ENERGY Graham, D. Mitchell, C. Bruce, M. Metha, G. Bowie, J. Buntine, Mark Production of acrylic acid through nickel-mediated coupling of ethylene and carbon dioxide - A DFT study |
| title | Production of acrylic acid through nickel-mediated coupling of ethylene and carbon dioxide - A DFT study |
| title_full | Production of acrylic acid through nickel-mediated coupling of ethylene and carbon dioxide - A DFT study |
| title_fullStr | Production of acrylic acid through nickel-mediated coupling of ethylene and carbon dioxide - A DFT study |
| title_full_unstemmed | Production of acrylic acid through nickel-mediated coupling of ethylene and carbon dioxide - A DFT study |
| title_short | Production of acrylic acid through nickel-mediated coupling of ethylene and carbon dioxide - A DFT study |
| title_sort | production of acrylic acid through nickel-mediated coupling of ethylene and carbon dioxide - a dft study |
| topic | MOLECULAR ALCULATIONS AUGMENTED BASIS-SETS COORDINATION CHEMISTRY OXANICKELACYCLOPENTENE COMPLEX POLARIZABLE CONTINUUM MODEL TRANSITION-METAL COMPLEXES REDUCTIVE ELIMINATION HOMOGENEOUS HYDROGENATION AB-INITIO CORRELATION-ENERGY |
| url | http://hdl.handle.net/20.500.11937/47030 |