Mechanism of Deoxygenation and Cracking of Fatty Acids by Gas-Phase Cationic Complexes of Ni, Pd, and Pt
Deoxygenation and subsequent cracking of fatty acids are key steps in production of biodiesel fuels from renewable plant sources. Despite the fact that multiple catalysts, including those containing group 10 metals (Ni, Pd, and Pt), are employed for these purposes, little is known about the mechanis...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-05-01
|
| Series: | Reactions |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2624-781X/2/2/9 |
| _version_ | 1827692442080509952 |
|---|---|
| author | Kevin Parker Victoria Pho Richard A. J. O’Hair Victor Ryzhov |
| author_facet | Kevin Parker Victoria Pho Richard A. J. O’Hair Victor Ryzhov |
| author_sort | Kevin Parker |
| collection | DOAJ |
| description | Deoxygenation and subsequent cracking of fatty acids are key steps in production of biodiesel fuels from renewable plant sources. Despite the fact that multiple catalysts, including those containing group 10 metals (Ni, Pd, and Pt), are employed for these purposes, little is known about the mechanisms by which they operate. In this work, we utilized tandem mass spectrometry experiments (MS<sup>n</sup>) to show that multiple types of fatty acids (saturated, mono-, and poly-unsaturated) can be catalytically deoxygenated and converted to smaller hydrocarbons using the ternary metal complexes [(phen)M(O<sub>2</sub>CR)]<sup>+</sup>], where phen = 1,10-phenanthroline and M = Ni, Pd, and Pt. The mechanistic description of deoxygenation/cracking processes builds on our recent works describing simple model systems for deoxygenation and cracking, where the latter comes from the ability of group 10 metal ions to undergo chain-walking with very low activation barriers. This article extends our previous work to a number of fatty acids commonly found in renewable plant sources. We found that in many unsaturated acids cracking can occur prior to deoxygenation and show that mechanisms involving group 10 metals differ from long-known charge-remote fragmentation reactions. |
| first_indexed | 2024-03-10T11:23:10Z |
| format | Article |
| id | doaj.art-a0a4acdf45704590b30f621928d49b06 |
| institution | Directory Open Access Journal |
| issn | 2624-781X |
| language | English |
| last_indexed | 2024-03-10T11:23:10Z |
| publishDate | 2021-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Reactions |
| spelling | doaj.art-a0a4acdf45704590b30f621928d49b062023-11-21T19:52:51ZengMDPI AGReactions2624-781X2021-05-012210211410.3390/reactions2020009Mechanism of Deoxygenation and Cracking of Fatty Acids by Gas-Phase Cationic Complexes of Ni, Pd, and PtKevin Parker0Victoria Pho1Richard A. J. O’Hair2Victor Ryzhov3Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USADepartment of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USASchool of Chemistry, Bio21 Institute of Molecular Science and Biotechnology, The University of Melbourne, Melbourne, VIC 3010, AustraliaDepartment of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USADeoxygenation and subsequent cracking of fatty acids are key steps in production of biodiesel fuels from renewable plant sources. Despite the fact that multiple catalysts, including those containing group 10 metals (Ni, Pd, and Pt), are employed for these purposes, little is known about the mechanisms by which they operate. In this work, we utilized tandem mass spectrometry experiments (MS<sup>n</sup>) to show that multiple types of fatty acids (saturated, mono-, and poly-unsaturated) can be catalytically deoxygenated and converted to smaller hydrocarbons using the ternary metal complexes [(phen)M(O<sub>2</sub>CR)]<sup>+</sup>], where phen = 1,10-phenanthroline and M = Ni, Pd, and Pt. The mechanistic description of deoxygenation/cracking processes builds on our recent works describing simple model systems for deoxygenation and cracking, where the latter comes from the ability of group 10 metal ions to undergo chain-walking with very low activation barriers. This article extends our previous work to a number of fatty acids commonly found in renewable plant sources. We found that in many unsaturated acids cracking can occur prior to deoxygenation and show that mechanisms involving group 10 metals differ from long-known charge-remote fragmentation reactions.https://www.mdpi.com/2624-781X/2/2/9biomassgas phasemass spectrometrycrackinghydrocarbons |
| spellingShingle | Kevin Parker Victoria Pho Richard A. J. O’Hair Victor Ryzhov Mechanism of Deoxygenation and Cracking of Fatty Acids by Gas-Phase Cationic Complexes of Ni, Pd, and Pt Reactions biomass gas phase mass spectrometry cracking hydrocarbons |
| title | Mechanism of Deoxygenation and Cracking of Fatty Acids by Gas-Phase Cationic Complexes of Ni, Pd, and Pt |
| title_full | Mechanism of Deoxygenation and Cracking of Fatty Acids by Gas-Phase Cationic Complexes of Ni, Pd, and Pt |
| title_fullStr | Mechanism of Deoxygenation and Cracking of Fatty Acids by Gas-Phase Cationic Complexes of Ni, Pd, and Pt |
| title_full_unstemmed | Mechanism of Deoxygenation and Cracking of Fatty Acids by Gas-Phase Cationic Complexes of Ni, Pd, and Pt |
| title_short | Mechanism of Deoxygenation and Cracking of Fatty Acids by Gas-Phase Cationic Complexes of Ni, Pd, and Pt |
| title_sort | mechanism of deoxygenation and cracking of fatty acids by gas phase cationic complexes of ni pd and pt |
| topic | biomass gas phase mass spectrometry cracking hydrocarbons |
| url | https://www.mdpi.com/2624-781X/2/2/9 |
| work_keys_str_mv | AT kevinparker mechanismofdeoxygenationandcrackingoffattyacidsbygasphasecationiccomplexesofnipdandpt AT victoriapho mechanismofdeoxygenationandcrackingoffattyacidsbygasphasecationiccomplexesofnipdandpt AT richardajohair mechanismofdeoxygenationandcrackingoffattyacidsbygasphasecationiccomplexesofnipdandpt AT victorryzhov mechanismofdeoxygenationandcrackingoffattyacidsbygasphasecationiccomplexesofnipdandpt |