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Insights into reaction mechanisms of catalytic hydrogen production from alcohols : a density functional theory study
Item metadata
dc.contributor.advisor | Bühl, Michael | |
dc.contributor.author | Ahmad, Shahbaz | |
dc.coverage.spatial | x, 86 p. | en_US |
dc.date.accessioned | 2018-04-03T13:46:16Z | |
dc.date.available | 2018-04-03T13:46:16Z | |
dc.date.issued | 2018 | |
dc.identifier.uri | https://hdl.handle.net/10023/13058 | |
dc.description.abstract | Securing the world's clean energy future in the form of sustainable H₂ generation is a key challenge. Alcohols (and eventually carbohydrates from bio-waste) are potential carriers for H₂ storage, from which H₂ needs to be liberated catalytically. Morton and Cole-Hamilton have presented a classic catalytic system for dehydrogenation and decarbonylation of primary alcohols including methanol (Morton and Cole-Hamilton et al. 1988). A water gas shift reaction (WGSR) would allow the liberation of another equivalent of H₂. We now present a Density Functional Theory (DFT) investigation, using the B97-D dispersion-corrected functional, to probe the viability of such a pathway and to help design a system that can catalyse all processes, including dehydrogenation, decarbonylation and WGSR, equally well. Two different catalytic cycles that depart from those in molecular hydrogen production under basic conditions catalysed by [RuH₂(CO)(PPh₃)₃] (22) have been studied, the first involving a WGSR and the second covers the formation of gem-diol-(ate), formic acid and finally the CO₂ elimination. The overall computed energy barrier for the attack of water (in the form of OH⁻) on the CO ligand of complex 22 is prohibitively high because this attack is predicted to be highly endergonic; therefore, a WGSR is not plausible with this species. An alternative catalytic cycle for this process has been characterised computationally, starting from the formaldehyde complex (35) through the formation of a gem-diolate species, subsequently forming formic acid and, finally, CO₂. The gem-diolate pathway has insurmountable barriers, too. Another catalytic cycle involving complex [RuH₂(CO)₂(PPh₃)₂] (58) is characterised as a result of a second decarbonylation reaction where the attack of OH⁻ on the CO ligand is reasonable. Complete dehydrogenation of alcohols could thus be possible under basic conditions. | en_US |
dc.language.iso | en | en_US |
dc.publisher | University of St Andrews | |
dc.subject | Catalysis | en_US |
dc.subject | Chemistry | en_US |
dc.subject | Computational chemistry | en_US |
dc.subject | Decarbonylation | en_US |
dc.subject | Dehydrogenation | en_US |
dc.subject | Density functional theory | en_US |
dc.subject | DFT | en_US |
dc.subject | Homogeneous catalysis | en_US |
dc.subject | Hydrogen generation | en_US |
dc.subject | Phosphines | en_US |
dc.subject | Ruthenium | en_US |
dc.subject | Thermodynamics | en_US |
dc.subject | Transition states | en_US |
dc.subject | Water gas shift reaction | en_US |
dc.subject | WGSR | en_US |
dc.subject.lcc | QD281.D4A5 | |
dc.subject.lcsh | Dehydrogenation | en |
dc.subject.lcsh | Homogeneous catalysis | en |
dc.subject.lcsh | Density functionals | en |
dc.subject.lcsh | Reaction mechanisms (Chemistry) | en |
dc.subject.lcsh | Hydrogen as fuel | en |
dc.title | Insights into reaction mechanisms of catalytic hydrogen production from alcohols : a density functional theory study | en_US |
dc.type | Thesis | en_US |
dc.type.qualificationlevel | Doctoral | en_US |
dc.type.qualificationname | MPhil Master of Philosophy | en_US |
dc.publisher.institution | The University of St Andrews | en_US |
dc.rights.embargodate | 2021-02-15 | |
dc.rights.embargoreason | Thesis restricted in accordance with University regulations. Print and electronic copy restricted until 15th February 2021. Restriction now expired. Awaiting final permissions to release or further restrict full text. | en |
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