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Towards an artificial formate dehydr...

Seu, Candace Sachi Wai Mei.

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Towards an artificial formate dehydrogenase: mechanistic studies of formate oxidation and carbon dioxide reduction by metal P2N2 complexes.

紀錄類型:	書目-語言資料,印刷品 : Monograph/item
正題名/作者:	Towards an artificial formate dehydrogenase: mechanistic studies of formate oxidation and carbon dioxide reduction by metal P2N2 complexes./
作者:	Seu, Candace Sachi Wai Mei.
面頁冊數:	206 p.
附註:	Source: Dissertation Abstracts International, Volume: 74-10(E), Section: B.
Contained By:	Dissertation Abstracts International74-10B(E).
標題:	Chemistry, Inorganic. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3567630
ISBN:	9781303194856

Towards an artificial formate dehydrogenase: mechanistic studies of formate oxidation and carbon dioxide reduction by metal P2N2 complexes.
Seu, Candace Sachi Wai Mei.

Towards an artificial formate dehydrogenase: mechanistic studies of formate oxidation and carbon dioxide reduction by metal P2N2 complexes. - 206 p.

Source: Dissertation Abstracts International, Volume: 74-10(E), Section: B.

Thesis (Ph.D.)--University of California, San Diego, 2013.

The efficient electrochemical production and use of CO2-based solar fuels is a problem of precisely coordinating the associated proton and electron transfers. One strategy for controlling these proton-coupled electron transfers is to use catalysts that contain proton relays in their secondary coordination spheres. The work described in this thesis explores the function of 1,5-diaza-3,7-diphosphacyclooctane (P2N2) ligands in molecular electrocatalysts for HCOOH/CO2 conversion. By focusing on a mechanistic understanding of the catalysis that occurs with these ligands, we seek to develop the chemistry of these systems and to guide the design of better CO2 catalysts.

ISBN: 9781303194856Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Towards an artificial formate dehydrogenase: mechanistic studies of formate oxidation and carbon dioxide reduction by metal P2N2 complexes.
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245 1 0 $a Towards an artificial formate dehydrogenase: mechanistic studies of formate oxidation and carbon dioxide reduction by metal P2N2 complexes.
300 $a 206 p.
500 $a Source: Dissertation Abstracts International, Volume: 74-10(E), Section: B.
500 $a Adviser: Clifford P. Kubiak.
502 $a Thesis (Ph.D.)--University of California, San Diego, 2013.
520 $a The efficient electrochemical production and use of CO2-based solar fuels is a problem of precisely coordinating the associated proton and electron transfers. One strategy for controlling these proton-coupled electron transfers is to use catalysts that contain proton relays in their secondary coordination spheres. The work described in this thesis explores the function of 1,5-diaza-3,7-diphosphacyclooctane (P2N2) ligands in molecular electrocatalysts for HCOOH/CO2 conversion. By focusing on a mechanistic understanding of the catalysis that occurs with these ligands, we seek to develop the chemistry of these systems and to guide the design of better CO2 catalysts.
520 $a A variety of NMR and electrochemical experiments were used to explore the likelihoods of several different proton or hydride transfer pathways for the oxidation of formate by [Ni(P2N2)2] 2+ complexes. The experiments suggest that oxidation occurs via a ratedetermining proton transfer from the Ni--O2CH beta-H to the pendant base, coupled with a 2e-- transfer to Ni(II). The measurement of electrocatalytic kH/kD KIEs between 3--7 suggests that this unexpected non-hydride process may be an unusual example of multi-site concerted proton-coupled electron transfer, which has been rarely observed in well-defined catalyst systems.
520 $a We attempted to develop a catalyst for the reduction of CO2 to formic acid by using metals with increased electron donating ability, as predicted by their hydride donating ability (hydricity). [Co(P2N 2)2]1-- complexes react with CO 2 even in the absence of extra protons, but are unstable under the high potentials necessary to generate these species. [Pd(P2N2) 2]2+ complexes crystallize in square planar or minimally tetrahedrally distorted geometries and exhibit a single quasi-reversible 2e -- Pd(II/0) redox couple in voltammetric studies. [Pd(P Ph2NBn2)2] 2+ and [Pd(PMe2NPh2 )2]2+ were tested for electrochemical CO 2 reduction in the presence of excess protons and found to preferentially produce H2. Comparative analysis of the intermediates involved in proton reduction by analogous [Pd(P2N2)2] 2+ and [Ni(P2N2)2]2+ complexes suggests that large reorganizational energy barriers render the Pd catalysts much less efficient than their Ni counterparts. The ability of the Ni-P2N2 metal-ligand combination to access multiple redox and protonation states with a minimum of reorganization appears to be essential to both proton reduction and formate oxidation.
590 $a School code: 0033.
650 4 $a Chemistry, Inorganic. $3 517253
650 4 $a Alternative Energy. $3 1035473
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710 2 $a University of California, San Diego. $b Chemistry. $3 1023460
773 0 $t Dissertation Abstracts International $g 74-10B(E).
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791 $a Ph.D.
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793 $a English
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