Asset Details
Do you wish to reserve the book?
Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO
Hey, we have placed the reservation for you!
By the way, why not check out events that you can attend while you pick your title.
Oops! Something went wrong.
Looks like we were not able to place the reservation. Kindly try again later.
Are you sure you want to remove the book from the shelf?
Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO
Do you wish to request the book?
Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO
Please be aware that the book you have requested cannot be checked out. If you would like to checkout this book, you can reserve another copy
We have requested the book for you!
Your request is successful and it will be processed during the Library working hours. Please check the status of your request in My Requests.
Oops! Something went wrong.
Looks like we were not able to place your request. Kindly try again later.
Journal Article
Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO
2012
Overview
The effective design of an artificial photosynthetic system entails the optimization of several important interactions. Herein we report stopped-flow UV-visible (UV-vis) spectroscopy, X-ray crystallographic, density functional theory (DFT), and electrochemical kinetic studies of the Re(bipy- t Bu)(CO) ₃(L) catalyst for the reduction of CO ₂ to CO. A remarkable selectivity for CO ₂ over H ⁺ was observed by stopped-flow UV-vis spectroscopy of [Re(bipy- t Bu)(CO) ₃] ⁻¹. The reaction with CO ₂ is about 25 times faster than the reaction with water or methanol at the same concentrations. X-ray crystallography and DFT studies of the doubly reduced anionic species suggest that the highest occupied molecular orbital (HOMO) has mixed metal-ligand character rather than being purely doubly occupied [Formula], which is believed to determine selectivity by favoring CO ₂ (σ + π) over H ⁺ (σ only) binding. Electrocatalytic studies performed with the addition of Brönsted acids reveal a primary H/D kinetic isotope effect, indicating that transfer of protons to Re -CO ₂ is involved in the rate limiting step. Lastly, the effects of electrode surface modification on interfacial electron transfer between a semiconductor and catalyst were investigated and found to affect the observed current densities for catalysis more than threefold, indicating that the properties of the electrode surface need to be addressed when developing a homogeneous artificial photosynthetic system.
Publisher
National Academy of Sciences,National Acad Sciences
