Substituent Effects in the Pyridinium Catalyzed Reduction of CO2 to Methanol: Further Mechanistic Insights

Cole, Emily E. Barton; Baruch, Maor F.; L'Esperance, Robert P.; Kelly, Michael T.; Lakkaraju, Prasad S.; Zeitler, Elizabeth L.; Bocarsly, Andrew Bruce

doi:10.1007/s11244-014-0343-z

Cited by 40 publications

(34 citation statements)

References 18 publications

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“…Interest has increased in the conversion of CO 2 into fuels and chemicals as a way to mitigate climate change, as a source of renewable feedstocks for fuels and industrial chemicals, and for energy storage . The electrolysis of CO 2 to form CO, formic acid, and other compounds has been observed at industrially relevant rates, and the processes have high selectivity . Thus, electrochemical conversion is a leading candidate for CO 2 utilization.…”

Section: Introductionsupporting

confidence: 93%

Sustainion Imidazolium‐Functionalized Polymers for Carbon Dioxide Electrolysis

et al. 2017

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CO2 electrolysis is a key step in CO2 conversion into fuels and chemicals as a way of mitigating climate change. We report the synthesis and testing of a series of new anion‐conductive membranes (tradenamed Sustainion™) for use in CO2 electrolysis. These membranes incorporate the functional character of imidazolium‐based ionic liquids as co‐catalysts in CO2 reduction into a solid membrane with a styrene backbone. We find that the addition of an imidazolium group onto the styrene side‐chains increases the selectivity of the reaction from approximately 25 % to approximately 95 %. The current at 3 V is increased by a factor of 14. So far we have been able to tune these parameters to achieve stable cells that provide current densities higher than 100 mA cm−2 at 3 V cell potential with a CO product selectivity over 98 %. Stable performance was observed for 6 months of continuous operation (>150 000 000 turnovers). These results demonstrate that imidazolium polymers are ideal membranes for CO2 electrolysis.

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Section: Introductionsupporting

confidence: 93%

Sustainion Imidazolium‐Functionalized Polymers for Carbon Dioxide Electrolysis

et al. 2017

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“…While carbon monoxide, methanol, and/or formic acid production has been reported on Pt surfaces, 242,266 similar reduction mechanisms, or those reported for other Pt and Ir electrodes 239,267,272,273,276 are unlikely in this case because, Au does not accommodate surface hydrides. Briefly, the peak current mirrors the solution pH for the duration of the 23 hour acquisition (see Figure 5.4.17).…”

Section: Carbon Dioxidesupporting

confidence: 79%

The electrochemical double layer in ionic liquids

Lucio¹

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First of all, I have the utmost thanks for my wife, Molly, for her support and sacrifices while pursuing my degree. She has kept me sane during our time in Iowa, especially during the more demanding times in graduate school. Secondly, I owe many thanks to my advisor, Prof. Scott K. Shaw for his guidance and mentorship throughout my studies. He is the definition of a good boss and it has been a pleasure working under his supervision. With his direction I have learned a lot during my time at Iowa and he has helped me in countless research endeavors with no biology. Thirdly, I would like to thank my Shaw group co-workers and many others in the department. We literally helped build the laboratory and it's been a fun ride learning with everyone along the way. I would also like to thank my mentors and collaborators Professors Alan M. Bond and Jie Zhang from Monash University. They welcomed me in 2015 during my three-month research visit to Monash University and have helped me grow as a scientist. Furthermore, I would also like to thank my parents and brother, Gerald, Sherrie and Adam, in addition to countless mentors I met throughout my undergraduate studies who all helped encourage and support me in pursuing a PhD degree. Lastly, I wish to thank the University of Iowa, Department of Chemistry and the administrators/staff. They have always treated me with respect and provided a platform to embark on research and teaching. Included in this list are my faculty committee members who have guided me during my studies. I am very grateful for your support.

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“…al, alluding to the potential selectivity one can achieve by varying the substituents on the aromatic ring. 9 However, their findings suggested that formic acid was inevitable regardless of substitution, ranging from trace amounts to 12% faradaic efficiency. 10 Formic acid isn't very beneficial, as it must be further derivatized to be useful.…”

Section: Introductionmentioning

confidence: 99%

“…9 However, their findings suggested that formic acid was inevitable regardless of substitution, ranging from trace amounts to 12% faradaic efficiency. 10 Formic acid isn't very beneficial, as it must be further derivatized to be useful. The utilization of surface chemistry has exhibited promising results to selectively convert to CH 3 OH only.…”

Section: Introductionmentioning

confidence: 99%

A Mechanistic Study of CO<sub>2</sub> Reduction at the Interface of a Gallium Phosphide (GaP) Surface using Core-level Spectroscopy - Oral Presentation

Flynn

2015

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Carbon dioxide (CO 2) emission into the atmosphere has increased tremendously through burning of fossil fuels, forestry, etc.. The increased concentration has made CO 2 reductions very attractive though the reaction is considered uphill. Utilizing the sun as a potential energy source, CO 2 has the possibility to undergo six electron and four proton transfers to produce methanol, a useable resource. This reaction has been shown to occur selectively in an aqueous pyridinium solution with a gallium phosphide (GaP) electrode. Though this reaction has a high faradaic efficiency, it was unclear as to what role the GaP surface played during the reaction. In this work, we aim to address the fundamental role of GaP during the catalytic conversion, by investigating the interaction between a clean GaP surface with the reactants, products, and intermediates of this reaction using X-ray photoelectron spectroscopy. We have determined a procedure to prepare atomically clean GaP and our initial CO 2 adsorption studies have shown that there is evidence of chemisorption and reaction to form carbonate on the clean surface at LN2 temperatures (80K), in contrast to previous theoretical calculations. These findings will enable future studies on CO 2 catalysis.

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Substituent Effects in the Pyridinium Catalyzed Reduction of CO2 to Methanol: Further Mechanistic Insights

Cited by 40 publications

References 18 publications

Sustainion Imidazolium‐Functionalized Polymers for Carbon Dioxide Electrolysis

Sustainion Imidazolium‐Functionalized Polymers for Carbon Dioxide Electrolysis

The electrochemical double layer in ionic liquids

A Mechanistic Study of CO<sub>2</sub> Reduction at the Interface of a Gallium Phosphide (GaP) Surface using Core-level Spectroscopy - Oral Presentation

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