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Operando Measurements, Reactor Design, and Kinetic Analyses for Electrochemical CO2Reduction.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Operando Measurements, Reactor Design, and Kinetic Analyses for Electrochemical CO2Reduction./
作者:	Aviles Acosta, Jaime E.
面頁冊數:	1 online resource (439 pages)
附註:	Source: Dissertations Abstracts International, Volume: 85-04, Section: B.
Contained By:	Dissertations Abstracts International85-04B.
標題:	Electrolytes. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=30615090click for full text (PQDT)
ISBN:	9798380470209

Operando Measurements, Reactor Design, and Kinetic Analyses for Electrochemical CO2Reduction.
Aviles Acosta, Jaime E.

Operando Measurements, Reactor Design, and Kinetic Analyses for Electrochemical CO2Reduction. - 1 online resource (439 pages)

Source: Dissertations Abstracts International, Volume: 85-04, Section: B.

Thesis (Ph.D.)--Stanford University, 2023.

Includes bibliographical references

As greenhouse gas emissions continue to rise, along with the probability of potentially devastating or catastrophic climate change scenarios, so does the need for technologies and processes to reduce or eliminate these emissions. Among them, electrochemical CO2 reduction (CO2R) combined with decreasing cost of low-emissions electricity, has the potential to turn the major driver of global warming, CO2, into a renewable feedstock for conversion to valuable chemicals and fuels. However, grand challenges remain before CO2R can compete on the market with well-established and cost-efficient petrochemical processes that provide the essential energy and products for a global, industrial economy. Among these challenges are the low activity of CO2R catalysts, their low selectivity for specific CO2R products versus the hydrogen evolution reaction (HER), and the low durability of CO2R catalysts. An incomplete understanding of the reaction mechanism of CO2R, the degradation mechanisms of catalysts, and how these depend on the local reaction environment and the catalyst itself are hindering efforts to improve the performance of CO2R catalysts. This dissertation describes four projects designed to address these key unknowns to solve the above grand challenges.First, we developed an electrochemical flow reactor and metal thin film synthesis procedure for operando attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS). The operando capability allows one to measure reaction rates and correlate them with observations within 10 nm of the catalyst-electrolyte interface, directly probing how the local reaction environment affects the catalyst's activity and selectivity. We demonstrate these capabilities with operando ATR-SEIRAS of CO2R on nanostructured Au thin films of different morphologies; the impact of electrode potential, electrolyte flow rate, and thin film morphology on the CO2R activity and the selectivity to CO versus the HER are shown. We were able to control the local CO2 concentration and demonstrate how it impacts CO2R activity. The morphology of the Au thin film is inferred to strongly affect the reaction mechanism of the HER, hinting that the interplay between Au surface structure and local pH can drastically affect how the electrolysis selectivity is affected by mass transport modulated by the electrolyte flow rate. These results strongly suggest that complex interactions between the catalyst and local reaction environment must be considered for designing CO2R electrolyzers with the desired selectivity and activity while highlighting the capability of this reactor to study various catalysts and electrochemical reactions.Second, we compiled and analyzed CO2R datasets from the literature for various catalysts and CO2R products. We supplemented the analysis with a review of the pertinent literature on in situ/operando characterization, theoretical modeling, and mechanistic studies. We found we could rationalize many of the reported strategies for improving CO2R activity and selectivity; among them, the roughness factor, electrode potential, surface composition and structure, and electrolyte composition, all had demonstratable effects. However, we also identified hints regarding how different CO2R pathways, and the reaction mechanism, are affected by the reaction parameters and local reaction conditions. We highlighted that many gaps remain in the reported wealth of CO2R data, which need to be filled to narrow down plausible CO2R mechanisms for all catalysts towards distinct products.

Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2023

Mode of access: World Wide Web

ISBN: 9798380470209Subjects--Topical Terms:

656992
Electrolytes.
Index Terms--Genre/Form:

542853
Electronic books.

Operando Measurements, Reactor Design, and Kinetic Analyses for Electrochemical CO2Reduction.
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245 1 0 $a Operando Measurements, Reactor Design, and Kinetic Analyses for Electrochemical CO2Reduction.
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500 $a Source: Dissertations Abstracts International, Volume: 85-04, Section: B.
500 $a Advisor: Jaramillo, Thomas;Dionne, Jennifer;Hahn, Christopher.
502 $a Thesis (Ph.D.)--Stanford University, 2023.
504 $a Includes bibliographical references
520 $a As greenhouse gas emissions continue to rise, along with the probability of potentially devastating or catastrophic climate change scenarios, so does the need for technologies and processes to reduce or eliminate these emissions. Among them, electrochemical CO2 reduction (CO2R) combined with decreasing cost of low-emissions electricity, has the potential to turn the major driver of global warming, CO2, into a renewable feedstock for conversion to valuable chemicals and fuels. However, grand challenges remain before CO2R can compete on the market with well-established and cost-efficient petrochemical processes that provide the essential energy and products for a global, industrial economy. Among these challenges are the low activity of CO2R catalysts, their low selectivity for specific CO2R products versus the hydrogen evolution reaction (HER), and the low durability of CO2R catalysts. An incomplete understanding of the reaction mechanism of CO2R, the degradation mechanisms of catalysts, and how these depend on the local reaction environment and the catalyst itself are hindering efforts to improve the performance of CO2R catalysts. This dissertation describes four projects designed to address these key unknowns to solve the above grand challenges.First, we developed an electrochemical flow reactor and metal thin film synthesis procedure for operando attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS). The operando capability allows one to measure reaction rates and correlate them with observations within 10 nm of the catalyst-electrolyte interface, directly probing how the local reaction environment affects the catalyst's activity and selectivity. We demonstrate these capabilities with operando ATR-SEIRAS of CO2R on nanostructured Au thin films of different morphologies; the impact of electrode potential, electrolyte flow rate, and thin film morphology on the CO2R activity and the selectivity to CO versus the HER are shown. We were able to control the local CO2 concentration and demonstrate how it impacts CO2R activity. The morphology of the Au thin film is inferred to strongly affect the reaction mechanism of the HER, hinting that the interplay between Au surface structure and local pH can drastically affect how the electrolysis selectivity is affected by mass transport modulated by the electrolyte flow rate. These results strongly suggest that complex interactions between the catalyst and local reaction environment must be considered for designing CO2R electrolyzers with the desired selectivity and activity while highlighting the capability of this reactor to study various catalysts and electrochemical reactions.Second, we compiled and analyzed CO2R datasets from the literature for various catalysts and CO2R products. We supplemented the analysis with a review of the pertinent literature on in situ/operando characterization, theoretical modeling, and mechanistic studies. We found we could rationalize many of the reported strategies for improving CO2R activity and selectivity; among them, the roughness factor, electrode potential, surface composition and structure, and electrolyte composition, all had demonstratable effects. However, we also identified hints regarding how different CO2R pathways, and the reaction mechanism, are affected by the reaction parameters and local reaction conditions. We highlighted that many gaps remain in the reported wealth of CO2R data, which need to be filled to narrow down plausible CO2R mechanisms for all catalysts towards distinct products.
533 $a Electronic reproduction. $b Ann Arbor, Mich. : $c ProQuest, $d 2023
538 $a Mode of access: World Wide Web
650 4 $a Electrolytes. $3 656992
650 4 $a Electrodes. $3 629151
650 4 $a Greenhouse gases. $3 797971
650 4 $a Electricity. $3 524507
650 4 $a Oxidation. $3 714629
650 4 $a Emissions. $3 3559499
650 4 $a Carbon. $3 604057
650 4 $a Energy efficiency. $3 3555643
650 4 $a Research & development--R&D. $3 3554335
650 4 $a Emission standards. $3 3681915
650 4 $a Electrocatalysis. $3 872243
650 4 $a Thin films. $3 626403
650 4 $a Climate change. $2 bicssc $3 2079509
650 4 $a Condensed matter physics. $3 3173567
650 4 $a Energy. $3 876794
650 4 $a Materials science. $3 543314
650 4 $a Physics. $3 516296
655 7 $a Electronic books. $2 lcsh $3 542853
690 $a 0404
690 $a 0611
690 $a 0791
690 $a 0794
690 $a 0605
710 2 $a ProQuest Information and Learning Co. $3 783688
710 2 $a Stanford University. $3 754827
773 0 $t Dissertations Abstracts International $g 85-04B.
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=30615090 $z click for full text (PQDT)