How symmetry factors cause potential- and facet-dependent pathway shifts during CO2 reduction to CH4 on Cu electrodes

Rendón-Calle, Alejandra; Low, Qi Hang; Hong, Samantha Hui Lee; Builes, Santiago; Yeo, Boon Siang; Calle‐Vallejo, Federico

doi:10.1016/j.apcatb.2020.119776

Cited by 34 publications

(30 citation statements)

References 67 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It remains unclear for decades how exactly to tune the symmetry factor and what material and/or interfacial property controls value of the symmetry factor. Nevertheless, present widely held assumption that the symmetry factor always has a value of 0.5 has no real foundation, which nowadays can be supported by computational models [33–35] . Therefore, the intrinsic link between exchange current and Tafel's slope is unknown.…”

Section: Resultsmentioning

confidence: 99%

“…Nevertheless, present widely held assumption that the symmetry factor always has a value of 0.5 has no real foundation, which nowadays can be supported by computational models. [33][34][35] Therefore, the intrinsic link between exchange current and Tafel's slope is unknown. Therefore, if one intends to establish any relevant structure-activity relations, all parameters that are comprised in the exchange current (Eq.…”

Section: "Dissection" Of the Rate Lawmentioning

confidence: 99%

See 1 more Smart Citation

Electrocatalysis Beyond 2020: How to Tune the Preexponential Frequency Factor

et al. 2021

View full text Add to dashboard Cite

After a century of research on electrocatalytic reactions, a universal theory of electrocatalysis is still not established due to limited understanding of complex energy conversion processes at electrified electrode‐electrolyte interfaces. Most of the research efforts directed toward the acceleration of important electrocatalytic reactions (e. g. hydrogen evolution reaction) were in the direction of minimizing activation energy by tuning the adsorption energies of key intermediates. This kind of approach is well‐established and, importantly, in some cases it was valuable by predicting the design of electrocatalysts with advanced properties. However, in some very important research endeavors, advancement in performance of newly designed electrocatalysts could not be attributed to altered/minimized activation energy. Important to note is that modern electrocatalysis almost completely disregards influence of the preexponential factor on reaction rate. In this work, we open some important questions relevant for future of electrocatalysis and electrochemical energy conversion, with special focus on preexponential factor as major contributor to electrocatalytic reaction rate.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: "Dissection" Of the Rate Lawmentioning

confidence: 99%

Electrocatalysis Beyond 2020: How to Tune the Preexponential Frequency Factor

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Catalytic reduction of CO 2 into high value-added carbon-based products is a promising strategy for tackling current energy demands and reducing greenhouse gas emissions 1 – 5 . In the past few years, tremendous efforts have been made to explore CO 2 reduction reaction (CO 2 RR), and several products, including CH 4 6 , CO 7 , CH 3 OH 8 , HCOOH 9 , HCHO 10 , C 2 H 4 11 , C 2 H 6 12 , C 2 H 5 OH 13 , and H 2 C 2 O 4 14 , have been generated from CO 2 reduction via photo-, electro-, or thermal activation 3 – 5 , 15 – 18 . To enhance the selectivity and the conversion efficiency of CO 2 RR, focus has primarily been on exploring novel catalysts 2 , 3 , 19 , 20 .…”

Section: Introductionmentioning

confidence: 99%

“…To demonstrate the proof-of-concept, this study explores the reduction reaction of CO 2 to CO using copper (Cu) as the catalyst. Cu is the only metal catalyst known to generate hydrocarbons through CO 2 RR 5 , 34 – 39 , but poor selectivity and reaction efficiency for value-added products significantly limit its commercial applications 6 , 40 . Although much effort has been made to understand the catalytic performance of Cu in CO 2 RR, available techniques that can clarify the underlying reaction mechanisms remain limited 41 .…”

Section: Introductionmentioning

confidence: 99%

Water coordinated on Cu(I)-based catalysts is the oxygen source in CO2 reduction to CO

Zheng

Yao

et al. 2022

Nat Commun

View full text Add to dashboard Cite

Catalytic reduction of CO2 over Cu-based catalysts can produce various carbon-based products such as the critical intermediate CO, yet significant challenges remain in shedding light on the underlying mechanisms. Here, we develop a modified triple-stage quadrupole mass spectrometer to monitor the reduction of CO2 to CO in the gas phase online. Our experimental observations reveal that the coordinated H2O on Cu(I)-based catalysts promotes CO2 adsorption and reduction to CO, and the resulting efficiencies are two orders of magnitude higher than those without H2O. Isotope-labeling studies render compelling evidence that the O atom in produced CO originates from the coordinated H2O on catalysts, rather than CO2 itself. Combining experimental observations and computational calculations with density functional theory, we propose a detailed reaction mechanism of CO2 reduction to CO over Cu(I)-based catalysts with coordinated H2O. This study offers an effective method to reveal the vital roles of H2O in promoting metal catalysts to CO2 reduction.

show abstract

“…Based on the numerous publications [6][7][8][9][10][11][12][13][14] on this subject, it can be found that different activity and selectivity of the catalyst can be observed by varying the reaction conditions. Several possible reactions can take place when reducing CO 2 with hydrogen as a function of pressure and temperature: For example, the first reaction shown on the right is the formation of carbon (graphite) via the Bosch reaction [15].…”

Section: Introductionmentioning

confidence: 99%

Exploiting In-Situ Characterization for a Sabatier Reaction to Reveal Catalytic Details

Yunes¹,

Kim²,

Nguyen³

et al. 2021

Chemistry

View full text Add to dashboard Cite

In situ characterization of catalysts provides important information on the catalyst and the understanding of its activity and selectivity for a specific reaction. TPX techniques for catalyst characterization reveal the role of the support on the stabilization and dispersion of the active sites. However, these can be altered at high temperature since sintering of active species can occur as well as possible carbon deposition through the Bosch reaction, which hinders the active species and deactivates the catalyst. In situ characterization of the spent catalyst, however, may expose the causes for catalyst deactivation. For example, a simple TPO analysis on the spent catalyst may produce CO and CO2 via a reaction with O2 at high temperature and this is a strong indication that deactivation may be due to the deposition of carbon during the Sabatier reaction. Other TPX techniques such as TPR and pulse chemisorption are also valuable techniques when they are applied in situ to the fresh catalyst and then to the catalyst upon deactivation.

show abstract

How symmetry factors cause potential- and facet-dependent pathway shifts during CO2 reduction to CH4 on Cu electrodes

Cited by 34 publications

References 67 publications

Electrocatalysis Beyond 2020: How to Tune the Preexponential Frequency Factor

Electrocatalysis Beyond 2020: How to Tune the Preexponential Frequency Factor

Water coordinated on Cu(I)-based catalysts is the oxygen source in CO2 reduction to CO

Exploiting In-Situ Characterization for a Sabatier Reaction to Reveal Catalytic Details

Contact Info

Product

Resources

About