Progress Toward the Electrocatalytic Production of Liquid Fuels from Carbon Dioxide

Rosenthal, Joel

doi:10.1002/9781118869994.ch04

Cited by 14 publications

(20 citation statements)

References 152 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…via the balanced process shown in Equation (3). In addition to the direct reduction of CO 2 to hydrocarbons and oxygenates, a secondary process that converts H 2 O into H 2 can be used in conjunction with the electrocatalytic CO production to produce syngas 2 of 12 (a CO/H 2 mixture), which is a primary feedstock that can be unconverted into liquid carbon-based fuels such as gasoline and diesel via Fischer-Tropsch processes [8].…”

Section: Introductionmentioning

confidence: 99%

Copper-Tin Alloys for the Electrocatalytic Reduction of CO2 in an Imidazolium-Based Non-Aqueous Electrolyte

et al. 2019

Self Cite

View full text Add to dashboard Cite

The ability to synthesize value-added chemicals directly from CO2 will be an important technological advancement for future generations. Using solar energy to drive thermodynamically uphill electrochemical reactions allows for near carbon-neutral processes that can convert CO2 into energy-rich carbon-based fuels. Here, we report on the use of inexpensive CuSn alloys to convert CO2 into CO in an acetonitrile/imidazolium-based electrolyte. Synergistic interactions between the CuSn catalyst and the imidazolium cation enables the electrocatalytic conversion of CO2 into CO at −1.65 V versus the standard calomel electrode (SCE). This catalyst system is characterized by overpotentials for CO2 reduction that are similar to more expensive Au- and Ag-based catalysts, and also shows that the efficacy of the CO2 reduction reaction can be tuned by varying the CuSn ratio.

show abstract

Section: Introductionmentioning

confidence: 99%

Copper-Tin Alloys for the Electrocatalytic Reduction of CO2 in an Imidazolium-Based Non-Aqueous Electrolyte

et al. 2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…CDR is most practically conducted in aqueous electrolytes, in which the undesirable reduction of protons to H 2 presents a principal selectivity challenge. Because the hydrogen evolution reaction (HER) is thermodynamically accessible over the same potential range as nearly all CDR reaction products (18)(19)(20), selective fuel formation relies on the electrode's ability to control the relative rates of these competing pathways.Computational investigations of CDR selectivity have largely applied the Sabatier principle, which states that an optimal catalyst is one that binds key intermediates neither too strongly nor too weakly (21). Within this framework, the relative binding energies of adsorbed H and CO, proposed intermediates along HER and CDR pathways, respectively (22-30), serve as descriptors for the relative rates of each reaction.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

Inhibited proton transfer enhances Au-catalyzed CO ₂ -to-fuels selectivity

Wuttig

Yaguchi

Motobayashi

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

351

480

View full text Add to dashboard Cite

CO 2 reduction in aqueous electrolytes suffers efficiency losses because of the simultaneous reduction of water to H 2 . We combine in situ surface-enhanced IR absorption spectroscopy (SEIRAS) and electrochemical kinetic studies to probe the mechanistic basis for kinetic bifurcation between H 2 and CO production on polycrystalline Au electrodes. Under the conditions of CO 2 reduction catalysis, electrogenerated CO species are irreversibly bound to Au in a bridging mode at a surface coverage of ∼0.2 and act as kinetically inert spectators. Electrokinetic data are consistent with a mechanism of CO production involving rate-limiting, single-electron transfer to CO 2 with concomitant adsorption to surface active sites followed by rapid one-electron, two-proton transfer and CO liberation from the surface. In contrast, the data suggest an H 2 evolution mechanism involving rate-limiting, single-electron transfer coupled with proton transfer from bicarbonate, hydronium, and/or carbonic acid to form adsorbed H species followed by rapid one-electron, one-proton, or H recombination reactions. The disparate proton coupling requirements for CO and H 2 production establish a mechanistic basis for reaction selectivity in electrocatalytic fuel formation, and the high population of spectator CO species highlights the complex heterogeneity of electrode surfaces under conditions of fuel-forming electrocatalysis.carbon dioxide reduction | catalyst selectivity | in situ spectroscopy | proton-coupled electron transfer P roduct selectivity is a principal design consideration for the development of practical catalysts. Catalyst selectivity is dictated by (i) the relative free energy barriers for progress along competing reaction pathways and (ii) the relative rates of reactant delivery to active sites (1). Enzymes fine tune these parameters with exquisite precision to achieve selectivity (2). Nature augments the coordination environment of metallocofactor active sites to optimize the binding strengths of reaction partners and preorganizes reaction participants toward low-barrier pathways (3). Additionally, many active sites reside at the terminus of molecular channels that gate the coordinated delivery of substrates (4, 5) required for selective transformations. Efforts to prepare artificial catalysts with product selectivities rivaling that of nature require a detailed understanding of these factors.Currently, our understanding of how to systematically modulate selectivity in heterogeneous catalysts remains poor (6-8). Unlike (bio)molecular catalysts, which ideally consist of a uniform ensemble of active sites, heterogeneous catalysts consist of a nonuniform distribution of surface sites (9), requiring an understanding of which are active and which are dormant. The surface site distribution is strongly dependent on the surface nanostructure, oxidation state, and degree of restructuring (7). Superimposed on this distribution are the rate-limiting elementary reaction steps that dictate kinetic branching ratios at surface active sites (1...

show abstract

“…[17][18][19] Relative to other energy conversion reactions such as ORR, OER, and HER, CO 2 reduction (CDR) is particularly sensitive to surface structure and composition because of the myriad array of CDR products thermodynamically accessible over a narrow potential range. [20][21][22] The development of practical CDR catalysts requires unparalleled control over product selectivity, which can be easily compromised by impurities that interact with or irreversibly alter the surface.…”

Section: Introductionmentioning

confidence: 99%

Impurity Ion Complexation Enhances Carbon Dioxide Reduction Catalysis

2015

View full text Add to dashboard Cite

Herein, we show that group 11 CO 2 reduction catalysts are rapidly poisoned by progressive deposition of trace metal ion impurities existent in high purity electrolytes. Metal impurity deposition was characterized by XPS and in situ stripping voltammetry and is coincident with loss of catalytic activity and selectivity for CO 2 reduction, favoring hydrogen evolution on poisoned surfaces. Metal deposition can be suppressed by complexing trace metal-ion impurities with ethylenediaminetetraacetic acid or solid supported iminodiacetate resins. Metal ion complexation allows for reproducible, sustained catalytic activity and selectivity for CO 2 reduction on Au, Ag, and Cu electrodes. Together, this study establishes the principle mode by which group 11 CO 2 reduction catalysts are poisoned and lays out a general approach for extending the lifetime of electrocatalysts subject to impurity metal deposition.

show abstract

Progress Toward the Electrocatalytic Production of Liquid Fuels from Carbon Dioxide

Cited by 14 publications

References 152 publications

Copper-Tin Alloys for the Electrocatalytic Reduction of CO2 in an Imidazolium-Based Non-Aqueous Electrolyte

Copper-Tin Alloys for the Electrocatalytic Reduction of CO2 in an Imidazolium-Based Non-Aqueous Electrolyte

Inhibited proton transfer enhances Au-catalyzed CO ₂ -to-fuels selectivity

Impurity Ion Complexation Enhances Carbon Dioxide Reduction Catalysis

Contact Info

Product

Resources

About

Progress Toward the Electrocatalytic Production of Liquid Fuels from Carbon Dioxide

Cited by 14 publications

References 152 publications

Copper-Tin Alloys for the Electrocatalytic Reduction of CO2 in an Imidazolium-Based Non-Aqueous Electrolyte

Copper-Tin Alloys for the Electrocatalytic Reduction of CO2 in an Imidazolium-Based Non-Aqueous Electrolyte

Inhibited proton transfer enhances Au-catalyzed CO 2 -to-fuels selectivity

Impurity Ion Complexation Enhances Carbon Dioxide Reduction Catalysis

Contact Info

Product

Resources

About

Inhibited proton transfer enhances Au-catalyzed CO ₂ -to-fuels selectivity