Cation-induced changes in the inner- and outer-sphere mechanisms of electrocatalytic CO2 reduction

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Ноя. 22, 2023

The underlying mechanism of cation effects on CO2RR remains debated. Herein, we study by simulating both outer-sphere electron transfer (OS-ET) and inner-sphere (IS-ET) pathways during via constrained density functional theory molecular dynamics (cDFT-MD) slow-growth DFT-MD (SG-DFT-MD), respectively. Our results show without any cations, only OS-ET is feasible with a barrier 1.21 eV. In the presence K+ (Li+), shows very high 2.93 eV (4.15 eV) thus being prohibited. However, cations promote CO2 activation through IS-ET 0.61 (K+) 0.91 generating key intermediate (adsorbed CO[Formula: see text]). Without CO2-to-CO[Formula: text](ads) conversion cannot proceed. findings reveal arise from short-range Coulomb interactions reaction intermediates. These disclose that modulate inner- CO2RR, offering substantial insights specificity in initial steps.

Язык: Английский

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Electrochemical Carbon Dioxide Reduction to Ethylene: From Mechanistic Understanding to Catalyst Surface Engineering

Nano-Micro Letters, Год журнала: 2023, Номер 15(1)

Опубликована: Июль 11, 2023

Electrochemical carbon dioxide reduction reaction (CO2RR) provides a promising way to convert CO2 chemicals. The multicarbon (C2+) products, especially ethylene, are of great interest due their versatile industrial applications. However, selectively reducing ethylene is still challenging as the additional energy required for C-C coupling step results in large overpotential and many competing products. Nonetheless, mechanistic understanding key steps preferred pathways/conditions, well rational design novel catalysts production have been regarded approaches achieving highly efficient selective CO2RR. In this review, we first illustrate CO2RR (e.g., adsorption/activation, formation *CO intermediate, step), offering conversion ethylene. Then alternative pathways conditions competitive products (C1 other C2+ products) investigated, guiding further development generation. Engineering strategies Cu-based CO2RR-ethylene summarized, correlations mechanism/pathways, engineering selectivity elaborated. Finally, major challenges perspectives research area proposed future practical

Язык: Английский

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The importance of a charge transfer descriptor for screening potential CO2 reduction electrocatalysts

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Май 5, 2023

Abstract It has been over twenty years since the linear scaling of reaction intermediate adsorption energies started to coin fields heterogeneous and electrocatalysis as a blessing curse at same time. established possibility construct activity volcano plots function single or two readily accessible descriptors, but also limited maximal catalytic conversion rate. In this work, it is found that these energy-based descriptor spaces are not applicable electrochemistry, because they lacking an important additional dimension, potential zero charge. This extra dimension arises from interaction electric double layer with intermediates which does scale energies. At example electrochemical reduction CO 2 shown addition breaks relations, opening up huge chemical space via charge-based material design. The charge explains product selectivity trends in close agreement reported experimental data highlighting its importance for electrocatalyst

Язык: Английский

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Advances and challenges in the electrochemical reduction of carbon dioxide

Chemical Science, Год журнала: 2024, Номер 15(21), С. 7870 - 7907

Опубликована: Янв. 1, 2024

This review highlights the structure–activity relationship of ECO 2 RR, provides a detailed summary advanced materials by analyzing electrocatalytic applications and reaction mechanisms, discusses challenges in both devices.

Язык: Английский

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Probing electrolyte effects on cation-enhanced CO2 reduction on copper in acidic media

Nature Catalysis, Год журнала: 2024, Номер 7(7), С. 807 - 817

Опубликована: Июнь 24, 2024

Язык: Английский

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Effects of Electrolyte Ionic Species on Electrocatalytic Reactions: Advances, Challenges, and Perspectives

Advanced Energy Materials, Год журнала: 2023, Номер 13(27)

Опубликована: Апрель 27, 2023

Abstract Electrolytes have a profound impact on the chemical environment of electrocatalysis, influencing reaction rate and selectivity products. Experimental theoretical studies extensively investigated interaction mechanisms between electrolyte ions (i.e., alkali metal cations, carbonate anions) reactants or catalyst surface in electrocatalytic reactions such as hydrogen evolution reaction, oxygen reduction water oxidation CO 2 reaction. Past demonstrated noticeable dependence electrochemical activity identity ions. However, few overviews comprehensively specifically discussed effects cations anions common reactions. In order to clarify give more insights this research area, review aims summarize highlight recent progress understanding various ionic species their influence diverse for splitting, H O production, reduction. The challenges perspectives effect electrocatalysis are also presented.

Язык: Английский

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Understanding the complexity in bridging thermal and electrocatalytic methanation of CO₂

Chemical Society Reviews, Год журнала: 2023, Номер 52(11), С. 3627 - 3662

Опубликована: Янв. 1, 2023

The selective methanation of CO2 is an important research area to meet the net-zero emission targets. Furthermore, it crucial develop solutions achieve carbon neutrality, hydrogen utilization, circularity, and chemical-energy storage. This conversion can be realized via thermocatalytic multistep power-to-X route or by direct electro- (or photoelectro)-catalytic technologies. Herein, we discuss need accelerate Improving these technologies requires a better understanding catalytic chemistry complexity aspects consider in bridging electrocatalytic methanation. In this tutorial review, initially analyze fundamental question competitive adsorption key reactants regulation strategies promote overall reaction. Then, approach used guide reader differences between thermocatalysis electrocatalysis. Finally, necessary include modelling designing next-generation electrocatalysts for analyzed.

Язык: Английский

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The Effect of Electrolytes on the Kinetics of the Hydrogen Evolution Reaction

Hydrogen, Год журнала: 2023, Номер 4(4), С. 776 - 806

Опубликована: Окт. 13, 2023

Amid global energy challenges, the hydrogen evolution reaction (HER) is gaining traction for green production. While catalyst research ongoing, recognizing electrolyte effects remains crucial sustainable production via renewable-powered water electrolysis. This review delves into intricate of electrolytes on kinetics HER. It examines key factors including pH, cations, anions, impurities, and concentration. discusses notion that pH alters catalyst–electrolyte interactions proton concentrations, thereby influencing such as binding energy, adsorption, overall kinetics. Moreover, this provides a briefing cations Li+ can impact HER positively or negatively, offering opportunities improvement based metal substrate. Interestingly, there potential be tuned using ions to modify M–H bond demonstrating flexibility beyond levels counter-ions. The varied adsorption energies electrodes are also found influence anions impurities discussed, emphasizing both positive negative impacts it pointed out electrolyte-engineering approach enhances without permanent surface modifications. underscores importance composition, highlighting challenges solutions in advancing

Язык: Английский

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Tuning the Interfacial Reaction Environment for CO₂ Electroreduction to CO in Mildly Acidic Media

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5242 - 5251

Опубликована: Фев. 13, 2024

A considerable carbon loss of CO2 electroreduction in neutral and alkaline media severely limits its industrial viability as a result the homogeneous reaction OH– under interfacial alkalinity. Here, to mitigate reactions, we conducted mildly acidic media. By modulating environment via multiple electrolyte effects, parasitic hydrogen evolution is suppressed, leading faradaic efficiency over 80% for CO on planar Au electrode. Using rotating ring-disk electrode technique, ring constitutes an situ collector pH sensor, enabling recording Faradaic monitoring while reduction takes place disk. The dominant branch switches from proton water changes alkaline. comparison, starts within region approaches near-neutral conditions. Thereafter, decays, place, protons are increasingly consumed by electrogenerated reduction. reaches maximum just before initiates. Slowing mass transport lowers current, hardly influenced. In contrast, appropriate protic anion, e.g., HSO4– our case, weakly hydrated cations, K+, accelerate reduction, with former providing extra flux but higher local pH, latter stabilizing *CO2– intermediate.

Язык: Английский

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Electronic Structure Design of Transition Metal-Based Catalysts for Electrochemical Carbon Dioxide Reduction

ACS Nano, Год журнала: 2024, Номер 18(14), С. 9823 - 9851

Опубликована: Март 28, 2024

With the increasingly serious greenhouse effect, electrochemical carbon dioxide reduction reaction (CO2RR) has garnered widespread attention as it is capable of leveraging renewable energy to convert CO2 into value-added chemicals and fuels. However, performance CO2RR can hardly meet expectations because diverse intermediates complicated processes, necessitating exploitation highly efficient catalysts. In recent years, with advanced characterization technologies theoretical simulations, exploration catalytic mechanisms gradually deepened electronic structure catalysts their interactions intermediates, which serve a bridge facilitate deeper comprehension structure-performance relationships. Transition metal-based (TMCs), extensively applied in CO2RR, demonstrate substantial potential for further modulation, given abundance d electrons. Herein, we discuss representative feasible strategies modulate catalysts, including doping, vacancy, alloying, heterostructure, strain, phase engineering. These approaches profoundly alter inherent properties TMCs interaction thereby greatly affecting rate pathway CO2RR. It believed that rational design modulation fundamentally provide viable directions development toward conversion many other small molecules.

Язык: Английский

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