Unintended cation crossover influences CO2 reduction selectivity in Cu-based zero-gap electrolysers

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

Опубликована: Апрель 12, 2023

Membrane electrode assemblies enable CO2 electrolysis at industrially relevant rates, yet their operational stability is often limited by formation of solid precipitates in the cathode pores, triggered cation crossover from anolyte due to imperfect ion exclusion anion exchange membranes. Here we show that concentration affects degree movement through membranes, and this substantially influences behaviors copper catalysts catholyte-free electrolysers. Systematic variation (KOH or KHCO3) ionic strength produced a distinct switch selectivity between either predominantly CO C2+ products (mainly C2H4) which closely correlated with quantity alkali metal (K+) crossover, suggesting cations play key role C-C coupling reaction pathways even cells without discrete liquid catholytes. Operando X-ray absorption quasi situ photoelectron spectroscopy revealed Cu surface speciation showed strong dependence on concentration, wherein dilute anolytes resulted mixture Cu+ Cu0 species, while concentrated led exclusively under similar testing conditions. These results cells, effects (including unintentional ones) significantly influence pathways, important consider future development devices.

Язык: Английский

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Cation-Induced Interfacial Hydrophobic Microenvironment Promotes the C–C Coupling in Electrochemical CO₂ Reduction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5532 - 5542

Опубликована: Фев. 16, 2024

The electrochemical carbon dioxide reduction reaction (CO2RR) toward C2 products is a promising way for the clean energy economy. Modulating structure of electric double layer (EDL), especially interfacial water and cation type, useful strategy to promote C–C coupling, but atomic understanding lags far behind experimental observations. Herein, we investigate combined effect alkali metal cations on coupling at Cu(100) electrode/electrolyte interface using ab initio molecular dynamics (AIMD) simulations with constrained MD slow-growth approach. We observe linear correlation between water-adsorbate stabilization effect, which manifests as hydrogen bonds, corresponding alleviation in free energy. role larger cation, compared smaller (e.g., K+ vs Li+), lies its ability approach through desolvation coordinates *CO+*CO moiety, partially substituting hydrogen-bonding stabilizing water. Although this only results marginal barrier it creates local hydrophobic environment scarcity bonds owing great ionic radius, impeding surrounding oxygen adsorbed *CO. This skillfully circumvents further hydrogenation *CO C1 pathway, serving predominant factor facilitates coupling. study unveils comprehensive mechanism cation–water–adsorbate interactions that can facilitate optimization electrolyte EDL efficient CO2RR.

Язык: Английский

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Modulating microenvironments to enhance CO2 electroreduction performance

eScience, Год журнала: 2023, Номер 3(3), С. 100119 - 100119

Опубликована: Март 17, 2023

Microenvironments of the catalytic center, which play a vital role in adjusting electrocatalytic CO2 reduction reaction (ECO2RR) activity, have received increasing attention during past few years. However, controllable microenvironment construction and effects multi-microenvironment variations for improving ECO2RR performance remain unclear. Herein, we summarize representative strategies tuning catalyst local microenvironments to enhance selectivity activity. The multifactor synergetic regulation enhancing accessibility, stabilizing key intermediates, catalysts are discussed detail, as well perspectives on challenges when investigating microenvironments. We anticipate that discussions this review will inspire further research engineering accelerate development practical application.

Язык: Английский

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Deciphering Electrolyte Selection for Electrochemical Reduction of Carbon Dioxide and Nitrogen to High‐Value‐Added Chemicals

Advanced Functional Materials, Год журнала: 2023, Номер 33(11)

Опубликована: Янв. 4, 2023

Abstract Electrochemical reduction of CO 2 (CO RR) and nitrogen (NRR) constitute alternatives to fossil fuel‐based technologies for the production high‐value‐added chemicals. Yet their practical application is still hampered by low energy Faradaic efficiencies although numerous efforts have been paid overcome fatal shortcomings. To date, most studies focused on designing developing advanced electrocatalysts, while understanding electrolyte, which would significantly influence reaction microenvironment, are not enough provide insight construct highly active selective electrochemical systems. Here, a comprehensive review different electrolytes participating in RR NRR provided, including acidic, neutral, alkaline, water‐in‐salt electrolyte as aqueous electrolytes, well organic ionic‐liquids mixture two non‐aqueous electrolytes. Through discussion roles these various it aimed grasp essential function during process how functions can be used design parameters improving electrocatalytic performance. Finally, priorities future suggested support in‐depth effects thus guide efficient selection next‐generation gas‐involving reactions.

Язык: Английский

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Electrocatalyst Microenvironment Engineering for Enhanced Product Selectivity in Carbon Dioxide and Nitrogen Reduction Reactions

ACS Catalysis, Год журнала: 2023, Номер 13(8), С. 5375 - 5396

Опубликована: Апрель 6, 2023

Carbon and nitrogen fixation strategies are regarded as alternative routes to produce valuable chemicals used energy carriers fertilizers that traditionally obtained from unsustainable energy-intensive coal gasification (CO CH4), Fischer–Tropsch (C2H4), Haber–Bosch (NH3) processes. Recently, the electrocatalytic CO2 reduction reaction (CO2RR) N2 (NRR) have received tremendous attention, with merits of being both efficient store renewable electricity while providing preparation fossil-fuel-driven reactions. To date, development CO2RR NRR processes is primarily hindered by competitive hydrogen evolution (HER); however, corresponding for inhibiting this undesired side still quite limited. Considering such complex reactions involve three gas–liquid–solid phases successive proton-coupled electron transfers, it appears meaningful review current improving product selectivity in light their respective mechanisms, kinetics, thermodynamics. By examining developments understanding catalyst design, electrolyte engineering, three-phase interface modulation, we discuss key NRR: (i) targeting molecularly defined active sites, (ii) increasing local reactant concentration at (iii) stabilizing confining intermediates.

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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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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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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Upgrading Cycling Stability and Capability of Hybrid Na‐CO₂ Batteries via Tailoring Reaction Environment for Efficient Conversion CO₂ to HCOOH

Advanced Energy Materials, Год журнала: 2024, Номер 14(16)

Опубликована: Фев. 29, 2024

Abstract Rechargeable Na‐CO 2 batteries are considered to be an effective way address the energy crisis and greenhouse effect due their dual functions of CO fixation/utilization storage. However, insolubility irreversibility solid discharge products lead poor capacity cycle performance. Herein, a novel strategy is proposed enhance electrochemical performance hybrid batteries, using water‐in‐salt electrolyte (WiSE) establish optimal reaction environment, regulate reduction pathway, ultimately convert product battery from Na 3 formic acid (HCOOH). This effectively resolves issue reversibility, allowing exhibit excellent (over 1200 cycles at 30 °C), especially under low‐temperature conditions (2534 −20 °C). Furthermore, density functional theory (DFT) calculations experiments indicate that by adjusting relative concentration H/O atoms electrolyte/catalyst interface, pathway in can regulated, thus enhancing capture capability consequently achieving ultra‐high specific 148.1 mAh cm −2 . work promotes practical application shall provide guidance for converting into with high‐value‐added chemicals.

Язык: Английский

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Switching the Symmetry of a Trinuclear Copper Cluster Catalyst for Electroreducing CO₂ to an Asymmetric C₂ Product in an Acidic Electrolyte

ACS Catalysis, Год журнала: 2024, Номер 14(2), С. 741 - 750

Опубликована: Янв. 2, 2024

Achieving CO2 electroreduction in an acidic electrolyte to obtain high-value products is a great challenge, but it has remained elusive so far due the high requirements for catalyst stability. Herein, we designed and constructed highly stable (acid- alkali-resistant) well-defined crystalline coordination compound catalyst, Inz-Cu3, which can switch structural symmetry by varying distance angle between adjacent synergistic Cu active sites, thus achieving selective conversion of C2 product electrolyte. At current density −320 mA·cm–2, achieved up 42.20% selectivity electrocatalytic reduction electrolyte, catalytic (66.79%, containing 35.27% FEC2H4 31.52% FEC2H5OH) also be conventional alkaline Moreover, functional theory (DFT) calculation control experiments revealed that asymmetric sites with close stabilize *CHOHCH3 intermediates, improving product. This work demonstrates strategy design catalysts enables achievement high-value-added

Язык: Английский

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