Tip carbon encapsulation customizes cationic enrichment and valence stabilization for low K+ acidic CO2 electroreduction

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Фев. 19, 2025

Abstract Acidic electrochemical CO 2 conversion is a promising alternative to overcome the low utilization. However, over-reliance on highly concentrated K + inhibit hydrogen evolution reaction also causes (bi)carbonate precipitation interfere with catalytic performance. In this work, under screening and guidance of computational simulations, we present carbon coated tip-like O 3 electrocatalyst for stable efficient acidic synthesize formic acid (HCOOH) concentration. The layer protects oxidized species higher intrinsic activity from reductive corrosion, peripherally formulates tip-induced electric field regulate adverse H attraction desirable enrichment. an electrolyte at pH 0.94, only 0.1 M required achieve Faradaic efficiency (FE) 98.9% 300 mA cm −2 HCOOH long-time stability over100 h. By up-scaling electrode into 25 electrolyzer setup, total current 7 A recorded sustain durable production 291.6 mmol L −1 h .

Язык: Английский

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Synergistic Effects in the Electrochemical Carbon Dioxide Reduction Reaction for Multi‐Carbon Product Formation

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

Abstract The synergistic effects in electrocatalysis can significantly enhance catalyst performance by improving catalytic activity, selectivity, and stability, optimizing reaction mechanisms electron transfer processes. This review summarizes recent advancements the of electrochemical reduction CO 2 (eCO RR) to multi‐carbon (C 2+ ) products. Starting with fundamental principles eCO RR for C product formation, paper outlines producing , 3 4 5 A comprehensive discussion is provided on critical impact structure–performance relationship production Subsequently, observed are classified various electrocatalysts different properties, including single/dual‐atom catalysts, multi‐centric single‐atom alloys, metal‐organic frameworks, heterojunction catalysts. Finally, challenges achieving selective formation through discussed, along corresponding strategies overcome obstacles.

Язык: Английский

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Experimental and Theoretical Insights into Single Atoms, Dual Atoms, and Sub‐Nanocluster Catalysts for Electrochemical CO₂ Reduction (CO₂RR) to High‐Value Products

Advanced Materials, Год журнала: 2024, Номер 36(52)

Опубликована: Ноя. 26, 2024

Abstract Electrocatalytic carbon dioxide (CO 2 ) conversion into valuable chemicals paves the way for realization of recycling. Downsizing catalysts to single‐atom (SACs), dual‐atom (DACs), and sub‐nanocluster (SNCCs) has generated highly active selective CO transformation reduced products. This is due introduction numerous sites, unsaturated coordination environments, efficient atom utilization, confinement effect compared their nanoparticle counterparts. Herein, recent Cu‐based SACs are first reviewed newly emerged DACs SNCCs expanding catalysis electrocatalytic reduction RR) high‐value products discussed. Tandem SAC–nanocatalysts (NCs) (SAC–NCs) also discussed RR Then, non‐Cu‐based SACs, DACs, SAC–NCs, theoretical calculations various transition‐metal summarized. Compared previous achievements less‐reduced products, this review focuses on double objective achieving full increasing selectivity formation rate toward C–C coupled with additional emphasis stability catalysts. Finally, through combined experimental research, future outlooks offered further develop over isolated atoms sub‐nanometal clusters.

Язык: Английский

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Non-rigid metal–oxygen bonding empowered nitrate reduction on ruthenium catalysts

Nano Energy, Год журнала: 2024, Номер 130, С. 110088 - 110088

Опубликована: Авг. 6, 2024

Electrocatalytic nitrate reduction (NitRR) offers exciting potential for mass production of ammonia (NH3) from renewables. However, the rigidity metal−ligand bonds in most electrocatalysts renders them unable to survive structural transformations required NitRR. Herein, we establish a type non-rigid metal−oxygen by employing graphene oxide (GO) sheets as 'micron-scale' ligand transition metals (TM). Because being confined interfaces between GO and TM, oxygenated groups can associate with dissociate TM response reaction dynamics. As proof-of-concept demonstration, an electrocatalyst was developed dispersing nanoscale ruthenium (Ru) on utilizing two-dimensional MXene compensate low electrical conductivity GO. This exhibits maximum NH3 yield over 5 mg cm−2 h−1, almost 100 % current-to-NH3 efficiency, far outperforming performance reported Ru-based materials. What's even more remarkable is achievement record-breaking performance: 200-hour stable electrolysis 40.2 using membrane electrode reactor. Our experimental theoretical investigations further reveal non-rigidity Ru–O how they self-regulate adapt diverse intermediates involved work provides approach fabricate high-performance featuring reversible bonds, opening new possibilities practical electrolysis.

Язык: Английский

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Unraveling the Mechanism of Cu/CeO₂ Interface Modulation for CO₂ Electroreduction Into C₂₊/CH₄

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 23, 2025

Abstract Cu shows unique characteristics for electrochemical CO 2 reduction reaction (CO RR) to hydrocarbons and oxygenates due the moderate adsorption energy of key intermediate *CO. However, it remains a challenge selectively control RR towards C 1 (e.g., CH 4 ) or 2+ H 5 OH) through simple interface engineering. Herein, series inverse catalysts, composed CeO nanoparticles over substrate (Cu‐CeO ‐x), are subtly designed tackle issues. It is verified decoration induces highly active Cu/CeO interfacial sites that enhance conversion *CO intermediates into , while conducive generation. With increase deposition, selectivity present volcano‐type increasing tendency with maximum faradic efficiency 62.6% 51.3%, respectively. In‐situ infrared spectroscopy theoretical calculations reveal loading allows cooperate efficiently promote coupling *CO/*CHO intermediates, thus enhancing selectivity. In contrast, excessive suppresses C─C but boosts unilaterally hydrogenation, promoting production. This work provides effective strategies regulate by modulating metal/oxide interfaces.

Язык: Английский

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Non-Stoichiometric BaxMn0.7Cu0.3O3 Perovskites as Catalysts for CO Oxidation: Optimizing the Ba Content

Nanomaterials, Год журнала: 2025, Номер 15(2), С. 103 - 103

Опубликована: Янв. 10, 2025

In this work, a series of BaxMn0.7Cu0.3O3 samples (x: 1, 0.9, 0.8, and 0.7, BxMC) was synthesized, characterized, used as catalysts for CO oxidation reaction. All formulations were active in the tested conditions. A correlation between electrical conductivity, obtained by impedance spectroscopy, reducibility samples, H2-TPR, observed. The Ba0.8Mn0.7Cu0.3O3 composition (B0.8MC) showed best catalytic performance (comparable to that 1% Pt/Al2O3 reference sample) during tests conducted under conditions similar those found exhaust gases current gasoline engines. characterization data suggest simultaneous presence high Mn(IV)/Mn(III) surface ratio, oxygen vacancies, reduced copper species, these two latter being key properties ensuring conversion percentage both are sites oxidation. reaction temperature reactant atmosphere seem be most important factors achieving good performance, they strongly determine location stability species.

Язык: Английский

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Electrochemical CO₂ Reduction on SnO: Insights into C₁ Product Dynamic Distribution and Reaction Mechanisms

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 3173 - 3183

Опубликована: Фев. 6, 2025

The precise synthesis of desirable products from the electrochemical CO2 reduction reaction (CO2RR) remains challenging, primarily due to unclear structure–activity relationships under in situ conditions. Recognized by their cost-effectiveness and nontoxic nature, Sn-based materials are extensively utilized CO2RR produce valuable chemicals. Notably, our large-scale data mining experimental literature reveals a significant trend: SnO2-based electrocatalysts generate HCOOH, while SnO-based counterparts demonstrate ability both HCOOH CO comparable quantities. Furthermore, findings indicate that SnO underexplored terms its surface speciation for compared materials. Addressing these issues is crucial field electrocatalysis, as understanding them will not only clarify why uniquely influences distribution C1 but also provide insights into how precisely control electrocatalytic processes targeted product synthesis. Herein, we employed constant-potential method combined with coverage reconstruction analyses simulate energetics intermediates elucidate dynamic on resting typical Our analysis effectively identifies active involved CO2RR. comparative simulations between pristine reconstructed surfaces reveal electrochemistry-induced oxygen vacancies direct distribution. By addressing critical issues, aim advance electrocatalysis contribute chemical production CO2, stimulating future exploration conditions other systems.

Язык: Английский

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Highly Dispersed Single Clusters Supported Porphyrinic Metal–Organic Frameworks for Synergetic CO₂ Electroreduction to CH₄

Small, Год журнала: 2025, Номер unknown

Опубликована: Фев. 25, 2025

The electrocatalytic CO2 reduction is a promising path toward the carbon-neutral goal but remains huge challenge due to high activation barrier for and poor selectivity. Herein, highly dispersed triruthenium single cluster (Ru3-SCs) confined into nanospace of pyrrole-3-carboxylic acid (PyrA)-modified nickel-porphyrin-based metal-organic framework (Ni-PCN-222-PyrA) form composite (Ru3-SCs@Ni-PCN-222-PyrA) through pre-coordination confinement strategy. prepared Ru3-SCs@Ni-PCN-222-PyrA can accelerate selective CH4 via electrocatalysis. Under -1.0 V versus reversible hydrogen electrode (RHE), affords electroreduction with selectivity 71.9% Faradaic efficiency. Mechanistic studies reveal that superior reactivity be attributed ensemble effect synergistic catalysis Ru3-SCs, in which one Ru atom responsible *CO another promotes water splitting generate *H, then two intermediates *H coupled key intermediate *CHO thermodynamically favorable way.

Язык: Английский

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Progress in Cu‐Based Catalyst Design for Sustained Electrocatalytic CO₂ to C₂₊ Conversion

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Фев. 27, 2025

Abstract The electrocatalytic conversion of CO 2 into valuable multi‐carbon (C 2+ ) products using Cu‐based catalysts has attracted significant attention. This review provides a comprehensive overview recent advances in catalyst design to improve C selectivity and operational stability. It begins with an analysis the fundamental reaction pathways for formation, encompassing both established emerging mechanisms, which offer critical insights design. In situ techniques, essential validating these by real‐time observation intermediates material evolution, are also introduced. A key focus this is placed on how enhance through manipulation, particularly emphasizing catalytic site construction promote C─C coupling via increasing * coverage optimizing protonation. Additionally, challenge maintaining activity under conditions discussed, highlighting reduction active charged Cu species materials reconstruction as major obstacles. To address these, describes strategies preserve sites control including novel utilization mitigation reconstruction. By presenting developments challenges ahead, aims guide future conversion.

Язык: Английский

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Enhancing the Performance of BaxMnO3 (x = 1, 0.9, 0.8 and 0.7) Perovskites as Catalysts for CO Oxidation by Decreasing the Ba Content

Nanomaterials, Год журнала: 2024, Номер 14(16), С. 1334 - 1334

Опубликована: Авг. 10, 2024

Mixed oxides featuring perovskite-type structures (ABO3) offer promising catalytic properties for applications focused on the control of atmospheric pollution. In this work, a series BaxMnO3 (x = 1, 0.9, 0.8 and 0.7) samples have been synthesized, characterized tested as catalysts CO oxidation reaction in conditions close to that found exhausts last-generation automotive internal combustion engines. All were observed be active during CO-TPRe tests, with Ba0.7MnO3 (B0.7M) being most one, it presents highest amount oxygen vacancies (which act sites oxidation) Mn (IV), which features levels reducibility best redox properties. B0.7M has also showcased high stability reactions at 300 °C, even though slightly lower conversion is achieved second consecutive cycle. This performance appears related decrease (IV)/Mn (III) ratio.

Язык: Английский

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