Multi-atomic loaded C₂N₁ catalysts for CO₂ reduction to CO or formic acid

Nanoscale, Год журнала: 2024, Номер 16(20), С. 9791 - 9801

Опубликована: Янв. 1, 2024

Triple-atom catalysts exhibit moderate adsorption energy for intermediate species, enabling the optimal performance of CO 2 electrocatalytic reduction reaction.

Язык: Английский

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Electronic metal-support interaction modulates Cu electronic structures for CO2 electroreduction to desired products

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

Опубликована: Фев. 25, 2025

In this work, the Cu single-atom catalysts (SACs) supported by metal-oxides (Al2O3-CuSAC, CeO2-CuSAC, and TiO2-CuSAC) are used as theoretical models to explore correlations between electronic structures CO2RR performances. For these catalysts, metal-support interaction (EMSI) induced charge transfer sites supports subtly modulates structure form different highest occupied-orbital. The occupied 3dyz orbital of Al2O3-CuSAC enhances adsorption strength CO weakens C-O bonds through 3dyz-π* electron back-donation. This reduces energy barrier for C-C coupling, thereby promoting multicarbon formation on Al2O3-CuSAC. 3dz2 TiO2-CuSAC accelerates H2O activation, lowers reaction forming CH4. over activated H2O, in turn, intensifies competing hydrogen evolution (HER), which hinders high-selectivity production CH4 TiO2-CuSAC. CeO2-CuSAC with 3dx2-y2 promotes CO2 activation its localized state inhibits coupling. moderate water activity facilitates *CO deep hydrogenation without excessively activating HER. Hence, exhibits Faradaic efficiency 70.3% at 400 mA cm−2. Rational regulation control electroreduction pathways is challenging. Here, authors report modulating single-sites via interaction, enabling switchable selectivity multicarbons methane.

Язык: Английский

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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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Transforming Adsorbate Surface Dynamics in Aqueous Electrocatalysis: Pathways to Unconstrained Performance

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 28, 2025

Abstract Developing highly efficient catalysts to accelerate sluggish electrode reactions is critical for the deployment of sustainable aqueous electrochemical technologies, yet remains a great challenge. Rationally integrating functional components tailor surface adsorption behaviors and adsorbate dynamics would divert reaction pathways alleviate energy barriers, eliminating conventional thermodynamic constraints ultimately optimizing flow within systems. This approach has, therefore, garnered significant interest, presenting substantial potential developing that simultaneously enhance activity, selectivity, stability. The immense promise rapid evolution this design strategy, however, do not overshadow challenges ambiguities persist, impeding realization breakthroughs in electrocatalyst development. review explores latest insights into principles guiding catalytic surfaces enable favorable contexts hydrogen oxygen electrochemistry. Innovative approaches tailoring adsorbate‐surface interactions are discussed, delving underlying govern these dynamics. Additionally, perspectives on prevailing presented future research directions proposed. By evaluating core identifying gaps, seeks inspire rational design, discovery novel mechanisms concepts, ultimately, advance large‐scale implementation electroconversion technologies.

Язык: Английский

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Elimination of Concentration Polarization Under Ultra‐High Current Density Zinc Deposition by Nanofluid Self‐Driven Ion Enrichment

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Март 4, 2025

Abstract The commercialization of zinc metal batteries aims at high‐rate capability and lightweight, which requires anodes working high current density, areal capacity, depth discharge. However, frequent anode fades drastically under extreme conditions. Herein, it is revealed that the primary reason for instability severe concentration polarization caused by imbalanced consumption rate transfer Zn 2+ Based on this finding, a nanofluid layer constructed to rapidly absorb mitigate induced nonlinear transport interfacial ions. modified sustains conditions over 1573 h (40 mA cm −2 , 40 mAh DOD = 75.97%) 490 (100 100 90.91%), achieving an unprecedented cumulative capacity 62.92 Ah . This work offers both fundamental practical insights interface design in energy storage devices.

Язык: Английский

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Promoting Water Activation via Molecular Engineering Enables Efficient Asymmetric C–C Coupling during CO₂ Electroreduction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(47), С. 32870 - 32879

Опубликована: Ноя. 13, 2024

Water activation plays a crucial role in CO

Язык: Английский

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Unveiling Key Descriptors of Ionomer Materials for Enhanced Electrochemical CO₂ Reduction

ACS Energy Letters, Год журнала: 2025, Номер 10(1), С. 620 - 628

Опубликована: Янв. 3, 2025

Polymeric ionomers near the catalyst surface of CO2 reduction reaction (CO2RR) electrodes affect their efficiency; however, multifaceted properties complicate structure–activity relationship elucidation. Here, we synthesized polycarbazole-based anion-exchange (QPC) bearing varying functionalized side chains to explore this relationship. Comprehensive analysis in physicochemical properties, electrochemical activity, and operando ATR-SEIRAS revealed that functional group modification significantly influenced intrinsic ionomer thereby affecting Ag microenvironments interfacial water structures, kinetics protonation step for CO2RR hydrogen evolution (HER). Notably, QPC-trimethyl phosphonium (TMP) induced favorable having a high proportion strong H-bonded with low Stark tuning slopes, which inhibit HER promote CO2RR. A CO Faradaic efficiency (>90%) was maintained using QPC-TMP membrane electrode assembly, even under concentrations (100–15%) elevated temperatures (28–72 °C). These findings suggest catalytic environment can be optimized by fine-tuning structure, contributing advancement high-performance ionomers.

Язык: Английский

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Emerging Supported Metal Atomic Clusters for Electrocatalytic Renewable Conversions

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 2434 - 2458

Опубликована: Янв. 27, 2025

Subnanometric supported metal atomic clusters (SMACs) composed of several to tens surface atoms have attracted increased research interest in electrocatalysis. SMACs been known show distinct properties compared their nanoparticles and single atom counterparts long developed for functional improvements. Tremendous advancements made the past few years, with a notable trend more precise design down an atomic/molecular level investigation transferring into practical devices, which motivates this timely review. To begin, review presents classifies classic latest synthetic strategies state-of-the-art characterization techniques SMACs. It then outlines discusses basic structure principles SMACs, highlighting importance organic ligands, size effect clusters, support-cluster interactions determining catalytic activity device stability. Thereafter, recent advances typical electrocatalysis processes from laboratory scale industrial are discussed obtain general understanding structure–activity correlations Current challenges future perspectives emerging field also discussed, aiming at practicing SMAC catalysts energy conversion devices.

Язык: Английский

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Reversible Angle Distortion-Dependent Electrochemical CO₂ Reduction on Cobalt Phthalocyanine

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 7, 2025

Deducing the local electronic and atomic structural changes in active sites during electrochemical carbon dioxide reduction is essential for elucidating intrinsic mechanisms developing highly catalysts that are stable a long duration. Herein, utilizing operando valence-to-core X-ray emission spectroscopy high energy-resolution fluorescence detected absorption near-edge structure, combined with spectroscopic calculations, structure evolutions of model cobalt phthalocyanine (CoPc) were quantitatively elucidated. Under real reaction conditions, CoPc undergoes reversible angle distortion while maintaining constant metal-ligand bond length, causing energy levels split d orbitals electron density molecular orbitals. The further influences interactions among ligands, intermediates, metal centers. change CO Faraday efficiency was also determined, demonstrating robustness. demonstrated findings serve as an important contribution to determine structure-performance relationship which enlightens rational design atomically dispersed site activity emphasize capabilities resolution toward analyzing metal-implanted N-doped catalysts.

Язык: Английский

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Observation of metal-organic interphase in Cu-based electrochemical CO2-to-ethanol conversion

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

Опубликована: Фев. 28, 2025

Interphases are critical in electrochemical systems, influencing performance by controlling ion transport and stability. This study explores a metal-organic interphase the electrocatalytic reduction of CO2 (CO2RR) on Cu, extending concept interphases to conversion. Investigating organic modifications CuOx, we discover over 10 nm thick highly ethanol-selective contrary expected monolayer adsorption. Using an automated platform, 1080 CO2RR experiments with 180 molecular modifiers identify functional groups affecting selectivity for ethanol multi-carbon (C2+) products. We find that these consistently produce Cu or CuOx surface. These modulate coordination, intermediates, interfacial water configuration, significantly improving performance. Testing across 11 CuOx-based catalysts validates this approach, culminating development two electrocatalysts achieve ~80% faradaic efficiency C2+ products partial current densities up 328 507 mA cm−2. highlights pivotal role CO2RR, advancing conversion technologies. crucial but their electroreduction remains underexplored. Here, authors report importance systematically investigating using automatic electrocatalysis platform.

Язык: Английский

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