Understanding the Role of Potential and Cation Effect on Electrocatalytic CO₂ Reduction in All-Alkynyl-Protected Ag₁₅ Nanoclusters

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

Опубликована: Янв. 8, 2025

Atomically precise metal nanoclusters (NCs) have emerged as an intriguing class of model catalysts for electrochemical CO2 reduction reactions (CO2RR). However, the interplay between interface environment (e.g., potential, cation concentration) and electron–proton transfer (ET/PT) kinetics─particularly in alkynyl-protected NCs─remains poorly understood. Here, we combined first-principles simulations experiments to investigate role potential effect on CO2RR performance a prototype all-alkynyl-protected Ag15(C≡C–CH3)+ cluster. Our revealed that applied triggers elimination alkynyl ligand via sequentially breaking two π-type Ag–C bonds one σ-type bond expose catalytically active Ag sites, barrier breakage monotonically decreases with lowering potential. Furthermore, show introducing inner-sphere Na+ ions greatly enhances *CO2 activation promotes proton generate *COOH *CO by forming Na+–CO2(*COOH) complexes, while competitive hydrogen evolution reaction (HER) from water dissociation is suppressed, thus dramatically improving selectivity electroreduction. The measurements further validated our predictions, where CO Faradaic efficiency (FECO) current density (jCO) pronounced dependence concentration. At optimal concentration 0.1 M NaCl, FECO can reach up ∼96%, demonstrating crucial cations promoting CO2RR. findings provide vital insights into atomic-level mechanism Ag15 NCs highlight important electrolyte governing electron/proton kinetics.

Язык: Английский

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Enhancing C-C Coupling in CO2 Electroreduction by Engineering Pore Size of Porous Carbon-Supported Cu Catalysts

Catalysts, Год журнала: 2025, Номер 15(3), С. 199 - 199

Опубликована: Фев. 20, 2025

The electroreduction of CO2 (CO2RR) is a promising and environmentally sustainable approach to closing the carbon cycle. However, achieving high activity selectivity for multicarbon (C2₊) products remains significant challenge due complexity reaction pathways. In this study, porous carbon-supported copper catalysts (CuHCS) with pore sizes 120 nm (CuHCS120) 500 (CuHCS500) were synthesized tailor microenvironment at electrode–electrolyte interface enhance product selectivity. CuHCS120 achieved maximum faradaic efficiency (FE) C2₊ 46%, double that CuHCS500 (23%). contrast, showed higher FE CO (36%) compared (14%) same potential. In-depth ex situ in investigations revealed smaller pores promote enrichment adsorption *CO intermediates, thereby enhancing C–C coupling formation products. These findings underscore critical role structural confinement modulating catalytic provide valuable insights rational design advanced CO2RR.

Язык: Английский

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Sequential addition of cations increases photoluminescence quantum yield of metal nanoclusters near unity

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

Опубликована: Янв. 11, 2025

Abstract Photoluminescence is one of the most intriguing properties metal nanoclusters derived from their molecular-like electronic structure, however, achieving high photoluminescence quantum yield (PLQY) core-dictated fluorescence remains a formidable challenge. Here, we report efficient suppression total structural vibrations and rotations, management pathways rates electron transfer dynamics to boost near-unity absolute PLQY, by decorating progressive addition cations. Specifically, with sequential Zn 2+ , Ag + Tb 3+ into 3-mercaptopropionic acids capped Au (NCs), low-frequency vibration core progressively decreases 144.0, 55.2 40.0 cm −1 coupling strength electrons-high-frequency related surface motifs gradually diminishes 40.2, 30.5 14.4 meV. Moreover, introducing cation additives significantly reduces time 40, 27 12 ps in pathway staple core. This benefits shrinkage structure that speeds up shell-core transition, particular, provides hopping platform for excited electrons as intrinsic ladder-like energy level structure. As result, it allows remarkable enhancement 51.2%, 83.4%, 99.5%.

Язык: Английский

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Computational and Experimental Elucidation of the Charge‐Dependent Acid‐Etching Dynamics and Electrocatalytic Performance of Au₂₅(SR)₁₈^q(q = −1, 0, +1) Nanoclusters

Small, Год журнала: 2025, Номер unknown

Опубликована: Фев. 24, 2025

Abstract Using thiolate‐protected Au 25 (SR) 18 nanocluster (NC) with different charge states as the test candidate, how effect affects etching dynamics of thiolate ligands in acid and electrocatalytic performance is explored. The ab initio molecular (AIMD) simulations revealed charge‐dependent reaction kinetics acid, where anionic neutral (SCH 3 ) q (q = −1, 0) favorably react partially remove via two‐step proton attack, while cationic + NC acid‐resistant no tendency for ‐SR removal. Density functional theory (DFT) calculations further predict that dethiolated sites exhibit enhanced catalytic activity CO 2 electroreduction to CO, − showing significantly superior activity. Acid experiments confirmed partial removal 0), NCs electroreduction, particularly exhibiting better than 0 . This work an interesting state‐mediated interface behaviors NCs, which can be applied modulate properties other atomically precise metal nanoclusters.

Язык: Английский

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Atomic-level insights into the synergistic effect between ligands on electrochemical CO2 reduction: based on Au7Ag8 series nanoclusters

Rare Metals, Год журнала: 2025, Номер unknown

Опубликована: Март 21, 2025

Язык: Английский

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Amino Acid-Regulated Biomimic Fe-MOF Nanozyme with Enhanced Activity and Specificity for Colorimetric Sensing of Uranyl Ions in Seawater

Analytical Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 23, 2025

Nanozymes are attracting widespread attention as effective alternatives to overcome the limitations of natural enzymes. However, their catalytic performance is unsatisfactory due low activity and specificity. In this work, an efficient metal-organic framework (MOF) nanozyme mimicking active centers enzymes has been developed its catalysis mechanism thoroughly investigated. The partial histidine- arginine-doped Fe-MOF (HA Fe-MOF) demonstrated activate structure reconstruction with abundant oxygen vacancy generation, which promotes binding capacity HA Fe-MOF. Fe sites in act for decomposition H2O2. Intriguingly, histidine arginine can form hydrogen bonds H2O2 observed enzymes, constituting a unique microenvironment that increases local concentration Benefiting from establishment such enzyme-mimicking centers, exhibits high peroxidase-like specificity activity. addition, holds great potential detecting uranyl ions limit detection 0.012 μM, surpassing most reported nanozymes. This work achieves rational design highly specific nanozymes by structure-selectivity relationship peroxidases, provides new insights into advanced configurations.

Язык: Английский

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Precision Metal Nanoclusters Meet Proteins: Crafting Next-Gen Hybrid Materials

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Янв. 24, 2025

Metal nanoclusters (NCs), owing to their atomic precision and unique molecule-like properties, have gained widespread attention for applications ranging from catalysis bioimaging. In recent years, proteins, with hierarchical structures diverse functionalities, emerged as good candidates functionalizing metal NCs, rendering NC–protein conjugates combined even synergistically enhanced properties featured by both components. this Perspective, we explore key questions regarding why proteins serve complementary partners the methodologies available conjugating characterization techniques necessary elucidate interactions within emerging bionano system. We also highlight of in biomedicine, catalysis, biosensing which hybrid demonstrate remarkable performance. Furthermore, challenges hampering further development conjugates, include understanding binding mechanisms, expanding diversity used conjugation, exploiting individual roles NCs systems, are discussed. This Perspective aims systemize current synthetic design principles adding acceptance nanotechnology.

Язык: Английский

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Dipropyne‐Modified N‐Heterocyclic Carbene Stabilized Atomically Precise Copper(I) Nanocluster Catalysts for CO₂ Electroreduction

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 25, 2025

Abstract Atomically precise copper(I) nanoclusters with stable active sites are highly sought‐after catalysts for the electrocatalytic CO₂ reduction reaction (CO₂RR), providing an exceptional platform to elucidate structure–activity relationships. However, rational synthesis of robust copper as effective electrocatalysts and understanding relationship between a more realistic site its performance remain significant challenge due their inherent instability. Here, novel dipropyne‐modified NHC ligand is elaborately devised two atomically nanoclusters, [Cu 17 H 6 (NHC ) 4 (dppm) ] 3+ ( Cu17a Ph Cu17b ), both exhibiting distinct unique square orthobicupola Cu core J 28 , Johnson solid). The σ‐ π‐bonding ligands imparts ultrahigh stability while coordination pattern μ 7 ‐ η σ 1 : π 2 facilitates exposure neighboring atoms, generating accessible catalytic sites. Electrocatalytic CO experiments show that achieves highest Faradaic efficiency ethylene production among reported nanoclusters. tandem mechanism RR elucidated through combination theoretical calculations attenuated total reflection‐surface‐enhanced IR absorption spectroscopy (ATR‐SEIRAS). This work not only introduces synthesizing but also offers critical insights into molecular design principles catalysts.

Язык: Английский

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When Metal Nanoclusters Meet Smart Synthesis

ACS Nano, Год журнала: 2024, Номер unknown

Опубликована: Сен. 24, 2024

Atomically precise metal nanoclusters (MNCs) represent a fascinating class of ultrasmall nanoparticles with molecule-like properties, bridging conventional metal-ligand complexes and nanocrystals. Despite their potential for various applications, synthesis challenges such as understanding varied synthetic parameters property-driven persist, hindering full exploitation wider application. Incorporating smart methodologies, including closed-loop framework automation, data interpretation, feedback from AI, offers promising solutions to address these challenges. In this perspective, we summarize the that has been demonstrated in nanomaterials explore research frontiers MNCs. Moreover, perspectives on inherent opportunities MNCs are discussed, aiming provide insights directions future advancements emerging field AI Science, while integration deep learning algorithms stands substantially enrich by offering enhanced predictive capabilities, optimization strategies, control mechanisms, thereby extending MNC synthesis.

Язык: Английский

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Mercaptan Ligand Effect in Determining the Geometric Structures of Silver Nanoclusters

Journal of Cluster Science, Год журнала: 2025, Номер 36(2)

Опубликована: Фев. 9, 2025

Язык: Английский

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