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

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

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

Catalysts, Journal Year: 2025, Volume and Issue: 15(3), P. 199 - 199

Published: Feb. 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.

Language: Английский

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

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 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%.

Language: 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, Journal Year: 2025, Volume and Issue: unknown

Published: March 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.

Language: Английский

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When Metal Nanoclusters Meet Smart Synthesis

ACS Nano, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 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.

Language: Английский

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Reprogramming the Microenvironment of Cobalt Phthalocyanine by a Targeted Multifunctional π-Conjugated Modulator Enables Concerted CO₂ Electroreduction

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8138 - 8147

Published: May 10, 2024

Architecting the interfacial microenvironment is highly desirable for achieving enhanced electrochemical CO2 reduction reaction (CO2RR), but it still a challenge. Herein, π-conjugated matrix of graphitic carbon nitride/graphene (C3N4/G) built to tailor cobalt phthalocyanine (CoPc) into an efficient electrocatalyst. The mechanism microenvironment-mediated CO2RR on CoPc/C3N4/G fully distinguished by integrating experimental and theoretical results. C3N4/G energetic enrichment H2O dissociation produce activated H* species, which enables ceaseless yet fast power injection kinetic process CO2RR. Meanwhile, electron structure Co active sites modulated also thermodynamically favors conversion intermediates. Consequently, in flow cell, delivers high turnover frequency value (50.5 s–1), gratifying CO selectivity (∼100%) as well current density (67.8 mA cm–2) at −1.1 V vs RHE, maintains Faradaic efficiency above 98% ultrawide potential window over 500 mV, ranking among state-of-the-art macrocyclic complex-based catalysts currently reported CO. This work underlines significance well-tailored design electrocatalytic system.

Language: Английский

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Engineering Metal Nanoclusters at the Atomic Level for Effective Electrocatalysis

SmartMat, Journal Year: 2025, Volume and Issue: 6(1)

Published: Jan. 9, 2025

ABSTRACT With the advances of nanochemistry in past several decades, a diverse set nanomaterials has been developed as electrocatalysts with enhanced activity, selectivity, and durability for electrocatalytic reactions. However, it remained long challenge to systematically understand mechanism reactions, which involves multiple protons‐coupled electron transfer processes varied products at atomic level, intrinsically because complexity polydispersity traditional nanomaterials. By sharp contrast, ligand‐protected metal nanoclusters (NCs) possess atomically precise structures abundant active sites, facilitating their applications effective model revealing This review summarizes recent progress atom‐level engineering NCs catalysts Specifically, we first discuss effects composition engineering, including doping size effects, on performance NCs. Then similar discussion extends ligand NCs, where type coverage are deciphered. Moreover, how overall charge morphology modify performance. The fundamental methodological insights summarized this should serve useful references guiding future development sectors industry.

Language: Английский

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Catalyst Ink Preparation Matters for Electrocatalytic Carbon Dioxide Reduction

ChemElectroChem, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 20, 2025

Abstract Electrocatalytic CO 2 reduction (CO R) offers a promising pathway for closing the carbon cycle. Metallic Cu‐based catalysts are only materials capable of converting to C 2+ products with significant selectivity and activity. Achieving industrially relevant current densities in R requires use gas diffusion electrodes (GDEs), making structure properties catalyst layer (CL) on GDEs critical performance Cu catalysts. However, limited research has explored how ink composition affects CL features and, consequently, under operating conditions. In this study, we investigate influence morphology, these affect performance. We find that water content modifies active site density, thickness, porosity CL, as well state Nafion binder, thereby altering microenvironment sites during R, including local concentration pH. Our results reveal strong correlation between structural characteristics CL. Specifically, optimizing ethanol‐to‐water ratio enhances product density 75 % 450 mA cm −2 , respectively. This approach provides simple yet effective strategy improve activity practical

Language: Английский

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Atomic-Level Engineering of Single Ag1+ Sites Distribution on Titanium-Oxo Cluster Surface to Boost CO2 Electroreduction

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Precise control over the distribution of active metal sites on catalyst surfaces is essential for maximizing catalytic efficiency. Addressing limitations traditional cluster catalysts with core-embedded sites, this work presents a strategy to position oxide clusters. We utilize calixarene-stabilized titanium-oxo (Ti12L6) as scaffold anchor Ag1+ in situ, forming unique nanocluster Ti12Ag4.5 six surface-exposed sites. The situ transformation from Ti12L6 into clusters was traced through mass spectrometry, revealing solvent-mediated dynamic process disintegration and reassembly macrocycle. cluster, featuring site configuration, efficiently catalyzes electroreduction CO2 CO broad potential window, achieving faradaic efficiencies exceeding 82.0% between -0.4 V -1.8 V. Its performance surpasses that bimetallic Ti2Ag2, which features more conventional design embedded within cluster. Theoretical calculations indicate synergy support single lowers activation energy, facilitating formation *COOH intermediate. This reveals engineered interactions surface could amplify activity, potentially defining new paradigm design.

Language: Английский

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

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

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