ACS Catalysis, Год журнала: 2025, Номер unknown, С. 5731 - 5759
Опубликована: Март 24, 2025
Язык: Английский
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
Процитировано
7
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(31)
Опубликована: Май 17, 2024
The electrochemical CO
Язык: Английский
Процитировано
11
Journal of Cleaner Production, Год журнала: 2024, Номер 450, С. 141849 - 141849
Опубликована: Март 25, 2024
Язык: Английский
Процитировано
10
Nano-Micro Letters, Год журнала: 2024, Номер 17(1)
Опубликована: Окт. 4, 2024
Abstract The current single-atom catalysts (SACs) for medicine still suffer from the limited active site density. Here, we develop a synthetic method capable of increasing both metal loading and mass-specific activity SACs by exchanging zinc with iron. constructed iron (h 3 -FNC) high 6.27 wt% an optimized adjacent Fe distance ~ 4 Å exhibit excellent oxidase-like catalytic performance without significant decay after being stored six months promising antibacterial effects. Attractively, “density effect” has been found at high-enough doping amount, which individual sites become close enough to interact each other alter electronic structure, resulting in significantly boosted intrinsic single-atomic h -FNCs 2.3 times compared low- medium-loading SACs. Consequently, overall -FNC is highly improved, mass that are, respectively, 66 315 higher than those commercial Pt/C. In addition, demonstrate efficiently enhanced capability catalyzing oxygen reduction into superoxide anion (O 2 · − ) glutathione (GSH) depletion. Both vitro vivo assays superior efficacy promoting wound healing. This work presents intriguing activity-enhancement effect exhibits impressive therapeutic combating bacterial infections.
Язык: Английский
Процитировано
10
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
Процитировано
2
Small, Год журнала: 2025, Номер unknown
Опубликована: Март 6, 2025
Ligand-protected copper nanoclusters (Cu NCs) with atomic precision have emerged rapidly due to their fascinating structural architectures and versatile catalytic properties, making them ideal for investigating structure-activity relationships. Despite potential, challenges such as stability issues limited diversity restricted deeper exploration. In this study, three distinct Cu NCs are synthesized using a one-pot reduction strategy by carefully modifying reaction conditions. Intriguingly, the same p-toluenethiol ligand produces two different geometries, while varying ligands m-aminobenzethiol-yielded clusters similar geometric architectures. These evaluated electrocatalytic CO2 reduction, uncovering diverse activities product selectivity. Experimental theoretical analyses reveal that interplay between core structure confinement surface environment governs behavior. Specifically, Cu11 NC exhibits selectivity toward HCOOH production (FEHCOOH∼45% at -1.2 V vs RHE), whereas substituting m-aminobenzethiol shifted competitive side (FEH2∼82% RHE). Conversely, altering geometry of Cu18 retaining decreases (FEHCOOH∼35% findings highlight tunability tailored applications through precise control chemistry.
Язык: Английский
Процитировано
2
Nanoscale, Год журнала: 2024, Номер 16(21), С. 10087 - 10107
Опубликована: Янв. 1, 2024
In the dynamic landscape of nanotechnology, atomically precise silver nanoclusters (Ag NCs) have emerged as a novel and promising category materials with their fascinating properties enormous potential. However, recent research endeavors surged towards stabilizing Ag-based NCs, leading to innovative strategies like connecting cluster nodes organic linkers construct hierarchical structures, thus forming cluster-assembled (CAMs). This approach not only enhances structural stability, but also unveils unprecedented opportunities for CAMs, overcoming limitations individual Ag NCs. this context, review delves into captivating realm nitrogen-based ligand bonded Ag(I)-based providing insights synthetic strategies, structure-property relationships, diverse applications. We navigate challenges advancements in integrating Ag(I) nodes, bound by argentophilic interactions, highly connected periodic frameworks different dimensionalities using linkers. Despite inherent diversity among CAMs demonstrate potential sensing, catalysis, bio-imaging, device fabrication, which all are discussed review. Therefore, gaining insight nanocluster assembly process will offer valuable information, can enlighten readers on design advancement state-of-the-art
Язык: Английский
Процитировано
9
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(34)
Опубликована: Июнь 7, 2024
Owing to the significant attention directed toward alloy metal nanoclusters, it is crucial explore relationship between their structures and performance during electrocatalytic CO
Язык: Английский
Процитировано
9
Nanoscale, Год журнала: 2024, Номер 16(26), С. 12329 - 12344
Опубликована: Янв. 1, 2024
Achieving atomic precision in nanostructured materials is essential for comprehending formation mechanisms and elucidating structure-property relationships. Within the realm of nanoscience technology, atomically precise ligand-protected noble metal nanoclusters (NCs) have emerged as a rapidly expanding area interest. These clusters manifest quantum confinement-induced optoelectronic, photophysical, chemical properties, along with remarkable catalytic capabilities. Among coinage metals, silver distinguishes itself fabrication stable nanoclusters, primarily due to its cost-effectiveness compared gold. This minireview provides an overview recent advancements since 2020 synthetic methodologies ligand selections toward attaining NCs boasting minimum two free valence electrons. Additionally, it explores strategies fine-tuning optical properties. The discussion extends surface reactivity, how exposure ligands, heat, light induces transformations size structure. Of paramount significance are applications reactions energy conversion, supplemented by in-depth mechanistic insights. Furthermore, review delineates challenges outlines future directions NC field, eye design new functional prospective diverse technologies, including optoelectronics, fine synthesis.
Язык: Английский
Процитировано
8
Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown
Опубликована: Окт. 26, 2024
Designing efficient catalysts for operating CO
Язык: Английский
Процитировано
7