Dinuclear Research Articles

Anomalous Structural Transformation of Cu(I) Clusters into Multifunctional CuAg Nanoclusters.

We report an anomalous structural transformation of a Cu(I) cluster into two different types of copper-silver (CuAg) alloy nanoclusters. Different from previous reports, we demonstrate that under specifically designed reaction conditions, the Ag-doping could induce a substantial growth of the starting Cu15 and a Ag13Cu20 nanocluster was obtained via the unexpected insertion of an Ag13 kernel inside the Cu(I)-S shell. Ag13Cu20 demonstrates high activity to initiate the photopolymerization of previously hard-to-print inorganic polymers in 3D laser microprinting. Interestingly, a slight modification of the reaction condition leads to the formation of another Ag18-xCuxS (8≤x) nanocluster templated by a central S2- anion, which possesses a unique electronic structure compared to conventional template-free CuAg nanoclusters. Overall, this work unveils the intriguing doping chemistry of Cu clusters, as well as their capability to create different types of alloy nanoclusters with previously unobtainable structures and multifunctionality.

In-situ construction of homogeneous Bi clusters by β-particle: MoS2/BiFeO3-x@POPs-β activate oxalate to photocatalytic oxidate hazardous oxygenated salts

The construction of heterojunction photocatalysts containing metal clusters to reduce the toxicity of metal oxides is essential for solving water pollution problems. In this study, heterostructures of MoS2/BiFeO3-x@POPs (MBFO@POPs) were successfully prepared. After irradiation, the samples showed in-situ growth of around 10 nm Bi clusters on rod MoS2 due to the domain-limiting effect of POPs. Bi clusters with a sub-nanometer scale and DFT calculations have proved that the existence of Bi clusters accelerated charge separation in the materials. Moreover, electrons transfer from Bi to MoS2 to BiFeO3-x along the heterogeneous interface. Besides, Ov (Oxygen vacancy) and Bi clusters also increased the number of active sites, leading to a significant improvement in the photocatalytic performance of the material. In this paper, a series of photocatalytic experiments were performed, employing As(III) and Sb(III) as simulated pollutants. The results revealed that the oxidation conversion of 10 mg∙L−1 As(III) and Sb(III) reached 84.7% and 78.7%, respectively, when oxalate was added at 0.2 mM. The results of EPR and bursting experiments showed that ·O2– and ·OH are the primary active substances in the photoreaction process. This research presents an improved solution for removing hazardous oxygenated salts from the water via the utilization of bismuth-iron-based photocatalysts and oxalates.

An Ab Initio Journey toward the Molecular‐Level Understanding and Predictability of Subnanometric Metal Clusters

Current advances in synthesizing and characterizing atomically precise monodisperse metal clusters (AMCs) at the subnanometer scale have opened up new possibilities in quantum materials research. Their quantizied “molecule‐like” electronic structure showcases unique stability, and physical and chemical properties differentiate them from larger nanoparticles. When integrated into inorganic materials that interact with the environment and sunlight, AMCs serve to enhance their (photo)catalytic activity and optoelectronic properties. Their tiny size makes AMCs isolated in the gas phase amenable to atom‐scale modeling using either density functional theory (DFT) or methods at a high level of ab initio theory, even addressing nonadiabatic (e.g., Jahn–Teller) effects. Surface‐supported AMCs can be routinely modeled using DFT, enabling long real‐time molecular dynamics simulations. Their optical properties can also be addressed using time‐dependent DFT or reduced density matrix (RDM) theory. These theoretical–computational efforts aim to achieve predictability and molecular‐level understanding of the stability and properties of AMCs as function of their composition, size, and structural fluxionality in different thermodynamical conditions (temperature and pressure). In this perspective, the potential of ab initio and DFT‐based modeling is illustrated through recent studies of unsupported and surface‐supported AMCs. Future directions of research are also discussed, including applications and methodological enhancements beyond the state‐of‐the‐art.

Zwitterionic Thiolate-Protected Ag22(0/I) and Ag20(I) Clusters: Assembly, Structural Characterization, and Antibacterial Activity.

Zwitterionic thiolate ligands have the potential to introduce novel assembly modes and functions for noble metal clusters. However, their utilization in the synthesis of silver clusters remains understudied, particularly for the clusters containing reductive Ag(0) species. In this article, we report the first synthesis of a mixed-valence silver(0/I) cluster protected by zwitterionic Tab as thiolate ligands (Tab = 4-(trimethylammonio)benzenethiolate), denoted as [Ag22(Tab)24](PF6)20·16CH3OH·6Et2O (Ag22·16CH3OH·6Et2O), alongside an Ag(I) cluster [Ag20(Tab)12(PhCOO)10(MeCN)2(H2O)](PF6)10·11MeCN (Ag20·11MeCN). Ag22 has a distinct hierarchical supratetrahedral structure with a central {Ag6} kernel surrounded by four [Ag4(Tab)6]4+ units. High-resolution electrospray ionization mass spectra demonstrate that Ag22 has two free electrons, indicating a superatomic core. Ag20 has a drum-like [Ag12(Tab)6(PhCOO)6(H2O)]6+ inner core capped by two tetrahedral-like [Ag4(Tab)3(PhCOO)2(MeCN)]2+ units. Ag20 can be transformed into Ag22 after its reaction with NaBH4 in solution. Antibacterial measurements reveal that Ag22 has a significantly lower minimum inhibitory concentration than that of the Ag20 cluster. This work not only extends the stabilization of silver(0/I) clusters to neutral thiol ligands but also offers new materials for the development of novel antibacterial materials.

Discovery of the Lipopeptides Albubactins A-H from Streptomyces albidoflavus RKJM0023 via Chemical Elicitation with Rhamnolipids and Synthesis of Albubactin A.

The marine tunicate-derived Streptomyces albidoflavus RKJM0023 was cultured in the presence of a rhamnolipid mixture in an effort to elicit the production of silent natural products. MS/MS-based molecular networking analysis enhanced with nonparametric statistics highlighted the upregulation of a molecular cluster (Kruskal-Wallis p = 1.6 e-6 for 1) in which no MS/MS features had library matches. Targeted isolation of these features resulted in the discovery of nine new N-acylated lipopeptides, albubactins A-H (1-8) each containing a unique glutamine tripeptide and a C-terminal ethyl ester moiety. Three related albubactin acids A-C (9-11) lacking the ethyl ester were also identified. NMR spectroscopy and UPLC-HR-ESI-MS/MS demonstrated that the albubactins were obtained as mixtures that shared a common m/z and differed only in their acylated terminal groups. Due to the complex spectroscopic elucidation with many overlapping shifts, a total synthesis of albubactin A (1) was completed and used to determine the absolute configuration of the new albubactins.

Unravelling the impact of ZIF-8, ZIF-67, and ZIF 8-67 on cement composites: insights into microstructure, mechanical strength and rheology

Zeolitic imidazolate frameworks (ZIFs) are a novel material, a sub-group of metal-organic frameworks (MOFs) with a sodalite-type structure similar to zeolites and are formed by the bridging of imidazole with metallic nodes or clusters which find applications such gas storage, energy storage, drug delivery, catalysis, and membrane technology. ZIF-8 denotes a MOF containing zinc metal ions; ZIF-67 comprises of cobalt metal linkers; and ZIF-8-67 signifies a MOF containing both zinc and cobalt linkers. In the present study, aforementioned nanomaterials are lab-synthesized and added to cement in concentration of 0.4%, 0.5%, 0.6%, and 0.7% by weight of cement and characterized using XRD, FTIR, and SEM analysis. Various fresh and hardened tests were conducted to evaluate rheology, flexural, and compressive strength. The flexural strength test resulted in an increase of up to 21.72% in ZIF-8-67 cement specimens. ZIFs tend to offer extra nucleation sites for the production of hydration products and result in strength increment and densification of microstructure. The optimum concentration among the selected trials was 0.5% for ZIF-8, 0.6% for ZIF-67, and 0.5% for ZIF-8-67 in cement based on the strength increment criteria. The flow test results indicated the hydrophobicity of the added nanomaterials, thereby increasing the workability.

QTAIM analysis of the bonding in anionic group 6 carbonyl selenide clusters: [Se2M3(CO)10]2- (M=Cr, Mo, W).

This research aims to offer a deeper understanding of the bonding interactions between M-Se and M-CO and how these interactions change across the group 6 transition metal series: [Se2M3(CO)10]2- (M = Cr, Mo, W). It also seeks to explore the impact of carbonyl groups on M-M interactions within the clusters. Seven criteria, which are based on QTAIM properties, have been considered and compared with the corresponding criteria in other transition metal clusters. The results confirm that no such bond critical points or bond baths occur between transition metals, which instead have 5c-7e bonding interactions delocalized over their five-membered M3(μ-Se)2 ring, as evidenced by the non-negligible nonbonding delocalization indices. The topological properties of three bond clusters, Cr-Se, Mo-Se, and W-Se, resemble those of "intermediate closed shell characters," which combine covalent and electrostatic properties. Source function calculations indicated that the bonded Se atom contributed the most to each Cr-Se and Mo-Se bcp. The OCO atoms and nonbonded Se atoms also contributed to some extent. However, metal atoms act as sinks rather than as sources of electron density. In contrast, the majority of the metal atoms, both bonded and nonbonded, contribute to Cr-W bcps. Analysis of the delocalization indices δ(M…O) in the three clusters indicates that CO significantly contributes to Cr π-back donation in cluster 1. In contrast, no π-back donation occurs from CO to Mo or W in clusters 2 or 3, respectively. The B3P86 hybrid functional was used for computations in the Gaussian 09 software. The LanL2DZ basis set was employed for Cr, Mo, and W, while the 6-31G (d, p) basis set was used for C, O, and Se atoms. We performed QTAIM analysis using the AIM2000 and Multiwfn packages, incorporating B3P86/WTBS for Cr, Mo, and W atoms. The 6-311++G(3df,3pd) basis set was used for C, O, and Se atoms. Additionally, we utilized the ELF and SF.

Unraveling active sites regulation and temperature-dependent thermodynamic mechanism in photothermocatalytic CO2 conversion with H2O

In the photothermal synergistic catalytic conversion of CO2 and H2O, the catalyst harnesses solar energy to accumulate heat, thereby elevating the reaction system’s temperature. The influence of this temperature effect on surface chemical reactions remains an underexplored area. Here the impact of temperature on the surface-level thermodynamic reactions and conversion of CO2 with H2O on oxide semiconductors at the atomic scale was investigated using first-principle calculations. 13 different metal oxides and 5 transition metal clusters were used to introduce surface functional sites on the TiO2 supporting catalyst. The potential metal oxide cocatalysts that could be most beneficial to the following conversion of CO2 by H2O were initially screened by calculating the degrees of promotion of CO2 adsorption and activation of surface H to provide protons. The proton donation and hydrogen evolution difficulty from H2O were further analyzed, identifying transition metal cocatalysts that promote direct CO2 hydrogenation. Upon introducing bifunctional sites to facilitate adsorption and reduction, the production of CH3OH and CH4 could be further enhanced through the facilitation of the proton donation process of H2O. The results of Gibbs free-energy calculations revealed that increasing temperature enhances the reaction thermodynamics for each C1 product formation at different surface sites to varying degrees. These findings offer valuable theoretical insights for designing and regulating active sites on oxide semiconductor surfaces for efficient photothermal catalytic CO2 reduction by H2O.

Extensive Polymerization of Atomically Precise Alloy Metal Clusters During Solid-State Reactions.

Exploring the reactions between atomically precise metal clusters and the consequences of such reactions has been an exciting field of research during the past decade. Initial studies in the area were on reactions between clusters in the solution phase, which proceed through the formation of dimers of reacting clusters. In the present work, we examine the interaction between two atomically precise clusters, [Au25(PET)18]- and [Ag25(DMBT)18]-, in the solid state, where PET and DMBT are 2-phenylethanethiol and 2,4-dimethylbenzenethiol, respectively. The experiments were performed using different ratios of these two clusters, and it was inferred that the kinetics of the reactions were faster compared with reactions in the solution. The metal exchange between these two clusters, due to their interactions in the solid state, leads to the formation of dimers, trimers, tetramers, and polymers of atomically precise alloy metal clusters. We observed polymer entities up to hexamers, which were observed for the first time. Control experiments revealed that metal exchange is a key factor leading to polymerization. Our work points to a new approach for synthesizing polymers of atomically precise alloy metal clusters.

Probing Basal and Prismatic Planes of Graphitic Materials for Metal Single Atom and Subnanometer Cluster Stabilization.

Supported metal single atom catalysis is a dynamic research area in catalysis science combining the advantages of homogeneous and heterogeneous catalysis. Understanding the interactions between metal single atoms and the support constitutes a challenge facing the development of such catalysts, since these interactions are essential in optimizing the catalytic performance. For conventional carbon supports, two types of surfaces can contribute to single atom stabilization: the basal planes and the prismatic surface; both of which can be decorated by defects and surface oxygen groups. To date, most studies on carbon-supported single atom catalysts focused on nitrogen-doped carbons, which, unlike classic carbon materials, have a fairly well-defined chemical environment. Herein we report the synthesis, characterization and modeling of rhodium single atom catalysts supported on carbon materials presenting distinct concentrations of surface oxygen groups and basal/prismatic surface area. The influence of these parameters on the speciation of the Rh species, their coordination and ultimately on their catalytic performance in hydrogenation and hydroformylation reactions is analyzed. The results obtained show that catalysis itself is an interesting tool for the fine characterization of these materials, for which the detection of small quantities of metal clusters remains a challenge, even when combining several cutting-edge analytical methods.

Modeling of the Hydrogen Bond-Induced Frequency Shifts of the HOH and HOD Bending Modes of Water.

The intramolecular bending mode of water is a possible useful probe of the hydrogen-bond situations in aqueous systems, but the behavior of its frequency and intensity should be further elucidated for better understanding on its nature and, hence, for its better utilization as a probe. Here, an analysis toward this goal is conducted by doing theoretical calculations on molecular clusters of normal isotopic and deuterated species of water and examining the correlations among the vibrational, structural, and electrostatic properties. It is shown that electrostatic interactions, particularly both of the in-plane components of the electric field along the OH bond and perpendicular to it, play a major role in controlling the hydrogen bond-induced shifts of the force constant, but additional factors, including the intermolecular structural and/or charge-transfer properties, are also important. Models of the hydrogen bond-induced shifts of the force constant are presented in a form that may be combined with classical molecular dynamics. With regard to the infrared intensity changes, it is shown on the basis of the electron density analysis that the intermolecular charge flux and polarization effect play an important role, depending on the angular characteristics of the hydrogen bond.

Nickel atom-clusters nanozyme for boosting ferroptosis tumor therapy

The translation of Fe-based agents for ferroptosis tumor therapy is restricted by the unstable iron valence state, the harsh catalytic environment, and the complex tumor self-protection mechanism. Herein, we developed a stable nickel-based single-atom-metal-clusters (NSAMCs) biocatalyst for efficient tumor ferroptosis therapy. NSAMCs with a nanowire-like nanostructure and hydrophilic functional groups exhibit good water-solubility, colloidal stability, negligible systemic toxicity, and target specificity. In particular, NSAMCs possess excellent peroxidase-like and glutathione oxidase-like activities through the synergistic influence between metal clusters and single atoms. The dual-enzymatic performance enables NSAMCs to synergistically promote efficient ferroptosis of cancer cells through lipid peroxidization aggregation and glutathione peroxidase 4 inactivation. Importantly, NSAMCs highlight the boost of ferroptosis tumor therapy via the synergistic effect between single-atoms and metal clusters, providing a practical and feasible paradigm for further improving the efficiency of ferroptosis tumor treatment.

P-Type ZnO Films Made by Atomic Layer Deposition and Ion Implantation.

Zinc oxide (ZnO) is a wide bandgap semiconductor that holds significant potential for various applications. However, most of the native point defects in ZnO like Zn interstitials typically cause an n-type conductivity. Consequently, achieving p-type doping in ZnO is challenging but crucial for comprehensive applications in the field of optoelectronics. In this work, we investigated the electrical and optical properties of ex situ doped p-type ZnO films. The p-type conductivity has been realized by ion implantation of group V elements followed by rapid thermal annealing (RTA) for 60 s or flash lamp annealing (FLA) on the millisecond time scale in nitrogen or oxygen ambience. The phosphorus (P)-doped ZnO films exhibit stable p-type doping with a hole concentration in the range of 1014 to 1018 cm-3, while antimony (Sb) implantation produces only n-type layers independently of the annealing procedure. Microstructural studies of Sb-doped ZnO show the formation of metallic clusters after ms range annealing and SbZn-oxides after RTA.

Structural insight into palladium-nickel clusters over mordenite zeolite for carbene-insertion reaction

The advancement of heterogeneous catalysts incorporating metal clusters in the nanometric size range has garnered significant attention due to their extraordinary catalytic activity and selectivity. The detailed characterization and understanding of the atomic structure of these metal clusters within catalysts is crucial for elucidating the underlying reaction mechanisms. In the present study, a distinctive three-atom PdNi cluster, characterized by two Pd atoms at terminal positions and a central Ni atom, was synthesized over mordenite zeolite. The presence of atomic PdNi clusters within the eight-membered ring side pocket area was confirmed by multiple advanced analytical techniques, including magic-angle spinning nuclear magnetic resonance spectroscopy, synchrotron X-ray powder diffraction, extended X-ray absorption fine structure spectroscopy, and high-angle annular dark-field scanning transmission electron microscopy. The catalytic activity of the confined active species was examined by the carbene-mediated reactions of ethyl-2-diazoacetate to ethyl-2-methoxyacetate as a model reaction. Compared to the Pd-mordenite and Ni-mordenite, the PdNi-mordenite catalyst incorporates a PdNi cluster, which demonstrates a superior performance, achieving 100% conversion and high selectivity under the same reaction conditions. Our study elucidates the potential of constructing bimetallic clusters in zeolites, providing valuable insights for developing new heterogeneous catalysts applicable to a wide range of catalytic processes.

Tracking Prenucleation Molecular Clustering of Salicylamide in Organic Solvents.

Crystal nucleation shapes the structure and product size distribution of solid-state pharmaceuticals and is seeded by early-stage molecular self-assemblies formed in host solution. Here, molecular clustering of salicylamide in ethyl acetate, methanol, and acetonitrile was investigated using photon correlation spectroscopy. Cluster size steadily increased over 3 days and with concentration across the range from undersaturated to supersaturated solutions. Solute concentration normalized by solubility provided more sensitive characterization of molecular-level conditions than concentration alone. In saturated solution, cluster size is independent of solvent, while at equal supersaturation, solvent-dependent cluster size increases as methanol < acetonitrile < ethyl acetate, commensurate with increasing nucleation propensity. In ethyl acetate, with largest prenucleation clusters, the driving force required for nucleation is lowest, compared to methanol with smallest clusters and highest driving force. To understand solvent-solute effects, we performed IR spectroscopy supported by molecular simulations. We observe solute-solvent interaction weakening in the same order: methanol < acetonitrile < ethyl acetate, quantifying the weaker solvent-solute interactions that permit the formation of larger prenucleation clusters. Our results support the hypothesis that nucleation is easier in weaker solvents because weak solute-solvent interactions favor growth of large clusters, as opposed to relying solely on ease of desolvation.

Supercritical Water: A Simulation Study to Unravel the Heterogeneity of Its Molecular Structures.

(1) Background: In the quest to accurately model the radiolysis of water in its supercritical state, a detailed understanding of water's molecular structure, particularly how water molecules are arranged in this unique state, is essential. (2) Methods: We conducted molecular dynamics simulations using the SPC/E water model to investigate the molecular structures of supercritical water (SCW) over a wide temperature range, extending up to 800 °C. (3) Results: Our results show that at a constant pressure of 25 MPa, the average intermolecular distance around a reference water molecule remains remarkably stable at ~2.9 Å. This uniformity persists across a substantial temperature range, demonstrating the unique heterogeneous nature of SCW under these extreme conditions. Notably, the simulations also reveal intricate patterns within SCW, indicating the simultaneous presence of regions with high and low density. As temperatures increase, we observe a rise in the formation of molecular clusters, which are accompanied by a reduction in their average size. (4) Conclusions: These findings highlight the necessity of incorporating the molecular complexity of SCW into traditional track-structure chemistry models to improve predictions of SCW behavior under ionizing radiation. The study establishes a foundational reference for further exploration of the properties of supercritical water, particularly for its application in advanced nuclear technologies, including the next generation of water-cooled reactors and their small modular reactor variants that utilize SCW as a coolant.

Autophagy-related molecular clusters identified as indicators for distinguishing active and latent TB infection in pediatric patients

BackgroundAutophagy is crucial for controlling the manifestation of tuberculosis. This study intends to discover autophagy-related molecular clusters as biomarkers for discriminating between latent tuberculosis (LTBI) and active tuberculosis (ATB) in children through gene expression profile analysis. MethodsThe expression of autophagy modulators was examined in pediatric patients with LTBI and ATB utilizing public datasets from the Gene Expression Omnibus (GEO) collection (GSE39939 and GSE39940).ResultsIn a training dataset (GSE39939), patients with LTBI and ATB exhibited the expression of autophagy-related genes connected with their active immune responses. Two molecular clusters associated with autophagy were identified. Compared to Cluster 1, Cluster 2 was distinguished through decreased adaptive cellular immune response and enhanced inflammatory activation, according to single-sample gene set enrichment analysis (ssGSEA). Per the study of gene set variation, Cluster 2’s differentially expressed genes (DEGs) played a role in synthesizing transfer RNA, DNA repair and recombination, and primary immunodeficiency. The peak variation efficiency, root mean square error, and area under the curve (AUC) (AUC = 0.950) were all lowered in random forest models. Finally, a seven-gene-dependent random forest profile was created utilizing the CD247, MAN1C1, FAM84B, HSZFP36, SLC16A10, DTX3, and SIRT4 genes, which performed well against the validation dataset GSE139940 (AUC = 0.888). The nomogram calibration and decision curves performed well in identifying ATB from LTBI.ConclusionsIn summary, according to the present investigation, autophagy and the immunopathology of TB might be correlated. Furthermore, this investigation established a compelling prediction expression profile for measuring autophagy subtype development risks, which might be employed as possible biomarkers in children to differentiate ATB from LTBI.

A Theoretical Investigation into the Oligomer Structure of Carbon Dots Formed from Small-Molecule Precursors.

In-depth insights into the oligomers of carbon dots (CDs) prepared from small-molecule precursors are important in the study of the carbonization mechanism of CDs and for our knowledge of their complex structure. Herein, citric acid (CA) and ethylenediamine (EDA) were used as small-molecule precursors to prepare CDs in an aqueous solution. The structure of oligomers acquired from CA and EDA in different molar ratios and their formation process were first studied using density functional theory, including the dispersion correction (DFT-D3) method. The results showed that the energy barrier of dimer cyclization was higher than that of its linear polymerization, but the free energy of the cyclized product was much lower than that of its reactant, and IPCA (5-oxo-1,-2,3,5-tetrahydroimidazo [1,2-a]pyridine-7-carboxylic acid) could therefore be obtained under certain conditions. The oligomers obtained from different molar ratios of EDA and CA were molecular clusters formed by short polyamide chains through intermolecular forces; with the exception of when the molar ratio of EDA to CA was 0.5, excessive CA did not undergo an amidation reaction but rather attained molecular clusters directly through intermolecular forces. These oligomers exhibited significant differences in their surface functional groups, which would affect the carbonization process and the surface structure of CDs.

CD147 regulates the formation and function of immune synapses

CD147 is a T cell activation-associated molecule which is closely involved in the formation of the immune synapse (IS). However, the precise role of CD147 in T cell activation and IS formation remains unclear. In the present study, we demonstrated that CD147 translocated to the IS upon T cell activation and was primarily distributed in the peripheral super molecular cluster (p-SMAC). The knock down of CD147 expression in T cells, but not in B cells, impaired IS formation. CD147 participated in IS formation between T cells and different types of antigen-presenting cells (APCs), including macrophages and dendritic cells. Ligation of CD147 with its monoclonal antibody (mAb) HAb18 effectively inhibited T cell activation and IL-2 secretion. CD98, a critical molecule interacting with CD147, was distributed in IS in a CD147-dependent way. Phosphorylation levels of T cell receptor (TCR) related molecules, like ZAP-70, ERK, and cJun, were down-regulated by CD147 ligation, which is crucial for the interaction of CD147 and TCR signaling transduction. CD147 is indispensable for the formation of immune synapses and plays an important role in the regulation of its function.

Supramolecular Modifying Nafion with Fluoroalkyl‐Functionalized Polyoxometalate Nanoclusters for High‐Selective Proton Conduction

Proton exchange membranes with high selectivity are urgently required in energy and electronic technologies. Nafion, a state‐of‐the‐art commercial proton exchange membrane material, faces significant challenges. It suffers from the permeation of undesirable substances, like hydrogen in fuel cells and vanadium ions in redox flow batteries, due to the unmatched sizes between its ionic domains (3~5 nm) and these substances. In this work, we present a supramolecular modification strategy that simultaneously enhances the proton conductivity and selectivity of Nafion. We employ fluoroalkyl‐grafted polyoxometalate (POMs) nanoclusters as supramolecular additives to modify Nafion via co‐assembly. These POMs can precisely and robustly decorate at Nafion ionic domains, with their fluoroalkyl chains anchoring into the perfluorinated matrix while their inorganic clusters stay in the ionic regions. The hybrid membranes, with continuous proton hopping sites and nanoscale steric hindrance offered by POMs, exhibit a 56% increase in proton conductivity and a 100% improvement in proton/vanadium selectivity. This leads to significantly enhanced power density and energy efficiency in fuel cells and vanadium flow batteries, respectively. These results underscore the intriguing potential of molecular cluster additives in improving the functions of ion‐conducting membranes.