Formation Of Nanoclusters Research Articles

Synthesis and characterization of monodispersed uniform-size aromatic thiolate-protected cobalt nanoclusters for antibacterial and dye degradation studies

In this work, we successfully synthesized monodispersed uniform-sized nanoclusters of less than 7 nm using a dual solvent interaction effect based on nanoclusters formation and growth of thiol-protected (TP) stabilized cobalt nanoclusters (CoNCs) mechanism. The spherical morphology synthesized nanoclusters was confirmed by high-resolution transmission electron microscopy (HRTEM) microscopy. The X-Ray diffraction analysis (XRD) and Selected area electron diffraction (SAED) pattern of the nanoclusters were confirmed the physical properties and crystallographic nature. The obtained small particles play a significant role in antibacterial studies using one gram-positive (Staphylococcus aureus) and one gram-negative (Escherichia coli) bacteria, and sensing of methyl orange in the detection range is 9.2615 × 10−6 to 2.1760 × 10−4 M for methyl orange (MO) rapid degradation.

Assemble-Disassemble-Reassemble Dynamics in Copper Nanocluster-Based Superstructures.

Assembling metal nanoclusters (MNCs) to form superstructures generates exciting photophysical properties distinct from those of their discrete precursors. Controlling the assembly process of MNCs and understanding the assembly-disassembly dynamics can have implications in achieving the reversible self-assembly of MNCs. The formation of self-assembled copper nanoclusters (CuNCs) as homogeneous superstructures and the underlying mechanisms governing such a process remain unexplored. Smart molecular imprinting of surface ligands can establish the forces necessary for the formation of such superstructures. Herein, we report highly luminescent, ordered superstructures of 4-phenylimidazole-2-thiol (4-PIT)-protected CuNCs with the help of l-ascorbic acid as a secondary ligand. Through a comprehensive spectroscopic analysis, we deciphered the mechanism of the self-assembly process, where the role of interligand H-bonding and C-H-π interactions was established. Notably, efficient reversibility of assembly-disassembly was demonstrated by re-establishing the interligand interactions and regenerating their photophysical and morphological signatures.

Small Copper Nanoclusters Synthesized through Solid-State Reduction inside a Ring-Shaped Polyoxometalate Nanoreactor.

Cu nanoclusters exhibit distinctive physicochemical properties and hold significant potential for multifaceted applications. Although Cu nanoclusters are synthesized by reacting Cu ions and reducing agents by covering their surfaces using organic protecting ligands or supporting them inside porous materials, the synthesis of surface-exposed Cu nanoclusters with a controlled number of Cu atoms remains challenging. This study presents a solid-state reduction method for the synthesis of Cu nanoclusters employing a ring-shaped polyoxometalate (POM) as a structurally defined and rigid molecular nanoreactor. Through the reduction of Cu2+ incorporated within the cavity of a ring-shaped POM using H2 at 140 °C, spectroscopic studies and single-crystal X-ray diffraction analysis revealed the formation of surface-exposed Cu nanoclusters with a defined number of Cu atoms within the cavities of POMs. Furthermore, the Cu nanoclusters underwent a reversible redox transformation within the cavity upon alternating the gas atmosphere (i.e., H2 or O2). These Cu nanoclusters produced active hydrogen species that can efficiently hydrogenate various functional groups such as alkenes, alkynes, carbonyls, and nitro groups using H2 as a reductant. We expect that this synthesis approach will facilitate the development of a wide variety of metal nanoclusters with high reactivity and unexplored properties.

Tailoring fluoride networks to precipitate hexagonal Ln1-yMyF3-y nanocrystals in glass: Towards short-wavelength upconversion PL of lanthanides

The AlF3-MF2-LnF3 (M = Ca; Sr; Ba; Ln = Yb/Tm) based pure fluoride GCs are essentially ideal candidates for the realization of PL in UV and VIS spectral region. However, the pure fluoride glasses are prone to precipitation of undesired nano-crystals while quenching and post annealing due to their poor chemical stability. Therefore, the development of such glass systems requires strict adherence to composition control right from the outset. This research employed extensive molecular dynamics (MD) simulations and incorporated the results into the experimental design to develop an efficient multicomponent fluoride glass system. Vivid simulation of M-F-Ln and M-F-Al nano-cluster formation via MD are observed in the glass matrix. These nano-clusters serve as the structural origins of the precipitated nano-crystals in GCs post heat treatment. Through meticulous manipulation of the Al/M ratio, it became feasible to theoretically forecast the transformation of the glass matrix from a cubic M1-xLnxF2+x to a hexagonal Ln1-yMyF3-y nano-crystal precipitated GCs, which could conceivably be manufactured experimentally. This transformation offers superior luminescent performance for Ln1-yMyF3-y containing GCs enabling short-wavelength PL realisation in near UV (∼361 nm with 8-fold enhancement) and VIS (∼478 nm with 1.7-fold enhancement) from Yb3+/Tm3+ transitions, in comparison to its cubic M1-xLnxF2+x counterpart. Hence, we propose an effective fluoride glass system for short-wavelength upconversion luminescent applications through the integration of MD simulations and experimental research.

Temperature‐Controlled Selective Formation of Silver Nanoclusters and Their Transformation to the Same Product

Herein, two atomically precise silver nanoclusters, Ag54 and Ag33, directed by inner anion templates (CrO42‐ and/or Cl‐), are initially isolated as a mixed phase from identical reactants across a wide temperature range (20‐80 °C). Interestingly, fine‐tuning the reaction temperature can realize pure phase synthesis of the two nanoclusters; that is, a metastable Ag54 is kinetically formed at a low temperature (20 °C), whereas such a system is steered towards a thermodynamically stable Ag33 at a relatively high temperature (80 °C). Electrospray ionization mass spectrometry illustrates that the stability of Ag33 is superior to that of Ag54, which is further supported by density functional theory calculations. Importantly, the difference in structural stability can influence the pathway of 1,4‐bis(pyrid‐4‐yl)benzene induced transformation reaction starting from Ag54 and Ag33. The former undergoes a dramatic breakage‐reorganization process to form an Ag31 dimer (Ag31), while the same product can be also achieved from the latter following a noninvasive ligand exchange process. Both the Ag54 and Ag33 have the potential for further remote laser ignition applications. This work not only demonstrates how temperature controls the isolation of a specific phase, but also sheds light on the structural transformation pathway of nanoclusters with different stability.

MAGNETO-OPTICAL KERR SPECTROSCOPY OF (СD 3 AS 2)100-X (MNAS) X COMPOSITES

Composite Films (Сd3As2)100-X(MnAs)X on silicon and sitall substrates with a concentration of Mn 5.8-16.4 at.% were obtained by vacuum-thermal evaporation. The structural properties of the films were investigated by X-ray phase analysis and scanning electron microscopy. Magneto-optical properties were studied by the method of the equatorial Kerr e ect (EEC) in the energy range of 0.5-4.0 eV in magnetic elds with a strength of up to 3 kE at a temperature of 20-300 K. In the geometry of the equatorial Kerr effect, spectral, field and temperature dependences of the EEC are obtained. The analysis of experimental data showed that with a Mn content of more than 12.9 at.% of the films contain the α′′-phase of the topological Dirac semimetal Cd3As2 in the form of large granules, as well as ferromagnetic MNAs granules. The Curie temperature of lms depends on the Mn content in them and is less than the temperature of bulk samples ofMPas. When the Mp content in the lm is 5.8 at.% and 6.4 at.%, the magneto-optical response is not detected, which indicates the formation of a superparamagnetic state or a spin glass state at low concentrations of Mn. With a film content of Mn 9.9 at%. A signi cant change in magneto-optical spectra was detected, which indicates the formation of MNAs nanoclusters and partial dissolution of Mn in the Cd3As2 matrix.

Synergistic effect of Ag2WO4 interconnected nanoclusters for enhanced photovoltaic performance

Tungsten oxide nanoparticles (PW NPs) and silver-doped tungsten oxide nanocomposites (SW NCs) were synthesized via hydrothermal method. Structural, optical, morphological, and electrical properties of the synthesized samples were characterized by X-ray powder diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive X-ray spectroscopy (EDAX), and UV–visible spectroscopy. XRD results confirmed the formation of Ag2WO4 NCs with an average crystallite size ranging from 38 to 9 nm. SEM analysis revealed the formation of nanoclusters. Further SW4NCs shows highest rate constant (0.108 min−1) for methyl blue (MB) dye degradation. Variation in the electrical conductivity and activation energy was studied by DC conductivity studies. Dye-sensitized solar cells (DSSCs) were fabricated using PW and SW NCs films as photoanodes simultaneously, and the photoconversion efficiency (PCE) was found to increase.

Membrane lipids drive formation of KRAS4b-RAF1 RBDCRD nanoclusters on the membrane

The oncogene RAS, extensively studied for decades, presents persistent gaps in understanding, hindering the development of effective therapeutic strategies due to a lack of precise details on how RAS initiates MAPK signaling with RAF effector proteins at the plasma membrane. Recent advances in X-ray crystallography, cryo-EM, and super-resolution fluorescence microscopy offer structural and spatial insights, yet the molecular mechanisms involving protein-protein and protein-lipid interactions in RAS-mediated signaling require further characterization. This study utilizes single-molecule experimental techniques, nuclear magnetic resonance spectroscopy, and the computational Machine-Learned Modeling Infrastructure (MuMMI) to examine KRAS4b and RAF1 on a biologically relevant lipid bilayer. MuMMI captures long-timescale events while preserving detailed atomic descriptions, providing testable models for experimental validation. Both in vitro and computational studies reveal that RBDCRD binding alters KRAS lateral diffusion on the lipid bilayer, increasing cluster size and decreasing diffusion. RAS and membrane binding cause hydrophobic residues in the CRD region to penetrate the bilayer, stabilizing complexes through β-strand elongation. These cooperative interactions among lipids, KRAS4b, and RAF1 are proposed as essential for forming nanoclusters, potentially a critical step in MAP kinase signal activation.

Postamplifying Cas12a Activation through Hybridization Chain Reaction-Triggered Fluorescent Nanocluster Formation for Ultrasensitive Nucleic Acid Detection.

CRISPR/Cas12a-based biosensing is advancing rapidly; however, achieving sensitive and cost-effective reporting of Cas12a activation remains a challenge. In response, we have developed a label-free system capable of postamplifying Cas12a activation by integrating hybridization chain reaction (HCR) and DNA-copper nanoclusters (DNA-CuNCs). The trans-cleavage of Cas12a triggers a silenced HCR, leading to the in situ assembly of fluorescent DNA-CuNCs, allowing for the turn-on reporting of Cas12a activation. Without preamplification, this assay can detect DNA with a detection limit of 5 fM. Furthermore, when coupled with preamplification, the system achieves exceptional sensitivity, detecting the monkeypox virus (MPXV) plasmid at 1 copy in human serum. In a MPXV pseudovirus-based validation test, the obtained results are in agreement with those obtained by qPCR, reinforcing the robustness of this method. Our study represents the first effort to manipulate DNA-CuNC formation on HCR for highly sensitive and cost-effective reporting of Cas12a, resulting in an efficient synthetic biology-enabled sensing platform for biosafety applications.

Angle‐Independent Top‐Emitting Quantum‐Dot Light‐Emitting Diodes Using a Solution‐Processed Subwavelength Scattering–Capping Layer

AbstractOwing to the excellent optoelectronic properties of colloidal quantum dots (QDs), light‐emitting diodes based on QDs (QLEDs) have been considered one of the most promising electroluminescence (EL) devices for full‐color displays with a wide color gamut. Particularly, top‐emission device architecture has been of interest to both academia and industry, because of the advantages in light outcoupling, aperture ratios, and integration with conventional backplanes. In this structure, however, angle‐dependent color shifts originating from a variation in microcavity length are a critical issue that needs to be resolved. Here, a solution‐processed dual‐functional scattering–capping layer (SCPL) using ZnO nanoparticles on top‐emitting QLEDs with ZnSeTe/ZnSe/ZnS QDs to modulate the optical interference is presented. By precisely controlling the thickness of the SCPL, the EL intensity and spectrum can be redistributed to produce a uniform color from any viewing angle. It is discovered that, unlike conventional CPLs, the formation of random nanocracks and nanoclusters in the SCPL adds subwavelength light‐scattering capabilities, which promotes light extraction. The QLEDs with the solution‐processed SCPL exhibit a 44% increase in the maximum external quantum efficiency, with completely imperceptible angle‐dependent spectral shifts. The SCPL is expected to be applied to the development of high‐performance and next‐generation QLED displays.

Emergence of periodic circumferential actin cables from the anisotropic fusion of actin nanoclusters during tubulogenesis

The periodic circumferential cytoskeleton supports various tubular tissues. Radial expansion of the tube lumen causes anisotropic tensile stress, which can be exploited as a geometric cue. However, the molecular machinery linking anisotropy to robust circumferential patterning is poorly understood. Here, we aim to reveal the emergent process of circumferential actin cable formation in a Drosophila tracheal tube. During luminal expansion, sporadic actin nanoclusters emerge and exhibit circumferentially biased motion and fusion. RNAi screening reveals the formin family protein, DAAM, as an essential component responding to tissue anisotropy, and non-muscle myosin II as a component required for nanocluster fusion. An agent-based model simulation suggests that crosslinkers play a crucial role in nanocluster formation and cluster-to-cable transition occurs in response to mechanical anisotropy. Altogether, we propose that an actin nanocluster is an organizational unit that responds to stress in the cortical membrane and builds a higher-order cable structure.

Formation of magnetic nanoclusters in Fe implanted amorphous and crystalline SiO2

Conversion electron Mössbauer Spectroscopy (CEMS) studies have been conducted on Fe implanted amorphous and crystalline SiO2 which were annealed in air up to a temperature of 1000oC. For both samples, dramatic changes set in after the 1000oC anneal and the CEM spectra are dominated by strong ferromagnetic sextets. In the amorphous sample, the sextet is characterized by magnetic hyperfine fields of 33T, 31T and 29 T, consistent with the formation α-Fe nanoclusters. In the crystalline sample the ferromagnetic sextet has spectral parameters of δ = 0.38(3) mm/s and Bhf = 52.3T, consistent with formation of α-Fe2O3 clusters, reflecting the precipitation of the implanted Fe into such clusters. The line ratios of lines 1, 2 and 3 (and 6, 5 and 4) of the sextet are 3:4:1, reflecting alignment of the magnetic moment of the precipitates normal to the c-axis of the sample surface.

Modeling defect formation in nano-ZrO2 under He and H+ irradiation

In the given work, compliance with the distribution law of defect vacancies formed in ZrO2 crystal irradiated with 2[Formula: see text]MeV energy H[Formula: see text] ions at room temperature was studied (The fluxes density for the H[Formula: see text] ion was chosen to be 1017 ions/cm2). The effect of H[Formula: see text] ions with fluxes density at different temperatures (500∘C, 600∘C, 700∘C, 800∘C and 900∘C) on W and S parameters was determined. The mechanism of formation of nanoclusters in the ZrO2 crystal structure under the influence of H[Formula: see text] radiation, the vacancy cluster formed by 2Zr vacancies and 4O vacancies, and its location in triple spaces with hydrogen atoms were determined. 2Zr and 4 vacancies were determined by the [Formula: see text] values of the vacancy clusters growing under the influence of radiation and the positions of hydrogen atoms in the 1VZr, 1VO, di-VZrO triple-VZrO2 vacancy groups.

Facile Synthesis of Stable Nanosized Silver Clusters in Plasma Discharge Under Ultrasonic Cavitation

This work is devoted to the study of plasma-chemical processes determined by the combination of the effect of thermally nonequilibrium, low-temperature plasma and intensive ultrasonic vibrations in the regime of intensive cavitation on liquid-phase media. This method for the realization of plasma-chemical transformations has been proven to be of significant interest and to have advantages for the creation of new nano-sized materials with special properties because it allows for varying the electrophysical and acoustic characteristics of the process when carrying out plasma-chemical reactions and fusion reactions. In this work, a novel facile technique for the synthesis of nanosized silver clusters in plasma discharge under ultrasonic cavitation is reported. Such a type of plasma involves the simultaneous effect of high-intensity cavitation and steady electric discharge in a liquid phase between electrodes of desired material. As a result, stable tiny silver nanoclusters with around a 1-nm size and a relatively narrow particle size distribution were obtained using toluene as a liquid medium. The nanoclusters were characterized with dynamic light scattering, transmission electron microscopy, electron diffraction, and optical methods. The results confirmed the formation of nanoclusters with an absorbance peak around 300 nm and the absence of 400-nm peaks typical for silver nanoparticles. Fluorescence tests allowed for establishing the amorphous structure of the synthesized nanoclusters occupying the intermediate position between few-atom nanoclusters and nanoparticles. The nanoclusters obtained were proven to be stable for more than 3 months. The experiments also revealed the possibility of performing high-temperature plasma-chemical reactions that can be applied in fusion technology.

Multimodal Golden DNA Superstructures (GDSs) for Highly Efficient Photothermal Immunotherapy.

DNA-templated metallization has emerged as an efficient strategy for creating nanoscale-metal DNA hybrid structures with a desirable conformation and function. Despite the potential of DNA-metal hybrids, their use as combinatory therapeutic agents has rarely been examined. Herein, we present a simple approach for fabricating a multipurpose DNA superstructure that serves as an efficient photoimmunotherapy agent. Specifically, we adsorb and locally concentrate Au ions onto DNA superstructures through induced local reduction, resulting in the formation of Au nanoclusters. The mechanical and optical properties of these metallic nanoclusters can be rationally controlled by their conformations and metal ions. The resulting golden DNA superstructures (GDSs) exhibit significant photothermal effects that induce cancer cell apoptosis. When sequence-specific immunostimulatory effects of DNA are combined, GDSs provide a synergistic effect to eradicate cancer and inhibit metastasis, demonstrating potential as a combinatory therapeutic agent for tumor treatment. Altogether, the DNA superstructure-templated metal casting system offers promising materials for future biomedical applications.

Configuration-entropy effects on BiFeO3–BaTiO3 relaxor ferroelectric ceramics for high-density energy storage

A high-configuration entropy results in the formation of grain boundaries and nanoclusters, which act as barriers for enhancing breakdown strength and energy-storage capability.

(Invited) Negative Ions, Nanoparticles and Their Transport to Substrates: Towards Better Control of Plasma-Based Fabrication of Surfaces with Tunable Wetting Properties

The removal of pollutants from water, such as oil residues, requires the production of materials with controlled surface properties, especially in terms of their specific surface area and wetting properties [1]. Environmentally friendly processes based on plasma techniques enable the production of surfaces with a wide variety of different properties in terms of their surface topography and chemical composition. An important component that often forms in low-temperature plasmas operated with organic monomers are nanoparticles. Although often considered an undesirable side effect in many applications, nanoparticles can also be used to create nanocomposites or to decorate surfaces to control their wetting properties and their surface roughness [2]. In order to harness the nanoparticles from a plasma it is therefore an essential task to control their formation and ultimately their transport to the reactor walls or to potential substrates. This contribution will focus on the formation of nanoparticles in low temperature, low pressure plasmas operated with different organic monomers as a precursor gas. Although the exact mechanism responsible for the creation of nanoparticles clearly depends on the nature of the process, it is believed that negative ions play a crucial role in the initial stages of the nucleation [3]. In contrast to neutral radicals or positive ions, which are rapidly lost due to diffusion to the reactor walls the residence time of negative ions in the plasma bulk is usually much larger. Negative ions can therefore more easily form larger molecules, which can serve as the basis for the formation of primary clusters in the nanometer or subnanometer range and in this way trigger the agglomeration processes that lead to the formation of larger particles. Since negative ions can leave the plasma during the plasma-off phase of a pulsed discharge, pulsing the plasma is a suitable means to control the accumulation of negative ions and thus the formation of nanoclusters. The experimental results show a complex interplay between pulse frequency or duty cycle and nanoparticle formation. Even the smallest changes in plasma off-time can lead either to a discharge regime that favors nanoparticle formation or to a discharge regime that prevents nanoparticle formation. The minimum plasma off time required to prevent the build- up of particles in a pulsed discharge depends strongly on parameters like power, pressure, gas mixture ratio and the plasma on time. Although the formation of nanoparticles can be very precisely controlled by an appropriate choice of pulse frequency and duty cycle, their transport and controlled deposition on substrates remains a difficult task. In this context, the use of new structured "filtering" electrodes [4] is discussed. The results show that these electrodes allow the deposition of materials with very different surface topographies. Depending on the plasma conditions and the DC voltages applied to parts of the electrodes, the resulting deposits can range from highly localized polymer structures to dense layers of nanoparticles or polymer films with Turing-like patterns. Literature [1] M. Padaki, R. Surya Murali , M.S. Abdullah, N. Misdan , A. Moslehyani , M.A. Kassim , N. Hilal , A.F. Ismail , Desalination, 357,P. 197 (2015)[2] Berndt, J., Acid, H., Kovacevic, E., Boufendi, L., Journal of Applied Physics, 113(6), p.063302. (2013)[3] Berndt, J., Kovacevic, E., Boufendi,L. Journal of Applied Physics, 106, 063309 (2009)[4] Sciacqua, D., Pattyn, C., Jagodar, A., von Wahl, E., Lecas, T., Strunskus, T., Kovacevic, E. and Berndt, J., 2020.. Scientific Reports, 10(1), pp.1-8. Acknowledgement Authors acknowledge the project PEGASUS (Plasma Enabled and Graphene Allowed Synthesis of Unique nano- Structures), funded by the European Union's Horizon research and innovation programme under grant agreement No 766894 and the EU Graphene Flagship FLAG-ERA III JTC 2021 project VEGA (PR-11938). TS, CB ,and JB want to thank HZB for the allocation of synchrotron radiation beamtime at Bessy II. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 730872 (Nr. 18207084-ST and 18207393- ST). TV, CB and JB acknowledge also support obtained via ARD MATEX Region Centre and Erasmus + Program with WHS Recklinghausen and Prof dr Franziska Traeger.

In Situ STM Investigations of Cu(100) and Bimetallic Ag/Cu(100) Model Catalysts for CO2 Electroreduction in Bicarbonate Solution

The electrochemical conversion of carbon dioxide (CO2RR) to valuable chemicals and fuels plays a crucial role in the sustainable energy economy as it represents a promising potential for the renewable energy storage as well as closing the carbon loop.[1,2] Thus, the design and development of a highly efficient and selective electrocatalyst for CO2RR has become a topic of great importance in recent years. Among elemental metals, copper exhibits unique catalytic behaviour to reduce CO2 towards multi-carbon products with reasonable Faradaic efficiency due to its moderate CO-binding energy.[3,4] However, the selectivity and activity of pure copper is still far away for a practical application. The integration of a secondary metal species provides a promising strategy to improve the catalytical performance of the copper catalyst. Combination with silver is particularly interesting for such bimetallic catalysts, since Ag is a highly efficient catalyst for CO2RR to CO, probably the most important intermediate in the CO2RR, and has been shown to promote the formation of multi-carbon products.[5]Here, we present in situ scanning tunnelling microscopy studies of well-defined Cu and AgCu electrodes in CO2-satured 0.1 M KHCO3, which is one of the most common electrolytes for CO2 electroreduction. For Cu(100) in the double layer potential range, coexistence of two ordered (bi)carbonate adlayer phases was observed (Fig. 1a,b, published in [6]). These adlayer phases have a highly complex structure, exhibit dynamic fluctuations, and undergo a potential dependent order-disorder transition at about 0 V vs. the reversible hydrogen electrode. Detailed density functional calculations reveal that the observed layer is composed of carbonate and water that coadsorb on the electrode surface, underlining the key role of water in the stabilization of the (bi)carbonate adlayers.[6]Upon decreasing the potential to the onset of CO2RR, the formation of Cu nanoclusters is observed on the Cu(100) surfaces by in situ STM. This surface restructuring can be assigned to the influence of CO intermediates formed in the CO2RR. Upon subsequent increase of the potential back into the double layer range, the clusters disperse, resulting in a highly disordered interface structure that contains Cu adatoms, (bi)carbonates, and further molecular adsorbates. This irreversible change of the molecular-scale electrode surface is supported by spectroscopic results.AgCu bimetallic model catalysts were prepared by electrodeposition of submonolayer Ag coverage on Cu(100) in 0.1 M H2SO4. Silver forms islands on Cu(100) with a hexagonal quasi-Ag(111) atomic lattice. After the preparation and characterization of the Ag-decorated Cu(100), the electrolyte was exchanged under potential control to 0.1 M KHCO3. The electrolyte exchange results in the distinct restructuring on the surface in the double layer potential range, in which the islands develop a strongly anisotropic shape. In addition, appearance of new islands and a reduced surface mobility are observed. Furthermore, in contrast to the Ag-free Cu(100), high-resolution STM images show a disordered molecular adlayer.Our results demonstrate the pronounced role of adsorbed (bi)carbonate at the catalyst/electrolyte interface and its impact on the surface morphology and dynamics already at potentials in the double layer regime. These adsorbate-induced structural changes need to be considered for a fundamental understanding and rational design of electrocatalysts for CO2RR.The Authors gratefully acknowledge financial support by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) via SPP 2080, project no. 327886311.

Laser-Ironing Induced Capping Layer on Co-ZIF-L Promoting In Situ Surface Modification to High-Spin Oxide-Carbon Hybrids on the "Real Catalyst" for High OER Activity and Stability.

Enhancing electrocatalytic performance through structural and compositional engineering attracts considerable attention. However, most materials only function as pre-catalysts and convert into "real catalysts" during electrochemical reactions. Such transition involves dramatic structural and compositional changes and disrupts their designed properties. Herein, for the first time, a laser-ironing (LI) approach capable of in-situ forming a laser-ironing capping layer (LICL) on the Co-ZIF-L flakes is developed. During the oxygen evolution reaction (OER) process, the LICL sustains the leaf-like morphology and promotes the formation of OER-active Co3 O4 nanoclusters with the highest activity and stability. In contrast, the pristine and conventional heat-treated Co-ZIF-Ls both collapse and transform to less active CoOOH. The density functional theory (DFT) calculations pinpoint the importance of the high spin (HS) states of Co ions and the narrowed band gap in Co3 O4 nanoclusters. They enhance the OER activity by promoting spin-selected electron transport, effectively lowering the energy barrier and realizing a spontaneous O2 -releasing step that is the potential determining step (pds) in CoOOH. This study presents an innovative approach for modulating both structural and compositional evolutions of electrocatalysts during the reaction, sustaining stability with high performance during dynamic electrochemical reactions, and providing new pathways for facile and high-precision surface microstructure control.

Heterogenized Molecular Electrocatalyst Based on a Hydroxo-Bridged Binuclear Copper(II) Phenanthroline Compound for Selective Reduction of CO2 to Ethylene.

Molecular copper catalysts have emerged as promising candidates for the electrochemical reduction of CO2 . Notable features of such systems include the ability of Cu to generate C2+ products and the well-defined active sites that allow for targeted structural tuning. However, the frequently observed in situ formation of Cu nanoclusters has undermined the advantages of the molecular frameworks. It is therefore desirable to develop Cu-based catalysts that retain their molecular structures during electrolysis. In this context, a heterogenized binuclear hydroxo-bridged phenanthroline Cu(II) compound with a short Cu···Cu distance is reported as a simple yet efficient catalyst for electrogeneration of ethylene and other C2 products. In an aqueous electrolyte, the catalyst demonstrates remarkable performance, with excellent Faradaic efficiency for C2 products (62%) and minimal H2 evolution (8%). Furthermore, it exhibits high stability, manifested by no observable degradation during 15 h of continuous electrolysis. The preservation of the atomic distribution of the active sites throughout electrolysis is substantiated through comprehensive characterizations, including X-ray photoelectron and absorption spectroscopy, scanning and transmission electron microscopy, UV-vis spectroscopy, as well as control experiments. These findings establish a solid foundation for further investigations into targeted structural tuning, opening new avenues for enhancing the catalytic performance of Cu-based molecular electrocatalysts.