Superhalogens inside fullerenes X@C2n (X = BO2, BeF3; 2n = 60, 70).

The exploration of endohedral fullerenes has garnered significant attention recently due to their distinctive chemical, electrochemical, and optoelectronic properties. Charge transfer, which usually occurs from encapsulated species to fullerenes, importantly affects the structures and properties of endohedral fullerenes. In this study, we theoretically investigated endohedral superhalogen fullerenes X@C2n (X = BO2, BeF3; 2n = 60, 70), in which the charge is reversely transferred from the fullerene to the superhalogen, by using density functional theory calculations and ab initio molecular dynamics simulations. Both natural population analysis and the quantum theory of atoms in molecules confirm about one electron transfer from the fullerene to the superhalogen, resulting in the formal valence state of X-@C2n+. Energy decomposition analysis on the interaction between the superhalogen and fullerene revealed that electrostatic energy contributes predominantly to the total interaction energy. These endohedral superhalogen fullerenes with cationic fullerenes were predicted to be able to serve as building blocks for one dimensional fullerene-based nanowires when combined with endohedral alkali-metallofullerenes with anionic fullerenes.

Vesicular self-assembly of copolymer-grafted nanoparticles with anisotropic shapes.

Plasmonic nanovesicles show broad applications in areas such as cancer theranostics and drug delivery, but the preparation of nanovesicles from shaped nanoparticles remains challenging. This article describes the vesicular self-assembly of shaped nanoparticles, such as gold nanocubes grafted with amphiphilic block copolymers, in selective solvents. The nanocubes assembled within the vesicular membranes exhibit two distinctive packing modes, namely square-like and hexagonal packing, depending on the relative dimensions of the copolymer ligands and nanocubes. The corresponding optical properties of the plasmonic nanovesicles can be tuned by varying the length of the grafted copolymers and the size of the nanocubes. This work provides guidance for the fabrication of functional plasmonic vesicles for applications in catalysis, nanomedicines and optical devices.

A theoretical study on hydrated sodium ion-phenylalanine clusters Na+(Phe)(H2O)n (n = 0-6; Phe = phenylalanine).

The cation-π interaction is of importance in many chemical and biological processes such as those involving protein geometries and functionals and ion channels. In this study, to understand the cation-π interaction between essential ions and protein in the water-aqueous environment, geometries, electronic structures, bonding properties, and dynamic stabilities of hydrated Na+-phenylalanine clusters Na+(Phe)(H2O)n (n = 0-6) were studied using density functional theory calculations and ab initio molecular dynamics simulations. After the addition of water molecules, Na+(Phe)(H2O)n structures change from a tridentate complex to quadridentate or pentadentate complexes while the cation-π interaction always exists. The fluctuation between quadridentate and pentadentate complexes results from the competition between cation-O bonding and hydrogen bonding. The charge analysis reveals that the positive charge is mainly located on the Na ion, whereas the further addition of water reduces the binding energy of water, electron affinity, and ionization potential. As the number of water molecules increases, the bonding interactions between the sodium ion and the remaining phenylalanine-water complex increase and correlate with the coordination number, in which the electrostatic interaction contributes more than the orbital interaction. The important orbital interaction terms come from the donation of the carboxyl and amino groups and water to the Na+ ion. Molecular dynamic simulations revealed that Na+(Phe)(H2O)6 is stable at 300 K.

Wearable Noninvasive Glucose Sensor Based on CuxO NFs/Cu NPs Nanocomposites.

Designing highly active material to fabricate a high-performance noninvasive wearable glucose sensor was of great importance for diabetes monitoring. In this work, we developed CuxO nanoflakes (NFs)/Cu nanoparticles (NPs) nanocomposites to serve as the sensing materials for noninvasive sweat-based wearable glucose sensors. We involve CuCl2 to enhance the oxidation of Cu NPs to generate Cu2O/CuO NFs on the surface. Due to more active sites endowed by the CuxO NFs, the as-prepared sample exhibited high sensitivity (779 µA mM-1 cm-2) for noninvasive wearable sweat sensing. Combined with a low detection limit (79.1 nM), high selectivity and the durability of bending and twisting, the CuxO NFs/Cu NPs-based sensor can detect the glucose level change of sweat in daily life. Such a high-performance wearable sensor fabricated by a convenient method provides a facile way to design copper oxide nanomaterials for noninvasive wearable glucose sensors.

Geometries, electronic structures, and bonding properties of endohedral Group-14 Zintl clusters TM@E10 (TM = Fe, Co, Ni; E = Ge, Sn, Pb).

The geometries, electronic structures, and bonding properties of the title endohedral Zintl clusters have been studied by using ab initio calculations. [Fe@Ge10 ]4- and [Co@Ge10 ]3- have D5h -symmetric pentagonal prismatic structure and [Fe@Sn10 ]4- adopts the C2v -symmetric structure as their ground-state structures, whereas all the other clusters possess D4d bicapped square antiprismatic structures, in consistent with the experimental values when available. Natural bonding orbital and electron localization function disclosed that the negative charges are localized on the central atoms rather than the cages while the TME ionic bonding interactions increase in the order of Ge < Sn < Pb. The energy decomposition analysis revealed that the total bonding energy ∆Eint between central TM and E10 cage is above 150 kcal/mol. The ionic bonding interaction termed as electrostatic interaction ∆Eelstat increases in the order of Ge < Sn < Pb and becomes higher than the covalent bonding interactions termed as total orbital interactions ∆Eorb . Among the total orbital interactions, the π back donations from the TM-d orbitals to the empty cage orbitals consisting of E-p orbitals, the magnitude of which is importantly affected by the cage symmetry, are dominant contributions.

Stable Noble Gas Compounds Based on Superelectrophilic Anions [B12 (BO)11 ]- and [B12 (OBO)11 ].

Superelectrophilic monoanions [B12 (BO)11 ]- and [B12 (OBO)11 ]- , generated from stable dianions [B12 (BO)12 ]2- and [B12 (OBO)12 ]2- , show great potential for binding with noble gases (Ngs). The binding energies, quantum theory of atoms in molecules (QTAIM), natural population analysis (NPA), energy decomposition analysis (EDA), and electron localization function (ELF) were carried out to understand the B-Ng bond in [B12 (BO)11 Ng]- and [B12 (OBO)11 Ng]- . The calculated results reveal that heavier noble gases (Ar, Kr, and Xe) bind covalently with both [B12 (BO)11 ]- and [B12 (OBO)11 ]- with large binding energies, making them potentially feasible to be synthesized. Only [B12 (OBO)11 ]- could form a covalent bond with helium or neon but the small binding energy of [B12 (OBO)11 He]- may pose a challenge for its experimental detection.

CoFe Nanoparticle-Decorated Reduced Graphene Oxide for the Highly Efficient Reduction of 4-Nitrophenol.

High-performance, nonprecious metal catalysts with special morphologies and easy-to-recycle properties are essential for the treatment of environmental pollutants. Herein, CoFe nanoparticle-decorated reduced graphene oxide (RGO) catalysts were designed and successfully fabricated, and the catalyst was then used to reduce 4-nitrophenol into 4-aminophenol. Outstanding catalytic properties with a reduction rate constant of 4.613 min-1 were achieved due to the synergistic properties of the CoFe metal alloy and the high-conductivity RGO components in the catalysts. In addition, the catalyst was conveniently recovered via magnets due to its inherent magnetic properties. The facile preparation, outstanding catalytic performance, structural stability, and low material costs make the CoFe/RGO nanocatalyst a promising candidate for potential applications in catalysis.

Endohedral group-14-element clusters TM@E9 (TM = Co, Ni, Cu; E = Ge, Sn, Pb) and their low-dimensional nanostructures: a first-principles study.

Endohedral group14-based clusters with the encapsulation of a transition metal, which are termed [TM@Em]n- (TM = transition metal and E = group-14 elements), have lots of potential applications and have been used as interesting building blocks in materials science. Nevertheless, their electronic structures and stability mechanism remain unclear. In this paper, we systematically study the geometries, electronic structures, and bonding properties of [TM@E9]n- clusters which are the smallest endohedral group-14-based clusters synthesized so far, by using density functional theory (DFT) calculations. The calculation results reveal the important role of TMs in affecting the structures and bonding interactions in the [TM@E9]n- cluster. In the presence of a TM, the cluster geometry could change from a monocapped square antiprism (C4v) for empty [E9]4- cages to a tricapped trigonal prismatic geometry (D3h) for [TM@E9]n-. By using the energy decomposition analysis (EDA) method, the bonding properties between the endohedral TM and E9 cluster have been thoroughly investigated. It was found that the origin of stability of these clusters is from the large electrostatic attraction with significantly reduced Pauli repulsion. In the case of orbital interactions, the π back-donations from d orbitals of the TM to the cluster make important contributions. More interestingly, the 1D-chain and 2D-sheet nanostructures based on the [Ni@E9] cluster have been theoretically predicted. The band structure and density of states analysis revealed that all of these nanostructures are metallic and their excellent thermodynamic stability has been confirmed by using ab initio molecular dynamics (AIMD) simulations.

Stabilities, Electronic Structures, and Bonding Properties of 20-Electron Transition Metal Complexes (Cp)2TMO and their One-Dimensional Sandwich Molecular Wires (Cp = C5H5, C5(CH3)H4, C5(CH3)5; TM = Cr, Mo, W).

First-principles calculations have been carried out for the 20-electron transition metal complexes (Cp)2TMO and their molecular wires (Cp = C5H5, C5(CH3)H4, C5(CH3)5; TM = Cr, Mo, W). The calculation results at the BP86/def2-TZVPP level reveal that the ground state is singlet and the optimized geometries are in good agreement with the experimental values. The analysis of frontier molecular orbitals shows that two electrons in the highest occupied molecular orbital HOMO-1 are mainly localized on cyclopentadienyl and oxygen ligands. Furthermore, the nature of the TM-O bond was investigated with the energy decomposition analysis-natural orbitals for chemical valence (EDA-NOCV). The attraction term in the intrinsic interaction energies ΔEint is mainly composed of two important parts, including electrostatic interaction (about 52% of the total attractive interactions ΔEelstat + ΔEorb) and orbital interaction, which might be the major determinant of the stability of these (Cp)2TMO complexes. All of the TM-O bonds should be described as electron-sharing σ single bonds [(Cp)2TM]+-[O]- with the contribution of 53-57% of ΔEorb and two π backdonations from the occupied p orbitals of oxygen ligands into vacant π* MOs of the [(Cp)2TM]+ fragments, which are 35-40% of ΔEorb. The results of bond order and interaction energy from EDA-NOCV calculations suggest the influence of the radius of TM and methyl in the interactions between TM and O in (Cp)2TMO. Additionally, the relativistic effects slightly amplify the strength of bonding with increasing ΔEorb for the EDA-NOCV calculations on three metal complexes (C5H5)2TMO. Finally, the geometries, electronic structures, and magnetics of infinitely extended systems, [(C5H5)TMO]∞, have also been explored. The results of the density of states (DOS) and band structure revealed that [(C5H5)CrO]∞ and [(C5H5)WO]∞ are semiconductors with the narrow bands, whereas [(C5H5)MoO]∞ behaves as metal.

Nanoporous copper oxide ribbon assembly of free-standing nanoneedles as biosensors for glucose.

Inspired by a sequential hydrolysis-precipitation mechanism, morphology-controllable hierarchical cupric oxide (CuO) nanostructures are facilely fabricated by a green water/ethanol solution-phase transformation of Cu(x)(OH)(2x-2)(SO4) precursors in the absence of any organic capping agents and without annealing treatment in air. Antlerite Cu3(OH)4(SO4) precursors formed in a low volume ratio between water and ethanol can transform into a two-dimensional (2D) hierarchical nanoporous CuO ribbon assembly of free-standing nanoneedle building blocks and hierarchical nanoneedle-aggregated CuO flowers. Brochantite Cu4(OH)6(SO4) precursors formed in a high volume ratio between water and ethanol can transform into hierarchical nanoplate-aggregated CuO nanoribbons and nanoflowers. Such 2D hierarchical nanoporous CuO ribbons serving as a promising electrode material for nonenzymatic glucose detection show high sensitivity, a low detection limit, fast amperometric response and good selectivity. Significantly, this green water-induced precursor-hydrolysis method might be used to control effectively the growth of other metal oxide micro-/nanostructures.

One-pot synthesis of etched Cu2O cubes with exposed {110} facets with enhanced visible-light-driven photocatalytic activity.

Novel etched Cu2O cubes with exposed {110} facets are synthesized via an oxidative etching method at room temperature. The photocatalytic performance indicates that these architectures show higher photocatalytic activity than that of the normal Cu2O cubes in the degradation of methylene orange.

One-pot fabrication of novel cuboctahedral Cu2O crystals enclosed by anisotropic surfaces with enhancing catalytic performance.

For the first time, one-pot solution-phase selective-etching to create cuboctahedral Cu2O crystals enclosed by both stepped {111} surfaces and smooth {100} surfaces has been demonstrated. Investigation of photocatalytic performances indicates that the stepped cuboctahedral Cu2O crystals have higher photocatalytic activities than those of the common smooth ones.

Sulfate-ion-assisted galvanic replacement tuning of silver dendrites to highly branched chains for effective SERS.

Morphology is a primary part of designing metal nanocrystals and nanomaterials with controlled functional properties. Here, we demonstrate the potential of foreign sulfate ions to tune the silver dendrites to highly branched chains through a simple galvanic replacement reaction without introducing any organic surfactants. We further illustrate the underlying mechanism according to diffusion-limited aggregation (DLA) in the presence of sulfate ions. The special aspects of this simple synthetic strategy are the control of both the nucleation process and the subsequent crystal growth stage by using sulfate ions as the ionic surfactants thereby tuning the total surface energies on various crystal facets in solution and transforming crystal growth habits of the products. Moreover, the highly branched silver chains (HBSCs) with pure surfaces have been successfully employed as a Raman probe for surface-enhanced Raman spectroscopic analysis of rhodamine 6G (R6G). The particular morphology of those HBSCs also makes them find potential applications in biosensing, catalysis and optics.

Selective CO2 Electroreduction to Multi-Carbon Products on Organic-Functionalized CuO Nanoparticles by Local Micro-Environment Modulation.

Surface functionalization of Cu-based catalysts has demonstrated promising potential for enhancing the electrochemical CO2 reduction reaction (CO2RR) toward multi-carbon (C2+) products, primarily by suppressing the parasitic hydrogen evolution reaction and facilitating a localized CO2/CO concentration at the electrode. Building upon this approach, we developed surface-functionalized catalysts with exceptional activity and selectivity for electrocatalytic CO2RR to C2+ in a neutral electrolyte. Employing CuO nanoparticles coated with hexaethynylbenzene organic molecules (HEB-CuO NPs), a remarkable C2+ Faradaic efficiency of nearly 90% was achieved at an unprecedented current density of 300 mA cm-2, and a high FE (> 80%) was maintained at a wide range of current densities (100-600 mA cm-2) in neutral environments using a flow cell. Furthermore, in a membrane electrode assembly (MEA) electrolyzer, 86.14% FEC2+ was achieved at a partial current density of 387.6 mA cm-2 while maintaining continuous operation for over 50 h at a current density of 200 mA cm-2. In-situ spectroscopy studies and molecular dynamics simulations reveal that reducing the coverage of coordinated K⋅H2O water increased the probability of intermediate reactants (CO) interacting with the surface, thereby promoting efficient C-C coupling and enhancing the yield of C2+ products. This advancement offers significant potential for optimizing local micro-environments for sustainable and highly efficient C2+ production.

Compressive strain in Cu catalysts: Enhancing generation of C2+ products in electrochemical CO2 reduction.

Elastic strain in Cu catalysts enhances their selectivity for the electrochemical CO2 reduction reaction (eCO2RR), particularly toward the formation of multicarbon (C2+) products. However, the reasons for this selectivity and the effect of catalyst precursors have not yet been clarified. Hence, we employed a redox strategy to induce strain on the surface of Cu nanocrystals. Oxidative transformation was employed to convert Cu nanocrystals to CuxO nanocrystals; these were subsequently electrochemically reduced to form Cu catalysts, while maintaining their compressive strain. Using a flow cell configuration, a current density of 1 A/cm2 and Faradaic efficiency exceeding 80% were realized for the C2+ products. The selectivity ratio of C2+/C1 was also remarkable at 9.9, surpassing that observed for the Cu catalyst under tensile strain by approximately 7.6 times. In-situ Raman and infrared spectroscopy revealed a decrease in the coverage of K+ ion-hydrated water (K·H2O) on the compressively strained Cu catalysts, consistent with molecular dynamics simulations and density functional theory calculations. Finite element method simulations confirmed that reducing the coverage of coordinated K·H2O water increased the probability of intermediate reactants interacting with the surface, thereby promoting efficient C-C coupling and enhancing the yield of C2+ products. These findings provide valuable insights into targeted design strategies for Cu catalysts used in the eCO2RR.

Elucidating a twin-dependent chemical activity of hierarchical copper sulfide nanocages.

We have demonstrated significant evidence of a solvent-dependent synthesis of hierarchical Cu7S4 polycrystalline nanocage assemblies with controllable aggregation-based building blocks by a sacrificial Cu2O template approach. The formation of a hierarchical Cu7S4 polycrystalline nanocage is essentially determined by a Kirkendall effect, which is attributed to the tailored-aggregation behaviour of the nanoscale building blocks during the replacement/etching process in different polarities of solvent. The hierarchical Cu7S4 polycrystalline nanocage assembly of nanoparticle building blocks was prepared in pure water, while the hierarchical Cu7S4 polycrystalline nanocage assembly of twinned nanoplate building blocks was successfully synthesized in an anhydrous ethanol capping environment. Such a hierarchical Cu7S4 polycrystalline nanocage assembly of twinned nanoplate building blocks exhibits a higher photocatalytic activity than that of the common polycrystalline ones. A nanotwin-dependent photochemical mechanism has been proposed. Significantly, this study is of great importance in bottom-up assembly of controllable ordered architectures, and offers a good opportunity to understand the fundamental importance of the formation mechanism and growth process of hierarchical Cu7S4 polycrystalline nanocages with controllable aggregation-based building blocks.

Hierarchical CuO nanoflowers: water-required synthesis and their application in a nonenzymatic glucose biosensor.

For the first time, a facile, one-pot water/ethanol solution-phase transformation of Cu2(NO3)(OH)3 precursors into bicomponent CuO hierarchical nanoflowers is demonstrated by a sequential in situ dissolution-precipitation formation mechanism. The first stage produces a precursory crystal (monoclinic Cu2(NO3)(OH)3) that is transformed into monoclinic CuO nanoflowers during the following stage. Water is a required reactant, and the morphology-controlled growth of CuO nanostructures can be readily achieved by adjusting the volume ratio between water and ethanol. Such a bicomponent CuO hierarchical nanoflower serving as a promising electrode material for a nonenzymatic glucose biosensor shows higher sensitivity and excellent selectivity. The findings reveal that the different Cu(x)M(y)(OH)(z) (M = acidic radical) precursors synthesized in a water/ethanol reaction environment can be utilized to obtain new forms of CuO nanomaterials, and this unique water-dependent precursor-transformation method may be used to effectively control the growth of other metal oxide nanostructures.

Controlled Growth Cu2S Nanoarrays with High-Performance Photothermal Properties.

The controlled growth of Cu2S nanoarrays was constructed by a facile two-step impregnation synthesis route. The as-synthesized Cu2S/CuO@Cu samples were precisely characterized in terms of surface morphology, phase, composition, and oxidation states. At the laser irradiation of 808 nm, Cu2S/CuO@Cu heated up to 106 °C from room temperature in 120 s, resulting in an excellent photothermal conversion performance. The Cu2S/CuO@Cu exhibited excellent cycling performance-sustaining the photothermal performance during five heating-cooling cycles. The finite difference time domain (FDTD) simulation of optical absorption and electric field distributions assured the accuracy and reliability of the developed experimental conditions for acquiring the best photothermal performance of Cu2S/CuO@Cu.

Deep mineralization of VOCs in an embedded hybrid structure CoFe2O4/MoS2/PMS wet scrubber system.

Peroxymonosulfate (PMS)-based advanced oxidation processes in liquid phase systems can actively degrade toluene. In this work, the catechol structural surfactant was introduced to synthesize the dispersed and homogeneous CoFe2O4 nanospheres and embedded into MoS2 nanoflowers to form magnetically separable heterojunction catalysts. The innovative approach effectively mitigated the traditionally low reduction efficiency of transition metal ions during the heterogeneous activation process. In CoFe2O4/MoS2/PMS system, the toluene removal efficiency remained 95% within 2 h. The contribution of SO4⋅-, ·O2-, ·OH, and 1O2 was revealed by radical quenching experiment and electron paramagnetic resonance spectroscopy. The results illustrated that MoS2 offers ample reduction sites for facilitating PMS activation via Fe3+/Fe2+ redox interactions. Furthermore, an investigation into the toluene degradation pathway within the CoFe2O4/MoS2/PMS system revealed its capability to suppress the formation of toxic byproducts. This ambient-temperature liquid-phase method presented promising route for the removal of industrial volatile organic pollutants.

Stabilities, Electronic Structures, and Bonding Properties of Iron Complexes (E1E2)Fe(CO)2(CNArTripp2)2 (E1E2=BF, CO, N2, CN-, or NO+).

The coordination of 10-electron diatomic ligands (BF, CO N2) to iron complexes Fe(CO)2(CNArTripp2)2 [ArTripp2=2,6-(2,4,6-(iso-propyl)3C6H2)2C6H3] have been realized in experiments very recently (Science, 2019, 363, 1203-1205). Herein, the stability, electronic structures, and bonding properties of (E1E2)Fe-(CO)2(CNArTripp2)2 (E1E2=BF, CO, N2, CN-, NO+) were studied using density functional (DFT) calculations. The ground state of all those molecules is singlet and the calculated geometries are in excellent agreement with the experimental values. The natural bond orbital analysis revealed that Fe is negatively charged while E1 possesses positive charges. By employing the energy decomposition analysis, the bonding nature of the E2E1-Fe(CO)2(CNArTripp2)2 bond was disclosed to be the classic dative bond E2E1→Fe(CO)2(CNArTripp2)2 rather than the electron-sharing double bond. More interestingly, the bonding strength between BF and Fe(CO)2(CNArTripp2)2 is much stronger than that between CO (or N2) and Fe(CO)2(CNArTripp2)2, which is ascribed to the better σ-donation and π back-donations. However, the orbital interactions in CN-→Fe(CO)2(CNArTripp2)2 and NO+→Fe(CO)2(CNArTripp2)2 mainly come from σ-donation and π back-donation, respectively. The different contributions from σ donation and π donation for different ligands can be well explained by using the energy levels of E1E2 and Fe(CO)2(CNArTripp2)2 fragments.