High Cohesive Energy Research Articles

Design and DFT study of new nano buds from the combination of C60 fullerene and nanobowl

In this research, new nano buds of C60 fullerene compound and nanobowls were designed and their structure, electrical properties and optical properties were calculated. The absence of imaginary frequency and high cohesive energies is proof of stability and confirmation of the possibility of their formation. Calculation of the relative population showed that the E configuration is the dominant population. The calculation of electrical properties showed that combining the structures with each other improves the electrical properties of nanobuds. The highest electric charge transfer from nanobowl to C60 was observed in the configuration of C nanobuds. A high improvement in NLO properties was observed in all nanobud configurations. Calculating the contribution of the dispersion term in the energy of the nanobuds showed that compared to the parents, larger dispersion energy was obtained for the designed nanobuds (especially configuration E). It was shown that the energy of nano buds and their parents decreases in the presence of solvents. The decrease in energy as a function of increasing the dielectric constant of the solvents may be due to the increase in the dipole moments of the nanobud as a result of the electron transfer from the nanobowl to the C60 fullerene.

Calix-like molecules with outstanding optical properties designed based on the Aza-BODIPY molecule: a DFT study

ABSTRACT Using aza-BODIPY chromophores 3–9 of aza-BODIPY units calix-like oligomers have been designed and studied structurally and thermodynamically. By performing optimisation calculations, it was found that firstly, all the structures are without imaginary frequency; secondly, they have high cohesive energy, which is proof of the stability of the structures. The highest amount of stability of the structures related to oligomer calix[9]-aza-BODIPY was determined by the cohesive energy about three times more than calix[8]-aza-BODIPY. To achieve the oligomers with higher colour intensity and improved optical and electrical properties, the H and F atoms from the upper edge of the calix structures were removed. It enlarges the resonance of the system and decreases the Eg of the systems. By removing the H and F atoms from the Calix molecules, the maximum absorption peaks were transferred to the visible area, and the intensity of light-colour properties in the structures was greatly increased. So, by increasing the size of the calixes, the optical properties are enhanced. Since it causes the most absorption for calixes 6, 7, 8 and 9 and the calix[8] -aza-BODIPY oligomer is detected as the most coloured molecule.

Two-dimensional-materials-based transistors using hexagonal boron nitride dielectrics and metal gate electrodes with high cohesive energy

Two-dimensional-materials-based transistors using hexagonal boron nitride dielectrics and metal gate electrodes with high cohesive energy

Solution-state self-assembly of novel poly(carbamoyl methacrylate)s synthesized via combining Passerini three-component reactions and free radical polymerizations

Coupling multicomponent reactions (MCRs) with other polymerizations has excellent advantages in inducing multifunctionality and syntheses of complex macromolecular structures. Herein, a straightforward combination method using aqueous Passerini three-component reaction (P3CR(aq)) and conventional free radical polymerization (FRP) (termed as P3CR(aq)-Є-FRP) was applied using mild conditions. Firstly, an environmental-friendly and efficient aqueous P3CR was applied to synthesize various carbamoyl methacrylate (CMA) monomers from methacrylic acid, cyclohexyl isocyanide, and four different aldehydes with high yield (ca. 90 %) and purity. This is plausibly prompted by the key factors of high cohesive energy density of water and facile isolation by the poor solubility of CMAs in aqueous. Then, poly(carbamoyl methacrylate)s (PCMAs) were obtained via FRP with 2,2′-azobis(isobutyronitrile) (AIBN) in dimethylformamide (DMF). Characterizations of both synthesized noble monomers, polymers, solubilities in different solvents, and thermal properties, as well as the solution-state self-assembly behaviors of the polymers by dynamic light scattering (DLS), scanning electron microscope (SEM), and small-angle X-ray scattering (SAXS), including micellized particle sizes, critical micelle concentrations (CMCs), and micelle morphology, were investigated. PCMAs can self-assemble into stable globular micellar nanoparticles (ca. 170–310 nm) with low CMC values (1.6 × 10−5–4.0 × 10−9 mg/mL).

Core–Shell Nanostructured Assemblies Enable Ultrarobust, Notch‐Resistant and Self‐Healing Materials

AbstractActuators based on stimulus‐responsive soft materials have attracted widespread attention due to their significant advantages in flexibility and structural adaptability over traditional rigid actuators. However, the development of fast‐actuating, mechanical robust and self‐healing actuators without compromising flexibility remains an ongoing challenge. Here, this study presents a photo‐responsive flexible actuator by incorporating core–shell liquid metal nano‐assemblies into a polyurethane matrix to construct a dynamic supramolecular interface. The nano‐assemblies are endowed with adaptive characteristics to external loading, being expected to dissipate energy via the reversible reconstruction of hydrogen bonding and deformation of nano‐assemblies. The obtained composites exhibit excellent mechanical strength (31 MPa), low modulus (2.02 MPa), high stretchability (1563.95%), autonomous self‐healing (92.5%), and NIR‐responsive actuation properties. Furthermore, the combination of high cohesive energy but fluxible nano‐liquid metal core, and strong dynamic interface not only achieves the balance of high tensile strength and high flexibility but also endows the actuators with outstanding notch‐resistant performance (fracture energy≈58.8 kJ m−2) through multiphase energy dissipation. This work provides a promising strategy for developing soft yet tough self‐healing materials in the fields of flexible robotics and artificial muscles.

Novel nanobuds from the combination of B12N12 nanocage and carbon nanotube: Design and DFT study

In this research, carbon nanotubes and B12N12 nanocage were combined together and, in different configurations, a covalent bond between them was created to design new nanobuds. After optimizing the designed structures, their vibration frequency was calculated to ensure the absence of imaginary frequencies. Also, the relative energy of the structures was calculated and used to analyze the relative population of different configurations and showed that about 99 % of the molecules belong to a specific configuration (configuration B) and about 1 % belong to another configuration (configuration C). Consequently, the population of other configurations can be ignored. To further investigate the stability of structures, it was shown that configuration B has the highest cohesive energy and the most stability. It was clearly shown that the designed nanobuds have electrical properties similar to nanotubes and higher electrical conductivity than B12N12, and the electric charge transfer from B12N12 to nanotubes been taken place. Polarizability and superpolarizability, which indicate linear and nonlinear optical properties, were calculated. it was shown that the hybridization of B12N12 and carbon nanotubes and the creation of nanobuds improve the linear and nonlinear optical properties to a great extent. Finally, it was shown that similar to the parent nanotube, the nanobuds absorb light in the visible region, while B12N12 absorbs light in the UV region. The resulting nanobuds have more absorption lines than nanotubes and thus, their optical activity is even improved compared to nanotubes.

Molecular dynamic simulation on comprehensive performance of ferrocene-based burning rate catalysts in a solid propellent

To determine the compatibility and interaction between ferrocene (Fc) and other components in AP/HTPB/Fc-based BRCs propellant, molecular dynamics simulation (MD simulation) method was used to study the binding energy, cohesive energy density (CED), mean square displacement (MSD) and mechanical properties of mononuclear ferrocenyl compounds (ethyl ferrocene, butyl ferrocene and octyl ferrocene), dinuclear ferrocenyl compounds (2,2′-(ethylferrocene)propane, 2,2′-(butylferrocene)propane) propane and hydroxymethyl bis-ferrocenyl propane), ionic ferrocenyl compounds (three ionic ferrocenes with ferrocene methyl dimethyl ammonium as cation, perchlorate, nitrate and picrate as anions respectively) and cyclic ferrocenyl compounds (1-ferrocenylmethyl-2-ferrocenyl-3-methylbenzimidazolium, binuclear ferrocene bridged by bridged biphenylferrocene and dihydropyrazole).The binding energy results show that alkyl groups, polar groups (such as hydroxyl groups) and cyclic substituents can improve the interaction between Fc and AP/HTPB. Moreover, the electrostatic interaction between ionic ferrocene and AP is strong, but the van der Waals interaction between ionic ferrocene and HTPB is weak. The CED data show that the mixed models based on alkyl mononuclear ferrocene, catocene, cyclic ferrocene and ionic ferrocene all have high cohesive energy with good safety performance. The MSD results show that the order of anti-migration ability is cyclic ferrocene > binuclear alkyl ferrocene > mononuclear alkyl ferrocene > binuclear hydroxyl ferrocene > ionic ferrocene. Regarding to the value of mechanical parameters (K, G, E and K/G), the mixed model of AP/HTPB/ dihydropyrazole bridged binuclear ferrocene possess the best mechanical properties among the 12 models. Based on the comprehensive data, we conclude that dihydropyrazole bridged binuclear ferrocene is the most ideal ferrocene-based burning rate catalyst among 12 ferrocenes.

Self-assembled lyotropic liquid crystals from natural surfactant: A study on their structural, rheological and antimicrobial behaviour

Soft self-assembled systems with smart functions have been explored over the past decades for diverse applications. However, the toxicity of synthetic surfactant based self-assembled systems and their stability always remain a point of concern. There is always a great quest to find an alternative to overcome such shortcomings of self-assembled systems. Hence, in this context, we made an effort to engineer self-assembled lyotropic liquid crystals (LLCs) using different concentrations of the medicinal plant Glycyrrhiza glabra L. in the nonaqueous polar media of glycerol, ethylene glycol and formamide. These nonaqueous solvents with considerable polarity, high cohesive energy, dipole moment and hydrogen bonding ability, not only offer the perfect environment for self-assembly, but also provide longtime stability. Nematic lyotropic ordering is obtained for studied systems at different concentrations of Glycyrrhiza glabra L./ nonaqueous solvents as confirmed via polarising optical microscopy (POM) and X-ray diffraction (XRD) analysis. Electrostatic and hydrogen bonding interactions among polar solvents and amphiphilic Glycyrrhiza glabra L. molecules could be responsible for nematic ordering. FTIR spectroscopy is employed to confirm the hydrogen bonding in LLCs. The prepared LLCs are studied through static, dynamic rheology under the shear range 1–100 s-1 to explore their fluidic behaviour and establish correlation with structural parameters. The studied LLC systems from three solvents exhibit non-Newtonian shear thinning behaviour at all concentrations. The dynamic rheology tests indicate the elastic behaviour of all LLC systems. LLCs derived from glycerol exhibit soft-solid gel-like behaviour, while weak gel-type behaviour is observed for ethylene glycol and formamide-based LLCs. Considering the medicinal value of prepared LLCs, their antibacterial activity has been checked against the gram-positive bacteria Bacillus subtilis. LLC phases show strong antibacterial activity, about 2–3 times better than that of the standard drug streptomycin used for this study.

RuAl intermetallic compound of low resistivity scaling and high thermal stability as potential interconnect metallization

Thin films of single-phase ruthenium aluminide (RuAl) intermetallic compound were deposited by magnetron co-sputtering. An ordered B2 body-centered cubic structure of high crystallinity was formed after rapid thermal annealing at 800 °C for 1 min. Data fittings using the Fuchs–Sondheimer and Mayadas–Shatzkes models suggested the very short mean free path of electrons of below 5 nm and the high specularity parameter of 0.9. The short mean free path and the much reduced diffuse scattering of electrons at the interface effectively suppressed the resistivity scaling of the B2 RuAl intermetallic compound as compared to ruthenium metal. At an ultra-small film thickness of below 5 nm, the reflection of electrons by grain boundaries or domain walls might alternatively dominate the increase in resistivity. The RuAl intermetallic compound with an ordered B2 structure and a high cohesive energy (a large negative mixing enthalpy) also demonstrated a superior thermal stability at an extreme temperature up to 900 °C. It could be a promising candidate for potential use as the next-generation interconnect metallization without the need of a diffusion barrier.

Design and evaluation of a kind of polymer-bonded explosives with improved mechanical sensitivity and thermal properties

The emergence of TKX-50, an energetic ionic salt with a high enthalpy of formation and low sensitivity, has opened a new path for the development of high-energetic, insensitive composite explosives. However, due to the poor interfacial binding properties of TKX-50 with conventional binders, there is a lack of effective guidance for the design of TKX-50 based composite explosives. To address the above issues, the interactions between carboxymethyl cellulose acetate butyrate (CMCAB) and other binders with explosives TKX-50/HMX were compared using the molecular dynamics method. Based on the simulations, TKX-50/HMX/CMCAB-based polymer-bonded explosives (PBXs) were prepared with CMCAB as binder, which displays a high binding energy (Ebind) with TKX-50 and high cohesive energy density (CED), and the effect of TKX-50 content on the performance of PBXs was investigated. The physical properties of PBXs, specifically the morphology, mechanical sensitivity, and thermal conductivity, were analyzed by SEM, sensitivity apparatus, and thermal conductivity meter, respectively. The specific heat capacity (Cp) and non-isothermal decomposition temperature of PBXs were tested by DSC, and then the corresponding thermal kinetic parameters were analyzed to evaluate their thermal safety. The adiabatic thermal decomposition processes of PBXs were tested using an ARC instrument. The decomposition mechanism and kinetics were also explored to further analyze their thermal stability and thermal safety under adiabatic conditions. The computer code EXPLO5 was used to predict the detonation parameters of PBXs. The results showed that CMCAB and TKX-50 displayed favorable interfacial bonding properties, and TKX-50 can be bonded with HMX to form a molding powder with a desirable morphology and safety profile. The TKX-50 in PBXs effectively improves the mechanical sensitivity and thermal safety of PBX and has a significant effect on the detonation performance of PBX. This research demonstrates a novel method suitable for screening and investigating high-energetic insensitive explosive systems compatible with TKX-50.

Shear-Induced Fabrication of Cellulose Nanofibril/Liquid Metal Nanocomposite Films for Flexible Electromagnetic Interference Shielding and Thermal Management.

To address electromagnetic interference (EMI) pollution in modern society, the development of ultrathin, high-performance, and highly stable EMI shielding materials is highly desired. Liquid metal (LM) based conductive materials have received enormous amounts of attention. However, the processing approach of LM/polymer composites represents great challenges due to the high surface tension and cohesive energy of LMs. In this study, we develop a universal one-step fabrication strategy to directly process composites containing LMs and cellulose nanofibrils (CNFs) and successfully fabricate the ultrathin, flexible, and stable EMI shielding films with an average specific EMI shielding efficiency (EMI SE) value of 429 dB/mm and small thickness of only 70 μm in the wide frequency range of 8.2-18 GHz. In addition, the resulting films also exhibit excellent mechanical performance and flexibility, which endow the film with the ability to withstand repeated folding, bending, and folding into complex shapes without producing cracks or fractures. Besides, the resulting films display excellent thermal conductivity with a λ of 4.90 W/(m K) and an α of 3.17 mm2/s. Thus, the presented approach shows great potential in fabricating advanced materials for EMI shielding applications.

Exploring NiCrAlYSiTa multicomponent coatings: Combining high-throughput synthesis and CALPHAD modeling

Multicomponent alloys pose great challenges for efficiently screening desired composition. Here, we combined high-throughput magnetron-sputtering experiments and CALculation of PHAse Diagrams (CALPHAD) methods to screen NiCrAlYSiTa coatings. The compositionally graded coatings showed increased amorphization with higher Si content, indicated by the steepen T0 curves and enlarged amorphous formation region. For the crystallized coatings, the phase structure transformed from Al- and Cr-rich bcc region to Ni-rich fcc, consistent with our calculated phase diagrams. Owing to the high cohesion energy and strong atomic bonding induced by large atomic radius difference and negative mixing enthalpy, the amorphous coatings exhibited superior hardness (25.8 GPa) and elastic modulus (415.8 GPa) compared to the reported multicomponent coatings. By combining high-throughput experimental and theoretical methods, this work pioneers an integrated framework for rapid development of new multicomponent alloy coatings.

Aza[5]helicene‐Derived Semiconducting Polymers for Improved Performance in Perovskite Solar Cells: Exploring Energetic and Morphological Influences

AbstractThe strategic design of solution‐processable semiconducting polymers possessing both matched energy levels and elevated glass transition temperatures is of urgent importance in the progression of thermally robust n‐i‐p perovskite solar cells with efficiencies exceeding 25 %. In this work, we employed direct arylation polymerization to achieve the high‐yield synthesis of three aza[5]helicene‐derived copolymers with distinct HOMO energy levels and exceptional glass transition temperatures. Upon integration of these semiconducting polymers into formamidinium lead triiodide‐based perovskite solar cells, marked disparities in photovoltaic parameters manifest, primarily stemming from variations in the electrical conductivity and film morphology of the hole transport layers. The p‐A5HP‐E‐POZOD‐E copolymer, featuring a main chain comprising alternating repeats of aza[5]helicene, ethylenedioxythiophene, phenoxazine, and ethylenedioxythiophene, attains an initial average efficiency of 25.5 %, markedly surpassing reference materials such as spiro‐OMeTAD (23.0 %), PTAA (17.0 %), and P3HT (11.6 %). Notably, p‐A5HP‐E‐POZOD‐E exhibits a high cohesive energy density, resulting in enhanced Young's modulus and diminished external species diffusion coefficients, thereby conferring perovskite solar cells with exceptional 85 °C tolerance and operational stability.

Aza[5]helicene-Derived Semiconducting Polymers for Improved Performance in Perovskite Solar Cells: Exploring Energetic and Morphological Influences.

The strategic design of solution-processable semiconducting polymers possessing both matched energy levels and elevated glass transition temperatures is of urgent importance in the progression of thermally robust n-i-p perovskite solar cells with efficiencies exceeding 25 %. In this work, we employed direct arylation polymerization to achieve the high-yield synthesis of three aza[5]helicene-derived copolymers with distinct HOMO energy levels and exceptional glass transition temperatures. Upon integration of these semiconducting polymers into formamidinium lead triiodide-based perovskite solar cells, marked disparities in photovoltaic parameters manifest, primarily stemming from variations in the electrical conductivity and film morphology of the hole transport layers. The p-A5HP-E-POZOD-E copolymer, featuring a main chain comprising alternating repeats of aza[5]helicene, ethylenedioxythiophene, phenoxazine, and ethylenedioxythiophene, attains an initial average efficiency of 25.5 %, markedly surpassing reference materials such as spiro-OMeTAD (23.0 %), PTAA (17.0 %), and P3HT (11.6 %). Notably, p-A5HP-E-POZOD-E exhibits a high cohesive energy density, resulting in enhanced Young's modulus and diminished external species diffusion coefficients, thereby conferring perovskite solar cells with exceptional 85 °C tolerance and operational stability.

Mechanistically Guided Materials Chemistry: Synthesis of Ternary Nitrides, CaZrN2 and CaHfN2.

Recent computational studies have predicted many new ternary nitrides, revealing synthetic opportunities in this underexplored phase space. However, synthesizing new ternary nitrides is difficult, in part because intermediate and product phases often have high cohesive energies that inhibit diffusion. Here, we report the synthesis of two new phases, calcium zirconium nitride (CaZrN2) and calcium hafnium nitride (CaHfN2), by solid state metathesis reactions between Ca3N2 and MCl4 (M = Zr, Hf). Although the reaction nominally proceeds to the target phases in a 1:1 ratio of the precursors via Ca3N2 + MCl4 → CaMN2 + 2 CaCl2, reactions prepared this way result in Ca-poor materials (CaxM2-xN2, x < 1). A small excess of Ca3N2 (ca. 20 mol %) is needed to yield stoichiometric CaMN2, as confirmed by high-resolution synchrotron powder X-ray diffraction. In situ synchrotron X-ray diffraction studies reveal that nominally stoichiometric reactions produce Zr3+ intermediates early in the reaction pathway, and the excess Ca3N2 is needed to reoxidize Zr3+ intermediates back to the Zr4+ oxidation state of CaZrN2. Analysis of computationally derived chemical potential diagrams rationalizes this synthetic approach and its contrast from the synthesis of MgZrN2. These findings additionally highlight the utility of in situ diffraction studies and computational thermochemistry to provide mechanistic guidance for synthesis.

High-Toughness CO2-Sourced Ionic Polyurea Adhesives.

Polyurea (PUa) adhesives are renowned for their exceptional adhesion to diverse substrates even in harsh environments. However, the presence of quadruple bidentate intermolecular hydrogen bonds in the polymer chains creates a trade-off between cohesive energy and interfacial adhesive energy. To overcome this challenge, a series of CO2-sourced ionic PUa adhesives with ultratough adhesion to various substrates are developed. The incorporated ionic segments within the adhesive serve to partially mitigate the intermolecular hydrogen bonding interactions while conferring unique electrostatic interactions, leading to both high cohesive energy and interfacial adhesive energy. The maximum adhesive strength of 10.9MPa can be attained by ionizing the CO2-sourced PUa using bromopropane and subsequently exchanging the anion with lithium bis(trifluoromethylsulfonyl)imide. Additionally, these ionic PUa adhesives demonstrate several desirable properties such as low-temperature stability (-80°C), resistance to organic solvents and water, high flame retardancy, antibacterial activity, and UV-fluorescence, thereby expanding their potential applications. This study presents a general and effective approach for designing high-strength adhesives suitable for a wide array of uses.

First-principles study of the effects of Vo on the magnetic and photocatalytic properties of bilayer anatase TiO2(001): C/N/S

In this study, we investigated the effect of Vo on the magnetic and photocatalytic properties of bilayer anatase TiO2 (001): C/N/S using first principles within the density functional theory framework. Through research, it has been discovered that the stability and electronic structure of oxygen vacancies can vary depending on their positions, ultimately resulting in diverse photocatalytic performances. When the distance between N and Vo is relatively close, bilayer TiO2(001) system exhibited a relatively low formation energy under Ti-rich conditions, a high cohesive energy, and no virtual frequency formed in the phonon spectrum. Thus, it has good stability. The bilayer Ti24O46N (001) system displayed the most evident red shift in the absorption spectrum, the largest electric dipole moment, the smallest work function, relatively high carrier activity, a notable difference in mobility between electrons and holes, reduced recombination of electrons and holes, an extended carrier lifetime, and superior oxidation reaction capability. Consequently, the bilayer Ti24O46N (001) surface system emerged as the most suitable catalyst for the photo-degradation of water to produce oxygen.

Interrelation between ink viscoelasticity and crack structure of fuel cell microporous layers

Cracks in the microporous layers of fuel cells greatly affect their performance. It is essential to understand the viscoelasticity of ink, the key precursor during MPL fabrication, to gain insights into crack formation and control. This work has comprehensively investigated ink rheology with different solid content and the resulting MPL crack structure from a theoretical and practical level. The network microstructure strength of the ink is evaluated by rheological measurements, and the interrelation between ink viscoelasticity and two distinct crack configurations is established. The detailed SEM characterization shows that an appropriate ink cohesive energy produces more intersected cracks within the MPL, while lower or higher cohesive energy is prone to unpenetrated and interlayer cracks. The range of CE in this study is 0.03–100 J/m3, the CE of ink is more likely to produce intersected cracks at about 10 J/m3. Moreover, the CE variation affects the PTFE distribution. A lower CE variation from 1 to 500 s−1 which is associated with the coating process promotes a homogeneous PTFE distribution.

Multi-bioinspired alginate-based gel coatings formed by dynamic metal–ligand assembly for enhancing foliar affinity and rain-fastness of pesticides

Insufficient deposition of pesticide droplets and rain erosion are significant factors in excessive pesticide wastage and pose a significant threat to public health and the ecological environment. Inspired by the adhesion mechanism of marine mussels and mayfly larvae, we developed a gel coating to improve pesticide retention efficiency and resistance to rainwater washout by sequential spraying polydopamine-functionalized alginate and Fe3+ ions onto the target leaf surface (SA-DA/Fe3+). Abundant catechol groups provide strong molecular-level interfacial bridging for alginate derivates, while the gel coating contains flexible, deformable, and complex nanoscale networks, inducing mutual coupling with micro/nanostructures on the leaf surface, ultimately resulting in the removal of the interface void and the improvement of deposition capacity at multiple scales. The gel coating shows high cohesive energy to better resist rain rinsing due to the dense carboxyl-Fe3+ and catechol-Fe3+ coordination bonds in the network architecture. By combining the above effects, the pesticide retention rate of SA-DA/Fe3+ gel coating on foliage could reach about 97 % after rain erosion and immersion. In addition, the SA-DA/Fe3+ gel coating can also achieve the sensitive photo-control effect of pesticides due to the intrinsic photosensitivity of the iron-carboxylate system. Using an alginate-based gel coating as a promising strategy for improving pesticide utilization, addressing the issues of easy runoff, susceptibility to erosion, and uneven coverage in traditional pesticide droplet form, thus bridging the fields of bionic materials science, bio-macromolecular chemistry, and agricultural science.

Electrical Resistivity Modification of Electrodeposited Mo and Mo–Co Nanowires for Interconnect Applications

Achieving historically anticipated improvement in the performance of integrated circuits is challenging, due to the increasing cost and complexity of the required technologies with each new generation. To overcome this limitation, the exploration and development of novel interconnect materials and processes are highly desirable in the microelectronics field. Molybdenum (Mo) is attracting attention as an advanced interconnect material due to its small resistivity size effect and high cohesive energy; however, effective processing methods for such materials have not been widely investigated. Here, we investigate the electrochemical behavior of ions in the confined nanopores that affect the electrical properties and microstructures of nanoscale Mo and Mo–Co alloys prepared via template-assisted electrodeposition. Additives in an electrolyte allow the deposition of extremely pure metal materials, due to their interaction with metal ions and nanopores. In this study, boric acid and tetrabutylammonium bisulfate (TBA) were added to an acetate bath to inhibit the hydrogen evolution reaction. TBA accelerated the reduction of Mo at the surface by inducing surface conduction on the nanopores. Metallic Mo nanowires with a 130 nm diameter synthesized through high-aspect-ratio nanopore engineering exhibited a resistivity of (63.0 ± 17.9) μΩ·cm. We also evaluated the resistivities of Mo–Co alloy nanowires at various compositions toward replacing irreducible conventional barrier/liner layers. An intermetallic compound formed at a Mo composition of 28.6 at%, the resistivity of the Mo–Co nanowire was (58.0 ± 10.6) μΩ·cm, indicating its superior electrical and adhesive properties in comparison with those of conventional barriers such as TaN and TiN. Furthermore, density functional theory and non-equilibrium Green’s function calculations confirmed that the vertical resistance of the via structure constructed from Mo-based materials was 21% lower than that of a conventional Cu/Ta/TaN structure.