Clusters Of Cu Research Articles

Oxidative and selective C–C cleavage of glycerol to glycolaldehyde with atom-like Cu on Cu-TiO2: Photocatalytic water reduction with concurrent glycerol oxidation in sunlight

Concurrent consumption of electrons and holes for the conversion of a biomass component to value added products represents a highly efficient and sustainable approach towards utilizing renewable energy, but difficult to achieve. The integration of hydrogen production with glycerol oxidation presents a novel and sustainable approach towards achieving a circular economy. In the current study, integration of atom-like Cu-clusters onto TiO2 substrate has been achieved using a facile photo-deposition technique (TC-PDO). Also, novel synthetic approaches have been employed to augment the surface coverage of Cu on TiO2 with atom-like clusters of Cu, either by borohydride treatment on TiO2 followed by Cu-deposition (TC-200) or oxygen-vacancy creation by UV illumination followed by Cu-deposition (TC-PDO). Increased dispersion and enhanced electronic integration of Cu with TiO2 lead to a corresponding increase in the efficiency of photocatalytic hydrogen evolution (13.8 mmol/h.g for TC-PDO at pH 9). Several atom-like Cu integrated with each TiO2 particle acts as photocatalytic reactor, and the same enhances electron-hole separation as well as activity. Sustainable aspect was also studied for TC-PDO up to 25 h at pH 9. Concurrently, glycerol oxidation displays the highest selectivity to C2 product (glycolaldehyde with 70 %) with a C–C cleavage. The investigation of this process holds significant potential for the extensive and simultaneous exploitation of electrons and holes in order to achieve water splitting and glycerol oxidation towards selective value-added products formation.

Cu Embedded in Co–P Nanosheets with Super Wetting Structure for Accelerated Overall Water Splitting under Simulated Industrial Conditions

AbstractThe development of advanced electrocatalysts with exceptional performance at high current densities is pivotal for reducing electric energy consumption in industrial water splitting for hydrogen production. Herein, a flexible one‐step electrodeposition approach is developed to synthesize superhydrophilic 3D flower‐like clusters of Cu–Co–P nanosheets grown in situ on nickel foam (NF). Introducing Cu into Co–P causes strong electron interactions, forming an electronic configuration favorable for the adsorption and desorption of intermediates, which significantly improves the intrinsic catalytic activity. The as‐deposited Cu–Co–P/NF display notable bifunctional catalytic activity with low overpotentials of 259 and 65 mV for the oxygen and hydrogen evolution reactions, respectively, at 10 mA cm−2. Superwetting 3D flower‐like nanostructures are conducive to the penetration of electrolytes and the rapid release of bubbles, enabling the efficient utilization of active sites and the timely release of bubble stress under high current densities. An assembled Cu–Co–P/NF(+, −) electrolyzer achieves an impressive voltage of 1.85 V at 500 mA cm−2 for water splitting and appreciable stability for over 220 h under simulated industrial conditions. This work offers an attractive strategy for regulating superaerophobic Co–P electrocatalysts for industrial water splitting, which can contribute to practical applications.

Theoretical investigation on the CO2 hydrogenation to methanol mechanism at electron-rich active interface over Cu/Ga-Ti-Al-O catalyst

Density functional theory investigations on CO2 hydrogenation to methanol mechanisms over Cu13 cluster loaded catalyst were performed. The results indicate that introducing TiO2 into Al2O3 promoted the residual electrons from Al2O3 surface directionally transmitted to the interface formed by the loaded Cu13 cluster and the support surface, thus created the electron-rich active interface. Incorporating single atom Ga promoter further gathered the residual electrons and stabilized the loaded Cu13 clusters. The electron-rich property of the active interface promoted the chemical adsorption and activation of both CO2 and the generated carbonyl species. Further favors the hydrogenating of carbonyl intermediates to methanol and effectively enhances the methanol selectivity. Moreover, CO2 priors to hydrogenated to methanol via reverse water gas shift pathway over Cu13/Ga-AT computational model with changed reaction rate controlling step with reduced activation energy. This work offers a simple approach for efficient copper-based methanol synthesis catalysts through control of interface electron structure.

Supramolecularly Dimeric Assemble of Planar Cu13 Clusters Controlled by the Length of Spacers of Diphosphine.

The controlled formation of dimeric clusters is challenging. Three copper(I) clusters, labeled as {Cu13[o-Ph(C≡C)2]6(L)4}(ClO4), were synthesized by using three different ligands, including 1,4-bis(diphenylphosphino)butane (dppb), 1,5-bis(diphenylphosphino)pentane (dpppe), and bis(diphenylphosphino)hexane (dpph). By increasing the flexibility of alkyl spacers in the diphosphine ligands, the relative positions of the phenyl rings could be optimized to achieve efficient packing with maximized intercluster interactions. In the crystal structures, cluster 1 with dppb ligands did not display interlocked structures. In contrast, cluster 2 with dpppe ligands formed supramolecularly interlocked polymers through weak π-π interactions and C-H···π interactions, while cluster 3 employing dpph ligands formed supramolecularly interlocked dimers with strong π-π interactions and C-H···π interactions. The supramolecular dimer of 3 was also evidenced by analyses through electrospray ionization mass spectrometry and transmission electron microscopy. Density functional theory calculation was used to understand the electronic structure and transitions. Supramolecularly interlocked polymers/dimers with rigid structures exhibited higher quantum efficiency. The solution of these clusters demonstrated remarkable aggregation-induced emission enhancements. This study presents unique examples of planar luminescent copper clusters, featuring the first serial dialkynyl-protected cluster. It underlines the importance of ligand flexibility in creating supramolecular cluster dimers.

Energetic metal-organic framework based on multinuclear clusters of Cu(II) and Fe(III) and its catalytic action on thermal decomposition of solid propellant components (RDX, HMX, CL-20 and AP)

Using nitrogen-rich tetrazole derivatives with multifunctional groups and ligand sites in metal–organic frameworks (MOFs) is a strategy to enhance their energy levels and broaden their applications. In the present study, a Cu(II) and Fe(III) heteronuclear {[CuFe3O(tza)6(H2O)3]·(NO3)2·OH}n (CuFe-MOF) based on the high-energy ligand tetrazole-1-acetic acid (Htza) was synthesized and its structures and properties were evaluated. The effects of CuFe-MOF as a catalyst on the thermal decomposition performance of the solid propellant components (RDX, HMX, CL-20 and AP) were investigated. The results demonstrated that the successfully prepared compound, an infinite 3D meshwork structure composed of [Fe3O(tza)6]+ and Cu2+, is in the ortho-hexagonal crystal system, P63/m space group. CuFe-MOF exhibited good thermal stability (Tdec = 238.9 °C) and insensitivity to impact (IS > 40 J) and friction (FS > 360 J). The addition of 5 % CuFe-MOF significantly reduces the decomposition peak temperature (1.9 °C, 5.8 °C, 5.7 °C and 71.4 °C) and apparent activation energy (38.5 kJ·mol−1, 38.3 kJ·mol−1, 63.9 kJ·mol−1, and 27.0 kJ·mol−1) of the RDX, HMX, CL-20, and AP compared to the raw materials while notably enhancing the heat release (509.8 J·g−1, 613.1 J·g−1, 578.4 J·g−1 and 584.3 J·g−1). Furthermore, good compatibility with RDX, HMX, CL-20, and AP was demonstrated using VST method. This research indicates the potential of {[CuFe3O(tza)6(H2O)3]·(NO3)2·OH}n as a promising alternative to the existing inert catalysts in propellants containing RDX, HMX, CL-20, and AP components, serving as an energetic combustion catalyst.

Ab initio molecular dynamics study of H2 dissociation mechanisms on Cu13 and defective graphene-supported Cu13 clusters: active sites, energy barriers and adsorption states.

Ab initio molecular dynamics calculations were performed to study H2 dissociation mechanisms on Cu13 and defective graphene-supported Cu13 clusters. The study reveals that seven types of corresponding dissociation processes are found on the two clusters. The average dissociation energy barriers are 0.51 eV on the Cu13 cluster and 0.12 eV on the defective graphene-supported Cu13 cluster, which are lowered by ~ 19% and ~ 81% compared with the pristine Cu(111) surface, respectively. Furthermore, compared with the pure Cu13 cluster, the average dissociation energy barrier on the defective graphene-supported Cu13 cluster is substantially reduced by about 76%. The preferred dissociation mechanisms on the two clusters are H2 located at a top-bridge site with the barrier heights of 0.30 eV on the Cu13 cluster and - 0.31 eV on the defective graphene-supported Cu13 cluster. Analysis of the H-Cu bond interactions in the transition states shows that the antibonding-orbital center shifts upwards on the defective graphene-supported Cu13 cluster compared with the one on the Cu13 cluster, which explains the reduction of the dissociation energy barrier. The average adsorption energy of dissociated H atoms is also greatly enhanced on the defective graphene-supported Cu13 cluster, about twice that on pure Cu13.

Electrochemical Approach for the Synthesis of Ultrasmall Cu13 Clusters and Their Application in the Detection of Endotoxin.

Ultrasmall metal nanoclusters are attractive for their size-dependent optical and electrochemical properties. Here, blue-emitting copper clusters stabilized with cetyltrimethylammonium bromide (CTAB) are synthesized using an electrochemical approach. The electrospray ionization (ESI) analysis reveals that the cluster has 13 copper atoms in the core. The clusters are then used for the electrochemical detection of endotoxin─a bacterial toxin in Gram-negative bacteria. Differential pulse voltammetry (DPV) is used to detect endotoxins with high selectivity and sensitivity. It shows a lower detection limit of 100 ag mL-1 with a linear range of 100 ag mL-1 to 10 ng mL-1. The sensor is efficient for detecting endotoxins from human blood serum samples.

Structure and Migration Mechanisms of Small Vacancy Clusters in Cu: A Combined EAM and DFT Study.

Voids in face-centered cubic (fcc) metals are commonly assumed to form via the aggregation of vacancies; however, the mechanisms of vacancy clustering and diffusion are not fully understood. In this study, we use computational modeling to provide a detailed insight into the structures and formation energies of primary vacancy clusters, mechanisms and barriers for their migration in bulk copper, and how these properties are affected at simple grain boundaries. The calculations were carried out using embedded atom method (EAM) potentials and density functional theory (DFT) and employed the site-occupation disorder code (SOD), the activation relaxation technique nouveau (ARTn) and the knowledge led master code (KLMC). We investigate stable structures and migration paths and barriers for clusters of up to six vacancies. The migration of vacancy clusters occurs via hops of individual constituent vacancies with di-vacancies having a significantly smaller migration barrier than mono-vacancies and other clusters. This barrier is further reduced when di-vacancies interact with grain boundaries. This interaction leads to the formation of self-interstitial atoms and introduces significant changes into the boundary structure. Tetra-, penta-, and hexa-vacancy clusters exhibit increasingly complex migration paths and higher barriers than smaller clusters. Finally, a direct comparison with the DFT results shows that EAM can accurately describe the vacancy-induced relaxation effects in the Cu bulk and in grain boundaries. Significant discrepancies between the two methods were found in structures with a higher number of low-coordinated atoms, such as penta-vacancies and di-vacancy absortion by grain boundary. These results will be useful for modeling the mechanisms of diffusion of complex defect structures and provide further insights into the structural evolution of metal films under thermal and mechanical stress.

Enhancement of CO adsorption energy on defective graphene-supported Cu13 cluster and prediction with an induction energy model

The adsorption of CO on Cu13 and defective graphene-supported Cu13 clusters is investigated using ab initio molecular dynamics methods. The results show that the CO adsorption energies on the defective graphene-supported Cu13 cluster are substantially enhanced compared to those on the Cu13 cluster. Furthermore, the average adsorption energy on the defective graphene-supported Cu13 cluster is significantly increased by 155% compared with the experimental one on pristine Cu surfaces, indicating that the defective graphene-supported Cu13 cluster can be an excellent catalyst for CO adsorption. The enhancement of the adsorption energies can be qualitatively explained in terms of the crystal orbital Hamilton population, that is, as the bond interaction increases, the adsorption energy increases. We propose an induction energy model to calculate the amount of the adsorption energy enhancement. The predicted adsorption energies on the defective graphene-supported Cu13 clusters are in quantitative agreement with those obtained from ab initio molecular dynamics simulations. The current study provides insights into designing highly active catalysts for CO adsorption.

Long-timescale transformations of self-interstitial atom clusters of Cu using the SEAKMC method: The effect of setting an activation energy threshold for saddle point searches

On-the-fly kinetic Monte Carlo (kMC), a computational technique for atomistic simulations, has attracted attention because it increases the simulation timescale beyond that of molecular dynamics (MD) simulations while maintaining atomistic fidelity. However, for most kMC methods, when events with high and low activation energies coexist in the event list, trivial events with extremely low activation energies that do not essentially affect the phenomena of interest, so-called flicker events, are frequently selected, making it challenging to observe the key dynamics. In this study, we use Self-Evolving Atomistic kMC (SEAKMC), one of the on-the-fly kMC methods, to model the unstable-to-stable transformations of irregular three-dimensional self-interstitial-atom (SIA) clusters in Cu generated through collision cascade. By setting an activation energy threshold once every five steps, transformations into stable configurations are enhanced. The algorithm renders the simulation timescales one or two orders of magnitude longer than those possible with MD simulations. Further, the probability of transformations into stable configurations is increased by 40 times compared to that of the original SEAKMC method. In addition, we find that the stable configurations obtained by the transformation of the SIA clusters are mostly Frank loops. In summary, this new algorithm for the SEAKMC method helps to resolve the inefficiency of kMC methods resulting from the selection of flicker events and will aid the study of meso-timescale atomistic dynamics.

Exploration of the atomic-level structures of the icosahedral clusters in Cu–Zr–Al ternary metallic glasses via first-principles theory

The atomic-level structures of the icosahedral clusters in Cu–Zr–Al ternary metallic glasses were studied via the first-principles theory. The rules of icosahedra stability were determined. Icosahedra with a better chemical order or with a better symmetry exhibited a better stability. The strong connectivity between Al atom and Cu and Zr atoms was observed as demonstrated by the obvious degree of ‘bond shortening’. The Al atom contributed more to the structural stability when used as the central atom than the other atoms. Therefore, the addition of even a small amount of Al atom to the Cu–Zr binary system remarkably improved the stability of the icosahedron structures. The continued addition of Al atoms had a lower contribution to the improvement to the glass-forming ability of the Cu–Zr–Al alloys.

Composition dependence in glass-forming ability of Cu–Ag binary alloys

Alloys around eutectic points are thought to be good glass formers. However, the glass-forming ability (GFA) as a function of composition from pure metals to the eutectic alloy has not been quantified and the underlying microstructural and dynamical origins are unclear. In this work, the GFA of Cu–Ag alloys at various compositions was thoroughly investigated by using molecular dynamics simulations. According to the results, the critical cooling rate for glass formation Rc (K/s) varies with solute content x′ (at%), following Rc ≈ Aexp(kx′) where A = 4.61 × 1012 and k = -0.25 on the Cu side and A = 4.43 × 1012 and k = -0.19 on the Ag side. The Rc of the eutectic alloy is about 5 orders of magnitude lower than that of the pure metals. Structurally, the number of densely packed icosahedral-like clusters in Cu–Ag metallic glasses increases with increasing solute content, resulting in the most densely packed structure at the eutectic composition. The dynamical properties of Cu–Ag melts are basically independent on composition at high temperatures, but obviously change with composition at low temperature. Besides the largest reduced glass transition temperature, the highest five-fold symmetry (FFS) local structure and more importantly the retarded dynamics of liquid atoms below the liquidus temperature around the eutectic composition impart the eutectic alloy with the best glass-forming ability.

The effect of different energy portions on the 2D/3D stability swapping for 13-atom metal clusters.

The complexity of Cu13, Ag13, and Au13 coinage-metal clusters was investigated through their energy contributions via a density functional theory study, considering improvements in the PBE functional, such as van der Waals (vdW) corrections, spin-orbit coupling (SOC), Hubbard term (+U), and their combinations. Investigating two-dimensional (planar 2D) and three-dimensional (distorted 3D, CUB - cuboctahedral, and ICO - icosahedral) configurations, we found that vdW corrections are dominant in modulating the stability swapping between 2D and ICO (3D) for Ag13 (Au13), whereas for Cu13 its role is increasing the relative stability between 2D (least stable) and 3D (most stable), setting ICO as the reference. Among the energy portions that constitute the relative total energy, the dimensionality difference correlates with the magnitude of the relative dispersion energy (large for 2D/ICO and small for 3D/ICO) as the causal factor responsible for an eventual stability swapping. For instance, empirical vdW corrections may favor Ag13 as ICO, while semi empirical ones tend to swap the stability by favoring 2D. The same tendency is observed for Au13, except when SOC is included, which enlarges the stability of 3D over 2D. Energy decomposition analysis combined with the natural orbitals for the chemical valence approach confirmed the correlations between the dimensionality difference and the magnitude of the relative dispersion energies. Our structural analysis protocol was able to capture the local distortion effects (or even their absence) through the quantification of the Hausdorff chirality measure. Here, ICO, CUB, and 2D are achiral configurations for all coinage-metal clusters, whereas Cu13 as 3D presents a slight chirality when vdW correction based on many body dispersion is used, at the same time Ag13 as 3D turned out to be chiral for all calculation protocols as evidence of the role of the chemical composition.

Impurity diffusion in magic-size icosahedral clusters.

Atomic diffusion is at the basis of chemical ordering transformations in nanoalloys. Understanding the diffusion mechanisms at the atomic level is therefore a key issue in the study of the thermodynamic behavior of these systems and, in particular, of their evolution from out-of-equilibrium chemical ordering types often obtained in the experiments. Here, the diffusion is studied in the case of a single-atom impurity of Ag or Au moving within otherwise pure magic-size icosahedral clusters of Cu or Co by means of two different computational techniques, i.e., molecular dynamics and metadynamics. Our simulations reveal unexpected diffusion pathways, in which the displacement of the impurity is coupled with the creation of vacancies in the central part of the cluster. We show that the observed mechanism is quite different from the vacancy-mediated diffusion processes identified so far, and we demonstrate that it can be related to the presence of non-homogeneous compressive stress in the inner part of the icosahedral structure.

Anionic Activation of CO2 via (Mn-CO2)- Complex on Magic-Numbered Anionic Coinage Metal Clusters Mn- (M = Cu, Ag, Au).

Given the immense challenge of excessive accumulation of carbon dioxide (CO2) in the earth's atmosphere, an extensive search is under way to convert atmospheric CO2 to compounds of more utility. With CO2 being thermodynamically extremely stable, activation of CO2 is the first and most important step toward its chemical conversion. Building upon our earlier model for the anionic activation of CO2 with azabenzene and inspired by the work of others on metal atom-CO2 complexes, we investigated the possibility of anionic activation of CO2 on small anionic metal clusters, which would have implications for catalytic conversion of CO2 on metal surfaces with atomic-scale structural irregularities. We carried out theoretical calculations using density functional theory to examine small anionic metal clusters of Cu, Ag, and Au to check whether they form a complex with CO2, with the sign of CO2 being chemically activated. We found that a class of anionic metal clusters Mn- with 1, 2, and 6 atoms consistently produced the activated complex (Mn-CO2)- for all three metals. There exists a strong interaction between the CO2 moiety and Mn- via a partially covalent M-C bond with a full delocalization of the electronic charge, as a result of electron transfer from the HOMO of Mn- to the LUMO of CO2 as in metal-CO2 π-backbonding. We examined the interaction of frontier orbitals from the viewpoints of the orbital geometry and orbital energetics and found that the above magic numbers are consistent with both aspects.

Intermetallic phases meet intermetalloid clusters.

In this article intermetalloid clusters of Cu-Zn, Cu-AI, Cu-Sn, and Cu-Pb are discussed. Intermetallic compounds based on these metal combinations are of the Hume-Rothery type with well-defined structures related to the valence electron count of the involved metals. Many Zintl-type and molecular clusters with these metals are known with remarkable structural parallels to the respective solid-state phases. On several examples, this article discusses intermetalloid clusters in terms of their metal core structures and relates them to structural principles in intermetallic solid-state phases. Also the syntheses of such clusters are addressed. Zintl-type and molecular clusters are most generally accessible from organometallic precursor complexes with redox processes between the different metals as an underlying synthesis concept.

New Materials to Battle the Transistor Interconnect Bottleneck

With ever decreasing transistor size, materials that combine both diffusion barrier and liner material properties are needed to successfully electroplate Cu and thus beat the current interconnect bottleneck. In order to facilitate coating of high aspect ratio vias, the material should be as thin as possible. One possibility to achieve this is presented in this study, where we investigate through density functional theory, the behavior Cu on Ru-doped and Ru passivated ε-TaN (1 1 0). Initially, the adsorption, diffusion and association of one and two Cu atoms on the different surfaces was studied in order to probe the early stages of film growth. This showed that, while surface diffusion of atoms was more favourable on the Ru-passivated surface, the Ru dopant acts as a nucleation site for Cu, with atoms preferentially diffusing towards it.In order to understand the mechanism of film growth on this surface in more detail and to fine-tune the barrier and liner properties of the material, the effect of different percentages of surface doping were studied. Further, the behavior of Cu13 and Cu29 clusters on different doped surfaces and on the passivated surfaces was investigated. In particular, the study focused on the pathways toward agglomeration as well as the associated activation energies. We find that on a Ru doped surface the atoms agglomerate spontaneously to form a two-layer film, whereas they remain in a monolayer on Ru-passivated TaN (1 1 0).

Source apportionment, chemometric pattern recognition and health risk assessment of groundwater from southwestern Punjab, India.

The groundwater quality of southwestern Punjab, India, is a serious cause of concern due to the presence of chemical contaminants in it. However, limited studies of groundwater quality, sources of chemical contaminants and their health risks are available for the region. Hence, this study was conducted to investigate the source, distribution and potential health risk assessment of groundwater quality in three districts of southwestern Punjab, India. The spatial distribution of groundwater chemical contaminants and their potential health risks have been illustrated using inverse distance weighting interpolation technique. The concentration of fluoride (F-; ranged from 0.08 to 4.79mgL-1) exceeded the WHO limit (1.5µgL-1) in 80 and 50% samples collected from Bathinda and Ludhiana districts, respectively. The uranium (U) concentration ranged from 0.5 to 432µgL-1 and shows ~ 85%, 75% and 10% of samples collected from Bathinda, Barnala and Ludhiana districts exceeded the WHO drinking water limit (30µgL-1), respectively. The groundwater quality of the Bathinda district is a matter of concern due to elevated levels of alkalinity, hardness, fluoride, uranium and nitrate (NO3-). The principal component analysis shows close association between F- and U, which indicates their geogenic origin. Further, they also seem to be subordinately influenced by diffuse anthropogenic activities. The clustering of Cu and Pb with NO3- and SO42- indicates their anthropogenic origin. The non-carcinogenic health risk assessment indicates that F-, NO3- and U are the major health risk pollutants in the study area. The carcinogenic health risk of As and Cr exceeded the USEPA limits (10-6) in the entire study area, but observed to be more serious for the district Bathinda (10-3-10-5). The spatial distribution maps illustrate that the health risk for Bathinda district inhabitants is higher than Barnala and Ludhiana districts.

Influence of post deposition annealing on microstructure and properties of laser additively manufactured titanium copper alloys

While copper is a potent strengthener in titanium alloys, its use in commercial alloys has been severely restricted due to the strong tendency for segregation during solidification, leading to heterogeneous microstructures and what has often been referred to as the “beta-fleck” problem. This problem can be largely obviated by using additive manufacturing (AM) for processing Ti-Cu alloys. This study focuses on AM of a binary Ti-4Cu and a ternary Ti-4Cu-4Al alloy using the laser engineered net shaping (LENS) process. The influence of post-deposition annealing treatments and the subsequent cooling rate on the microstructure and tensile properties of these alloys has been investigated in detail. The phase fraction of the eutectoid alpha + Ti2Cu product is dependent on the cooling rate from above the beta transus temperature. Additionally, the Ti2Cu phase exhibited a far-from equilibrium composition in case of the water-quenched Ti-4Cu-4Al alloy. Both the yield stress (∼550−650 MPa) as well as the ductility (∼15–18 %) were also higher in case of the ternary alloy. The high strengths exhibited by the water-quenched samples of both alloys, while maintaining appreciable tensile ductility, could be attributed to clustering of Cu within the α laths, revealed by atom probe tomography.

Uncovering the structural, electronic and vibrational properties of atomically precise PdmCun clusters and their interaction with CO2 molecule.

In this work, we address the structural stability, electronic properties and effect of metal-metal interaction on Raman spectra of icosahedral (Ih) PdmCun (m+n=13) clusters using first principles calculations based on dispersion-corrected density functional theory (DFT-D2). Initially, we investigated the relative stability of Ih PdmCun clusters over monometallic Ih Pd13 and Cu13 clusters by calculating the average binding energy per atom, mixing energy, second order energy difference and average bond length. The Ih Pd5Cu8 is the most stable bimetallic cluster with the 2.88eV, -0.218eV and 0.678eV average binding energy per atom, mixing energy and second order energy difference, respectively. The main goals of the present study are to figure out the chemical enhancement, modulation in electronic properties and Pd-Cu bond length in Ih PdmCun clusters after systematic doping of Cu-atom. Further, to examine the doping effect of Cu atom in Pd cluster, we have also analysed the Raman spectra of Ih PdmCun clusters. In case of Ih Cu13 cluster, the contraction of Cu-Cu bond length as compared to its bulk form resulted in a significant blue-shift of characteristic Raman peak (212cm-1) of Ih Pd13 cluster. Finally, the interaction mechanism of the CO2 gas molecule over Pd-Cu alloy clusters have also been studied to understand the effect of composition on reactivity of CO2 gas molecule.