Cu4 Cluster Research Articles

Nonadiabatic Effects in the Molecular Oxidation of Subnanometric Cu5 Clusters.

The electronic structure of subnanometric clusters, far off the bulk regime, is still dominated by molecular characteristics. The spatial arrangement of the notoriously undercoordinated metal atoms is strongly coupled to the electronic properties of the system, which makes this class of materials particularly interesting for applications including luminescence, sensing, bioimaging, theranostics, energy conversion, catalysis, and photocatalysis. Opposing a common rule of thumb that assumes an increasing chemical reactivity with smaller cluster size, Cu5 clusters have proven to be exceptionally resistant to irreversible oxidation, i.e., the dissociative chemisorption of molecular oxygen. Besides providing reasons for this behavior in the case of heavy loading with molecular oxygen, we investigate the competition between physisorption and molecular chemisorption from the perspective of nonadiabatic effects. Landau–Zener theory is applied to the Cu5(O2)3 complex to estimate the probability for a switching between the electronic states correlating the neutral O2 + Cu5(O2)2 and the ionic O2– + (Cu5(O2)2)+ fragments in a diabatic representation. Our work demonstrates the involvement of strong nonadiabatic effects in the associated charge transfer process, which might be a common motive in reactions involving subnanometric metal structures.

Stepwise Assembly of a Multicomponent Heterometallic Metal-Organic Framework via Th6-Based Metalloligands.

Herein we present a new metalloligand, Th6L12 [IHEP-10; L = 4-pyrazolecarboxylic acid (H2PyC)], which can be used to generate a novel multicomponent heterometallic metal-organic framework (MOF), [[Cu3(μ3-OH)(NO3)(H2O)2]2Th6(μ3-O)4(μ3-OH)4(PyC)6(HPyC)6(H2O)6](NO3)2 (IHEP-11), through further assembly with second [Cu3(μ3-OH)(PyC)3] clusters. In IHEP-11, six Cu3 clusters are connected by six NO3- anions to form an unprecedented annular Cu18 cluster, which can be viewed as a 12-connected node to link with 12 Th6 clusters, resulting a 4,12-connected shp net. Benefiting from the cationic framework and 3D porous structure, IHEP-11 can efficiently remove ReO4- (an analogue of radioactive 99TcO4-) from aqueous solution in a wide pH range. This work highlights the feasibility of constructing multicomponent MOFs through a step-by-step synthesis strategy based on metalloligands.

Synthesis, Structures, and Sorption Properties of Two New Metal-Organic Frameworks Constructed by the Polycarboxylate Ligand Derived from Cyclotriphosphazene.

Solvothermal reactions of hexakis(4-carboxyphenoxy)cyclotriphospazene (H6L1) with copper ions in DMF/H2O produced one complex, {[Cu6(L1)2(OH)(H2O)3]·guest}n (1), but with copper ions and auxiliary rigid 4,4-bipyridine (bpy) produced another new complex, namely, {[Cu3(L1)(bpy)(H2O)6]·guest}n (2). These complexes had been characterized by IR spectroscopy, elemental analysis, and X-ray structural determination. 1 exhibits a 3D anionic structure with the binodal 4,8-connected network with Schläfli symbol {46}2{49·618·8}, consisting of Cu6 clusters and L1 ligands. In contrast, complex 2 possesses a different 3D network with trinodal 3,4,6-c topology with Schläfli symbol {4·62}2{42·66·85·102}{64·8·10}. In these two complexes, the semirigid hexacarboxylate ligands adopt distinct conformations to connect metal ions/clusters, which must be ascribed to the addition of the auxiliary rigid ligand in reaction systems. In addition, gas absorption properties of 1 and 2 including CO2 and N2 were further investigated.

New insight into the mechanism of carbon dioxide activation on copper-based catalysts: A theoretical study

A combination of Artificial Bee Colony algorithm, eXtended Tight Binding and Density functional theory methods were performed to study the activation process of carbon dioxide (CO2) over copper (Cu4 cluster) based catalytic systems. The findings revealed that the activation of the C–O bond resulted from the electron transfer to σ*, π* - MO of CO2. The more the electrons are transferred to CO2, the more the C–O bond is activated and elongated. The suitability of several metal oxide supports (Fe2O3, Al2O3, MgO, ZnO) is estimated using calculated electronic parameters (global electrophilicity index, vertical ionization potential and vertical electron affinity). Aside from demonstrating the appropriateness of Al2O3 and ZnO, a thorough examination of MgO revealed that, due to the formation of stable carbonate products, this oxide is not really appropriate as a support for copper-based catalysts in CO2 conversion. Our studies have also shown that the electron enrichment of copper atoms plays a key role in the activation of C–O bonds. Alkali metal doping (Li, K, Cs) significantly improves the catalytic efficiency of the Cu4 cluster. Based on the results of electron transfer to the CO2 molecule, the effect of doping alkali metal atoms may be organized in the following order: Cs > K > Li. A new core/shell catalytic system with potassium atoms in the core and copper atoms in the shell has been proposed and has proven to be a promising, efficient catalytic system in the CO2 adsorption and activation.

Effect of structural variation on enzymatic activity in tetranuclear (Cu4) clusters with defective cubane core

The stimulus to the modeling of enzyme functioning sites comes from their potential to give insight into the natural enzyme’s mechanistic pathways, ascertain the role of that different metal ion in the active site and construct better catalysts motivated by nature. The presence of metal ion leads to the activation of molecular oxygen in the metalloenzymes. The metalloenzymes such as the catechol oxidase (CO) enzyme that oxidizes the catechol to corresponding quinones which eventually protect damage tissues from plant and pathogen. Thus, the design and characterization of catalysts used as selectively and efficiently oxidation reactions have grown to be unique challenges for modern inorganic chemists. In this work, two novel tetranuclear complexes (1 and 2) have been synthesized in excellent yield. The complexes were characterized using various spectroscopic techniques such as FTIR, UV–Visible and PXRD pattern. The structure of 1 and 2 was elucidated by SC-XRD (single crystal X-ray diffraction) analysis. The magnetic study reveals the presence of the antiferromagnetic nature of 1 and 2. Both 1 and 2 shows a very good catecholase-like activity by oxidizing the catechol to analogous quinone in methanolic solution. Thus, a structure-activity relationship can further help us design other substituted tetranuclear complexes with enhanced catecholase like activity. Communicated by Ramaswamy H. Sarma

Outstanding nobility observed in Cu5 clusters reveals the key role of collective quantum effects

Outstanding nobility observed in Cu5 clusters reveals the key role of collective quantum effects

DFT study of the interaction between carbon monoxide and Rh-Cu bimetallic nanoclusters

The interaction between CO and RhxCu4-x(x = 0–4) nanoclusters was studied using B3PW91 hybrid functional. The values of adsorption energies for the most stable structures that were in the range between −1.25 eV to -2.41 eV indicated chemisorption of CO on the clusters along with the formation of chemical bond(s). The nature of these chemical bonds was investigated by NBO analysis and calculation of Wiberg bond indexes as well as considering the change in CO bond length and frequency. It was concluded that the cluster−CO bonds arose mainly from the cluster→(CO) π-back-donation. Also, the NBO analyses revealed that for the adsorption of CO in the bridge and on the top sites, availability of d orbitals and s&p orbitals of cluster atoms was required respectively. Therefore, on the one hand for RhCu3 and Cu4 clusters adsorption in the bridge site was not observed because of the fully occupied d orbitals of Cu atoms but for Rh4, Rh3Cu, and Rh2Cu2 clusters, on the other hand, the adsorption in the bridge of two Rh atoms was the most stable structure. More favorable adsorption on Rh-Cu bimetallic clusters compared to pure Cu4 cluster was also observed.

The active site of ethanol formation from syngas over Cu4 cluster modified MoS2 catalyst: A theoretical investigation

In order to clarify the active site of Cu4 and MoS2 on the conversion of syngas to ethanol over the Cu4 cluster modified MoS2(001) [Cu4/MoS2(001)] surface, we have explored the reaction mechanism of ethanol formation by using density functional theory (DFT) method. It is concluded that CO is first hydrogenated to formyl (CHO) over the Cu4/MoS2 catalyst. The formed CHO is preferentially dissociated to form CH2 by hydrogenation, which is the most favorable CHx monomer. C-C bond is formed by CHO insertion into CH2 leading to the C2 oxygenate CH2CHO, which results in the formation of C2H5OH by successive hydrogenation. The microstructure analysis shows that the Cu4 cluster provides undissociated CO and CHO, while the interface between Cu4 and MoS2 promotes the dissociation of CH2O to form CH2 monomer and promotes the formation of ethanol C-C bond. This work can provide valuable information for the synergistic effect of Cu4 cluster and MoS2 to improve the selectivity of ethanol synthesis.

Cis and trans linkage of spin frustrated copper triangles creating Cu6 clusters

Two C3-symmetric guanidine-based copper triangles bridged by acetates in a cis manner and by chloride anions in a trans manner, respectively gave rise to two antiferromagnetically coupled hexanuclear CuII compounds, namely [Cu6L2Cl(μ-OAc)(DMF)3]·DMF (Cu6) and [Cu6L2(μ-Cl)2(DMF)4] (Cu6Cl)(where L stands for fully deprotonated tris (2-hydroxybenzylidene) triaminoguanidinium chloride, H5L). The experimental magnetic data of the two compounds were analyzed theoretically. A relatively good agreement with the experimental data was obtained when using the wavefunction theory (CASSCF) in combination with DFT (B3LYP) calculations for the very strong antiferromagnetic coupling within the Cu3 triangles (Javg = − 300 cm−1 for Cu6 and Javg = − 250 cm−1 for Cu6Cl), leading to spin-frustrated systems. It is worth mentioning that the electronic structure of each CuII center remains very similar in each complex with a Kramers ground state well separated from the first excited state (over 12000 cm−1) and weakly anisotropic (g∥ ≈ 2.40 and g⊥ ≈ 2.10).

Structural and electronic properties of the adsorption of nitric oxide molecule on copper clusters CuN(N = 1–7): A DFT study

The interconversion between different isomers of copper clusters has been investigated using density functional theory. Seven distinct transition states have been located for the isomerization of the Cu3, Cu4, Cu5, Cu6 and Cu7 clusters. The chemisorption of nitric oxide on copper clusters has been studied and the approach of nitric oxide to produce either the nitrosyl (–NO) or the isonitrosyl (–ON) complexes has been compared. The interaction of NO with the copper cluster complexes leads to significant odd–even oscillations of the spin density differences (ΔSD), mean polarizability (α¯) and HOMO-LUMO gaps. The computed binding energies and ionization potentials of the copper clusters are in excellent agreement with the experimental values. The binding energy, charge transfer, forward donation, υ(NO) and bond ellipticity values are higher in the nitrosyl complexes than their isonitrosyl counterparts. The relationship between the ΔSD and the NO stretching frequencies is approximately linear with high correlation coefficients of R2 = 0.94 and 0.96 for nitrosyl and isonitrosyl complexes, respectively. The stable copper clusters have been reoptimized at couple cluster singles and doubles method with Dunning double-ζ basis sets (CCSD/cc-pVDZ level).

Impact of Electronic and Steric Changes of Ligands on the Assembly, Stability, and Redox Activity of Cu4(μ4-S) Model Compounds of the CuZ Active Site of Nitrous Oxide Reductase (N2OR).

Model compounds have been widely utilized in understanding the structure and function of the unusual Cu4(μ4-S) active site (CuZ) of nitrous oxide reductase (N2OR). However, only a limited number of model compounds that mimic both structural and functional features of CuZ are available, limiting insights about CuZ that can be gained from model studies. Our aim has been to construct Cu4(μ4-S) clusters with tailored redox activity and chemical reactivity via modulating the ligand environment. Our synthetic approach uses dicopper(I) precursor complexes (Cu2L2) that assemble into a Cu4(μ4-S)L4 cluster with the addition of an appropriate sulfur source. Here, we summarize the features of the ligands L that stabilize precursor and Cu4(μ4-S) clusters, along with the alternative products that form with inappropriate ligands. The precursors are more likely to rearrange to Cu4(μ4-S) clusters when the Cu(I) ions are supported by bidentate ligands with 3-atom bridges, but steric and electronic features of the ligand also play crucial roles. Neutral phosphine donors have been found to stabilize Cu4(μ4-S) clusters in the 4Cu(I) oxidation state, while neutral nitrogen donors could not stabilize Cu4(μ4-S) clusters. Anionic formamidinate ligands have been found to stabilize Cu4(μ4-S) clusters in the 2Cu(I):2Cu(II) and 3Cu(I):1Cu(II) states, with both the formation of the dicopper(I) precursors and subsequent assembly of clusters being governed by the steric factor at the ortho positions of the N-aryl substituents. Phosphaamidinates, which combine a neutral phosphine donor and an anionic nitrogen donor in the same ligand, form multinuclear Cu(I) clusters unless the negative charge is valence-trapped on nitrogen, in which case the resulting dicopper precursor is unable to rearrange to a multinuclear cluster. Taken together, the results presented in this study provide design criteria for successful assembly of synthetic model clusters for the CuZ active site of N2OR, which should enable future insights into the chemical behavior of CuZ.

Study on the Adsorption and Activation Behaviours of Carbon Dioxide over Copper Cluster (Cu4) and Alumina-Supported Copper Catalyst (Cu4/Al2O3) by means of Density Functional Theory

The adsorption and activation of carbon dioxide over copper cluster (Cu4) and copper doped on the alumina support (Cu4/Al2O3) catalytic systems have been investigated by using density functional theory and climbing image nudged elastic band. The adsorption energies, geometrical configurations, and electronic properties are analysed. The results show the strong chemical interaction between the copper cluster and the alumina support. Both the Cu4 cluster and Cu4/Al2O3 systems have a high adsorption ability for CO2, and the adsorption process is of chemical nature. The role of the alumina support in the adsorption and activation of CO2 has been addressed. The calculated results show that the “synergistic effect” between Al2O3 and Cu4 is the key factor in the activation of CO2.

Formula omitted] active sites stabilization through Mott-Schottky effect for promoting highly efficient conversion of carbon monoxide into n-propanol

The conversion of carbon monoxide into value-added liquid alcohols has recently attracted considerable attention (Li et al., 2014; De Luna et al., 2018; Pang et al., 2019). However, the ongoing reports for novel catalysts possessing excellent efficiency are still rare due to the high barriers of the reactions involved in the upgradation of the carbon-chains. Cuδ+ sites have been found to promote multi-carbon products, whereas the long-term stability of Cuδ+ sites under reduction conditions remains a challenge for copper-based catalysts. Here, we demonstrate a Mott-Schottky catalyst composed of a copper trimer and the newly synthesized holey C2N semiconductor to stabilize the Cuδ+ sites. The formed metal-semiconductor Schottky barrier promotes electron transfer from the Cu3 cluster to the semiconducting C2N substrate and retains the Cu trimer oxidation state throughout the reaction. The Cu3@C2N catalyst exhibits significantly promoted CC bond formation and hydrogenation activity that outperforms Cu (1 1 1) and Cu (1 0 0) surfaces. In addition, we screened various possible intermediates and provided a plausible thermodynamic reaction pathway for producing n-propanol with a limiting potential of only 0.53 V. Our work offers a promising strategy to maintain the oxidation state of metal sites during the electrocatalysis.

On the Stability of Cu5 Catalysts in Air Using Multireference Perturbation Theory.

An ab initio study of the interaction of O2, the most abundant radical and oxidant species in the atmosphere, with a Cu5 cluster, a new generation atomic metal catalyst, is presented. The open-shell nature of the reactant species is properly accounted for by using the multireference perturbation theory, allowing the experimentally confirmed resistivity of Cu5 clusters toward oxidation to be investigated. Approximate reaction pathways for the transition from physisorption to chemisorption are calculated for the interaction of O2 with quasi-iso-energetic trapezoidal planar and trigonal bipyramidal structures. Within the multireference approach, the transition barrier for O2 activation can be interpreted as an avoided crossing between adiabatic states (neutral and ionic), which provides new insights into the charge-transfer process and gives better estimates for this hard to localize and therefore often neglected first intermediate state. For Cu5 arranged in a bipyramidal structure, the O–O bond cleavage is confirmed as the rate-determining step. However, for planar Cu5, the high energy barrier for O2 activation, related to a very pronounced avoided crossing when going from physisorption to chemisorption, determines the reactivity in this case.

Exploring the Catalytic Properties of Unsupported and TiO2-Supported Cu5 Clusters: CO2 Decomposition to CO and CO2 Photoactivation.

In this work, we explore the decomposition of CO2 on unsupported and TiO2-supported Cu5 clusters via computational modeling, using both finite cluster and periodic slab structures of the rutile TiO2(110) surface. While the energy needed for C=O bond breaking is already significantly reduced upon adsorption onto the unsupported metal catalyst (it drops from 7.8 to 1.3 eV), gas desorption before bond activation is still the inevitable outcome due to the remaining barrier height even at 0 K. However, when the Cu5 cluster itself is supported on TiO2, reactant and product adsorption is strongly enhanced, the barrier for bond breaking is further reduced, and a spontaneous decomposition of the molecule is predicted. This finding is linked to our previous work on charge-transfer processes in the Cu5–TiO2 system triggered by solar photons, since a combination of both phenomena at suitable temperatures would allow for a photoinduced activation of CO2 by sunlight.

Structure and 3/7-like Magnetization Plateau of Layered Y2Cu7(TeO3)6Cl6(OH)2 Containing Diamond Chains and Trimers.

We have synthesized a new spin-1/2 antiferromagnet, Y2Cu7(TeO3)6Cl6(OH)2, via a traditional hydrothermal method. This compound crystallizes in the triclinic crystal system with space group P1̅. The magnetic ions constitute a two-dimensional layered lattice with a novel topological structure in which the Cu4 clusters make up distorted diamond chains along the a axis and these chains are connected by the Cu3 trimers. The magnetic susceptibility and specific heat measurements show that the compound is antiferromagnetically ordered at TN = 4.1 K. This antiferromagnetic ordering is further supported by electron spin resonance (ESR) data. The magnetization curve presents a field-induced metamagnetic transition at 0.2 T, followed by a magnetization plateau within a wide magnetic field range from 7 T to at least 55 T, which corresponds to 3/7 of the saturated magnetization with g = 2.15 obtained from ESR. The possible mechanism for the magnetization plateau is discussed.

Interaction of CO, O, and CO2 with Cu cluster supported on Cu(1 1 1): a density functional theory study

We performed density functional theory (DFT) based calculations to investigate the interaction of CO2 and its dissociated species (CO and O) on Cu3 cluster supported on Cu(1 1 1) (Cu3/Cu(1 1 1)) surfaces. Similar investigations were conducted on Cu(1 1 1) for purpose of comparison. In general, adsorption of CO and O are stronger on the cluster region than on the terrace region of Cu3/Cu and on the flat Cu surface. CO2, on the other hand, is weakly adsorbed on the surfaces. With reference to CO2 dissociation on Cu(1 1 1), we found that the cluster lowers the activation barrier and provides a more stable adsorption of the dissociated species. The presence of co-adsorbed CO in the cluster, however, will increase the activation energy. The variation in the activation barrier with the amount of CO is influenced by the stability of the O atom from the dissociated CO2. We further found that the adsorption energy of O atom is a possible descriptor for CO2 dissociation on the cluster region. The Cu cluster supported on Cu surface could be a promising catalyst for CO2 related reactions based on the lower activation energy for CO2 dissociation on the system than on Cu(1 1 1).

Partially Fluorinated Cu(I) Triazolate Frameworks with High Hydrophobicity, Porosity, and Luminescence Sensitivity.

Solvothermal reactions of 3-methyl-5-trifluoromethyl-1,2,4-triazole (Hfmtz) with Cu(CH3COO)2 at 120 °C in the presence of Cl- generate two partially fluorinated coordination polymers: i.e., [Cu4Cl(fmtz)3] (1 or MAF-51) and [Cu7Cl(fmtz)6] (2 or MAF-52). Single-crystal X-ray diffraction revealed 1 to have a three-dimensional (3D) nonporous structure with pcu topology consisting of 6-connected Cu4(μ4-Cl) clusters and 2 to possess a highly porous (void ratio 48%) 3D bnn network consisting of 5-connected Cu5(μ5-Cl) clusters. Benefiting from the hydrophobic pendant groups, complete coordination of the ligand N atoms, and strong M-N coordination bonds, 1 and 2 possess high water stability (exposed to water for at least 1 year) and hydrophobicity (water contact angles of 141° and 148°, respectively). The N2 sorption isotherm of activated 2 gave Langmuir/BET surface areas of 1023/848 m2 g-1 and a pore volume of 0.365 cm3 g-1. Moreover, 2 can adsorb large amounts of benzene and methanol but barely adsorb water. Both 1 and 2 show phosphorescence of Cu(I) complexes, but only that of porous 2 is sensitive to O2, showing a linear Stern-Volmer response below 1 mbar with an ultrahigh Ksv value of 5234 bar-1 and ultralow limit of detection of 1.9 ppm.

Insight into the diffusion mechanism of Cu cluster over Cu(111) surface: Effect of syngas and H2S atmosphere on Cu diffusion

Understanding the diffusion mechanism of Cu cluster over Cu surface is one of the important issues to predict and improve the stability of Cu-based catalyst. The diffusion of Cu adatom, Cu2 and Cu3 cluster over Cu(111) surface under different atmospheres (vacuum, CO, H2 and H2S atmosphere) at different temperatures have been investigated using density functional theory calculations. The results suggest that CO accelerates Cu surface diffusion at different temperatures, while H2 atmosphere has little effect depending on the temperature. Further, under H2S atmosphere, the negative formation energy of Cu-S complexes indicate that Cu-S species are more facile to form on Cu(111) surface. The diffusivity of CuS complex increases significantly with the decreasing of temperature and the increasing of H2S concentration, which suggests that ppm H2S results in the fast sintering of Cu surface significantly. This is consistent with the experimental result.

Competitive Metal Coordination of Hexaaminotriphenylene on Cu(111) by Intrinsic Copper Versus Extrinsic Nickel Adatoms.

The interplay between the self-assembly and surface chemistry of 2,3,6,7,10,11-hexaaminotriphenylene (HATP) on Cu(111) was complementarily studied by high-resolution scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) under ultra-high vacuum conditions. To shed light on the competitive metal coordination, comparative experiments were carried out on pristine and nickel-covered Cu(111). Directly after room-temperature deposition of HATP onto pristine Cu(111), self-assembled aggregates were observed by STM, and XPS results indicated still protonated amino groups. Annealing up to 200 °C activated the progressive single deprotonation of all amino groups as indicated by chemical shifts of both the N 1s and C 1s core levels in the XP spectra. This enabled the formation of topologically diverse π-d conjugated coordination networks with intrinsic copper adatoms. The basic motif of these networks was a metal-organic trimer, in which three HATP molecules were coordinated by Cu3 clusters, as corroborated by the accompanying density functional theory (DFT) simulations. Additional deposition of more reactive nickel atoms resulted in both chemical and structural changes with deprotonation and formation of bis(diimino)-Ni bonded networks already at room temperature. Even though fused hexagonal metal-coordinated pores were observed, extended honeycomb networks remained elusive, as tentatively explained by the restricted reversibility of these metal-organic bonds.