Theoretical study of CO adsorption on FexCuy(x+y=3) clusters and reactive activity of their carbonyl complexes

doi:10.21203/rs.3.rs-1784756/v1

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Theoretical study of CO adsorption on FexCuy(x+y=3) clusters and reactive activity of their carbonyl complexes

https://doi.org/10.21203/rs.3.rs-1784756/v1

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In this paper, the adsorption of CO on Fe_xCu_y (x + y = 3) clusters were studied by BPW91 method, all conceivable geometries and electronic states of carbonyl complexes were explored. The results show that bimetallic clusters tend to have higher stepwise CO adsorption energy than corresponding pure clusters, and the adsorption capacity of FeCu₂(CO)₃ with CO is substantially larger than that of other carbonyl complexes. Moreover, the frontier molecular orbital theory was used to analyze the effect of the second element in the ligand reactions, which also confirmed that the reactions of CO with bimetallic clusters are easier than that of pure cluster systems. Finally, the energy gaps of HOMO and LUMO were use to explore the reactive activity of carbonyl complexes, it was found that the bimetallic clusters are lower than that of the Fe₃ or Cu₃, and the Fe₂Cu(CO)₁ has lower energy gap than that of other carbonyl complexes. This suggests that it may be possible to tune bimetallic cluster to get higher activity carbonyl complexes in the reactions.

FexCuy (x+y=3)

Carbonyl complexes

Density functional theory

Energy gap

In recent decades, carbonyls and their derivatives have received particular attention due to they play a central role in modern organometallics chemistry [1]. Extensive experimental and theoretical research has been conducted on their synthesis, characterization, and applications, especially for the interaction of metals with metals in these compounds [2–8]. The better known iron and copper carbonyls including mononuclear Fe(CO)₅ and Cu(CO)₃, dinuclear Fe₂(CO)₉ and Cu₂(CO)_x (x = 1–6), trinuclear Fe₃(CO)_n (n = 12, 11, 10, 9), Cu₃(CO)₇⁺, Cu₃(CO)₈⁺ and Cu₃(CO)₉⁺, tetranuclear Cu₄(CO)₈⁺ [9–13] and so on.

Practically carbonyl complexes consist of not only homonuclear carbonyl but also included heteronuclear carbonyl such as CuNi(CO)_n^0/1−(n = 1–4), MNi(CO)₇⁻ (M = V, Nb, Ta), CuFe(CO)_n⁻ (n = 4–7) and PbFe(CO)₄⁻ [14–17]. The most unsaturated neutral species apparently have been studied focus on the one carbon monoxide on clusters [18–20]. In a subsequent development, it was shown that the other unsaturated neutral species have special function in synthetic chemistry, just as Fe(CO)₄, is isolobal with CH₃⁺, which has been used to study both the structure and the bonding in related compounds [21]. Different ligands have been investigated for their interactions with the Fe(CO)₄ fragment, and found that the structures of metal-π ligand complexes are remarkable, lending an almost inventive aspect to the organometallic chemistry [22–26].

The purpose of this work is to investigate the adsorption of CO with Fe_xCu_y (x + y = 3) clusters, and compare the reactive activity of carbonyl complexes, using quantum chemistry methods. Therefore, analysis of the structural stability and electronic properties of carbonyl complexes are needed, and understand of the molecular orbital information of species are necessary.

Energies and geometries of the reaction intermediates were calculated using the density functional theory (DFT) method. Exchange-correlation functional consists of the combination of Becke’s exchange and Perdew-Wang’s correlation functions, which is commonly known as BPW91, within the generalized gradient approximation (GGA) [27–29]. For the present calculations, this functional was combined with the standard 6-311 + G(2d) basis set level[30, 31]. Vibrational frequency calculations were used to characterize all stationary points as either minima (the number of imaginary frequencies NIMAG = 0). All of the DFT computations were carried out with the GAUSSIAN 09 program [32]. The adsorption energies were evaluated from the calculated energies of cluster with adsorbate, E(total), E(Fe_xCu_y) and E(CO) are the energies of Fe_xCu_y(CO)_n cluster, bare Fe_xCu_y cluster and CO molecule, respectively, and using the following equation,

E_ad = E(total) - E(Fe_xCu_y) -nE(CO)

For the metal carbonyl species, only the most stable ones are listed, other optimized geometries and feasible spin multiplicities of the reaction can be obtained from the Supporting Information (Table 1 and Fig S1-S4). Three typical adsorption sites are considered, including top sites, bridge sites and a facet site. The calculated adsorption energies are in agreement with previous experiment and calculations [33, 34].

Table 1

Vibrational frequency, total energy E_T and stepwise CO adsorption energy E_ad (kJ/mol) for the Fe₃(CO)_n (n = 0–12).
Species	NIMAG (cm^− 1)	E_T (hartree)	E_ad (kJ/mol)	Species	NIMAG (cm^− 1)	E_T (hartree)	E_ad (kJ/mol)
¹¹Fe₃	73.94	-3791.41	-	⁵Fe₃(CO)₇	12.79	-4585.20	-132.61
⁹Fe₃(CO)₁	46.02	-3904.81	-168.79	³Fe₃(CO)₈	30.41	-4698.60	-144.87
⁹Fe₃(CO)₂	18.97	-4018.22	-187.03	¹Fe₃(CO)₉	22.92	-4811.99	-136.06
⁹Fe₃(CO)₃	20.79	-4131.62	-166.55	¹Fe₃(CO)₁₀	20.29	-4925.38	-152.60
⁷Fe₃ (CO)₄	29.24	-4245.02	-167.80	¹Fe₃(CO)₁₁	7.79	-5038.75	-66.52
⁷Fe₃ (CO)₅	16.39	-4358.42	-152.62	¹Fe₃(CO)₁₂	32.44	-5152.14	-139.11
⁵Fe₃(CO)₆	31.15	-4471.81	-140.83	CO	2126.25	-113.34	-

3.1 Fe₃(CO)_n (n = 1–12)

The geometrical parameters of the Fe₃(CO)_n (n = 1–12) cluster systems are shown in Fig. 1. Vibrational frequency, total energies E_T, and stepwise CO adsorption energy for the Fe₃ systems are collected in Table 1. According to our study and previous experimental study, the Fe₃ electronic ground state is found to be ¹¹A'. Table 1 indicates the following, all CO adsorption steps are exothermic, from n = 1–12 for Fe₁₃, the most CO adsorption energy (-187.63 kJ/mol) is found for n = 2 in Fe₃ system. According to research, the most stable geometries tend to occur on one Fe atom to form Fe₂-Fe(CO)₄ structure, and then on the second Fe atom until it is saturated, last, up to the last structure Fe₃(CO)₁₂. According to the calculated results, the bond length of CO molecule is 1.139 Å. It is clear from Fig. 1, after CO molecules adsorbed on these Fe₃ clusters, the elongation of C-O are extended with the range from 1.3–4.5%, it can think that CO has been activated. The most adsorption energy structure of Fe₃ carbonyl species is ⁹Fe₃(CO)₂ with C_s symmetry, with the most stepwise CO adsorption energy by 187.03 kJ/mol.

3.2 Fe₂Cu (CO)_n (n = 1–11)

According to the theoretical calculation, the geometries and parameters of Fe₂Cu (CO)_n (n = 1–11) are listed in the Fig. 2 and Table 2. On the basis of the theoretical studies, the ground state of Fe₂Cu is ⁸A', which is slower than ⁶A' and ¹⁰A'' by 30.6 and 46.5 kJ/mol, respectively. We first study CO adsorption behavior on both Fe and Cu tops. In contrast, the corresponding adsorption energy value on one Fe side of Fe₂Cu is 188.02 kJ/mol, and the corresponding adsorption energy value on Cu is 121.99 kJ/mol, which is slower than that on Fe atom by 66.03 kJ/mol. The most stable structure of Fe₂Cu(CO)_n (n = 1–11) is found that the CO coordination tend to occur on one Fe atom, later, on the next Fe atom to constitute Fe(CO)₁₋₃-Cu-Fe₂(CO)₄, last, up to the saturated CO coordination structure. In the carbonyl species, the ⁶Fe₂Cu(CO)₁ with the most E_ads by 188.02 kJ/mol, in which, Fe-CO and C-O distances are 1.768 and 1.178 Å, respectively. In ²Fe₂Cu(CO)₁₁ complex, the energy of a structure with top site adsorption of CO (doublet state with C_2v symmetry) is only 6.71 kJ/mol.

Table 2

Vibrational frequency, total energy E_T and stepwise CO adsorption energy E_ad (kJ/mol) for the Fe₂Cu (CO)_n (n = 0–11).
Species	NIMAG (cm^− 1)	E_T (hartree)	E_ad (kJ/mol)	Species	NIMAG (cm^− 1)	E_T (hartree)	E_ad (kJ/mol)
⁸Fe₂Cu	73.25	-4168.25	-	²Fe₂Cu(CO)₆	27.45	-4848.66	-146.82
⁶Fe₂Cu(CO)₁	46.49	-4281.66	-188.02	²Fe₂Cu(CO)₇	7.77	-4962.05	-120.35
⁶Fe₂Cu(CO)₂	37.55	-4395.06	-163.76	²Fe₂Cu(CO)₈	19.98	-5075.43	-128.27
⁶Fe₂Cu(CO)₃	31.10	-4508.46	-161.69	²Fe₂Cu(CO)₉	20.30	-5188.81	-114.97
⁴Fe₂Cu(CO)₄	33.98	-4621.87	-185.43	²Fe₂Cu(CO)₁₀	17.99	-5302.17	-41.33
⁴Fe₂Cu(CO)₅	22.35	-4735.27	-155.02	²Fe₂Cu(CO)₁₁	15.38	-5415.51	-6.71

3.3 FeCu₂(CO)_n (n = 1–10)

Figure 3 shows the most stable geometries of FeCu₂(CO)_n (n = 1–10). There are several possible ways to evaluate the feature of the FeCu₂(CO)_n (n = 1–10) structures predicted in Table 3. The BPW91 calculations showed that the FeCu₂ ground state is the quintet state, which is slower than the triplet and septet states are 20.74 and 61.99 kJ/mol respectively. Analysis of the entire geometries of FeCu₂(CO)_n (n = 1–4) shows that the isomer with CO adsorbed on Fe atom have more stable compared to those with CO combine with Cu atoms. For the FeCu₂(CO)₆, it is found that the CO coordination prefer to take place on different Cu atoms, which has lower energy than that of CO coordination on only one Cu atom. In the carbonyl species, the ¹FeCu₂(CO)₄ has the most E_ads by 190.58 kJ/mol.

Table 3

Vibrational frequency, total energy E_T and stepwise CO adsorption energy E_ad (kJ/mol) for the FeCu₂(CO)_n (n = 1–10).
Species	NIMAG (cm^− 1)	E_T (hartree)	E_ad (kJ/mol)	Species	NIMAG (cm^− 1)	E_T (hartree)	E_ad (kJ/mol)
⁵FeCu₂	110.47	-4545.09	-	¹FeCu₂(CO)₆	18.47	-5225.50	-118.18
³FeCu₂(CO)₁	49.61	-4658.51	-189.67	¹FeCu₂(CO)₇	15.42	-5338.85	-34.52
³FeCu₂(CO)₂	31.99	-4771.91	-170.23	¹FeCu₂(CO)₈	14.07	-5452.20	-44.43
¹FeCu₂(CO)₃	33.93	-4885.32	-181.31	¹FeCu₂(CO)₉	3.01	-5565.55	-30.41
¹FeCu₂(CO)₄	14.87	-4998.73	-190.58	¹FeCu₂(CO)₁₀	13.92	-5678.90	-34.58
¹FeCu₂(CO)₅	18.27	-5112.11	-122.57

3.4 Cu₃(CO)_n (n = 1–8)

On the basis of calculation, the Cu₃ ground state is the doublet state, which is lower than the quartet state 166.96 kJ/mol in energy. For Cu₃(CO)_n (n = 1–8), most stable structures and the corresponding geometrical parameters are shown in Fig. 4 and Table 4. In the beginning of the chemisorption process, we study CO adsorption behavior on difference sites of Cu₃ cluster. For the Cu₃CO, the lowest energy state of the complex is a doublet with C_2v symmetry, in which CO is adsorbed on the top adsorption site. In the Cu₃(CO)₂ complex, a CO molecule is adsorbed on the one of the other two Cu atoms of Cu₂-CuCO, the lowest energy state of the complex is a doublet with C_2v symmetry. For the Cu₃(CO)₅, the stepwise CO adsorption tend to adsorbed on the top site of last Cu atom of Cu₃(CO)₄. In the Cu₃ carbonyl species, the ²Cu₃(CO)₁ has the most E_ads by 138.93 kJ/mol.

Table 4

Vibrational frequency, total energy E_T and stepwise CO adsorption energy E_ad (kJ/mol) for the Cu₃(CO)_n (n = 1–8).
Species	NIMAG (cm^− 1)	E_T (hartree)	E_ad (kJ/mol)	Species	NIMAG (cm^− 1)	E_T (hartree)	E_ad (kJ/mol)
²Cu₃	105.60	-4921.96	-	²Cu₃ (CO)₅	18.21	-5488.83	-68.03
²Cu₃(CO)₁	38.18	-5035.35	-138.93	²Cu₃(CO)₆	13.00	-5602.19	-56.90
²Cu₃(CO)₂	30.30	-5148.72	-100.32	²Cu₃(CO)₇	6.22	-5715.55	-64.98
²Cu₃(CO)₃	15.38	-5262.09	-78.72	²Cu₃(CO)₈	18.19	-5828.90	-33.72
²Cu₃ (CO)₄	19.54	-5375.46	-91.61

3.4 Adsorption energy and molecular orbital properties

The change curve of CO adsorption energy on Fe_xCu_y (x + y = 3) are collected in Fig. 5. Overall, the Cu₃ system has lower CO adsorption capacity on ground state, while the Fe₃ system has a relatively high value of stepwise CO adsorption energy. For the bimetallic clusters, it has been found that the stepwise CO adsorption energy of Fe₂Cu is higher than that on Fe₃ and Cu₃ with n = 1, 4, 5 and 6, that the stepwise CO adsorption energy of FeCu₂ is higher than that on Fe₃ and Cu₃ with n = 1, 3 and 4, respectively. For bimetallic systems with n ≥ 7, the stepwise CO adsorption energy are between Fe₃ and Cu₃. The largest stepwise CO coordination energy (-190.58 kJ· mol^− 1) is found for FeCu₂(CO)₄.

Frontier molecular orbitals of Fe_xCu_y (x + y = 3) cluster systems are collected in Fig. 6 and Supporting Information (Tables S2), where HOMO is the highest occupied molecular orbital of Fe_xCu_y (x + y = 3) carbonyl complexes, ΔE is the energy level difference between the HOMO of carbonyl complexes and the LUMO of CO. In the case of the CO adsorbs on the Fe_xCu_y (x + y = 3) carbonyl complexes, CO molecule obtains electrons from the HOMO of clusters. Based on the study, the molecular reaction can happen only if the ΔE is less than 0.2205 a.u. (579 kJ/mol) [35]. The LUMO energy of free CO is -0.3855 a.u., while the HOMO energies of Fe_xCu_y (x + y = 3) carbonyl complexes are all less than − 0.1650 a.u., it means the transfer of electrons from the HOMO of Fe_xCu_y (x + y = 3) carbonyl complexes to the LUMO of CO is possible. In brief, the smaller of the ΔE is, the easier of the electron transfer to CO would be, also, the reactions of CO with bimetallic carbonyl complexes are easier than pure clusters system, except Fe₃ cluster with first CO molecular.

Frontier molecular orbital theory predicts that the smaller the energy gap (Eg) between the HOMO and LUMO of reactant involved is, the more reactive activity of the molecular would be [36]. The Eg of Fe_xCu_y (x + y = 3) carbonyl complexes are showed in Fig. 7 and Supporting Information (Tables S2). Collectively, we can obtain that bimetallic carbonyl complexes have lower value of Eg than that of corresponding monometallic carbonyl complexes, except Fe₂Cu and FeCu₂(CO)₁₀. This study also gets a good relation of contacting the values of the adsorption energy with Eg of carbonyl complexes, observing in this case that the smaller Eg is, on the contrary, the greater adsorption energy is. The lowest Eg of all carbonyl species is ²Fe₂Cu(CO)₈ with the value of 2.63 kJ/mol.

The ligand addition reactions of the CO adsorption over the clusters of Fe_xCu_y (x + y = 3) have been studied by BPW91 method. For monometallic clusters, all CO coordination steps are exothermic, the largest CO coordination energy (-187.03 and − 138.93 kJ/mol) are found for n = 1 in Fe₃ and Cu₃ system. For bimetallic clusters, the largest CO coordination energies are found − 188.02 and − 190.58 kJ/mol for Fe₂Cu(CO)₁ and FeCu₂(CO)₄, respectively. The most stable molecules are approaching CO coordinate with Fe atoms, then, on the Cu atoms. Moreover, the FMOs were used to analyze the Eg between the HOMO and LUMO of the Fe_xCu_y (x + y = 3) carbonyl complexes, and found that the bimetallic carbonyl complexes have smaller Eg than corresponding pure metallic. Our findings show that the bimetallic clusters can have higher adsorption energy, and the decrease of Eg implied that carbonyl complexes might show the higher activity than the pure clusters.

Acknowledgement

This study was supported by the Scientific Research Foundation of Guizhou Minzu University (GZMUZK[2021]YB11) and (GZMUZK[2019]YB31), Guizhou Provincial Science and Technology Projects ([2019]1158), Guizhou Provincial Science and Technology Projects for Youth Talents (KY[2018]149), Higher Education Innovation Foundation of Gansu Province (2021A-254).

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Theoretical study of CO adsorption on FexCuy(x+y=3) clusters and reactive activity of their carbonyl complexes

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