Full Length ArticleUnveiling the critical role of p-d hybridization interaction in M13−nGan clusters on CO2 adsorption
Graphical abstract
Introduction
It has been demonstrated that sub-nanometre sized metal clusters consisting of limited number of atoms with unique physical and chemical properties [1] have improved catalytic performances [2], [3], [4], [5]. Experiments also showed that the sizes of metal catalysts can be tuned by the loading contents [3], [6], which means that compared with bulk catalysts, clusters with a few atoms can largely reduce the loading amounts and thus reduce the costs of industrial processes. In addition, the electronic and magnetic properties of sub-nanometre sized clusters are largely changed compared to their bulk analogues and larger nanoparticles [1]. Among sub-nanometre sized clusters, transition metal 13-atom clusters TM13 (TM = Fe [7], [8], Co [8], Ni [8], [9], Cu [10], [11], Pd [12], Ag [13], Pt [9], [14], [15], [16] and Au [17]) have been extensively investigated experimentally and theoretically because of their large surface areas. In particular, TM13 clusters can exhibit a high symmetric Ih structure even though some do not represent the lowest energy structures, including Au13[18], Pd13[19], and Pt13[20].
It is well known that CO2 capture [21], [22] and chemical and electrochemical processes for CO2 reduction to fuels [23], [24], [25], [26], [27] have brought widespread attention of researchers because of its continuous increasing concentration in the atmosphere. Among the reduction products, methanol (CH3OH) is an easily marketable and useful feedstock. Although the studies on effective catalysts aiming for CO2 reduction to CH3OH have emerged in numerous publications [28], [29], [30], [31], [32]; however, the existing catalysts still have a long way before commercial utilization due to the low process and cost-efficiency. Therefore, great efforts still have to be dedicated to the design of new catalysts.
A large number of experimental and theoretical studies proved that compared with monometallic catalysts, bimetallic catalysts have higher catalytic activities [12], [33]. For all the bimetallic combinations applicable for CO2 reduction to CH3OH, Ga contained transition metal catalysts would be promising choices due to their good catalytic effects. For example, the studies performed by Studt et al. [34] and Fiordaliso et al. [35] respectively showed that Ni-Ga and Pd-Ga bimetallic catalysts are more effective for CO2 reduction to methanol than traditional Cu/ZnO/Al2O3 catalysts. Ga plays an important role in the reaction. In Ga doped Cu/ZnO/ZrO2 catalysts [36], the presence of Ga increases surface Cu and metallic Cu0 and thus the active sites for CO2 hydrogenation to CH3OH due to the segregation of Cu to the surface. The same conclusion was obtained by Toyir et al. [37]. In addition, Collins et al. [38], [39] concluded that on a Pd/Ga2O3 catalyst, CO2 is stepwise hydrogenated to CH3OH on the surface sites of gallium oxide in the process of CO2 hydrogenation. In this reaction the role of Pd or Pd-Ga particles is to provide atomic hydrogen to the sites via spillover. Medina et al. [40] carried out a comparative study of Cu/SiO2 and Ga doped Cu/SiO2 in the hydrogenation of CO2 to CH3OH, and found that formate can adsorb on both Cu and Ga. This suggests that Ga may create new active sites for CH3OH formation and thus cause the increase of CH3OH formation rate.
With the development of computational approaches including DFT methods, more and more catalytic reactions could be investigated without spending much time and money. For example, theoretical study by Santiago-Rodríguez et al. [41] suggested that Ga doped Cu(1 1 1) surface may be among the promising catalysts for CO2 hydrogenation. In particular, using computational methods the structure parameters and the electronic properties can be well described, providing basis for predicting their catalytic effects. Previous studies [8], [42] showed that the activation of CO2 is one of the most important descriptors in the CO2 reduction process.
In this work, aiming to screening potential catalysts for CO2 conversion, we designed a series of Ga doped Ih symmetry 13-atom clusters (M13, Ga-centered M12Ga, M-centered M12Ga, Ga-centered M11Ga2 and M-centered M11Ga2 clusters (M = Fe, Co, Ni, Cu, Ru, Rh, Pd and Ag)) for the activation of CO2 by using DFT level computational studies. The stabilities of these clusters were initially investigated; and then the adsorption activities of CO2 were calculated. To further probe into the effect of Ga atoms on CO2 adsorption, the electronic properties of M13−nGan clusters were analyzed. The study can make advancement in understanding the effect of Ga in bimetallic catalysts towards the adsorption of CO2, and provide the possibility of designing highly efficient catalysts for CO2 conversion to CH3OH.
Section snippets
Computational methods
In this work, all the first principles calculations were performed by the Vienna ab initio simulation package (VASP) [43], [44], [45] code. The exchange-correlation function was described by the generalized gradient approximation (GGA) with the formula of Perdew-Burke-Ernzerhof (PBE)[46]. The projector augmented wave (PAW) [47], [48] pseudopotentials was used to treat the ion-electron interactions. A plane wave cut off energy of 400 eV was used to expand the electron function. The Brillouin
Structure stabilities of M13−nGan clusters
To evaluate the stabilities of M13−nGan clusters, the binding energy per atom () is calculated, the used equation is as follows:where is the total energy of M13−nGan cluster; and represent the chemical potentials of M and Ga atoms, respectively. The lower the is, the more stable the cluster is. The of M13−nGan clusters are listed in Table 1. As is shown for Fe, Co, Ni, Ru and Rh, the pure metal clusters have lower than their corresponding Ga
Conclusions
Comprehensive DFT calculations were preformed to study activation of CO2 by pure and Ga doped 3d and 4d 13-atom transition metal clusters (M13−nGan). We concluded that Ga doped Cu, Pd and Ag clusters are more stable than their analogues pure metal clusters. M-centered clusters are more stable than their corresponding Ga-centered clusters except Ga doped Pd and Ag clusters. For all the clusters, CO2 favors to adsorb at the M composed bridge or hollow sites on M13−nGan clusters except on Ag13−nGan
CRediT authorship contribution statement
Qingli Tang: Conceptualization, Data curation, Formal analysis, Funding acquisition, Project administration, Visualization, Writing - original draft, Writing - review & editing. Feng Shi: Investigation, Methodology, Visualization, Writing - review & editing. Kan Li: Investigation, Methodology, Visualization, Writing - review & editing. Wenchao Ji: Formal analysis, Software. Jerzy Leszczynski: Software, Validation, Writing - original draft, Writing - review & editing. Armistead G. Russell:
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
This work was funded by China Postdoctoral Science Foundation (2018M641999). Also, the authors also thank the USNSF-sponsored NCAR-Wyoming Supercomputing Center (NWSC), and National Science Foundation (NSF 1632899 and 1430001).
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2021, Surface ScienceCitation Excerpt :The exchange-correlation function was described by the generalized gradient approximation (GGA) with the formula of Perde-Burke-Ernzerh (PBE) [19]. The projector augmented wave (PAW) [20–23] is used to treat the ion-electron interactions [24]. We adopted the Bloch-corrected tetrahedral method to perform adsorption energy, band structure, and density of states (DOS).