Theoretical approach to factors influencing the charge distribution of bimetallic Pd-Pt clusters.

Carlos Celis1, Jos L. Gmez1, Cristian Blanco-Tirado2*, Sonia A. Giraldo1, Aristbulo Centeno
1

Centro de Investigacin en Catlisis (CICAT), Escuela de Ing. Qumica. 2Grupo de Investigacin en Fisicoqumica Terica y Experimental (GIFTEX), Escuela de Qumica. Universidad Industrial de Santander, Cra 27 Calle 9, Bucaramanga, Colombia.

CORRESPONDING AUTHOR *E-mail: cris@ciencias.uis.edu.co

ABSTRACT: The influence of particle size and composition on the electronic charge distribution in bimetallic Pd-Pt nanoparticles was studied using Density Functional Theory (DFT) calculations. Clusters with particle size of 13 and 55 atoms with different PdxPty composition were selected. The charge distribution analysis was carried out using the Bader charge analysis, assuming neutral nanoparticles. External Pd atoms were found to be charged positively due to an electron transfer from Pt to Pd as in agreement with previous experimental and theoretical studies. These results indicate the presence of electron-deficient Pd + surface species which, according to XPS studies for reduced PdPt/Al2O3 catalysts, have been determined to be related to the selectivity to the hydrogenation route in hydrodesulfurization of dibenzothiophene.

KEYWORDS : Pd-Pt/Al2O3; Bader; ab initio; DFT. 1. INTRODUCTION Heterogeneous catalysts usually consisting of uniformly dispersed metal nanoparticles supported on highly porous materials such as metal oxides have drawn the attention to the study of their structure in 1

order to gain a better understanding of their properties. In contrast with monometallic nanoparticles, bimetallic nanoparticles show a significant improvement in specific properties, due to synergic effects1. A different and occasionally enhanced behavior, even if the second metal shows to have poor activity, has been observed due to the mutual influence of the different neighbor atoms involved in complex metal-metal and metal-support interactions2.

Supported bimetallic nanoparticles such as Pd-Pt/ -Al2O3 have been widely investigated as catalysts in hidrodesulfurization (HDS) of dibenzothiophenes (DBTs). In a previous experimental study, a significantly improved selectivity to hydrogenation (HYD) route was observed at a molar ratio Pd/(Pt+Pd) of 0.82. The XPS analysis of samples at different compositions showed an increment in the electro-deficient to metal species ratio (Pd +/Pd0) at the same composition of 0.8. Therefore, it has been suggested that these Pd + species are presumably responsible of such catalytic behavior2.

Several Pd-Pt bimetallic systems have been modeled using semi-empirical potentials3,4. Previous theoretical studies have clearly shown that Pd tends to preferably occupy the nanoparticle surface3-6. The same trend has been observed in experiments6,7. This has been denominated Pd surface segregation phenomena. However, currently there are very few quantum mechanical studies available about these systems. Monometallic platinum clusters has been studied using DFT7. The most energetically favored structures were found to be icosahedra over other crystalline structures such as cuboctahedra (fcc)7. The extent of the present work about the electronic behavior of Pd-Pt bimetallic nanoparticles, is limited by the number of atoms considered in our system due to the complexity of quantum mechanics calculations. It is the objective of the work described here to analyze the distribution of partial atomic charges in bimetallic Pd-Pt clusters and some of the factors influencing this phenomenon through quantum mechanics calculations based on the Density Functional Theory (DFT) and using the topological analysis of Bader for the charge distribution.

2. COMPUTATIONAL DETAILS Electronic structure calculations were performed using density functional theory (DFT) as implemented in the Gaussian 03 suite of programs. The UB3PW91 exchange correlation hybrid functional along with the LANL2DZ basis set, given that relativistic effects heavily influence Pt. Coreshell structures with icosahedral point group symmetry of 13 and 55 atoms were considered for different compositions. In all the cases the nanoparticles were neutral (qnet=0), septet spin multiplicity for 13atom and undectet for 55-atom clusters. The most energetically favored structures from the 166 possible homotops for 13-atom clusters at each composition were selected and for 55-atom clusters discrete compositions were considered Pt55, Pt49Pd6, Pt42Pd13, Pt12Pd43 Pd50Pt5 y Pd55 due to their elevated computational cost. Energy optimizations were not performed due to the fact that for 10 group transition metals (Ni, Pd, Pt) it has been observed that SCF calculations do not converge because of the molecular orbitals lying close to the HOMO undergo a quasy-degeneracy effect7,10. The support effect was not taken into account. In previous studies It has been observed that support affects the magnitude of charges but not their distribution and also that there is a slight tendency for the metallic clusters to become positively charged when the support is hydroxilated. A Bader Topological Analysis scheme was used to quantify the charge around each atom in our calculations.

3. RESULTUS/DISCUSSION 3.1. Charge distribution analysis for 13 atoms clusters. The figure 1 shows the chosen candidates of the 166 possible structures. It is found in figure 1 that the Pd atoms tend to occupy preferentially the cluster surface, this is the well known Pd segregation phenomenon2-4,6,7. Figure 1. Chosen candidates of the 166 possible structures for the 13 atoms clusters. The absolute energy in [a.u.] is listed below for each composition.

The Bader charge analysis was carried out after calculating the electron density of the chosen candidates. Figure 2 shows the Bader charge analysis for Pd. It is observed the presence of electrondeficient species of Pd +, due to the charge transfer phenomenon5,8, which is evident in figure 3 when the charge of the Pt atoms increase while the number of Pd atoms decrease. This phenomenon is explained by the analysis of the electronic structure (See Table 1). The charge migration occurs form the system with the greatest chemical potential to the lowest. Table 1. Electronic chemical potential = (EHOMO+ELUMO)/2 in [eV]. Clusters Pt13 Pd13
CALC EXP

-5.34 -4.58

-5.3 [12] -4.45 [13]

Figure 2. Deviation analysis of Pd charges. The numbers in parentheses indicate the amount of atoms which have the corresponding charge at the current composition.

Figure 2. Deviation analysis of Pd charges. The numbers in parentheses indicate the amount of atoms which have the corresponding charge at the current composition.

3.2. Charge distribution analysis for 55 atoms clusters. Table 2 shows the result of the charge analysis. Notice that the charge magnitude is slightly weaker than the calculated for 13 atoms clusters, but the behavior is similar, the charge migrates from Pt to Pd. It is observed a polarization effect of the shells of the cluster, that is clearly seen in the pure Pt and Pd arrangements but not well define in bimetallic clusters. The Palladium electron-deficient species are

presumed to be located on the edges of the icosahedron, due to a higher coordination number compared with the atoms located on the vertex, for Pd rich nanoparticles. Despite the effect of the polarization of the shells over the charge migration on the surface atoms, it is possible to observe the electron-deficient species (Pd +) behavior at this cluster size. Table 2. Charge average and deviation for 55 atoms clusters.
Position Center Inner Shell Edge Vertex Atom Pt Pd Pt Pd Pt Pd Pt Pd Pt55
-0.028 0.1250.011 -0,0160.021 -0,0910.018

Pt49Pd6
-0.048 0.1140.017 -0,0410.022 -0,0920.006 0.0730.010

Pt42Pd13
0.049 0.1040.010 -0.0700.007

Pt12Pd43
-0.026 0.0040.007

Pd50Pt5
-0.114 -0.0080.027 0.1040.015 -0.0060.016

Pd55
-0.042 0.0640.008 -0.0040.010

0.0130.005 0.0620.011 -0.0340.016

-0.0310.0155 -0.0400.007

CONCLUSION The Pd segregation phenomenon was observed and it occurs due to the difference of the interactions intensity between the two species. The trend found by the charge analysis on the Pd atoms, confirms the presence of Pd + electron-deficient species, as a result of a charge transfer process that originates in the electronic chemical potential gradient between the atoms in the nanoparticle.

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