Ab initio Molecular Dynamics Simulations on the Structures and Stabilities of Pd Clusters Encapsulated UiO-66 Materials†

doi:10.7503/cjcu20170078

Abstract

Abstract:

In order to understand the structuresand electronic properties of Pd_n@UiO-66(n=1—32) at atomic level, ab initio molecular dynamics simulations combined with density functional theory was used to search thermodynamically stable structures. And then the bonding characteristics between the metal cluster and the framework, binding energies, deformation energies of the framework, as well as the charge transfer between the metal cluster and the framework were analyzed. The modeling show that the Pd_n clusters were confined in the small cage, i.e., the tetrahedral cage of the UiO-66, and Pd₂₈@UiO-66 was found to be the thermodynamically most stable composite with the number of Pd atoms up to 32, which is a result of the interplay of the binding energy for the metal cluster and the deformation energy of the framework. The calculations indicate that the results can be successfully used to locate stable structures for metal nanoparticle(MNP) encapsulated UiO-66, which could be used as the models for further investigations of the reaction mechanism using MNP@UiO-66 as catalysts.

Key words: UiO-66, Pd metal cluster, Ab initio molecular dynamics, Density functional theory, Charge transfer

TrendMD:

CHEN Deli, YANG Pengyong, WU Shengnan, HE Sihui, WANG Fangfang. Ab initio Molecular Dynamics Simulations on the Structures and Stabilities of Pd Clusters Encapsulated UiO-66 Materials^†[J]. Chem. J. Chinese Universities, 2017, 38(7): 1210.

Figures/Tables 5

Fig.1 Octahedral(A) and tetrahedral(B) cages of UiO-66

Fig.2 Diffusion path for Pd4 cluster from octahedral to tetrahedral cage in UiO-66The four snapshots represent different simulation time of 0, 5.6, 10.4, and 40.0 ps, respectively. The red, white, gray, cyan, and green balls represent the oxygen, hydrogen, carbon, zirconium, and palladium atoms, respectively.

Fig.3 Computed charge density difference of Pd1@UiO-66(A) and Pd2@UiO-66(B) The yellow and blue colors represent the electron accumulation and depletion, respectively.

Table 1 Average binding energy, charge transfer, and deformation energy of Pdn@UiO-66

Cluster	n	E_Pd(n)/eV	Charge/\|e\|	E_d/eV
Pd₁	1	-1.99	0.21	0.25
Pd₄	4	-2.22	0.27	0.38
Pd₈	8	-2.59	0.69	1.41
Pd₁₂	12	-2.82	0.92	2.82
Pd₁₆	16	-2.91	1.21	3.02
Pd₂₀	20	-2.91	1.55	2.98
Pd₂₄	24	-2.92	1.78	3.75
Pd₂₈	28	-2.93	2.00	4.67
Pd₃₂	32	-2.90	1.89	6.86

Fig.4 Computed stable configurations for the Pdn@UiO-66(A) Pd2@UiO-66; (B) Pd8@UiO-66; (C) Pd28@UiO-66; (D) Pd32@UiO-66.

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