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Influence of the metal − support and metal − metal interactions on Pd nucleation and NO adsorption in a Pd4/γ-Al2O3 (110D) model

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Abstract

The role played by the metal − support (MSI) and metal − metal (MMI) interactions on two important processes in controlling the catalyst performance — nucleation and molecular adsorption — has been investigated using density functional theory (DFT), by means of B3LYP functional, combined with localized molecular orbital energy decomposition analysis (LMOEDA), and natural bond orbital (NBO) calculations, with aid of a Pd4/γ-alumina (110D) model (Pd4/Al13O23H7). Our results indicate the occurrence of an electronic metal − support interaction (EMSI) which induces a most intense charge transfer in the Pd4 → γ-alumina backdonation direction, most expressive in Pd → Al, promoting an electronic redistribution within the units and attenuating the MMI. Nevertheless, the MSI/MMI synergistic effect seems to favor slightly the nucleation of a fifth palladium atom, leading to a distorted square pyramidal arrangement for Pd5. The LMOEDA analysis points to a mostly covalent character in the Pd − Al bonds, whereas the Pd − O bonds are mainly electrostatic in nature. The palladium atoms deposited on oxygen anions are the acid centers, where both NO molecule and an additional palladium atom anchor more strongly. In addition, the MSI/MMI effect, through the electronic and geometric contributions, drives the adsorption of the NO molecule to the mode which most favors the Pd → NO (4dz2 → 2π*) backdonation (bridge mode).

Graphical Abstract

MSI and MMI effects on the nature of the Pd − O (electrostatic) and Pd − Al (covalent) bonds, charge transfer into Pd4/γ-Al2O3 (110D) interface (back donation) and preferential site for adsorption of a single NO molecule and an additional Pd atom (Pd − O).

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Data availability

The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

Notes

  1. This value is in the same order of magnitude as the HOMO − LUMO gap for NO/Pdn clusters (n = 1 − 6) (1.6 − 2.3 eV) [127].

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Acknowledgements

The authors are grateful for the financial support given by the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq − grant 478302/2012-6) and Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro (FAPERJ − grant E-26/201.302/2014 and E-26/111.708/2013). CNPq research grants for J. W. de M. Carneiro are also acknowledged. This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior—Brasil (CAPES)—Finance Code 001 (grant 88882.450884/2019-01) (L. M. P.).

Funding

This work was financially supported by the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq − grant 478302/2012–6), Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro (FAPERJ − grant E-26/201.302/2014 and E-26/111.708/2013) and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior—Brasil (CAPES − Finance Code 001 − grant 88882.450884/2019–01) (L. M. P.).

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  1. ªDepartamento de Química Geral E Inorgânica, Instituto de Química, Universidade Do Estado Do Rio de Janeiro, Campus Maracanã, Rio de Janeiro, RJ, 20550-900, Brazil

    Letícia M. Prates & Maurício T. De M. Cruz

  2. Departamento de Química Inorgânica, Instituto de Química, Universidade Federal Fluminense, Campus Do Valonguinho, Niterói, RJ, 24020-141, Brazil

    José W. De M. Carneiro

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  1. Letícia M. Prates
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  3. Maurício T. De M. Cruz
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Correspondence to Maurício T. De M. Cruz.

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Prates, L.M., De M. Carneiro, J.W. & De M. Cruz, M.T. Influence of the metal − support and metal − metal interactions on Pd nucleation and NO adsorption in a Pd4/γ-Al2O3 (110D) model. J Mol Model 28, 394 (2022). https://doi.org/10.1007/s00894-022-05374-7

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