DFT calculations on selectivity enhancement by Br addition on Pd catalysts in the direct synthesis of hydrogen peroxide

Min Woo Lee; Deok Yeon Jo; Geun Ho Han; Kwan Young Lee

doi:10.1016/j.cattod.2021.09.030

DFT calculations on selectivity enhancement by Br addition on Pd catalysts in the direct synthesis of hydrogen peroxide

Min Woo Lee, Deok Yeon Jo, Geun Ho Han, Kwan Young Lee

Research output: Contribution to journal › Article › peer-review

9 Citations (Scopus)

Abstract

Although the direct synthesis of hydrogen peroxide (DSHP) is a potential alternative to the current anthraquinone auto-oxidation process, the low H₂O₂ selectivity of the former presents a major challenge. Previous studies have reported that the addition of halides improves the H₂O₂ selectivity of Pd-based catalysts. In this study, the H₂O₂ selectivity of Pd/SiO₂ and PdBrx/SiO₂ catalysts was observed to increase with the Br content. Furthermore, density functional theory (DFT) calculations on clean and Br-adsorbed Pd (1 1 1), (1 0 0), and (2 1 1) surfaces confirmed that the activation energies of the side reactions on the Pd (1 1 1) surface increased slightly after Br adsorption, whereas those of the main reactions were less affected. The repulsion between Br and O on the Pd (1 0 0) surface increased the O₂ dissociation barrier by changing reaction configurations. Considering that the Pd (1 0 0) surface adsorbed O₂ more strongly than did the Pd (1 1 1) surface, inhibiting O₂ dissociation on the Pd (1 0 0) surface improved the H₂O₂ selectivity of PdBrx/SiO₂ catalysts. On the Pd (2 1 1) surface, Br blocked an edge site and induced the reactions on the Pd (1 1 1) surface. In conclusion, DFT calculation confirmed that the repulsion and site blocking by adsorbed Br improved the H₂O₂ selectivity of PdBrx/SiO₂ catalysts.

Original language	English
Pages (from-to)	232-239
Number of pages	8
Journal	Catalysis Today
Volume	397-399
DOIs	https://doi.org/10.1016/j.cattod.2021.09.030
Publication status	Published - 2022 Aug 1

Bibliographical note

Funding Information:
This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIP) ( NRF-2016M3D1A1021143 ).

Funding Information:
This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIP) (NRF-2016M3D1A1021143). This work was supported by the National Supercomputing Center with supercomputing resources including technical support (KSC-2020-CRE-0215).

Funding Information:
This work was supported by the National Supercomputing Center with supercomputing resources including technical support ( KSC-2020-CRE-0215 ).

Publisher Copyright:
© 2021 Elsevier B.V.

Keywords

Density functional theory
Halide addition
Hydrogen peroxide
Palladium
Surface modification

ASJC Scopus subject areas

Catalysis
General Chemistry

Access to Document

10.1016/j.cattod.2021.09.030

Cite this

@article{d375fdbcfcb141159c0285eb0d1f17de,

title = "DFT calculations on selectivity enhancement by Br addition on Pd catalysts in the direct synthesis of hydrogen peroxide",

abstract = "Although the direct synthesis of hydrogen peroxide (DSHP) is a potential alternative to the current anthraquinone auto-oxidation process, the low H2O2 selectivity of the former presents a major challenge. Previous studies have reported that the addition of halides improves the H2O2 selectivity of Pd-based catalysts. In this study, the H2O2 selectivity of Pd/SiO2 and PdBrx/SiO2 catalysts was observed to increase with the Br content. Furthermore, density functional theory (DFT) calculations on clean and Br-adsorbed Pd (1 1 1), (1 0 0), and (2 1 1) surfaces confirmed that the activation energies of the side reactions on the Pd (1 1 1) surface increased slightly after Br adsorption, whereas those of the main reactions were less affected. The repulsion between Br and O on the Pd (1 0 0) surface increased the O2 dissociation barrier by changing reaction configurations. Considering that the Pd (1 0 0) surface adsorbed O2 more strongly than did the Pd (1 1 1) surface, inhibiting O2 dissociation on the Pd (1 0 0) surface improved the H2O2 selectivity of PdBrx/SiO2 catalysts. On the Pd (2 1 1) surface, Br blocked an edge site and induced the reactions on the Pd (1 1 1) surface. In conclusion, DFT calculation confirmed that the repulsion and site blocking by adsorbed Br improved the H2O2 selectivity of PdBrx/SiO2 catalysts.",

keywords = "Density functional theory, Halide addition, Hydrogen peroxide, Palladium, Surface modification",

author = "Lee, {Min Woo} and Jo, {Deok Yeon} and Han, {Geun Ho} and Lee, {Kwan Young}",

note = "Funding Information: This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIP) ( NRF-2016M3D1A1021143 ). Funding Information: This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIP) (NRF-2016M3D1A1021143). This work was supported by the National Supercomputing Center with supercomputing resources including technical support (KSC-2020-CRE-0215). Funding Information: This work was supported by the National Supercomputing Center with supercomputing resources including technical support ( KSC-2020-CRE-0215 ). Publisher Copyright: {\textcopyright} 2021 Elsevier B.V.",

year = "2022",

month = aug,

day = "1",

doi = "10.1016/j.cattod.2021.09.030",

language = "English",

volume = "397-399",

pages = "232--239",

journal = "Catalysis Today",

issn = "0920-5861",

publisher = "Elsevier B.V.",

}

TY - JOUR

T1 - DFT calculations on selectivity enhancement by Br addition on Pd catalysts in the direct synthesis of hydrogen peroxide

AU - Lee, Min Woo

AU - Jo, Deok Yeon

AU - Han, Geun Ho

AU - Lee, Kwan Young

N1 - Funding Information: This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIP) ( NRF-2016M3D1A1021143 ). Funding Information: This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIP) (NRF-2016M3D1A1021143). This work was supported by the National Supercomputing Center with supercomputing resources including technical support (KSC-2020-CRE-0215). Funding Information: This work was supported by the National Supercomputing Center with supercomputing resources including technical support ( KSC-2020-CRE-0215 ). Publisher Copyright: © 2021 Elsevier B.V.

PY - 2022/8/1

Y1 - 2022/8/1

N2 - Although the direct synthesis of hydrogen peroxide (DSHP) is a potential alternative to the current anthraquinone auto-oxidation process, the low H2O2 selectivity of the former presents a major challenge. Previous studies have reported that the addition of halides improves the H2O2 selectivity of Pd-based catalysts. In this study, the H2O2 selectivity of Pd/SiO2 and PdBrx/SiO2 catalysts was observed to increase with the Br content. Furthermore, density functional theory (DFT) calculations on clean and Br-adsorbed Pd (1 1 1), (1 0 0), and (2 1 1) surfaces confirmed that the activation energies of the side reactions on the Pd (1 1 1) surface increased slightly after Br adsorption, whereas those of the main reactions were less affected. The repulsion between Br and O on the Pd (1 0 0) surface increased the O2 dissociation barrier by changing reaction configurations. Considering that the Pd (1 0 0) surface adsorbed O2 more strongly than did the Pd (1 1 1) surface, inhibiting O2 dissociation on the Pd (1 0 0) surface improved the H2O2 selectivity of PdBrx/SiO2 catalysts. On the Pd (2 1 1) surface, Br blocked an edge site and induced the reactions on the Pd (1 1 1) surface. In conclusion, DFT calculation confirmed that the repulsion and site blocking by adsorbed Br improved the H2O2 selectivity of PdBrx/SiO2 catalysts.

AB - Although the direct synthesis of hydrogen peroxide (DSHP) is a potential alternative to the current anthraquinone auto-oxidation process, the low H2O2 selectivity of the former presents a major challenge. Previous studies have reported that the addition of halides improves the H2O2 selectivity of Pd-based catalysts. In this study, the H2O2 selectivity of Pd/SiO2 and PdBrx/SiO2 catalysts was observed to increase with the Br content. Furthermore, density functional theory (DFT) calculations on clean and Br-adsorbed Pd (1 1 1), (1 0 0), and (2 1 1) surfaces confirmed that the activation energies of the side reactions on the Pd (1 1 1) surface increased slightly after Br adsorption, whereas those of the main reactions were less affected. The repulsion between Br and O on the Pd (1 0 0) surface increased the O2 dissociation barrier by changing reaction configurations. Considering that the Pd (1 0 0) surface adsorbed O2 more strongly than did the Pd (1 1 1) surface, inhibiting O2 dissociation on the Pd (1 0 0) surface improved the H2O2 selectivity of PdBrx/SiO2 catalysts. On the Pd (2 1 1) surface, Br blocked an edge site and induced the reactions on the Pd (1 1 1) surface. In conclusion, DFT calculation confirmed that the repulsion and site blocking by adsorbed Br improved the H2O2 selectivity of PdBrx/SiO2 catalysts.

KW - Density functional theory

KW - Halide addition

KW - Hydrogen peroxide

KW - Palladium

KW - Surface modification

UR - http://www.scopus.com/inward/record.url?scp=85116482984&partnerID=8YFLogxK

U2 - 10.1016/j.cattod.2021.09.030

DO - 10.1016/j.cattod.2021.09.030

M3 - Article

AN - SCOPUS:85116482984

SN - 0920-5861

VL - 397-399

SP - 232

EP - 239

JO - Catalysis Today

JF - Catalysis Today

ER -

DFT calculations on selectivity enhancement by Br addition on Pd catalysts in the direct synthesis of hydrogen peroxide

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this