Single-atom Pt promotion of industrial Co-Mo-S catalysts for ultra-deep hydrodesulfurization

Christian Frederik Weise; Hanne Falsig; Poul Georg Moses; Stig Helveg; Michael Brorson; Lars Pilsgaard Hansen

doi:10.1016/j.jcat.2021.03.008

Single-atom Pt promotion of industrial Co-Mo-S catalysts for ultra-deep hydrodesulfurization

Christian Frederik Weise, Hanne Falsig, Poul Georg Moses, Stig Helveg, Michael Brorson, Lars Pilsgaard Hansen^*

^*Corresponding author for this work

Haldor Topsoe AS

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Abstract

We introduce a tertiary transition metal sulfide nanostructure, Pt-Co-Mo-S, for catalytic hydrodesulfurization (HDS) of sulfur-containing molecules in crude oil distillates with the aim to produce ultra-low sulfur transport fuels. The addition of ppm-levels of Pt to a standard industrial Co-Mo-S catalyst boosts the HDS activity by up to 46%. The promotional effect is examined by combining atomic-resolution Scanning Transmission Electron Microscopy (STEM), Energy Dispersive X-ray Spectroscopy (EDX), X-ray Absorption Near Edge Spectroscopy (XANES) and Density Functional Theory (DFT). It is shown that the Pt-Co-Mo-S catalyst contains predominantly single-layer MoS₂ nanocrystals with Co atoms fully covering the S-edge terminations and Pt atoms uniquely attached to corner and edge sites in a platinum(IV) sulfide-like structural motif. Platinum is suggested to reduce the sulfur binding energy and increase the abundance of coordinately undersaturated sites (CUS) and not necessarily changing the reactivity towards 4,6-DMDBT molecules, although more elaborate studies are needed to address this in detail.

Original language	English
Journal	Journal of Catalysis
Volume	403
Pages (from-to)	74-86
ISSN	0021-9517
DOIs	https://doi.org/10.1016/j.jcat.2021.03.008
Publication status	Published - 2021

Bibliographical note

Funding Information:
The authors gratefully acknowledge Christoffer Tyrsted for help with XANES measurements. We acknowledge use of facilities at NMI Natural and Medical Sciences Institute at the University of Tübingen (Germany), Center for Nanoanalysis, for part of this work, and Clementine Warres for kind support. This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors. SH acknowledges support from Danish National Research Foundation Center for Visualizing Catalytic Processes (VISION) (DNRF146).

Funding Information:
The authors gratefully acknowledge Christoffer Tyrsted for help with XANES measurements. We acknowledge use of facilities at NMI Natural and Medical Sciences Institute at the University of T?bingen (Germany), Center for Nanoanalysis, for part of this work, and Clementine Warres for kind support. This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors. SH acknowledges support from Danish National Research Foundation Center for Visualizing Catalytic Processes (VISION) (DNRF146).

Publisher Copyright:
© 2021 The Authors

Keywords

Active sites
Co-Mo-S
Hydrotreating
Promoters
Pt
Ultra-low sulfur diesel

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title = "Single-atom Pt promotion of industrial Co-Mo-S catalysts for ultra-deep hydrodesulfurization",

abstract = "We introduce a tertiary transition metal sulfide nanostructure, Pt-Co-Mo-S, for catalytic hydrodesulfurization (HDS) of sulfur-containing molecules in crude oil distillates with the aim to produce ultra-low sulfur transport fuels. The addition of ppm-levels of Pt to a standard industrial Co-Mo-S catalyst boosts the HDS activity by up to 46%. The promotional effect is examined by combining atomic-resolution Scanning Transmission Electron Microscopy (STEM), Energy Dispersive X-ray Spectroscopy (EDX), X-ray Absorption Near Edge Spectroscopy (XANES) and Density Functional Theory (DFT). It is shown that the Pt-Co-Mo-S catalyst contains predominantly single-layer MoS2 nanocrystals with Co atoms fully covering the S-edge terminations and Pt atoms uniquely attached to corner and edge sites in a platinum(IV) sulfide-like structural motif. Platinum is suggested to reduce the sulfur binding energy and increase the abundance of coordinately undersaturated sites (CUS) and not necessarily changing the reactivity towards 4,6-DMDBT molecules, although more elaborate studies are needed to address this in detail.",

keywords = "Active sites, Co-Mo-S, Hydrotreating, Promoters, Pt, Ultra-low sulfur diesel",

author = "Weise, {Christian Frederik} and Hanne Falsig and Moses, {Poul Georg} and Stig Helveg and Michael Brorson and Hansen, {Lars Pilsgaard}",

note = "Funding Information: The authors gratefully acknowledge Christoffer Tyrsted for help with XANES measurements. We acknowledge use of facilities at NMI Natural and Medical Sciences Institute at the University of T{\"u}bingen (Germany), Center for Nanoanalysis, for part of this work, and Clementine Warres for kind support. This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors. SH acknowledges support from Danish National Research Foundation Center for Visualizing Catalytic Processes (VISION) (DNRF146). Funding Information: The authors gratefully acknowledge Christoffer Tyrsted for help with XANES measurements. We acknowledge use of facilities at NMI Natural and Medical Sciences Institute at the University of T?bingen (Germany), Center for Nanoanalysis, for part of this work, and Clementine Warres for kind support. This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors. SH acknowledges support from Danish National Research Foundation Center for Visualizing Catalytic Processes (VISION) (DNRF146). Publisher Copyright: {\textcopyright} 2021 The Authors",

year = "2021",

doi = "10.1016/j.jcat.2021.03.008",

language = "English",

volume = "403",

pages = "74--86",

journal = "Journal of Catalysis",

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T1 - Single-atom Pt promotion of industrial Co-Mo-S catalysts for ultra-deep hydrodesulfurization

AU - Weise, Christian Frederik

AU - Falsig, Hanne

AU - Moses, Poul Georg

AU - Helveg, Stig

AU - Brorson, Michael

AU - Hansen, Lars Pilsgaard

N1 - Funding Information: The authors gratefully acknowledge Christoffer Tyrsted for help with XANES measurements. We acknowledge use of facilities at NMI Natural and Medical Sciences Institute at the University of Tübingen (Germany), Center for Nanoanalysis, for part of this work, and Clementine Warres for kind support. This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors. SH acknowledges support from Danish National Research Foundation Center for Visualizing Catalytic Processes (VISION) (DNRF146). Funding Information: The authors gratefully acknowledge Christoffer Tyrsted for help with XANES measurements. We acknowledge use of facilities at NMI Natural and Medical Sciences Institute at the University of T?bingen (Germany), Center for Nanoanalysis, for part of this work, and Clementine Warres for kind support. This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors. SH acknowledges support from Danish National Research Foundation Center for Visualizing Catalytic Processes (VISION) (DNRF146). Publisher Copyright: © 2021 The Authors

PY - 2021

Y1 - 2021

N2 - We introduce a tertiary transition metal sulfide nanostructure, Pt-Co-Mo-S, for catalytic hydrodesulfurization (HDS) of sulfur-containing molecules in crude oil distillates with the aim to produce ultra-low sulfur transport fuels. The addition of ppm-levels of Pt to a standard industrial Co-Mo-S catalyst boosts the HDS activity by up to 46%. The promotional effect is examined by combining atomic-resolution Scanning Transmission Electron Microscopy (STEM), Energy Dispersive X-ray Spectroscopy (EDX), X-ray Absorption Near Edge Spectroscopy (XANES) and Density Functional Theory (DFT). It is shown that the Pt-Co-Mo-S catalyst contains predominantly single-layer MoS2 nanocrystals with Co atoms fully covering the S-edge terminations and Pt atoms uniquely attached to corner and edge sites in a platinum(IV) sulfide-like structural motif. Platinum is suggested to reduce the sulfur binding energy and increase the abundance of coordinately undersaturated sites (CUS) and not necessarily changing the reactivity towards 4,6-DMDBT molecules, although more elaborate studies are needed to address this in detail.

AB - We introduce a tertiary transition metal sulfide nanostructure, Pt-Co-Mo-S, for catalytic hydrodesulfurization (HDS) of sulfur-containing molecules in crude oil distillates with the aim to produce ultra-low sulfur transport fuels. The addition of ppm-levels of Pt to a standard industrial Co-Mo-S catalyst boosts the HDS activity by up to 46%. The promotional effect is examined by combining atomic-resolution Scanning Transmission Electron Microscopy (STEM), Energy Dispersive X-ray Spectroscopy (EDX), X-ray Absorption Near Edge Spectroscopy (XANES) and Density Functional Theory (DFT). It is shown that the Pt-Co-Mo-S catalyst contains predominantly single-layer MoS2 nanocrystals with Co atoms fully covering the S-edge terminations and Pt atoms uniquely attached to corner and edge sites in a platinum(IV) sulfide-like structural motif. Platinum is suggested to reduce the sulfur binding energy and increase the abundance of coordinately undersaturated sites (CUS) and not necessarily changing the reactivity towards 4,6-DMDBT molecules, although more elaborate studies are needed to address this in detail.

KW - Active sites

KW - Co-Mo-S

KW - Hydrotreating

KW - Promoters

KW - Pt

KW - Ultra-low sulfur diesel

U2 - 10.1016/j.jcat.2021.03.008

DO - 10.1016/j.jcat.2021.03.008

M3 - Journal article

AN - SCOPUS:85104675425

SN - 0021-9517

VL - 403

SP - 74

EP - 86

JO - Journal of Catalysis

JF - Journal of Catalysis

ER -

Single-atom Pt promotion of industrial Co-Mo-S catalysts for ultra-deep hydrodesulfurization

Abstract

Bibliographical note

Keywords

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