Title: Compositional dependence of hydrodeoxygenation pathway selectivity for Ni _{2− x} Rh _x P nanoparticle catalysts

Abstract

Transition-metal phosphides (TMPs) are promising materials for biomass conversion processes, where their metal–acid bifunctionality provides active sites for the necessary variety of catalytic reactions (e.g., hydrogenation, hydrogenolysis, decarbonylation, and dehydration). Aiming to understand the catalytic performance of ternary TMP catalysts for the hydrodeoxygenation (HDO) reaction of biomass-derived oxygenates, a synthetic protocol was developed herein to prepare a series of ternary Ni_2–xRh_xP nanoparticles (NPs), incorporating Rh into a parent Ni₂P template. This solution synthesis method allowed for a series of NPs to be prepared having precisely controlled compositions with similar morphology and crystalline structure. Detailed characterization of this series of Ni_2–xRh_xP (x ≤ 1) NPs revealed that Rh substituted into the parent hexagonal crystal lattice of Ni2P with concomitant expansion of the lattice. The influence of composition on the catalytic performance of silica-supported Ni_2–xRh_xP (x = 0 to 0.8, and cubic Rh₂P) NPs was investigated through the HDO reaction of m-cresol. Whereas Rh₂P was more selective for direct deoxygenation relative to Ni₂P, increasing concentrations of Rh in Ni_2–xRh_xP resulted in a decreased selectivity to direct deoxygenation products (i.e., toluene, benzene, xylene), and an associated increased selectivity to hydrogenation products (i.e., methylcyclohexene). Through in situ high energy X-ray diffraction and density functionalmore » theory modeling, we identified OH* adsorption energy and surface-P sp-band center as effective descriptors for the observed shift in selectivities across this series of TMPs. Furthermore, the calculated electronic-structure changes were found to exert greater influence over the observed product selectivity than the subtle geometric changes associated with lattice expansion. In conclusion, identification of this structure–function relationship demonstrates that the controlled synthesis of TMPs enables an understanding of composition-dependent selectivity for the HDO reaction of phenolic molecules and this approach could be extended to other ternary TMP compositions for diverse catalytic applications.« less

Authors:

LiBretto, Nicole J. ^[1]; Tacey, Sean A.  ^[1];

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Zubair, Muhammad  ^[2];

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Bui, Tuong V. ^[1]; Unocic, Kinga A.  ^[3];

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Baddour, Frederick G.  ^[1];

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Griffin, Michael B.  ^[1];

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Schaidle, Joshua A.  ^[1];

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Farberow, Carrie A.  ^[1];

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Ruddy, Daniel A.  ^[1];

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Bedford, Nicholas M.  ^[2];

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Habas, Susan E.  ^[1]

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• Search DOE PAGES for ORCID "0000-0002-3893-8454"

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+ Show Author Affiliations

1. National Renewable Energy Laboratory, Catalytic Carbon Transformation and Scale-up Center, Golden, CO, USA
2. University of New South Wales, School of Chemical Engineering, Sydney, NSW, Australia
3. Oak Ridge National Laboratory, Center for Nanophase Materials Sciences, Oak Ridge, TN, USA

Publication Date:

Tue Aug 08 00:00:00 EDT 2023

Research Org.:

National Renewable Energy Laboratory (NREL), Golden, CO (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Org.:

USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office, Chemical Catalysis for Bioenergy (ChemCatBio) Consortium; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

OSTI Identifier:

1992535

Alternate Identifier(s):

OSTI ID: 1996227

Report Number(s):

NREL/JA-5100-84954
Journal ID: ISSN 2050-7488; JMCAET

Grant/Contract Number:  

AC36-08GO28308; AC05-00OR22725; AC02-06CH11357; ACI-1548562

Resource Type:

Published Article

Journal Name:

Journal of Materials Chemistry. A

Additional Journal Information:

Journal Name: Journal of Materials Chemistry. A Journal Volume: 11 Journal Issue: 31; Journal ID: ISSN 2050-7488

Publisher:

Royal Society of Chemistry (RSC)

Country of Publication:

United Kingdom

Language:

English

Subject:

09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; biomass catalysis; composition-dependent selectivity; computational descriptor; density functional theory; hydrodeoxygenation; nanoparticles; transition metal phosphide