Understanding selectivity in co2 hydrogenation to methanol for mop nanoparticle catalysts using in situ techniques

Melis S. Duyar; Alessandro Gallo; Samuel K. Regli; Jonathan L. Snider; Joseph A. Singh; Eduardo Valle; Joshua McEnaney; Stacey F. Bent; Magnus Rønning; Thomas F. Jaramillo

doi:10.3390/catal11010143

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Understanding selectivity in co2 hydrogenation to methanol for mop nanoparticle catalysts using in situ techniques

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Understanding selectivity in co2 hydrogenation to methanol for mop nanoparticle catalysts using in situ techniques

Melis S. Duyar, Alessandro Gallo, Samuel K. Regli, Jonathan L. Snider, Joseph A. Singh, Eduardo Valle, Joshua McEnaney, Stacey F. Bent, Magnus Rønning and Thomas F. Jaramillo

Catalysts, Vol.11(1), 143

19/01/2021

DOI: https://doi.org/10.3390/catal11010143

Abstract

methanol synthesis

in situ characterization

CO2 hydrogenation

support effects

MoP

Molybdenum phosphide (MoP) catalyzes the hydrogenation of CO, CO2, and their mixtures to methanol, and it is investigated as a high-activity catalyst that overcomes deactivation issues (e.g., formate poisoning) faced by conventional transition metal catalysts. MoP as a new catalyst for hydrogenating CO2 to methanol is particularly appealing for the use of CO2 as chemical feedstock. Herein, we use a colloidal synthesis technique that connects the presence of MoP to the formation of methanol from CO2, regardless of the support being used. By conducting a systematic support study, we see that zirconia (ZrO2) has the striking ability to shift the selectivity towards methanol by increasing the rate of methanol conversion by two orders of magnitude compared to other supports, at a CO2 conversion of 1.4% and methanol selectivity of 55.4%. In situ X-ray Absorption Spectroscopy (XAS) and in situ X-ray Diffraction (XRD) indicate that under reaction conditions the catalyst is pure MoP in a partially crystalline phase. Results from Diffuse Reflectance Infrared Fourier Transform Spectroscopy coupled with Temperature Programmed Surface Reaction (DRIFTS-TPSR) point towards a highly reactive monodentate formate intermediate stabilized by the strong interaction of MoP and ZrO2. This study definitively shows that the presence of a MoP phase leads to methanol formation from CO2, regardless of support and that the formate intermediate on MoP governs methanol formation rate.

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Title: Understanding selectivity in co2 hydrogenation to methanol for mop nanoparticle catalysts using in situ techniques
Creators: Melis S. Duyar - University of Surrey, School of Chemistry and Chemical Engineering
Alessandro Gallo - SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 443 Via Ortega, Stanford, CA 94305, USA
Samuel K. Regli - Department of Chemical Engineering, Norwegian University of Science and Technology, N-7491 Trondheim, Norway
Jonathan L. Snider - SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 443 Via Ortega, Stanford, CA 94305, USA
Joseph A. Singh - SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 443 Via Ortega, Stanford, CA 94305, USA
Eduardo Valle - SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 443 Via Ortega, Stanford, CA 94305, USA
Joshua McEnaney - SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 443 Via Ortega, Stanford, CA 94305, USA
Stacey F. Bent - SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 443 Via Ortega, Stanford, CA 94305, USA
Magnus Rønning - Department of Chemical Engineering, Norwegian University of Science and Technology, N-7491 Trondheim, Norway
Thomas F. Jaramillo - SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 443 Via Ortega, Stanford, CA 94305, USA
Publication Details: Catalysts, Vol.11(1), 143
Publisher: MDPI AG
Publication Date: 19/01/2021
Date accepted for publication: 16/01/2021
Grant note: This research was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis. Use of Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory is supported by the US Department of Energy, Office of Science, Office of Basic Energy Science, under Contract DE-AC02-76SF00515. We acknowledge the Swiss-Norwegian Beamlines (SNBL) at the European Synchrotron Radiation Facility for provision of synchrotron radiation facilities and we would like to thank Wouter van Beek and Dragos Stoian for assistance (SNBL-BM31). Transmission electron microscopy (TEM) and X-ray Photoelectron Spectroscopy were performed at the Stanford Nano Shared Facilities (SNSF) at Stanford University, supported by the National Science Foundation under award ECCS-1542152. Ex situ X-ray Diffraction (XRD) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) were performed at the Environmental Measurements Facility (EMF) at Stanford University. Support from iCSI (industrial Catalysis Science and Innovation) Centre for Research-based Innovation is acknowledged, which receives financial support from the Research Council of Norway under contract no. 237922.
Identifiers: 99548720602346; WOS:000610007900001
Copyright: Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/).
Academic Unit: School of Chemistry and Chemical Engineering
Language: English
Resource Type: Journal article
SDG (Scopus 2023): SDG 13

Understanding selectivity in co2 hydrogenation to methanol for mop nanoparticle catalysts using in situ techniques

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