Synthesis Gas Conversion over Rh-Based Catalysts Promoted by Fe and Mn

Liu, Yifei; Göeltl, Florian; Ro, Insoo; Ball, Madelyn R.; Sener, Canan; Aragão, Isaias Barbosa; Zanchet, Daniela; Huber, George W.; Mavrikakis, Manos; Dumesic, James A.

doi:10.1021/acscatal.7b01381

Synthesis Gas Conversion over Rh-Based Catalysts Promoted by Fe and Mn

Journal Article · Tue Jun 13 00:00:00 EDT 2017 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.7b01381· OSTI ID:1396009

Liu, Yifei ^[1]; Göeltl, Florian ^[2]; Ro, Insoo ^[2]; Ball, Madelyn R. ^[2]; Sener, Canan ^[2]; Aragão, Isaias Barbosa ^[3]; ^[4]; Huber, George W. ^[2]; ^[2]; ^[5]

Department of Chemical and Biological Engineering, University of Wisconsin—Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States; Department of Chemical and Biological Engineering, University of Wisconsin—Madison
Department of Chemical and Biological Engineering, University of Wisconsin—Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States
Department of Chemical and Biological Engineering, University of Wisconsin—Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States; Institute of Chemistry, University of Campinas (UNICAMP), P.O. Box 6154, 13083-970 Campinas, São Paulo, Brazil
Institute of Chemistry, University of Campinas (UNICAMP), P.O. Box 6154, 13083-970 Campinas, São Paulo, Brazil
Department of Chemical and Biological Engineering, University of WisconsinâMadison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States

Rh/SiO2 catalysts promoted with Fe and Mn are selective for synthesis gas conversion to oxygenates and light hydrocarbons at 523 K and 580 psi. Selective anchoring of Fe and Mn species on Rh nanoparticles was achieved by controlled surface reactions and was evidenced by ultraviolet–visible absorption spectroscopy, scanning transmission electron microscopy, and inductively coupled plasma absorption emission spectroscopy. The interaction between Rh and Fe promotes the selective production of ethanol through hydrogenation of acetaldehyde and enhances the selectivity toward C2 oxygenates, which include ethanol and acetaldehyde. The interaction between Rh and Mn increases the overall reaction rate and the selectivity toward C2+ hydrocarbons. The combination of Fe and Mn on Rh/SiO2 results in trimetallic Rh-Fe-Mn catalysts that surpass the performance of their bimetallic counterparts. The highest selectivities toward ethanol (36.9%) and C2 oxygenates (39.6%) were achieved over the Rh-Fe-Mn ternary system with a molar ratio of 1:0.15:0.10, as opposed to the selectivities obtained over Rh/SiO2, which were 3.5% and 20.4%, respectively. The production of value-added oxygenates and C2+ hydrocarbons over this trimetallic catalyst accounted for 55% of the total products. X-ray photoelectron spectroscopy measurements suggest that significant fractions of the Fe and Mn species exist as metallic iron and manganese oxides on the Rh surface upon reduction. These findings are rationalized by density functional theory (DFT) calculations, which reveal that the exact state of metals on the surfaces is condition-dependent, with Mn present as Mn(I) and Mn(II) oxide on the Rh (211) step edges and Fe present as Fe(I) oxide on the step edge and metallic subsurface iron on both Rh steps and terraces. CO Fourier transform infrared spectroscopy and DFT calculations suggest that the binding of CO to Rh (211) step edges modified by Fe and/or manganese oxide is altered in comparison to CO adsorption on a clean Rh (211) surface. These results suggest that Mn2Ox species and Fe and Fe2O modify bonding at Rh step edges and shift reaction selectivity away from CH4.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Contributing Organization:: Wisconsin Materials Research Science and Engineering Center; Environmental Molecular Sciences Laboratory (EMSL); the Center for Nanoscale Materials (CNM) at Argonne National Laboratory; and the National Energy Research Scientific Computing Center (NERSC)

Grant/Contract Number:: EE0006878

OSTI ID:: 1396009

Alternate ID(s):: OSTI ID: 1396167

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 7 Vol. 7; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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