Synthesis Gas Conversion over Rh/Mo Catalysts Prepared by Atomic Layer Deposition

Zhang, Lifeng; Ball, Madelyn R.; Liu, Yifei; Kuech, Thomas F.; Huber, George W.; Mavrikakis, Manos; Hermans, Ive; Dumesic, James A.

doi:10.1021/acscatal.8b04649

Title: Synthesis Gas Conversion over Rh/Mo Catalysts Prepared by Atomic Layer Deposition

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Abstract

Conversion of synthesis gas into value-added products, including oxygenates and C₂₊ hydrocarbons, was studied at 523 K, 580 psi, and a 1/1 CO/H₂ ratio over Rh catalysts on catalyst supports prepared by atomic layer deposition (ALD) of molybdenum and tungsten species on silica. The reactivity measurements showed that coating the silica support with molybdenum and tungsten species helped to suppress the methane selectivity and promote the overall conversion rate. When the silica support was coated with five cycles of β-Mo₂C, the methane selectivity decreased from 32% (1% Rh/SiO₂) to 13% (1% Rh/5c-Mo₂C/SiO₂), and the overall product rate increased 33 times from 0.4 to 12.7 mmol min^–1 (g of Rh)^–1. CO-FTIR results showed that supporting Rh on silica led to the formation of Rh(211) facets, which favored the formation of methane and had a higher CO conversion rate. Rh on a MoO₃/SiO₂ support prepared by ALD was found to be the most active catalyst while maintaining the suppression of methane selectivity, showing an overall rate ~60 times higher than that of 1% Rh/SiO₂. A reaction pathway is proposed, in which hydrogenation steps are promoted most significantly by Mo and W species, followed by promotion of CO insertion steps for ethanol synthesismore »« less

Authors:

Zhang, Lifeng ^[1]; Ball, Madelyn R. ^[1]; Liu, Yifei ^[1]; Kuech, Thomas F. ^[1]; Huber, George W. ^[1]; Mavrikakis, Manos ^[1];

^[1];

^[1]

Univ. of Wisconsin-Madison, Madison, WI (United States)

Publication Date:: Wed Jan 16 00:00:00 EST 2019

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

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1542657

Grant/Contract Number:: SC0014058

Resource Type:: Accepted Manuscript

Journal Name:: ACS Catalysis

Additional Journal Information:: Journal Volume: 9; Journal Issue: 3; Journal ID: ISSN 2155-5435

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; synthesis gas conversion; rhodium; molybdenum; atomic layer deposition (ALD); metal carbides

Citation Formats


                    Zhang, Lifeng, Ball, Madelyn R., Liu, Yifei, Kuech, Thomas F., Huber, George W., Mavrikakis, Manos, Hermans, Ive, and Dumesic, James A. Synthesis Gas Conversion over Rh/Mo Catalysts Prepared by Atomic Layer Deposition.  United States: N. p., 2019. 
Web.  doi:10.1021/acscatal.8b04649.

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                    Zhang, Lifeng, Ball, Madelyn R., Liu, Yifei, Kuech, Thomas F., Huber, George W., Mavrikakis, Manos, Hermans, Ive, & Dumesic, James A. Synthesis Gas Conversion over Rh/Mo Catalysts Prepared by Atomic Layer Deposition.  United States.  https://doi.org/10.1021/acscatal.8b04649

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                    Zhang, Lifeng, Ball, Madelyn R., Liu, Yifei, Kuech, Thomas F., Huber, George W., Mavrikakis, Manos, Hermans, Ive, and Dumesic, James A. Wed .  
"Synthesis Gas Conversion over Rh/Mo Catalysts Prepared by Atomic Layer Deposition".  United States.  https://doi.org/10.1021/acscatal.8b04649.  https://www.osti.gov/servlets/purl/1542657.

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@article{osti_1542657,

  title        = {Synthesis Gas Conversion over Rh/Mo Catalysts Prepared by Atomic Layer Deposition},

  author       = {Zhang, Lifeng and Ball, Madelyn R. and Liu, Yifei and Kuech, Thomas F. and Huber, George W. and Mavrikakis, Manos and Hermans, Ive and Dumesic, James A.},

  abstractNote = {Conversion of synthesis gas into value-added products, including oxygenates and C2+ hydrocarbons, was studied at 523 K, 580 psi, and a 1/1 CO/H2 ratio over Rh catalysts on catalyst supports prepared by atomic layer deposition (ALD) of molybdenum and tungsten species on silica. The reactivity measurements showed that coating the silica support with molybdenum and tungsten species helped to suppress the methane selectivity and promote the overall conversion rate. When the silica support was coated with five cycles of β-Mo2C, the methane selectivity decreased from 32% (1% Rh/SiO2) to 13% (1% Rh/5c-Mo2C/SiO2), and the overall product rate increased 33 times from 0.4 to 12.7 mmol min–1 (g of Rh)–1. CO-FTIR results showed that supporting Rh on silica led to the formation of Rh(211) facets, which favored the formation of methane and had a higher CO conversion rate. Rh on a MoO3/SiO2 support prepared by ALD was found to be the most active catalyst while maintaining the suppression of methane selectivity, showing an overall rate ~60 times higher than that of 1% Rh/SiO2. A reaction pathway is proposed, in which hydrogenation steps are promoted most significantly by Mo and W species, followed by promotion of CO insertion steps for ethanol synthesis and C–C coupling steps for hydrocarbon formation. CO-FTIR results showed that 1% Rh/MoO3/SiO2 has the highest proportion of gem-dicarbonyl adsorption sites and the lowest proportion of bridge-bonded CO adsorption sites. As a result, the rate of methanol formation shows a positive correlation with the number of sites that form gem-dicarbonyl species.},

  doi          = {10.1021/acscatal.8b04649},

  journal      = {ACS Catalysis},

  number       = 3,

  volume       = 9,

  place        = {United States},

  year         = {Wed Jan 16 00:00:00 EST 2019},

  month        = {Wed Jan 16 00:00:00 EST 2019}

}

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