Synthesis Gas Conversion over Rh-Mn-WxC/SiO2 Catalysts Prepared by Atomic Layer Deposition

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

doi:10.1021/acscatal.8b02461

Title: Synthesis Gas Conversion over Rh-Mn-W_xC/SiO₂ Catalysts Prepared by Atomic Layer Deposition

Abstract

The catalytic conversion of synthesis gas to value-added oxygenates and light hydrocarbons was studied here on Rh and Rh–Mn clusters on tungsten carbide-overcoated silica (W_xC/SiO₂) at 523 K, 580 psi, and CO/H₂ = 1/1. The W_xC-modified SiO₂ support was prepared by the overcoating of WO_x on SiO₂ using atomic layer deposition (ALD) followed by carburization. The reactivities of Rh/W_xC/SiO₂ catalysts with varying number of ALD cycles (number of cycles = 2, 5, 10, 20, and 30) were measured and showed that 5 ALD cycles of WxC suppressed the formation of methane. All W_xC-modified catalysts showed enhancement in selectivity toward methanol and ethanol through CO hydrogenation and acetaldehyde hydrogenation, respectively. These catalysts also improved the overall turnover frequency (TOF). The addition of Mn species further promoted the activity and the selectivity toward ethanol and C₂₊ hydrocarbons, especially light alkenes. The best performing Rh-2Mn/5cycle-W_xC/SiO₂ catalyst (Rh:Mn molar ratio = 1:2) achieved 84.7% selectivity toward valuable oxygenates and C₂₊ hydrocarbons with a ratio of alkenes to alkanes equal to 1.7, compared to Rh/SiO₂ which exhibited 80.4% selectivity toward the products aforementioned with a ratio of 0.5. The overall TOF was 20 times higher than that over Rh/SiO₂ (i.e., 5.6 × 10^–2 s^–1 vsmore »« less

Authors:

Liu, Yifei ^[1]; Zhang, Lifeng ^[1];

^[1]; Ball, Madelyn R. ^[1];

^[2]; Kuech, Thomas F. ^[1]; Mavrikakis, Manos ^[1];

^[1]

Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering
Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering. Dept. of Chemistry

Publication Date:: Thu Oct 11 00:00:00 EDT 2018

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

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office; USDOE Office of Science (SC), Biological and Environmental Research (BER); National Science Foundation (NSF)

OSTI Identifier:: 1494808

Grant/Contract Number:: FG02-05ER15731; EE0006878; AC02-06CH11357; AC02-05CH11231; DMR-1121288

Resource Type:: Accepted Manuscript

Journal Name:: ACS Catalysis

Additional Journal Information:: Journal Volume: 8; Journal Issue: 11; 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; atomic layer deposition; manganese; rhodium; support effect; synthesis gas; tungsten carbide

Citation Formats


                    Liu, Yifei, Zhang, Lifeng, Göltl, Florian, Ball, Madelyn R., Hermans, Ive, Kuech, Thomas F., Mavrikakis, Manos, and Dumesic, James A. Synthesis Gas Conversion over Rh-Mn-WxC/SiO2 Catalysts Prepared by Atomic Layer Deposition.  United States: N. p., 2018. 
Web.  doi:10.1021/acscatal.8b02461.

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                    Liu, Yifei, Zhang, Lifeng, Göltl, Florian, Ball, Madelyn R., Hermans, Ive, Kuech, Thomas F., Mavrikakis, Manos, & Dumesic, James A. Synthesis Gas Conversion over Rh-Mn-WxC/SiO2 Catalysts Prepared by Atomic Layer Deposition.  United States.  https://doi.org/10.1021/acscatal.8b02461

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                    Liu, Yifei, Zhang, Lifeng, Göltl, Florian, Ball, Madelyn R., Hermans, Ive, Kuech, Thomas F., Mavrikakis, Manos, and Dumesic, James A. Thu .  
"Synthesis Gas Conversion over Rh-Mn-WxC/SiO2 Catalysts Prepared by Atomic Layer Deposition".  United States.  https://doi.org/10.1021/acscatal.8b02461.  https://www.osti.gov/servlets/purl/1494808.

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@article{osti_1494808,

  title        = {Synthesis Gas Conversion over Rh-Mn-WxC/SiO2 Catalysts Prepared by Atomic Layer Deposition},

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

  abstractNote = {The catalytic conversion of synthesis gas to value-added oxygenates and light hydrocarbons was studied here on Rh and Rh–Mn clusters on tungsten carbide-overcoated silica (WxC/SiO2) at 523 K, 580 psi, and CO/H2 = 1/1. The WxC-modified SiO2 support was prepared by the overcoating of WOx on SiO2 using atomic layer deposition (ALD) followed by carburization. The reactivities of Rh/WxC/SiO2 catalysts with varying number of ALD cycles (number of cycles = 2, 5, 10, 20, and 30) were measured and showed that 5 ALD cycles of WxC suppressed the formation of methane. All WxC-modified catalysts showed enhancement in selectivity toward methanol and ethanol through CO hydrogenation and acetaldehyde hydrogenation, respectively. These catalysts also improved the overall turnover frequency (TOF). The addition of Mn species further promoted the activity and the selectivity toward ethanol and C2+ hydrocarbons, especially light alkenes. The best performing Rh-2Mn/5cycle-WxC/SiO2 catalyst (Rh:Mn molar ratio = 1:2) achieved 84.7% selectivity toward valuable oxygenates and C2+ hydrocarbons with a ratio of alkenes to alkanes equal to 1.7, compared to Rh/SiO2 which exhibited 80.4% selectivity toward the products aforementioned with a ratio of 0.5. The overall TOF was 20 times higher than that over Rh/SiO2 (i.e., 5.6 × 10–2 s–1 vs 2.9 × 10–3 s–1). X-ray diffraction revealed that the existence of W2C, which was the dominant phase in Rh/5cycle-WxC/SiO2, favored the suppression of methane and enhanced the production of alcohols and C2+ hydrocarbons compared to the WC support. Density functional theory calculations for Rh19, Rh31, and Rh37 clusters on various WC surfaces suggested that the shape of Rh clusters is condition dependent and subject to H2 pressure. The C- and O- binding energies on various sites for the clusters were used with scaling relations to probe their catalytic activity. With the use of this approach, the increase in the O binding energy when moving from the SiO2-supported Rh37 cluster to the WC-supported cluster leads to an increase in the activity of Rh/WxC/SiO2 at the expense of the reduction in the number of sites that are selective toward C2 oxygenates.},

  doi          = {10.1021/acscatal.8b02461},

  journal      = {ACS Catalysis},

  number       = 11,

  volume       = 8,

  place        = {United States},

  year         = {Thu Oct 11 00:00:00 EDT 2018},

  month        = {Thu Oct 11 00:00:00 EDT 2018}

}

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Cited by: 17 works

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Figure 1: Summary of selectivities for syngas conversion over Rh/SiO₂ and W_xC-modified Rh/SiO₂ catalysts.

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Title: Synthesis Gas Conversion over Rh-Mn-WxC/SiO2 Catalysts Prepared by Atomic Layer Deposition

Abstract

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Title: Synthesis Gas Conversion over Rh-Mn-W_xC/SiO₂ Catalysts Prepared by Atomic Layer Deposition