Development of Molybdenum Phosphide Catalysts for Higher Alcohol Synthesis from Syngas by Exploiting Support and Promoter Effects
Abstract
Molybdenum phosphide (MoP) catalysts have recently gained attention because of their robust methanol synthesis activity from CO/CO2. Synthesis strategies are used to steer MoP selectivity toward higher alcohols by investigating the promotion effects of alkali (K) and CO-dissociating (Co, Ni) and non-CO-dissociating (Pd) metals. Systematic research with transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy (XAS) showed that critical parameters governing the activity of MoP catalysts are P/Mo ratio and K loading, both facilitating MoP formation. The kinetic studies of mesoporous silica-supported MoP catalysts show a twofold role of K, which also acts as an electronic promoter by increasing the total alcohol selectivity and chain length. Palladium (Pd) increases CO conversion, but decreases alcohol chain length. The use of mesoporous carbon (MC) support has the most significant effect on catalyst performance and yields a KMoP/MC catalyst that ranks among the state-of-the-art in terms of selectivity to higher alcohols.
- Authors:
-
[1];
[2];
[2];
- Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. of Utrecht (Netherlands)
- Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE; National Science Foundation (NSF)
- OSTI Identifier:
- 1547286
- Alternate Identifier(s):
- OSTI ID: 1506724
- Grant/Contract Number:
- AC02-76SF00515; ECCS-1542152
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energy Technology
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 5; Journal ID: ISSN 2194-4288
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 10 SYNTHETIC FUELS; higher alcohol synthesis; molybdenum phosphide; promoter effects; support effects; syngas conversion
Citation Formats
ten Have, Iris C., Valle, Eduardo, Gallo, Alessandro, Snider, Jonathan L., Duyar, Melis S., and Jaramillo, Thomas F. Development of Molybdenum Phosphide Catalysts for Higher Alcohol Synthesis from Syngas by Exploiting Support and Promoter Effects. United States: N. p., 2019.
Web. doi:10.1002/ente.201801102.
ten Have, Iris C., Valle, Eduardo, Gallo, Alessandro, Snider, Jonathan L., Duyar, Melis S., & Jaramillo, Thomas F. Development of Molybdenum Phosphide Catalysts for Higher Alcohol Synthesis from Syngas by Exploiting Support and Promoter Effects. United States. https://doi.org/10.1002/ente.201801102
ten Have, Iris C., Valle, Eduardo, Gallo, Alessandro, Snider, Jonathan L., Duyar, Melis S., and Jaramillo, Thomas F. Tue .
"Development of Molybdenum Phosphide Catalysts for Higher Alcohol Synthesis from Syngas by Exploiting Support and Promoter Effects". United States. https://doi.org/10.1002/ente.201801102. https://www.osti.gov/servlets/purl/1547286.
@article{osti_1547286,
title = {Development of Molybdenum Phosphide Catalysts for Higher Alcohol Synthesis from Syngas by Exploiting Support and Promoter Effects},
author = {ten Have, Iris C. and Valle, Eduardo and Gallo, Alessandro and Snider, Jonathan L. and Duyar, Melis S. and Jaramillo, Thomas F.},
abstractNote = {Molybdenum phosphide (MoP) catalysts have recently gained attention because of their robust methanol synthesis activity from CO/CO2. Synthesis strategies are used to steer MoP selectivity toward higher alcohols by investigating the promotion effects of alkali (K) and CO-dissociating (Co, Ni) and non-CO-dissociating (Pd) metals. Systematic research with transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy (XAS) showed that critical parameters governing the activity of MoP catalysts are P/Mo ratio and K loading, both facilitating MoP formation. The kinetic studies of mesoporous silica-supported MoP catalysts show a twofold role of K, which also acts as an electronic promoter by increasing the total alcohol selectivity and chain length. Palladium (Pd) increases CO conversion, but decreases alcohol chain length. The use of mesoporous carbon (MC) support has the most significant effect on catalyst performance and yields a KMoP/MC catalyst that ranks among the state-of-the-art in terms of selectivity to higher alcohols.},
doi = {10.1002/ente.201801102},
journal = {Energy Technology},
number = 5,
volume = 7,
place = {United States},
year = {2019},
month = {2}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 10 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Nano- and Microscale Engineering of the Molybdenum Disulfide-Based Catalysts for Syngas to Ethanol Conversion
journal, July 2014
- Konarova, Muxina; Tang, Fengqiu; Chen, Jiuling
- ChemCatChem, Vol. 6, Issue 8
Synthesis, characterization, and hydrotreating activity of carbon-supported transition metal phosphides
journal, June 2005
- Shu, Yuying; Oyama, S. Ted
- Carbon, Vol. 43, Issue 7
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
A Review of Molybdenum Catalysts for Synthesis Gas Conversion to Alcohols: Catalysts, Mechanisms and Kinetics
journal, January 2012
- Zaman, Sharif; Smith, Kevin J.
- Catalysis Reviews, Vol. 54, Issue 1
Activity and Selectivity Trends in Synthesis Gas Conversion to Higher Alcohols
journal, October 2013
- Medford, Andrew J.; Lausche, Adam C.; Abild-Pedersen, Frank
- Topics in Catalysis, Vol. 57, Issue 1-4
Nanoscale design to enable the revolution in renewable energy
journal, January 2009
- Baxter, Jason; Bian, Zhixi; Chen, Gang
- Energy & Environmental Science, Vol. 2, Issue 6
Higher alcohol and oxygenate synthesis over cesium-doped Cu/Zno catalysts
journal, March 1989
- Nunan, J.
- Journal of Catalysis, Vol. 116, Issue 1
Status and prospects in higher alcohols synthesis from syngas
journal, January 2017
- Luk, Ho Ting; Mondelli, Cecilia; Ferré, Daniel Curulla
- Chemical Society Reviews, Vol. 46, Issue 5
Synthesis of higher alcohols from syngas over Fischer–Tropsch elements modified K/β-Mo2C catalysts
journal, April 2008
- Xiang, M.; Li, D.; Xiao, H.
- Fuel, Vol. 87, Issue 4-5, p. 599-603
XAFS Characterization of Highly Active Alumina-Supported Molybdenum Phosphide Catalysts (MoP/Al 2 O 3 ) for Hydrotreating
journal, May 2001
- Oyama, S. T.; Clark, P.; Teixeira da Silva, V. L. S.
- The Journal of Physical Chemistry B, Vol. 105, Issue 21
Ni-decorated carbon nanotube-promoted Ni–Mo–K catalyst for highly efficient synthesis of higher alcohols from syngas
journal, October 2010
- Ma, Chun-Hui; Li, Hai-Yan; Lin, Guo-Dong
- Applied Catalysis B: Environmental, Vol. 100, Issue 1-2
The effect of cobalt addition to bulk MoP and Ni2P catalysts for the hydrodesulfurization of 4,6-dimethyldibenzothiophene
journal, July 2006
- Abu, I.; Smith, K.
- Journal of Catalysis, Vol. 241, Issue 2
Quality management and method Validation in EDXRF analysis
journal, January 2007
- Álvarez, R. Padilla; Markowicz, A.; Wegrzynek, D.
- X-Ray Spectrometry, Vol. 36, Issue 1
Kinetic Analysis of Mixed Alcohol Synthesis from Syngas over K/MoS 2 Catalyst
journal, December 1997
- Park, Tae Yun; Nam, In-Sik; Kim, Young Gul
- Industrial & Engineering Chemistry Research, Vol. 36, Issue 12
High Pressure CO Hydrogenation Over Bimetallic Pt–Co Catalysts
journal, March 2014
- Christensen, Jakob M.; Medford, Andrew J.; Studt, Felix
- Catalysis Letters, Vol. 144, Issue 5
Metal Phosphides: Preparation, Characterization and Catalytic Reactivity
journal, November 2012
- Prins, Roel; Bussell, Mark E.
- Catalysis Letters, Vol. 142, Issue 12
Effects of H2S and process conditions in the synthesis of mixed alcohols from syngas over alkali promoted cobalt-molybdenum sulfide
journal, September 2009
- Christensen, J. M.; Mortensen, P. M.; Trane, R.
- Applied Catalysis A: General, Vol. 366, Issue 1
Synthesis, Characterization, and Hydrotreating Activity of Several Iron Group Transition Metal Phosphides
journal, June 2002
- Wang, Xianqin; Clark, Paul; Oyama, S. Ted
- Journal of Catalysis, Vol. 208, Issue 2
Role of impurities in the enhancement of C2-oxygenates activity
journal, June 1990
- Nonneman, L. E. Y.; Bastein, A. G. T. M.; Ponec, V.
- Applied Catalysis, Vol. 62, Issue 1
Mixed Alcohol Synthesis over Sulfided Molybdenum-Based Catalysts
journal, June 2013
- Toyoda, Takashi; Minami, Takayuki; Qian, Eika W.
- Energy & Fuels, Vol. 27, Issue 7
Mechanistic Insight into the Synthesis of Higher Alcohols from Syngas: The Role of K Promotion on MoS 2 Catalysts
journal, June 2013
- Santos, Vera P.; van der Linden, Bart; Chojecki, Adam
- ACS Catalysis, Vol. 3, Issue 7
Characterization and testing of silica-supported cobalt–palladium catalysts for conversion of syngas to oxygenates
journal, May 2012
- Kumar, Nitin; Smith, Miranda L.; Spivey, J. J.
- Journal of Catalysis, Vol. 289
Heterogeneous catalytic synthesis of ethanol from biomass-derived syngas
journal, January 2007
- Spivey, James J.; Egbebi, Adefemi
- Chemical Society Reviews, Vol. 36, Issue 9
Synthesis of mixed alcohols from synthesis gas over alkali and Fischer–Tropsch metals modified MoS2/Al2O3-montmorillonite catalysts
journal, June 2014
- Liu, Yanyong; Murata, Kazuhisa; Inaba, Megumu
- Reaction Kinetics, Mechanisms and Catalysis, Vol. 113, Issue 1
Envisaging the Physicochemical Processes during the Preparation of Supported Catalysts: Raman Microscopy on the Impregnation of Mo onto Al 2 O 3 Extrudates
journal, November 2004
- Bergwerff, Jaap A.; Visser, Tom; Leliveld, G.
- Journal of the American Chemical Society, Vol. 126, Issue 44
Potassium and nickel doped β-Mo2C catalysts for mixed alcohols synthesis via syngas
journal, March 2007
- Xiang, Minglin; Li, Debao; Li, Wenhuai
- Catalysis Communications, Vol. 8, Issue 3
Higher Alcohol Synthesis Using K-Doped CoRhMoS2/MWCNT Catalysts: Influence of Pelletization, Particle Size and Incorporation of Binders
journal, December 2013
- Boahene, Philip E.; Surisetty, Venkateswara R.; Sammynaiken, Ramaswami
- Topics in Catalysis, Vol. 57, Issue 6-9
Catalytic conversion of syngas into C2 oxygenates over Rh-based catalysts—Effect of carbon supports
journal, September 2009
- Fan, Zhongli; Chen, Wei; Pan, Xiulian
- Catalysis Today, Vol. 147, Issue 2
Graphitic mesoporous carbon-supported molybdenum carbides for catalytic hydrogenation of carbon monoxide to mixed alcohols
journal, April 2013
- Chai, Song-Hai; Schwartz, Viviane; Howe, Jane Y.
- Microporous and Mesoporous Materials, Vol. 170
An efficient Ni–Mo–K sulfide catalyst doped with CNTs for conversion of syngas to ethanol and higher alcohols
journal, November 2013
- Wang, Ji-Jie; Xie, Jian-Rong; Huang, Yan-Hui
- Applied Catalysis A: General, Vol. 468
Rh-MnO Interface Sites Formed by Atomic Layer Deposition Promote Syngas Conversion to Higher Oxygenates
journal, August 2017
- Yang, Nuoya; Yoo, Jong Suk; Schumann, Julia
- ACS Catalysis, Vol. 7, Issue 9
The effects of carbon dioxide, methanol, and alkali promoter concentration on the higher alcohol synthesis over a Cu/ZnO/Cr2O3 catalyst
journal, August 1991
- Calverley, E.
- Journal of Catalysis, Vol. 130, Issue 2
Synthesis gas conversion over MoP catalysts
journal, January 2009
- Zaman, S.; Smith, K.
- Catalysis Communications, Vol. 10, Issue 5
Graphitic mesoporous carbon as a support of promoted Rh catalysts for hydrogenation of carbon monoxide to ethanol
journal, April 2012
- Chai, Song-Hai; Howe, Jane Y.; Wang, Xiqing
- Carbon, Vol. 50, Issue 4
Synthesis of higher alcohols on copper catalysts supported on alkali-promoted basic oxides
journal, May 1998
- Hilmen, Anne-Mette; Xu, Mingting; Gines, Marcelo J. L.
- Applied Catalysis A: General, Vol. 169, Issue 2
Synthesis, Characterization, and Hydrodesulfurization Properties of Silica-Supported Molybdenum Phosphide Catalysts
journal, April 2002
- Phillips, Diana C.; Sawhill, Stephanie J.; Self, Randy
- Journal of Catalysis, Vol. 207, Issue 2
A Highly Active Molybdenum Phosphide Catalyst for Methanol Synthesis from CO and CO 2
journal, October 2018
- Duyar, Melis S.; Tsai, Charlie; Snider, Jonathan L.
- Angewandte Chemie International Edition, Vol. 57, Issue 46
Carbon monoxide hydrogenation on potassium promoted Mo 2 N catalysts
journal, February 2017
- Zaman, Sharif F.; Pasupulety, Nagaraju; Al-Zahrani, Abdulrahim A.
- Applied Catalysis A: General, Vol. 532
Synthesis gas conversion over a Rh–K–MoP/SiO2 catalyst
journal, August 2011
- Zaman, Sharif F.; Smith, Kevin J.
- Catalysis Today, Vol. 171, Issue 1
Layered Molybdenum (Oxy)Pyrophosphate as Cathode for Lithium-Ion Batteries
journal, August 2013
- Wen, Bohua; Chernova, Natasha A.; Zhang, Ruibo
- Chemistry of Materials, Vol. 25, Issue 17
Alumina-supported molybdenum phosphide hydroprocessing catalysts
journal, August 2003
- Clark, P.
- Journal of Catalysis, Vol. 218, Issue 1
Different role of H2S and dibenzothiophene in the incorporation of sulfur in the surface of bulk MoP during hydrodesulfurization
journal, April 2013
- Bai, Jin; Li, Xiang; Wang, Anjie
- Journal of Catalysis, Vol. 300
Remarkably efficient CoGa catalyst with uniformly dispersed and trapped structure for ethanol and higher alcohol synthesis from syngas
journal, August 2016
- Ning, Xun; An, Zhe; He, Jing
- Journal of Catalysis, Vol. 340
Mechanism and microkinetics of the Fischer–Tropsch reaction
journal, January 2013
- van Santen, R. A.; Markvoort, A. J.; Filot, I. A. W.
- Physical Chemistry Chemical Physics, Vol. 15, Issue 40
Molybdenum Phosphosulfide: An Active, Acid-Stable, Earth-Abundant Catalyst for the Hydrogen Evolution Reaction
journal, October 2014
- Kibsgaard, Jakob; Jaramillo, Thomas F.
- Angewandte Chemie International Edition, Vol. 53, Issue 52
Experimental and computational study of syngas and ethanol conversion mechanisms over K-modified transition metal sulfide catalysts
journal, December 2016
- Dorokhov, V. S.; Permyakov, E. A.; Nikulshin, P. A.
- Journal of Catalysis, Vol. 344
Tuning of higher alcohol selectivity and productivity in CO hydrogenation reactions over K/MoS2 domains supported on mesoporous activated carbon and mixed MgAl oxide
journal, April 2015
- Taborga Claure, Micaela; Chai, Song-Hai; Dai, Sheng
- Journal of Catalysis, Vol. 324
A study of K-promoted MoP–SiO2 catalysts for synthesis gas conversion
journal, April 2010
- Zaman, Sharif F.; Smith, Kevin J.
- Applied Catalysis A: General, Vol. 378, Issue 1
Correlation patterns and effect of syngas conversion level for product selectivity to alcohols and hydrocarbons over molybdenum sulfide based catalysts
journal, February 2012
- Andersson, Robert; Boutonnet, Magali; Järås, Sven
- Applied Catalysis A: General, Vol. 417-418
Effect of potassium addition method on MoS2 performance for the syngas to alcohol reaction
journal, July 2013
- Ferrari, D.; Budroni, G.; Bisson, L.
- Applied Catalysis A: General, Vol. 462-463
Co-decorated carbon nanotube-supported Co–Mo–K sulfide catalyst for higher alcohol synthesis
journal, November 2006
- Ma, Xiao-Ming; Lin, Guo-Dong; Zhang, Hong-Bin
- Catalysis Letters, Vol. 111, Issue 3-4
MWCNT-Supported Ni–Mo–K Catalyst for Higher Alcohol Synthesis from Syngas
journal, April 2010
- Ma, Chun-Hui; Li, Hai-Yan; Lin, Guo-Dong
- Catalysis Letters, Vol. 137, Issue 3-4
The Effect of Size-Dependent Nanoparticle Energetics on Catalyst Sintering
journal, October 2002
- Campbell, C. T.
- Science, Vol. 298, Issue 5594
Molybdenum Phosphide: A Conversion-type Anode for Ultralong-Life Sodium-Ion Batteries
journal, August 2017
- Huang, Zhaodong; Hou, Hongshuai; Wang, Chao
- Chemistry of Materials, Vol. 29, Issue 17
Molybdenum Phosphosulfide: An Active, Acid-Stable, Earth-Abundant Catalyst for the Hydrogen Evolution Reaction
journal, October 2014
- Kibsgaard, Jakob; Jaramillo, Thomas F.
- Angewandte Chemie, Vol. 126, Issue 52
A Highly Active Molybdenum Phosphide Catalyst for Methanol Synthesis from CO and CO 2
journal, October 2018
- Duyar, Melis S.; Tsai, Charlie; Snider, Jonathan L.
- Angewandte Chemie, Vol. 130, Issue 46
Heterogeneous Catalytic Synthesis of Ethanol from Biomass-Derived Syngas
journal, December 2007
- Spivey, James J.; Egbebi, Adefemi
- ChemInform, Vol. 38, Issue 50
Methanol synthesis
journal, December 1995
- Grzybowska, B.
- Applied Catalysis A: General, Vol. 133, Issue 2