Development of Molybdenum Phosphide Catalysts for Higher Alcohol Synthesis from Syngas by Exploiting Support and Promoter Effects

ten Have, Iris C.; Valle, Eduardo; Gallo, Alessandro; Snider, Jonathan L.; Duyar, Melis S.; Jaramillo, Thomas F.

doi:10.1002/ente.201801102

Title: Development of Molybdenum Phosphide Catalysts for Higher Alcohol Synthesis from Syngas by Exploiting Support and Promoter Effects

Journal Article · 05 February 2019 · Energy Technology

DOI: https://doi.org/10.1002/ente.201801102 · OSTI ID:1547286

^[1]; Valle, Eduardo ^[2];

^[2]; Snider, Jonathan L. ^[2];

^[2]; Jaramillo, Thomas F. ^[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)

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.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1547286

Journal Information:: Energy Technology, Journal Name: Energy Technology Journal Issue: 5 Vol. 7; ISSN 2194-4288

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (64)

Molybdenum Phosphosulfide: An Active, Acid-Stable, Earth-Abundant Catalyst for the Hydrogen Evolution Reaction Kibsgaard, Jakob; Jaramillo, Thomas F. Angewandte Chemie, Vol. 126, Issue 52 https://doi.org/10.1002/ange.201408222	journal	October 2014
A Highly Active Molybdenum Phosphide Catalyst for Methanol Synthesis from CO and CO ₂ Duyar, Melis S.; Tsai, Charlie; Snider, Jonathan L. Angewandte Chemie, Vol. 130, Issue 46 https://doi.org/10.1002/ange.201806583	journal	October 2018
Molybdenum Phosphosulfide: An Active, Acid-Stable, Earth-Abundant Catalyst for the Hydrogen Evolution Reaction Kibsgaard, Jakob; Jaramillo, Thomas F. Angewandte Chemie International Edition, Vol. 53, Issue 52 https://doi.org/10.1002/anie.201408222	journal	October 2014
A Highly Active Molybdenum Phosphide Catalyst for Methanol Synthesis from CO and CO ₂ Duyar, Melis S.; Tsai, Charlie; Snider, Jonathan L. Angewandte Chemie International Edition, Vol. 57, Issue 46 https://doi.org/10.1002/anie.201806583	journal	October 2018
Nano- and Microscale Engineering of the Molybdenum Disulfide-Based Catalysts for Syngas to Ethanol Conversion Konarova, Muxina; Tang, Fengqiu; Chen, Jiuling ChemCatChem, Vol. 6, Issue 8 https://doi.org/10.1002/cctc.201402067	journal	July 2014
Heterogeneous Catalytic Synthesis of Ethanol from Biomass-Derived Syngas Spivey, James J.; Egbebi, Adefemi ChemInform, Vol. 38, Issue 50 https://doi.org/10.1002/chin.200750248	journal	December 2007
Quality management and method Validation in EDXRF analysis Álvarez, R. Padilla; Markowicz, A.; Wegrzynek, D. X-Ray Spectrometry, Vol. 36, Issue 1 https://doi.org/10.1002/xrs.923	journal	January 2007
Synthesis, Characterization, and Hydrodesulfurization Properties of Silica-Supported Molybdenum Phosphide Catalysts Phillips, Diana C.; Sawhill, Stephanie J.; Self, Randy Journal of Catalysis, Vol. 207, Issue 2 https://doi.org/10.1006/jcat.2002.3524	journal	April 2002
Synthesis, Characterization, and Hydrotreating Activity of Several Iron Group Transition Metal Phosphides Wang, Xianqin; Clark, Paul; Oyama, S. Ted Journal of Catalysis, Vol. 208, Issue 2 https://doi.org/10.1006/jcat.2002.3604	journal	June 2002
Co-decorated carbon nanotube-supported Co–Mo–K sulfide catalyst for higher alcohol synthesis Ma, Xiao-Ming; Lin, Guo-Dong; Zhang, Hong-Bin Catalysis Letters, Vol. 111, Issue 3-4 https://doi.org/10.1007/s10562-006-0154-3	journal	November 2006
MWCNT-Supported Ni–Mo–K Catalyst for Higher Alcohol Synthesis from Syngas Ma, Chun-Hui; Li, Hai-Yan; Lin, Guo-Dong Catalysis Letters, Vol. 137, Issue 3-4 https://doi.org/10.1007/s10562-010-0343-y	journal	April 2010
Methanol Synthesis Waugh, K. C. Catalysis Letters, Vol. 142, Issue 10 https://doi.org/10.1007/s10562-012-0905-2	journal	September 2012
Metal Phosphides: Preparation, Characterization and Catalytic Reactivity Prins, Roel; Bussell, Mark E. Catalysis Letters, Vol. 142, Issue 12 https://doi.org/10.1007/s10562-012-0929-7	journal	November 2012
High Pressure CO Hydrogenation Over Bimetallic Pt–Co Catalysts Christensen, Jakob M.; Medford, Andrew J.; Studt, Felix Catalysis Letters, Vol. 144, Issue 5 https://doi.org/10.1007/s10562-014-1220-x	journal	March 2014
Synthesis of mixed alcohols from synthesis gas over alkali and Fischer–Tropsch metals modified MoS2/Al2O3-montmorillonite catalysts Liu, Yanyong; Murata, Kazuhisa; Inaba, Megumu Reaction Kinetics, Mechanisms and Catalysis, Vol. 113, Issue 1 https://doi.org/10.1007/s11144-014-0725-z	journal	June 2014
Activity and Selectivity Trends in Synthesis Gas Conversion to Higher Alcohols Medford, Andrew J.; Lausche, Adam C.; Abild-Pedersen, Frank Topics in Catalysis, Vol. 57, Issue 1-4 https://doi.org/10.1007/s11244-013-0169-0	journal	October 2013
Higher Alcohol Synthesis Using K-Doped CoRhMoS2/MWCNT Catalysts: Influence of Pelletization, Particle Size and Incorporation of Binders Boahene, Philip E.; Surisetty, Venkateswara R.; Sammynaiken, Ramaswami Topics in Catalysis, Vol. 57, Issue 6-9 https://doi.org/10.1007/s11244-013-0210-3	journal	December 2013
Higher alcohol and oxygenate synthesis over cesium-doped Cu/Zno catalysts Nunan, J. Journal of Catalysis, Vol. 116, Issue 1 https://doi.org/10.1016/0021-9517(89)90086-9	journal	March 1989
The effects of carbon dioxide, methanol, and alkali promoter concentration on the higher alcohol synthesis over a Cu/ZnO/Cr2O3 catalyst Calverley, E. Journal of Catalysis, Vol. 130, Issue 2 https://doi.org/10.1016/0021-9517(91)90141-P	journal	August 1991
Methanol Synthesis Waugh, K. C. Catalysis Today, Vol. 15, Issue 1 https://doi.org/10.1016/0920-5861(92)80122-4	journal	May 1992
Methanol synthesis Grzybowska, B. Applied Catalysis A: General, Vol. 133, Issue 2 https://doi.org/10.1016/0926-860x(96)80011-1	journal	December 1995
Novel catalysts for advanced hydroprocessing: transition metal phosphides Oyama, S. Ted Journal of Catalysis, Vol. 216, Issue 1-2, p. 343-352 https://doi.org/10.1016/S0021-9517(02)00069-6	journal	May 2003
Alumina-supported molybdenum phosphide hydroprocessing catalysts Clark, P. Journal of Catalysis, Vol. 218, Issue 1 https://doi.org/10.1016/S0021-9517(03)00086-1	journal	August 2003
Role of impurities in the enhancement of C2-oxygenates activity Nonneman, L. E. Y.; Bastein, A. G. T. M.; Ponec, V. Applied Catalysis, Vol. 62, Issue 1 https://doi.org/10.1016/S0166-9834(00)82230-7	journal	June 1990
Methanol Synthesis Klier, K. Advances in Catalysis https://doi.org/10.1016/S0360-0564(08)60455-1	book	January 1982
Advances in catalytic synthesis and utilization of higher alcohols Herman, R. G. Catalysis Today, Vol. 55, Issue 3 https://doi.org/10.1016/S0920-5861(99)00246-1	journal	January 2000
Synthesis of higher alcohols on copper catalysts supported on alkali-promoted basic oxides Hilmen, Anne-Mette; Xu, Mingting; Gines, Marcelo J. L. Applied Catalysis A: General, Vol. 169, Issue 2 https://doi.org/10.1016/S0926-860X(98)00025-8	journal	May 1998
Advances in bifunctional catalysis for higher alcohol synthesis from syngas Xiao, Kang; Bao, Zhenghong; Qi, Xingzhen Chinese Journal of Catalysis, Vol. 34, Issue 1 https://doi.org/10.1016/S1872-2067(11)60496-8	journal	January 2013
Effects of H2S and process conditions in the synthesis of mixed alcohols from syngas over alkali promoted cobalt-molybdenum sulfide Christensen, J. M.; Mortensen, P. M.; Trane, R. Applied Catalysis A: General, Vol. 366, Issue 1 https://doi.org/10.1016/j.apcata.2009.06.034	journal	September 2009
A study of K-promoted MoP–SiO2 catalysts for synthesis gas conversion Zaman, Sharif F.; Smith, Kevin J. Applied Catalysis A: General, Vol. 378, Issue 1 https://doi.org/10.1016/j.apcata.2010.01.046	journal	April 2010
Correlation patterns and effect of syngas conversion level for product selectivity to alcohols and hydrocarbons over molybdenum sulfide based catalysts Andersson, Robert; Boutonnet, Magali; Järås, Sven Applied Catalysis A: General, Vol. 417-418 https://doi.org/10.1016/j.apcata.2011.12.033	journal	February 2012
Effect of potassium addition method on MoS2 performance for the syngas to alcohol reaction Ferrari, D.; Budroni, G.; Bisson, L. Applied Catalysis A: General, Vol. 462-463 https://doi.org/10.1016/j.apcata.2013.05.006	journal	July 2013
An efficient Ni–Mo–K sulfide catalyst doped with CNTs for conversion of syngas to ethanol and higher alcohols Wang, Ji-Jie; Xie, Jian-Rong; Huang, Yan-Hui Applied Catalysis A: General, Vol. 468 https://doi.org/10.1016/j.apcata.2013.08.026	journal	November 2013
Carbon monoxide hydrogenation on potassium promoted Mo 2 N catalysts Zaman, Sharif F.; Pasupulety, Nagaraju; Al-Zahrani, Abdulrahim A. Applied Catalysis A: General, Vol. 532 https://doi.org/10.1016/j.apcata.2016.12.015	journal	February 2017
Ni-decorated carbon nanotube-promoted Ni–Mo–K catalyst for highly efficient synthesis of higher alcohols from syngas Ma, Chun-Hui; Li, Hai-Yan; Lin, Guo-Dong Applied Catalysis B: Environmental, Vol. 100, Issue 1-2 https://doi.org/10.1016/j.apcatb.2010.07.040	journal	October 2010
Synthesis, characterization, and hydrotreating activity of carbon-supported transition metal phosphides Shu, Yuying; Oyama, S. Ted Carbon, Vol. 43, Issue 7 https://doi.org/10.1016/j.carbon.2005.01.036	journal	June 2005
Graphitic mesoporous carbon as a support of promoted Rh catalysts for hydrogenation of carbon monoxide to ethanol Chai, Song-Hai; Howe, Jane Y.; Wang, Xiqing Carbon, Vol. 50, Issue 4 https://doi.org/10.1016/j.carbon.2011.11.036	journal	April 2012
Potassium and nickel doped β-Mo2C catalysts for mixed alcohols synthesis via syngas Xiang, Minglin; Li, Debao; Li, Wenhuai Catalysis Communications, Vol. 8, Issue 3 https://doi.org/10.1016/j.catcom.2006.07.028	journal	March 2007
Synthesis gas conversion over MoP catalysts Zaman, S.; Smith, K. Catalysis Communications, Vol. 10, Issue 5 https://doi.org/10.1016/j.catcom.2008.10.022	journal	January 2009
Catalytic conversion of syngas into C2 oxygenates over Rh-based catalysts—Effect of carbon supports Fan, Zhongli; Chen, Wei; Pan, Xiulian Catalysis Today, Vol. 147, Issue 2 https://doi.org/10.1016/j.cattod.2009.03.004	journal	September 2009
Synthesis gas conversion over a Rh–K–MoP/SiO2 catalyst Zaman, Sharif F.; Smith, Kevin J. Catalysis Today, Vol. 171, Issue 1 https://doi.org/10.1016/j.cattod.2011.02.017	journal	August 2011
Synthesis of higher alcohols from syngas over Fischer–Tropsch elements modified K/β-Mo₂C catalysts Xiang, M.; Li, D.; Xiao, H. Fuel, Vol. 87, Issue 4-5, p. 599-603 https://doi.org/10.1016/j.fuel.2007.01.041	journal	April 2008
The effect of cobalt addition to bulk MoP and Ni2P catalysts for the hydrodesulfurization of 4,6-dimethyldibenzothiophene Abu, I.; Smith, K. Journal of Catalysis, Vol. 241, Issue 2 https://doi.org/10.1016/j.jcat.2006.05.010	journal	July 2006
Characterization and testing of silica-supported cobalt–palladium catalysts for conversion of syngas to oxygenates Kumar, Nitin; Smith, Miranda L.; Spivey, J. J. Journal of Catalysis, Vol. 289 https://doi.org/10.1016/j.jcat.2012.02.011	journal	May 2012
Different role of H2S and dibenzothiophene in the incorporation of sulfur in the surface of bulk MoP during hydrodesulfurization Bai, Jin; Li, Xiang; Wang, Anjie Journal of Catalysis, Vol. 300 https://doi.org/10.1016/j.jcat.2013.01.015	journal	April 2013
Tuning of higher alcohol selectivity and productivity in CO hydrogenation reactions over K/MoS2 domains supported on mesoporous activated carbon and mixed MgAl oxide Taborga Claure, Micaela; Chai, Song-Hai; Dai, Sheng Journal of Catalysis, Vol. 324 https://doi.org/10.1016/j.jcat.2015.01.015	journal	April 2015
Remarkably efficient CoGa catalyst with uniformly dispersed and trapped structure for ethanol and higher alcohol synthesis from syngas Ning, Xun; An, Zhe; He, Jing Journal of Catalysis, Vol. 340 https://doi.org/10.1016/j.jcat.2016.05.014	journal	August 2016
Experimental and computational study of syngas and ethanol conversion mechanisms over K-modified transition metal sulfide catalysts Dorokhov, V. S.; Permyakov, E. A.; Nikulshin, P. A. Journal of Catalysis, Vol. 344 https://doi.org/10.1016/j.jcat.2016.08.005	journal	December 2016
Graphitic mesoporous carbon-supported molybdenum carbides for catalytic hydrogenation of carbon monoxide to mixed alcohols Chai, Song-Hai; Schwartz, Viviane; Howe, Jane Y. Microporous and Mesoporous Materials, Vol. 170 https://doi.org/10.1016/j.micromeso.2012.11.025	journal	April 2013
Molybdenum Phosphide: A Conversion-type Anode for Ultralong-Life Sodium-Ion Batteries Huang, Zhaodong; Hou, Hongshuai; Wang, Chao Chemistry of Materials, Vol. 29, Issue 17 https://doi.org/10.1021/acs.chemmater.7b02193	journal	August 2017
Rh-MnO Interface Sites Formed by Atomic Layer Deposition Promote Syngas Conversion to Higher Oxygenates Yang, Nuoya; Yoo, Jong Suk; Schumann, Julia ACS Catalysis, Vol. 7, Issue 9 https://doi.org/10.1021/acscatal.7b01851	journal	August 2017
Layered Molybdenum (Oxy)Pyrophosphate as Cathode for Lithium-Ion Batteries Wen, Bohua; Chernova, Natasha A.; Zhang, Ruibo Chemistry of Materials, Vol. 25, Issue 17 https://doi.org/10.1021/cm401946h	journal	August 2013
Mechanistic Insight into the Synthesis of Higher Alcohols from Syngas: The Role of K Promotion on MoS ₂ Catalysts Santos, Vera P.; van der Linden, Bart; Chojecki, Adam ACS Catalysis, Vol. 3, Issue 7 https://doi.org/10.1021/cs4003518	journal	June 2013
Mixed Alcohol Synthesis over Sulfided Molybdenum-Based Catalysts Toyoda, Takashi; Minami, Takayuki; Qian, Eika W. Energy & Fuels, Vol. 27, Issue 7 https://doi.org/10.1021/ef400262a	journal	June 2013
Kinetic Analysis of Mixed Alcohol Synthesis from Syngas over K/MoS ₂ Catalyst Park, Tae Yun; Nam, In-Sik; Kim, Young Gul Industrial & Engineering Chemistry Research, Vol. 36, Issue 12 https://doi.org/10.1021/ie9605701	journal	December 1997
Envisaging the Physicochemical Processes during the Preparation of Supported Catalysts: Raman Microscopy on the Impregnation of Mo onto Al ₂ O ₃ Extrudates Bergwerff, Jaap A.; Visser, Tom; Leliveld, G. Journal of the American Chemical Society, Vol. 126, Issue 44 https://doi.org/10.1021/ja040107c	journal	November 2004
XAFS Characterization of Highly Active Alumina-Supported Molybdenum Phosphide Catalysts (MoP/Al ₂ O ₃ ) for Hydrotreating Oyama, S. T.; Clark, P.; Teixeira da Silva, V. L. S. The Journal of Physical Chemistry B, Vol. 105, Issue 21 https://doi.org/10.1021/jp004500q	journal	May 2001
Status and prospects in higher alcohols synthesis from syngas Luk, Ho Ting; Mondelli, Cecilia; Ferré, Daniel Curulla Chemical Society Reviews, Vol. 46, Issue 5 https://doi.org/10.1039/C6CS00324A	journal	January 2017
Heterogeneous catalytic synthesis of ethanol from biomass-derived syngas Spivey, James J.; Egbebi, Adefemi Chemical Society Reviews, Vol. 36, Issue 9 https://doi.org/10.1039/b414039g	journal	January 2007
Nanoscale design to enable the revolution in renewable energy Baxter, Jason; Bian, Zhixi; Chen, Gang Energy & Environmental Science, Vol. 2, Issue 6 https://doi.org/10.1039/b821698c	journal	January 2009
Mechanism and microkinetics of the Fischer–Tropsch reaction van Santen, R. A.; Markvoort, A. J.; Filot, I. A. W. Physical Chemistry Chemical Physics, Vol. 15, Issue 40 https://doi.org/10.1039/c3cp52506f	journal	January 2013
A Review of Molybdenum Catalysts for Synthesis Gas Conversion to Alcohols: Catalysts, Mechanisms and Kinetics Zaman, Sharif; Smith, Kevin J. Catalysis Reviews, Vol. 54, Issue 1 https://doi.org/10.1080/01614940.2012.627224	journal	January 2012
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
The Effect of Size-Dependent Nanoparticle Energetics on Catalyst Sintering Campbell, C. T. Science, Vol. 298, Issue 5594 https://doi.org/10.1126/science.1075094	journal	October 2002

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