Stable and selective catalysts for propane dehydrogenation operating at thermodynamic limit

Motagamwala, Ali Hussain; Almallahi, Rawan; Wortman, James; Igenegbai, Valentina Omoze; Linic, Suljo

doi:10.1126/science.abg7894

Stable and selective catalysts for propane dehydrogenation operating at thermodynamic limit

Journal Article · Thu Jul 08 00:00:00 EDT 2021 · Science

DOI:https://doi.org/10.1126/science.abg7894· OSTI ID:1806595

^[1]; ^[1]; ^[1]; ^[1]; ^[1]

Department of Chemical Engineering, University of Michigan, Ann Arbor, MI, USA., Catalysis Science and Technology Institute, University of Michigan, Ann Arbor, MI, USA.

Intentional (“on-purpose”) propylene production through nonoxidative propane dehydrogenation (PDH) holds great promise for meeting the increasing global demand for propylene. For stable performance, traditional alumina-supported platinum-based catalysts require excess tin and feed dilution with hydrogen; however, this reduces per-pass propylene conversion and thus lowers catalyst productivity. We report that silica-supported platinum-tin (Pt ₁ Sn ₁ ) nanoparticles (<2 nanometers in diameter) can operate as a PDH catalyst at thermodynamically limited conversion levels, with excellent stability and selectivity to propylene (>99%). Atomic mixing of Pt and Sn in the precursor is preserved upon reduction and during catalytic operation. The benign interaction of these nanoparticles with the silicon dioxide support does not lead to Pt-Sn segregation and formation of a tin oxide phase that can occur over traditional catalyst supports.

View Journal Article

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0021008; EE0007888

OSTI ID:: 1806595

Alternate ID(s):: OSTI ID: 1848651

Journal Information:: Science, Journal Name: Science Journal Issue: 6551 Vol. 373; ISSN 0036-8075

Publisher:: American Association for the Advancement of Science (AAAS)Copyright Statement

Country of Publication:: United States

Language:: English

References (57)

Thermally Stable and Regenerable Platinum–Tin Clusters for Propane Dehydrogenation Prepared by Atom Trapping on Ceria Xiong, Haifeng; Lin, Sen; Goetze, Joris Angewandte Chemie, Vol. 129, Issue 31 https://doi.org/10.1002/ange.201701115	journal	June 2017
Subnanometer Bimetallic Platinum–Zinc Clusters in Zeolites for Propane Dehydrogenation Sun, Qiming; Wang, Ning; Fan, Qiyuan Angewandte Chemie, Vol. 132, Issue 44 https://doi.org/10.1002/ange.202003349	journal	May 2020
Al ₂ O ₃ Nanosheets Rich in Pentacoordinate Al ³⁺ Ions Stabilize Pt-Sn Clusters for Propane Dehydrogenation Shi, Lei; Deng, Gao-Ming; Li, Wen-Cui Angewandte Chemie International Edition, Vol. 54, Issue 47 https://doi.org/10.1002/anie.201507119	journal	September 2015
Thermally Stable and Regenerable Platinum-Tin Clusters for Propane Dehydrogenation Prepared by Atom Trapping on Ceria Xiong, Haifeng; Lin, Sen; Goetze, Joris Angewandte Chemie International Edition, Vol. 56, Issue 31 https://doi.org/10.1002/anie.201701115	journal	June 2017
Subnanometer Bimetallic Platinum–Zinc Clusters in Zeolites for Propane Dehydrogenation Sun, Qiming; Wang, Ning; Fan, Qiyuan Angewandte Chemie International Edition, Vol. 59, Issue 44 https://doi.org/10.1002/anie.202003349	journal	May 2020
Dehydrogenation of Propane over Silica-Supported Platinum-Tin Catalysts Prepared by Direct Reduction: Effects of Tin/Platinum Ratio and Reduction Temperature Deng, Lidan; Miura, Hiroki; Shishido, Tetsuya ChemCatChem, Vol. 6, Issue 9 https://doi.org/10.1002/cctc.201402306	journal	August 2014
Carbon Dynamics on the Molybdenum Carbide Surface during Catalytic Propane Dehydrogenation Frank, Benjamin; Cotter, Thomas P.; Schuster, Manfred E. Chemistry - A European Journal, Vol. 19, Issue 50 https://doi.org/10.1002/chem.201302420	journal	November 2013
Propane Dehydrogenation over Supported Pt and Pt–Sn Catalysts: Catalyst Preparation, Characterization, and Activity Measurements Bariås, Odd A.; Holmen, Anders; Blekkan, Edd A. Journal of Catalysis, Vol. 158, Issue 1 https://doi.org/10.1006/jcat.1996.0001	journal	January 1996
Effect of Sodium Addition to PtSn/AlSBA-15 on the Catalytic Properties in Propane Dehydrogenation Duan, Yongzheng; Zhou, Yuming; Zhang, Yiwei Catalysis Letters, Vol. 141, Issue 1 https://doi.org/10.1007/s10562-010-0445-6	journal	November 2010
Development of Dehydrogenation Catalysts and Processes Vora, Bipin V. Topics in Catalysis, Vol. 55, Issue 19-20 https://doi.org/10.1007/s11244-012-9917-9	journal	November 2012
FTIR study of bimetallic Pt-Sn/Al2O3 catalysts Balakrishnan, K. Journal of Catalysis, Vol. 138, Issue 2 https://doi.org/10.1016/0021-9517(92)90301-W	journal	December 1992
Thermolytic molecular precursor routes to Cr/Si/Al/O and Cr/Si/Zr/O catalysts for the oxidative dehydrogenation and dehydrogenation of propane Fujdala, K. Journal of Catalysis, Vol. 218, Issue 1 https://doi.org/10.1016/S0021-9517(03)00141-6	journal	August 2003
Dehydrogenation and oxydehydrogenation of paraffins to olefins Bhasin, M. M.; McCain, J. H.; Vora, B. V. Applied Catalysis A: General, Vol. 221, Issue 1-2, p. 397-419 https://doi.org/10.1016/S0926-860X(01)00816-X	journal	November 2001
Dehydrogenation of propane to propene over gallium oxide in the presence of CO2 Michorczyk, P. Applied Catalysis A: General, Vol. 251, Issue 2 https://doi.org/10.1016/S0926-860X(03)00368-5	journal	September 2003
H2 reduction behaviors and catalytic performance of bimetallic tin-modified platinum catalysts for propane dehydrogenation Salmones, José; Wang, Jin-An; Galicia, José A. Journal of Molecular Catalysis A: Chemical, Vol. 184, Issue 1-2 https://doi.org/10.1016/S1381-1169(01)00525-8	journal	June 2002
XPS and EXAFS study of supported PtSn catalysts obtained by surface organometallic chemistry on metals Siri, Guillermo J.; Ramallo-López, José M.; Casella, Mónica L. Applied Catalysis A: General, Vol. 278, Issue 2 https://doi.org/10.1016/j.apcata.2004.10.004	journal	January 2005
Non-oxidative propane dehydrogenation over Pt–Zn-containing zeolites De Cola, Patrizia Laura; Gläser, Roger; Weitkamp, Jens Applied Catalysis A: General, Vol. 306 https://doi.org/10.1016/j.apcata.2006.03.028	journal	June 2006
Mass and heat transfer effects on the oxidative dehydrogenation of propane (ODP) over a low loaded VOx/Al2O3 catalyst Frank, Benjamin; Dinse, Arne; Ovsitser, Olga Applied Catalysis A: General, Vol. 323 https://doi.org/10.1016/j.apcata.2007.02.006	journal	April 2007
Light alkane dehydrogenation over mesoporous Cr2O3/Al2O3 catalysts Shee, Debaprasad; Sayari, Abdelhamid Applied Catalysis A: General, Vol. 389, Issue 1-2 https://doi.org/10.1016/j.apcata.2010.09.013	journal	December 2010
Controlling the acid-base properties of alumina for stable PtSn-based propane dehydrogenation catalysts Jang, Eun Jeong; Lee, Jaekyoung; Jeong, Hu Young Applied Catalysis A: General, Vol. 572 https://doi.org/10.1016/j.apcata.2018.12.024	journal	February 2019
Propane dehydrogenation on PtSn/ZSM-5 catalyst: Effect of tin as a promoter Zhang, Yiwei; Zhou, Yuming; Qiu, Anding Catalysis Communications, Vol. 7, Issue 11 https://doi.org/10.1016/j.catcom.2006.03.016	journal	November 2006
Effect of reduction method on the activity of Pt–Sn/SiO2 for dehydrogenation of propane Deng, Lidan; Shishido, Tetsuya; Teramura, Kentaro Catalysis Today, Vol. 232 https://doi.org/10.1016/j.cattod.2013.10.064	journal	September 2014
Role of acid solvent to prepare highly active PtSn/θ-Al 2 O 3 catalysts in dehydrogenation of propane to propylene Prakash, Natarajan; Lee, Mi-Hyun; Yoon, Sungho Catalysis Today, Vol. 293-294 https://doi.org/10.1016/j.cattod.2017.02.027	journal	September 2017
Improved catalytic performance in propane dehydrogenation of PtSn/γ-Al2O3 catalysts by doping indium Liu, Xue; Lang, Wan-Zhong; Long, Liu-Liu Chemical Engineering Journal, Vol. 247 https://doi.org/10.1016/j.cej.2014.02.084	journal	July 2014
Dehydrogenation of propane to propene over different polymorphs of gallium oxide Zheng, B.; Hua, W.; Yue, Y. Journal of Catalysis, Vol. 232, Issue 1 https://doi.org/10.1016/j.jcat.2005.03.001	journal	May 2005
Support effect in dehydrogenation of propane in the presence of CO2 over supported gallium oxide catalysts Xu, B.; Zheng, B.; Hua, W. Journal of Catalysis, Vol. 239, Issue 2 https://doi.org/10.1016/j.jcat.2006.02.017	journal	April 2006
Dehydrogenation of propane over spinel-type gallia–alumina solid solution catalysts Chen, M.; Xu, J.; Su, F. Journal of Catalysis, Vol. 256, Issue 2 https://doi.org/10.1016/j.jcat.2008.03.021	journal	June 2008
Catalyst performance of novel Pt/Mg(Ga)(Al)O catalysts for alkane dehydrogenation Siddiqi, Georges; Sun, Pingping; Galvita, Vladimir Journal of Catalysis, Vol. 274, Issue 2 https://doi.org/10.1016/j.jcat.2010.06.016	journal	September 2010
A combined in situ time-resolved UV–Vis, Raman and high-energy resolution X-ray absorption spectroscopy study on the deactivation behavior of Pt and PtSn propane dehydrogenation catalysts under industrial reaction conditions Iglesias-Juez, Ana; Beale, Andrew M.; Maaijen, Karin Journal of Catalysis, Vol. 276, Issue 2 https://doi.org/10.1016/j.jcat.2010.09.018	journal	December 2010
Novel Pt/Mg(In)(Al)O catalysts for ethane and propane dehydrogenation Sun, Pingping; Siddiqi, Georges; Vining, William C. Journal of Catalysis, Vol. 282, Issue 1 https://doi.org/10.1016/j.jcat.2011.06.008	journal	August 2011
Sn surface-enriched Pt–Sn bimetallic nanoparticles as a selective and stable catalyst for propane dehydrogenation Zhu, Haibo; Anjum, Dalaver H.; Wang, Qingxiao Journal of Catalysis, Vol. 320 https://doi.org/10.1016/j.jcat.2014.09.013	journal	December 2014
Size effect of TS-1 supports on the catalytic performance of PtSn/TS-1 catalysts for propane dehydrogenation Li, Jiacheng; Li, Jianmei; Zhao, Zhen Journal of Catalysis, Vol. 352 https://doi.org/10.1016/j.jcat.2017.05.024	journal	August 2017
Propane dehydrogenation over supported Pt-Sn nanoparticles Kaylor, Nicholas; Davis, Robert J. Journal of Catalysis, Vol. 367 https://doi.org/10.1016/j.jcat.2018.09.006	journal	November 2018
γ-Al2O3 sheet-stabilized isolate Co2+ for catalytic propane dehydrogenation Dai, Yihu; Gu, Jingjing; Tian, Suyang Journal of Catalysis, Vol. 381 https://doi.org/10.1016/j.jcat.2019.11.026	journal	January 2020
Ultrasmall PtZn bimetallic nanoclusters encapsulated in silicalite-1 zeolite with superior performance for propane dehydrogenation Wang, Yansu; Hu, Zhong-Pan; Lv, Xianwei Journal of Catalysis, Vol. 385 https://doi.org/10.1016/j.jcat.2020.02.019	journal	May 2020
Effect of tin and potassium addition on the nature of platinum supported on silica Rodríguez, D.; Sánchez, J.; Arteaga, G. Journal of Molecular Catalysis A: Chemical, Vol. 228, Issue 1-2 https://doi.org/10.1016/j.molcata.2004.09.067	journal	March 2005
Comparative study of bimetallic Pt-Sn catalysts supported on different supports for propane dehydrogenation Zhang, Yiwei; Zhou, Yuming; Shi, Junjun Journal of Molecular Catalysis A: Chemical, Vol. 381 https://doi.org/10.1016/j.molcata.2013.10.007	journal	January 2014
Combined DRIFTS and DFT Study of CO Adsorption and Segregation Modes in Pt–Sn Nanoalloys Wang, Qing; Tichit, Didier; Meunier, Frederic The Journal of Physical Chemistry C, Vol. 124, Issue 18 https://doi.org/10.1021/acs.jpcc.0c01296	journal	April 2020
Dynamic Phase Diagram of Catalytic Surface of Hexagonal Boron Nitride under Conditions of Oxidative Dehydrogenation of Propane Zhang, Zisheng; Jimenez-Izal, Elisa; Hermans, Ive The Journal of Physical Chemistry Letters, Vol. 10, Issue 1 https://doi.org/10.1021/acs.jpclett.8b03373	journal	December 2018
Isolated Fe ^II on Silica As a Selective Propane Dehydrogenation Catalyst Hu, Bo; Schweitzer, Neil M.; Zhang, Guanghui ACS Catalysis, Vol. 5, Issue 6 https://doi.org/10.1021/acscatal.5b00248	journal	May 2015
Role of Sn in the Regeneration of Pt/γ-Al ₂ O ₃ Light Alkane Dehydrogenation Catalysts Pham, Hien N.; Sattler, Jesper J. H. B.; Weckhuysen, Bert M. ACS Catalysis, Vol. 6, Issue 4 https://doi.org/10.1021/acscatal.5b02917	journal	March 2016
Oxidative Dehydrogenation of Propane over a High Surface Area Boron Nitride Catalyst: Exceptional Selectivity for Olefins at High Conversion Chaturbedy, Piyush; Ahamed, Momin; Eswaramoorthy, Muthusamy ACS Omega, Vol. 3, Issue 1 https://doi.org/10.1021/acsomega.7b01489	journal	January 2018
Sustainable Process Design Approach for On-Purpose Propylene Production and Intensification Agarwal, Ashwin; Sengupta, Debalina; El-Halwagi, Mahmoud ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 2 https://doi.org/10.1021/acssuschemeng.7b03854	journal	December 2017
Catalytic Dehydrogenation of Light Alkanes on Metals and Metal Oxides Sattler, Jesper J. H. B.; Ruiz-Martinez, Javier; Santillan-Jimenez, Eduardo Chemical Reviews, Vol. 114, Issue 20 https://doi.org/10.1021/cr5002436	journal	August 2014
Sn-Modified ZSM-5 As Support for Platinum Catalyst in Propane Dehydrogenation Zhang, Yiwei; Zhou, Yuming; Huang, Li Industrial & Engineering Chemistry Research, Vol. 50, Issue 13 https://doi.org/10.1021/ie1024694	journal	July 2011
Surface Chemistry of SO ₂ on Sn and Sn/Pt(111) Alloys: Effects of Metal−Metal Bonding on Reactivity toward Sulfur Rodriguez, José A.; Jirsak, Tomas; Chaturvedi, Sanjay Journal of the American Chemical Society, Vol. 120, Issue 43 https://doi.org/10.1021/ja982174a	journal	November 1998
XPS and XAFS Pt L _2,3 -Edge Studies of Dispersed Metallic Pt and PtSn Clusters on SiO ₂ Obtained by Organometallic Synthesis: Structural and Electronic Characteristics Ramallo-López, José M.; Santori, Gerardo F.; Giovanetti, Lisandro The Journal of Physical Chemistry B, Vol. 107, Issue 41 https://doi.org/10.1021/jp030579y	journal	October 2003
Microcalorimetric, Infrared Spectroscopic, and DFT Studies of Ethylene Adsorption on Pt/SiO ₂ and Pt−Sn/SiO ₂ Catalysts Shen, Jianyi; Hill, Josephine M.; Watwe, Ramchandra M. The Journal of Physical Chemistry B, Vol. 103, Issue 19 https://doi.org/10.1021/jp9902452	journal	May 1999
Equilibrated Adsorption of CO on Silica-Supported Pt Catalysts Podkolzin, Sergei G.; Shen, Jianyi; de Pablo, Juan J. The Journal of Physical Chemistry B, Vol. 104, Issue 17 https://doi.org/10.1021/jp993833o	journal	May 2000
Propane Dehydrogenation on Mixed Ga/Cr Oxide Pillared Zirconium Phosphate Materials Alcántara-Rodríguez, Manuel; Rodríguez-Castellón, Enrique; Jiménez-López, Antonio Langmuir, Vol. 15, Issue 4 https://doi.org/10.1021/la981042s	journal	February 1999
Dehydrogenation of Propane over Chromia-Pillared Zirconium Phosphate Catalysts Pérez-Reina, F. J.; Rodríguez-Castellón, E.; Jiménez-López, A. Langmuir, Vol. 15, Issue 24 https://doi.org/10.1021/la990504e	journal	November 1999
Regioselective generation and reactivity control of subnanometric platinum clusters in zeolites for high-temperature catalysis Liu, Lichen; Lopez-Haro, Miguel; Lopes, Christian W. Nature Materials, Vol. 18, Issue 8 https://doi.org/10.1038/s41563-019-0412-6	journal	July 2019
Direct PtSn Alloy Formation by Pt Electrodeposition on Sn Surface Schwämmlein, Jan N.; Torres, Paulette A. Loichet; Gasteiger, Hubert A. Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-019-56749-5	journal	January 2020
Structural modulation and direct measurement of subnanometric bimetallic PtSn clusters confined in zeolites Liu, Lichen; Lopez-Haro, Miguel; Lopes, Christian W. Nature Catalysis, Vol. 3, Issue 8 https://doi.org/10.1038/s41929-020-0472-7	journal	June 2020
Direct evidence by in situ IR CO monitoring of the formation and the surface segregation of a Pt–Sn alloy Moscu, Alina; Schuurman, Yves; Veyre, Laurent Chemical Communications, Vol. 50, Issue 62 https://doi.org/10.1039/C4CC03208J	journal	January 2014
Operando UV-Vis spectroscopy of a catalytic solid in a pilot-scale reactor: deactivation of a CrOx/Al2O3 propane dehydrogenation catalyst Sattler, J. J. H. B.; González-Jiménez, I. D.; Mens, A. M. Chemical Communications, Vol. 49, Issue 15 https://doi.org/10.1039/c2cc38978a	journal	January 2013
Selective oxidative dehydrogenation of propane to propene using boron nitride catalysts Grant, J. T.; Carrero, C. A.; Goeltl, F. Science, Vol. 354, Issue 6319 https://doi.org/10.1126/science.aaf7885	journal	December 2016

Similar Records

Stable and selective catalysts for propane dehydrogenation operating at thermodynamic limit

Journal Article · Fri Jul 09 00:00:00 EDT 2021 · Science · OSTI ID:1848651

Overcoming limitations in propanedehydrogenation by codesigning catalyst-membrane systems

Journal Article · Thu Mar 21 00:00:00 EDT 2024 · Science · OSTI ID:2338159

Stable and selective catalysts for propane dehydrogenation operating at thermodynamic limit

Citation Formats

References (57)

Similar Records

Related Subjects