Subsurface catalysis-mediated selectivity of dehydrogenation reaction

doi:10.1126/sciadv.aar5418

Title: Subsurface catalysis-mediated selectivity of dehydrogenation reaction

Progress in heterogeneous catalysis is often hampered by the difficulties of constructing active architectures and understanding reaction mechanisms at the molecular level due to the structural complexity of practical catalysts, in particular for multicomponent catalysts. Although surface science experiments and theoretical simulations help understand the detailed reaction mechanisms over model systems, the direct study of the nature of nanoparticle catalysts remains a grand challenge. This paper describes a facile construction of well-defined Pt-skin catalysts modified by different 3d transition metal (3dTM) atoms in subsurface regions. However, on the catalyst containing both surface and subsurface 3dTMs, the selectivity of propane dehydrogenation decreases in the sequences of Pt ~ PtFe > PtCo > PtNi due to the easier C–C cracking on exposed Co and Ni sites. After the exposed 3dTMs were removed completely, the C ₃H ₆ selectivity was found to increase markedly in the row Pt < PtNi@Pt < PtCo@Pt < PtFe@Pt, which is in line with the calculated trend of d-band center shifting. The established relationship between reactivity and d-band center shifting illustrates the role of subsurface catalysis in dehydrogenation reaction.

Authors:

; ; ; Sun, Guodong ^[1] ; Chen, Sai ^[1] ; ; ; Tian, Hao ^[1] ; ; ; Zeng, Liang ^[1] ;

Tianjin University (China); Collaborative Innovation Center of Chemical Science and Engineering, Tianjin (China)
Univ. of Kansas, Lawrence, KS (United States)
(Feng) [Univ. of Kansas, Lawrence, KS (United States)

Publication Date:: 2018-08-10

Grant/Contract Number:: SC0014561

Type:: Accepted Manuscript

Journal Name:: Science Advances

Additional Journal Information:: Journal Volume: 4; Journal Issue: 8; Journal ID: ISSN 2375-2548

Publisher:: AAAS

Research Org:: Univ. of Kansas, Lawrence, KS (United States)

Sponsoring Org:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

OSTI Identifier:: 1499915


                    Cai, Weiting, Mu, Rentao, Zha, Shenjun, Sun, Guodong, Chen, Sai, Zhao, Zhi-Jian, Li, Hao, Tian, Hao, Tang, Yu, Tao, Franklin, Zeng, Liang, and Gong, Jinlong. Subsurface catalysis-mediated selectivity of dehydrogenation reaction.  United States: N. p.,  
        Web.  doi:10.1126/sciadv.aar5418.

Copy to clipboard


                    Cai, Weiting, Mu, Rentao, Zha, Shenjun, Sun, Guodong, Chen, Sai, Zhao, Zhi-Jian, Li, Hao, Tian, Hao, Tang, Yu, Tao, Franklin, Zeng, Liang, & Gong, Jinlong. Subsurface catalysis-mediated selectivity of dehydrogenation reaction.  United States.  doi:10.1126/sciadv.aar5418.

Copy to clipboard


                    Cai, Weiting, Mu, Rentao, Zha, Shenjun, Sun, Guodong, Chen, Sai, Zhao, Zhi-Jian, Li, Hao, Tian, Hao, Tang, Yu, Tao, Franklin, Zeng, Liang, and Gong, Jinlong. 2018.  
        "Subsurface catalysis-mediated selectivity of dehydrogenation reaction".  United States.  
        doi:10.1126/sciadv.aar5418.  https://www.osti.gov/servlets/purl/1499915.

Copy to clipboard


                    
@article{osti_1499915,

  title        = {Subsurface catalysis-mediated selectivity of dehydrogenation reaction},

  author       = {Cai, Weiting and Mu, Rentao and Zha, Shenjun and Sun, Guodong and Chen, Sai and Zhao, Zhi-Jian and Li, Hao and Tian, Hao and Tang, Yu and Tao, Franklin and Zeng, Liang and Gong, Jinlong},

  abstractNote = {Progress in heterogeneous catalysis is often hampered by the difficulties of constructing active architectures and understanding reaction mechanisms at the molecular level due to the structural complexity of practical catalysts, in particular for multicomponent catalysts. Although surface science experiments and theoretical simulations help understand the detailed reaction mechanisms over model systems, the direct study of the nature of nanoparticle catalysts remains a grand challenge. This paper describes a facile construction of well-defined Pt-skin catalysts modified by different 3d transition metal (3dTM) atoms in subsurface regions. However, on the catalyst containing both surface and subsurface 3dTMs, the selectivity of propane dehydrogenation decreases in the sequences of Pt ~ PtFe > PtCo > PtNi due to the easier C–C cracking on exposed Co and Ni sites. After the exposed 3dTMs were removed completely, the C3H6 selectivity was found to increase markedly in the row Pt < PtNi@Pt < PtCo@Pt < PtFe@Pt, which is in line with the calculated trend of d-band center shifting. The established relationship between reactivity and d-band center shifting illustrates the role of subsurface catalysis in dehydrogenation reaction.},

  doi          = {10.1126/sciadv.aar5418},

  journal      = {Science Advances},

  number       = 8,

  volume       = 4,

  place        = {United States},

  year         = {2018},

  month        = {8}

}

Copy to clipboard

Free Publicly Accessible Full Text
Accepted Manuscript (DOE)
Publisher's Version of Record
10.1126/sciadv.aar5418
https://doi.org/10.1126/sciadv.aar5418

Works referenced in this record:

Preferential CO Oxidation in Hydrogen: Reactivity of Core?Shell Nanoparticles
journal, June 2010

Nilekar, Anand Udaykumar; Alayoglu, Selim; Eichhorn, Bryan
Journal of the American Chemical Society, Vol. 132, Issue 21, p. 7418-7428
DOI: 10.1021/ja101108w

Special points for Brillouin-zone integrations
journal, June 1976

Monkhorst, Hendrik J.; Pack, James D.
Physical Review B, Vol. 13, Issue 12, p. 5188-5192
DOI: 10.1103/PhysRevB.13.5188

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Kresse, G.; Joubert, D.
Physical Review B, Vol. 59, Issue 3, p. 1758-1775
DOI: 10.1103/PhysRevB.59.1758

Stabilization of Platinum Oxygen-Reduction Electrocatalysts Using Gold Clusters
journal, January 2007

Zhang, J.; Sasaki, K.; Sutter, E.
Science, Vol. 315, Issue 5809, p. 220-222
DOI: 10.1126/science.1134569

Ru�Pt core�shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen
journal, March 2008

Alayoglu, Selim; Nilekar, Anand U.; Mavrikakis, Manos
Nature Materials, Vol. 7, Issue 4, p. 333-338
DOI: 10.1038/nmat2156

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

Henkelman, Graeme; Uberuaga, Blas P.; J�nsson, Hannes
The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
DOI: 10.1063/1.1329672

Improved Oxygen Reduction Activity on Pt₃Ni(111) via Increased Surface Site Availability
journal, January 2007

Stamenkovic, V. R.; Fowler, B.; Mun, B. S.
Science, Vol. 315, Issue 5811, p. 493-497
DOI: 10.1126/science.1135941

Similar Records

Similar records in DOE PAGES and OSTI.GOV collections:

The effect of host structure on the selectivity and mechanism of supramolecular catalysis of Prins cyclizations

Journal Article Hart-Cooper, William M. ; Zhao, Chen ; Triano, Rebecca M. ; ... November 2014 - Chemical Science

The effect of host structure on the selectivity and mechanism of intramolecular Prins reactions is evaluated using K ₁₂Ga ₄L ₆ tetrahedral catalysts. The host structure was varied by modifying the structure of the chelating moieties and the size of the aromatic spacers. While variation in chelator substituents was generally observed to affect changes in rate but not selectivity, changing the host spacer afforded differences in efficiency and product diastereoselectivity. An extremely high number of turnovers (up to 840) was observed. Maximum rate accelerations were measured to be on the order of 10 ⁵, which numbers among the largest magnitudesmore »« less
Cited by 22Full Text Available
Study on catalysis by uranium oxide and its mixed catalysts. IV. Catalytic selectivity of uranium oxide catalyst for dehydrogenation and dehydration of ethanol.

Journal Article - in OSTI.gov collection Nozaki, F. ; Inami, I. January 1972 - Nippon Kagaku Kaishi No. 11, 2202-2204(1972).
NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction

Journal Article Shan, Junjun ; Liu, Jilei ; Li, Mengwei ; ... December 2017 - Applied Catalysis. B, Environmental

Here, NiCu single atom alloy (SAA) nanoparticles supported on silica are reported to catalyze the non-oxidative dehydrogenation of ethanol, selectively to acetaldehyde and hydrogen products by facilitating the C—H bond cleavage. The activity and selectivity of the NiCu SAA catalysts were compared to monometallic copper and to PtCu and PdCu single atom alloys, in a flow reactor at moderate temperatures. In-situ DRIFTS showed that the silica support facilitates the O—H bond cleavage of ethanol to form ethoxy intermediates over all the supported alloy catalysts. However, these remain unreactive up to 250°C for the Cu/SiO ₂ monometallic nanoparticles, while in themore »« less
Cited by 4Full Text Available
Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C=C Unsaturation on Reaction Selectivity

Journal Article Zugic, Branko ; Karakalos, Stavros ; Stowers, Kara J. ; ... February 2016 - ACS Catalysis

We demonstrate the gas-phase catalytic production of methyl acrylates by oxygen-assisted coupling of methanol with the unsaturated alcohols allyl alcohol and methylallyl alcohol over nanoporous gold (npAu) at atmospheric pressure. Analogous investigations on O-activated Au(110) exhibit the same pattern of reactivity and are used to establish that the competition between methoxy and allyloxy (or methallyloxy) reaction intermediates for adsorption sites, mediated by the reactants themselves, determines the selectivity of reaction. These results clearly show that the C=C bond substantially increases the binding efficacy of the allyloxy (or methallyloxy), thus requiring extremely high methanol mole fractions (>0.99) in order to achievemore »« less
Cited by 12Full Text Available
State-to-state mode selectivity in the HD + OH reaction: Perspectives from two product channels

Journal Article Zhao, Bin ; Sun, Zhigang ; Guo, Hua June 2016 - Journal of Chemical Physics

The state-to-state quantum dynamics (J _tot = 0) of the HD + OH(υ ₂ = 0,1) reaction is studied using a reactant coordinate based method, which allows the analysis of both the H + DOH and D + HOH channels with a single propagation. The stretching vibration of the newly formed bond, namely, the OD bond in DOH and one OH bond in HOH, is excited, thanks to its strong coupling with the reaction coordinate at the transition state. On the other hand, the vibrational energy deposited into the OH reactant (υ ₂ = 1) is sequestered during the reactionmore »« less
Cited by 6Full Text Available

Access journal articles and accepted manuscripts resulting from DOE research funding

Title: Subsurface catalysis-mediated selectivity of dehydrogenation reaction

Access journal articles and accepted manuscripts
resulting from DOE research funding