Well-Defined Rhodium–Gallium Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes [Well-Defined Rh–Ga Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes]

doi:10.1021/jacs.8b08550

Title: Well-Defined Rhodium–Gallium Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes [Well-Defined Rh–Ga Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes]

Abstract

Promoters are ubiquitous in industrial heterogeneous catalysts. The wider roles of promoters in accelerating catalysis and/or controlling selectivity are, however, not well understood. A model system has been developed where a heterobimetallic active site comprising an active metal (Rh) and a promoter metal (Ga) are preassembled and delivered into a metal-organic framework (MOF) support. The Rh-Ga sites in the MOF selectively catalyze the hydrogenation of acyclic alkynes to E-alkenes, which is complementary to Lindlar’s catalyst, which generates only Z-alkenes. The role of the Ga in promoting this unusual selectivity is underscored by the lack of semi-hydrogenation selectivity when Ga is absent and only Rh is present in the active site. We acknowledge Dr. Camille Malonzo May (UMN), Dr. David Kaphan (Argonne), Dr. Tata Gopinath (UMN), and Dr. Zhanyong Li (NW) for experimental assistance, and Dr. Dale Pahls for preliminary theoretical calculations. This work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award No. DE-SC0012702. This research used resources of: (1) the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility; and, (2)more »« less

Authors:

Desai, Sai Puneet ^[1];

^[1];

^[2]; Ferrandon, Magali S. ^[3];

^[1];

^[4]; Duan, Jiaxin ^[1]; Garcia-Holley, Paula ^[5];

^[2];

^[6];

^[3];

^[5];

^[2];

^[1]; Lercher, Johannes A. ^[7];

^[1];

^[1]

Univ. of Minnesota, Minneapolis, MN (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. Autonoma de Madrid, Madrid (Spain); Argonne National Lab. (ANL), Argonne, IL (United States)
Northwestern Univ., Evanston, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Stony Brook Univ., Stony Brook, NY (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Technische Univ. Munchen, Garching (Germany)

Publication Date:: 2018-10-23

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC); Argonne National Lab. (ANL), Argonne, IL (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1484223

Alternate Identifier(s):: OSTI ID: 1507435

Report Number(s):: PNNL-SA-137231
Journal ID: ISSN 0002-7863; 148161

Grant/Contract Number:: AC02-06CH11357; AC05-76RL01830

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 140; Journal Issue: 45; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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

Citation Formats


                    Desai, Sai Puneet, Ye, Jingyun, Zheng, Jian, Ferrandon, Magali S., Webber, Thomas E., Platero-Prats, Ana E., Duan, Jiaxin, Garcia-Holley, Paula, Camaioni, Donald M., Chapman, Karena W., Delferro, Massimiliano, Farha, Omar K., Fulton, John L., Gagliardi, Laura, Lercher, Johannes A., Penn, R. Lee, Stein, Andreas, and Lu, Connie C. Well-Defined Rhodium–Gallium Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes [Well-Defined Rh–Ga Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes].  United States: N. p., 2018. 
        Web.  doi:10.1021/jacs.8b08550.

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                    Desai, Sai Puneet, Ye, Jingyun, Zheng, Jian, Ferrandon, Magali S., Webber, Thomas E., Platero-Prats, Ana E., Duan, Jiaxin, Garcia-Holley, Paula, Camaioni, Donald M., Chapman, Karena W., Delferro, Massimiliano, Farha, Omar K., Fulton, John L., Gagliardi, Laura, Lercher, Johannes A., Penn, R. Lee, Stein, Andreas, & Lu, Connie C. Well-Defined Rhodium–Gallium Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes [Well-Defined Rh–Ga Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes].  United States.  doi:10.1021/jacs.8b08550.

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                    Desai, Sai Puneet, Ye, Jingyun, Zheng, Jian, Ferrandon, Magali S., Webber, Thomas E., Platero-Prats, Ana E., Duan, Jiaxin, Garcia-Holley, Paula, Camaioni, Donald M., Chapman, Karena W., Delferro, Massimiliano, Farha, Omar K., Fulton, John L., Gagliardi, Laura, Lercher, Johannes A., Penn, R. Lee, Stein, Andreas, and Lu, Connie C. Tue .  
        "Well-Defined Rhodium–Gallium Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes [Well-Defined Rh–Ga Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes]".  United States.  doi:10.1021/jacs.8b08550.  https://www.osti.gov/servlets/purl/1484223.

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@article{osti_1484223,

  title        = {Well-Defined Rhodium–Gallium Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes [Well-Defined Rh–Ga Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes]},

  author       = {Desai, Sai Puneet and Ye, Jingyun and Zheng, Jian and Ferrandon, Magali S. and Webber, Thomas E. and Platero-Prats, Ana E. and Duan, Jiaxin and Garcia-Holley, Paula and Camaioni, Donald M. and Chapman, Karena W. and Delferro, Massimiliano and Farha, Omar K. and Fulton, John L. and Gagliardi, Laura and Lercher, Johannes A. and Penn, R. Lee and Stein, Andreas and Lu, Connie C.},

  abstractNote = {Promoters are ubiquitous in industrial heterogeneous catalysts. The wider roles of promoters in accelerating catalysis and/or controlling selectivity are, however, not well understood. A model system has been developed where a heterobimetallic active site comprising an active metal (Rh) and a promoter metal (Ga) are preassembled and delivered into a metal-organic framework (MOF) support. The Rh-Ga sites in the MOF selectively catalyze the hydrogenation of acyclic alkynes to E-alkenes, which is complementary to Lindlar’s catalyst, which generates only Z-alkenes. The role of the Ga in promoting this unusual selectivity is underscored by the lack of semi-hydrogenation selectivity when Ga is absent and only Rh is present in the active site. We acknowledge Dr. Camille Malonzo May (UMN), Dr. David Kaphan (Argonne), Dr. Tata Gopinath (UMN), and Dr. Zhanyong Li (NW) for experimental assistance, and Dr. Dale Pahls for preliminary theoretical calculations. This work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award No. DE-SC0012702. This research used resources of: (1) the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility; and, (2) the University of Minnesota Characterization Facility, which is supported by the NSF through the MRSEC, ERC, MRI, and NNIN programs. X-ray crystallographic data have been deposited in the Cambridge Crystallographic Data Centre database (CCDC 1842577 to 1842581).},

  doi          = {10.1021/jacs.8b08550},

  journal      = {Journal of the American Chemical Society},

  number       = 45,

  volume       = 140,

  place        = {United States},

  year         = {2018},

  month        = {10}

}

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DOI: 10.1021/jacs.8b08550

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Cited by: 10 works

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Figure 1: (a) Single-crystal x-ray structures of the RhGa and Rh molecular precursors. (b) DFT-optimized structures of 1 and 2 in the ca. 8.5Å-pore (see SI for details on DFT models A and G, respectively). (c) N₂ sorption isotherms of NU-1000, 1, and 2. (d) DED map of 1. (e)more »

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CCDC 1842577: Experimental Crystal Structure Determination: QIQBAW : (μ-N,N',N''-[nitrilotri(ethane-2,1-diyl)]tri(pyridin-2-aminido))-(phenolato)-gallium-rhodium benzene solvate
dataset, May 2018

Desai, Sai Puneet; Ye, Jingyun; Zheng, Jian
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1zvbz4

CCDC 1842578: Experimental Crystal Structure Determination: QIQBEA : (ethene)-(phenolato)-(N2-(pyridin-2-yl)-N1,N1-bis{2-[(pyridin-2-yl)amino]ethyl}ethane-1,2-diamine)-rhodium
dataset, May 2018

Desai, Sai Puneet; Ye, Jingyun; Zheng, Jian
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1zvc06

CCDC 1842579: Experimental Crystal Structure Determination: QIQBIE : (μ-N,N',N''-[nitrilotri(ethane-2,1-diyl)]tri(pyridin-2-aminido))-chloro-gallium-rhodium dichloromethane solvate
dataset, May 2018

Desai, Sai Puneet; Ye, Jingyun; Zheng, Jian
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1zvc17

CCDC 1842580: Experimental Crystal Structure Determination: QIQBOK : (μ-N,N',N''-[nitrilotri(ethane-2,1-diyl)]tri(pyridin-2-aminido))-methyl-gallium-rhodium acetonitrile solvate
dataset, May 2018

Desai, Sai Puneet; Ye, Jingyun; Zheng, Jian
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1zvc28

CCDC 1842581: Experimental Crystal Structure Determination: QIQBUQ : (diphenylacetylene)-(phenolato)-(N2-(pyridin-2-yl)-N1,N1-bis{2-[(pyridin-2-yl)amino]ethyl}ethane-1,2-diamine)-rhodium
dataset, May 2018

Desai, Sai Puneet; Ye, Jingyun; Zheng, Jian
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1zvc39

Synthesis of nickel/gallium nanoalloys using a dual-source approach in 1-alkyl-3-methylimidazole ionic liquids
journal, January 2019

Simon, Ilka; Hornung, Julius; Barthel, Juri
Beilstein Journal of Nanotechnology, Vol. 10
DOI: 10.3762/bjnano.10.171

Heterobimetallic scandium–group 10 metal complexes with LM → Sc (LM = Ni, Pd, Pt) dative bonds
journal, January 2020

Cui, Peng; Xiong, Chunyan; Du, Jun
Dalton Transactions, Vol. 49, Issue 1
DOI: 10.1039/c9dt04369a

Heterobimetallic scandium–group 10 metal complexes with LM → Sc (LM = Ni, Pd, Pt) dative bonds
journal, January 2020

Cui, Peng; Xiong, Chunyan; Du, Jun
Dalton Transactions, Vol. 49, Issue 1
DOI: 10.1039/c9dt04369a

Synthesis of nickel/gallium nanoalloys using a dual-source approach in 1-alkyl-3-methylimidazole ionic liquids
journal, January 2019

Simon, Ilka; Hornung, Julius; Barthel, Juri
Beilstein Journal of Nanotechnology, Vol. 10
DOI: 10.3762/bjnano.10.171

Fast and Selective Semihydrogenation of Alkynes by Palladium Nanoparticles Sandwiched in Metal–Organic Frameworks
journal, January 2020

Choe, Kwanghak; Zheng, Fengbin; Wang, Hui
Angewandte Chemie, Vol. 132, Issue 9
DOI: 10.1002/ange.201913453

Catalyst as colour indicator for endpoint detection to enable selective alkyne trans-hydrogenation with ethanol
journal, June 2019

Wang, Yulei; Huang, Zhidao; Huang, Zheng
Nature Catalysis, Vol. 2, Issue 6
DOI: 10.1038/s41929-019-0299-2

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Figures / Tables:

CCDC 1842577: Experimental Crystal Structure Determination: QIQBAW : (μ-N,N',N''-[nitrilotri(ethane-2,1-diyl)]tri(pyridin-2-aminido))-(phenolato)-gallium-rhodium benzene solvate dataset, May 2018

CCDC 1842578: Experimental Crystal Structure Determination: QIQBEA : (ethene)-(phenolato)-(N2-(pyridin-2-yl)-N1,N1-bis{2-[(pyridin-2-yl)amino]ethyl}ethane-1,2-diamine)-rhodium dataset, May 2018

CCDC 1842579: Experimental Crystal Structure Determination: QIQBIE : (μ-N,N',N''-[nitrilotri(ethane-2,1-diyl)]tri(pyridin-2-aminido))-chloro-gallium-rhodium dichloromethane solvate dataset, May 2018

CCDC 1842580: Experimental Crystal Structure Determination: QIQBOK : (μ-N,N',N''-[nitrilotri(ethane-2,1-diyl)]tri(pyridin-2-aminido))-methyl-gallium-rhodium acetonitrile solvate dataset, May 2018

CCDC 1842581: Experimental Crystal Structure Determination: QIQBUQ : (diphenylacetylene)-(phenolato)-(N2-(pyridin-2-yl)-N1,N1-bis{2-[(pyridin-2-yl)amino]ethyl}ethane-1,2-diamine)-rhodium dataset, May 2018

Synthesis of nickel/gallium nanoalloys using a dual-source approach in 1-alkyl-3-methylimidazole ionic liquids journal, January 2019

Heterobimetallic scandium–group 10 metal complexes with LM → Sc (LM = Ni, Pd, Pt) dative bonds journal, January 2020

Heterobimetallic scandium–group 10 metal complexes with LM → Sc (LM = Ni, Pd, Pt) dative bonds journal, January 2020

Synthesis of nickel/gallium nanoalloys using a dual-source approach in 1-alkyl-3-methylimidazole ionic liquids journal, January 2019

Fast and Selective Semihydrogenation of Alkynes by Palladium Nanoparticles Sandwiched in Metal–Organic Frameworks journal, January 2020

Catalyst as colour indicator for endpoint detection to enable selective alkyne trans-hydrogenation with ethanol journal, June 2019

CCDC 1842577: Experimental Crystal Structure Determination: QIQBAW : (μ-N,N',N''-[nitrilotri(ethane-2,1-diyl)]tri(pyridin-2-aminido))-(phenolato)-gallium-rhodium benzene solvate
dataset, May 2018

CCDC 1842578: Experimental Crystal Structure Determination: QIQBEA : (ethene)-(phenolato)-(N2-(pyridin-2-yl)-N1,N1-bis{2-[(pyridin-2-yl)amino]ethyl}ethane-1,2-diamine)-rhodium
dataset, May 2018

CCDC 1842579: Experimental Crystal Structure Determination: QIQBIE : (μ-N,N',N''-[nitrilotri(ethane-2,1-diyl)]tri(pyridin-2-aminido))-chloro-gallium-rhodium dichloromethane solvate
dataset, May 2018

CCDC 1842580: Experimental Crystal Structure Determination: QIQBOK : (μ-N,N',N''-[nitrilotri(ethane-2,1-diyl)]tri(pyridin-2-aminido))-methyl-gallium-rhodium acetonitrile solvate
dataset, May 2018

CCDC 1842581: Experimental Crystal Structure Determination: QIQBUQ : (diphenylacetylene)-(phenolato)-(N2-(pyridin-2-yl)-N1,N1-bis{2-[(pyridin-2-yl)amino]ethyl}ethane-1,2-diamine)-rhodium
dataset, May 2018

Synthesis of nickel/gallium nanoalloys using a dual-source approach in 1-alkyl-3-methylimidazole ionic liquids
journal, January 2019

Heterobimetallic scandium–group 10 metal complexes with LM → Sc (LM = Ni, Pd, Pt) dative bonds
journal, January 2020

Heterobimetallic scandium–group 10 metal complexes with LM → Sc (LM = Ni, Pd, Pt) dative bonds
journal, January 2020

Synthesis of nickel/gallium nanoalloys using a dual-source approach in 1-alkyl-3-methylimidazole ionic liquids
journal, January 2019

Fast and Selective Semihydrogenation of Alkynes by Palladium Nanoparticles Sandwiched in Metal–Organic Frameworks
journal, January 2020

Catalyst as colour indicator for endpoint detection to enable selective alkyne trans-hydrogenation with ethanol
journal, June 2019