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Title: Silicon Nitride Surface Enabled Propane Dehydrogenation Catalyzed by Supported Organozirconium

Journal Article · · Journal of the American Chemical Society
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  1. Argonne National Laboratory (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Argonne National Laboratory (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Northwestern University, Evanston, IL (United States)
  3. Ames Laboratory (AMES), Ames, IA (United States). Chemical and Biological Sciences Division; Iowa State University, Ames, IA (United States)
+ Show Author Affiliations

Mesoporous silicon nitride (Si3N4) is a nontraditional support for the chemisorption of organometallic complexes with the potential for enhancing catalytic activity through features such as the increased Lewis basicity of nitrogen for heterolytic bond activation, increased ligand donor strength, and metal–ligand orbital overlap. In this report tetrabenzyl zirconium (ZrBn4) was chemisorbed on Si3N4, and the resulting supported organometallic species was characterized by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), Dynamic Nuclear Polarization-enhanced Solid State Nuclear Magnetic Resonance (DNP-SSNMR), and X-ray Absorption Spectroscopy (XAS). Based on the hypothesis that the nitride might enable facile heterolytic C–H bond activation along the Zr–N bond, this material was found to be a highly active (1.53 molpropene molZr–1 h–1 at 450 °C) and selective (99% to propylene) catalyst for propane dehydrogenation. In contrast, the homologous silica supported complex exhibited negligible activity under these conditions.

Research Organization:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Science Foundation (NSF)
Grant/Contract Number:
AC02-07CH11358; AC02-06CH11357
OSTI ID:
2367356
Report Number(s):
IS-J--11,340
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 21 Vol. 146; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (38)

Structure and Reactivity of a Mononuclear Gold-Complex Catalyst Supported on Magnesium Oxide journal February 2003
Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study journal August 2016
Bridging the Gap between Industrial and Well-Defined Supported Catalysts journal March 2018
Small Changes Have Consequences: Lessons from Tetrabenzyltitanium and -zirconium Surface Organometallic Chemistry journal November 2012
Well-Defined Silica-Supported Zirconium-Benzyl Cationic Species: Improved Heterogenization of Single-Site Polymerization Catalysts journal January 2014
Porous Silicon Nitride as a Superbase Catalyst journal July 2001
Solid-state NMR investigations of Si-29 and N-15 enriched silicon nitride journal September 2009
Surface Organometallic and Coordination Chemistry toward Single-Site Heterogeneous Catalysts: Strategies, Methods, Structures, and Activities journal January 2016
X–H Bond Activation on Cr(III),O Sites (X = R, H): Key Steps in Dehydrogenation and Hydrogenation Processes journal November 2016
Nontraditional Catalyst Supports in Surface Organometallic Chemistry journal September 2020
Mechanism and Kinetics of n -Butane Dehydrogenation to 1,3-Butadiene Catalyzed by Isolated Pt Sites Grafted onto ≡SiOZn–OH Nests in Dealuminated Zeolite Beta journal February 2022
Mechanism and Kinetics of Propane and n-Butane Dehydrogenation over Isolated and Nested ≡SiOZn–OH Sites Grafted onto Silanol Nests of Dealuminated Beta Zeolite journal February 2024
Isolated Fe II on Silica As a Selective Propane Dehydrogenation Catalyst journal May 2015
Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration journal November 2015
Mechanistic Aspects of a Surface Organovanadium(III) Catalyst for Hydrocarbon Hydrogenation and Dehydrogenation journal November 2019
Zirconium Modification Promotes Catalytic Activity of a Single-Site Cobalt Heterogeneous Catalyst for Propane Dehydrogenation journal September 2018
Heterolytic Activation of C–H Bonds on Cr III –O Surface Sites Is a Key Step in Catalytic Polymerization of Ethylene and Dehydrogenation of Propane journal March 2015
Surface organometallic chemistry: reaction of tris(allyl)rhodium with surfaces of silica, alumina, titania and magnesia journal May 1992
High-Resolution Solid-State 13 C NMR Studies of Chemisorbed Organometallics. Chemisorptive Formation of Cation-like and Alkylidene Organotantalum Complexes on High Surface Area Inorganic Oxides journal June 2002
Novel Route to Periodic Mesoporous Aminosilicas, PMAs:  Ammonolysis of Periodic Mesoporous Organosilicas journal September 2003
Molecular Understanding of Alumina Supported Single-Site Catalysts by a Combination of Experiment and Theory journal June 2006
Bipodal Surface Organometallic Complexes with Surface N-Donor Ligands and Application to the Catalytic Cleavage of C–H and C–C Bonds in n -Butane journal November 2013
Mono- and Dinuclear Silica-Supported Titanium(IV) Complexes and the Effect of TiOTi Connectivity on Reactivity journal August 1999
Propane Dehydrogenation Catalyzed by Isolated Pt Atoms in ≡SiOZn–OH Nests in Dealuminated Zeolite Beta journal December 2021
C–H Activation on Co,O Sites: Isolated Surface Sites versus Molecular Analogs journal November 2016
Rhodium Complex with Ethylene Ligands Supported on Highly Dehydroxylated MgO:  Synthesis, Characterization, and Reactivity journal January 2006
Vanadium Oxo Organometallic Species Supported on Silica for the Selective Non-oxidative Dehydrogenation of Propane journal October 2013
C–H and C–C Activation of n -Butane with Zirconium Hydrides Supported on SBA15 Containing N-Donor Ligands: [(≡SiNH−)(≡SiX−)ZrH 2 ], [(≡SiNH−)(≡SiX−) 2 ZrH], and[(≡SiN═)(≡SiX−)ZrH] (X = −NH–, −O−). A DFT Study journal July 2014
Surface Organometallic Chemistry of Hf(CH 2 t Bu) 4 on Silica and Silica−Alumina: Reaction of the Resulting Grafted Hafnium Neopentyl with Dihydrogen journal March 2010
Formation of Gold Clusters on TiO 2 from Adsorbed Au(CH 3 ) 2 (C 5 H 7 O 2 ): Characterization by X-ray Absorption Spectroscopy journal May 2004
Sol–gel preparation of low oxygen content, high surface area silicon nitride and imidonitride materials journal January 2016
Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts journal January 2017
Surface organometallic chemistry in heterogeneous catalysis journal January 2018
Propane dehydrogenation: catalyst development, new chemistry, and emerging technologies journal January 2021
Heterogeneous alkane dehydrogenation catalysts investigated via a surface organometallic chemistry approach journal January 2021
Pore size engineering of mesoporous silicon nitride materials journal March 2002
Heterolytic cleavage of ammonia N–H bond by bifunctional activation in silica-grafted single site Ta(V) imido amido surface complex. Importance of the outer sphere NH3 assistance journal January 2011
A well-defined mesoporous amine silica surface via a selective treatment of SBA-15 with ammonia journal January 2012

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
heterogeneous catalysis
propane dehydrogenation
surface organometallic chemistry
zirconium