About

Kenton Whitmire is a Professor of Chemistry, Associate Dean for Academic Affairs of the Wiess School of Natural Sciences, and the College Magister of Sid Richardson College at Rice University. He received his BS in Chemistry from Roanoke College in 1977 and completed his Ph.D. studies on carbon monoxide activation and metal carbonyl clusters with Duward F. Shriver at Northwestern University. Following his Ph.D., he held a NATO Postdoctoral Fellowship with Jack Lewis at Cambridge University and began his faculty career at Rice University in 1982. His research interests focus on synthetic, structural, and mechanistic inorganic and organometallic chemistry, with recent efforts directed towards designing molecules to serve as single-source precursors for advanced solid state materials. His work includes studying inorganic and organometallic compounds for their use as precursors in solid-state compounds, particularly metal pnictides, which have superior magnetic, magneto-optical, magnetoresistive, and magnetocaloric properties, and can catalyze industrial processes such as water splitting. He has published more than 200 peer-reviewed papers, supervised sixteen Ph.D. and three M.S. students, and has been recognized with awards including an Alexander von Humboldt Foundation Research Award. He also served as an associate editor for Organometallics from 1997 through 2007.

Research topics

• Chemistry
• Organic chemistry
• Computational chemistry
• Combinatorial chemistry
• Inorganic chemistry
• Nanotechnology
• Materials science

Selected publications

• The oxido clusters of bismuth

  Coordination Chemistry Reviews · 2023 · 10 citations

  1st authorCorresponding
  • Chemistry
  • Inorganic chemistry
  • Nanotechnology

  The oxido clusters of bismuth have received increasing attention over the past several decades. This can in part be attributed to the use of bismuth compounds as pharmaceuticals, dating back hundreds of years for treating gastrointestinal disorders and as general antimicrobial and antifungal agents. This is enabled by bismuth's low toxicity compared to its more infamous neighbors in the periodic table. The field received a substantial boost in activity aimed at producing precursor compounds to homo- and heterometallic metal oxides via sol gel syntheses thanks to the discovery of various high TC superconducting bismuth-containing phases. More recently these compounds have shown interesting catalytic, electronic and optical properties. There is a strong resemblance of the structures of the oxido species to solid state bismuth oxides, and the chemistry of the oxido clusters is strongly intertwined with the fundamental coordination chemistry of bismuth, which shows strong Lewis acidity and high coordination numbers. As a result, the oxido clusters of bismuth have proven to have a rich structural chemistry with nuclearities ranging from two to fifty bismuth atoms, and many structures are known that incorporate other metals including the alkali metals, alkaline earth metals, transition metals and lanthanides as part of the oxido core. Compounds with a [Bi6O4(OH)4]6+ core are particularly prevalent, but Bi4, Bi9 and Bi38 structures are also well-represented. The ligand sets that support the formation and stabilization of these structures include a wide variety of organic alkoxides, siloxides, carboxylates, sulfonates, phosphonates and acetylacetonates. Multifunctional ligands have been used for the production of MOF-like structures via hydrothermal methods that can result in discrete bismuth oxido clusters linked via ligand bridges or polymeric bismuth oxido structures decorated with the organic ligands and organized into 1-, 2- or 3-dimensional structures. This review is designed to summarize the synthetic methods used to prepare them, present key aspects of their physical and chemical properties as well as discussing the important features of the structures reported to date. Of significant importance is the obvous blurring of the boundaries between the discrete bismuth oxido clusters that can be described as conventional inorganic coordination compounds, organobismuth oxides and oxido bismuth compounds where the bismuth oxido core is itself a polymer.

  PublisherDOI

• Ethylene Dehydroaromatization over Ga‐ZSM‐5 Catalysts: Nature and Role of Gallium Speciation

  Angewandte Chemie · 2020 · 2 citations

  • Chemistry
  • Organic chemistry
  • Combinatorial chemistry

  Abstract Bifunctional catalysis in zeolites possessing both Brønsted and Lewis acid sites offers unique opportunities to tailor shape selectivity and enhance catalyst performance. Here, we examine the impact of framework and extra‐framework gallium species on enriched aromatics production in zeolite ZSM‐5. We compare three distinct methods of preparing Ga‐ZSM‐5 and reveal direct (single step) synthesis leads to optimal catalysts compared to post‐synthesis methods. Using a combination of state‐of‐the‐art characterization, catalyst testing, and density functional theory calculations, we show that Ga Lewis acid sites strongly favor aromatization. Our findings also suggest Ga(framework)–Ga(extra‐framework) pairings, which can only be achieved in materials prepared by direct synthesis, are the most energetically favorable sites for reaction pathways leading to aromatics. Calculated acid site exchange energies between extra‐framework Ga at framework sites comprised of either Al or Ga reveal a site‐specific preference for stabilizing Lewis acids, which is qualitatively consistent with experimental measurements. These findings indicate the possibility of tailoring Lewis acid siting by the placement of Ga heteroatoms at distinct tetrahedral sites in the zeolite framework, which can have a marked impact on catalyst performance relative to conventional H‐ZSM‐5.

  PublisherOA PDFDOI

• Ethylene Dehydroaromatization over Ga‐ZSM‐5 Catalysts: Nature and Role of Gallium Speciation

  Angewandte Chemie International Edition · 2020 · 83 citations

  • Chemistry
  • Combinatorial chemistry
  • Computational chemistry

  Bifunctional catalysis in zeolites possessing both Brønsted and Lewis acid sites offers unique opportunities to tailor shape selectivity and enhance catalyst performance. Here, we examine the impact of framework and extra-framework gallium species on enriched aromatics production in zeolite ZSM-5. We compare three distinct methods of preparing Ga-ZSM-5 and reveal direct (single step) synthesis leads to optimal catalysts compared to post-synthesis methods. Using a combination of state-of-the-art characterization, catalyst testing, and density functional theory calculations, we show that Ga Lewis acid sites strongly favor aromatization. Our findings also suggest Ga(framework)-Ga(extra-framework) pairings, which can only be achieved in materials prepared by direct synthesis, are the most energetically favorable sites for reaction pathways leading to aromatics. Calculated acid site exchange energies between extra-framework Ga at framework sites comprised of either Al or Ga reveal a site-specific preference for stabilizing Lewis acids, which is qualitatively consistent with experimental measurements. These findings indicate the possibility of tailoring Lewis acid siting by the placement of Ga heteroatoms at distinct tetrahedral sites in the zeolite framework, which can have a marked impact on catalyst performance relative to conventional H-ZSM-5.

  PublisherOA PDFDOI

• CCDC 1862751: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2019-01-01

  datasetOpen access1st authorCorresponding

  An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  PublisherDOI

• Transition metal complexes of the naked pnictide elements

  Coordination Chemistry Reviews · 2018-08-15 · 53 citations

  articleOpen access1st authorCorresponding
  PublisherOA PDFDOI

• Advances in MOCVD Production of Complex Materials from Single Source Precursors: Phase Pure Metal Phosphide Thin Films for Catalysis and Energy Applications

  TechConnect Briefs · 2018-05-13

  article1st authorCorresponding
  Publisher

• In pursuit of advanced materials from single-source precursors based on metal carbonyls

  Dalton Transactions · 2018-12-18 · 6 citations

  article1st authorCorresponding

  In this perspective, the development of single-source precursors and their relative advantages over multiple source approaches for the synthesis of metal pnictide solid state materials is explored. Particular efforts in the selective production of iron phosphide materials for catalytic applications are discussed, especially directed towards the hydrogen evolution and oxygen evolution reactions of water splitting.

  PublisherDOI

• CCDC 1846323: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2018-01-01

  datasetOpen accessSenior author

  An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  PublisherDOI

• Effects of Catalyst Phase on the Hydrogen Evolution Reaction of Water Splitting: Preparation of Phase-Pure Films of FeP, Fe₂P, and Fe₃P and Their Relative Catalytic Activities

  Chemistry of Materials · 2018-04-26 · 156 citations

  articleOpen accessSenior authorCorresponding

  The comparative catalytic activities of iron phosphides, FexP (x = 1–3), have been established with phase-pure material grown by chemical vapor deposition (CVD) from single-source organometallic precursors. This is the first report of the preparation of phase-pure thin films of FeP and Fe2P, and their identity was established with scanning-electron microscopy, X-ray photoelectron spectroscopy, and powder X-ray diffraction. All materials were deposited on fluorine-doped tin oxide (FTO) for evaluation of their activities toward the hydrogen evolution reaction (HER) of water splitting in 0.5 M H2SO4. HER activity follows the trend Fe3P > Fe2P > FeP, with Fe3P having the lowest overpotential of 49 mV at a current density of 10 mA cm–2. Density functional theory (DFT) calculations are congruent with the observed activity trend with hydrogen binding favoring the iron-rich terminating surfaces of Fe3P and Fe2P over the iron-poor terminating surfaces of FeP. The results present a clear trend of activity with iron-rich phosphide phases outperforming phosphorus rich phases for hydrogen evolution. The films of Fe2P were grown using Fe(CO)4PH3 (1), while the films of FeP were prepared using either Fe(CO)4PtBuH2 (2) or the new molecule {Fe(CO)4P(H)tBu}2 (3) on quartz and FTO. Compound 3 was prepared from the reaction of PCl2tBu with a mixture of Na[HFe(CO)4] and Na2[Fe(CO)4] and characterized by single-crystal X-ray diffraction, ESI-MS, elemental analysis, and 31P/1H NMR spectroscopies. Films of Fe3P were prepared as previously described from H2Fe3(CO)9PtBu (4).

  PublisherOA PDFDOI

• A structural survey of the binary transition metal phosphides and arsenides of the d-block elements

  Coordination Chemistry Reviews · 2017-10-11 · 68 citations

  articleSenior authorCorresponding
  PublisherDOI

Recent grants

• PostDoctoral Research Fellowship

  NSF · $37k · 2005–2006

• Discrete and Extended Arrays of Main Group Elements and Transition Metals

  NSF · $403k · 2007–2011

• Preparation of Advanced Nanomaterials from Single Source Designer Precursors

  NSF · $390k · 2014–2017

Frequent coauthors

• Henry J. Shine

  Texas Tech University

  66 shared

• T. Ould-Ely

  University of California, Santa Barbara

  66 shared

• J.H. Thurston

  64 shared

• J.N. Marx

  University of Bremen

  49 shared

• I.Y. Guzman-Jimenez

  42 shared

• Desmond Schipper

  The University of Texas at Austin

  40 shared

• Bingjun Zhao

  33 shared

• Jean‐Yves Saillard

  Université de Rennes

  29 shared

Education

• PhD in Chemistry, Chemistry

  Northwestern University

  1981

• M.S., Chemistry

  Northwestern University

  1978

• B.S. in Chemistry, Chemistry

  Roanoke College

  1977

Awards & honors

• Alexander von Humboldt Foundation Research Award