Jon Smieja

Jon Smieja

St Paul, Minnesota, United States
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Experienced Sustainability and Circularity expert with a demonstrated history over a…

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Experience

  • Trellis Group Graphic

    Trellis Group

    Minnesota, United States

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    Bayport, MN

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    Greater Grand Rapids, Michigan Area

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    La Jolla, CA

Education

Volunteer Experience

  • Environmental Commission Member

    City of Mahtomedi, MN

    - Present 2 years 5 months

    Environment

  • Market Leadership Advisory Board Member - Minnesota

    US Green Building Council

    - 2 years 1 month

    Environment

Publications

  • Direct observation of the reduction of carbon dioxide by rhenium bipyridine catalysts

    Energy & Environmental Science

    In order to further efforts in synthesis and catalysis, the mechanisms of catalysts must be completely understood. The Re(bpy)(CO)3Cl molecular catalysts are some of the most robust and well-characterized CO2 reduction catalysts known to date. Stopped-flow infrared spectroscopy is reported as a technique for studying the kinetics and mechanisms of the reactions of catalytically-relevant [Re(bpy-R)(CO)3]− anions (R = tBu or H) with CO2/H+. [Re(bpy-tBu)(CO)3]− reacts approximately ten times…

    In order to further efforts in synthesis and catalysis, the mechanisms of catalysts must be completely understood. The Re(bpy)(CO)3Cl molecular catalysts are some of the most robust and well-characterized CO2 reduction catalysts known to date. Stopped-flow infrared spectroscopy is reported as a technique for studying the kinetics and mechanisms of the reactions of catalytically-relevant [Re(bpy-R)(CO)3]− anions (R = tBu or H) with CO2/H+. [Re(bpy-tBu)(CO)3]− reacts approximately ten times faster with CO2 than does [Re(bpy)(CO)3]−. These reactions occur via a direct two-electron oxidative addition of CO2 to the metal center and result in the formation of an intermediate CO2 reduction product, Re(bpy-R)(CO)3(CO2H). This is the first in situ identification of this key intermediate. Evidence for this Re–CO2H species includes isotopic labeling studies, stopped-flow experiments of the kinetics of its formation in the presence of proton sources, comparison with genuine Re(bpy)(CO)3(CO2H), and DFT calculations.

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  • The Electronic States of Rhenium Bipyridyl Electrocatalysts for CO2 Reduction as Revealed by X-ray Absorption Spectroscopy and Computational Quantum Chemistry

    Angewandte Chemie International Edition

    Where are the electrons that allow a highly reduced rhenium bipyridyl catalyst to attack CO2, but not H+? XAS and computational quantum chemistry indicate that the negative charge in [Re(bpy)(CO)3]− and [Re(bpy-tBu)(CO)3]− is not stored in a localized Re 5d state, but rather in the bipyridine ligand . The active states of this family of catalysts possess formally Re0 metal centers with singly reduced bipyridine ligands.

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  • Manganese as a Substitute for Rhenium in CO2 Reduction Catalysts: The Importance of Acids

    Inorganic Chemistry

    Electrocatalytic properties, X-ray crystallographic studies, and infrared spectroelectrochemistry (IR-SEC) of Mn(bpy-tBu)(CO)3Br and [Mn(bpy-tBu)(CO)3(MeCN)](OTf) are reported. Addition of Brönsted acids to CO2-saturated solutions of these Mn complexes and subsequent reduction of the complexes lead to the stable and efficient production of CO from CO2. Unlike the analogous Re catalysts, these Mn catalysts require the addition of Brönsted acids for catalytic turnover. Current densities up to 30…

    Electrocatalytic properties, X-ray crystallographic studies, and infrared spectroelectrochemistry (IR-SEC) of Mn(bpy-tBu)(CO)3Br and [Mn(bpy-tBu)(CO)3(MeCN)](OTf) are reported. Addition of Brönsted acids to CO2-saturated solutions of these Mn complexes and subsequent reduction of the complexes lead to the stable and efficient production of CO from CO2. Unlike the analogous Re catalysts, these Mn catalysts require the addition of Brönsted acids for catalytic turnover. Current densities up to 30 mA/cm2 were observed during bulk electrolysis using 5 mM Mn(bpy-tBu)(CO)3Br, 1 M 2,2,2-trifluoroethanol, and a glassy carbon working electrode. During bulk electrolysis at −2.2 V vs SCE, a TOF of 340 s–1 was calculated for Mn(bpy-tBu)(CO)3Br with 1.4 M trifluoroethanol, corresponding to a Faradaic efficiency of 100 ± 15% for the formation of CO from CO2, with no observable production of H2. When compared to the analogous Re catalysts, the Mn catalysts operate at a lower overpotential and exhibit similar catalytic activities. X-ray crystallography of the reduced species, [Mn(bpy-tBu)(CO)3]−, shows a five-coordinate Mn center, similar to its rhenium analogue. Three distinct species were observed in the IR-SEC of Mn(bpy-tBu)(CO)3Br. These were of the parent Mn(bpy-tBu)(CO)3Br complex, the dimer [Mn(bpy-tBu)(CO)3]2, and the [Mn(bpy-tBu)(CO)3]− anion.

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  • Structural and spectroscopic studies of reduced [Re(bpy-R)(CO)3]−1 species relevant to CO2 reduction

    Polyhedron

    Spectroscopic and structural comparisons are made between the rhenium anions with bpy-R ligands spanning a wide range of electron-withdrawing and donating abilities (R = CF3, H, Me, tBu, OMe). The synthesis and characterization of the rhenium anions [Re(bpy-R)(CO)3]−1 (bpy-R = 4,4′-disubstitued-2,2′-bipyridine; R = CF3, Me, OMe) are reported. The anions [Re(bpy-R)(CO)3]−1 (R = Me and OMe) were structurally characterized. X-ray characterization of [Re(bpy-CF3)(CO)3]−1 was unsuccessful. However…

    Spectroscopic and structural comparisons are made between the rhenium anions with bpy-R ligands spanning a wide range of electron-withdrawing and donating abilities (R = CF3, H, Me, tBu, OMe). The synthesis and characterization of the rhenium anions [Re(bpy-R)(CO)3]−1 (bpy-R = 4,4′-disubstitued-2,2′-bipyridine; R = CF3, Me, OMe) are reported. The anions [Re(bpy-R)(CO)3]−1 (R = Me and OMe) were structurally characterized. X-ray characterization of [Re(bpy-CF3)(CO)3]−1 was unsuccessful. However, the structure of a mono-reduced complex, [Re(bpy-CF3)(CO)3Cl][K(18-crown-6)] was obtained. This compound is a rare example of a structurally characterized “19e−” intermediate formed in the chemical and electrochemical reduction of a Re(bpy-R)(CO)3Cl species.

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  • Artificial photosynthesis of CO: Kinetic and structural studies, origins of selectivity, and importance of interfacial charge transfer

    Proceedings of the National Academy of Sciences

    The effective design of an artificial photosynthetic system entails the optimization of several important interactions. Herein we report stopped-flow UV-visible (UV-vis) spectroscopy, X-ray crystallographic, density functional theory (DFT), and electrochemical kinetic studies of the Re(bipy-tBu)(CO)3(L) catalyst for the reduction of CO2 to CO. A remarkable selectivity for CO2 over H+ was observed by stopped-flow UV-vis spectroscopy of [Re(bipy-tBu)(CO)3]-1. The reaction with CO2 is about 25…

    The effective design of an artificial photosynthetic system entails the optimization of several important interactions. Herein we report stopped-flow UV-visible (UV-vis) spectroscopy, X-ray crystallographic, density functional theory (DFT), and electrochemical kinetic studies of the Re(bipy-tBu)(CO)3(L) catalyst for the reduction of CO2 to CO. A remarkable selectivity for CO2 over H+ was observed by stopped-flow UV-vis spectroscopy of [Re(bipy-tBu)(CO)3]-1. The reaction with CO2 is about 25 times faster than the reaction with water or methanol at the same concentrations. X-ray crystallography and DFT studies of the doubly reduced anionic species suggest that the highest occupied molecular orbital (HOMO) has mixed metal-ligand character rather than being purely doubly occupied dz2, which is believed to determine selectivity by favoring CO2 (σ + π) over H+ (σ only) binding. Electrocatalytic studies performed with the addition of Brönsted acids reveal a primary H/D kinetic isotope effect, indicating that transfer of protons to Re-CO2 is involved in the rate limiting step. Lastly, the effects of electrode surface modification on interfacial electron transfer between a semiconductor and catalyst were investigated and found to affect the observed current densities for catalysis more than threefold, indicating that the properties of the electrode surface need to be addressed when developing a homogeneous artificial photosynthetic system.

    Other authors
    • Eric Benson
    • Bhupendra Kumar
    • Kyle Grice
    • Candace Seu
    • Alexander Miller
    • James Mayer
    • Clifford Kubiak
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  • Re(bipy-tBu)(CO)3Cl – improved catalytic activity for reduction of carbon dioxide. IR-Spectroelectrochemical and mechanistic studies

    Inorganic Chemistry

    Five Re(bipy)(CO)3Cl complexes were prepared and studied where bipy was 4,4′-dicarboxyl-2,2′-bipyridine (1), 2,2′-bipyridine (2), 4,4′-dimethyl-2,2′-bipyridine (3), 4,4′-di-tert-butyl-2,2′-bipyridine (4), and 4,4′-dimethoxy-2,2′-bipyridine (5). From this group, a significantly improved catalyst, Re(bipy-tBu)(CO)3Cl (4), for the reduction of carbon dioxide to carbon monoxide was found. The complex shows two one-electron reductions under argon, one reversible at −1445 mV (vs SCE), and one…

    Five Re(bipy)(CO)3Cl complexes were prepared and studied where bipy was 4,4′-dicarboxyl-2,2′-bipyridine (1), 2,2′-bipyridine (2), 4,4′-dimethyl-2,2′-bipyridine (3), 4,4′-di-tert-butyl-2,2′-bipyridine (4), and 4,4′-dimethoxy-2,2′-bipyridine (5). From this group, a significantly improved catalyst, Re(bipy-tBu)(CO)3Cl (4), for the reduction of carbon dioxide to carbon monoxide was found. The complex shows two one-electron reductions under argon, one reversible at −1445 mV (vs SCE), and one irreversible at −1830 mV. Under CO2 the second irreversible wave displays a large catalytic enhancement in current. Diffusion coefficients were determined using the Levich−Koutecky method (1.1 × 10−5 cm2/s for the neutral complex and 8.1 × 10−6 cm2/s for the singly reduced species), and a second order rate constant for the electrochemical reduction with CO2 of 1000 M−1 s−1 was measured. Bulk electrolysis studies were performed to measure Faradaic efficiencies for the primary gaseous products, ηCO = 99 ± 2% in acetonitrile.

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    • Clifford Kubiak
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  • Electrocatalytic and homogeneous approaches to conversion of CO2 to liquid fuels

    Chemical Society Reviews

    Research in the field of catalytic reduction of carbon dioxide to liquid fuels has grown rapidly in the past few decades. This is due to the increasing amount of carbon dioxide in the atmosphere and a steady climb in global fuel demand. This tutorial review will present much of the significant work that has been done in the field of electrocatalytic and homogeneous reduction of carbon dioxide over the past three decades. It will then extend the discussion to the important conclusions from…

    Research in the field of catalytic reduction of carbon dioxide to liquid fuels has grown rapidly in the past few decades. This is due to the increasing amount of carbon dioxide in the atmosphere and a steady climb in global fuel demand. This tutorial review will present much of the significant work that has been done in the field of electrocatalytic and homogeneous reduction of carbon dioxide over the past three decades. It will then extend the discussion to the important conclusions from previous work and recommendations for future directions to develop a catalytic system that will convert carbon dioxide to liquid fuels with high efficiencies.

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Organizations

  • USGBC Minnesota

    MLAB Board Member

    - Present

  • Sustainable Growth Coalition

    Steering Committee Member

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  • Morrison County Area Foundation

    Board Chair

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