John C. Linehan

A Cobalt-Based Catalyst for the Hydrogenation of CO2 under Ambient Conditions

Because of the continually rising levels of CO2 in the atmosphere, research for the conversion of CO2 into fuels using carbon-neutral energy is an important and current topic in catalysis. Recent research on molecular catalysts has led to improved rates for conversion of CO2 to formate, but the catalysts are based on precious metals such as iridium, ruthenium and rhodium and require high temperatures and high pressures. Using established thermodynamic properties of hydricity (ΔGH(-)) and acidity (pKa), we designed a cobalt-based catalyst system for the production of formate from CO2 and H2. The complex Co(dmpe)2H (dmpe is 1,2-bis(dimethylphosphino)ethane) catalyzes the hydrogenation of CO2, with a turnover frequency of 3400 h(-1) at room temperature and 1 atm of 1:1 CO2:H2 (74,000 h(-1) at 20 atm) in tetrahydrofuran. These results highlight the value of fundamental thermodynamic properties in the rational design of catalysts.

In Situ Multinuclear NMR Spectroscopic Studies of the Thermal Decomposition of Ammonia Borane in Solution

The development of condensed phase hydrogen storage materials for fuel cell powered vehicles capable of meeting the 2015 system target goals of >82 g H2 L-1 volumetric density and >90 g H2 kg-1 gravimetric density has attracted recent interest. The details of the mechanisms for hydrogen release from AB are not completely understood; however, significant progress has been made in furthering our understanding of these mechanisms. This work was funded by the Office of Energy Efficiency and Renewable Energy, U.S. Department of Energy (DOE) as part of the Chemical Hydrogen Storage Center and carried out at the Pacific Northwest National Laboratory (operated by Battelle for DOE).

Coordination of aminoborane, NH2BH2, dictates selectivity and extent of H2 release in metal-catalysed ammonia borane dehydrogenation

In situ(11)B NMR monitoring, computational modeling, and external trapping studies show that selectivity and extent of H(2) release in metal-catalysed dehydrogenation of ammonia borane, NH(3)BH(3), are determined by coordination of reactive aminoborane, NH(2)BH(2), to the metal center.

Iridium Catalyzed Dehydrogenation of Substituted Amine Boranes: Kinetics, Thermodynamics and Implications for Hydrogen Storage.

Dehydrogenation of amine boranes is catalyzed efficiently by the iridium pincer complex (kappa (3)-1,3-(OP ( t )Bu 2) 2C 6H 3)Ir(H) 2 ( 1). With CH 3NH 2BH 3 (MeAB) and with AB/MeAB mixtures (AB = NH 3BH 3), the rapid release of 1 equiv of H 2 is observed to yield soluble oligomeric products at rates similar to those previously reported for the dehydrogenation of AB catalyzed by 1. Delta H for the dehydrogenation of AB, MeAB, and AB/MeAB mixtures has been determined by calorimetry. The experimental heats of reaction are compared to results from computational studies.

The influence of microbial activity and sedimentary organic carbon on the isotope geochemistry of the Middendorf Aquifer

Microorganisms present in deep Atlantic coastal plain sediments affect the geochemical evolution of groundwater and its chemical and isotopic composition, yet the factors controlling their origin, distribution, and diversity are poorly understood. The evolution of the groundwater chemistry, the fractionation of stable carbon isotopes, and the groundwater age are all indicators of the inorganic and microbial reactions occurring along a given flow path from groundwater recharge to groundwater discharge. In this study, tritium, 14C, and groundwater chemistry along three flow paths of the Middendorf aquifer in South Carolina were analyzed. The 14C ranged from 89 percent modern carbon (pmC) in the recharge zone to 9.9 pmC in the distal borehole; the δ13C remained relatively constant at ∼−22‰, suggesting microbial oxidation of organic carbon. Carbon isotope analyses of particulate organic carbon from core sediments and groundwater chemistry were used to model the carbon chemistry; the groundwater ages obtained from 14C ranged from modern to 11,500 years B.P. The highest frequencies of occurrence, numbers, and diversity of aerobic and anaerobic bacteria were found in boreholes near the recharge zone where the calculated ages were <1000 years B.P. The transport of microorganisms from the recharge zone may be responsible for this distribution as well as the electron acceptors necessary to support this diverse community of bacteria. The presence of both aerobic heterotrophs and anaerobic sulfate- and iron-reducing bacteria in the core sediments suggested the occurrence of anaerobic microsites throughout this otherwise aerobic aquifer. The highest in situ microbial respiration rate, as determined by modeling, was found along a flow path near the recharge area. It is likely that the electron acceptors necessary for supporting a diverse microbial community are depleted by the time the groundwater residence time in the Middendorf aquifer exceeds several hundred years.

Surface-induced mineralization: a new method for producing calcium phosphate coatings.

Calcium phosphate coatings were nucleated and grown from aqueous solution onto titanium metal substrates via surface-induced mineralization (SIM) processing techniques. This process is based on the observation that in nature organisms use biopolymers to produce ceramic composites, such as teeth, bones, and shells. The SIM process involves modification of a surface to introduce surface functionalization followed by immersion in aqueous supersaturated calcium phosphate solutions. This low-temperature process (< 100 degrees C) has advantages over conventional methods of calcium phosphate deposition in that uniform coatings are produced onto complex-shaped and/or microporous samples. Additionally, because it is a low-temperature process, control of the phase and crystallinity of the deposited material can be maintained.

Interaction of lithium hydride and ammonia borane in THF

The two-step reaction between LiH and NH(3)BH(3) in THF leads to the production of more than 14 wt% of hydrogen at 40 degrees C.

Defining active catalyst structure and reaction pathways from ab initio molecular dynamics and operando XAFS: Dehydrogenation of dimethylaminoborane by rhodium clusters

We present the results of a detailed operando XAFS and density functional theory (DFT)-based ab initio molecular dynamics (AIMD) investigation of a proposed mechanism of the dehydrogenation of dimethylaminoborane (DMAB) by a homogeneous Rh(4) cluster catalyst. Our AIMD simulations reveal that previously proposed Rh structures, based on XAFS measurements, are highly fluxional, exhibiting both metal cluster and ligand isomerizations and dissociation that can only be accounted for by examining a finite temperature ensemble. It is found that a fluxional species Rh(4)(H(2)BNMe(2))(8)(2+) is fully compatible with operando XAFS measurements, suggesting that this species may be the observed catalyst resting state. On the basis of this assignment, we propose a mechanism for catalytic DMAB dehydrogenation that exhibits an energy barrier of approximately 28 kcal/mol.

Anhydrous tertiary alkanolamines as hybrid chemical and physical CO2 capture reagents with pressure-swing regeneration

Anhydrous DMEA, DEEA and DIPEA are found to absorb carbon dioxide under pressure via chemical binding and physical absorption. The chemical CO2-bound derivatives of these materials are zwitterionic alkylcarbonate salts which are characterized by high-pressure 13C NMR. DMEA, DEEA and DIPEA absorb 20 wt.%, 17 wt.% and 16 wt.% carbon dioxide, respectively, at 300 psig (20.6 ATM). An increasing chemical carbon dioxide uptake capacity trend of DMEA > DEEA > DIPEA is observed while the physical CO2 absorption trend is DIPEA > DEEA > DMEA. DMEA captures up to 45 mole % (20 wt.%) of CO2 at 500 psig via both chemical binding and physical absorption. The amount of chemically bound and physically absorbed CO2 is directly linked to the CO2 pressure over the liquid. The zwitterion DMEA-CO2 regenerates CO2 and DMEA upon depressurization, allowing for an economical pressure swing regeneration rather than thermal regeneration. DMEA absorbs/releases CO2 repeatedly with no decline in capacity.

Molecular dynamics study of the proposed proton transport pathways in [FeFe]-hydrogenase

Possible proton transport pathways in Clostridium pasteurianum (CpI) [FeFe]-hydrogenase were investigated with molecular dynamics simulations. This study was undertaken to evaluate the functional pathway and provide insight into the hydrogen bonding features defining an active proton transport pathway. Three pathways were evaluated, two of which consist of water wires and one of predominantly amino acid residues. Our simulations suggest that protons are not transported through water wires. Instead, the five-residue motif (Glu282, Ser319, Glu279, H2O, Cys299) was found to be the likely pathway, consistent with previously made experimental observations. The pathway was found to have a persistent hydrogen bonded core (residues Cys299 to Ser319), with less persistent hydrogen bonds at the ends of the pathway for both H2 release and H2 uptake. Single site mutations of the four residues have been shown experimentally to deactivate the enzyme. The theoretical evaluation of these mutations demonstrates redistribution of the hydrogen bonds in the pathway, resulting in enzyme deactivation. Finally, coupling between the protein dynamics near the proton transport pathway and the redox partner binding regions was also found as a function of H2 uptake and H2 release states, which may be indicative of a correlation between proton and electron movement within the enzyme.