The role of solvent and the outer coordination sphere on H2 oxidation using [Ni(PCy2NPyz2)2]2+

Dutta, Arnab; Lense, Sheri J.; Roberts, John A.; Helm, Monte L.; Shaw, Wendy J.

doi:10.1002/ejic.201500732

The role of solvent and the outer coordination sphere on H₂ oxidation using [Ni(P^Cy₂N^Pyz₂)₂]²⁺

Journal Article · Fri May 01 04:00:00 EDT 2015 · European Journal of Inorganic Chemistry (Online)

DOI:https://doi.org/10.1002/ejic.201500732· OSTI ID:1233766

Dutta, Arnab; Lense, Sheri J.; Roberts, John A.; Helm, Monte L.; Shaw, Wendy J.

Hydrogenase enzymes are reversible catalysts for H₂ production/oxidation, operating with fast rates and minimal overpotentials in water. Many synthetic catalyst mimics of hydrogenase operate in organic solvents. However, recent work has demonstrated the importance of water in the performance of some model complexes. In this work, the H₂oxidation activity of [Ni(P^Cy₂N^{(3–pyridazyl)methyl}₂)₂]²⁺ (CyPyz) was compared as a function of acetonitrile, methanol, and water. The reactivity was compared under neutral and acidic conditions in all three solvents and improvement in catalytic activity, from 2 to 40 s^-1, was observed with increasing hydrogen bonding ability of the solvent. In addition, the overpotential for catalysis drops significantly in the presence of acid in all solvents, from as high as 600 mV to as low as 70 mV, primarily due to the shift in the equilibrium potential under these conditions. Finally, H₂ production was also observed in the same solution, demonstrating bidirectional (irreversible) homogeneous H₂ production/oxidation. A structurally and electronically similar complex with a benzyl instead of a pyridazyl group was not stable under these conditions, limiting the evaluation of the contributions of the outer coordination sphere. Collectively, we show that by tuning conditions we can promote fast, efficient H₂ oxidation and bidirectional catalysis.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL); Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)

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

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1233766

Report Number(s):: PNNL-SA-105208; 44681; KC0302010

Journal Information:: European Journal of Inorganic Chemistry (Online), Journal Name: European Journal of Inorganic Chemistry (Online) Journal Issue: 31 Vol. 2015; ISSN 1099-0682

Publisher:: ChemPubSoc Europe

Country of Publication:: United States

Language:: English

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