A bio-inspired mononuclear manganese catalyst for high-rate electrochemical hydrogen production

Abstract

[FeFe]-hydrogenases (H2ase) catalyze hydrogen evolution reaction (HER) with excellent performances that rival that of platinum, the active site of which is built with crucial structural features required for efficient H−H...

Manganese(I) Tricarbonyl Complexes with Bidentate Pyridine-Based Actor Ligands: Reversible Binding of CO2 and Benzaldehyde via Cooperative C–C and Mn–O Bond Formation at Ambient Temperature

“…Great efforts are spent to develop robust and potent catalysts based on abundant first-row transition metals enabling reactions relevant to a sustainable energy and natural resource management. In this regard, manganese­(I) carbonyl complexes have attracted increased attention during the last decade owing to their utilization, for instance, in homogeneous catalysis with relevance to (atom economic) environmentally benign reaction schemes addressing fundamental chemical − and electrocatalytic transformations. − They have been explored as homogeneous catalysts facilitating C–C bond formations − and have been also discussed in photo-therapeutic applications. − Against this background, the concept of metal–ligand cooperation (MLC) is a central feature for substrate/small molecule activation in first-row transition metal complexes . Examples for MLC processes in Mn­(I) tricarbonyls with bidentate actor ligands were given, e.g., by Khusnutdinova and co-workers for a Mn­(I) tricarbonyl complex carrying a pyridine-based P,N-donor ligand.…”

The hangman effect boosts hydrogen production by a manganese terpyridine complex

“…In the last two decades, numerous transition metal complexes have been prepared to mimic the natural pathway for proton transfer. 3,6 For example, a mononuclear Mn pyridine–quinoline tricarbonyl complex with a pendent aniline, 8 biomimetic diiron dithiolate complexes resembling H 2 ase, 9 mononuclear Fe( ii ) cyclopentadienyl complexes, 10 and Co( ii ) 11 and Ni( ii ) 12 complexes containing cyclic diazadiphosphine ligands, all exhibited excellent catalytic activity in the HER. However, all of these complexes require a strong Brønsted acid source to match the p K a of the proton relay group and an overpotential of over 300 mV for the HER.…”

Multiple‐Site Concerted Proton–Electron Transfer in a Manganese‐Based Complete Functional Model for [FeFe]‐Hydrogenase

“…Taking into account of the influence of the mixed solvent on the thermodynamic potential for H + reduction and the uncertain change of the equilibrium potential of the H + /H 2 couple in different solvents,t he ). b) Catalytic Tafel plots relating TOF and the driving force of H 2 evolution,a nd benchmarking of the performance of 1 (this work) with that of previously reported electrocatalysts:MnPQ-aniline, [23] FeTPP, [24] Co(dmgH) 2 (Py) [25] and [Ni(P 2 Ph N 2 Ph ) 2 ] 2+ . [26] Angewandte Chemie overpotential was estimated to range between 20 to 120 mV (Figure S28, detailed in the supplementary information).…”