Remarkable stability of a molecular ruthenium complex in PEM water electrolysis

Bellini, Marco; Bösken, Jonas; Bartoli, Francesco; Miller, Hamish A.; Thöny, Debora; Poggini, Lorenzo; Wörle, Michael; Oberhauser, Werner; Gamboa‐Carballo, Juan José; Lavacchi, Alessandro; Krumeich, Frank; Vizza, Francesco

doi:10.1039/d1sc07234j

Cited by 12 publications

(24 citation statements)

References 53 publications

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“…Furthermore, we discovered that the reaction of the dihydride complex 8 with base forms the anionic bridged monohydride complex 12 . Complex 12 is also accessible from 8 , by sequential oxidation to complex 11 and reduction [46] . Importantly, these experiments demonstrate that the terminal hydride ligand in 8 is (i) the reactive site and (ii) can be removed as a proton by a sufficiently strong base.…”

Section: Resultsmentioning

confidence: 77%

Reduction of Nitrous Oxide by Light Alcohols Catalysed by a Low‐Valent Ruthenium Diazadiene Complex

Bösken

Rodríguez-Lugo

Nappen

et al. 2023

Chemistry A European J

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Decomposition of the environmentally harmful gas nitrous oxide (N2O) is usually performed thermally or catalytically. Selective catalytic reduction (SCR) is currently the most promising technology for N2O mitigation, a multicomponent heterogeneous catalytic system that employs reducing agents such as ammonia, hydrogen, hydrocarbons, or a combination thereof. This study reports the first homogenous catalyst that performs the reduction of nitrous oxide employing readily available and cheap light alcohols such as methanol, ethanol or ethylene glycol derivatives. During the reaction, these alcohols are transformed in a dehydrogenative coupling reaction to carboxylate derivatives, while N2O is converted to N2 and H2O, later entering the reaction as substrate. The reaction is catalysed by the low‐valent dinuclear ruthenium complex [Ru2H(μ‐H)(Me2dad)(dbcot)2] that carries a diazabutadiene, Me2dad, and two rigid dienes, dbcot, as ligands. The reduction of nitrous oxide proceeds with low catalyst loadings under relatively mild conditions (65–80 °C, 1.4 bar N2O) achieving turnover numbers of up to 480 and turnover frequencies of up to 56 h−1.

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Section: Resultsmentioning

confidence: 77%

Reduction of Nitrous Oxide by Light Alcohols Catalysed by a Low‐Valent Ruthenium Diazadiene Complex

Bösken

Rodríguez-Lugo

Nappen

et al. 2023

Chemistry A European J

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“…Titanium suboxide and antimony oxide show promise. Nanostructured thin film electrodes (NSTF) stand out 285‐290 …”

Section: Sun Heat and Electricity For Water Splitting‐based Hydrogen ...mentioning

confidence: 99%

“…Nanostructured thin film electrodes (NSTF) stand out. [285][286][287][288][289][290] The main advances throughout the history of alkaline electrolysis and PEM have been synthesized in the scheme of Figure 13.…”

Section: Solid Polymer Electrolysis (Spe) or Proton Exchange Membrane...mentioning

confidence: 99%

Sun, heat and electricity. A comprehensive study of non‐pollutant alternatives to produce green hydrogen

Mancera

Segura

Andújar

et al. 2022

Intl J of Energy Research

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Summary Water‐based hydrogen production is currently an attractive research field, as it provides a greener method to produce hydrogen than existing alternatives. Green hydrogen is expected to progressively replace fossil fuels, which are highly harmful environmentally. This paper presents a critical analysis over time of the main water splitting technologies currently in use for sustainable hydrogen production. As a result of the critical analysis, all the studied techniques have been ordered chronologically in the way that it is possible to understand how new materials have driven to new techniques, more efficient and less expensive. This allows having a complete vision of these technologies. A high level of maturity has been reached in electrolysis, while other techniques still have a long way to go, although many improvements and relevant advancements have been made over the years. The paper offers a global and comparative vision of each technology. From this, it is possible to identify the different paths where efforts are needed to make water‐based hydrogen production a mature, stable and efficient technology.

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“…The synthesis and characterization of COT-based complexes contribute to our understanding of bonding in metal complexes . Furthermore, 1 will pave the way for heavier analogues that would be relevant for applications in areas such as catalysis, , molecular nanowires, small-molecule activation, and single-molecule magnetism. ,− In addition, compounds of this class representing polycyclic systems will be potentially relevant in photoredox chemistry …”

Section: Introductionmentioning

confidence: 99%

Linear, Electron-Rich, Homoleptic Rare Earth Metallocene and Its Redox Activity

Castellanos

Demir

2023

Inorg. Chem.

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The first homoleptic sandwich complex of dibenzocyclooctatetraene (dbCOT), representing a large cyclooctatetraene (COT) ligand with two fused benzene moieties, for any metal was accessed through salt metathesis of YCl 3 with K 2 dbCOT in the presence of 2.2.2-cryptand. Single-crystal X-ray diffraction analysis on red-brown [K(crypt-222)][Y(dbCOT) 2 ], 1, revealed a remarkably linear anionic yttrocene complex featuring a centroid−yttrium−centroid angle of 180.0°. The anionic moiety adopts a pseudo D 2d geometry, where the carbon atoms of the central COT ring exhibit a staggered geometry. In total, 36 πelectrons are stored on both dbCOT anions, rendering it the largest isolated sandwich complex containing only fused aromatic rings. The solution-state structure of 1 was probed through a series of techniques involving cyclic voltammetry, UV−vis, and 1D and 2D nuclear magnetic resonance (NMR) spectroscopy, including 89 Y NMR. The density functional theory (DFT) and natural bond orbital (NBO) analysis uncovered an ionic bonding interaction between the (dbCOT) 2− ligands and Y III ion. NICS calculations support the experimentally observed aromatic character of 1, despite the deviation from planarity found in the dbCOT moieties. The cyclic voltammograms allude to the accessibility of a radical oxidation state, dbCOT 3−• , based on a quasi-reversible feature. Excitingly, the chemical one-electron reduction of 1 through exposure to potassium graphite yielded a paramagnetic molecule, which was detected by electron paramagnetic resonance (EPR) techniques. Notably, this EPR spectrum is the first one for any sandwich complex containing a COT radical. Remarkably, 1 is thermally stable, and its isolation may provide access to mono-and multinuclear complexes comprising heavier metals with applications in small-molecule activation, single-molecule magnetism, and molecular nanowires.

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Remarkable stability of a molecular ruthenium complex in PEM water electrolysis

Abstract: The dinuclear Ru diazadiene olefin complex, [Ru2(OTf)(µ‒H)(Me2dad)(dbcot)2], is an active catalyst for hydrogen evolution in a Proton Exchange Membrane (PEM) water electrolyser. When supported on high surface area carbon black...

Cited by 12 publications

References 53 publications

Reduction of Nitrous Oxide by Light Alcohols Catalysed by a Low‐Valent Ruthenium Diazadiene Complex

Reduction of Nitrous Oxide by Light Alcohols Catalysed by a Low‐Valent Ruthenium Diazadiene Complex

Sun, heat and electricity. A comprehensive study of non‐pollutant alternatives to produce green hydrogen

Linear, Electron-Rich, Homoleptic Rare Earth Metallocene and Its Redox Activity

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