New catalysts in the photo-oxidation of water

Lyris, Emmanuel; Argyropoulos, Dimitris S.; Mitsopoulou, Christiana A.; Katakis, D.; Vrachnou, E.

doi:10.1016/s1010-6030(96)04432-2

Cited by 20 publications

(12 citation statements)

References 15 publications

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“…Owing to the unique electronic properties of dithiolene ligands, the electron density of metal–dithiolene complexes is delocalized over the metal–sulfur core, which allows electron storage and the access to several stable anionic oxidation states. These properties have led to the investigation of metal dithiolenes as catalysts in the reductive side of water splitting . Thus, the groups of Eisenberg and Holland reported Co dithiolenes to be very active catalysts for the photocatalytic and electrocatalytic hydrogen evolution reactions, followed by reports on similar Mo and Ni benzene‐1,2‐dithiolate complexes .…”

Section: Introductionmentioning

confidence: 99%

Proton‐Reduction Reaction Catalyzed by Homoleptic Nickel–bis‐1,2‐dithiolate Complexes: Experimental and Theoretical Mechanistic Investigations

et al. 2017

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A series of homoleptic monoanionic nickel dithiolene complexes [Ni(bdt)2](NBu4), [Ni(tdt)2](NBu4), and [Ni(mnt)2](NBu4) containing the ligands benzene‐1,2‐dithiolate (bdt2−), toluene‐3,4‐dithiolate (tdt2−), and maleonitriledithiolate (mnt2−), respectively, were employed as electrocatalysts in the hydrogen‐evolution reaction with trifluoroacetic acid as the proton source in acetonitrile. All complexes are active catalysts with TONs reaching 113, 158, and 6 for [Ni(bdt)2](NBu4), [Ni(tdt)2](NBu4), and [Ni(mnt)2](NBu4), respectively. The Faradaic yield for the hydrogen evolution reaction reaches 88 % for 2−, which also displays the minimal overpotential requirement value (467 mV) within the series. Two pathways for H2 evolution can be hypothesized that differ in the sequence of protonation and reduction steps. DFT calculations are in agreement with experimental data and indicate that protonation at sulfur follows the reduction to the dianion. Hydrogen evolves from the direduced–diprotonated form via a highly distorted nickel hydride intermediate. The effects of acid strength and concentration in the hydrogen‐evolving mechanism are also discussed.

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Section: Introductionmentioning

confidence: 99%

Proton‐Reduction Reaction Catalyzed by Homoleptic Nickel–bis‐1,2‐dithiolate Complexes: Experimental and Theoretical Mechanistic Investigations

et al. 2017

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“…For several technological reasons, however, it has not been used in great extent up to now. In order to achieve a commercial and widespread use of hydrogen as a fuel and versatile energy carrier, feasible chemical technologies for storage systems [1][2][3][4][5][6][7] and large-scale hydrogen production [8][9][10] have to be developed.…”

Section: Introductionmentioning

confidence: 99%

Effect of curvature and chirality for hydrogen storage in single-walled carbon nanotubes: A Combined ab initio and Monte Carlo investigation

Mpourmpakis

Froudakis

Lithoxoos

et al. 2007

The Journal of Chemical Physics

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Combined ab initio and grand canonical Monte Carlo simulations have been performed to investigate the dependence of hydrogen storage in single-walled carbon nanotubes (SWCNTs) on both tube curvature and chirality. The ab initio calculations at the density functional level of theory can provide useful information about the nature of hydrogen adsorption in SWCNT selected sites and the binding under different curvatures and chiralities of the tube walls. Further to this, the grand canonical Monte Carlo atomistic simulation technique can model large-scale nanotube systems with different curvature and chiralities and reproduce their storage capacity by calculating the weight percentage of the adsorbed material (gravimetric density) under thermodynamic conditions of interest. The author's results have shown that with both computational techniques, the nanotube's curvature plays an important role in the storage process while the chirality of the tube plays none.

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“…Although in the literature kinetic studies reveal that the dithiolene complexes act as catalysts for hydrogen evolution in their monoanionic state regardless of the metal ion, herein, it is well documented that the neutral forms of the corresponding complexes can also act as catalysts, although lower yields are achieved (Table ). [4h], [17b], [18a], , The same order of activity of these catalysts ( 2 – > 3 – > 1 – > 2 > 3 > 1 > 4 – ) was achieved when different photosensitizers as [ReBr(CO) 3 (bpy)] and [ReBr(CO) 3 (amphen)] were used (Figure S3, Figure S4).…”

Section: Resultsmentioning

confidence: 82%

Establishing Structure–Activity Relationships in Photocatalytic Systems by Using Nickel Bis(dithiolene) Complexes as Proton Reduction Catalysts

et al. 2019

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Herein, we present an artificial photocatalytic system for H2 evolution based on a series of proton reduction catalysts, namely [Ni{S2C2(Ph)2}2] (1), [Ni{S2C2(Ph)2}2](NEt4) (1–), [Ni{S2C2(Ph)(Ph–OCH3‐4)}2] (2), [Ni{S2C2(Ph)(Ph–OCH3‐4)}2](NEt4) (2–), [Ni{S2C2(Ph–OCH3‐4)2}2] (3) and [Ni{S2C2(Ph–OCH3‐4)2}2](NEt4) (3–), [Ni(mnt)2] (NBu4) (4–), [Ni(mnt)(S2C2(Ph)2)](NBu4) (5–). These complexes are different of both in charge and the substituents on dithiolene ligand and represent a group of active catalysts for the reduction of protons with high TONs. A series of ReI complexes, [ReBr(CO)3 (bpy)], [ReCl(CO)3(bpy)], [Re(NCS)(CO3)(bpy)], [ReBr(CO)3(amphen)] and [ReBr(CO)3 (pq)] were used as photosensitizers, in combination with triethanolamine as a sacrificial electron donor and acetic acid as a proton source. The differences of the ligands in the electron donating properties and reactivity are discussed in the light of the experimental data. We also present the physicochemical characterization of a previously reported heteroleptic monoanionic complex (5–), by UV/Vis spectroscopy, FTIR spectroscopy, cyclic voltammetry and single‐crystal X‐ray diffraction studies.

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New catalysts in the photo-oxidation of water

Cited by 20 publications

References 15 publications

Proton‐Reduction Reaction Catalyzed by Homoleptic Nickel–bis‐1,2‐dithiolate Complexes: Experimental and Theoretical Mechanistic Investigations

Proton‐Reduction Reaction Catalyzed by Homoleptic Nickel–bis‐1,2‐dithiolate Complexes: Experimental and Theoretical Mechanistic Investigations

Effect of curvature and chirality for hydrogen storage in single-walled carbon nanotubes: A Combined ab initio and Monte Carlo investigation

Establishing Structure–Activity Relationships in Photocatalytic Systems by Using Nickel Bis(dithiolene) Complexes as Proton Reduction Catalysts

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