Iron Polypyridyl Complexes for Photocatalytic Hydrogen Generation.

A series of Fe(III) complexes were recently reported that are stable and active electrocatalysts for reducing protons into hydrogen gas. Herein, we report the incorporation of these electrocatalysts into a photocatalytic system for hydrogen production. Hydrogen evolution is observed when these catalysts are paired with fluorescein (chromophore) and triethylamine (sacrificial electron source) in a 1:1 ethanol:water mixture. The photocatalytic system is highly active and stable, achieving TONs > 2100 (with respect to catalyst) after 24 h. Catalysis proceeds through a reductive quenching pathway with a quantum yield of over 3%.

Sulfinato iron(III) complex for electrocatalytic proton reduction.

We report the first example of a sulfinato Fe(III) complex acting as a highly active electrocatalyst for proton reduction. The sulfinate binds to the metal through oxygen, resulting in a seven-membered chelate ring that is likely hemilabile during catalysis. Proton reduction occurs at -1.57 V versus Fc/Fc(+) in CH3CN with an ic/ip = 13 in CH3CN (kobs = 3300 s(-1)) and an overpotential of 800 mV. The catalysis is first order with respect to [catalyst] and second order with respect to [trifluoracetic acid]. An 11% increase in catalytic activity is observed in the presence of water, suggesting that sulfinate moieties are viable functional groups for aqueous proton reduction catalysts.

Cobalt-dithiolene complexes for the photocatalytic and electrocatalytic reduction of protons in aqueous solutions.

Artificial photosynthesis (AP) is a promising method of converting solar energy into fuel (H(2)). Harnessing solar energy to generate H(2) from H(+) is a crucial process in systems for artificial photosynthesis. Widespread application of a device for AP would rely on the use of platinum-free catalysts due to the scarcity of noble metals. Here we report a series of cobalt dithiolene complexes that are exceptionally active for the catalytic reduction of protons in aqueous solvent mixtures. All catalysts perform visible-light-driven reduction of protons from water when paired with Ru(bpy)(3)(2+) as the photosensitizer and ascorbic acid as the sacrificial donor. Photocatalysts with electron withdrawing groups exhibit the highest activity with turnovers up to 9,000 with respect to catalyst. The same complexes are also active electrocatalysts in 11 acetonitrile/water. The electrocatalytic mechanism is proposed to be ECEC, where the Co dithiolene catalysts undergo rapid protonation once they are reduced to CoL(2)(2-). Subsequent reduction and reaction with H(+) lead to H(2) formation. Cobalt dithiolene complexes thus represent a new group of active catalysts for the reduction of protons.

Cobalt complexes as artificial hydrogenases for the reductive side of water splitting.

The generation of H2 from protons and electrons by complexes of cobalt has an extensive history. During the past decade, interest in this subject has increased as a result of developments in hydrogen generation that are driven electrochemically or photochemically. This article reviews the subject of hydrogen generation using Co complexes as catalysts and discusses the mechanistic implications of the systems studied for making H2. This article is part of a Special Issue entitled: Metals in Bioenergetics and Biomimetics Systems.

A cobalt-dithiolene complex for the photocatalytic and electrocatalytic reduction of protons.

The complex [Co(bdt)(2)](-) (where bdt = 1,2-benzenedithiolate) is an active catalyst for the visible light driven reduction of protons from water when employed with Ru(bpy)(3)(2+) as the photosensitizer and ascorbic acid as the sacrificial electron donor. At pH 4.0, the system exhibits very high activity, achieving >2700 turnovers with respect to catalyst and an initial turnover rate of 880 mol H(2)/mol catalyst/h. The same complex is also an active electrocatalyst for proton reduction in 1:1 CH(3)CN/H(2)O in the presence of weak acids, with the onset of a catalytic wave at the reversible redox couple of -1.01 V vs Fc(+)/Fc. The cobalt-dithiolene complex [Co(bdt)(2)](-) thus represents a highly active catalyst for both the electrocatalytic and photocatalytic reduction of protons in aqueous solutions.

Iron polypyridyl complex adsorbed on carbon surfaces for hydrogen generation.

A series of homogeneous Fe(iii) complexes were recently reported that are active for electrocatalytic hydrogen generation. Herein we report a naphthalene-terminated Fe(iii) complex for use in the functionalization of glassy carbon surfaces for electrocatalytic hydrogen generation with retention of catalytic activity.

Acetylacetonate anchors for robust functionalization of TiO2 nanoparticles with Mn(II)-terpyridine complexes.

A novel class of derivatized acetylacetonate (acac) linkers for robust functionalization of TiO2 nanoparticles (NPs) under aqueous and oxidative conditions is reported. The resulting surface adsorbate anchors are particularly relevant to engineering photocatalytic and photovoltaic devices since they can be applied to attach a broad range of photosensitizers and photocatalytic complexes and are not affected by humidity. Acac is easily modified by CuI-mediated coupling reactions to provide a variety of scaffolds, including substituted terpy complexes (terpy = 2,2':6,2''-terpyridine), assembled with ligands coordinated to transition-metal ions. Since Mn-terpy complexes are known to be effective catalysts for oxidation chemistry, functionalization with Mn(II) is examined. This permits visible-light sensitization of TiO2 nanoparticles due to interfacial electron transfer, as evidenced by UV-vis spectroscopy of colloidal thin films and aqueous suspensions. The underlying ultrafast interfacial electron injection is complete on a subpicosecond time scale, as monitored by optical pump-terahertz probe transient measurements and computer simulations. Time-resolved measurements of the Mn(II) EPR signal at 6 K show that interfacial electron injection induces Mn(II) --> Mn(III) photooxidation, with a half-time for regeneration of the Mn(II) complex of ca. 23 s.

Cobalt Schiff-base complexes for electrocatalytic hydrogen generation.

Two cobalt(iii) complexes containing inexpensive Schiff-base ligands have been found to be active for proton reduction at low overpotentials. The dinitro and tetranitro derivatized Schiff-base complexes show catalytic activity at -0.96 V and -1.1 V vs. Fc+/Fc, respectively, resulting in overpotentials of 120 mV and 280 mV. Foot-of-the-wave analysis is used to examine the kinetic properties of these complexes, yielding a theoretical TOFmax of up to 4100 s-1. Experimental TOFs of 7 s-1and 3 s-1 are observed. Catalytic Tafel plots are also presented in order to benchmark the relationship between turnover frequency and overpotential.

Hydrogen evolution catalyzed by a cobalt complex containing an asymmetric Schiff-base ligand.

A cobalt(iii) complex containing an asymmetric Schiff-base ligand has been found to be active for proton reduction. Catalysis occurs at -1.2 V vs. Fc(+)/Fc (0.56 V vs. NHE), resulting in an overpotential of 350 mV. Additionally, the complex is active with a turnover frequency of 420 s(-1). An enhancement in activity is observed upon addition of water.

A nickel complex of a conjugated bis-dithiocarbazate Schiff base for the photocatalytic production of hydrogen.

We report a nickel complex containing a conjugated bis-dithiocarbazate ligand that is an active catalyst for the reduction of protons into hydrogen gas. Light-driven hydrogen generation is observed from a system containing this molecular nickel catalyst coupled with a fluorescein photosensitizer and triethylamine sacrificial donor. The photocatalytic system is stable for over 70 hours, achieving 3300 turnovers with respect to catalyst. The complex is also an active electrocatalyst for proton reduction with catalysis occurring at -1.7 V vs. Fc(+)/Fc. The nickel bis-dithiocarbazate complex represents a highly active and stable catalyst for hydrogen generation.

Reversible visible-light photooxidation of an oxomanganese water-oxidation catalyst covalently anchored to TiO2 nanoparticles.

Several polynuclear transition-metal complexes, including our own dinuclear di-µ-oxo manganese compound [H(2)O(terpy)Mn(III)(µ-O)(2)Mn(IV)(terpy)H(2)O](NO(3))(3) (1, terpy = 2,2':6',2''-terpyridine), have been reported to be homogeneous catalysts for water oxidation. This paper reports the covalent attachment of 1 onto nanoparticulate TiO(2) surfaces using a robust chromophoric linker L. L, a phenylterpy ligand attached to a 3-phenyl-acetylacetonate anchoring moiety via an amide bond, absorbs visible light and leads to photoinduced interfacial electron transfer into the TiO(2) conduction band. We characterize the electronic and structural properties of the 1-L-TiO(2) assemblies by using a combination of methods, including computational modeling and UV-visible, IR, and EPR spectroscopies. We show that the Mn(III,IV) state of 1 can be reversibly advanced to the Mn(IV,IV) state by visible-light photoexcitation of 1-L-TiO(2) nanoparticles (NPs) and recombines back to the Mn(III,IV) state in the dark, in the absence of electron scavengers. Our findings also indicate that a high degree of crystallinity of the TiO(2) NPs is essential for promoting photooxidation of the adsorbates by photoinduced charge separation when the TiO(2) NPs serve as electron acceptors in artificial photosynthetic assemblies. The reported results are particularly relevant to the development of photocatalytic devices for oxidation chemistry based on inexpensive materials (e.g., TiO(2) and Mn complexes) that are robust under aqueous and oxidative conditions.