Light-driven Water Oxidation Catalyst Research Articles

Bioinspired polyoxometalates as light-driven water oxidation catalysts

The design of molecular systems with capabilities to carry out the water oxidation reaction and thereby overcome the bottleneck of artificial photosynthesis is one of the scientific fields of most significant interest and urgency due to its potential to address energy demand and climate change. Nevertheless, the search for efficient and robust catalysts has been limited by the degradation of carbon-based ligands under oxidative conditions, leading to the search for fully inorganic catalysts. Polyoxometalates (POMs), an emerging class of carbon-free ligands with oxygen-enriched surfaces, offer a unique alternative as inorganic scaffolds to self-assemble and stabilize transition-metal clusters with unique redox properties. Under catalytic working conditions, POMs can undergo electron transfer reactions coupled to O2 formation without modifying their parental structure. As a result, these materials have recently entered the scene as catalytic players in designing new artificial photosynthetic platforms for water oxidation. We focus on the methods used to create these compounds, their unique structural characteristics, and how effectively they function as catalysts. We also explore the proposed mechanisms behind their ability to produce O2 and their potential use in designing photosynthetic devices.

Giant iron polyoxometalate that works as a catalyst for water oxidation

A polyoxometalate (POM) cluster [Mo72Fe30O252(CH3COO)12{Mo2O7(H2O)}2 {H2Mo2O8(H2O)} (H2O)91]. ca. 150 H2O (catalyst I) has been explored as a light-driven water oxidation catalyst. The catalyst is stable and could be reused/recycled several times.

One-Step Solvothermal Formation of Pt Nanoparticles Decorated Pt2+-Doped α-Fe2O3 Nanoplates with Enhanced Photocatalytic O2 Evolution

The photooxidation of water into O2 has been identified as the barrier of water-splitting, and light-driven water oxidation catalysts have been intensively explored to develop highly active water splitting materials. Despite the fascinating advantages for photocatalytic water oxidation, such as abundance in nature, inexpensiveness, low toxicity, thermo/photostability, and suitable electronic band structures, hematite α-Fe2O3 is a poor photocatalyst for water oxidation due to its short exciton lifetime and hole diffusion length, weak carrier mobility, and shallow sunlight penetration depth. In this work, we have synthesized Pt nanoparticles decorated Pt2+-doped α-Fe2O3 nanoplates (Pt/Pt-Fe2O3 NPs) by a one-step solvothermal route which exhibit the enhanced photoactivity and photostability for water oxidation. The introduction of the Pt into the α-Fe2O3 by the means of elemental doping and nanoparticle decoration accounts for the enhanced performance. The doping of Pt2+ into α-Fe2O3 improves the isolation e...

Polynuclear Cobalt Complexes as Catalysts for Light-Driven Water Oxidation: A Review of Recent Advances

Photochemical water oxidation, as a half-reaction of water splitting, represents a great challenge towards the construction of artificial photosynthetic systems. Complexes of first-row transition metals have attracted great attention in the last decade due to their pronounced catalytic efficiency in water oxidation, comparable to that exhibited by classical platinum-group metal complexes. Cobalt, being an abundant and relatively cheap metal, has rich coordination chemistry allowing construction of a wide range of polynuclear architectures for the catalytic purposes. This review covers recent advances in application of cobalt complexes as (pre)catalysts for water oxidation in the model catalytic system comprising [Ru(bpy)3]2+ as a photosensitizer and S2O82− as a sacrificial electron acceptor. The catalytic parameters are summarized and discussed in view of the structures of the catalysts. Special attention is paid to the degradation of molecular catalysts under catalytic conditions and the experimental methods and techniques used to control their degradation as well as the leaching of cobalt ions.

Binuclear polyoxometalates based on abundant metals as efficient homogeneous photocatalytic water oxidation catalysts

The exploration of efficient, stable and cheap water oxidation catalysts (WOCs) is essential for overcoming the bottleneck of water splitting. A series polyoxometalates (POMs) based dinuclear clusters, [M2(β-SiW8O31)2]16− (M=Co2+, Ni2+, Cu2+ and Zn2+) are reported as efficient, robust visible light-driven water oxidation catalysts for the first time. The quite high catalytic turnover number (TON 925), turnover frequency (TOF 7.0s−1) and 24% quantum yield of [Co2(β-SiW8O31)2]16− (Co-POM) for oxygen evolution are achieved at pH 9.0 using [Ru(bpy)3]2+ as photosensitizer and persulfate as sacrificial electron acceptor. Various experiments including laser flash photolysis, X-ray photoelectron spectra (XPS), UV–vis spectra and IR confirm that Co-POM is the dominant catalyst during water oxidation process. The results offer a utile insight into the design of water oxidation catalysts.

Correction: [{β-SiNi2W10O36(OH)2(H2O)}4]24-: a new robust visible light-driven water oxidation catalyst based on nickel-containing polyoxometalate.

Correction for '[{β-SiNi2W10O36(OH)2(H2O)}4]24-: a new robust visible light-driven water oxidation catalyst based on nickel-containing polyoxometalate' by Li Yu et al., Chem. Commun., 2016, DOI: 10.1039/c6cc02728h.

Recent advances in ruthenium complex-based light-driven water oxidation catalysts

The light driven splitting of water is one of the most attractive approaches for direct conversion of solar energy into chemical energy in the future. Ruthenium complexes as the water oxidation catalysts (WOCs) and light sensitizers have attracted increasing attention, and have made a great progress. This mini-review highlights recent progress on ruthenium complex-based photochemical and photoelectrochemical water oxidation catalysts. The recent representative examples of these ruthenium complexes that are in homogeneous solution or immobilized on solid electrodes, are surveyed. In particular, special attention has been paid on the supramolecular dyads with photosensitizer and WOC being covalently hold together, and grafted onto the solid electrode.

Polyoxometalate-based nickel clusters as visible light-driven water oxidation catalysts.

Three new polyoxometalate(POM)-based polynuclear nickel clusters, Na24[Ni12(OH)9(CO3)3(PO4)(SiW9O34)3]·56H2O (1), Na25[Ni13(H2O)3(OH)9(PO4)4(SiW9O34)3]·50H2O (2), and Na50[Ni25(H2O)2OH)18(CO3)2(PO4)6(SiW9O34)6]·85H2O (3) were synthesized and structurally characterized. Compounds 1-3 contain {Ni12}, {Ni13} and {Ni25} core, respectively, connected by the inorganic {OH}, {PO4} and/or {CO3} linkers and encapsulated by the lacunary A-α-{SiW9O34} POM units. Compound 3 represents the currently largest POM-based Ni clusters. All three compounds contain {Ni3O3} quasi-cubane or {Ni4O4} cubane units, which are similar to the natural oxygen-evolving center {Mn4O5Ca} in photosystem II (PSII). Visible light-driven water oxidation experiments with compounds 1-3 as the homogeneous catalysts indicate that all three compounds show good photocatalytic activities. The O2 evolution amount corresponds to a high TON of 128.2 for 1, 147.6 for 2, and 204.5 for 3, respectively. Multiple experiments including dynamic light-scattering, UV-vis absorption, catalysts aged experiments, tetra-n-heptylammonium nitrate (THpANO3) toluene extraction, and capillary electrophoretic measurements results confirm that compounds 1-3 are dominant active catalysts but not Ni(2+) ions(aq) or nickel oxide under the photocatalytic conditions. The above research results indicate a new and all-inorganic polynuclear Ni-based structural model as the visible light-driven water oxidation catalysts.

Photosynthetic water oxidation: insights from manganese model chemistry.

Catalysts for light-driven water oxidation are a critical component for development of solar fuels technology. The multielectron redox chemistry required for this process has been successfully deployed on a global scale in natural photosynthesis by green plants and cyanobacteria using photosystem II (PSII). PSII employs a conserved, cuboidal Mn4CaOX cluster called the O2-evolving complex (OEC) that offers inspiration for artificial O2-evolution catalysts. In this Account, we describe our work on manganese model chemistry relevant to PSII, particularly the functional model [Mn(III/IV)2(terpy)2(μ-O)2(OH2)2](NO3)3 complex (terpy = 2,2';6',2″-terpyridine), a mixed-valent di-μ-oxo Mn dimer with two terminal aqua ligands. In the presence of oxo-donor oxidants such as HSO5(-), this complex evolves O2 by two pathways, one of which incorporates solvent water in an O-O bond-forming reaction. Deactivation pathways of this catalyst include comproportionation to form an inactive Mn(IV)Mn(IV) dimer and also degradation to MnO2, a consequence of ligand loss when the oxidation state of the complex is reduced to labile Mn(II) upon release of O2. The catalyst's versatility has been shown by its continued catalytic activity after direct binding to the semiconductor titanium dioxide. In addition, after binding to the surface of TiO2 via a chromophoric linker, the catalyst can be oxidized by a photoinduced electron-transfer mechanism, mimicking the natural PSII process. Model oxomanganese complexes have also aided in interpreting biophysical and computational studies on PSII. In particular, the μ-oxo exchange rates of the Mn-terpy dimer have been instrumental in establishing that the time scale for μ-oxo exchange of high-valent oxomanganese complexes with terminal water ligands is slower than O2 evolution in the natural photosynthetic system. Furthermore, computational studies on the Mn-terpy dimer and the OEC point to similar Mn(IV)-oxyl intermediates in the O-O bond-forming mechanism. Comparison between the OEC and the Mn-terpy dimer indicates that challenges remain in the development of synthetic Mn water-oxidation catalysts. These include redox leveling to couple multielectron reactions with one-electron steps, avoiding labile Mn(II) species during the catalytic cycle, and protecting the catalyst active site from undesired side reactions. As the first example of a functional manganese O2-evolution catalyst, the Mn-terpy dimer exemplifies the interrelatedness of biomimetic chemistry with biophysical studies. The design of functional model complexes enriches the study of the natural photosynthetic system, while biology continues to provide inspiration for artificial photosynthetic technologies to meet global energy demand.

Visible-light-induced water oxidation mediated by a mononuclear-cobalt(II)-substituted silicotungstate.

A mononuclear-cobalt(II)-substituted silicotungstate, K10[Co(H2O)2(γ-SiW10O35)2]⋅23 H2O (POM-1), has been evaluated as a light-driven water-oxidation catalyst. With in situ photogenerated [Ru(bpy)3](3+) (bpy=2,2'-bipyridine) as the oxidant, quite high catalytic turnover number (TON; 313), turnover frequency (TOF; 3.2 s(-1)), and quantum yield (Φ(QY); 27%) for oxygen evolution at pH 9.0 were acquired. Comparison experiments with its structural analogues, namely [Ni(H2O)2(γ-SiW10O35)2](10-) (POM-2) and [Mn(H2O)2(γ-SiW10O35)2](10-) (POM-3), gave the conclusion that the cobalt center in POM-1 is the active site. The hydrolytic stability of the title polyoxometalate (POM) was confirmed by extensive experiments, including UV/Vis spectroscopy, linear sweep voltammetry (LSV), and cathodic adsorption stripping analysis (CASA). As the [Ru(bpy)3](2+)/visible light/sodium persulfate system was introduced, a POM-photosensitizer complex formed within minutes before visible-light irradiation. It was demonstrated that this complex functioned as the active species, which remained intact after the oxygen-evolution reaction. Multiple experimental parameters were investigated and the catalytic activity was also compared with the well-studied POM-based water-oxidation catalysts (i.e., [Co4(H2O)2(α-PW9O34)2](10-) (Co4-POM) and [Co(III)Co(II)(H2O)W11O39](7-) (Co2-POM)) under optimum conditions.

A Ru–Co hybrid material based on a molecular photosensitizer and a heterogeneous catalyst for light-driven water oxidation

A novel approach to anchor a molecular photosensitizer onto a heterogeneous water oxidation catalyst via coordination bonds is presented. A photosensitizer (1) based on [Ru(bpy)3](2+) and decorated with two methylenediphosphonate (M2P) groups has been designed and synthesized for this purpose. The M2P groups in complex 1 allow for coordination of cobalt ions to afford a novel molecular-heterogeneous hybrid material P1. Scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize P1 as an amorphous, non-uniform material that contains Ru and Co in a ratio of 1 : 2. A suspension of P1 in a buffered aqueous solution is active as a light-driven water oxidation catalyst in the presence of persulfate (S2O8(2-)) as electron acceptor. The yield of oxygen is higher when P1 is prepared in situ by mixing and illuminating 1 and Co(2+) in the presence of S2O8(2-). After oxygen evolution ceases, a second material P2 can be isolated from the reaction mixture. P2 is characterized by a lower Ru content than P1, and contains Co in a higher oxidation state. Interestingly, P2 as a freshly prepared suspension is also active for light-driven water oxidation. It is shown that 1 resides in the interior of P1 and P2, and is thus in a location where undesirable quenching pathways of the photo-excited state of 1 limit the oxygen production yields for both P1 and P2.

Catalytic activity of NiMnO3 for visible light-driven and electrochemical water oxidation

NiMnO3 was found to be an efficient catalyst for light-driven water oxidation using [Ru(bpy)3](2+) and S2O8(2-) as a photosensitiser and a sacrificial oxidant, respectively. NiMnO3 exhibited remarkably high catalytic activity in comparison with manganese oxides and nickel oxide. For electrochemical water oxidation, the highest catalytic current was also obtained with NiMnO3 among the manganese oxides.

Enabling light-driven water oxidation via a low-energy RuIVO intermediate

The discovery of catalysts capable of driving water oxidation at relatively low overpotential is a key challenge for efficient photoinduced water oxidation. The mononuclear Ru(II) polypyridyl complex (1) [Ru(NPM)(H2O)(pic)2](2+) (NPM = 4-tert-butyl-2,6-di-(1',8'-naphthyrid-2'-yl)-pyridine, pic = 4-picoline) has been examined as a catalyst for visible-light-driven water oxidation in a three-component homogeneous system containing [Ru(bpy)3](2+) as a photosensitizer, persulfate as a sacrificial electron acceptor and catalyst 1. In contrast to the well-established water oxidation mechanism via the nucleophilic attack of a water molecule on the high-energy [Ru(V)=O](3+) species, a lower-energy "direct pathway" for O-O bond formation via a [Ru(IV)=O](2+) intermediate was proposed for the first time for the catalyst 1 (Polyansky et al., J. Am. Chem. Soc., 2011, 133, 14649). In this report we successfully demonstrate that this unique proton-coupled low-energy pathway actually takes place with the use of a mild oxidant such as the photogenerated [Ru(bpy)3](3+) (1.26 V vs. NHE) to drive water oxidation. The overall quantum yield of 9%, TOF of 0.12 s(-1) and TON of 103 (limited solely by a drop in pH) were found for photochemical water oxidation with 1 using [Ru(bpy)3](2+) as a photosensitizer and [S2O8](2-) as a sacrificial electron acceptor. These values render catalyst 1 as one of the most active mononuclear ruthenium-based catalysts for light-driven water oxidation in a homogeneous system. The utilization of a pH-dependent pathway for water oxidation is a new and promising direction as a low-energy pathway. Furthermore, the detailed analysis of individual photochemical steps leading to O2 evolution provides benchmarks for future mechanistic studies of photo-induced water oxidation catalysis.

Wateroxidation catalysed by manganese compounds: from complexes to ‘biomimetic rocks’

One of the most fundamental processes of the natural photosynthetic reaction sequence is the light-driven oxidation of water to molecular oxygen. In vivo, this reaction takes place in the large protein ensemble Photosystem II, where a μ-oxido-Mn(4)Ca- cluster, the oxygen-evolving-complex (OEC), has been identified as the catalytic site for the four-electron/four-proton redox reaction of water oxidation. This Perspective presents recent progress for three strategies which have been followed to prepare functional synthetic analogues of the OEC: (1) the synthesis of dinuclear manganese complexes designed to act as water-oxidation catalysts in homogeneous solution, (2) heterogeneous catalysts in the form of clay hybrids of such Mn(2)-complexes and (3) the preparation of manganese oxide particles of different compositions and morphologies. We discuss the key observations from the studies of such synthetic manganese systems in order to shed light upon the catalytic mechanism of natural water oxidation. Additionally, it is shown how research in this field has recently been motivated more and more by the prospect of finding efficient, robust and affordable catalysts for light-driven water oxidation, a key reaction of artificial photosynthesis. As manganese is an abundant and non-toxic element, manganese compounds are very promising candidates for the extraction of reduction equivalents from water. These electrons could consecutively be fed into the synthesis of "solar fuels" such as hydrogen or methanol.