Molecular Water Oxidation Research Articles

Metamorphic oxygen-evolving molecular Ru and Ir catalysts.

Today sustainable and clean energy conversion strategies are based on sunlight and the use of water as a source of protons and electrons, in a similar manner as it happens in Photosystem II. To achieve this, the charge separation state induced by light has to be capable of oxidising water by 4 protons and 4 electrons and generating molecular oxygen. This oxidation occurs by the intermediacy of a catalyst capable of finding low-energy pathways via proton-coupled electron transfer steps. The high energy involved in the thermodynamics of water oxidation reaction, coupled with its mechanistic complexity, is responsible for the difficulty of discovering efficient and oxidatively robust molecules capable of achieving such a challenging task. A significant number of Ru coordination complexes have been identified as water oxidation catalysts (WOCs) and are among the best understood from a mechanistic perspective. In this review, we describe the catalytic performance of these complexes and focus our attention on the factors that influence their performance during catalysis, especially in cases where a detailed mechanistic investigation has been carried out. The collective information extracted from all the catalysts studied allows one to identify the key features that govern the complex chemistry associated with the catalytic water oxidation reaction. This includes the stability of trans-O-Ru-O groups, the change in coordination number from CN6 to CN7 at Ru high oxidation states, the ligand flexibility, the capacity to undergo intramolecular proton transfer, the bond strain, the axial ligand substitution, and supramolecular effects. Overall, combining all this information generates a coherent view of this complex chemistry.

BiVO4 photoanode modification by synergic dual-conjugated organic materials

Organic conjugated materials have presented considerable application potential in the field of photoelectrochemical (PEC) water splitting. In this study, two organic conjugated materials, two dimension carbon nitride (2D-C 3 N 4 ) and organic cobalt molecular catalyst ((H 3 O) 6 ·[Co 4 (H 2 O) 4 (HPMIDA) 2 (PMIDA) 2 )]·2H 2 O) (OCM), are fabricated in turn on the surface of bismuth vanadate (BVO) photoanode. Basing on the synergistic effect of 2D-C 3 N 4 and OCM, the PEC property of the modified BVO photoanode increases three times higher than that of bare BVO photoanode at 1.23 V vs. RHE by increasing reaction active surface, promoting charge separation, and reducing reaction overpotential. This study shows that organic conjugated materials can not only form an effective heterojunction system with semiconductor materials and improve surface catalytic activity, but also assemble easily by the strong affinity between g-C 3 N 4 and OCM. Therefore, it provides a novel and efficient modification method by dual-conjugated organic materials to improve the PEC performance of photoelectrodes. • Development of 2D-C 3 N 4 /organic cobalt molecular dual-conjugated water oxidation catalyst. • 2D-C 3 N 4 /organic cobalt molecular catalyst modified BiVO 4 photoanode was prepared by first time. • A synergistic effect was found between conjugated 2D-C 3 N 4 and organic cobalt molecular. • A photocurrent density of BiVO 4 photoanode increased three times after dual-conjugated molecular modification.

Dinuclear Cobalt Complexes for Homogeneous Water Oxidation: Tuning Rate and Overpotential through the Non-Innocent Ligand.

In this study, dinuclear cobalt complexes (1 and 2) featuring bis(benzimidazole)pyrazolide-type ligands (H2 L and Me2 L) were prepared and evaluated as molecular electrocatalysts for water oxidation. Notably, 1 bearing a non-innocent ligand (H2 L) displayed faster catalytic turnover than 2 under alkaline conditions, and the base dependence of water oxidation and kinetic isotope effect analysis indicated that the reaction mediated by 1 proceeded by a different mechanism relative to 2. Spectroelectrochemical, cold-spray ionization mass spectrometric and computational studies found that double deprotonation of 1 under alkaline conditions cathodically shifted the catalysis-initiating potential and further altered the turnover-limiting step from nucleophilic water attack on (H2 L)CoIII 2 (superoxo) to deprotonation of (L)CoIII 2 (OH)2 . The rate-overpotential analysis and catalytic Tafel plots showed that 1 exhibited a significantly higher rate than previously reported Ru-based dinuclear electrocatalysts at similar overpotentials. These observations suggest that using non-innocent ligands is a valuable strategy for designing effective metal-based molecular water oxidation catalysts.

Water Oxidation by Pentapyridyl Base Metal Complexes? A Case Study.

The design of molecular water oxidation catalysts (WOCs) requires a rational approach that considers the intermediate steps of the catalytic cycle, including water binding, deprotonation, storage of oxidizing equivalents, O–O bond formation, and O2 release. We investigated several of these properties for a series of base metal complexes (M = Mn, Fe, Co, Ni) bearing two variants of a pentapyridyl ligand framework, of which some were reported previously to be active WOCs. We found that only [Fe(Py5OMe)Cl]+ (Py5OMe = pyridine-2,6-diylbis[di-(pyridin-2-yl)methoxymethane]) showed an appreciable catalytic activity with a turnover number (TON) = 130 in light-driven experiments using the [Ru(bpy)3]2+/S2O82– system at pH 8.0, but that activity is demonstrated to arise from the rapid degradation in the buffered solution leading to the formation of catalytically active amorphous iron oxide/hydroxide (FeOOH), which subsequently lost the catalytic activity by forming more extensive and structured FeOOH species. The detailed analysis of the redox and water-binding properties employing electrochemistry, X-ray absorption spectroscopy (XAS), UV–vis spectroscopy, and density-functional theory (DFT) showed that all complexes were able to undergo the MIII/MII oxidation, but none was able to yield a detectable amount of a MIV state in our potential window (up to +2 V vs SHE). This inability was traced to (i) the preference for binding Cl– or acetonitrile instead of water-derived species in the apical position, which excludes redox leveling via proton coupled electron transfer, and (ii) the lack of sigma donor ligands that would stabilize oxidation states beyond MIII. On that basis, design features for next-generation molecular WOCs are suggested.

Boosting Efficiency in Light‐Driven Water Splitting by Dynamic Irradiation through Synchronizing Reaction and Transport Processes**

This work elaborates the effect of dynamic irradiation on light‐driven molecular water oxidation to counteract deactivation. It highlights the importance of overall reaction engineering to overcome limiting factors in artificial photosynthesis reactions. Systematic investigation of a homogeneous three‐component ruthenium‐based water oxidation system revealed significant potential to enhance the overall catalytic efficiency by synchronizing the timescales of photoreaction and mass transport in a capillary flow reactor. The overall activity could be improved by a factor of more than 10 with respect to the turnover number and a factor of 31 referring to the external energy efficiency by controlling the local availability of photons. Detailed insights into the mechanism of light driven water oxidation could be obtained using complementary methods of investigation like Raman, IR, and UV/Vis/emission spectroscopy, unraveling the importance of avoiding high concentrations of excited photosensitizers.

On the Homogeneity of a Cobalt-Based Water Oxidation Catalyst

The homogeneity of molecular Co-based water oxidation catalysts (WOCs) has been a subject of debate over the last 10 years as assumed various homogeneous Co-based WOCs were found to actually form CoOx under operating conditions. The homogeneity of the Co(HL) (HL = N,N-bis(2,2′-bipyrid-6-yl)amine) system was investigated with cyclic voltammetry, electrochemical quartz crystal microbalance, and X-ray photoelectron spectroscopy. The obtained experimental results were compared with heterogeneous CoOx. Although it is shown that Co(HL) interacts with the electrode during electrocatalysis, the formation of CoOx was not observed. Instead, a molecular deposit of Co(HL) was found to be formed on the electrode surface. This study shows that deposition of catalytic material is not necessarily linked to the decomposition of homogeneous cobalt-based water oxidation catalysts.

Molecular water oxidation catalysts based on first-row transition metal complexes

Molecular water oxidation catalysts based on first-row transition metal complexes

Heterogenization of Molecular Water Oxidation Catalysts in Electrodes for (Photo)Electrochemical Water Oxidation

Water oxidation is still one of the most important challenges to develop efficient artificial photosynthetic devices. In recent decades, the development and study of molecular complexes for water oxidation have allowed insight into the principles governing catalytic activity and the mechanism as well as establish ligand design guidelines to improve performance. However, their durability and long-term stability compromise the performance of molecular-based artificial photosynthetic devices. In this context, heterogenization of molecular water oxidation catalysts on electrode surfaces has emerged as a promising approach for efficient long-lasting water oxidation for artificial photosynthetic devices. This review covers the state of the art of strategies for the heterogenization of molecular water oxidation catalysts onto electrodes for (photo)electrochemical water oxidation. An overview and description of the main binding strategies are provided explaining the advantages of each strategy and their scope. Moreover, selected examples are discussed together with the the differences in activity and stability between the homogeneous and the heterogenized system when reported. Finally, the common design principles for efficient (photo)electrocatalytic performance summarized.

Homogeneous Water Oxidation Catalyzed by First-Row Transition Metal Complexes: Unveiling the Relationship between Turnover Frequency and Reaction Overpotential.

The utilization of earth-abundant low-toxicity metal ions in the construction of highly active and efficient molecular catalysts promoting the water oxidation reaction is important for developing a sustainable artificial energy cycle. However, the kinetic and thermodynamic properties of the currently available molecular water oxidation catalysts (MWOCs) have not been comprehensively investigated. This Review summarizes the current status of MWOCs based on first-row transition metals in terms of their turnover frequency (TOF, a kinetic property) and overpotential (η, a thermodynamic property) and uses the relationship between log(TOF) and η to assess catalytic performance. Furthermore, the effects of the same ligand classes on these MWOCs are discussed in terms of TOF and η, and vice versa. The collective analysis of these relationships provides a metric for the direct comparison of catalyst systems and identifying factors crucial for catalyst design.

Dangling Carboxylic Group That Participates in O-O Bond Formation Reaction to Promote Water Oxidation Catalyzed by a Ruthenium Complex: Experimental Evidence of an Oxide Relay Pathway.

Two mononuclear ruthenium(II) complexes of the types [Ru(trpy)(HL1)(OH2)]2+ (1Aq) and [Ru(trpy)(L2-κ-N2O)] (2) [where trpy = 2,2':6',2″-terpyridine, HL1 = 2-(2-pyridyl)benzimidazole, H2L2 = 2-(pyridin-2-yl)-1H-benzo[d]imidazole-4-carboxylic acid] have been synthesized and thoroughly characterized by analytical and spectroscopic [UV-vis, NMR, high-resolution mass spectrometry, and IR] techniques. Complex 1Aq has been further characterized by X-ray crystallography. In an acidic aqueous medium (pH 1), complex 2 undergoes carboxylate/water exchange readily to form an aqua-ligated complex, [Ru(trpy)(H2L2-κ-N2)(OH2)]2+ (2Aq), having a dangling carboxylic group. This exchange phenomenon has been followed by IR, 1H NMR, and UV-vis spectroscopic techniques. Electrochemical analyses of 1Aq and 2Aq (Pourbaix diagram) suggest the generation of a formal RuV═O species that can potentially promote the oxidation of water. A comparative study of the water oxidation activity catalyzed by 1Aq and 2Aq is reported here to see the effect of a dangling carboxylic group in the catalytic performance. Complex 2Aq shows an enormously higher rate of reaction than 1Aq. The pendant carboxylic group in 2Aq participates in an intramolecular O-O bond formation reaction with the reactive formal RuV═O unit to form a percarboxylate intermediate and provides an electron-deficient carbon center where water nucleophilic attack takes place. The isotope labeling experiment using 18O-labeled water verifies the attack of water at the carbon center of the carboxylic group rather than a direct attack at the oxo of the formal RuV═O unit. The present work provides experimental evidence of the uncommon functionality of the carboxylic group, the oxide relay, in molecular water oxidation chemistry.

Photoelectrochemical water oxidation improved by pyridine N-oxide as a mimic of tyrosine-Z in photosystem II.

Artificial photosynthesis provides a way to store solar energy in chemical bonds with water oxidation as a major challenge for creating highly efficient and robust photoanodes that mimic photosystem II. We report here an easily available pyridine N-oxide (PNO) derivative as an efficient electron transfer relay between an organic light absorber and molecular water oxidation catalyst on a nanoparticle TiO2 photoanode. Spectroscopic and kinetic studies revealed that the PNO/PNO+˙ couple closely mimics the redox behavior of the tyrosine/tyrosyl radical pair in PSII in improving light-driven charge separation via multi-step electron transfer. The integrated photoanode exhibited a 1 sun current density of 3 mA cm−2 in the presence of Na2SO3 and a highly stable photocurrent density of >0.5 mA cm−2 at 0.4 V vs. NHE over a period of 1 h for water oxidation at pH 7. The performance shown here is superior to those of previously reported organic dye-based photoanodes in terms of photocurrent and stability.

Iron-N-heterocyclic carbene complexes as efficient electrocatalysts for water oxidation under acidic conditions.

The development of stable, Earth-abundant, and high-activity molecular water oxidation catalysts under acidic and neutral conditions remains a great challenge. Here, the use of N-heterocyclic carbene (NHC)-based iron(III) complex 1 {[phenyl(tris(3-methylimidazol-1-ylidene))borate]2Fe(III)}+ as a catalyst for water oxidation under acidic and neutral conditions was investigated. Two iron(II) carbene complexes, 2 {[2,6-bis(3-methylimidazolium-1-yl)pyridine]2Fe}2+ and 3 {[2,6-bis(3-methylimidazolium-1-yl)pyridine-4-carboxylic acid]2Fe}2+, were also used for comparison. A series of experiments demonstrate that complex 1 has excellent performance in terms of both catalytic activity and stability. In addition, the faradaic efficiency and turnover frequency (TOF) reach 95.0% and 2.8 s-1, respectively. An overpotential of ca. 490 mV is obtained at pH 1.5. Density functional theory (DFT) calculations indicate that dehydrogenation is the potential-determining step (PDS) in water oxidation. Complex 1 has a lower free energy barrier in this process than 2 and 3. High-valent Fe species are further proven in 1 by spectroelectrochemical measurements, which are crucial in promoting water oxidation. This study is expected to contribute to the development of homogeneous water oxidation catalysis under acidic and neutral conditions.

Bias-Free Photoelectrochemical Water Splitting Cells Constructed by Calixarene Dyes and Molecular Ru Catalysts via Pyridyl Anchoring Groups

Two metal-free calix[4]arene dyes with pyridyl anchoring groups (C4BTP and C4STP) and a comparative single-chain dye (M-BTP) for comparison have been synthesized and applied in dye-sensitized photoelectrochemical cells in corporation with a pyridyl anchor-based molecular water oxidation catalyst (RuPy). All the devices based on the three dyes can conduct overall water splitting reaction under visible light with low or zero bias. It is confirmed that the cone structure and multiple light-harvesting units of calixarene dyes bring superior durability and photoelectroconversion property compared with chain dyes M-BTP, and the introduction of alkalinous pyridyl anchoring groups improves the adsorption firmness on TiO2 in aqueous solution through the Ti–N bond. The optimized TiO2|C4BTP+RuPy photoanode gives the highest photocurrent density of over 800 μA cm–2, while the TiO2|C4STP+RuPy photoanode exhibits the best Faradaic efficiency of 64.9% for O2 evolution. To meet the needs of practical applications, the TiO2|C4BTP+RuPy photoanode is utilized in a two-electrode system with 0 V bias, giving a steady photocurrent density of 42 μA cm–2 in 3600 s and a Faradaic efficiency of 45.9% for O2 evolution. This study offers an inspiration for developing efficient and durable organic photosensitizers in photocatalytic water-splitting devices.

Bioinspired Trinuclear Copper Catalyst for Water Oxidation with a Turnover Frequency up to 20000 s-1.

Solar-powered water splitting is a dream reaction for constructing an artificial photosynthetic system for producing solar fuels. Natural photosystem II is a prototype template for research on artificial solar energy conversion by oxidizing water into molecular oxygen and supplying four electrons for fuel production. Although a range of synthetic molecular water oxidation catalysts have been developed, the understanding of O-O bond formation in this multielectron and multiproton catalytic process is limited, and thus water oxidation is still a big challenge. Herein, we report a trinuclear copper cluster that displays outstanding reactivity toward catalytic water oxidation inspired by multicopper oxidases (MCOs), which provides efficient catalytic four-electron reduction of O2 to water. This synthetic mimic exhibits a turnover frequency of 20000 s-1 in sodium bicarbonate solution, which is about 150 and 15 times higher than that of the mononuclear Cu catalyst (F-N2O2Cu, 131.6 s-1) and binuclear Cu2 complex (HappCu2, 1375 s-1), respectively. This work shows that the cooperation between multiple metals is an effective strategy to regulate the formation of O-O bond in water oxidation catalysis.

Efficient Electrochemical Water Oxidation Mediated by Pyridylpyrrole-Carboxylate Ruthenium Complexes.

Spurred by the rapid growth of Ru-based complexes as molecular water oxidation catalysts (WOCs), we propose novel ruthenium(II) complexes bearing pyridylpyrrole-carboxylate (H2ppc) ligands as members of the WOC family. The structure of these complexes has 4-picoline (pic)/dimethyl sulfoxide (DMSO) in [Ru(ppc)(pic)2(dmso)] and pic/pic in [Ru(ppc)(pic)3] as axial ligands. Another ppc2- ligand and one pic ligand are located at the equatorial positions. [Ru(ppc)(pic)2(dmso)] behaves as a WOC as determined by electrochemical measurement and has an ultrahigh electrocatalytic current density of 8.17 mA cm-2 at 1.55 V (vs NHE) with a low onset potential of 0.352 V (vs NHE), a turnover number of 241, a turnover frequency of 203.39 s-1, and kcat of 16.34 s-1 under neutral conditions. The H2O/pic exchange of the complexes accompanied by oxidation of a ruthenium center is the initial step in the catalytic cycle. The cyclic voltametric measurements of [Ru(ppc)(pic)2(dmso)] at various scan rates, Pourbaix diagrams (plots of E vs pH), and kinetic studies suggested a water nucleophilic attack mechanism. HPO42- in a phosphate buffer solution is invoked in water oxidation as the proton acceptor.

Substituent Effects on the Activity of Cp*Ir(pyridine-carboxylate) Water Oxidation Catalysts: Which Ligand Fragments Remain Coordinated to the Active Ir Centers?

Identifying structure–property correlations for molecular water oxidation catalysts (WOCs) is strongly hampered by the complexity of the water oxidation (WO) reaction mechanism and catalyst in situ...

Strategic Factors to Design the Next Generation of Molecular Water Oxidation Catalysts: Lesson Learned from Ruthenium Complexes

Strategic Factors to Design the Next Generation of Molecular Water Oxidation Catalysts: Lesson Learned from Ruthenium Complexes

Isolation and Identification of Pseudo Seven-Coordinate Ru(III) Intermediate Completing the Catalytic Cycle of Ru-bda Type of Water Oxidation Catalysts

Isolation and Identification of Pseudo Seven-Coordinate Ru(III) Intermediate Completing the Catalytic Cycle of Ru-bda Type of Water Oxidation Catalysts

Anode Based on a Molecular Ru Water Oxidation Catalyst Covalently Bonded to Polythiophene

Anode Based on a Molecular Ru Water Oxidation Catalyst Covalently Bonded to Polythiophene

High-throughput screening and rational design to drive discovery in molecular water oxidation catalysis

The difficulty of the oxygen evolution reaction (OER) is a fundamental impediment to the sustainable production of hydrogen, in which molecular catalysts show the most impressive activity in terms of turnover frequency. Here, we interrogate 444 automatically generated molecular water oxidation catalysts composed of well-known ligand scaffolds and 6 different transition metals (Cr, Mn, Fe, Ru, Co, and Ni). These data confirm the method-independent universal scaling relationship for water oxidation catalysts, describe routes toward circumventing this relationship, and justify the ascendency of Ru catalysts for this reaction. Leveraging this information while applying catalyst design principles, we summarize experimental results, giving credence to our prediction of 9 earth-abundant molecular catalysts with theoretical overpotentials ranging from 200 to 400 mV as promising leads for experimental investigation. We also establish insights into spin-dependent scaling relations for key OER intermediates. Altogether, this work outlines the first steps toward enabling inverse design for molecular OER catalysts. Generate total of 444 OER catalysts by combining well-known ligands and low-cost metals Demonstrate functional-independent scaling relations Establish metal-specific scaling relations and their implications Identify three Cr-based complexes as promising molecular OER catalysts Green hydrogen production could see widespread adoption if cost-effective catalysts for the oxygen evolution reaction were developed. Here, Craig et al. report a high-throughput screening of complexes generated by combining established ligands and low-cost metals, thereby identifying candidate catalysts for experimental realization and providing guidance for future studies.