Artificial photosynthesis: molecular systems for catalytic water oxidation.

The development of new energy materials that can be utilized to make renewable and clean fuels from abundant and easily accessible resources is among the most challenging and demanding tasks in science today. Solar-powered catalytic water-splitting processes can be exploited as a source of electrons and protons to make clean renewable fuels, such as hydrogen, and in the sequestration of CO2 and its conversion into low-carbon energy carriers. Recently, there have been tremendous efforts to build up a stand-alone solar-to-fuel conversion device, the "artificial leaf", using light and water as raw materials. An overview of the recent progress in electrochemical and photo-electrocatalytic water splitting devices is presented, using both molecular water oxidation complexes (WOCs) and nano-structured assemblies to develop an artificial photosynthetic system.

Water‐Splitting Catalysis and Solar Fuel Devices: Artificial Leaves on the Move

Applications Dennis L. Ashford,† Melissa K. Gish,† Aaron K. Vannucci,‡ M. Kyle Brennaman,† Joseph L. Templeton,† John M. Papanikolas,† and Thomas J. Meyer*,† †Department of Chemistry, University of North Carolina at Chapel Hill, CB 3290, Chapel Hill, North Carolina 27599, United States ‡Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States

https://pubs.acs.org/doi/pdfplus/10.1021/acs.chemrev.5b00229

Molecular Chromophore–Catalyst Assemblies for Solar Fuel Applications

Artificial photosynthesis-reduction of CO2 into chemicals and fuels with water oxidation in the presence of sunlight as the energy source-mimics natural photosynthesis in green plants, and is considered to have a significant part to play in future energy supply and protection of our environment. The high quantum efficiency and easy manipulation of heterogeneous molecular photosystems based on metal complexes enables them to act as promising platforms to achieve efficient conversion of solar energy. This Review describes recent developments in the heterogenization of such photocatalysts. The latest state-of-the-art approaches to overcome the drawbacks of low durability and inconvenient practical application in homogeneous molecular systems are presented. The coupling of photocatalytic CO2 reduction with water oxidation through molecular devices to mimic natural photosynthesis is also discussed.

Heterogeneous Molecular Systems for Photocatalytic CO2 Reduction with Water Oxidation

A broad and critical description of the state-of-the-art in water oxidation electrocatalysts for the oxygen-evolving reaction is given. Technologically relevant catalysts for energy production from earth-abundant metals are highlighted.

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Water Oxidation at Electrodes Modified with Earth‐Abundant Transition‐Metal Catalysts

Clean energy carriers obtained from renewable, earth-abundant materials and by using the virtually unlimited supply of sunlight have potential to serve as future sustainable power sources. A quest for new materials for oxygen evolution from catalytic water oxidation and carbon dioxide reduction, which aim to build up solar-to-fuel conversion devices that use water as raw material, has been developing during the last two decades. Most of the research in the field of materials science and chemistry has been focused on the development of inorganic materials and molecular complexes for water oxidation, in particular bioinspired catalytic systems. Recently, various molecular water-oxidation complexes with mono- or multinuclear catalytic sites have been tested for solution-phase dioxygen generation. Catalyst immobilization and functionalization on an electrode surface is required for electrocatalytic or photoelectrochemical water oxidation devices; however, there are only a few examples in which a molecular catalyst has been placed on a transparent conducting surface in an electro- or photoelectrochemical system. Herein, a brief overview of surface-immobilized molecular assemblies for electrochemical water oxidation is presented, and an analysis of recent progress in catalyst design and performance is provided, including systems integration of modules for future stand-alone solar-to-fuel conversion devices. A view on the thermodynamics features of various intermediates and the mechanism of OO bond formation in single-site complexes and binuclear water oxidation catalysts is also presented.

Molecular Catalytic Assemblies for Electrodriven Water Splitting

Using first-principles molecular dynamics, we predict the reaction coordinate and mechanism of the first charge-separation step in the reaction center of photosynthetic bacteria in a model including the special pair (P) and closest relevant residues. In the ground state, a dynamical localization of the highest occupied orbital is found to be a defining characteristic of P. This feature is linked to the tuning of the orbital energy levels by the coupling with two collective low-frequency vibrational modes. After electronic excitation, we demonstrate one specific mode that couples to P*, representing the reaction coordinate along which the excited state develops. The characteristic vibrational coordinate we predict to be the rotation of an axial histidine (HisM202), which selectively lowers the energy of one (PM) of the two bacteriochlorophylls in P. This leads to a unidirectional displacement of electron density to establish PL(+)PM(-) charge-transfer character, a hypothesis well-supported by an extensive framework of experimental evidence.

Mechanism and Reaction Coordinate of Directional Charge Separation in Bacterial Reaction Centers.

Using first-principles molecular dynamics (AIMD) and constrained density functional theory (CDFT) we identify the pathway of primary electron transfer in the R. Sphaeroides reaction center from the special pair excited state (P*) to the accessory bacteriochlorophyll (BA). Previous AIMD simulations on the special pair (PLPM) predicted a charge-transfer intermediate formation through the excited-state relaxation along a reaction coordinate characterized by the rotation of an axial histidine (HisM202). To account for the full electron transfer we extend the model to include the primary acceptor BA. In this extended model, the LUMO is primarily localized on the acceptor BA and extends over an interstitial water (water A) that is known to influence the rate of electron transfer (Potter et al. Biochemistry 2005 280, 27155-27164). A vibrational analysis of the dynamical trajectories gives a frequency of 30-35 cm(-1) for a molecular motion involving the hydrogen-bond network around water A, in good agreement with experimental findings (Yakovlev et al. Biochemistry, 2003, 68, 603-610). In its binding pocket water A can act as a switch by breaking and forming hydrogen bonds. With CDFT we calculate the energy required to the formation of the charge-separated state and find it to decrease along the predicted anisotropic reaction coordinate. Furthermore, we observe an increased coupling between the ground and charge-separated state. Water A adapts its hydrogen-bonding network along this reaction coordinate and weakens the hydrogen bond with HisM202. We also present AIMD simulations on the radical cation (P(•+)) showing a weakening of the hydrogen bond between HisL168 and the 3(1)-acetyl of PL. This work demonstrates how proton displacements are crucially coupled to the primary electron transfer and characterizes the reaction coordinate of the initial photoproduct formation.

Proton displacements coupled to primary electron transfer in the Rhodobacter sphaeroides reaction center.

Photoinduced electron transfer (ET) and proton-coupled electron transfer (PCET) are fundamental processes in natural phenomena, most noticeably in photosynthesis. Time-resolved spectroscopic evidence of coherent oscillatory behavior associated with these processes has been reported both in complex biological environments, as well as in biomimetic models for artificial photosynthesis. Here, we consider a few biomimetic models to investigate these processes in real-time simulations based on ab initio molecular dynamics and Ehrenfest dynamics. This allows for a detailed analysis on how photon-to-charge conversion is promoted by a coupling of the electronic excitation with specific vibrational modes and with proton displacements. The ET process shows a characteristic coherence that is linked to the nuclear motion at the interface between donor and acceptor. We also show real-time evidence of PCET in a benzimidazole-phenol redox relay.

Thomas J. Eisenmayer

Papers

Molecular Catalytic Assemblies for Electrodriven Water Splitting

Mechanism and Reaction Coordinate of Directional Charge Separation in Bacterial Reaction Centers.

Proton displacements coupled to primary electron transfer in the Rhodobacter sphaeroides reaction center.

Real‐time Simulations of Photoinduced Coherent Charge Transfer and Proton‐Coupled Electron Transfer