Basic Research Needs for Solar Energy Utilization - Office of ...
Basic Research Needs for Solar Energy Utilization - Office of ...
Basic Research Needs for Solar Energy Utilization - Office of ...
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Bio-inspired Approaches to Photochemical <strong>Energy</strong> Conversion<br />
A major scientific challenge is the preparation <strong>of</strong> bio-inspired, molecular assemblies that<br />
integrate light absorption, photoinduced charge separation, and catalytic water oxidation/fuel<br />
<strong>for</strong>mation into a single unit. These integrated assemblies must take full advantage <strong>of</strong> both<br />
molecular and supramolecular organization to collect light energy and transfer the resulting<br />
excitation to artificial RCs. These centers must separate charge and inject electrons and holes<br />
into charge transport structures that deliver the oxidizing and reducing equivalents to catalytic<br />
sites where water oxidation and CO2 reduction occur. It is critical to understand how excitation<br />
energy flow from the antenna to a RC depends on molecular structure. In addition, charge<br />
transport structures <strong>for</strong> delivery <strong>of</strong> redox equivalents to catalysts must be developed. By analogy<br />
to natural photosynthesis, it is important to provide control elements, or “throttles,” to optimize<br />
energy and charge flow within an artificial photosynthetic system as it responds to varying light<br />
intensities and spectral distributions. One <strong>of</strong> the most difficult tasks critical to achieving system<br />
integration is coupling single-photon events to the accumulation <strong>of</strong> multiple-redox equivalents<br />
necessary to drive multi-electron, fuel-<strong>for</strong>ming chemistry within a catalyst.<br />
The assembly <strong>of</strong> complex photoconversion systems with synergistic functionality depends on a<br />
variety <strong>of</strong> weak, intermolecular interactions, rather than strong, individual covalent chemical<br />
bonds. A critical step toward fully functional photoconversion systems is the ability to create<br />
increasingly larger arrays <strong>of</strong> interactive molecules. Covalent synthesis <strong>of</strong> near-macromolecular<br />
arrays becomes highly inefficient and costly, thus requiring that practical photoconversion<br />
systems be prepared using self-assembly to achieve ordered architectures from properly<br />
functionalized building blocks. Self-assembly is based on a variety <strong>of</strong> weak interactions — such<br />
as hydrogen bonding, electrostatic, metal-ligand, and π-π interactions — that give rise to ordered<br />
structures. Achieving the goal <strong>of</strong> producing a functional, integrated artificial photosynthetic<br />
system <strong>for</strong> efficient solar fuels production requires the following: (1) developing innovative<br />
architectures <strong>for</strong> coupling light-harvesting, photoredox, and catalytic components;<br />
(2) understanding the relationships between electronic communication and the molecular<br />
interactions responsible <strong>for</strong> self-assembly; (3) understanding and controlling the reactivity <strong>of</strong><br />
hybrid molecular assemblies on many length scales; and (4) applying new synthetic discoveries<br />
in nanoscale materials (e.g., shape and pore control, nano- and microphase separation) to<br />
organize functional parts <strong>of</strong> an integrated artificial photosynthetic system <strong>for</strong> efficient fuel<br />
<strong>for</strong>mation.<br />
Biological systems, such as photosynthesis, have built-in repair mechanisms that can restore<br />
useful function following damage to the system. This contrasts strongly with the lack <strong>of</strong> such<br />
mechanisms the complex molecules used to develop artificial photosynthetic systems <strong>for</strong> solar<br />
fuels production. The development <strong>of</strong> active repair and photoprotection strategies <strong>for</strong> artificial<br />
photosynthetic systems is a major scientific challenge that is critical to the long-term efficient<br />
per<strong>for</strong>mance <strong>of</strong> these systems. The usual strategy used by photosynthetic organisms to repair<br />
photochemical damage is to degrade the pigment-protein complex and replace it with a newly<br />
synthesized complex. Photosynthetic systems are continuously subjected to photochemical<br />
damage, especially when the incident light intensity is high. The major scientific challenge lies in<br />
understanding the photoprotection and repair mechanisms in natural systems and exploiting these<br />
findings to engineer robust artificial systems. To ensure that complex, artificial, photosynthetic<br />
systems designed <strong>for</strong> solar fuels production maintain their efficiency over long lifetimes, the<br />
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