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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USING A BIO-INSPIRED SMART MATRIX TO OPTIMIZE ENERGY<br />
LANDSCAPES FOR SOLAR FUELS PRODUCTION<br />
In photosynthesis, complex protein structures control and optimize energy flow in a dynamic<br />
fashion, leading to efficient solar energy conversion and storage. No artificial systems currently<br />
implement this approach in a useful fashion, and assembly <strong>of</strong> such systems is currently beyond<br />
the state-<strong>of</strong>-the-art <strong>for</strong> chemists. Development and use <strong>of</strong> smart matrices would revolutionize our<br />
ability to control and implement solar-fuel-<strong>for</strong>ming systems at the molecular level.<br />
EXECUTIVE SUMMARY<br />
A central challenge <strong>for</strong> solar fuels production is the development <strong>of</strong> efficient new photocatalysts<br />
<strong>for</strong> solar energy capture, conversion, and storage. Biology has achieved the ideal <strong>of</strong> solarinitiated<br />
water-splitting coupled to chemical energy storage using abundant, renewable, selfassembling<br />
“s<strong>of</strong>t” materials. The catalytic power and specificity that are key attributes <strong>of</strong><br />
enzyme-mediated catalysis have their origins in the active environment provided by the protein.<br />
The proteins involved in the photosynthetic light-harvesting complexes and the reaction centers<br />
are not mere inert scaffolds. They provide much more than just a means <strong>of</strong> optimally positioning<br />
the chromophores and the electron-transfer c<strong>of</strong>actors. The medium provided by the protein<br />
actively promotes, enhances, and indeed controls the light-harvesting and electron-transfer<br />
reactions. This is a key feature <strong>of</strong> the natural system that allows it to operate efficiently. Current<br />
bio-inspired solar-energy conversion systems have been able to replicate in a limited fashion the<br />
light harvesting, directed energy transfer, and charge separation seen in photosynthesis.<br />
However, so far, this has been achieved by using strong covalent bonds to link the molecular<br />
components in the required configurations. Due to major limitations imposed by covalent<br />
synthesis <strong>of</strong> large assemblies, construction <strong>of</strong> the next generation <strong>of</strong> bio-inspired solar-energy<br />
conversion systems will require self-assembly <strong>of</strong> the molecular components into a “smart<br />
matrix” that controls their key electronic properties. Understanding how the smart matrix<br />
exercises dynamic control over the energy landscape <strong>of</strong> the active components within it is critical<br />
to optimizing solar energy conversion efficiency. This control extends from the attosecond-long<br />
electronic dynamics associated with nascent photon absorption and charge separation to the<br />
minutes-and-longer control <strong>of</strong> atomic motions during the catalytic production <strong>of</strong> solar fuels.<br />
Achieving efficient solar-energy conversion systems using smart matrices will require<br />
(1) engineering proteins, polymers, membranes, gels, and other ordered materials to provide<br />
tailored active environments (i.e., smart matrices); (2) incorporating bio-inspired c<strong>of</strong>actors<br />
within the designed matrix; (3) integrating multiple c<strong>of</strong>actor-matrix assemblies to per<strong>for</strong>m the<br />
overall function; (4) characterizing the coupling between the c<strong>of</strong>actors and the matrix in natural<br />
and bio-inspired systems using advanced techniques; (5) integrating experimental measurements<br />
<strong>of</strong> structural and electronic dynamics with multi-scale theoretical approaches to achieve<br />
fundamental breakthroughs in system design paradigms <strong>for</strong> solar energy capture and conversion<br />
by supramolecular structures; and (6) mapping out and predicting optimized electronic and<br />
structural energy landscapes <strong>for</strong> efficient <strong>for</strong>mation <strong>of</strong> solar fuels.<br />
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