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Figure 7.3: Nitrogenase metal active site (left), function-based engineering design (center, reproduced with permission from [11]), and a low complexity engineering model of an N2-reducing catalyst (right). The low complexity catalyst illustrates the interplay of three compartments, each representing a DP: a channel for proton transfer, a conductor for electron transfer, and a molecular catalytic site with a distance between active sites, d. Every compartment serves only one DP and FR to (a) maintain independence of the functional requirements and (b) minimize the information content of the design, which are the two engineering axioms for establishing robustness [11]. Optimization of proton and electron transfer rate process variables involves chemical engineering at the interfaces with the molecular catalytic site, and the distance, d, between the two Fe atoms that bind N2 is thought to be an important parameter for tuning the N2 reduction rate process variable of the active site. this systems engineering framework will extend from the scale of molecules and atoms to that of devices and their applications (ideally at high TRL levels, e.g. 6-9), it will address cross-scale sys- tems engineering challenges, identify control points, and predict system-wide effects of individual molecular components. This should extend even to the level of public willingness to act, which is the ultimate FR for success. Challenging chemical conversions will require systems engineering of chiral responsive matri- ces that go beyond the adiabatic and nonadiabatic state of the art in catalysis (e.g. Marcus theory and transition state theory) and reproduce the enhanced substrate reactivity in proteins. This may be achieved by tuning matrix dynamics for semiclassical, coherent conversion of reactants into prod- ucts with high forward reaction rates and low back reaction rates and recombination losses [1]. A comprehensive systems engineering framework will also enable the rational design of semisynthetic systems, i.e. with components obtained from a biological source with subsequent modification, and hybrid systems, which combine biological modules and artificial components (Figure 7.4). These approaches for engineering artificial components and existing natural systems with artificial motifs provide a route to enhanced energy conversion performance and optimized catalysis. To this end, optimization of the attachment of enzymes to surfaces will be necessary for direct electrochemical or photocatalytic conversions. Enzyme-based reaction cascades, or “assembly lines,” can be utilized for increased product selectivity. 73PDF Image | sustainable production of fuels and chemicals
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