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ABSTRACT In this article, bioplastic polyethylene furanoate (PEF) is synthesized using polycondensation of 2,5‐furandicarboxylic acid and ethylene glycol at a temperature of 220°C using a solid nanowire based super‐acid catalyst. The super acid catalyst is made by phosphating titania nanowires. Specifically, the reactions resulted in over 90% FDCA conversion and 85% PEF yield in a short period of 3 h using superacid catalysts at a loading of < 1% by wt. The mechanical properties of PEF, including glass transition temperature (84°C), melting point (210°C), and crystallinity (1.48 g/cm ³ ), demonstrate the high quality of the PEF produced. Barocaloric properties of resulting PEF polymers are also studied which show promise.

Carbon dioxide (CO2) utilization offers an economical solution to the global challenge of reducing greenhouse gas emissions and in creating a new circular economy for recycling CO2. CO2 to methanol conversion offers a promising route to reduce emissions, but its use as a feedstock remains a challenge. Advanced Energy Materials, LLC (ADEM) developed and demonstrated a plasma catalytic technology (PlasCatTM) for economical and energy efficient conversion of CO2 to CO, syngas and methanol. Phase I studies have shown the techno-economic feasibility of the PlasCat™ technology to convert CO2 in two major pathways: First, a plasma catalysis scheme is demonstrated for CO2 to CO conversion using hydrogen. Second, a plasma catalytic process exhibited synergistic effect with efficient conversion of tri-reforming reaction involving CO2, H2O and CH4 to produce syngas at a desired H2/CO ratio ~2.2. ADEM also demonstrated a bimetallic catalyst for syngas to methanol at low pressures of 20 bar with much higher conversion than the state of art, commercial catalyst. Plasma catalytic studies involving CO2 with higher amounts of hydrogen exhibited 3% methanol yield and overall CO2 conversion around 60% at atmospheric pressure. In Phase II, ADEM optimized and scaled up the processes using a unique Plasma flame integrated with a fluidized bed catalytic reactor. The results showed several aspects: (i) CO production can be made efficiently and economically using either hydrogen or methane as co-reactants using a microwave plasma catalytic reactor involving a packed bed with a specially design nanowire based catalysts; (ii) Demonstrated tri-reforming of CO2, H2O, CH4 and O2 in a plasma catalytic reactor to produce syngas along with methanol and developed a catalyst for highly efficient conversion of syngas to methanol at moderate pressures (20 bar) under thermo-catalytic process; (iii) developed and demonstrated a plasma-catalytic reactor and nanowire catalysts involving fluidized bed and achieved a yield of 8.4% for methanol when using CO2 and hydrogen and achieved a yield of over 13% when using recycled stream containing CO and CO2. The condensation of resulting methanol showed composition >87% in water. The above results are all obtained with a throughput of 18 lpm/kW. Commercial Applications and Other Benefits: PlasCat™ technology allows economical routes for conversion of CO2 to value-added fuels/chemicals such as methanol and CO near atmospheric pressures. Also, the technology can be implemented at mini GTL scale by directly using CO2 rich exhausts from certain industry segments. CO production on demand and on-site can be beneficial to customers as the supply, transportation and storage can be uncertain and costly due to toxicity. Life cycle analysis suggests that the PlasCatTM technology can result in significant reduction in GHG emissions (<300 Kg-CO2/Kg-Methanol versus >2.2 tons of CO2/Kg-Methanol with current production).