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Abstract The earth abundant and environmentally friendly element iron (Fe) forms various functional materials of metallic iron, iron oxides, iron carbides, natural iron ore, and iron-based metallic-organic frameworks. The Fe-based materials have been intensively studied as oxygen carriers, catalysts, adsorbents, and additives in bioenergy production. This review was to provide a fundamental understanding of the syntheses and characteristics of various Fe-based materials for further enhancing their functionalities and facilitating their applications in various bioenergy conversion processes. The syntheses, characteristics, and applications of various iron-based materials for bioenergy conversion published in peer-reviewed articles were first reviewed. The challenges and perspectives of the wide applications of those functional materials in bioenergy conversion were then discussed. The functionalities, stability, and reactivity of Fe-based materials depend on their structures and redox phases. Furthermore, the phase and composition of iron compounds change in a process. More research is needed to analyze the complex phase and composition changes during their applications, and study the type of iron precursors, synthesizing conditions, and the use of promoters and supports to improve their performance in bioenergy conversion. More studies are also needed to develop multifunctional Fe-based materials to be used for multi-duties in a biorefinery and develop green processes to biologically, economically, and sustainably produce those functional materials at a large scale.more » « less
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Abstract High surface area graphitic mesoporous carbons (M‐mGMC; M=Ni, Fe, Co or Ni‐Fe) were synthesizedviacatalytic graphitization using a hard template based synthesis method. In house prepared SBA‐15 silica material was impregnated with metal precursors to obtain M/SBA‐15, template for M‐mGMC synthesis. These materials were studied using different material characterization techniques, such as nitrogen adsorption desorption (BET), X‐ray diffraction (XRD) analysis, Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Specific surface area ranging from 1,227.9 m2g−1to 1,320.7 m2g−1was observed for four M‐mGMCs. Raman spectroscopy, XPS and wide angle XRD suggested presence of graphitic structure in these materials along with disorders. Electrocatalytic performance of these materials along with conventional carbon black (Vulcan XC‐72) were evaluated in a single‐stack proton exchange membrane fuel cell (PEMFC). Pt/NiFe‐mGMC exhibited enhanced electrocatalytic activity compared to Pt/Ni‐mGMC, Pt/Fe‐mGMC and Pt/Co‐mGMC electrocatalysts. However, Pt/NiFe‐mGMC lacked adequate proton transport in membrane electrode assembly (MEA) compared to Pt/Vulcan XC‐72. This exploratory study showed that NiFe‐mGMC may find application as electrocatalyst support material in PEMFC.more » « less
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We have developed a class of phosphido-boranes (BoPh’s) with formula X+[R2PBH3–] that bind CO2 with exceptional strength (ΔG = −8.2 to −24.0 kcal/mol) at ambient conditions. We use quantum mechanics (QM) to determine how the choice of electron-donating versus electron-withdrawing ligand impacts the CO2 binding strength, in the presence of a donating borane moiety. We also examine the role of the cation in CO2 binding, finding that the ion position relative to the bound CO2 dramatically alters binding strength. We find that the BoPh with two ethyl ligands Li[Et2PBH3] leads to ΔG = −24.0 kcal/mol upon CO2 binding while Li[Ph2PBH3] leads to ΔG = −12.8 kcal/mol. We synthesized the BoPh with two phenyl ligands Li[Ph2PBH3] to validate the QM-predicted stability and predicted pKa.more » « less
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With the ever-increasing demand for plastics, sustainable recycling methods are key necessities. The current plastics industry can manage to recycle only 10% of the 400 million metric tons of plastic produced globally. Waste plastics, in the current infrastructure, land up mostly in landfills. Although a lot of research efforts have been spent on processing and recycling co-mingled mixed plastics, energy-efficient sustainable and scalable routes for plastic upcycling are still lacking. Catalytic valorization of waste plastic feedstock is one of the potential scalable routes for plastic upcycling. Silica-alumina based materials, and zeolites have shown a lot of promise. A major interest lies in restricting catalyst deactivation, and refining product selectivity and yield for such catalytic processes. This article highlights ChemPren technology as a clean energy solution to waste plastic recycling. Co-mingled, mixed plastic feedstock along with spray dried, attrition resistant, ZSM-5 containing catalysts is preprocessed with an extruder to form optimally sized particles and fed into a fluidized bed reactor for short contact times to produce selectively and in high yields ethylenes, propylenes and butylenes. This techno-economic perspective indicates that the ChemPren technology can produce propylene at $0.16 per lb, whereas the current selling price of virgin propylene is $0.54 per lb. This technology can serve as a platform for mixed plastic upcycling, with more advancements necessary in the form of robust and resilient catalysts and reactor operation strategies for tuning product selectivity.more » « less
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Algae is a promising sustainable feedstock for the generation of bio-crude oil, which is a sustainable alternative to fossil fuels, through the thermochemical process of hydrothermal liquefaction (HTL). However, this process also generates carbon particles (algae-derived carbon, ADC) as a significant byproduct. Herein, we report a brand-new and value-added use of ADC particles as a reinforcing agent for epoxy matrix composites (EMCs). ADC particles were synthesized through HTL processing of Chlorella vulgaris (a green microalgae) and characterized for morphology, average size, specific surface area, porosity, and functional groups. The ADC particles were subsequently integrated into a representative epoxy resin (EPON 862) as a reinforcing filler at loading levels of 0.25%, 0.5%, 1%, and 2% by weight. The tensile, flexural, and Izod impact properties, as well as the thermal stability, of the resulting EMCs were evaluated. It is revealed that the ADC particles are a sustainable and effective reinforcing agent for EMCs at ultra-low loading. Specifically, the ADC-reinforced EMC with 1 wt.% ADC showed improvements of ~24%, ~30%, ~31%, and ~57% in tensile strength, Young’s modulus, elongation at break, and work of fracture (WOF), respectively, and improvements of ~10%, ~37%, ~24%, and ~39% in flexural strength, flexural modulus, flexural elongation at break, and flexural WOF, respectively, as well as an improvement of ~54% in Izod impact strength, compared to those corresponding properties of neat epoxy. In the meantime, the thermal decomposition temperatures at 60% and 80% weight loss of the abovementioned ADC-reinforced EMC increased from 410 °C to 415 °C and from 448 °C to 515 °C in comparison with those of neat epoxy. This study highlighted the potential of sustainable ADC particles as a reinforcing agent in the field of polymer matrix composite materials, which represented a novel and sustainable approach that would mitigate greenhouse gas remission and reduce reliance on nonrenewable reinforcing fillers in the polymer composite industry.more » « less
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Synthesis of amine incorporated hierarchical metal organic framework (MOF) MIL-101(Cr)/SBA-15, meso/ micro-porous composites, with tailored properties for CO 2 capture is reported. The synthesized composites were characterized in terms of their crystallinity, morphology, functional groups, and textural properties. Isothermal adsorption of CO 2 from concentrated sites as well as ambient conditions were evaluated by gravimetric and volumetric measurements. The optimized composite i.e., MIL-101(Cr)/SBA-15/PEI-25 showed improved pseudo- equilibrium adsorption capacity of 3.2 mmol/g at 303 K and 1 bar, compared to nascent SBA-15 (0.8 mmol/g) and the MOF, i.e., MIL-101(Cr) (1.3 mmol/g). Such adsorption performance can be attributed to the basic sites of the impregnated polyethyleneimine (PEI), unsaturated Cr(III) metal sites, and the hierarchical pore structure of the composite which imparts chemical as well physical adsorption forces towards CO 2 lower amine loading of 25 wt% in the composite resulted in facile CO 2 uptake. Interestingly, desorption at much lower temperature ofmore » « less
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We report a transformative epoxy system with a microalgae-derived bio-binder from hydrothermal liquefaction processing (HTL). The obtained bio-binder not only served as a curing agent for conventional epoxy resin (e.g., EPON 862), but also acted as a modifying agent to enhance the thermal and mechanical properties of the conventional epoxy resin. This game-changing epoxy/bio-binder system outperformed the conventional epoxy/hardener system in thermal stability and mechanical properties. Compared to the commercial EPON 862/EPIKURE W epoxy product, our epoxy/bio-binder system (35 wt.% bio-binder addition with respect to the epoxy) increased the temperature of 60% weight loss from 394 °C to 428 °C and the temperature of maximum decomposition rate from 382 °C to 413 °C, while the tensile, flexural, and impact performance of the cured epoxy improved in all cases by up to 64%. Our research could significantly impact the USD 38.2 billion global market of the epoxy-related industry by not only providing better thermal and mechanical performance of epoxy-based composite materials, but also simultaneously reducing the carbon footprint from the epoxy industry and relieving waste epoxy pollution.more » « less
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The effects of adding Mn and Na promoter metals to graphene oxide (GO)-supported iron-based catalysts for Ficher-Tropsch Synthesis (FTS) reactions to olefins at 20 bars were investigated in a 3D-printed stainless steel (SS) Microreactor. While promoter metals encourage reduction of iron oxide to iron to form iron carbide, the active metal catalysts in GO allow hydrogenation of CO. These catalysts were synthesized by layer deposition method and characterized by different techniques. The TEM images show the integration of graphene oxide into the catalysts. The XRD and XPS studies confirmed the crystal structure and oxidation states of the metals. The catalytic activity and product selectivity were studied in the temperature range of 200–350°Cwith a 2:1 M ratio of H2: CO. Higher CO conversion with greater selectivity for olefins was observed in the presence of the promoters. FeMnNa@GO showed better stability than both Fe@GO and FeMn@GO catalysts in time-on-stream studies.more » « less
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The earth abundant and environmentally friendly element iron (Fe) forms various functional materials of metallic iron, iron oxides, iron carbides, natural iron ore, and iron-based metallic-organic frameworks. The Fe-based materials have been intensively studied as oxygen carriers, catalysts, adsorbents, and additives in bioenergy production. This review was to provide a fundamental understanding of the syntheses and characteristics of various Fe-based materials for further enhancing their functionalities and facilitating their applications in various bioenergy conversion processes. The syntheses, characteristics, and applications of various iron-based materials for bioenergy conversion published in peer-reviewed articles were first reviewed. The challenges and perspectives of the wide applications of those functional materials in bioenergy conversion were then discussed. The functionalities, stability, and reactivity of Fe-based materials depend on their structures and redox phases. Furthermore, the phase and composition of iron compounds change in a process. More research is needed to analyze the complex phase and composition changes during their applications, and study the type of iron precursors, synthesizing conditions, and the use of promoters and supports to improve their performance in bioenergy conversion. More studies are also needed to develop multifunctional Fe-based materials to be used for multi-duties in a biorefinery and develop green processes to biologically, economically, and sustainably produce those functional materials at a large scale.more » « less
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