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At least 235 records · Page 13

Comparison of the Chemical Composition of Liquids from the Pyrolysis and Hydrothermal Liquefaction of Lignocellulosic Materials

Major differences in thermal stability and hydrotreatment behavior of HTL and pyrolysis oils have been reported in the literature. However, little is known about the variations in the chemical composition of these oils that could explain such differences. Two commercial wood pyrolysis oils (Pyrovac and BTG), and their water-soluble (WS) and water-insoluble fractions (WIS) were analyzed and compared with the aqueous (WS WD-57 ) and oily (WIS WS-57 ) fractions obtained from hydrothermal liquefaction (HTL) of Douglas-fir. The samples were characterized by GC/MS, Karl Fischer titration, carbonyl content, total acid number, elemental composition, calorific value, proximate analysis, Fourier Transform Infrared Spectroscopy (FTIR), Folin-Ciocalteu (FC), and UV fluorescence. All the fractions were also analyzed by Fourier Transform Ion Cyclotron Resonance Mass Spectroscopy (FT-ICR-MS) and by Electrospray Ionization (EI). The most prevalent class of compounds in the water insoluble phases were phenols derived from lignin. Water-soluble phases contain mostly the oxygenated compounds derived from cellulose and hemicellulose and were richer in carbonyl functional groups. The water content of the resulting aqueous phases were between: 65 (WS BTG ) and 96 (WS Pyrovac ) wt. %. The bio-oil from BTG has higher water content and lower HHV, compared to Pyrovac oil. The GC/MS results of BTG oil show the presence of a more prominent acetic acid peak and higher TAN number than the Pyrovac oil. The GC/MS of Pyrovac oil showed more obvious mono-phenol peaks. The quantification of this family by Folin-Ciocalteu method confirmed higher content of monophenolic compounds compared with the BTG oil. The lower thermal stability of pyrolysis oils compared with HTL biocrudes can be partially explained by the fact that pyrolysis oils (BTG and Pyrovac) contain carbohydrates while HTL biocrude (WIS WD-57 ) doesn’t. Thus, we decided to further investigate the chemical differences between the phenolic rich fractions insoluble in water and the holocellulose derived compounds soluble in water. Even after water extraction, the acid content of the water insoluble fraction from BTG (WISBTG) was higher than the acid content of the water insoluble fraction obtained by HTL (WISWSD-57). Likewise, the acid content of the aqueous phases derived from pyrolysis oils (WS Pyrovac , WS BTG ) was also higher than for the aqueous phase obtained by HTL (WSWSD-57). This result is in part due to the use of bases in the HTL process that neutralizes the acid formed in that process. Moreover, the starting feedstock may also influence the differences between the oils. Although, the UV-Fluorescence spectra, ICR-MS and the EI analyses showed some minor differences in the molecular weight and chemical make-up of the oligomers soluble and insoluble in water from pyrolysis and HTL; the differences observed were not large enough to justify the differences in behavior between these oils reported in the literature. Our results suggest that the differences observed between HTL biocrudes and pyrolysis oils are likely partially due to the presence of holocellulose derived products in the pyrolysis oils and higher acid contents.

09 BIOMASS FUELS↗

A small molecule antagonizes jasmonic acid perception and auxin responses in vascular and nonvascular plants

The phytohormone jasmonoyl-L-isoleucine (JA-Ile) regulates many stress responses and developmental processes in plants. A co-receptor complex formed by the F-box protein Coronatine Insensitive 1 (COI1) and a Jasmonate (JA) ZIM-domain (JAZ) repressor perceives the hormone. JA-Ile antagonists are invaluable tools for exploring the role of JA-Ile in specific tissues and developmental stages, and for identifying regulatory processes of the signaling pathway. Using two complementary chemical screens, we identified three compounds that exhibit a robust inhibitory effect on both the hormone-mediated COI–JAZ interaction and degradation of JAZ1 and JAZ9 in vivo. One molecule, J4, also restrains specific JA-induced physiological responses in different angiosperm plants, including JA-mediated gene expression, growth inhibition, chlorophyll degradation, and anthocyanin accumulation. Interaction experiments with purified proteins indicate that J4 directly interferes with the formation of the Arabidopsis (Arabidopsis thaliana) COI1–JAZ complex otherwise induced by JA. The antagonistic effect of J4 on COI1–JAZ also occurs in the liverwort Marchantia polymorpha, suggesting the mode of action is conserved in land plants. Besides JA signaling, J4 works as an antagonist of the closely related auxin signaling pathway, preventing Transport Inhibitor Response1/Aux–indole-3-acetic acid interaction and auxin responses in planta, including hormone-mediated degradation of an auxin repressor, gene expression, and gravitropic response. However, J4 does not affect other hormonal pathways. Altogether, our results show that this dual antagonist competes with JA-Ile and auxin, preventing the formation of phylogenetically related receptor complexes. J4 may be a useful tool to dissect both the JA-Ile and auxin pathways in particular tissues and developmental stages since it reversibly inhibits these pathways. One-sentence summary: A chemical screen identified a molecule that antagonizes jasmonate perception by directly interfering with receptor complex formation in phylogenetically distant vascular and nonvascular plants.

59 BASIC BIOLOGICAL SCIENCES↗

A Generic Sacrificial Layer for Wide-Range Freestanding Oxides with Modulated Magnetic Anisotropy

Freestanding oxide nanomembranes have promising applications because of their novel electronic states and flexible crystalline structures. Several materials have been developed as sacrificial layers to exfoliate thin films from substrates via wet-etching. However, these materials face great challenges in terms of either complicated crystalline structures or corrosive solutions. Herein, a new sacrificial material, SrCoO 2.5 , is presented, which can be coherently grown with wide-range strains and crystalline orientations and is also soluble in eco-friendly solutions such as acetic acid, vinegar, and even carbonated drinks. With SrCoO 2.5 as the sacrificial layer, high-quality freestanding ferromagnetic SrRuO 3 membranes are achieved from wide-range epitaxial strains and different crystalline orientations. By investigating the evolution of the magnetic properties of these samples, it is discovered that epitaxial strain causes a distinct modification of the magnetic anisotropy of (001) pc -oriented SrRuO 3 samples, while its influence on the (110) pc and (111) pc samples is insignificant. This study not only demonstrates the freestanding SrRuO 3 as a promising material for flexible spintronic devices, but also offers a great opportunity to engineer a wide range of strained and oriented complex oxides for novel freestanding electronics using this newly developed sacrificial material.

36 MATERIALS SCIENCE↗

Self‐Assembly of Helical Nanofibrous Chiral Covalent Organic Frameworks

Abstract Despite significant progress on the design and synthesis of covalent organic frameworks (COFs), precise control over microstructures of such materials remains challenging. Herein, two chiral COFs with well‐defined one‐handed double‐helical nanofibrous morphologies were constructed via an unprecedented template‐free method, capitalizing on the diastereoselective formation of aminal linkages. Detailed time‐dependent experiments reveal the spontaneous transformation of initial rod‐like aggregates into the double‐helical microstructures. We have further demonstrated that the helical chirality and circular dichroism signal can be facilely inversed by simply adjusting the amount of acetic acid during synthesis. Moreover, by transferring chirality to achiral fluorescent molecular adsorbents, the helical COF nanostructures can effectively induce circularly polarized luminescence with the highest luminescent asymmetric factor ( g lum ) up to ≈0.01.

Tang, Xihao↗

Designing Heteroatom-Codoped Iron Metal–Organic Framework for Promotional Photoreduction of Carbon Dioxide to Ethylene

Rational engineering active sites and vantage defects of catalysts are promising but grand challenging task to enhance photoreduction CO 2 to high value-added C2 products. In this study, we designed an N,S-codoped Fe-based MIL-88B catalyst with well-defined bipyramidal hexagonal prism morphology via a facile and effective process, which was synthesized by addition of appropriate 1,2-benzisothiazolin-3-one (BIT) and acetic acid to the reaction solution. Under simulated solar irradiation, the designed catalyst exhibits high C 2 H 4 evolution yield of 17.7 μmol g -1 ∙h, which has been rarely achieved in photocatalytic CO 2 reduction process. The synergistic effect of Fe-N coordinated sites and reasonable defects in the N,S-codoped photocatalyst can accelerate the migration of photogenerated carriers, resulting in high electron density, and this in turn helps to facilitate the formation and dimerization of C-C coupling intermediates for C 2 H 4 effectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self-Assembly of Helical Nanofibrous Chiral Covalent Organic Frameworks

Despite significant progress on the design and synthesis of covalent organic frameworks (COFs), precise control over microstructures of such materials remains challenging. Herein, two chiral COFs with well-defined one-handed double-helical nanofibrous morphologies were constructed via an unprecedented template-free method, capitalizing on the diastereoselective formation of aminal linkages. Detailed time-dependent experiments reveal the spontaneous transformation of initial rod-like aggregates into the double-helical microstructures. Impoirtantly, we have further demonstrated that the helical chirality and circular dichroism signal can be facilely inversed by simply adjusting the amount of acetic acid during synthesis. Moreover, by transferring chirality to achiral fluorescent molecular adsorbents, the helical COF nanostructures can effectively induce circularly polarized luminescence with the highest luminescent asymmetric factor (g lum ) up to ≈0.01.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of cellulose reducing ends and primary hydroxyl groups modifications on cellulose-cellulase interactions and cellulose hydrolysis

Cellulose reducing ends are believed to play a vital role in the cellulose recalcitrance to enzymatic conversion. However, their role in insoluble cellulose accessibility and hydrolysis is not clear. Thus, in this study, reducing ends of insoluble cellulose derived from various sources were modified by applying reducing and/or oxidizing agents. Here, the effects of cellulose reducing ends modification on cellulose reducing ends, cellulose structure, and cellulose accessibility to cellulase were evaluated along with the impact on cellulose hydrolysis with complete as well purified cellulase components. Sodium borohydride (NaBH 4 ) reduction and sodium chlorite-acetic acid (SC/AA) oxidation were able to modify more than 90% and 60% of the reducing ends, respectively, while the bicinchoninic acid (BCA) reagent applied for various cycles oxidized cellulose reducing ends to various extents. X-ray diffractograms of the treated solids showed that these treatments did not change the cellulose crystalline structure and the change in crystallinity index was insignificant. Surprisingly, it was found that the cellulose reducing ends modification, either through selective NaBH 4 reduction or BCA oxidation, had a negligible impact on cellulose accessibility as well on cellulose hydrolysis rates or final conversions with complete cellulase at loadings as low as 0.5 mg protein/g cellulose. In fact, in contrast to what is traditionally believed, modifications of cellulose reducing ends by these two methods had no apparent impact on cellulose conversion with purified cellulase components and their synergy. However, SC/AA oxidation resulted in significant drop in cellulose conversion (10%–50%) with complete as well purified cellulase components. Nonetheless, further research revealed that the cause for drop in cellulose conversion for the SC/AA oxidation case was due to primary hydroxyl groups (PHGs) oxidation and not the oxidation of reducing ends. Furthermore, it was found that the PHGs modification affects cellulose accessibility and slows the cellulase uptake as well resulting in significant drop in cellulose conversions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and Characterization of a Masked Terminal Nickel-Oxide Complex

In exploring terminal nickel-oxo complexes, postulated to be the active oxidant in natural and non-natural oxidation reactions, we report the synthesis of the pseudo-trigonal bipyramidal Ni II complexes (K)[Ni II (L Ph )(DMF)] (1[DMF]) and (NMe 4 ) 2 [Ni II (L Ph )(OAc)] (1[OAc]) (L Ph =2,2’,2’’-nitrilo-tris-(N-phenylacetamide); DMF=N,N-dimethylformamide; - OAc=acetate). Both complexes were characterized using NMR, FTIR, ESI-MS, and X-ray crystallography, showing the L Ph ligand to bind in a tetradentate fashion, together with an ancillary donor. The reaction of 1[OAc] with peroxyphenyl acetic acid (PPAA) resulted in the formation of [(L Ph )Ni III -O-H∙∙∙OAc] 2- , 2, that displays many of the characteristics of a terminal Ni=O species. 2 was characterized by UV-Vis, EPR, and XAS spectroscopies and ESI-MS. 2 decayed to yield a Ni II -phenolate complex 3 (through aromatic electrophilic substitution) that was characterized by NMR, FTIR, ESI-MS, and X-ray crystallography. 2 was capable of hydroxylation of hydrocarbons and epoxidation of olefins, as well as oxygen atom transfer oxidation of phosphines at exceptional rates. While the oxo-wall remains standing, this complex represents an excellent example of a masked metal-oxide that displays all of the properties expected of the ever elusive terminal M=O beyond the oxo-wall.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

UV + Damp Heat Induced Power Losses in Fielded Utility N-Type Si PV Modules

A recent trend in commercial PV modules is a transition to n-type silicon cells, including passivated emitter rear totally diffused (n-PERT), tunnel oxide passivated contact (TOPCon), and silicon heterojunction (SHJ). There is evidence via lab studies that some of these cells are more susceptible to UV induced degradation (UVID), yet there is a lack of confirmation that such degradation occurs in the field. Current IEC standards designed to screen for early module failures require only minimal UV exposure (15 kWh/m2 280-400 nm, ~2-3 months equivalent outdoor exposure). Here, we investigate fielded n-PERT silicon (Si) modules from a commercial utility that show power losses of ~2%/year. We present a comprehensive picture of the physics and chemistry of degradation supported by both module and cell electronic characterization (EL, PL, IV, EQE, and DLIT) and materials-level morphological and chemical analysis (SEM, EDS, XPS, FTIR, and HPLC). All sampled site modules show short circuit current (Isc) and open circuit voltage (Voc) losses when compared to unfielded spares, with the most severely degraded also having losses in fill factor (FF). We identify two different degradation modes contributing to overall power loss: (1) external quantum efficiency (EQE) measurements show losses in the blue range of the spectra, indicative of cell surface recombination losses, and (2) variations in high series resistance (Rs) at the cell level that are correlated with compositional differences in cell metallization. Using unfielded spares, we were able to reproduce Voc, Isc, and EQE losses via a minimum UV stress of 67.5 kWh/m2 (280-400 nm), 4.5x the exposure currently required in IEC 61215-2 (MQT 10). Degradation continued with additional UV dosage equivalent to the fielded modules (405 kWh/m2 total), with power loss leveling out at an average of 6.1%. Subsequent 1000 h of 85% RH/85degrees C damp heat testing showed that cells exposed to UV underwent additional severe series resistance degradation, even those without the susceptible paste composition seen in the field, whereas non-UV exposed cells saw little change. We attribute this to higher concentrations of acetic acid generated on the UV exposed area of the module, leading to degradation of the gridline/cell interface and high Rs. This study is unique in that it reproduces field observed utility scale UVID with an accelerated test and supports the need for standards development for longer UV exposure combined with other stress factors to catch materials interplay within a module package.

14 SOLAR ENERGY↗

The denatured state of HIV ‐1 protease under native conditions

Abstract The denatured state of several proteins has been shown to display transient structures that are relevant for folding, stability, and aggregation. To detect them by nuclear magnetic resonance (NMR) spectroscopy, the denatured state must be stabilized by chemical agents or changes in temperature. This makes the environment different from that experienced in biologically relevant processes. Using high‐resolution heteronuclear NMR spectroscopy, we have characterized several denatured states of a monomeric variant of HIV‐1 protease, which is natively structured in water, induced by different concentrations of urea, guanidinium chloride, and acetic acid. We have extrapolated the chemical shifts and the relaxation parameters to the denaturant‐free denatured state at native conditions, showing that they converge to the same values. Subsequently, we characterized the conformational properties of this biologically relevant denatured state under native conditions by advanced molecular dynamics simulations and validated the results by comparison to experimental data. We show that the denatured state of HIV‐1 protease under native conditions displays rich patterns of transient native and non‐native structures, which could be of relevance to its guidance through a complex folding process.

60 APPLIED LIFE SCIENCES↗

Establishing the accuracy of position–specific carbon isotope analysis of propane by GC–pyrolysis–GC–IRMS

Rationale: Position-specific (PS) δ 13 C values of propane have proven their ability to provide valuable information on the evolution history of natural gases. Two major approaches to measure PS δ 13 C values of propane are isotopic 13 C nuclear magnetic resonance (NMR) and gas chromatography-pyrolysis-gas chromatography-isotope ratio mass spectrometry (GC-Py-GC-IRMS). Measurement accuracy of the isotopic 13 C NMR has been verified, but the requirements of large sample size and long experimental time limit its applications. GC-Py-GC-IRMS is a more versatile method with a small sample size, but its accuracy has not been demonstrated. Methods: We measured the PS δ 13 C values of propane from nine natural gases using both 13 C NMR and GC-Py-GC-IRMS, then evaluated the accuracy of the GC-Py-GC-IRMS method. Results: The results show that large carbon isotope fractionations occurred for both terminal and central carbons within propane during pyrolysis. The isotope fractionations during the pyrolysis are reproducible at optimum conditions, but vary between the two GC-Py-GC-IRMS systems tested, affected by experimental conditions (e.g., pyrolysis temperature, flow rate, and reactor conditions). Conclusions: It is necessary to evaluate and calibrate each GC-Py-GC-IRMS system using propane gases with accurately determined PS δ 13 C values. Finally, this study also highlights a need for PS isotope standards for propane and other molecules (e.g., butane and acetic acid).

03 NATURAL GAS↗

Structure Development in Cross-Linked, Soybean Oil-based Waterborne Polyurethanes

Development of waterborne polyurethanes (WPU) using bio-based sources represents a step towards sustainable materials science and industry. We synthesized bio-based cationic water-dispersed crosslinked polyurethanes from high oleic soybean oil (HOSO) polyol, isophorone diisocyanate, and methyldiethanol amine, with varying ionic group contents after neutralization with acetic acid. Our primary objective was to analyze how crosslinking affects the dispersion process and film properties in multifunctional systems. The synthesis-structure-property relationship is elucidated through comprehensive analyses of the products at different stages of the synthesis. The dispersion of the WPU particles in water must occur prior to gelation during the final preparation, leading to incomplete conversion and the formation of imperfect networks. Insight into the synthesis process and polymer structure was gained by simulating polymer network parameters. Morphological analyses using synchrotron-based X-ray scattering and atomic force microscopy revealed a hierarchical structure within the WPU films. Importantly, all the films prepared in this study, without using coalescence agents, have low water absorption and high water contact angles, demonstrating their potential for textile and leather coatings and other applications.

bio-based polymers↗

Techno-economic and Life Cycle Analysis of MixAlco® Processes for Mixed Alcohol Production from Brown Algae

The need for producing renewable fuels from biomass has increased due to depleting fossil resources and environmental concerns. However, the low fraction of biomass carbon converted to product is an undeniable drawback for most current biofuel productions from fermentation due to undecomposed lignin in biomass composition and carbon loss as CO 2 . In this work, two main production routes of the MixAlco® process, the ketonization route (KR) and esterification route (ER) are evaluated for the mixed alcohol production by brown algae, a third-generation biomass without lignin. A novel fermentation process using syntrophic bacteria consortia (SBC) is developed to produce acetic acid from waste gas produced by KR and ER process. The paper investigates the integrated flowsheet for these alternative routes, using techno-economic and life cycle analysis to compare the minimum selling price and environmental impacts. From TEA, we find that the overall costs for KR and ER are lower than the SBC processes. The cost of ketonization routes is lower than esterification routes. The capital cost and operating cost for the ER+SBC process are the highest. Raw materials and utilities are the two major costs for all the processing routes examined. Here, the MSP for the ER+SBC process is the lowest out of all four routes. ER process performs the best in terms of environmental impacts except in water depletion compared with other processes, while the KR process performs the worst regarding the environmental metrics.

59 BASIC BIOLOGICAL SCIENCES↗

Balancing sugar recovery and inhibitor generation during energycane processing: Coupling cryogenic grinding with hydrothermal pretreatment at low temperatures

Pretreatment of lignocellulosic biomass at high temperatures or with oxidizing chemicals generate various inhibitors that restrict the efficient bioconversion of sugars in subsequent steps. The present study systematically investigates individual and combinatorial effects of pretreatment parameters on the generation of inhibitors. Herein, a plot between pretreatment temperature and inhibitor revealed optimum pretreatment temperature for energycane bagasse i.e., 170 °C beyond which total inhibitor production increased exponentially. No inhibitor production was observed on mechanical processing i.e., disk milling/cryogenic grinding of biomass. Evaluation of response surface regression exhibited that biomass solids loading has a significant effect on inhibitor generation at higher temperatures. The concentrations of certain inhibitors such as acetic acid, furfurals, and HMF increased more than 3-folds on doubling the solids loading. Furthermore, a novel low-severity approach of low-temperature hydrothermal pretreatment coupled with cryogenic grinding for lignocellulosic biomasses has been introduced which improved sugar yields while maintaining a low inhibitor concentration.

09 BIOMASS FUELS↗

Chemical insights into the multi-regime low-temperature oxidation of di-n-propyl ether: Jet-stirred reactor experiments and kinetic modeling

To further understand the combustion characteristics and the reaction pathways of acyclic ethers, in this work the oxidation of di-n-propyl ether (DPE) was investigated in a jet-stirred reactor (JSR) combined with a photoionization molecular-beam mass spectrometer. The experiments were carried out at near-atmospheric pressure (700 Torr) and over a temperature range of 425–850 K. Based on the experimental data and previous studies on ether oxidation, a new kinetic model was constructed and used to interpret the oxidation chemistry of DPE. In DPE oxidation, a high reactivity at low temperatures and two negative temperature coefficient (NTC) zones were observed. These behaviors are explained in this work by taking advantage of the obtained species information and the modeling analyses: the two NTC zones are caused by the competition of chain branching and termination reactions of the fuel itself and specific oxidation intermediates, respectively. Furthermore, the general requirements to have double-NTC behavior are discussed. A variety of crucial fuel-specific C 6 species, such as ketohydroperoxides and diones, were detected in the species pool of DPE oxidation. Their formation pathways are illuminated based on rate-of-production (ROP) analyses. Propanal was identified as the most abundant small molecule intermediate, and its related reactions have an important impact on the oxidation process of DPE. Both acetic acid and propionic acid were detected in high concentrations. A new formation pathway of propionic acid is proposed and incorporated into the kinetic model to achieve a more accurate prediction for propionic acid mole fractions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A wide range experimental study and further development of a kinetic model describing propane oxidation

This work presents an experimental and kinetic modeling study of propane oxidation. Ignition delay times of propane were measured in a high-pressure shock tube and in rapid compression machines in the temperature range 689 - 1700 K at equivalence ratios of 0.5, 1.0 and 2.0 in 'air', for a wide range of pressures from 20 to 90 bar. CO and H 2 O mole fraction profiles for propane oxidation were measured in a shock tube behind reflected shock waves in the temperature range 1370-1840 K at equivalence ratios of 0.5, 1.0 and 2.0 and at a pressure of approximately 1.3 atm. Moreover, propane oxidation was studied using a jet-stirred reactor coupled to a synchrotron vacuum ultraviolet photoionization mass spectrometer at low temperatures in the range 565 - 690 K and at a pressure of 1 atm. Further, this wide range of experimental datasets for propane oxidation was used to reoptimize and update our previous kinetic mechanisms, AramcoMech3.0 and NUIGMech1.1. In the current mechanism, NUIGMech1.3, the thermo-chemical parameters of all species relevant to low-temperature propane oxidation chemistry, including propyl-peroxyl, hydroperoxyl-propyl, hydroperoxyl-propyl-peroxyl, and carbonyl-hydroperoxide radicals, are updated based on newly calculated values at the CCSD(T)-F12/TZ-F12//B2PLYPD3/TZ///B2PLYP-D3/TZ level of theory. The improvements made in the thermochemical values and in the kinetic parameters for the low-temperature propane oxidation reactions in NUIGMech1.3 result in better model agreement with the new IDTs and speciation data, including carbon monoxide, formaldehyde, propene, acetaldehyde and various minor products such as ethylene, acetic acid, acrolein as well as various hydroperoxide and cyclic ether species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microalgal and bacterial auxin biosynthesis: implications for algal biotechnology

Optimization of microalgal growth and high-value metabolite production are key steps in microalgal mass culture for the algae industry. An emerging technology is the use of phytohormones, like indole-3-acetic acid (IAA), to promote microalgal growth. This requires an understanding of the biosynthesis of IAA in microalgae-bacteria associations and its function in regulating algal physiology and metabolite production. We review the current advances in understanding of microalgal and bacterial auxin biosynthesis and their implications for algal biotechnology.

09 BIOMASS FUELS↗

Green hydrogen from microalgal liquefaction byproducts with ammonia recovery and effluent recycle for developing circular processes

Hydrothermal liquefaction is a promising technology for microalgae-based biofuel production. However, hydrothermal liquefaction’s aqueous wastes have little established reuse, and contain significant fractions of toxic ammoniacal nitrogen. Careful reuse of this waste can assure microalgae-based biofuels are produced with less environmental impact and larger energy efficiency. Microbial electrolysis cells were investigated to valorize this waste product by converting the leftover organics into hydrogen and remove ammonia. Waste hydrothermal liquefaction aqueous phase from two microalgal strains, Tetraselmis sp. and Chlorella sp. were used as feedstocks for hydrogen production in microbial electrolysis cells. Chlorella and Tetraselmis aqueous phase-fed microbial electrolysis cells reach an average current density of 5.1 ± 0.19 A/m 2 and 3.8 ± 0.08 A/m 2 . Compound removal rates and mass removal percentages were also investigated for each feedstock. Additionally, acetic acid, propionic acid, ethanol, and glycerol were effectively removed from the aqueous byproduct. Further, microbial electrolysis cells separated up to 34.3% of ammoniacal nitrogen present in the aqueous phase. Charge transfer analysis indicated that proton transfer, not ammonium transfer, contributed to the majority of the hydrogen production in the cathode. Finally, the microbial electrolysis cell effluent was reused to grow the same microalgal strains, leading to the development of a circular biofuel production system. Microalgae regrowth studies using microbial electrolysis cell effluent showed nearly complete removal of total organic carbon, but significantly less removal of total nitrogen. Tetraselmis sp. growth occurred with the Tetraselmis-derived MEC effluent, however, the control medium without effluent produced the most growth. These findings support the possibility of a circular biofuel framework using MECs, but additional constraints, including the removal of inorganic contaminants, are necessary to realize the circular processes.

09 BIOMASS FUELS↗