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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 703 records · Page 39
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Corrosivity Screening of Pyrolysis Bio-Oils by Short-Term Alloy Exposures. Laboratory Analytical Procedure (LAP), Issue Date: May 12, 2022

Bio-oils contain organic acids and oxygenated compounds that can lead to corrosion issues during bio-oil processing and storage. This Laboratory Analytical Procedure (LAP) allows for rapid screening of a bio-oil's corrosivity without the need for complex equipment and long-term exposures. A robust and repeatable method for assessing the corrosivity of bio-oils is necessary in order to remove materials degradation as an obstacle to research, upgrading, use and storage of bio-oils. This LAP involves the incubation of a representative alloy, 410 stainless steel (410 SS), specimen in bio-oil over a period of 48 hours at 50 degrees C in a sealed container. The corrosive species in the bio-oil react with and deplete alloy elements such as iron (Fe) and/or chromium (Cr) from the specimen into the bio-oil solution. The depletion of Fe and Cr from the specimen results in a significant mass loss that can be recorded. The mass loss is directly correlated to the corrosivity of a bio-oil. Examples of bio-oils in scope include the ones produced by fast pyrolysis and catalytic fast pyrolysis, as well as liquids produced from hydrothermal liquefaction.

09 BIOMASS FUELS↗
DOE OSTI2020

Single-Facet Dominant Anatase TiO 2 (101) and (001) Model Catalysts to Elucidate the Active Sites for Alkanol Dehydration

Alkanol dehydration on Lewis acid-base pairs of transition metal oxide catalysts is a reaction of importance in oxygen removal from biomass-derived feedstocks and their conversion to chemicals in general. However, catalysts with a high degree of structural heterogeneity, such as commercial TiO 2 powders, are not well-suited to establish rigorous structure-function relationships at an atomic level. Here, we provide compelling evidence for the effects of surface orientation of TiO 2 catalyst on elimination reactions of alcohols. Two anatase titania model catalysts, with preferential exposure of (101) and (001) facets, were synthesized and studied for 2-propanol dehydration using kinetic, isotopic, microscopic, and spectroscopic measurements, coupled with DFT calculations. Surface Lewis acid sites were found to be active for 2-propanol dehydration and (101) facets are more reactive than (001) facets under the reaction conditions studied. On both anatase surfaces, 2-propanol was found to dehydrate via concerted E2 elimination pathways, but with different initial states and thus also different intrinsic activation barriers. Molecular 2-propanol dehydration dominates on TiO2 (101) while on TiO 2 (001), 2-propanol simultaneously converts to more stable 2-propoxide before dehydration, which then requires higher activation energies for E2 elimination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Controlled electrochemical nutrient delivery to enhance marine primary productivity

Oceanic photosynthesis contributes to approximately half of the Earth’s net annual primary productivity. Marine photosynthetic productivity has a high degree of heterogeneity due to spatial and temporal co-limitations of light, temperature, and/or nutrients. Across coastal, near-shore, and open ocean regions, insufficient concentrations of key nutrients (e.g., N, P, Fe) can limit primary productivity. Although studies have shown a significant increase in primary productivity with the addition of low doses of trace nutrients, a sustainable approach to reliably deliver and maintain low doses of nutrients and ensure their bioavailability, remains a challenge. Chemical nutrient addition has relied on the use of chelating agents to ensure nutrient bioavailability, but synthetic chelators are persistent environmental pollutants. In this study, we demonstrate for the first time the use of a controlled electrochemical nutrient delivery (CEND) approach to accelerate the growth of phytoplankton without the need for such chelators. Our study uses commercial stainless-steel electrodes to deliver low concentrations of iron to enhance growth rates in the microalga Picochlorum celeri TG2. To demonstrate the process control offered by the CEND method, we evaluate iron delivery as a function of pulse time, pulse frequency, and rest time between pulses. Our data show that at the same total Fe dose of 163 ppb, electrochemical iron delivery can achieve 9.54 ± 0.58 mg biomass/µg Fe, which is comparable to 9.14 ± 0.17 mg biomass/µg Fe achieved with chemical iron additions that include the synthetic chelating agent ethylenediaminetetraacetic acid (EDTA). Further, when different total iron doses (163 ppb, 325 ppb, and 650 ppb) were delivered over 72 h using CEND, biomass yield per iron dose was higher at lower doses: 9.54 ± 0.58 mg biomass/µg Fe at 163 ppb vs. 4.32 ± 0.32 mg biomass/µg Fe at 650 ppb. This highlights the benefits of CEND in delivering frequent and low doses of nutrients for improved process efficiency. Preliminary assessments show both lower cost and reduced greenhouse gas emissions from electrochemical over chemical iron additions with EDTA. The CEND approach opens new pathways to enhance marine primary productivity, without the unintended environmental impacts of synthetic chelators.

analytical chemistry↗
DOE OSTI2022

Ecosystems and Networks Integrated with Genes and Molecular Assemblies (ENIGMA). Final report

The goal of the Stahl lab is to use a combination of isotopic, genomic, and activity-based analyses in the field, of selected field isolates, and defined synthetic communities to identify sources and sinks of different nitrogen species in the field, focusing on the FRC at the ORNL. The most general research objective is to characterize variants in the pathway for denitrification among field isolates and synthetic microbial assemblies as a foundation for predicting the biotic and abiotic controls of nitrogen and carbon transformations in the field. Specifically, we have focused on characterizing environmental controls of nitrous oxide emissions, an important greenhouse gas and ozone depleting molecule. Studies have mapped the flux of nitrous oxide and controlling genetic elements within the FRC subsurface, indicating the importance of different enzyme variants in nitrous oxide production and consumption in controlling surface emissions. We have developed methods to quantify and catalog the isotopic signatures imparted on nitrous oxide by different nitrous oxide reductase variants in isolated organisms and model synthetic communities. We have developed methods to quantify and catalog the nitrous oxide affinity of field relevant isolates and their biomass yield when respiring nitrous oxide on different carbon substrates. We continue to expand the collection of field-relevant microbial isolates within ENIGMA by focused enrichment and isolation from field material. These objectives have been facilitated by the development of new technologies, including: 1) the development of a multiplexed automated optical density measurement system for quantifying growth kinetics of microorganisms dependent on gaseous substrates in monoculture or gas exchange in synthetic communities and 2) the development of a microcalorimetric analysis format to quantify the impact of environmental stress on microbial maintenance energy. Since field relevant processes are mediated by assemblies of organisms interacting with each other and their local environment, we have also collaborated with other ENIGMA investigators on the assembly and characterization of synthetic communities. These studies have evaluated the role of organisms lacking a complete pathway for denitrification in the control of field processes, measuring process rates of assemblies of organisms that individually lack the full denitrification pathway but mediate the complete denitrification when growing together. These efforts have so far resulted in the publication of 18 peer reviewed papers ranging from ecological and physiological drivers of pathway optimization to field-scale process characterization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Opportunistic experiments to constrain aerosol effective radiative forcing

Aerosol–cloud interactions (ACIs) are considered to be the most uncertain driver of present-day radiative forcing due to human activities. The nonlinearity of cloud-state changes to aerosol perturbations make it challenging to attribute causality in observed relationships of aerosol radiative forcing. Using correlations to infer causality can be challenging when meteorological variability also drives both aerosol and cloud changes independently. Natural and anthropogenic aerosol perturbations from well-defined sources provide “opportunistic experiments” (also known as natural experiments) to investigate ACI in cases where causality may be more confidently inferred. These perturbations cover a wide range of locations and spatiotemporal scales, including point sources such as volcanic eruptions or industrial sources, plumes from biomass burning or forest fires, and tracks from individual ships or shipping corridors. We review the different experimental conditions and conduct a synthesis of the available satellite datasets and field campaigns to place these opportunistic experiments on a common footing, facilitating new insights and a clearer understanding of key uncertainties in aerosol radiative forcing. Cloud albedo perturbations are strongly sensitive to background meteorological conditions. Strong liquid water path increases due to aerosol perturbations are largely ruled out by averaging across experiments. Opportunistic experiments have significantly improved process-level understanding of ACI, but it remains unclear how reliably the relationships found can be scaled to the global level, thus demonstrating a need for deeper investigation in order to improve assessments of aerosol radiative forcing and climate change.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Catalytic strategy for conversion of fructose to organic dyes, polymers, and liquid fuels

We illustrate a process to produce a versatile platform chemical from biomass-derived fructose for organic dye, polymer, and liquid fuel industries. An aldol-condensed chemical (HAH) is synthesized as a platform chemical from fructose by catalytic reactions in acetone/water solvent with non-noble metal catalysts (e.g., HCl, NaOH). Then, selective reactions (e.g., etherification, reduction, dimerization) of the functional groups, such as enone and hydroxyl groups, in the HAH molecule enable applications in organic dyes and polyether precursors. High yields of target products, such as 5-(hydroxymethyl) furfural (HMF) (85.9% from fructose) and HAH (86.3% from HMF) are achieved by sequential dehydration and aldol-condensation with a simple purification process (>99% HAH purity). The use of non-noble metal catalysts, the high yield of each reaction, and the simple purification of the target product allow for beneficial economics of the process. Techno-economic analysis indicates that the process produces HAH at minimum selling price (MSP) of $1958 per ton. The MSP of HAH product allows the economic viability of applications in organic dye and polyether markets by replacing its counterparts, such as anthraquinone ($3200-$3900 per ton) and bisphenol-A ($1360-$1720 per ton).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Structural characterization of sugarcane lignins extracted from different protic ionic liquid pretreatments

Previous studies based on protic ionic liquids have shown them to be effective for extracting lignins from biomass. Moreover, ILs synthesized with amine cations can promote the insertion of nitrogen into lignin, favoring its valorization for industrial applications. Here, lignins extracted from sugarcane bagasse by eight different PILs were analyzed. Several techniques of characterization were employed (2D HSQC NMR, 31P NMR, GPC, Py-GC/MS, TGA, FTIR, and elemental analysis), seeking a deeper understanding of lignin structure post-PILS treatment. In particular, lignin obtained with acetate and lactate anions with monoethanolamonium cations showed similar structural compositions. Lignins obtained from ethylenediamonium cation combined anions acetate and lactate exhibited relatively higher molecular weights compared to the other lignins studied. The elemental analysis of these lignins further revealed the presence of nitrogen in their structures, suggesting that amination occurred. In this work we used PILs not yet reported in the literature for this purpose, and consequently obtained lignins with specific structures. Overall, our results demonstrated that depending on the PILs used, lignins with distinct properties could be obtained which might be used for value-added applications. This work covered new advances in elucidation of lignin chemical structure and opened a new path for lignin valorization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Scale-Up Studies for the Dehydration of C 4+ Alcohols into Drop-In Diesel Fuel

Herein, we demonstrate the production of liter quantities of drop-in diesel-range ethers from biomass-derived alcohols. We report scale-up resultsfor the dehydration of a mixture of C 4+ alcohols using powder and pellet zeolite Ycatalyst in continuous flow and batch reactors. The activity of zeolite Y decreaseswith the introduction of an alumina binder. Large alcohols, as well as branchedand secondary alcohols, increase the coke content over the pellet Y catalyst. Thepellet formulation had lower carbon balances and selectivity to C 10+ ethers,suggesting that the pellet formulation increases alcohol absorption and cokeproduction. Crushing the pellet Y catalyst to smaller particle sizes does notrecover the activity of zeolite Y in its powder form. Cold flow experiments showthat particle agglomeration contributes to pressure buildup in the continuous flowreactor. C 10+ ether blends can be produced in batch reactors at high alcohol conversion regimes. One liter of a diesel #2 blend wasproduced by scaling up this reaction. The final blend consists of a substantial portion of C 10+ ethers (63.7 wt %), followed by heavyunknown products (27.4 wt %). Furthermore, the final alcohol and butyl ether concentration values were 7.3 and 1.5 wt %, respectively. Theblendstock reported in this paper can satisfy diesel #2 ASTM standards for density, cloud point, flashpoint, and cetane number.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Cellulose nanofibrils-based packaging films synergistically reinforced by lignin and tea polyphenols for strawberry preservation

Developing biomass-based food packaging materials could alleviate resource scarcity and environmental pollution. Here, this study successfully fabricated cellulose nanofibrils-based packaging films synergistically reinforced by lignin and tea polyphenols for fruit preservation. Thanks to the abundant carboxyl and hydroxyl groups in modified lignin and tea polyphenol, the composite film delivered the highest tensile strength and Young’s modulus of 230.7 MPa and 11.9 GPa, respectively. The water vapor permeability (WVP) and oxygen permeability (OP) of composite film were as low as 2.53 × 10 –11 gm –1 s –1 Pa –1 and 1.69 × 10 –16 cm m –2 s–1 Pa –1 , respectively, demonstrating excellent barrier performance. Furthermore, the composite film possessed remarkable antibacterial (100 % antibacterial activity against two types of bacteria), antioxidant (DPPH free radical scavenging activity of 90 %), and UV shielding properties (impressive UV shielding rate of 99.0 %). Strawberry preservation experiments showed that these composite films could significantly extend shelf life, owing to the excellent barrier and antimicrobial properties. Our research indicated that these composite films could be promising food packaging material compared with traditional plastic and showed great application potential in fruit preservation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Flexible polyurethanes, renewable fuels, and flavorings from a microalgae oil waste stream

Renewable polymers have become an important focus in next-generation materials, and algae biomass offers an environmentally low-impact feedstock that can serve multiple uses. This study aims to develop a scalable methodology for production of microalgae-based polyols for polyurethane synthesis from waste oils derived from algae biomass. Following separation of omega-3 fatty acids from algae oil, residual oils can offer valuable building blocks for petrochemical replacements. However, unlike vegetable oils, algae oils contain organic contaminants, including photosynthetic pigments and hydrophobic cofactors that can complicate preparative methodologies. Here we convert and purify waste streams from omega-3 depleted Nannochloropsis salina algae oil, with major components consisting of palmitic and palmitoleic acid, into azelaic acid (AA) as a building block for flexible polyurethanes, with a simultaneous production of heptanoic acid (HA) as a flavor and fragrance precursor. Conversion of free fatty acid mixtures into a soft soap allows extraction of organic contaminants, and urea complexation provides isolated palmitoleic acid, which is subsequently ozonolyzed to produce AA and HA. Bio-based polyester diols are prepared from AA via esterification to provide a polyol monomer for flexible polyurethane foam preparation. The HA co-product is modified to produce the flavoring agent methyl heptanoate and also decarboxylated to produce hexane as a renewable solvent. This scalable process can be performed on oils from multiple algal species, offering valuable monomers from a highly sustainable source.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Effect of Solvent on the Interaction of Lignin with a Zeolite Nanosheet in the Condensed Phase

Lignin is the essential building block of lignocellulosic biomass, an excellent renewable source of different aromatic monomers for the polymer and biofuel industry. The depolymerization of lignin into value-added chemicals and fuels through the catalytic process poses a significant challenge due to the complex structure of lignin. Understanding lignin’s conformational diversity and dynamics in the liquid phase is crucial to designing an effective depolymerization process. Here, we conducted all-atom molecular dynamics simulations to understand the conformation and dynamics of softwood lignin on the all-silica zeolite nanosheet based on the MFI topology in a binary mixture of water–methanol at three different molar compositions (0%, 50%, and 100% methanol). We observed that the methanol–surface interaction is stronger than the water–surface interaction, and methanol readily diffused into the MFI core. Lignin surface contacts decrease with increasing methanol composition due to higher solubility and dynamics. Lignin dynamics on the surface in neat water is an order of magnitude smaller than methanol. Here, we also found that lignin adopts a slightly extended conformation when it stays on the surface than in the bulk solution phase for the pure water case, whereas for pure methanol and the binary solution structures are statistically similar.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

A hybrid chemical-biological approach can upcycle mixed plastic waste with reduced cost and carbon footprint

Derived from renewable feedstocks, such as biomass, polylactic acid (PLA) is considered a more environmentally friendly plastic than conventional petroleum-based polyethylene terephthalate (PET). However, PLA must still be recycled, and its growing popularity and mixture with PET plastics at the disposal stage poses a cross-contamination threat in existing recycling facilities and results in low-value and low-quality recycled products. Hybrid upcycling has been proposed as a promising sustainable solution for mixed plastic waste, but its techno-economic and life cycle environmental performance remain understudied. We propose a hybrid upcycling approach using a biocompatible ionic liquid (IL) to first chemically depolymerize plastics and then convert the depolymerized stream via biological upgrading with no extra separation. Here we show that over 95% of mixed PET/PLA was depolymerized into the respective monomers, which then served as the sole carbon source for the growth of Pseudomonas putida, enabling the conversion of the depolymerized plastics into biodegradable polyhydroxyalkanoates (PHAs). In comparison to conventional commercial PHAs, the estimated optimal production cost and carbon footprint are reduced by 62% and 29%, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Pyrolysis temperature and soil depth interactions determine PyC turnover and induced soil organic carbon priming

Pyrogenic organic carbon (PyC) is a complex, heterogeneous class of thermally altered organic substrates, but its dynamics and how its behavior changes with soil depth remain poorly understood. We conducted a laboratory incubation study to investigate the interactive effects of pyrolysis temperature and soil depth on the turnover of PyC compared to its precursor wood and native SOC (NSOC). We incubated dual-labeled (13C and 15N) jack pine pyrogenic organic matter produced at 300 °C (PyC300), 450 °C (PyC450), and their precursor pine wood in a fine-loamy, mixed-conifer forest soil for 745 days. A mixture of surface (0–10 cm) and subsurface (50–70 cm) forest soils, with and without labeled biomass were incubated in the dark at 55% soil water field capacity and 25 °C. Total 13C from PyC and wood mineralized as 13C-CO2 (as % of C added to soil) declined with an increase in pyrolysis temperature as follows: 54 ± 7.7% for wood, 3.1 ± 0.2% for PyC300, and 0.94 ± 0.08% for PyC450. Furthermore, after 2 years, soil depth interacted with pyrolysis temperature to affect C turnover, with total wood C losses significantly declining from 70.6% in surface soils to 37.5% in subsurface soil, while total losses of PyC300 and PyC450 were unaffected by differences between surface and subsurface soils. Wood induced negative priming (i.e., decreased mineralization rates) in surface soil at days 3 and 60, while PyC300 induced positive priming (i.e., increased mineralization rates) in subsurface soil at day 60. After 2 years, unlabeled NSOC losses increased from 9.2 ± 0.8% of NSOC in unamended treatments to 16.5 ± = 2.6% of NSOC with PyC450 additions. Our results suggest that PyC pyrolyzed at a given temperature can mineralize at similar rates between soil depths, and high amounts of PyC450 in subsurface soils can stimulate NSOC losses. These findings indicate that soil depth imposes critical controls on PyC dynamics belowground.

13C-labeling↗
DOE OSTI2020

A carbon molecular sieve membrane-based reactive separation process for pre-combustion CO 2 capture

In this study, we discuss a hybrid system combining a membrane reactor (MR) and an adsorptive reactor (AR), with the MR's reject stream serving as the AR's feed. We apply this system for the water gas shift (WGS) reaction for H 2 generation and simultaneous CO 2 capture in the context of the Integrated Gas Combined Cycle (IGCC) process for power generation from coal and biomass. This MR-AR system attains a high conversion exceeding equilibrium, produces a pure H 2 product for power generation, and delivers a high-pressure CO 2 stream ready for sequestration. Specifically, in our study we use carbon molecular sieve membranes (CMSMs) and a commercial sour-shift WGS catalyst. Lab experiments were carried-out to determine the membrane characteristics, and the MR performance under IGCC-relevant conditions, i.e., for temperatures up to 250 °C and pressures up to 25 bar, employing a model coal gasifier syngas. The CMSM and the catalyst have displayed robust and stable performance during a long-term run (~750 h of syngas exposure). We evaluated the MR-AR system in multi-cycle runs and it has demonstrated superior performance to that of a conventional packed-bed reactor, producing a high-purity H 2 product directly useable in a turbine for power generation. We conclude from the study, that the CMSM-based MR-AR system is a good candidate technology for environmentally-benign power generation. We are currently constructing a pilot-scale system for field demonstration of the technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Mechanistic Insights and Rational Design of Ca-Doped CeO 2 Catalyst for Acetic Acid Ketonization

Carboxylic acid ketonization has recently gained significant attention to produce biomass-derived hydrocarbon fuels as it not only removes the highly reactive carboxylic functional group but also increases the size of the carbon chain. In this work, Ca-doped CeO 2 -based catalysts were investigated for acetic acid ketonization using a combined experimental and computational approach. Acetic acid conversion was performed across a range of temperatures including higher temperatures relevant to catalytic hot gas filtration (450 °C). Ca addition slightly decreases overall acetic acid ketonization reactivity yet stabilizes the catalyst at the higher temperatures necessary for catalytic hot gas filtration. From density functional theory calculations of the ketonization reaction mechanism, the C–C coupling and water formation steps are identified as two of the most energy-consuming steps on a CeO 2 surface with a proximal oxygen vacancy and the presence of a Ca dopant stabilizes the key intermediates. Calculations predict an optimal structure comprising three Ca ensembles to minimize the reaction free energies for C–C coupling and water formation steps. These findings provide a priori information to guide future experiments for ketonization catalyst design and development.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Catalytic Activity of Ti-based MXenes for the Hydrogenation of Furfural

Here, we report on the catalytic activity of Ti-based MXenes (Ti 3 CNT z and Ti 3 C 2 T z ) for biomass transformation. MXenes were found to be active catalysts for the hydrogenation of furfural using either gaseous hydrogen or 2-propanol as solvent and hydrogen source. Both catalysts showed good activity in the conversion of furfural to furfuryl alcohol, with furfuryl ether as the main by-product. Stability tests indicated that Ti 3 CNT z is more stable than Ti 3 C 2 T z against deactivation. Ab initio calculations were used to examine the hydrogenation and etherification reactions pathways and their corresponding reaction energetics on the Ti 3 CNT z MXene. The results indicate that the hydrogenation of the carbonyl bond efficiently proceeds via the heterolytic activation of hydrogen over the metal-oxygen site pair followed by the addition of the proton and hydride to the C and O atoms of the carbonyl. The subsequent hydrogenation of the unsaturated furan ring via metal bound hydrogen, however, is calculated to be much more difficult. Protons bound to the oxygen of the MXene are acidic and can also catalyze the etherification of the resulting alcohols. Finally, the bifunctional acid-metal site pairs also selectively catalyze the hydrogenolysis of the furfuryl alcohol to form 2-methyl furan.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Performance characterization of nanofiltration, reverse osmosis, and ion exchange technologies for acetic acid separation

A major obstacle to widespread implementation of bio-based fuels and chemicals is the lack of efficient and costeffective separation methods. To purify acetic acid produced by biochemical conversion of biomass via anaerobic digestion, this work employs two commonly used separation technologies: (1) ion-exchange (IX) resin and (2) pressure-driven membranes. This study tested five commercially available strong- and weak-base anion-exchange resins and five commercially available nanofiltration (NF) and reverse osmosis (RO) membranes. The pH of the feed solution significantly affected adsorption capacity. At pH 6.3, a strong-base IX resin (IRN-78) performed best (95.1% acetate removal). With strong-base IX resins, the Langmuir isotherm model fit well, whereas for weak-base IX resins, the Freundlich isotherm provided a better fit. A pseudo-second-order kinetic model fit well for both IRN-78 and IRA-67. Regarding membrane separation, RO (BW30XFR membrane) achieved the highest rejection (98.6% acetate rejection), whereas an NF membrane (NF*) achieved the best combination of permeate flux (105 L/(h∙m 2 )) and rejection (83.1% acetate rejection). For membrane performance, the experimental data were fit using the solution diffusion model. Increased pH in the feed solution lowered permeate flux but increased acetic acid rejection. Finally, then the acetic acid concentration in the feed solution increased, both permeate flux and acetic acid rejection decreased for membrane NF*.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Impact of Electrolyte Composition on Bulk Electrolysis of Furfural over Platinum Electrodes

Partial oxidation of furanic biomass derivatives such as furfural is of interest for the sustainable production of chemicals including furoic acid, maleic acid, and 2,5-furandicarboxylic acid (FDCA). The oxidative bulk electrolysis of furfural is here investigated on platinum electrodes in acidic media. The effects of potential, concentration, pH, and supporting anion are studied, and selectivity trends are coupled with attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) to illuminate adsorbate structures that influence the catalysis. Increasing potential is found to shift selectivity from primarily C 5 products to C 4 products, coincident with oxidation of the Pt surface. Selectivity changes are also observed moving from pH 1 to pH 4, with an increase in C 5 products at higher pH. Furthermore, changing from the weakly adsorbing perchlorate anion to the specifically-adsorbing phosphate anion results in a number of changes that manifest differently depending on potential and pH. Selectivity to furoic acid is found to be highest above the pKa of phosphoric acid due to the strongly adsorbed phosphate ions suppressing flat-lying configurations of furfural that lead to C−C cleavage. These results point toward opportunities to use electrolyte engineering to tune selectivity and optimize surface conditions to disfavor binding of inhibitory products.

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