Toward net-zero sustainable aviation fuel with wet waste-derived volatile fatty acids.

With the increasing demand for net-zero sustainable aviation fuels (SAF), new conversion technologies are needed to process waste feedstocks and meet carbon reduction and cost targets. Wet waste is a low-cost, prevalent feedstock with the energy potential to displace over 20% of US jet fuel consumption; however, its complexity and high moisture typically relegates its use to methane production from anaerobic digestion. To overcome this, methanogenesis can be arrested during fermentation to instead produce C2 to C8 volatile fatty acids (VFA) for catalytic upgrading to SAF. Here, we evaluate the catalytic conversion of food waste-derived VFAs to produce n-paraffin SAF for near-term use as a 10 vol% blend for ASTM "Fast Track" qualification and produce a highly branched, isoparaffin VFA-SAF to increase the renewable blend limit. VFA ketonization models assessed the carbon chain length distributions suitable for each VFA-SAF conversion pathway, and food waste-derived VFA ketonization was demonstrated for >100 h of time on stream at approximately theoretical yield. Fuel property blending models and experimental testing determined normal paraffin VFA-SAF meets 10 vol% fuel specifications for "Fast Track." Synergistic blending with isoparaffin VFA-SAF increased the blend limit to 70 vol% by addressing flashpoint and viscosity constraints, with sooting 34% lower than fossil jet. Techno-economic analysis evaluated the major catalytic process cost-drivers, determining the minimum fuel selling price as a function of VFA production costs. Life cycle analysis determined that if food waste is diverted from landfills to avoid methane emissions, VFA-SAF could enable up to 165% reduction in greenhouse gas emissions relative to fossil jet.

Improving Rare-Earth Mineral Separation with Insights from Molecular Recognition: Functionalized Hydroxamic Acid Adsorption onto Bastnäsite and Calcite.

Enhancing the separation of rare-earth elements (REEs) from gangue materials in mined ores requires an understanding of the fundamental interactions driving the adsorption of collector ligands onto mineral interfaces. In this work, we examine five functionalized hydroxamic acid ligands as potential collectors for the REE-containing bastnäsite mineral in froth flotation using density functional theory calculations and a suite of surface-sensitive analytical spectroscopies. These include vibrational sum frequency generation, attenuated total reflectance Fourier transform infrared, Raman, and X-ray photoelectron spectroscopies. Differences in the chemical makeup of these ligands on well-defined bastnäsite and calcite surfaces allow for a systematic relationship connecting the structure to adsorption activity to be framed in the context of interfacial molecular recognition. We show how the intramolecular hydrogen bonding of adsorbed ligands requires the inclusion of explicit water solvent molecules to correctly map energetic and structural trends measured by experiments. We anticipate that the results and insights from this work will motivate and inform the design of improved flotation collectors for REE ores.

Photoinduced Strong Metal-Support Interaction for Enhanced Catalysis.

Strong metal-support interaction (SMSI) construction is a pivotal strategy to afford thermally robust nanocatalysts in industrial catalysis, but thermally induced reactions (>300 °C) in specific gaseous atmospheres are generally required in traditional procedures. In this work, a photochemistry-driven methodology was demonstrated for SMSI construction under ambient conditions. Encapsulation of Pd nanoparticles with a TiOx overlayer, the presence of Ti3+ species, and suppression of CO adsorption were achieved upon UV irradiation. The key lies in the generation of separated photoinduced reductive electrons (e-) and oxidative holes (h+), which subsequently trigger the formation of Ti3+ species/oxygen vacancies (Ov) and then interfacial Pd-Ov-Ti3+ sites, affording a Pd/TiO2 SMSI with enhanced catalytic hydrogenation efficiency. The as-constructed SMSI layer was reversible, and the photodriven procedure could be extended to Pd/ZnO and Pt/TiO2.

Defect-Mediated Phase Transformation in Anisotropic Two-Dimensional PdSe2 Crystals for Seamless Electrical Contacts.

The failure to achieve stable Ohmic contacts in two-dimensional material devices currently limits their promised performance and integration. Here we demonstrate that a phase transformation in a region of a layered semiconductor, PdSe2, can form a contiguous metallic Pd17Se15 phase, leading to the formation of seamless Ohmic contacts for field-effect transistors. This phase transition is driven by defects created by exposure to an argon plasma. Cross-sectional scanning transmission electron microscopy is combined with theoretical calculations to elucidate how plasma-induced Se vacancies mediate the phase transformation. The resulting Pd17Se15 phase is stable and shares the same native chemical bonds with the original PdSe2 phase, thereby forming an atomically sharp Pd17Se15/PdSe2 interface. These Pd17Se15 contacts exhibit a low contact resistance of ∼0.75 kΩ µm and Schottky barrier height of ∼3.3 meV, enabling nearly a 20-fold increase of carrier mobility in PdSe2 transistors compared to that of traditional Ti/Au contacts. This finding opens new possibilities in the development of better electrical contacts for practical applications of 2D materials.

Compatibility between Various Ionic Liquids and an Organic Friction Modifier as Lubricant Additives.

Tribological performance of a boundary lubrication contact is largely dominated by the friction modifier (FM) and antiwear (AW) additives in the lubricant. While oil-soluble ionic liquids (ILs) have recently demonstrated promising AW functionality, their compatibility with FMs is little known and even less understood for nonferrous alloys. Here, we report the latest results for several selected ILs when used together with an organic FM (OFM) in lubricating a steel-bronze contact. Depending on the IL chemistry, either synergistic or antagonistic effects were observed. The three aprotic ILs ([P8888][DEHP], [P66614][BTMPP], and [P66614][C17H35COO]) seemed to degrade the OFM's lubricating performance. In contrast, the protic IL [N888H][DEHP] exhibited a strong synergistic effect with the OFM, yielding an ultralow steady-state friction coefficient (0.02) and a low wear rate (<10-8 mm3/(N m)), which significantly outperformed the IL or the OFM alone. Surface characterization found no chemically reacted tribofilm on the bronze worn surface. On the other hand, a unique physically adsorbed surface film as a result of interconnection between the IL and OFM molecules by hydrogen bonds is proposed on the basis of chemical analysis. Such an adsorption surface film is expected to be difficult to compress vertically but easy to shear horizontally, leading to low friction and wear.

In situ capping for size control of monochalcogenide (ZnS, CdS and SnS) nanocrystals produced by anaerobic metal-reducing bacteria.

Metal monochalcogenide quantum dot nanocrystals of ZnS, CdS and SnS were prepared by anaerobic, metal-reducing bacteria using in situ capping by oleic acid or oleylamine. The capping agent preferentially adsorbs on the surface of the nanocrystal, suppressing the growth process in the early stages, thus leading to production of nanocrystals with a diameter of less than 5 nm.

Studies on supercapacitor electrode material from activated lignin-derived mesoporous carbon.

We synthesized mesoporous carbon from pre-cross-linked lignin gel impregnated with a surfactant as the pore-forming agent and then activated the carbon through physical and chemical methods to obtain activated mesoporous carbon. The activated mesoporous carbons exhibited 1.5- to 6-fold increases in porosity with a maximum Brunauer-Emmett-Teller (BET) specific surface area of 1148 m(2)/g and a pore volume of 1.0 cm(3)/g. Both physical and chemical activation enhanced the mesoporosity along with significant microporosity. Plots of cyclic voltammetric data with the capacitor electrode made from these carbons showed an almost rectangular curve depicting the behavior of ideal double-layer capacitance. Although the pristine mesoporous carbon exhibited a range of surface-area-based capacitance similar to that of other known carbon-based supercapacitors, activation decreased the surface-area-based specific capacitance and enhanced the gravimetric specific capacitance of the mesoporous carbons. A vertical tail in the lower-frequency domain of the Nyquist plot provided additional evidence of good supercapacitor behavior for the activated mesoporous carbons. We have modeled the equivalent circuit of the Nyquist plot with the help of two constant phase elements (CPE). Our work demonstrated that biomass-derived mesoporous carbon materials continue to show potential for use in specific electrochemical applications.

Exploring Lead Zirconate Titanate, the Potential Advancement as an Anode for Li-Ion Batteries.

Graphite, widely adopted as an anode for lithium-ion batteries (LIBs), faces challenges such as an unsustainable supply chain and sluggish rate capabilities. This emphasizes the urgent need to explore alternative anode materials for LIBs, aiming to resolve these challenges and drive the advancement of more efficient and sustainable battery technologies. The present research investigates the potential of lead zirconate titanate (PZT: PbZr0.53Ti0.47O3) as an anode material for LIBs. Bulk PZT materials were synthesized by using a solid-state reaction, and the electrochemical performance as an anode was examined. A high initial discharge capacity of approximately 686 mAh/g was attained, maintaining a stable capacity of around 161 mAh/g after 200 cycles with diffusion-controlled intercalation as the primary charge storage mechanism in a PZT anode. These findings suggest that PZT exhibits a promising electrochemical performance, positioning it as a potential alternative anode material for LIBs.

Low-temperature dechlorination of polyvinyl chloride (PVC) for production of H2 and carbon materials using liquid metal catalysts.

Polyvinyl chloride (PVC) is ubiquitous in everyday life; however, it is not recycled because it degrades uncontrollably into toxic products above 250°C. Therefore, it is of interest to controllably dechlorinate PVC at mild temperatures to generate narrowly distributed carbon materials. We present a catalytic route to dechlorinate PVC (~90% reduction of Cl content) at mild temperature (200°C) to produce gas H2 (with negligible coproduction of corrosive gas HCl) and carbon materials using Ga as a liquid metal (LM) catalyst. A LM was used to promote intimate contact between PVC and the catalytic sites. During dechlorination of PVC, Cl is sequestrated in the carbonaceous solid product. Later, chlorine is easily removed with an acetone wash at room temperature. The Ga LM catalyst is reusable, outperforms a traditional supported metal catalyst, and successfully converts (untreated) discarded PVC pipe.

Low-Temperature Molten Salt Electrochemical CO2 Upcycling for Advanced Energy Materials.

One strategy for addressing the climate crisis caused by CO2 emissions is to efficiently convert CO2 to advanced materials suited for green and clean energy technology applications. Porous carbon is widely used as an advanced energy storage material because of its enhanced energy storage capabilities as an anode. Herein, we report electrochemical CO2 upcycling to solid carbon with a controlled microstructure and porosity in a ternary molten carbonate melt at 450 °C. Controlling the electrochemical parameters (voltage, temperature, cathode material) enabled the conversion of CO2 to porous carbon with a tunable morphology and porosity for the first time at such a low temperature. Additionally, a well-controlled morphology and porosity are beneficial for reversible energy storage. In fact, these carbon materials delivered high specific capacity, stable cycling performances, and exceptional rate capability even under extremely fast charging conditions when integrated as an anode in lithium-ion batteries (LIBs). The present approach not only demonstrated efficient upcycling of CO2 into porous carbon suitable for enhanced energy storage but can also contribute to a clean and green energy technology that can reduce carbon emissions to achieve sustainable energy goals.

Functionalized Silicon Particles for Enhanced Half- and Full-Cell Cycling of Si-Based Li-Ion Batteries.

Vinylene carbonate (VC) and polyethylene oxide (PEO) have been investigated as functional agents that mimic the solid electrolyte interphase (SEI) chemistry of silicon (Si). VC and PEO are known to contribute to the stability of Si-based lithium-ion batteries as an electrolyte additive and as a SEI component, respectively. In this work, covalent surface functionalization was achieved via a facile route, which involves ball-milling the Si particles with sacrificial VC and PEO. Thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy indicate that the additives are strongly bound to Si. In particular, MAS NMR shows Si-R or Si-O-R groups, which confirm functionalization of the Si after milling in VC or PEO. Particle size analysis by dynamic light scattering reveals that the additives facilitate particle size reduction and that the functionalized particles result in more stable dispersions based on zeta potential measurements. Raman mapping of the electrodes fabricated from the VC and PEO-coated active material with a polyacrylic acid (PAA) binder reveals a more homogenous distribution of Si and the carbon conductive additive compared to the electrodes prepared from the neat Si. Furthermore, the VC-milled Si strikingly exhibited the highest capacity in both half- and full-cell configurations, with more than 200 mAh g-1 measured capacity compared to the neat Si in the half-cell format. This is linked to an improved electrode processing based on the Raman and zeta potential measurements as well as a thinner SEI (with more organic components for the functionalized Si relative to the neat Si) based on XPS analysis of the cycled electrodes. The effect of binder was also investigated by comparing PAA with P84 (polyimide type), where an increased capacity is observed in the latter case.

Robust Copper-Based Nanosponge Architecture Decorated by Ruthenium with Enhanced Electrocatalytic Performance for Ambient Nitrogen Reduction to Ammonia.

Electrochemical conversion of nitrogen to green ammonia is an attractive alternative to the Haber-Bosch process. However, it is currently bottlenecked by the lack of highly efficient electrocatalysts to drive the sluggish nitrogen reduction reaction (N2RR). Herein, we strategically design a cost-effective bimetallic Ru-Cu mixture catalyst in a nanosponge (NS) architecture via a rapid and facile method. The porous NS mixture catalysts exhibit a large electrochemical active surface area and enhanced specific activity arising from the charge redistribution for improved activation and adsorption of the activated nitrogen species. Benefiting from the synergistic effect of the Cu constituent on morphology decoration and thermodynamic suppression of the competing hydrogen evolution reaction, the optimized Ru0.15Cu0.85 NS catalyst presents an impressive N2RR performance with an ammonia yield rate of 26.25 µg h-1 mgcat.-1 (corresponding to 10.5 µg h-1 cm-2) and Faradic efficiency of 4.39% as well as superior stability in alkaline medium, which was superior to that of monometallic Ru and Cu nanostructures. Additionally, this work develops a new bimetallic combination of Ru and Cu, which promotes the strategy to design efficient electrocatalysts for electrochemical ammonia production under ambient conditions.

Multiple Promotional Effects of Vanadium Oxide on Boron Nitride for Oxidative Dehydrogenation of Propane.

Featuring high olefin selectivity, hexagonal boron nitride (h-BN) has emerged recently as an attractive catalyst for oxidative dehydrogenation of propane (ODHP). Herein, we report that dispersion of vanadium oxide onto BN facilitates the oxyfunctionalization of BN to generate more BO x active sites to catalyze ODHP via the Eley-Rideal mechanism and concurrently produce nitric oxide to initiate additional gas-phase radical chemistry and to introduce redox VO x sites to catalyze ODHP via the Mars-van Krevelen mechanism, all of which promote the catalytic performance of BN for ODHP. As a result, loading 0.5 wt % V onto BN has doubled the yield of light alkene (C2-C3) at 540-580 °C, and adding an appropriate concentration of NO in the reactants further enhances the catalytic performance. These results provide a potential strategy for developing efficient h-BN-based catalysts through coupling gas-phase and surface reactions for the ODHP process.

Low-Cost Transformation of Biomass-Derived Carbon to High-Performing Nano-graphite via Low-Temperature Electrochemical Graphitization.

Graphite, an essential component of energy storage devices, is traditionally synthesized via an energy-intensive thermal process (Acheson process) at ∼3300 K. However, the battery performance of such graphite is abysmal under fast-charging conditions, which is deemed essential for the propulsion of electric vehicles to the next level. Herein, a low-temperature electrochemical transformation approach has been demonstrated to afford a highly crystalline nano-graphite with the capability of tuning interlayer spacing to enhance the lithium diffusion kinetics in molten salts at 850 °C. The essence of our strategy lies in the effective electrocatalytic transformation of carbon to graphite at a lower temperature that could significantly increase the energy savings, reduce the cost, shorten the synthesis time, and replace the traditional graphite synthesis. The resulting graphite exhibits high purity, crystallinity, a high degree of graphitization, and a nanoflake architecture that all ensure fast lithium diffusion kinetics (∼2.0 × 10-8 cm2 s-1) through its nanosheet. Such unique features enable outstanding electrochemical performance (∼200 mA h g-1 at 5C for 1000 cycles, 1C = 372 mA g-1) as a fast-charging anode for lithium-ion batteries. This finding paves the way to make high energy-density fast-charging batteries that could boost electromobility.

Operando Analysis of Gas Evolution in TiNb2O7 (TNO)-Based Anodes for Advanced High-Energy Lithium-Ion Batteries under Fast Charging.

TiNb2O7 (TNO) is regarded as one of the promising next-generation anode materials for lithium-ion batteries (LIBs) due to its high rate capabilities, higher theoretical capacity, and higher lithiation voltage. This enables the cycling of TNO-based anodes under extreme fast charging (XFC) conditions with a minimal risk of lithium plating compared to that of graphite anodes. Here, the gas evolution in real time with TNO-based pouch cells is first reported via operando mass spectrometry. The main gases are identified to be CO2, C2H4, and O2. A solid-electrolyte interphase is detected on TNO, which continues evolving, forming, and dissolving with the lithiation and delithiation of TNO. The gas evolution can be significantly reduced when a protective coating is applied on the TNO particles, reducing the CO2 and C2H4 evolution by ∼2 and 5 times, respectively, at 0.1C in a half-cell configuration. The reduction on gas generation in full cells is even more pronounced. The surface coating also enables 20% improvement in capacity under XFC conditions.

Formation of LiF Surface Layer During Direct Fluorination of High-Capacity Co-Free Disordered Rocksalt Cathodes.

Disordered rocksalt (DRX) cathodes have attracted interest due to their high capacity and compositional flexibility (e.g., Co-free chemistries). However, the sloping voltage profile and gradual capacity fade during cycling have hindered the widespread adoption of these materials. Simulations predict that fluorine substitution in DRX cathodes will improve their capacity, rate performance, and cyclability. In this study, we use a fluidized bed reactor to fluorinate a model Li-rich DRX composition (Li1.15Ni0.375Ti0.375Mo0.1O2, NTMO) to investigate how fluorine content impacts the cathode's structure and electrochemical performance. Instead of substituting O with F to form oxyfluoride phases, direct fluorination of DRX cathodes leads to the formation of LiF surface films, which improves the specific energy and capacity retention. This study demonstrates the feasibility of direct fluorination to improve the electrochemical performance of high-voltage cathodes by tuning the material's surface chemistry.

Constructing Ultrathin W-Doped NiFe Nanosheets via Facile Electrosynthesis as Bifunctional Electrocatalysts for Efficient Water Splitting.

Exploring cost-effective and efficient bifunctional electrocatalysts via simple fabrication strategies is strongly desired for practical water splitting. Herein, an easy and fast one-step electrodeposition process is developed to fabricate W-doped NiFe (NiFeW)-layered double hydroxides with ultrathin nanosheet features at room temperature and ambient pressure as bifunctional catalysts for water splitting. Notably, the NiFeW nanosheets require overpotentials of only 239 and 115 mV for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively, to reach a current density of 10 mA/cm2 in alkaline media. Their exceptional performance is further demonstrated in a full electrolyzer configuration with the NiFeW as both anode and cathode catalysts, which achieves a low cell voltage of 1.59 V at 10 mA/cm2, 110 mV lower than that of the commercial IrO2 (anode) and Pt (cathode) catalysts. Moreover, the NiFeW nanosheets are superior to various recently reported bifunctional electrocatalysts. Such remarkable performances mainly ascribe to W doping, which not only effectively modulates the electrocatalyst morphology but also engineers the electronic structure of NiFe hydroxides to boost charge-transfer kinetics for both the OER and HER. Hence, the ultrathin NiFeW nanosheets with an efficient fabrication strategy are promising as bifunctional electrodes for alkaline water electrolyzers.

Polymer, Additives, and Processing Effects on N95 Filter Performance.

The current severe acute respiratory syndrome coronavirus 2 (SARS-COV-2) pandemic has highlighted the need for personal protective equipment, specifically filtering facepiece respirators like N95 masks. While it is common knowledge that polypropylene (PP) is the industry standard material for filtration media, trial and error is often required to identify suitable commercial precursors for filtration media production. This work aims to identify differences between several commercial grades of PP and demonstrate the development of N95 filtration media with the intent that the industry partners can pivot and help address N95 shortages. Three commercial grades of high melt flow index PP were melt blown at Oak Ridge National Laboratory and broadly characterized by several methods including differential scanning calorimetry (DSC), X-ray diffraction (XRD), and neutron scattering. Despite the apparent similarities (high melt flow and isotacticity) between PP feedstocks, the application of corona charging and charge enhancing additives improve each material to widely varying degrees. From the analysis performed here, the most differentiating factor appears to be related to crystallization of the polymer and the resulting electret formation. Materials with higher crystallization onset temperatures, slower crystallization rates, and larger number of crystallites form a stronger electret and are more effective at filtration.

Probing defect sites on CeO2 nanocrystals with well-defined surface planes by Raman spectroscopy and O2 adsorption.

Defect sites play an essential role in ceria catalysis. In this study, ceria nanocrystals with well-defined surface planes have been synthesized and utilized for studying defect sites with both Raman spectroscopy and O(2) adsorption. Ceria nanorods ({110} + {100}), nanocubes ({100}), and nano-octahedra ({111}) are employed to analyze the quantity and quality of defect sites on different ceria surfaces. On oxidized surfaces, nanorods have the most abundant intrinsic defect sites, followed by nanocubes and nano-octahedra. When reduced, the induced defect sites are more clustered on nanorods than on nanocubes, although similar amounts (based on surface area) of such defect sites are produced on the two surfaces. Very few defect sites can be generated on the nano-octahedra due to the least reducibility. These differences can be rationalized by the crystallographic surface terminations of the ceria nanocrystals. The different defect sites on these nanocrystals lead to the adsorption of different surface dioxygen species. Superoxide on one-electron defect sites and peroxide on two-electron defect sites with different clustering degree are identified on the ceria nanocrystals depending on their morphology. Furthermore, the stability and reactivity of these oxygen species are also found to be surface-dependent, which is of significance for ceria-catalyzed oxidation reactions.

Ultralow Boundary Lubrication Friction by Three-Way Synergistic Interactions among Ionic Liquid, Friction Modifier, and Dispersant.

Interactions among antiwear additives (AWs), friction modifiers (FMs), and dispersant in a lubricating oil are critical for tribological performance. This study investigates compatibilities of three oil-soluble ionic liquids (ILs, candidate AWs) with an FM, molybdenum dithiocarbamate (MoDTC), and a dispersant, polyisobutene succinimide (PIBSI) under boundary lubrication. Either synergistic or antagonistic effects were observed depending on the IL's chemistry. Adding an aprotic phosphonium-alkylphosphate or phosphonium-alkylphosphinate IL into the oil containing MoDTC and PIBSI had detrimental impact on the friction and wear behavior. PIBSI was found to preferably interact/react with the aprotic IL to lose its ability of suspending MoDTC and to partially consume or even deplete the IL. In contrast, a protic ammonium-alkylphosphate IL seemed to be able to coexist with PIBSI and work synergistically with MoDTC, yielding a sustainable, ultralow boundary friction. A three-stage tribochemical process is proposed to explain how this IL + MoDTC pair interacts with the contact surface to form a chemically reacted, wear-protective tribofilm supporting a physically adsorbed, friction-reducing film on top. This study provides fundamental insights of the compatibilities among three common lubricant components, antiwear, friction modifier, and dispersant, which can be used to guide future lubricant development.