15 Search Results

Sustainable aviation fuel (SAF) production from biomass and biowaste streams is an attractive option for decarbonizing the aviation sector, one of the most-difficult-to-electrify transportation sectors. Despite ongoing commercialization efforts using ASTM-certified pathways (e.g., lipid conversion, Fischer-Tropsch synthesis), production capacities are still inadequate due to limited feedstock supply and high production costs. New conversion technologies that utilize lignocellulosic feedstocks are needed to meet these challenges and satisfy the rapidly growing market. Combining bio- and chemo-catalytic approaches can leverage advantages from both methods, i.e., high product selectivity via biological conversion, and the capability to build C-C chains more efficiently via chemical catalysis.more » Herein, conversion routes, catalysis, and processes for such pathways are discussed, while key challenges and meaningful R&D opportunities are identified to guide future research activities in the space. Bio and chemo-catalytic conversion primarily utilize the carbohydrate fraction of lignocellulose, leaving lignin as a waste product. This makes lignin conversion to SAF critical in order to utilize whole biomass, thereby lowering overall production costs while maximizing carbon efficiencies. Thus, lignin valorization strategies are also reviewed herein with vital research areas identified, such as facile lignin depolymerization approaches, highly integrated conversion systems, novel process configurations, and catalysts for the selective cleavage of aryl C–O bonds. The potential efficiency improvements available via integrated conversion steps, such as combined biological and chemo-catalytic routes, along with the use of different parallel pathways, are identified as key to producing all components of a cost-effective, 100% SAF.« less

Transition metal carbides have been adopted in energy storage, conversion, and extreme environment applications. Advancements in their 2D counterparts, known as MXenes, enable the design of unique structures at the ~1 nm thickness scale. Alkali cations have been essential in MXenes manufacturing processing, storage, and applications, however, exact interactions of these cations with MXenes are not fully understood. In this study, using Ti₃C₂T_x, Mo₂TiC₂T_x, and Mo₂Ti₂C₃T_x MXenes, we present how transition metal vacancy sites are occupied by alkali cations, and their effect on MXene structure stabilization to control MXene’s phase transition. We examine this behavior using in situ high-temperature x-raymore » diffraction and scanning transmission electron microscopy, ex situ techniques such as atomic-layer resolution secondary ion mass spectrometry, and density functional theory simulations. In MXenes, this represents an advance in fundamentals of cation interactions on their 2D basal planes for MXenes stabilization and applications. Broadly, this study demonstrates a potential new tool for ideal phase-property relationships of ceramics at the atomic scale.« less

Abstract Sulfide‐based solid‐state electrolytes (SSEs) exhibit many tantalizing properties including high ionic conductivity and favorable mechanical properties for next‐generation solid‐state batteries. Widespread adoption of these materials is hindered by their intrinsic instability under ambient conditions, which makes them difficult to process at scale, and instability at the Li||SSE and cathode||SSE interfaces, which limits cell performance and lifetime. Atomic layer deposition is leveraged to grow thin Al ₂ O ₃ coatings on Li ₆ PS ₅ Cl powders to address both issues simultaneously. These coatings can be directly grown onto Li ₆ PS ₅ Cl particles with negligible chemical modification ofmore » the underlying material and enable exposure of powders to pure and H ₂ O‐saturated oxygen environments for ≥4 h with minimal reactivity, compared with significant degradation of the uncoated powder. Pellets fabricated from coated powders exhibit ionic conductivities up to 2× higher than those made from uncoated material, with a simultaneous decrease in electronic conductivity and significant suppression of chemical reactivity at the Li‐SSE interface. These benefits result in significantly improved room temperature cycle life at high capacity and current density. It is hypothesized that this enhanced performance derives from improved intergranular properties and improved Li metal adhesion. This work points to a completely new framework for designing active, stable, and scalable materials for next‐generation solid‐state batteries.« less

2,3-Butanediol (2,3-BDO), a critical C₄ platform chemical derived from biomass, syngas, or CO₂, can be converted to C₃₊ olefins, serving as important renewable feedstocks for producing sustainable aviation fuels to decarbonize the hard-to-electrify air transportation sector. Herein, we report a bifunctional Cu-modified diffusion-free 2D pillared MFI catalyst (Cu/PMFI) which can selectively catalyze 2,3-BDO conversion to butene-rich C₃₊ olefins (95% selectivity at 97% conversion, 523 K). 2,3-BDO conversion to butenes over Cu/PMFI primarily occurs via methyl ethyl ketone intermediate while 2-methyl propanal is also observed as another minor dehydration product that leads to butene formation. In comparison with a control mesoporousmore » Cu/ZSM-5 sample prepared by the postsynthetic approach, Cu/PMFI shows favorable C₃₊ olefin selectivity (95% over Cu/PMFI vs 80% over Cu/ZSM-5 at ~5.1 h TOS). The coke formation over Cu/PMFI is dramatically suppressed by >50% in contrast to Cu/ZSM-5 in 90 h 2,3-BDO conversion due to the reduced diffusion length. Cu/PMFI also favors butene formation and minimizes nonbutene C₃₊ olefins by inhibiting the downstream oligomerization and cracking reactions. This study highlights the usefulness of the diffusion-free 2D PMFI materials in catalytic conversion of biomass-derived platform molecules and the significance of diffusion impact on catalyst coke formation and product distributions.« less

Direct and selective production of C₃₊ olefins from bioethanol remains a critical challenge and important for the production of renewable transportation fuels such as aviation biofuels. In this study, we report a Cu–Zn–Y/Beta catalyst for selective ethanol conversion to butene-rich C₃₊ olefins (88% selectivity at 100% ethanol conversion, 623 K), where the Cu, Zn, and Y sites are all highly dispersed. The ethanol-to-butene reaction network includes ethanol dehydrogenation, aldol condensation to crotonaldehyde, and hydrogenation to butyraldehyde, followed by further hydrogenation and dehydration reactions to form butenes. Cu sites play a critical role in promoting hydrogenation of the crotonaldehyde C═C bondmore » to form butyraldehyde in the presence of hydrogen, making this a distinctive pathway from crotyl alcohol-based ethanol-to-butadiene reaction. Reaction rate measurements in the presence of ethanol and acetaldehyde (543 K, 12 kPa ethanol, 1.2 kPa acetaldehyde, 101.9 kPa H₂) over monometallic Zn/Beta and Y/Beta catalysts indicate that Y sites have higher C–C coupling rates than over Zn sites (initial C–C coupling rate, 6.1 × 10^–3 mol mol_Y^–1 s^–1 vs 1.2 × 10^–3 mol mol_Zn^–1 s^–1). Further, Lewis-acidic Y-site densities over Cu–Zn–Y/Beta with varied Y loadings are linearly correlated with the initial C–C coupling rates, suggesting that Lewis-acidic Y sites are the predominant sites that catalyze C–C coupling in Cu–Zn–Y/Beta catalysts. Control experiments show that the dealuminated Beta support is important to form higher density of Lewis-acidic Y sites in comparison with other supports such as silica, or deboronated MWW despite similar atomic dispersion of Y sites and Y–O coordination numbers over these supports, leading to more than 9 times higher C–C coupling rate per mole Y over dealuminated Beta relative to other supports. This study highlights the significance of unique combination of metal sites in contributing to the selective valorization of ethanol to C₃₊ olefins, motivating for exploring multifunctional zeolite catalysts, where the presence of multiple sites with varying reactivities and functions allows for controlling the predominant molecular fluxes toward the desired products in complex reactions.« less

Despite progress in small scale electrocatalytic production of hydrogen peroxide (H₂O₂) using a rotating ring-disk electrode, further work is needed to develop a non-toxic, selective, and stable O₂-to-H₂O₂ electrocatalyst for realizing continuous on-site production of neutral hydrogen peroxide. We report ultrasmall and monodisperse colloidal PtP₂ nanocrystals that achieve H₂O₂ production at near zero-overpotential with near unity H₂O₂ selectivity at 0.27 V vs. RHE. Density functional theory calculations indicate that P promotes hydrogenation of OOH* to H₂O₂ by weakening the Pt-OOH* bond and suppressing the dissociative OOH* to O* pathway. Atomic layer deposition of Al₂O₃ prevents NC aggregation and enables applicationmore » in a polymer electrolyte membrane fuel cell (PEMFC) with a maximum r(H₂O₂) of 2.26 mmol h^-1 cm^-2 and a current efficiency of 78.8% even at a high current density of 150 mA cm^-2. Catalyst stability enables an accumulated neutral H₂O₂ concentration in 600 mL of 3.0 wt% (pH = 6.6).« less

Production of biomass-derived sustainable alternative jet fuels (SAJF) has been considered as an important approach to decarbonize the aviation industry but still possesses various challenges in technology advancement, particularly in achieving high carbon efficiency. Here we report a hybrid pathway to SAJF from 2,3-butanediol (2,3-BDO), integrating biologically converting biomass to 2,3-BDO with catalytically upgrading of 2,3-BDO to jet-range hydrocarbons. This pathway is demonstrated to have a high carbon recovery to liquid hydrocarbons from corn stover (25–28%) (74–82% of the theoretical maximum efficiency). The catalytic conversion steps involve 2,3-BDO to C₃₊ olefins, oligomerization, and hydrogenation where the first two steps aremore » the focus of this study. Under optimum reaction conditions (523 K, 115 kPa, 1.0 h^-1 weight hourly space velocity), 2,3-BDO conversion and C₃₊ olefin selectivity are >97% and 94–98% during 40 h time on stream, respectively. To demonstrate the adaptability of this technology with bio-derived 2,3-BDO, we also investigated the impact of water and other organic coproducts (acetoin and acetic acid) inherited from the fermentation broth on the catalyst performance and product selectivities. We have shown that the catalyst can handle a significant amount of water in the liquid feed (40 wt% water/60 wt% 2,3-BDO) and maintain catalyst stability for ~40 h. Acetoin can be converted to similar C₃₊ olefins as 2,3-BDO with complete conversion of acetoin. Co-feeding 10 wt% acetoin with 2,3-BDO is found to have no impact on 2,3-BDO conversion, C₃₊ olefin selectivity, and catalyst stability. The utilization of organic coproduct like acetoin can help to improve overall carbon conversion efficiency when using real biomass-derived 2,3-BDO. On the other hand, the presence of 10 wt% acetic acid is shown to drastically inhibit methyl ethyl ketone (MEK) hydrogenation and butene oligomerization as revealed by the increased MEK and butene selectivities, implying the importance of separating organic acids when feeding bio-derived 2,3-BDO. The formed C₃–C₆ olefins from 2,3-BDO are further oligomerized over Amberlyst-36 catalyst to longer-chain hydrocarbons with >70 wt% jet-range hydrocarbons including predominantly iso-olefins/iso-paraffins. Finally, the overall carbon efficiency for the jet-range hydrocarbons is 19–22%, exceeding most of the reported biojet pathways, which makes it a promising approach for SAJF production.« less

Developing earth-abundant and efficient electrocatalysts for photoelectrochemical water splitting is critical to realizing a high-performance solar-to-hydrogen energy conversion process. Here in this paper, phosphorus-rich colloidal cobalt diphosphide nanocrystals (CoP₂ NCs) are synthesized via hot injection. The CoP₂ NCs show a Pt-like hydrogen evolution reaction (HER) electrocatalytic activity in acidic solution with a small overpotential of 39 mV to achieve -10 mA cm^-2 and a very low Tafel slope of 32 mV dec^-1. Density functional theory (DFT) calculations reveal that the high P content both physically separates Co atoms to prevent H from over binding to multiple Co atoms, while simultaneouslymore » stabilizing H adsorbed to single Co atoms. The catalytic performance of the CoP₂ NCs is further demonstrated in a metal–insulator–semiconductor photoelectrochemical device consisting of bottom p-Si light absorber, atomic layer deposition Al–ZnO passivation layers, and the CoP₂ cocatalyst. The p-Si/AZO/TiO₂/CoP₂ photocathode shows a photocurrent density of -16.7 mA cm^-2 at 0 V versus reversible hydrogen electrode (RHE) and an output photovoltage of 0.54 V. The high performance and stability are attributed to the junction between p-Si and AZO, the corrosion-resistance of the pinhole-free TiO₂ protective layer, and the fast HER kinetics of the CoP₂ NCs.« less

Biomass pyrolysis to produce biofuel and hydrogen yields large amounts of charred byproducts with low commercial value. A study was conducted to evaluate their potential for being converted into higher value activated carbons by a low-cost process. Six chars derived from various lignocellulosic precursors were activated in CO₂ at 800 °C to 30–35% weight loss, and their surface area and porosity were characterized by nitrogen adsorption at 77 K. It was found that, in similar activation conditions, the surface area of the activated carbons correlates with the activation energy of the oxidation reaction by CO₂, which in turn varies inverselymore » with the carbon yield after thermolysis in nitrogen at 1000 °C. Since lignin is the most thermally-stable component of lignocellulosic biomass, these results demonstrate, indirectly, that robust, lignin-rich vegetal precursors are to be preferred to produce higher quality activated carbons. The chars derived from white pine (pinus strobus) and chestnut oak (quercus prinus) were converted to activated carbons with the highest surface area (900–1100 m²/g) and largest mesopores volume (0.85–1.06 cm³/g). These activated carbons have properties similar to those of commercially-available activated carbons used successfully for removal of pollutants from aqueous solutions.« less

Visible light active photocatalytic performance of g-C₃N₄/NSON-X heterojunctions.