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At least 307 records · Page 17

Evolution of silicate coordination in architected amorphous and crystalline magnesium silicates during carbon mineralization

Advancing durable solutions for carbon storage and removal at the gigaton scale to produce solid carbonates via carbon mineralization requires harnessing earth abundant magnesium silicate resources. Calibrated insights linking the structural and morphological features of earth abundant amorphous and crystalline magnesium silicate phases to their reactivity are essential for scalable deployment but remain underdeveloped. To resolve the influence of silica coordination and mass transfer on carbon mineralization behavior, magnesium silicates bearing amorphous and crystalline phases (AC Mg-silicate) are synthesized. The structural and morphological transitions starting from colloidal precursors to their final synthesized form on heating are delineated using operando ultra small/small/wide angle X-ray scattering (USAXS/SAXS/WAXS) measurements. The evolution of the silicate phases on carbon mineralization of AC Mg-silicate is contrasted with that of highly crystalline Mg-silicate (HC Mg-silicate) when reacted at 200 °C and a CO 2 partial pressure of 20 atm in water and 1 M NaHCO 3 solution in stirred and unstirred environments. These experimental conditions are analogous to those of the water–gas-shift reaction for sustainable recovery of H 2 with inherent carbon mineralization. Enhancement in the extent of carbon mineralization by 13.3–19.5% noted in the presence of NaHCO 3 compared to water in AC and HC Mg-silicate with and without stirring, is attributed to the buffering effect which aids simultaneous silicate dissolution and carbon mineralization. Enhanced extents of carbon mineralization in the presence of NaHCO 3 correspond to the formation of MgSiO 3 and SiO 2 phases from the starting Mg 2 SiO 4 precursors in AC and HC Mg-silicate. Unlocking these silicate transformations during carbon mineralization by harnessing architected Mg-silicate precursors reveals the feasibility of integrating these chemical pathways with sustainable H 2 conversion pathways with inherent carbon mineralization.

Gao, Xun [Cornell Univ., Ithaca, NY (United States↗

Tuning Methanol Transformation Pathways for Sustainable Steam Reforming: Na-Promotion Effects on Ag/m-ZrO 2 Catalysts

This work investigates the influence of sodium promotion on Ag/m-ZrO 2 catalysts for methanol steam reforming (MSR), focusing on activity, selectivity, surface chemistry, and mechanistic pathways. Temperature programmed reduction (TPR), XANES/EXAFS, CO 2 TPD, DRIFTS, and temperature programmed surface reaction methods were combined with fixed bed MSR testing to develop an integrated structure–function understanding of Na-modified Ag-ZrO 2 interfaces. Na addition systematically increases surface basicity, stabilizes strongly basic O 2− sites, and weakens the ν(CH) vibrational mode of surface formate, thereby facilitating C–H bond scission and accelerating decarboxylation to CO 2 . At moderate promoter levels (0.5–1.0 wt.% Na), the catalysts show significantly enhanced CO 2 selectivity and increased conversion relative to unpromoted Ag/m-ZrO 2 , while CH 4 formation remains negligible. Excessive Na (≥1.8 wt.%) leads to slower formate decomposition, greater carbonate stabilization, and suppressed conversion, revealing a narrow optimum around 1 wt.% Na. Short-term stability testing demonstrates steady conversion and product selectivity for both unpromoted and Na-promoted catalysts, with the latter maintaining markedly higher CO 2 selectivity. Although Pt/YSZ retains far superior intrinsic activity at ~10× higher space velocity, Ag offers a cost-advantaged alternative where lower cost metals are desirable. Collectively, these findings show that Na promotion enables tunable MSR selectivity on Ag/m-ZrO 2 by directing formate decomposition toward the CO 2 -forming pathway.

CO2 selectivity↗

NREL's Capabilities in Algae-Based Chemicals, Polymers, and Fuels

NREL is advancing research and development (R&D) to maximize photosynthetic carbon capture into biomass for conversion to a broad portfolio of valuable products. Areas of focus include: (1) Carbon capture improvement through photosynthesis engineering; (2) Biotechnology and genetic toolbox development for broad species portfolio; (3) Conversion and fractionation of algal biomass to create high-value products and fuels; (4) Biological seaweed conversion to volatile fatty acids as fuel and product feedstocks; (5) Novel polyurethane production synthesis from fully renewable algae-based feedstocks; (6) Advanced analytical characterization of biomass feedstocks; and (7) Process techno-economic and life cycle modeling.

algae↗

Getting to Neutral: Options for Negative Carbon Emissions in California

This report is an assessment of negative emissions pathways - ones that physically remove CO 2 from the atmosphere - that can help California achieve carbon neutrality by 2045, or sooner. It integrates original research findings with current published research on three main pillars of negative emissions: natural and working lands, carbon capture from biomass conversion to fuels, and direct air capture. The focus and scope of this report is unique: it only addresses practices and technologies for removing carbon dioxide from the air. It also encompasses the entire breadth of strategies, from land management to the latest technological options, and it evaluates the cost of every step of the solution, from waste biomass collection to carbon dioxide transport and geologic storage. The methods are intended to be transparent; details of the calculations and underlying data are included in the report body and appendices. This study intentionally avoids any discussion of policies and does not include current incentives; it provides a range of options, tradeoffs and costs that can be used to inform future policies. The key finding of this report is that carbon neutrality is achievable.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Hybrid biological-chemical strategy for converting polyethylene into a recyclable plastic monomer using engineered Corynebacterium glutamicum

Converting polyethylene (PE) into valuable materials, particularly ones that are better for the environment than the incumbent plastics, not only helps mitigate environmental issues caused by plastic waste but also alleviates the long-standing problem of microbial fermentation competing with food supplies. However, the inherent robustness of PE due to its strong carbon-carbon bonds and high molecular weight necessitates harsh decomposition conditions, resulting in diverse decomposition outcomes that present significant challenges for downstream applications, especially for bioconversion. In this study, we demonstrate a hybrid biological-chemical conversion process for PE, converting its decomposition products, namely short-chain diacids, into a monomer, β-keto-δ-lactone (BKDL), for highly recyclable polydiketoenimine plastics using engineered Corynebacterium glutamicum. Since BKDL synthesis requires a substantial supply of malonyl-CoA, we employed an alternative biosynthesis pathway that leverages C. glutamicum's natural proficiency in amino acid production. We optimized this pathway in vivo by minimizing carbon loss to CO2 and byproducts, improving the transporter system, and maximizing co-factor regeneration. Furthermore, we co-optimized the PE deconstruction process to produce predominantly C4 to C6 diacids and integrated three catabolic pathways into the engineered strain to enhance diacid utilization, maximizing the carbon conversion from PE. Finally, an engineered polyketide synthase was introduced into C. glutamicum to enable BKDL synthesis. This work demonstrates the potential of a chemo-biological hybrid strategy for recycling plastic waste, highlighting its promise in addressing environmental challenges and promoting sustainable materials.

Zhan, Chunjun↗

Future bioenergy expansion could alter carbon sequestration potential and exacerbate water stress in the United States

The maximum future projected bioenergy expansion potential, in scenarios limiting warming to 2°C or below, is equivalent to half of present-day croplands. We quantify the impacts of large-scale bioenergy expansion against re/afforestation, which remain elusive, using an integrated human-natural system modeling framework with explicit representation of perennial bioenergy crops. The end-of-century net carbon sequestration due to bioenergy deployment coupled with carbon capture and storage largely depends on fossil fuel displacement types, ranging from 11.4 to 31.2 PgC over the conterminous United States. These net carbon sequestration benefits are inclusive of a 10 PgC carbon release due to land use conversions and a 2.4 PgC loss of additional carbon sink capacity associated with bioenergy-driven deforestation. Moreover, nearly one-fourth of U.S. land areas will suffer severe water stress by 2100 due to either reduced availability or deteriorated quality. These broader impacts of bioenergy expansion should be weighed against the costs and benefits of re/afforestation-based strategies.

09 BIOMASS FUELS↗

Microwave Catalysis for Process Intensified Modular Production of Carbon Nanomaterials from Natural Gas

The objective of this project was to develop a novel, low-cost process intensified modular process to directly convert flare gas or stranded gas to carbon nanomaterials and co-product hydrogen (H 2 ) with high conversion, selectivity, and stability. The proposed project was based on our exciting exploratory research on a patent pending technology for one-step conversion of natural gas to carbon nanotubes (CNTs) and carbon fibers (CNFs) without emitting CO 2 : CH 4 → H 2 + C (CNT, Carbon Fibers).

03 NATURAL GAS↗

Comparative study of three yttrium organometallic compounds for the stabilization of the cubic phase in YSZ deposited by PE-CVD

In this work, the efficiencies of three organometallic yttrium precursors used to produce YSZ coatings by plasma-enhanced chemical vapor deposition were studied. Yttrium (III) acetylacetonate, Y (acac) 3 , yttrium (III) hexafluoroacetylacetonate, Y (acacF 6 ) 3 , and yttrium (III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), Y (tmhd) 3 , were used to stabilize the cubic phase in zirconia deposited at temperatures from 500 to 800 °C. Our results showed that at temperatures between 500 and 600 °C, Y (tmhd) 3 appeared to be the most efficient dopant as it introduced the highest concentration of yttria (1–2.7 mol%) with only 6.4–5.6 at.% carbon. However, at 700 and 800 °C, Y (acac) 3 introduced twice as much yttria (8–15 mol%) as Y (tmhd) 3 with almost the same amount of carbon (5.4–3 at.%). Conversely, Y (acacF6)3 was the least efficient as it maintained a low concentration of yttria of around 0.7–1.8 mol% with 3.6–8.2 at.% carbon for all the deposition temperatures. Among these precursors, only Y (acac) 3 surpassed 8 mol% yttria and achieved a fully stabilized cubic phase at 800 °C, with the remaining samples stabilizing only the tetragonal phase. The tetragonal phase was stabilized due to the formation of crystallites of around 10 nm. The observed difference in the efficiency of the three precursors was correlated to important differences in their decomposition behavior as observed by mass spectrometry and thermogravimetry/differential scanning calorimetry.

36 MATERIALS SCIENCE↗

High-yield growth kinetics and spatial mapping of single-walled carbon nanotube forests at wafer scale

Emerging commercial applications of vertically aligned, single-walled carbon nanotube (SWCNT) “forests” require synthesis that minimizes nanotube diameter while maximizing number density across substrate areas exceeding centimeter scale. To address this need, we synthesized SWCNT forests on full silicon wafers with notable reproducibility and uniformity, and co-optimized growth for small diameters and high densities across large areas to access new territory in this 3D parameter space. We mapped the spatial uniformity of key structural features using Raman microscopy, synchrotron X-ray scattering, and Rutherford backscattering spectrometry. Low C 2 H 2 flux over sub-nm Fe/Mo catalysts produced small-diameter SWCNTs (2.1 nm) at high number densities (2.26 × 10 12 cm -2 ) on wafers up to 6 in. Although removing Mo resulted in larger SWCNT diameters and lower densities (<0.7 × 10 12 cm -2 ), mass conversion rates from C 2 H 2 to SWCNT product were high and remarkably invariant for catalyst compositions and densities (i.e., 47.7% or 1.30 × 10 6 % g-catalyst -1 on 4-in. wafers). These carbon conversion efficiencies far exceed typical benchtop reactors and are on par with the best reported literature values. Our detailed elucidation of correlations among structural characteristics within this resource-efficient process is expected to guide future scale-up efforts of SWCNT forest growth beyond wafer scale.

36 MATERIALS SCIENCE↗

Long-Range Metal–Sorbent Interactions Determine CO 2 Capture and Conversion in Dual-Function Materials

Carbon capture and utilization involve multiple energy- and cost-intensive steps. Dual-function materials (DFMs) can reduce these demands by coupling CO 2 adsorption and conversion into a single material with two functionalities: a sorbent phase and a metal for catalytic CO 2 conversion. The role of metal catalysts in the conversion process seems salient from previous work, but the underlying mechanisms remain elusive and deserve deeper investigation to achieve maximum utilization of the two phases. Here, for this work, preformed colloidal Ru nanoparticles were deposited onto a “NaOx”/Al 2 O 3 sorbent to prepare prototypical DFMs with controlled phases for CO 2 capture and hydrogenation to CH 4 . Ru addition was found to double the high-temperature CO 2 adsorption capacity by activating the “NaOx”/Al 2 O 3 sorbent phase during a reductive pretreatment step. Most importantly, low Ru loadings were sufficient to ensure maximum CO 2 adsorption and conversion. This was attributed to the key role of the metal–sorbent interactions, wherein Ru was required to hydrogenate strongly bound CO 2 on the “NaO x ”/Al 2 O 3 sorbent to CH 4 via the H 2 activated on Ru. This interaction facilitated rate-determining carbonate migration and subsequent hydrogenation at the metal–sorbent interface. Overall, Ru controlled the CO 2 hydrogenation reaction rate, while the “NaO x ”/Al 2 O 3 sorbent dictated the CO 2 uptake capacity. By controlling metal–sorbent interactions at the molecular level, we demonstrate the critical role of the two phases and their synergy, facilitating the design of DFMs with maximum CO 2 capture and conversion efficiency.

carbon capture↗

Valorization of CO 2 through lithoautotrophic production of sustainable chemicals in Cupriavidus necator

Coupling recent advancements in genetic engineering of diverse microbes and gas-driven fermentation provides a path toward sustainable commodity chemical production. Cupriavidus necator H16 is a suitable species for this task because it effectively utilizes H 2 and CO 2 and is genetically tractable. Here, we demonstrate the versatility of C. necator for chemical production by engineering it to produce three products from CO 2 under lithotrophic conditions: sucrose, polyhydroxyalkanoates (PHAs), and lipochitooligosaccharides (LCOs). We engineered sucrose production in a co-culture system with heterotrophic growth 30 times that of WT C. necator. We engineered PHA production (20-60% DCW) and selectively altered product composition by combining different thioesterases and phaCs to produce copolymers directly from CO 2 . And, we engineered C. necator to convert CO 2 into the LCO, a plant growth enhancer, with titers of ~1.4 mg/L—equivalent to yields in its native source, Bradyrhizobium. Here, we applied the LCOs to germinating seeds as well as corn plants and observed increases in a variety of growth parameters. Taken together, these results expand our understanding of how a gas-utilizing bacteria can promote sustainable production.

09 BIOMASS FUELS↗

Rainforest-to-pasture conversion stimulates soil methanogenesis across the Brazilian Amazon

The Amazon rainforest is a biodiversity hotspot and large terrestrial carbon sink threatened by agricultural conversion. Rainforest-to-pasture conversion stimulates the release of methane, a potent greenhouse gas. The biotic methane cycle is driven by microorganisms; therefore, this study focused on active methane-cycling microorganisms and their functions across land-use types. We collected intact soil cores from three land use types (primary rainforest, pasture, and secondary rainforest) of two geographically distinct areas of the Brazilian Amazon (Santarém, Pará and Ariquemes, Rondônia) and performed DNA stable-isotope probing coupled with metagenomics to identify the active methanotrophs and methanogens. At both locations, we observed a significant change in the composition of the isotope-labeled methane-cycling microbial community across land use types, specifically an increase in the abundance and diversity of active methanogens in pastures. We conclude that a significant increase in the abundance and activity of methanogens in pasture soils could drive increased soil methane emissions. Furthermore, we found that secondary rainforests had decreased methanogenic activity similar to primary rainforests, and thus a potential to recover as methane sinks, making it conceivable for forest restoration to offset greenhouse gas emissions in the tropics. These findings are critical for informing land management practices and global tropical rainforest conservation.

59 BASIC BIOLOGICAL SCIENCES↗

Conversion of marginal land into switchgrass conditionally accrues soil carbon but reduces methane consumption

Abstract Switchgrass is a deep-rooted perennial native to the US prairies and an attractive feedstock for bioenergy production; when cultivated on marginal soils it can provide a potential mechanism to sequester and accumulate soil carbon (C). However, the impacts of switchgrass establishment on soil biotic/abiotic properties are poorly understood. Additionally, few studies have reported the effects of switchgrass cultivation on marginal lands that have low soil nutrient quality (N/P) or in areas that have experienced high rates of soil erosion. Here, we report a comparative analyses of soil greenhouse gases (GHG), soil chemistry, and microbial communities in two contrasting soil types (with or without switchgrass) over 17 months (1428 soil samples). These soils are highly eroded, ‘Dust Bowl’ remnant field sites in southern Oklahoma, USA. Our results revealed that soil C significantly increased at the sandy-loam (SL) site, but not at the clay-loam (CL) site. Significantly higher CO2 flux was observed from the CL switchgrass site, along with reduced microbial diversity (both alpha and beta). Strikingly, methane (CH4) consumption was significantly reduced by an estimated 39 and 47% at the SL and CL switchgrass sites, respectively. Together, our results suggest that soil C stocks and GHG fluxes are distinctly different at highly degraded sites when switchgrass has been cultivated, implying that carbon balance considerations should be accounted for to fully evaluate the sustainability of deep-rooted perennial grass cultivation in marginal lands.

54 ENVIRONMENTAL SCIENCES↗

Synthesis of Carbohydrates from Methanol Using Electrochemical Partial Oxidation over Palladium with the Integrated Formose Reaction

Electrochemically derived multicarbon products are a golden target for valorization of captured carbon dioxide due to the potential of turning a waste product into useful commodity chemicals with renewable energy sources. As a tantalizing approach toward their synthesis, the formose reaction utilizes catalytic condensation of formaldehyde to generate carbohydrates. Furthermore, while a sustainable approach to artificial carbohydrate production through electrochemical generation of formaldehyde is desirable, to date, it has not been fully realized. Here, we study the electrocatalytic conversion of methanol to formaldehyde on palladium with faradaic efficiency of over 90% at 0.9 V vs Ag/AgCl and with the partial current density of nearly 3 mA cm -2 at 1.6 V vs Ag/AgCl. We observe the concurrent generation of palladium oxides as a consequence of the high overpotentials employed, which may partially explain the higher selectivity toward the partial oxidation product. Moreover, we demonstrate that formaldehyde produced electrochemically from methanol is feasible for formose reactions without the need for further purification, achieving 21-28% carbon conversion to carbohydrates. This process, therefore, represents a potential avenue for the electrochemical generation of formaldehyde and its utilization in generating multicarbon products inaccessible by other electrocatalytic means.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Conversion of cellulose to high-yield glucose in water over sulfonated mesoporous carbon fibers with optimized acidity

The hydrolysis of cellulose to high-yield glucose in water remains challenging owing to the limited acidity and substrate contact of sulfonated carbons. In this study, we report a unique sulfonated mesoporous carbon fiber with optimized acidity prepared by the pyrolysis of FeCl 3 -impregnated wipe fibers followed by acid treatment. The Bronsted acidity (especially for SO 3 H) was produced by sulfonation of the magnetic carbon fiber intermediate, while Lewis acidity originated from small Fe 3 O 4 nanoparticles and the remaining defects. The balanced Bronsted and Lewis acidity combined with hydrophilic functionalities was simultaneously tailored by varying the Fe/wipe fiber (WF) feed ratio and pyrolysis temperature to change the porous structure of the final catalysts. The elaborately fabricated MCF-SO 3 H-20-500 (20% Fe/WF feed ratio and pyrolysis at 500 degrees C) delivered 66.0% glucose yield as cellulose was completely converted. This is the highest glucose yield achieved by the hydrolysis of untreated cellulose in water over a sulfonated carbon catalyst. The optimized Bronsted and Lewis acidity was mainly responsible for the controlled conversion of cellulose to glucose, while the rich hydrophilic functionalities and superior mesoporous structure of the catalyst facilitated contact to cellulose and mass transfer. This investigation will open new avenues to design high-performance carbon sulfoacid catalysts toward cellulose hydrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coal direct chemical looping process: 250 kW pilot-scale testing for power generation and carbon capture

Chemical looping combustion (CLC) is an energy conversion technology that can produce concentrated CO 2 stream without the need for a gas separation step, and thus, has the potential to drastically reduce the energy consumption and cost associated with CO 2 capture in power generation. The coal-direct chemical looping (CDCL) process is a CLC technology that uses a moving bed reducer configuration that can directly consume coal as a feedstock without requiring an upstream gasification step. An integrated 250 kW th CDCL pilot unit using iron-based oxygen carriers was constructed and demonstrated for over 1000 h of testing. The principles for the CDCL pilot unit design and operation are summarized in this article. During the 288-hour continuous operation testing, the CDCL pilot unit achieved >96% coal conversion with a CO 2 purity of >97%. Low carbon carryover into the combustor, i.e. <2%, was also confirmed during the test, which shows the capability of the moving bed reactor to retain and convert coal using the oxygen available on the iron-based oxygen carrier. The results from the pilot unit testing confirms the CDCL concept as a promising coal combustion technology for heat and power generation with CO 2 capture.

10 SYNTHETIC FUELS↗

Plasma technology for lignocellulosic biomass conversion toward an electrified biorefinery

Lignocellulosic biomass conversion to renewable, carbon-neutral materials, fuels, and chemicals is the cornerstone of the transition to a sustainable future bioeconomy. Green energy in the form of electricity needs to be coupled with or substitute conventional thermally driven processes to realize small-scale, economically viable and environmentally friendly biorefineries. Gas discharge plasmas enable the conversion of renewable electric energy, supplied in the form of an electric field, to chemical energy through the formation of a highly reactive environment that can induce several transformations related to agricultural waste valorization processes. Herein, we review the application of plasma technology to lignocellulosic biomass upgrade, aiming to provide the scientific background and technical challenges in this rapidly emerging research field. To bridge the gap between plasma science and biomass valorization technologies, we initially present the technical aspects of plasma reactors related to biomass processing and further discuss the advances in plasma processing for each biomass conversion technology, providing insights into the related plasma chemistry and interaction mechanisms. Here, we first focus on the low and medium-temperature biomass conversion processes, including biomass pretreatment and delignification to promote enzyme or acid-catalyzed hydrolysis to sugars and biomass liquefaction using plasma electrolysis. Then we discuss the high and very high-temperature conversion processes, such as plasma-assisted pyrolysis and gasification to syngas and plasma application to tar removal, combustion, and vitrification. Overall, this review provides knowledge at the interface of plasma science and biomass conversion technology to promote the interaction between the individual communities, which is crucial for the further advancement of the field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗