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At least 253 records · Page 14

Water-stable direct air capture of CO 2 with microcapsules of task-specific ionic liquid and their electrothermal regeneration

Microcapsules of the task specific ionic liquid (TSIL) 1-ethyl-3-methylimidazolium 2-cyanopyrrolide [EMIM][2CNpyr] with composite polydimethylsiloxane (PDMS) shells were fabricated for use in CO 2 direct air capture (DAC) conditions. The TSIL was encapsulated using an oil-in-oil emulsion as a templating procedure through two different approaches. In the first approach, a PDMS-polyurea (PU) shell was constructed by interfacial polymerization, while in the second approach, a graphene oxide (GO)-PDMS shell was constructed by cross-linking GO sheets. The composition and structure of both capsule types were fully characterized, and their CO 2 DAC performance was evaluated by gravimetric and breakthrough analysis. Both capsules exhibited competitive capacities, with the PDMS-PU capsules and the GO-PDMS capsules reaching 0.75 mol kg −1 and 0.66 mol kg −1 , respectively. We further demonstrate that both capsule systems can be regenerated with complementary electrothermal methods. Microwave (MW) regeneration was used for the PDMS-PU capsules, effectively releasing absorbed CO 2 in less than an hour. Owing to the electrical conductivity of GO, GO-PDMS capsules were regenerated via radio frequency heating (RF). This work highlights the importance and opportunity of tuning solid–liquid composite performance for advanced applications, including direct air capture of carbon dioxide.

Al-Mahbobi, Luma [Texas A&M University, College St↗

Growth and passivation of individual carbon nanoparticles by C2H2 addition at high temperatures: Dependence of growth rate and evolution on material and size

Absolute kinetics for reactions of C2H2 with a series of ∼60 individual carbon nanoparticles (NPs) from graphite, graphene, graphene oxide, carbon black, diamond, and nano-onion feedstocks were measured for temperatures (TNP) ranging from 1200 to 1700 K. All the NPs were observed to gain mass by carbon addition under conditions that varied with feedstock but with large variations in initial growth rate. Long reaction periods were studied to allow the evolution of growth rates over time to be observed. Diamond NPs were found to passivate against C2H2 addition if heated above ∼1400 K, and the highly variable initial reactivity for carbon nano-onions was found to depend on the presence of non-onion-structure surface carbon. For graphitic and carbon black NPs, three distinct growth modes were observed, correlated with the initial NP mass (Minitial). Smallest graphitic and carbon black NPs, with masses <∼25 MDa, initially grew rapidly but also passivated quickly after adding <4% of Minitial. NPs in the 20–50 MDa range also passivated but only after multiple waves of fast growth separated by periods of low reactivity, with up to ∼11% total mass gain before passivation. The largest carbon black and graphitic NPs, with Minitial >50 MDa, grew rapidly and continuously, adding up to ∼300% of Minitial with no sign of rate slowing as long as C2H2 was present. The efficiencies for C2H2 addition and etching by O2 are strongly correlated, but the correlation changes as the NPs passivate. Growth and passivation mechanisms are discussed.

Chemistry↗

Experimental Images and Videos of Foam Stability (Half-life)

The experimental data obtained in this project is the thermal stability data of various foams measured using the setup established at Temple University during this study. The setup is installed with a portable digital camera which can take images and videos of foam evolution at a given pressure and temperature condition. Consequently, the half-life data was recorded from the images/videos, which are used as a measure of the thermal stability for foams. Over the 3 years of this project, four different surfactants and five different stabilizing agents were studied. The surfactants are, Alfa Olefin Sulfonate (AOS), Sodium Dodecyl Sulphate (SDS), Tergitol (NP-40), and Cetyltrimethylammonium chloride (CTAC). The stabilizing agents are, guar gum, bentonite clay, crosslinking agents, silicon dioxide nanoparticles (60 to 70nm), and graphene oxide dispersions. Foam stability was evaluated at different temperatures between 100C and 200cC, while the foam generation pressure varied between atmospheric pressure (14.7 psi) and 1000 psi. The images are saved as .jpg file and videos are saved as .avi files.

15 GEOTHERMAL ENERGY↗

Resource Recovery and Environmental Protection in Wyoming’s Greater Green River Basin Using Selective Nanostructured Membranes (Final Report)

Produced water (PW) represents a sizable waste stream that is co-generated with oil and natural gas production. In 2021 Wyoming ranked 8th and 9th, respectively in domestic oil and natural gas production. In 2017 Wyoming ranked as the 4th highest generator of PW in the U.S, accounting for 7% of the total volume generated. In the context of being the 3rd most arid state in the U.S., the value of water reuse becomes obvious. PW reuse, and resource recovery, in any form requires some level of treatment to remove particulates, residual (free, dispersed) hydrocarbons, organics, and salts. The level of treatment depends on the requirements of the reuse, or resource recovery, application. PW management systems in Wyoming employ in order of volume of PW managed the following management strategies: reinjection for enhanced oil recovery, surface discharge, deep well injection, evaporation ponds (impoundments), and commercial management/treatment. Complicating treatment efforts are the relatively high concentrations of organics (natural and synthetic), dispersed/free hydrocarbons, benzene-toluene-ethylbenzene, and xylenes (BTEX) compounds, biologicals, salts, and minerals. Hydrocarbons (dispersed/dissolved crude oils) and BTEX compounds, as well as synthetic organics, present economic and environmental concerns. The former represents lost revenue, while the latter results in negative environmental impacts like emissions from surface impoundments. The overall objective of this proposal was to synthesize superhydrophilic/oleophobic and superhydrophobic/oleophilic membranes for selectively concentrating and then separating BTEX compounds and oil and grease (O&G) from PW originating from the Greater Green River Basin (GGRB) in Wyoming. Three specific research aims were pursued to accomplish this overall objective. This final report details the development of the superhydrophobic and superhydrophilic membranes, as well as the design of the membrane module prototypes specifically. The technoeconomic assessment is separately reported in another document. 1. Aim #1 – Material optimization and performance evaluation of superhydrophilic/oleophobic and superhydrophobic/oleophilic membranes made by electrospinning/spraying. 2. Aim #2 – Design and construction of cross-flow membrane modules for selectively concentrating and then separating BTEX/oil from GGRB produced water. 3. Aim #3 – Techno-economic assessment of BTEX/oil recovery, and clean water production, using superhydrophilic/oleophobic and superhydrophobic/oleophilic membrane separation for GGRB PW. Superhydrophobic membranes were synthesized by electrospinning poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibers onto polyester (PET) substrates and electrospraying nano-carbon black/PVDF-HFP onto the nanofibrous layer. These membranes were characterized by high (>8000 liters per square meter per hour per bar (LMH/bar)) permeance values for pure hydrocarbon phases and a high hydrocarbon selectivity (>96%) when treating GGRB PW. All results were obtained when operating the membrane in a crossflow configuration representative of actual field operating conditions. Solvent/oil properties, specifically viscosity and total surface energy/tension, affected permeance across the membrane, which resulted in light mineral oil (394 LMH/bar) and o-xylene (1834 LMH/bar) being characterized by lower permeance values in the pure phase tests. Mixed phase fluxes between 40 to 80 LMH were obtained for the PW when operating the membrane at a feed pressure of 0.3 bar. Flux decreased as the mixed phase concentration in the feed decreased pointing to the importance of maximizing the collision efficiency between the emulsion and the membrane surface and maximizing the emulsion concentration in the feed and the turbulence within the feed channel. These tests demonstrated that the superhydrophobic membranes developed here are a viable hydrocarbon recovery method for GGRB PWs and should be pursued for testing in pilot-scale trials. Superhydrophilic membranes were successfully synthesized via electrospinning/spraying using polyacrylonitrile (PAN) nanofibers as a base nanofibrous matrix. Integration of polyaniline (PANI) into the nanofibrous matrix produced a superior membrane, for water filtration applications, relative to PAN alone and reduced graphene oxide (RGO) when integrated into the nanofibrous matrix. This conclusion was based on the PANI-PAN resistance to flux loss (fouling) when treating model solvent/oil solutions representative of GGRB PWs and field collected PW from the GGRB. The synthesized PAN membranes outperformed a commercially available PAN membrane designed for oil/water separation. This finding indicates that the surface chemical and physical characteristics of the electrospun membranes presents improved properties for filtration of challenging waters like GGRB PWs. The electrospun membranes therefore show promise overall as a substitute for conventionally polymerized membranes in PW treatment applications. The PANI-PAN membrane specifically presents superior performance characteristics for concentration O&G prior to treatment by the hydrocarbon recovery membrane and producing high-quality filtrate for reuse and/or additional treatment (desalination).

02 PETROLEUM↗

Living Filter Designs for In-Line Recovery and Sorting of Critical materials

This project explored “bio-mining” of critical materials from electronic waste (E-waste) streams by developing living filters arrays capable of recovering these materials, focusing on the platinum group metals (PGMs) and rare earth elements (REEs). While highly toxic, E-waste is considered a valuable “urban mine” as it contains critical materials such as PGMs and REEs with orders of magnitude higher purity than the richest ores. The aim of the project was to: (1) develop mechanically robust, silk-based biomaterial filtration membranes that can capture REEs from dilute aqueous waste; (2) design and build 3D bioprinted living filters containing encapsulated electrochemically active bacteria (EAB) capable of bio-reducing PGMs and recovering them from waste streams; and (3) constructing combined living filter arrays using both components to efficiently capture REE and PGM from the same waste stream. The developed silk-based filtration membranes were self-assembled using silk-nanofibrils (SNFs) derived from silkworm (Bombyx mori) cocoons in conjunction with recombinant silk-elastin-like proteins (SELPs), which contained lanthanide-binding peptide tags (LBTs) with a high affinity and specificity towards REEs. These 100% biodegradable protein-based membranes were capable of recovering up to 85% of model REE ions (Tb 3+ ) filtered through the membrane, with ~50% recovery achieved in the presence of high concentrations (100X) of common interfering metals (Ca 2+ , Cu 2+ , Fe 3+ , Zn 2+ ). REE captured by the membranes were easily recovered by applying a low pH desorption buffer. The membranes also demonstrated substantial reusability, with only a 30% loss in binding capacity after 4 cycles of REE binding and recovery. To recover the PGMs, we created a bottom-up assembling strategy to construct a living hydrogel composed of a seamlessly integrated living catalyst, Shewanella loihica PV-4 (PV-4), for metal reduction, and their structural and functional linkers, bio-reduced graphene oxide (B-rGO). This hydrogel demonstrated a close to 90% recovery of model metal ions, Pd, from a simulated e-waste leaching stream with minimum-to-no biomass production. It’s also worth noting that the Pd recovery is initiated immediately after the introduction of living hydrogel, compared to conventional biocarriers that required start-up times within hours to days. Overall, these living hydrogels demonstrated superior bioactivity, structural integrity, and agility over existing biocarriers, which offers extensive opportunities to advance the biological metal recovery with unparallel efficiency, reduced energy/material consumption, and minimal environmental impact.

36 MATERIALS SCIENCE↗

Field Validation of a Pilot-scale Black Liquor Membrane for Water Removal at Ahlstrom-Munksjö Paper Mill in Mosinee, WI

Project Background: The Industrial Technology Validation (ITV) program aims to identify and demonstrate the performance of new, emerging, and underutilized technologies in the industrial sector to help inform decisions towards accelerating commercialization and deployment. Pulp and paper is considered one of the most energy-intensive industries in the manufacturing sector. There are several methodologies for converting wood into pulp in the paper-making industry. The kraft process is a chemical method for producing wood pulp. The kraft process generates black liquor as a byproduct of pulp production. Traditionally, water is evaporated from the liquor by a set of multi-effect evaporators (MEEs), which concentrate weak black liquor (WBL) into strong black liquor (SBL) to support efficient combustion in a recovery boiler. Concentrating black liquor is an energy-intensive step in recovering pulping chemicals and generating high-pressure steam from dissolved wood solids. About 7% of pulp and paper energy usage, or nearly 164 trillion Btu, is used to remove water from black liquor in U.S. kraft pulp mills per year. The U.S. DOE’s IEDO is interested in the black liquor membrane technology evaluated in this report because it offers the potential for a more energy-efficient and less carbon-intensive kraft pulping process across 99 kraft pulp mills in 24 states (Agenda 2020 Technology Alliance 2016). This ITV project validates an innovative black liquor membrane technology for kraft pulp mills to understand its impact and benefits. Via Separations is a technology vendor that developed a graphene oxide membrane system to remove water from WBL before entering the evaporator set. High-pressure positive displacement (HPR) pumps move the black liquor through membranes that separate water and create a more concentrated black liquor. The vendor claims their pre-commercial technology reduces evaporator steam consumption by dewatering WBL before entering the evaporators. They also claim their technology has non-energy benefits such as enhanced soap collection and improved pulp throughput. This evaluation focuses on validating the energy and carbon dioxide (CO 2 e) emissions benefits associated with the membrane system.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Transformational Nano-confined Ionic Liquid Membrane for Greater than or Equal to 97 Percent Carbon Dioxide Capture from Natural Gas Combined Cycle Flue Gas

A transformational process based on nano-confined ionic liquid (NCIL) membranes was developed for capturing ≥97% CO 2 from natural gas combined cycle (NCCC) flue gas. The NCIL membranes were prepared by loading amino acid ionic liquid into a framework composed of single-walled carbon nanotube mesh filled with graphene oxide quantum dots. The membranes exhibited CO 2 permeance as high as 2,000 GPU with a CO 2 /N2 selectivity of 2,300 for a typical NGCC flue gas composition. When H 2 O vapor sweep was applied in the permeate side, 96.6% CO2 dry-basis purity and 97.6% CO 2 capture rate were achieved for a simulated NGCC flue gas with single stage. In the process design, a highly H 2 O-selective membrane would be needed to recover majority of the H 2 O vapor, and the recovered H 2 O vapor could be recycled to the permeate side of the NCIL membrane. Sulfonated poly(ether ether ketone) membranes were successfully developed for this purpose. These membranes exhibited H 2 O permeance great than 11,000 GPU and H 2 O/CO 2 selectivity greater than 1,000 at 70ºC for a feed mixture consisting of 14.5 vol% H2O and balanced CO 2 . A standalone membrane model using MATLAB platform was developed for process simulation. The model was validated with experimental data. Techno-economic analysis based on the testing data collected during the current program suggests this transformational membrane process can achieve 97% CO 2 capture efficiency with a cost of $47.8/tonne of CO 2 , which is a 21% reduction versus DOE’s reference case B31B.97.

03 NATURAL GAS↗

Multiplexed Anodic Stripping Voltammetry Detection of Heavy Metals in Water Using Nanocomposites Modified Screen-Printed Electrodes Integrated With a 3D-Printed Flow Cell

In this study, we present multiplexed anodic stripping voltammetry (ASV) detection of heavy metal ions (HMIs)—As(III), Cd(II), and Pb(II)—using a homemade electrochemical cell consisting of dual working, reference and counter screen-printed electrodes (SPE) on polyimide substrate integrated with a 3D-printed flow cell. Working and counter electrodes were fabricated by the screen-printing of graphite paste while the Ag/AgCl paste was screen-printed as a reference electrode (Ag/AgCl quasi-reference electrode). The working electrodes were modified with (BiO) 2 CO 3 -reduced graphene oxide (rGO)-Nafion [(BiO) 2 CO 3 -rGO-Nafion] and Fe 3 O 4 magnetic nanoparticles (Fe 3 O 4 MNPs) decorated Au nanoparticles (AuNPs)-ionic liquid (IL) (Fe 3 O 4 -Au-IL) nanocomposites separately to enhance HMIs sensing. Electrochemical detection was achieved using square wave ASV technique. The desired structure of the flow electrochemical cell was optimized by the computational fluid dynamic (CFD). Different experimental parameters for stripping analysis of HMIs were optimized including deposition time, deposition potential and flow rate. The linear range of calibration curves with the sensing nanocomposites modified SPE for the three metal ions was from 0–50 μg/L. The limits of detection (S/N = 3) were estimated to be 2.4 μg/L for As(III), 1.2 μg/L for Pb(II) and 0.8 μg/L for Cd(II). Furthermore, the homemade flow anodic stripping sensor platform was used to detect HMIs in simulated river water with a 95–101% recovery, indicating high selectivity and accuracy and great potential for applicability even in complex matrices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

From Pollutant Removal to Renewable Energy: MoS2-Enhanced P25-Graphene Photocatalysts for Malathion Degradation and H2 Evolution

The widespread presence of pesticides—especially malathion—in aquatic environments presents a major obstacle to conventional remediation strategies, while the ongoing global energy crisis underscores the urgency of developing renewable energy sources such as hydrogen. In this context, photocatalytic water splitting emerges as a promising approach, though its practical application remains limited by poor charge carrier dynamics and insufficient visible-light utilization. Herein, we report the design and evaluation of a series of TiO2-based ternary nanocomposites comprising commercial P25 TiO2, reduced graphene oxide (rGO), and molybdenum disulfide (MoS2), with MoS2 loadings ranging from 1% to 10% by weight. The photocatalysts were fabricated via a two-step method: hydrothermal integration of rGO into P25 followed by solution-phase self-assembly of exfoliated MoS2 nanosheets. The composites were systematically characterized using X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), UV-Vis diffuse reflectance spectroscopy (DRS), and photoluminescence (PL) spectroscopy. Photocatalytic activity was assessed through two key applications: the degradation of malathion (20 mg/L) under simulated solar irradiation and hydrogen evolution from water in the presence of sacrificial agents. Quantification was performed using UV-Vis spectroscopy, gas chromatography–mass spectrometry (GC-MS), and thermal conductivity detection (GC-TCD). Results showed that the integration of rGO significantly enhanced surface area and charge mobility, while MoS2 served as an effective co-catalyst, promoting interfacial charge separation and acting as an active site for hydrogen evolution. Nearly complete malathion degradation (~100%) was achieved within two hours, and hydrogen production reached up to 6000 µmol g−1 h−1 under optimal MoS2 loading. Notably, photocatalytic performance declined with higher MoS2 content due to recombination effects. Overall, this work demonstrates the synergistic enhancement provided by rGO and MoS2 in a stable P25-based system and underscores the viability of such ternary nanocomposites for addressing both environmental remediation and sustainable energy conversion challenges.

Chemistry↗

Facilitated Transport Membranes with Tunable Amine-CO 2 Chemistry for CO 2 /H 2 Separation

CO 2 -selective, amine-containing facilitated transport membranes are of great interest for syngas purification since high-pressure H 2 can be retained upon CO 2 removal. A variety of amine-containing polymers have shown decent chemical and thermal stability at aggressive conditions, but their CO 2 /H 2 separation properties are largely limited by the hydrostatic compaction and severe carrier saturation associated with the high syngas pressure. Herein, we report a new approach to enhance the CO 2 permeability by manipulating the steric hindrance of the amine carriers. A series of α-aminoacids with different alkyl or hydroxyethyl substituents are deprotonated by 2-(1-piperazinyl)ethylamine, leading to nonvolatile amine carriers with different degrees of steric hindrance. For hosting the low MW amine carriers, a highly crosslinked poly(vinyl acetal) is synthesized as a water-swellable polymer network. In order to avoid membrane compaction, perforated graphene oxide mono-sheets are dispersed as reinforcement fillers. In the presence of moisture, a bulkier alkyl substituent to the amino site (increasing steric hindrance) destabilizes the carbamate adduct and thus drastically increases the chemisorption of CO 2 , while the incorporation of ethylene oxide groups provides additional physisorption of CO 2 . The enhanced CO 2 solubility significantly mitigates the carrier saturation behavior, and an unprecedented CO 2 /H 2 selectivity greater than 100 is demonstrated at 107 °C and 12.5 atm of CO 2 partial pressure. As the CO 2 partial pressure reduces to 0.4 atm, a less hindered amine yields a higher reactive diffusivity of CO 2 , resulting in a CO 2 permeance of 435 GPU with a selectivity greater than 500. These reaction-mediated polymeric membranes are well above the theoretical upper bound, and they are of great interest for designing a highly-selective membrane process for syngas purification.

08 HYDROGEN↗

High-Temperature Stability of Aqueous Foams as Potential Waterless Hydrofracking Fluid for Geothermal Reservoir Stimulation

Hydraulic fracturing is the process of fracturing rock formations with high-pressure water-based fluids. In Enhanced Geothermal Systems (EGS) hydraulic fracturing is carried out by injecting high-pressure fluids into the Hot Dry Rocks (HDR) under carefully controlled conditions. The fluid used for fracturing is an important component for EGS, not only concerning the technical approch but also environmental impact. Recent research has been carried out to develop waterless fracturing technologies for EGS, including foam-based hydrofracking, where foams are mixtures of gas and liquid fluids. Foam fracturing fluids have potential benefits over water-based fluids because of less water consumption, less damage in water sensitive formations, and less liquid to recover and handle after fracturing process. One challenge for implementing foam fracturing in EGS is to achieve stable foams at high temperatures, as the foam stability tends to decay with increase in temperature.This research is focused on investigating the stability of foams at high temperatures. Preliminary results show that 1) N2 foams are more stable compared to CO2 foams, 2) foams containing only surfactants were not stable at high temperatures, and 3) addition of different stabilizing agents increased the thermal stability of all the foams. It was observed that different stabilizing agents interacted differently with anionic, nonionic, and cationic surfactants. It was further shown that the crosslinking agent with a base solution of pH 6 and graphene oxide dispersion was the most effective stabilizing agent for anionic surfactant AOS, while bentonite clay effectively enhanced thermal stability for another anionic surfactant SDS. SiO2 nanoparticles showed limited improvement in thermal stability at high temperatures compared to other stabilizing agents.

Thakore, Virensinh↗

System and method for cooling using a heat exchanger having a membrane

A heat exchanger that includes a membrane of graphene oxide is disclosed, as is a heat exchange system employing such a heat exchanger. The heat exchanger permits the use of water from non-traditional sources, such as waste water, brackish and sea water, in a cooling loop. Clean water and sensible heat permeate through the membrane, simultaneously cooling and purifying water in the cooling loop.

42 ENGINEERING↗

Method of manufacturing a three-dimensional carbon structure

The present invention is directed to a method of manufacturing a three-dimensional carbon structure. The method requires graphene layers and/or graphene oxide layers. The layers can be provided such that they correspond to the cross-section of a pre-defined shape. In this regard, the method of the present invention can be employed to manufacture a three-dimensional carbon structure having a custom shape.

36 MATERIALS SCIENCE↗