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At least 1,783 records · Page 99

Continuous Flow Processing of ZIF-8 Membranes on Polymeric Porous Hollow Fiber Supports for CO 2 Capture

We have utilized an environmentally friendly synthesis approach for the accelerated growth of a selective inorganic membrane on a polymeric hollow fiber support for postcombustion carbon capture. Specifically, continuous defect-free ZIF-8 thin films were grown and anchored using continuous flow synthesis on the outer surface of porous supports using water as solvent. These membranes demonstrated CO 2 permeance of 22 GPU and the highest reported CO 2 /N 2 selectivity of 52 for a continuous flow synthesized ZIF-8 membrane.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced Polymer Crystallinity in Mixed-Matrix Membranes Induced by Metal–Organic Framework Nanosheets for Efficient CO 2 Capture

The design and fabrication of novel mixed-matrix membranes (MMMs) with simultaneously enhanced gas permeability and selectivity are highly sought for the industrial deployment of membrane technology for large-scale CO 2 capture and storage. Conventional isotropic bulky particle fillers often exhibit limited interfacial compatibility that eventually leads to significant selectivity loss in MMMs. Here, we report the incorporation of chemically stable metal organic framework (MOF) nanosheets into a highly permeable polymer matrix to prepare defect-free MMMs. MOF nanosheets are homogeneously dispersed within the polymer matrix, owing to their high aspect ratios that improve the polymer filler integration. The strong hydrogen bonding and pi-pi interactions between the two components not only enhance the interfacial compatibility but also favor the efficient polymer chain packing along the surface of MOF nanosheets, leading to enhanced polymer crystallinity as well as size-sieving capability of the membranes. The as-prepared MMMs demonstrate high CO 2 -selective separation performance, good antipressure, and antiaging abilities, thus offering new opportunities in developing advanced membranes for industrial gas separation applications.

36 MATERIALS SCIENCE↗

Trends in Solid Adsorbent Materials Development for CO 2 Capture

A review summarizing trends in materials development for CO 2 adsorption focusing on recent studies is given. Trends in computational investigations along with experimental findings are covered to find promising candidates in light of practical challenges imposed by process economics. Topics covered here include: introduction (climate change, CO 2 emissions mitigation, overview of classical computational CO 2 adsorption studies); CO 2 capture materials (C based materials [activated C {AC}, ordered porous C, C fiber, graphene], SiO 2 /Al 2 O 3 /zeolite [SiO 2 , Al 2 O 3 and nanoclays, zeolite], porous cryst. solids [metal-org. frameworks (MOF) {metal type and open metal sites, functionalized MOF, mol. sieves, MOF computational modeling, MOF databases}, zeolite imidazolate frameworks, covalent org. frameworks and polymers], metal oxides); and conclusions and future perspectives.

36 MATERIALS SCIENCE↗

Silver-Loaded Xerogel Nanostructures for Iodine Capture: A Comparison of Thiolated versus Unthiolated Sorbents

Here this paper describes the development and provides comparisons of thiolated (-SH) and unthiolated Ag-Al-Si-O xerogels for iodine gas capture. These xerogels were produced from alkoxides and then heat-treated at 350 °C to provide mechanical strength for subsequent processing steps. Then, a portion of the xerogels was thiolated using (3-mercaptopropyl)trimethoxysilane. Next, thiolated and unthiolated batches were ion-exchanged in AgNO 3 solutions where Ag + replaced Na + in the gel network on a near 1:1 molar basis. Subsamples of the Ag-exchanged xerogels were subjected to a reduction step in H 2 /Ar to convert Ag + to Ag 0 where the rest of the Ag-exchanged (Ag + ) were not reduced. X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy revealed nanoscale Ag 0 in the Ag + samples despite no active reduction where actively reduced samples had bimodal Ag 0 distribution of ~2-3 nm hexagonal and ~6-7 nm cubic crystallites. Synchrotron X-ray absorption spectroscopy was used to assess the oxidization states of Ag, S, and I within the different xerogel samples. The specific surface areas of the base xerogels decreased as subsequent treatments were performed on the as-made samples, albeit the decreases were smaller than aerogel equivalents of these samples from a previous study. All iodine-loaded Ag-based samples showed a mixture of β-AgI and γ-AgI. Comparisons of iodine-loading results with other Ag-based iodine sorbents show that the thiolated Ag 0 -xerogels in this work have one of the highest iodine-loading capacities (q e ) reported to date in saturated conditions with the thiolated Ag 0 -xerogel showing 522 mg iodine per g of the sorbent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Iodine Capture with Metal-Functionalized Polyacrylonitrile Composite Beads Containing Ag 0 , Bi 0 , Cu 0 , or Sn 0 Particles

The capture of radioiodine from nuclear processes and the mitigation of environmental release are important topic areas of research. Some of the more commonly employed chemisorption-type iodine scavengers reported in the literature are based on metal-exchanged porous sorbents such as Ag-zeolites or metal-functionalized aerogels and xerogels. However, another option is to use zero-valent metals directly that have known high affinities for iodine gas [i.e., I2(g)]. In this study, fine metal particles of Ag0, Bi0, Cu0, and Sn0 were embedded in porous polyacrylonitrile (PAN) substrates at 75 mass% metal loadings within the form of ellipsoidal beads with maximum diameters of ~2–3 mm. These composite beads showed extremely high iodine loadings that are directly related to the metal particle loadings. The X-ray diffraction (XRD) analyses of Ag0, Bi0, Cu0, and Sn0 particles as well as metal-PAN composite beads reacted with iodine gas at 120 ± 1 °C showed phases of AgI, BiI3, CuI, and SnI4, respectively. For the Ag-PAN, Cu-PAN, and Sn-PAN beads, no other crystalline peaks were observed in XRD for unreacted metal or oxidized metals after 48 h in saturated I2(g) at 120 ± 1 °C, whereas unreacted metallic Bi0 was observed within the Bi-PAN composites. However, after a 72 h exposure at 120 ± 1 °C, both the Bi0 particles and the Bi-PAN composites showed full conversion from Bi0 to BiI3 with XRD. Comparisons between mass uptake data and X-ray absorption spectroscopy were used to better understand the phase distribution of the Bi phases present in the Bi-PAN+I composites. The iodine loadings (mg iodine per g sorbent, or qe) for these materials were 1120 (Ag-Particle), 1382 (Bi-Particle-72h), 1033 (Cu-Particle), 3000 (Sn-Particle), 753 (Ag-PAN), 1012 (Bi-PAN-72h), 1457 (Cu-PAN), and 1669 (Sn-PAN). It is possible that inexpensive sorbents such as these could be deployed to help limit or prevent release of radioiodine to the environment.

36 MATERIALS SCIENCE↗

Bicarbonate-Carbonate Selectivity through Nanofiltration for Direct Air Capture of Carbon Dioxide

Direct air capture (DAC) of carbon dioxide is one approach among many proposed that is capable of offsetting hard-to-avoid emissions. In previous work, we developed the alkalinity concentration swing (ACS) method, which is driven through concentrating an alkaline solution that has been loaded with atmospheric CO 2 by desalination technologies, such as reverse osmosis or capacitive deionization. Though the ACS is promising in terms of energy usage and implementation, its absorption rate and water requirements are infeasible for a large-scale DAC process. Here, we propose an improvement on the ACS, the bicarbonate-enriched alkalinity concentration swing (BE-ACS), which selects bicarbonate ions from a stream of aqueous alkaline solution that has absorbed atmospheric CO 2 . The bicarbonate-rich stream is then concentrated, which greatly increases its CO 2 partial pressure, and then CO 2 is extracted from solution. We experimentally investigate the use of pressure-driven nanofiltration (NF) membrane-based separation to select bicarbonate ions over carbonate ions. We screen commercial membranes and select one high-performance membrane for detailed studies, quantifying its bicarbonate-carbonate selectivity factor and bicarbonate-passage factor. Feed pH, the combined concentration of aqueous CO 2 , bicarbonate, and carbonate species (or dissolved inorganic carbon), alkalinity, and permeation flux are systematically varied to study NF separation properties. We find that the selectivity factor, which exceeds 30 times in certain regimes, increases with higher feed pH and higher alkalinity. Lastly, the performance metrics of the selected NF membrane are input into a theoretical BE-ACS cycle analysis, and the required energy input and cycle capacity output are evaluated. Ideal cycle energy is found to be as low as around 250 kJ/mol, with opportunities identified for further decreases through process engineering and forward osmosis energy recovery.

animal feed↗

Ultrafast carrier capture and Auger recombination in single GaN/InGaN multiple quantum well nanowires

Ultrafast optical microscopy is an important tool for examining fundamental phenomena in semiconductor nanowires with high temporal and spatial resolution. In this paper, we used this technique to study carrier dynamics in single GaN/InGaN core–shell nonpolar multiple quantum well nanowires. We find that intraband carrier–carrier scattering is the main channel governing carrier capture, while subsequent carrier relaxation is dominated by three-carrier Auger recombination at higher densities and bimolecular recombination at lower densities. Finally, the Auger constants in these nanowires are approximately 2 orders of magnitude lower than in planar InGaN multiple quantum wells, highlighting their potential for future light-emitting devices.

36 MATERIALS SCIENCE↗

Incorporating Diurnal and Meter-Scale Variations of Ambient CO 2 Concentrations in Development of Direct Air Capture Technologies

To be implemented on climate-relevant scales, direct air capture of CO 2 (DAC) will require large capital-intensive facilities and careful attention to cost minimization. In making decisions among potential sites for DAC facilities, all of the factors that will impact process cost and efficiency should be considered. In this paper we focus on a factor that has previously received little attention in the DAC community, namely variations in atmospheric conditions on hourly time scales and length scales of meters. We present data curated from extensive previous studies of biosphere-atmosphere fluxes with observations of CO 2 concentration, temperature, and relative humidity (RH) with hourly resolution from many sites in North America. These include locations where typical diurnal variations in CO 2 concentration during summer months exceeds 150 ppm. These variations are larger than the seasonal variations that exist between averaged CO 2 concentrations in winter and summer, and they are highly correlated with diurnal variations in temperature and RH. Diurnal variations are dependent on the height above ground at which CO 2 concentrations are measured, with smaller variations existing at heights of 10 m or more than at ground level. We illustrate the potential implications of these short-term variations for the operation and optimization of a DAC process with process-level calculations for a specific adsorption-based process using amine-rich adsorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Methodology for Phased Development of a Hypothetical Pipeline Network for CO 2 Transport during Carbon Capture, Utilization, and Storage

If implemented on a commercial scale, carbon capture, utilization, and storage (CCUS) has the potential to significantly reduce carbon dioxide (CO 2 ) emissions. Moving the CO 2 from the point sources to the geologic storage locations will likely require a pipeline network. The Plains CO 2 Reduction (PCOR) Partnership developed a four-step methodology that can be used to estimate the length, cost, and time frame of a hypothetical pipeline network that would be built in phases. The methodology was tested during a case study in which a hypothetical phased pipeline network was estimated for the PCOR Partnership region. The hypothetical pipeline network consisted of trunk lines roughly 10 780 km in total length that could provide an overall CO 2 reduction for the region of about 555.6 Mtonnes of CO 2 /year by 2050. Furthermore, the results also indicate that an extensive pipeline network may not be required to transport to storage locations the quantity of CO 2 required to meet the emission reduction targets for the PCOR Partnership region.

54 ENVIRONMENTAL SCIENCES↗

Reversible capture and release of Cl 2 and Br 2 with a redox-active metal–organic framework

Extreme toxicity, corrosiveness, and volatility pose serious challenges for the safe storage and transportation of elemental chlorine and bromine, which play critical roles in the chemical industry. Solid materials capable of forming stable nonvolatile compounds upon reaction with elemental halogens may partially mitigate these challenges by allowing safe halogen release on demand. Here we demonstrate that elemental halogens quantitatively oxidize coordinatively unsaturated Co(II) ions in a robust azolate metal-organic framework (MOF) to produce stable and safe-to-handle Co(III) materials featuring terminal Co(III)-halogen bonds. Thermal treatment of the oxidized MOF causes homolytic cleavage of the Co(III)-halogen bonds, reduction to Co(II), and concomitant release of elemental halogens. The reversible chemical storage and thermal release of elemental halogens occur with no significant losses of structural integrity, as the parent cobaltous MOF retains its crystallinity and porosity even after three oxidation/reduction cycles. Finally, these results highlight a material operating via redox mechanism that may find utility in the storage and capture of other noxious and corrosive gases.

36 MATERIALS SCIENCE↗

Aqueous Carbon Capture Using Guanidinium-Functionalized Hollow Fiber Sorbent Contactors

As part of the growing suite of technologies aimed at combatting rising temperatures, negative emissions technologies have become a powerful tool in the global effort to minimize the consequences of human-induced climate change. Among these, carbon removal from aqueous sources, which contain much higher carbon concentrations than the atmosphere, remains largely unexplored. Indeed, developing robust and efficient carbon capture materials for usage in complex aqueous environments remains a significant challenge. Here, we explore the potential of functionalizing polyvinylidene fluoride (PVDF) hollow fiber contactors grafted with a guanidinium-derived polymer sorbent for carbon removal from aqueous sources, including saline waters. Computational screening against amine-based analogs is utilized to identify guanidinium as a promising motif for bicarbonate (HCO 3 – ) ions binding. To leverage this finding, synthesis of a guanidinium polymer and subsequent covalent grafting onto PVDF hollow fibers is employed to structured polymer–sorbent–grafted hollow fiber contactors. Our prototype achieves an initial HCO 3 – removal of 34% with an increase to 98% after four cycles. The functionalized fibers demonstrate aqueous stability over 13 adsorption/desorption cycles in model NaHCO 3 solutions where regeneration is facilitated by a mild pH swing. Importantly, the system maintains selective performance in the presence of competitive chloride ions over multiple cycles; carbon removal remained above 10% even at high (10:1) NaCl/NaHCO 3 ratios. These findings demonstrate the feasibility of sorbent-based aqueous carbon removal and highlight its potential as a promising approach for negative emissions.

carbon capture↗

Environmental trade-offs of direct air capture technologies in climate change mitigation toward 2100

Abstract Direct air capture (DAC) is critical for achieving stringent climate targets, yet the environmental implications of its large-scale deployment have not been evaluated in this context. Performing a prospective life cycle assessment for two promising technologies in a series of climate change mitigation scenarios, we find that electricity sector decarbonization and DAC technology improvements are both indispensable to avoid environmental problem-shifting. Decarbonizing the electricity sector improves the sequestration efficiency, but also increases the terrestrial ecotoxicity and metal depletion levels per tonne of CO 2 sequestered via DAC. These increases can be reduced by improvements in DAC material and energy use efficiencies. DAC exhibits regional environmental impact variations, highlighting the importance of smart siting related to energy system planning and integration. DAC deployment aids the achievement of long-term climate targets, its environmental and climate performance however depend on sectoral mitigation actions, and thus should not suggest a relaxation of sectoral decarbonization targets.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Large-scale spatially explicit analysis of carbon capture at cellulosic biorefineries

The large-scale production of cellulosic biofuels would involve spatially distributed systems including biomass fields, logistics networks and biorefineries. Better understanding of the interactions between landscape-related decisions and the design of biorefineries with carbon capture and storage (CCS) in a supply chain context is needed to enable efficient systems. Here we analyse the cost and greenhouse gas mitigation potential for cellulosic biofuel supply chains in the US Midwest using realistic spatially explicit land availability and crop productivity data and consider fuel conversion technologies with detailed CCS design for their associated CO 2 streams. Optimization methods identify trade-offs and design strategies leading to systems with attractive environmental and economic performance. Strategic and operational decisions depend on underlying spatial features and are sensitive to biofuel demand and CCS incentives. US CCS incentives neglect to motivate greenhouse gas mitigation from all supply chain emission sources, which leverage spatial interactions between CCS, electricity prices and the biomass landscape.

09 BIOMASS FUELS↗

Carbon capture turned upside down: high-temperature adsorption & low-temperature desorption (HALD)

Carbon capture & sequestration (CCS) could reduce CO 2 emissions from large fossil-fuel power plants on the short term, but the high energy penalty of the process hinders its industrial deployment. Moreover, the utility of nanoporous materials, known to be selective for the CO 2 /N 2 separation, is drastically reduced due to the competitive adsorption with H 2 O. Taking advantage of the power plant's waste heat to perform CCS while at the same time surmounting the negative effect of H 2 O is therefore an attractive idea. We propose an upside-down approach for CCS in nanoporous materials, high-temperature adsorption & low-temperature desorption (HALD), that exploits the temperature-dependent competitive adsorption of CO 2 and H 2 O. First, we provide a theoretical background for this entropy-driven behavior and demonstrate under what conditions competitive adsorption can be in favor of CO 2 at high temperature and in favor of H 2 O at low temperature. Then, molecular simulations in all-silica MFI provide a proof of concept. The International Zeolite Association database is subsequently screened for potential candidates and finally, the most promising materials are selected using a post-Pareto search algorithm. The proposed post-Pareto approach is able to select the material that shows an optimal combination of multiple criteria, such as CO 2 /H 2 O selectivity, CO 2 /N 2 selectivity, CO 2 uptake and H 2 O uptake. As a conclusion, this work provides new perspectives to reduce the energy requirement for CCS and to overcome the competitive adsorption of H 2 O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct flue gas capture for algae cultivation and subsequent valorization: evaluating life cycle emissions and costs

Algae cultivation and processing is an important pathway under discussion within the broader CO 2 capture and utilization umbrella. Here, we discuss the results of a life-cycle analysis and techno-economic analysis of a pilot-scale photobioreactor that uses flue gas directly from natural gas or biogas combustion at 3–5% CO 2 concentration. The system requires minimal freshwater use as it has been successfully run with industrial wastewater and has a much smaller areal footprint compared with open pond cultivation. Introducing the flue gas directly to the photobioreactor avoids the need for CO 2 separation and pressurization, which is undertaken in many other algae cultivation systems. For the end-use of the biomass, the default case assumes conversion of algae to liquid fuels via hydrothermal liquefaction. The results indicate that the pilot-scale system has a higher cost, and comparable greenhouse gas emissions compared to pond-based systems, especially as the grid is anticipated to evolve to a lower carbon intensity. The costs of algae biofuel production range from $\$12–16$ per GGE at the current pilot scale. Depending on whether the source of the carbon is fossil or biogenic, the net emissions are 68 g CO 2 e per MJ and −4 g CO 2 e per MJ respectively. If the marine algae species is used instead of the freshwater species, it offers an additional 16 g CO 2 e per MJ carbon fixation in the form of calcium carbonate. The findings point to broadly desirable trends in GHG emissions and costs, while the discussion aims to shed light on areas that could further improve the scalability of the system.

20 FOSSIL-FUELED POWER PLANTS↗

Formation of negative hydrogen ion: Polarization electron capture and nonthermal shielding

The influence of the nonthermal shielding on the formation of the negative hydrogen ion (H{sup -}) by the polarization electron capture are investigated in partially ionized generalized Lorentzian plasmas. The Bohr-Lindhard method has been applied to obtain the negative hydrogen formation radius and cross section as functions of the collision energy, de Broglie wave length, Debye length, impact parameter, and spectral index of the plasma. The result shows that the nonthermal character of the plasma enhances the formation radius of the negative hydrogen, especially, for small Debye radii. It is found that the nonthermal effect increases the formation cross section of the negative hydrogen. It is also found that the maximum position of the formation cross section approaches to the collision center with an increase of the spectral index. In addition, it is found that the formation cross section significantly decreases with an increase of the Debye length, especially, for small spectral indices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗