National Energy Technology Laboratory

Carbon capture and storage (CCS) is vital to climate change mitigation, and has application across the economy, in addition to facilitating atmospheric carbon dioxide removal resulting in emissions offsets and net negative emissions. This contribution reviews the state-of-the-art and identifies key challenges which must be overcome in order to pave the way for its large-scale deployment.

For the past three decades, discussion of naturally-occurring gas hydrates has been framed by a series of assessments that indicate enormous global volumes of methane present within gas hydrate accumulations. At present, these estimates continue to range over several orders of magnitude, creating great uncertainty in assessing those two gas hydrate issues that relate most directly to resource volumes – gas hydrate’s potential as an energy resource and its possible role in ongoing climate change. However, a series of recent field expeditions have provided new insights into the nature of gas hydrate occurrence; perhaps most notably, the understanding that gas hydrates occur in a wide variety of geologic settings and modes of occurrence. These fundamental differences - which include gas hydrate concentration, host lithology, distribution within the sediment matrix, burial depth, water depth, and many others - can now be incorporated into evaluations of gas hydrate energy resource and environmental issues. With regard to energy supply potential, field data combined with advanced numerical simulation have identified gas-hydrate-bearing sands as the most feasible initial targets for energy recovery. The first assessments of potential technically-recoverable resources are now occurring, enabling a preliminary estimate of ultimate global recoverable volumes on the order of ~3 × 1014 m3 (1016 ft3; ∼150 GtC). Other occurrences, such as gas hydrate-filled fractures in clay-dominated reservoirs, may also become potential energy production targets in the future; but as yet, no production concept has been demonstrated. With regard to the climate implications of gas hydrate, an analogous partitioning of global resources to determine that portion most prone to dissociation during specific future warming scenarios is needed. At present, it appears that these two portions of total gas hydrate resources (those that are the most likely targets for gas extraction and those that are the most likely to respond in a meaningful way to climate change) will be largely exclusive, as those deposits that are the most amenable to production (the more deeply buried and localized accumulations) are also those that are the most poorly coupled to oceanic and atmospheric conditions.

Experiments combined with the density functional theory (DFT) calculation have been performed to understand the underlying photocatalysis mechanism of the nitrogen-doped titania nanobelts. Nitrogen-doped anatase titania nanobelts are prepared via hydrothermal processing and subsequent heat treatment in NH(3). Both the nitrogen content and the oxygen vacancy concentration increase with increasing the NH(3) treatment temperature. Nitrogen doping leads to an add-on shoulder on the edge of the valence band, the localized N 2p levels above the valence band maximum, and the 3d states of Ti(3+) below the conduction band, which is confirmed by DFT calculation and X-ray photoelectron spectroscopy (XPS) measurement. Extension of the light absorption from the ultraviolet (UV) region to the visible-light region arises from the N 2p levels near the valence band and from the color centers induced by the oxygen vacancies and the Ti(3+) species. Nitrogen doping allows visible-light-responsive photocatalytic activity but lowers UV-light-responsive photocatalytic activity. The visible-light photocatalytic activity originates from the N 2p levels near the valence band. The oxygen vacancies and the associated Ti(3+) species act as the recombination centers for the photoinduced electrons and holes. They reduce the photocatalytic activity although they contribute to the visible light absorbance.

This article reviews the storage of captured CO2 in coal seams. Other geologic formations, such as depleted petroleum reservoirs, deep saline aquifers and others have received considerable attention as sites for sequestering CO2. This review focuses on geologic sequestration of CO2 in unmineable coalbeds as the geologic host. Key issues for geologic sequestration include potential storage capacity, the storage integrity of the geologic host, and the chemical and physical processes initiated by the deep underground injection of CO2. The review topics include (i) the estimated CO2 storage capacity of coal, along with the estimated amount and composition of coalbed gas; (ii) an evaluation of the coal seam properties relevant to CO2 sequestration, such as density, surface area, porosity, diffusion, permeability, transport, rank, adsorption/desorption, shrinkage/swelling, and thermochemical reactions; and (iii) a treatment of how coalbed methane (CBM) recovery and CO2-enhanced coalbed methane (ECBM) recovery are performed (in addition, the use of adsorption/desorption isotherms, injection well characterization, and gas injection are described, as well as reservoir screening criteria and field tests operating in the United States and abroad); (iv) leak detection using direct measurements, chemical tracers, and seismic monitoring; (v) economic considerations using CO2 injection, flue gas injection, and predictive tools for CO2 capture/sequestration decisions; (vi) environmental safety and health (ES&H) aspects of CO2-enhanced coalbed methane/sequestration, hydrodynamic flow through the coal seam, accurate gas inventory, ES&H aspects of produced water and practices relative to ECBM recovery/sequestration; (vii) an initial set of working hypotheses concerning the chemical, physical, and thermodynamic events initiated when CO2 is injected into a coalbed; and (viii) a discussion of gaps in our knowledge base that will require further research and development. Further development is clearly required to improve the technology and economics while decreasing the risks and hazards of sequestration technology. These concerns include leakage to the surface, induced seismic activity, and long-term monitoring to verify the storage integrity. However, these concerns should not overshadow the major advances of an emerging greenhouse gas control technology that are reviewed in this paper.

As one important component of sulfur cathodes, the carbon host plays a key role in the electrochemical performance of lithium‐sulfur (Li‐S) batteries. In this paper, a mesoporous nitrogen‐doped carbon (MPNC)‐sulfur nanocomposite is reported as a novel cathode for advanced Li‐S batteries. The nitrogen doping in the MPNC material can effectively promote chemical adsorption between sulfur atoms and oxygen functional groups on the carbon, as verified by X‐ray absorption near edge structure spectroscopy, and the mechanism by which nitrogen enables the behavior is further revealed by density functional theory calculations. Based on the advantages of the porous structure and nitrogen doping, the MPNC‐sulfur cathodes show excellent cycling stability (95% retention within 100 cycles) at a high current density of 0.7 mAh cm ‐2 with a high sulfur loading (4.2 mg S cm ‐2 ) and a sulfur content (70 wt%). A high areal capacity (≈3.3 mAh cm ‐2 ) is demonstrated by using the novel cathode, which is crucial for the practical application of Li‐S batteries. It is believed that the important role of nitrogen doping promoted chemical adsorption can be extended for development of other high performance carbon‐sulfur composite cathodes for Li‐S batteries.

Pressure swing adsorption (PSA) and temperature swing adsorption (TSA) are some of the potential techniques that could be applicable for removal of CO2 from high-pressure fuel gas streams. Molecular sieves and activated carbons are some of the sorbents that could be utilized in the PSA process. Volumetric adsorption studies of CO2, N2, or H2 on molecular sieve 13X, molecular sieve 4A, and activated carbon were conducted at 25 °C up to a pressure of 300 psi (∼2× 106 Pa). Preferential adsorption of CO2 was observed with all three sorbents. The adsorption capacity of CO2 for molecular sieve 13X was higher than that for molecular sieve 4A at all pressures up to 300 psi. At low pressures (<25 psi) the adsorption capacity for CO2 of activated carbon was lower than that of molecular sieve 13X, but at higher pressures (>25 psi) activated carbon exhibited significantly higher CO2 capacities than were found for molecular sieves. Competitive adsorption of CO2 from gas mixtures also indicated that both molecular sieve 13X and activated carbon can be utilized for separation of CO2 from gas mixtures.

Solid oxide fuel cells (SOFCs) have the potential to be one of the cleanest and most efficient energy technologies for direct conversion of chemical fuels to electricity. Economically competitive SOFC systems appear poised for commercialization, but widespread market penetration will require continuous innovation of materials and fabrication processes to enhance system lifetime and reduce cost. One early technical opportunity is minimization of resistance to the oxygen reduction reaction (ORR) at the cathode, which contributes the most to performance degradation and efficiency loss in the existing SOFCs, especially at temperatures <700 °C. Detailed study over the past 15 years has revealed the positive impact of catalyst infiltration on SOFC cathode performance, both in power density and durability metrics. However, realizable performance improvements rely upon strongly-coupled relationships in materials and morphology between the infiltrate and the backbone, and therefore efficacious systems cannot be simply generated with a set of simple heuristics. This article reviews recent progress in enhancing SOFC cathode performance by surface modification through a solution-based infiltration process, focusing on two backbone architectures – inherently functional and skeletal – infiltrated using wet-chemistry processes. An efficient cathode consists of a porous mixed-conducting backbone and an active coating catalyst; the porous backbone provides excellent ionic and electronic conductivity, while the infiltrated surface coating possesses high catalytic activity and stability. As available, performance comparisons are emphasized and reaction schematics for specific infiltrate/backbone systems are summarized. While significant progress has been achieved in enhancing surface catalytic activity and durability, the detailed mechanisms of performance enhancement are insufficiently understood to obtain critical insights and a scientific basis for rational design of more efficient catalysts and novel electrode architectures. Recent progress in characterization of surfaces and interfaces is briefly discussed with challenges and perspectives in surface modification of SOFC electrodes. Surface modification through infiltration is expected to play an increasingly important role in current and next-generation commercial SOFC development, and this review illustrates the sophisticated technical considerations required to inform judicious selection of an infiltrate for a given SOFC system.

Carbon nanotubes have aroused great interest since their discovery in 1991. Because of the vast potential of these materials, researchers from diverse disciplines have come together to further develop our understanding of the fundamental properties governing their electronic structure and susceptibility towards chemical reaction. Carbon nanotubes show extreme sensitivity towards changes in their local chemical environment that stems from the susceptibility of their electronic structure to interacting molecules. This chemical sensitivity has made them ideal candidates for incorporation into the design of chemical sensors. Towards this end, carbon nanotubes have made impressive strides in sensitivity and chemical selectivity to a diverse array of chemical species. Despite the lengthy list of accomplishments, several key challenges must be addressed before carbon nanotubes are capable of competing with state-of-the-art solid-state sensor materials. The development of carbon nanotube based sensors is still in its infancy, but continued progress may lead to their integration into commercially viable sensors of unrivalled sensitivity and vanishingly small dimensions.

Over the past few decades, optical fibers have been widely deployed to implement various applications in high-speed long-distance telecommunication, optical imaging, ultrafast lasers, and optical sensors. Distributed optical fiber sensors characterized by spatially resolved measurements along a single continuous strand of optical fiber have undergone significant improvements in underlying technologies and application scenarios, representing the highest state of the art in optical sensing. This work is focused on a review of three types of distributed optical fiber sensors which are based on Rayleigh, Brillouin, and Raman scattering, and use various demodulation schemes, including optical time-domain reflectometry, optical frequency-domain reflectometry, and related schemes. Recent developments of various distributed optical fiber sensors to provide simultaneous measurements of multiple parameters are analyzed based on their sensing performance, revealing an inherent trade-off between performance parameters such as sensing range, spatial resolution, and sensing resolution. This review highlights the latest progress in distributed optical fiber sensors with an emphasis on energy applications such as energy infrastructure monitoring, power generation system monitoring, oil and gas pipeline monitoring, and geothermal process monitoring. This review aims to clarify challenges and limitations of distributed optical fiber sensors with the goal of providing a pathway to push the limits in distributed optical fiber sensing for practical applications.

Despite the high theoretical capacity of lithium-sulfur batteries, their practical applications are severely hindered by a fast capacity decay, stemming from the dissolution and diffusion of lithium polysulfides in the electrolyte. A novel functional carbon composite (carbon-nanotube-interpenetrated mesoporous nitrogen-doped carbon spheres, MNCS/CNT), which can strongly adsorb lithium polysulfides, is now reported to act as a sulfur host. The nitrogen functional groups of this composite enable the effective trapping of lithium polysulfides on electroactive sites within the cathode, leading to a much improved electrochemical performance (1200 mAh g(-1) after 200 cycles). The enhancement in adsorption can be attributed to the chemical bonding of lithium ions by nitrogen functional groups in the MNCS/CNT framework. Furthermore, the micrometer-sized spherical structure of the material yields a high areal capacity (ca. 6 mAh cm(-2)) with a high sulfur loading of approximately 5 mg cm(-2), which is ideal for practical applications of the lithium-sulfur batteries.

Carbon dioxide adsorption from a simulated flue gas stream was successfully performed with a hyperbranched aminosilica (HAS) material. The HAS was synthesized by a one-step reaction, spontaneous aziridine ring-opening polymerization off of surface silanols, to form a 32 wt % organic/inorganic hybrid material. The adsorption measurements were performed in a fixed-bed flow reactor using humidified CO2. The advantage of this adsorbent over previously reported adsorbents is the stability of the organic groups covalently bound to the silica support compared to those made by physisorbed methods. Furthermore, a large CO2 capacity (∼3 mmol CO2/g adsorbent) associated with the high loading of amines was observed.

The topic of global warming as a result of increased atmospheric CO2 concentration is arguably the most important environmental issue that the world faces today. It is a global problem that will need to be solved on a global level. The link between anthropogenic emissions of CO2 with increased atmospheric CO2 levels and, in turn, with increased global temperatures has been well established and accepted by the world. International organizations such as the United Nations Framework Convention on Climate Change (UNFCCC) and the Intergovernmental Panel on Climate Change (IPCC) have been formed to address this issue. Three options are being explored to stabilize atmospheric levels of greenhouse gases (GHGs) and global temperatures without severely and negatively impacting standard of living: (1) increasing energy efficiency, (2) switching to less carbon-intensive sources of energy, and (3) carbon sequestration. To be successful, all three options must be used in concert. The third option is the subject of this review. Specifically, this review will cover the capture and geologic sequestration of CO2 generated from large point sources, namely fossil-fuel-fired power gasification plants. Sequestration of CO2 in geological formations is necessary to meet the President's Global Climate Change Initiative target of an 18% reduction in GHG intensity by 2012. Further, the best strategy to stabilize the atmospheric concentration of CO2 results from a multifaceted approach where sequestration of CO2 into geological formations is combined with increased efficiency in electric power generation and utilization, increased conservation, increased use of lower carbon-intensity fuels, and increased use of nuclear energy and renewables. This review covers the separation and capture of CO2 from both flue gas and fuel gas using wet scrubbing technologies, dry regenerable sorbents, membranes, cryogenics, pressure and temperature swing adsorption, and other advanced concepts. Existing commercial CO2 capture facilities at electric power-generating stations based on the use of monoethanolamine are described, as is the Rectisol process used by Dakota Gasification to separate and capture CO2 from a coal gasifier. Two technologies for storage of the captured CO2 are reviewed--sequestration in deep unmineable coalbeds with concomitant recovery of CH4 and sequestration in deep saline aquifers. Key issues for both of these techniques include estimating the potential storage capacity, the storage integrity, and the physical and chemical processes that are initiated by injecting CO2 underground. Recent studies using computer modeling as well as laboratory and field experimentation are presented here. In addition, several projects have been initiated in which CO2 is injected into a deep coal seam or saline aquifer. The current status of several such projects is discussed. Included is a commercial-scale project in which a million tons of CO2 are injected annually into an aquifer under the North Sea in Norway. The review makes the case that this can all be accomplished safely with off-the-shelf technologies. However, substantial research and development must be performed to reduce the cost, decrease the risks, and increase the safety of sequestration technologies. This review also includes discussion of possible problems related to deep injection of CO2. There are safety concerns that need to be addressed because of the possibilities of leakage to the surface and induced seismic activity. These issues are presented along with a case study of a similar incident in the past. It is clear that monitoring and verification of storage will be a crucial part of all geological sequestration practices so that such problems may be avoided. Available techniques include direct measurement of CO2 and CH4 surface soil fluxes, the use of chemical tracers, and underground 4-D seismic monitoring. Ten new hypotheses were formulated to describe what happens when CO2 is pumped into a coal seam. These hypotheses provide significant insight into the fundamental chemical, physical, and thermodynamic phenomena that occur during coal seam sequestration of CO2.

The alloy-design strategy of combining multiple elements in near-equimolar ratios has shown great potential for producing exceptional engineering materials, often known as ‘high-entropy alloys’. Understanding the elemental distribution, and, thus, the evolution of the configurational entropy during solidification, is undertaken in the present study using the Al1.3CoCrCuFeNi model alloy. Here we show that, even when the material undergoes elemental segregation, precipitation, chemical ordering and spinodal decomposition, a significant amount of disorder remains, due to the distributions of multiple elements in the major phases. The results suggest that the high-entropy alloy-design strategy may be applied to a wide range of complex materials, and should not be limited to the goal of creating single-phase solid solutions. Alloys containing multiple elements of equal distributions are known to show enhanced properties as they tend to form single phases. Here, the authors demonstrate that even in cases of elemental segregation and chemical ordering, these alloys can still maintain enhanced properties.

We report atomistic simulations for both self- and transport diffusivities of light gases in carbon nanotubes and in two zeolites with comparable pore sizes. We find that transport rates in nanotubes are orders of magnitude faster than in the zeolites we have studied or in any microporous material for which experimental data are available. The exceptionally high transport rates in nanotubes are shown to be a result of the inherent smoothness of the nanotubes. We predict that carbon nanotube membranes will have fluxes that are orders of magnitude greater than crystalline zeolite membranes.

Advancement in hydrogen storage techniques represents one of the most important areas of today's materials research. While extensive efforts have been made to the existing techniques, there is no viable storage technology capable of meeting the DOE cost and performance targets at the present time. New materials with significantly improved hydrogen adsorption capability are needed. Microporous metal coordination materials (MMOM) are promising candidates for use as sorbents in hydrogen adsorption. These materials possess physical characteristics similar to those of single-walled carbon nanotubes (SWNTs) but also exhibit a number of improved features. Here, we report a novel MMOM structure and its room-temperature hydrogen adsorption properties.

This report establishes performance and cost data for fossil energy power systems, pulverized coal (PC) plants fueled with bituminous coal and natural gas combined cycle (NGCC) plants, all with and without carbon capture and storage. The analyses were performed on a consistent technical and economic basis that reflects current market conditions. The study serves as a benchmark to track the progress of DOE Fossil Energy R&D and as a baseline for analyzing fossil energy plant options. This is believed to provide the most comprehensive set of cost and performance data using bituminous coal available in the public literature to date. The cost and performance data were compiled from published reports, information obtained from vendor quotes and users of the technology, and data from designing and building utility projects.

Packing them in: Based on zinc and aromatic-rich dicarboxylic acids these new coordination networks (see structure; green Cl, red O, yellow Zn, blue N, gray C) have hydrogen uptakes comparable to those of the best carbon nanotubes and metal–organic frameworks. The highly interpenetrating nature of these networks points to a new design strategy for hydrogen-storage materials that employ an entrapment mechanism. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2005/z461214_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

The U.S. Department of Energy's National Energy Technology Laboratory (NETL) located in Albany, OR (formerly the Albany Research Center) has studied ex situ mineral carbonation as a potential option for carbon dioxide sequestration. Studies focused on the reaction of Ca-, Fe-, and Mg-silicate minerals with gaseous CO2 to form geologically stable, naturally occurring solid carbonate minerals. The research included resource evaluation, kinetic studies, process development, and economic evaluation. An initial cost estimate of approximately $69/ton of CO2 sequestered was improved with process improvements to $54/ton. The scale of ex situ mineral carbonation operations, requiring 55 000 tons of mineral to carbonate, the daily CO2 emissions from a 1-GW, coal-fired power plant, may make such operations impractical.

This paper presents a sandwich-structured CdS-Au-TiO2 nanorod array as the photoanode in a photoelectrochemical cell (PEC) for hydrogen generation via splitting water. The gold nanoparticles sandwiched between the TiO2 nanorod and the CdS quantum dot (QD) layer play a dual role in enhancing the solar-to-chemical energy conversion efficiency. First, the Au nanoparticles serve as an electron relay, which facilitates the charge transfer between CdS and TiO2 when the CdS QDs are photoexcited by wavelengths shorter than 525 nm. Second, the Au nanoparticles act as a plasmonic photosensitizer, which enables the solar-to-hydrogen conversion at wavelengths longer than the band edge of CdS, extending the photoconversion wavelength from 525 to 725 nm. The dual role of Au leads to a photocurrent of 4.07 mA/cm(2) at 0 V (vs Ag|AgCl) under full solar spectrum irradiation and a maximum solar-to-chemical energy conversion efficiency of 2.8%. An inversion analysis is applied to the transient absorption spectroscopy data, tracking the transfer of electrons and holes in the heterostructure, relating the relaxation dynamics to the underlying coupled rate equation and revealing that trap-state Auger recombination is a dominant factor in interfacial charge transfer. It is found that addition of Au nanoparticles increases the charge-transfer lifetime, reduces the trap-state Auger rate, suppresses the long-time scale back transfer, and partially compensates the negative effects of the surface trap states. Finally, the plasmonic energy-transfer mechanism is identified as direct transfer of the plasmonic hot carriers, and the interfacial Schottky barrier height is shown to modulate the plasmonic hot electron transfer and back transfer. Transient absorption characterization of the charge transfer shows defect states cannot be ignored when designing QD-sensitized solar cells. This facile sandwich structure combines both the electrical and the optical functions of Au nanoparticles into a single structure, which has implications for the design of efficient solar-energy-harvesting devices.

Experiments were conducted to assess the durability of cements in wells penetrating candidate formations for geologic sequestration of CO2. These experiments showed a significant variation in the initial degradation (9 days of exposure) based on the curing conditions. The high-temperature (50 degrees C) and high-pressure (30.3 MPa) curing environment increased the degree of hydration and caused a change in the microstructure and distribution of the Ca(OH)2(s) phase within the cement. Cement cured at 50 degrees C and 30.3 MPa (representing sequestration conditions) proved to be more resistant to carbonic acid attack than cement cured at 22 degrees C and 0.1 MPa. The cement cured at 50 degrees C and 30.3 MPa exhibited a shallower depth of degradation and displayed a well-defined carbonated zone as compared to cement cured under ambient conditions. This is likely due to smaller, more evenly distributed Ca(OH)2(s) crystals that provide a uniform and effective barrier to CO2 attack.