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At least 199 records · Page 11

Electrolyte Reactivity at the Charged Ni-Rich Cathode Interface and Degradation in Li-Ion Batteries

The chemical and electrochemical reactions at the positive electrode–electrolyte interface in Li-ion batteries are hugely influential on cycle life and safety. Ni-rich layered transition metal oxides exhibit higher interfacial reactivity than their lower Ni-content analogues, reacting via mechanisms that are poorly understood. Here, we study the pivotal role of the electrolyte solvent, specifically cyclic ethylene carbonate (EC) and linear ethyl methyl carbonate (EMC), in determining the interfacial reactivity at charged LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NMC111) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes by using both single-solvent model electrolytes and the mixed solvents used in commercial cells. While NMC111 exhibits similar parasitic currents with EC-containing and EC-free electrolytes during high voltage holds in NMC/Li 4 Ti 5 O 12 (LTO) cells, this is not the case for NMC811. Online gas analysis reveals that the solvent-dependent reactivity for Ni-rich cathodes is related to the extent of lattice oxygen release and accompanying electrolyte decomposition, which is higher for EC-containing than EC-free electrolytes. Combined findings from electrochemical impedance spectroscopy (EIS), TEM, solution NMR, ICP, and XPS reveal that the electrolyte solvent has a profound impact on the degradation of the Ni-rich cathode and the electrolyte. Higher lattice oxygen release with EC-containing electrolytes is coupled with higher cathode interfacial impedance, a thicker oxygen-deficient rock-salt surface reconstruction layer, more electrolyte solvent and salt breakdown, and higher amounts of transition metal dissolution. These processes are suppressed in the EC-free electrolyte, highlighting the incompatibility between Ni-rich cathodes and conventional electrolyte solvents. Finally, new mechanistic insights into the chemical oxidation pathways of electrolyte solvents and, critically, the knock-on chemical and electrochemical reactions that further degrade the electrolyte and electrodes curtailing battery lifetime are provided.

25 ENERGY STORAGE↗

Natural Gas Combined Cycle Power Plants with Carbon Capture and Exhaust Gas Recycle

This is a presentation given at the 3rd International Conference on Energy and Environment. The presentation highlights analysis work conducted by NETL to assess the cost and performance for natural gas combined cycle (NGCC) power plants that incorporate solvent-based post combustion carbon dioxide (CO2) capture and exhaust gas recycle (EGR). Increasing the inlet CO2 concentration by EGR is expected to improve the efficiency of the capture system and reduce its cost, however the analysis results show that the cost improvement is minimal as is the cost of capture reduction.

Hackett, Gregory↗

System and method for forming activated carbon aerogels and performing 3D printing

Making a carbon aerogel involves 3-D printing an ink to make a printed part, removing the solvent from the printed part, and carbonizing the printed part (with the solvent removed) to make the aerogel. The ink is based on a solution of a resorcinol-formaldehyde resin (RF resin), water, and an organic thickener. Advantageously, the RF resin contains an acid catalyst, which tends to produce carbon aerogels with higher surface areas upon activation than those produced from methods involving an ink composition containing a base catalyzed resin.

36 MATERIALS SCIENCE↗

Resolving Graphite‐Electrolyte Interphase of Lithium‐Ion Batteries using Air‐Tight Ambient Mass Spectrometry

Abstract The formation of a stable solid electrolyte interphase (SEI) at graphite electrode is necessary for lithium‐ion batteries (LIB) to prevent excessive degradation of electrolytes. Until now, the exact organic composition of SEI has not been decisively determined with lithium ethylene mono‐carbonate (LEMC) being one of the debated components. An air‐tight ambient mass spectrometry (MS) platform is developed to directly characterize the air‐sensitive organic components present in SEI. Ionization occurs via a solvent‐free field‐induced process at atmospheric pressure. Our experimental data, based on tandem MS analysis, revealed LEMC to be the major organic component in SEI. This result resolves a long‐standing mystery surrounding the composition of native SEI in LIB, where no trace of the other debated compound, lithium ethylene dicarbonate, was detected. The energetics of fragmentation of LEMC and the corresponding stabilities of various ionic species detected during the air‐tight ambient MS analysis were calculated using density functional theory (DFT). Our findings confirmed favorable protonation energies and suggested the molecular structures for many of the detected species. Solvent (i. e., ethylene carbonate)‐induced stabilization effects observed during the ionization process were also confirmed by DFT. The reported study encourages the routine use of ambient mass spectrometry to characterize both anodic and cathodic electrodes of all battery types as well as to study other air‐sensitive materials in their native state.

25 ENERGY STORAGE↗

Electrolytes with Improved Safety Developed for High Specific Energy Li-Ion Cells with Si-Based Anodes

A number of electrolyte formulations that have improved safety characteristics have been developed for use with high capacity silicon-based anodes. To improve the compatibility with Si-based anodes, a number of technical approaches have been employed, including: (1) the use of mono-fluoroethylene carbonate (FEC) in conjunction with, or in lieu of, ethylene carbonate (EC), (2) the use of high proportions of fluorinated co-solvents, (3) the use of vinylene carbonate (VC) to stabilize the Si/C electrode, and (4) the use of lithium bis(oxalato)borate (LiBOB) to improve the compatibility of the electrolyte when Si/C electrodes are used in conjunction with high voltage cathodes. Candidate electrolytes were studied in Li/Si-C and Si-C/ Li(MnNiCo)O2 (NMC) coin cells, as well as in larger Si-C/NMC three-electrode cells equipped with lithium reference electrodes. In summary, many electrolytes that contain triphenyl phosphate (TPP), which is used as a flame retardant additive up to concentrations of 15 volume percent, and possess FEC as a co-solvent have been demonstrated to outperform the all-carbonate baseline electrolytes when evaluated in Si-C/ Li(MnNiCo)O2 cells.

Silicon-Based Anode↗

Solvent-free synthesis of Co single atom and nanocluster decorated N-doped carbon for efficient oxygen reduction

The advancement of efficient, cheap, and durable catalysts for oxygen reduction reaction (ORR) to substitute Pt/C in metal-air batteries is of paramount importance. However, traditional solvent-based methods fall short in terms of environmental benign and scalability. Herein, a solvent-free organic-inorganic self-assembly approach is explored to construct cobalt single atom and cobalt nanocluster decorated nitrogen-doped porous carbon spheres (Co-SA/NC@NCS). The solvent-free synthesis demonstrates an impressively high yield (282 g/L) and the resultant Co-SA/NC@NCS possesses a high N content (6.9 wt%). Density functional theory calculations disclose that the Co-SAs and Co-NCs are able to optimize the surface oxygen adsorption capability and enhance the conductivity of the NCS, thereby facilitating the ORR performance. Here, the solvent-free synthesis is also feasible for the synthesis of other non-noble metal element (Fe, Ni, and Zn) decorated nitrogen-doped porous carbon spheres.

Nitrogen-doped carbon↗

Transition Metal Dissolution in Lithium-Ion Cells: A Piece of the Puzzle

Static leaching tests were performed using the chemically delithiated positive electrode materials, LiFePO 4 , LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , and LiNi 0.8 Mn 0.1 Co 0.1 O 2 . Instead of the common electrolyte, which contains LiPF 6 , the solvent consisted of only ethylene carbonate (EC) and ethyl methyl carbonate (EMC), limiting the possible reactions to only those that depend on the solvent. The product liquids from these experiments showed that there were lithium-bearing species in common, such as Li(EC) + and Li(EMC) + . Interestingly, we found evidence of electrolyte degradation products in both the positive-and negative-ion mass spectral results. The positive-ion results showed that the products tended to coordinate to lithium. In conclusion, the negative-ion results showed that most of the products tended to complex with transition metals. It was difficult to discern which positive ion was associated with which negative ion.

25 ENERGY STORAGE↗

Intercalation of Lithium in Pitch-Based Graphitized Carbon Fibers Chemically Modified by Fluorine: Soft Carbon With or Without an Oxide Surface

The effects of carbon structure and surface oxygen on the carbon's performance as the anode in lithium-ion battery were studied. Two carbon materials were used for the electrochemical tests: soft carbon made from defluorination of graphite fluoride, and the carbon precursor from which the graphite fluoride was made. In this research the precursor was graphitized carbon fiber P-100. It was first fluorinated to form CF(0.68), then defluorinated slowly at 350 to 450 C in bromoform, and finally heated in 1000 C nitrogen before exposed to room temperature air, producing disordered soft carbon having basic surface oxides. This process caused very little carbon loss. The electrochemical test involved cycles of lithium intercalation and deintercalation using C/saturated LiI-50/50 (vol %) EC and DMC/Li half cell. The cycling test had four major results. (1) The presence of a basic oxide surface may prevent solvent from entering the carbon structure and therefore prolong the carbon's cycle life for lithium intercalation-deintercalation. (2) The disordered soft carbon can store lithium through two different mechanisms. One of them is lithium intercalation. which gives the disordered carbon an electrochemical behavior similar to its more ordered graphitic precursor. The other is unknown in its chemistry, but is responsible for the high-N,oltage portion (less than 0.3V) of the charge-discharge curve. (3) Under certain conditions, the disordered carbon can store more lithium than its precursor. (4) These sample and its precursor can intercalate at 200 mA/g. and deintercalate at a rate of 2000 mA/g without significant capacity loss.

Hung, Ching-Chen↗

Gating ion and fluid transport with chiral solvent

Nonlinear spectroscopy and electrokinetic measurements reveal that the electrochemical properties of a solid–liquid interface in salt solutions in propylene carbonate are dependent on the solvent chirality.

Chemistry↗

NMR and Theoretical Study of In-Pore Diffusivity of Ionic Liquid–Solvent Mixtures

We report despite having a lower energy density than common batteries, electric double-layer capacitors (EDLCs) offer several advantages for high-power applications, including high power density, quick charge and discharge time, and long cycle life. Room-temperature ionic liquids (RTILs) have been intensely studied as promising electrolytes for applications in ELDCs because of their wide potential window, low volatility, as well as thermal and chemical stability. The main deficiency of neat RTILs in such applications is the sluggish diffusivity, which restricts the EDLCs’ power density. To alleviate the slow diffusivity, RTILs can be used in a mixture with organic solvents. In this study, we applied two-dimensional exchange nuclear magnetic resonance spectroscopy (2D EXSY NMR) and molecular dynamics (MD) simulations to investigate the diffusivity of anions of an RTIL, namely, 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide (BMIM + –TFSI – ), dissolved in five different organic solvents, in the micropores of activated carbon. We determined that the relative concentrations of ions in solutions in the micropores were higher than those in the bulk solutions and were also solvent-dependent. The ion diffusivities in the pores were found to be almost 2 orders of magnitude slower than in the bulk solutions, with methanol showing the largest relative disparity. These results suggested that the interactions of solvents with the activated carbon are critical not only to the power density of EDLCs but also to the energy density. The comparisons of ion diffusivities between the experiments and the MD simulations suggest the need to consider also the surface functionalities of activated carbon for the simulation of ion diffusion in the micropores of activated carbon.

electric double layer capacitors↗

Tailoring Chemical Absorption-Precipitation to Lower the Regeneration Energy of a CO 2 Capture Solvent

Solvent-based CO 2 capture consumes significant amounts of energy for solvent regeneration. To improve energy efficiency, this study investigates CO 2 fixation in a solid form through solvation, followed by ionic self-assembly-aided precipitation. Based on the hypothesis that CO 3 2- ions may bind with monovalent metal ions, we introduced Na + into an aqueous hexane-1,6-diamine solution where CO 2 forms carbamate and bicarbonate. Then, Na + ions in the solvent act as a seed for ionic self-assembly with diamine carbamate to form an intermediate ionic complex. The recurring chemical reactions lead to the formation of an ionic solid from a mixture of organic carbamate/carbonate and inorganic sodium bicarbonate (NaHCO 3 ), which can be easily removed from the aqueous solvent through sedimentation or centrifugation and heated to release the captured CO 2 . Mild-temperature heating of the solids at 80–150 °C causes decomposition of the solid CO 2 -diamine-Na molecular aggregates and discharge of CO 2 . This sorbent regeneration process requires 6.5–8.6 GJ/t CO 2 . It was also found that the organic carbamate/carbonate solid, without NaHCO 3 , contains a significant amount of CO 2 , up to 6.2 mmol CO 2 /g-sorbent, requiring as low as 2.9–5.8 GJ/t CO 2 . In conclusion, molecular dynamic simulations support the hypothesis of using Na + to form relatively less stable, yet sufficiently solid, complexes for the least energy-intensive recovery of diamine solvents compared to bivalent carbonate–forming ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mixed-Salt/Ester Electrolytes for Low-Temperature Li+ Cells

Electrolytes comprising, variously, LiPF6 or LiPF6 plus LiBF4 dissolved at various concentrations in mixtures of alkyl carbonates and alkyl esters have been found to afford improved low-temperature performance in rechargeable lithium-ion electrochemical cells. These and other electrolytes have been investigated in a continuing effort to extend the lower limit of operating temperatures of such cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles, the most recent being Ester-Based Electrolytes for Low-Temperature Li-Ion Cells (NPO-41097), NASA Tech Briefs, Vol. 29, No. 12 (December 2005), page 59. The ingredients of the solvent mixtures include ethylene carbonate (EC), ethyl methyl carbonate (EMC), methyl butyrate (MB), and methyl propionate (MP). The electrolytes were placed in Li-ion cells containing carbon anodes and LiNi0.8Co0.2O2 cathodes, and the electrical performances of the cells were measured over a range of temperatures down to 60 C. The electrolytes that yielded the best low-temperature performances were found to consist, variously, of 1.0 M LiPF6 + 0.4 M LiBF4 or 1.4 LiPF6 in 1EC + 1EMC + 8MP or 1EC + 1EMC + 8MB, where the concentrations of the salts are given in molar units and the proportions of the solvents are by relative volume.

Smart, Marshall↗

Concepts for Actinide Recovery from TRISO Used Nuclear Fuel

The work described in this report has developed a preliminary conceptual flowsheet based on limited published literature for the head-end of a TRISO oxycarbide UNF reprocessing plant. The essential function of the head-end is to prepare the UNF for subsequent separation of actinides. The main steps of the conceptual TRISO UNF head-end reprocessing flowsheet are: 1. Fragmentation of the graphite moderator to expose the fuel particles. 2. Separation of fuel particles from fragmented graphite moderator by sieving and fluidization. 3. Fragmentation of the fuel particles to expose the fuel kernel. 4. Dissolution of the fuel kernel in nitric acid. Noteworthy at this step is the formation of organic acids (mainly oxalic and mellitic acids) from the carbon associated with the fuel and TRISO coatings. These acids can interfere with actinide separations and solvent extraction hydraulic performance and carbon dioxide gas generation. 5. Clarification of the dissolved fuel solution to separate the coating fragments. 6. Dissolver off-gas treatment with specific emphasis on managing generation of carbon dioxide gas containing carbon-14. The quantity of carbon dioxide is projected to be 100 to 1000 times greater than that arising from dissolving LWR UNF. Pre or post treatment of the exposed fuel kernels could be undertaken to mitigate the formation of organic acids but there still exists a significant off-gas treatment challenge. The literature on reprocessing uranium nitride UNF was reviewed but a flowsheet was not specifically developed since its scope and uncertainties are expected to be encompassed by the oxycarbide flowsheet. Overall, the predominant feature of processing TRISO UNF is carbon management to reduce waste volume and mitigate the formation of carbon dioxide and organic acids. This report recommends broad areas of research that will help to further define the head-end flowsheet.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Soluble Organic Matter (SOM) analysis of the Hayabusa2 samples: The first results

The Hayabusa2 spacecraft successfully collected the surface and possible sub-surface materials of the asteroid 162173 Ryugu. Ryugu is a C-type asteroid characterized by a low-albedo surface probably consisting of hydrous minerals and carbonaceous materials. [1] The direct optical and spectral analysis of the returned samples indicates that Ryugu material is dominated by hydrous carbonaceous chondrite-like matter (similar to CI chondrites) [2]. Since carbonaceous chondrites have generally yielded various types of organic matter, the collected Ryugu grains are expected to contain diverse types of organic compounds including bio-related molecules. The occurrence of organic compounds in the Ryugu surface will provide clues to the evolution of prebiotic molecules and their preservations associated with aqueous alteration of the primitive asteroid. The initial analysis of soluble organic matter (SOM) of the Hayabusa2-returned samples has been performed by an international team consisting of 32 members. Because the sample amount available for comprehensive SOM analyses is limited, and because the SOM is expected to be present as a complex mixture of various types of organic compounds with very small concentrations of each compound, high-sensitivity and high-resolution analytical techniques have been developed using carbonaceous meteorites [e.g. 3]. Two aggregate samples of the Ryugu grains (A106 and C107) were allocated for the solvent extractions and bulk carbon (C), hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) measurements. The A106 sample was collected during the 1st sampling in February 2019 and the C107 sample was collected during the 2nd sampling in July 2019 after the Small Carry Impactor (SCI) operation. They consist mainly of particles smaller than 1 mm in diameter, and each sample mass was 38-39 mg. They were firstly investigated spectroscopically in the near infrared wavelength range by the Stone Team prior to the solvent extractions. Other small grains (A0080 and C0057) were also allocated for this study to investigate the spatial distribution of organic compounds on the sample surface. The extraction and analytical measurements implemented by the SOM Team are summarized in Figure 1. Each powder sample was extracted sequentially with non-polar to polar solvents, i.e., hexane, dichloromethane (DCM), methanol (MeOH) and H2O, for non-targeted analysis to reveal the compound composition. Each solvent extract was analyzed by solution state nuclear magnetic resonance (NMR) spectroscopy [4], Fourier transform- ion cyclotron resonance/mass spectrometry (FT-ICR/MS) with ESI and APPI ionization [5] and by high-resolution mass spectroscopy using Orbitrap MS coupled with nano-liquid chromatography (nanoLC/Orbitrap MS) [6], and using two dimensional gas chromatography/mass spectrometry (GC×GC/MS). The extracted residues were passed to the Chemistry Team for further inorganic element analysis. The other powder sample was subjected to the hot water extraction for amino acid analyses including chiral isomer separation, which was performed by three-dimensional (3D) high-performance liquid chromatography (HPLC) with high-sensitivity fluorescence detection (FD) [7] and by HPLC/FD coupled with quadrupole-time of flight/mass spectrometry (QToF/MS) [8]. After the hot water extraction, the residue was split into two halves. One half was further extracted with hydrochloric acid (HCl) to analyze for amino acids in bound-form. The other half was sequentially extracted with DCM/MeOH (1/1) to analyze semi-polar compounds such as polycyclic aromatic hydrocarbons (PAHs) by GC/MS, followed by further extraction with formic acid to analyze polar heterocyclic compounds, and subsequent extraction with HCl to detect bound-form polar compounds. The extracted residues were passed to the IOM Team for the analysis of insoluble organic matter (IOM). Compound-specific stable isotope analyses will be performed using GC/combustion/isotope ratio mass spectrometry (GC/C/IRMS) if the compound concentration is high enough to enable such an isotopic measurement. All extraction procedures were performed on an ISO 6 (Class 100) clean bench inside an ISO 5 (Class 1000) clean room. Baked serpentine powder was also analyzed as a procedural blank. In situ organic compound analysis with the molecular imaging was performed using desorption electrospray ionization (DESI) equipped with Orbitrap MS [9, 10], followed by spatial imaging of organic compounds using ToF/secondary ion mass spectrometry (ToF/SIMS) [11]. The bulk chemical and isotopic compositions of CNS and HO were determined using nano-elemental analysis/isotope ratio mass spectrometry (nanoEA/IRMS) [12] and EA/pyrolysis/IRMS, respectively. We have identified a variety of indigenous organic compounds in the extracts of both A106 and C107 samples. The Ryugu grains host organic molecules under the high-vacuum and cosmic-ray irradiation environment of the asteroid surface. The analysis of extracted molecules is in progress, and the first results will be presented at the symposium.

Hiroshi Naraoka↗

The influence of random packed column parameters on the liquid holdup and interfacial area

Abstract Carbon dioxide capture via solvent absorption in packed columns has emerged as a potential technology to mitigate coal‐fired power plant CO 2 emissions. Parameters, including packing types, solvent properties, and operating conditions, could potentially affect the packed column CO 2 capture efficiency. To understand the importance of those parameters and help packed column optimization, a design of experiments (DoEs) method was proposed to generate input parameter matrix. Combined with multiphase computational fluid dynamics (CFD), the random packed column parameter influence on the liquid holdup and interfacial area can be efficiently investigated. Surrogate‐based sensitivity analysis shows that the solvent flow rate and contact angle are key factors dictating liquid holdup and interfacial area. On the other hand, solvent viscosity has a marginal impact on the interfacial area. The sensitivity scores were calculated for each input parameter to guide the selection of dimensionless numbers for the liquid holdup and interfacial area correlation development.

42 ENGINEERING↗

Mesoporous silica-encapsulated gold core–shell nanoparticles for active solvent-free benzyl alcohol oxidation

Silica-encapsulated gold core@shell nanoparticles (Au@SiO2 CSNPs) were synthesized via a bottom-up procedure and used to catalyze the selective oxidation of benzyl alcohol. The pore size, morphology, crystallinity and composition of Au@SiO2 was evaluated using non-local density functional theory, transmission electron microscopy, high-energy x-ray diffraction and inductively coupled plasma-mass spectroscopy, respectively. The nanoparticles exhibit a mesoporous shell with an average thickness of 25.5 Å which can enhance selectivity via preferential transport of the desired product (i.e., benzaldehyde) relative to larger, undesired products (i.e, benzoic acid/benzyl benzoate). GC-FID analysis revealed the addition of potassium carbonate to the solvent-free oxidation of benzyl alcohol increased conversion from 17.3 to 60.4% while decreasing selectivity from 98.7 to 75.0%. Under equivalent conditions, a bare gold nanoparticle control catalyst deposited on a silica support with a similar gold surface area took 6 times as long to reach the same conversion, achieving only 49.4% selectivity. These results suggest that the pore size distribution within the inert silica shell of Au@SiO2 CSNPs inhibits the formation of undesired products to facilitate the selective oxidation of benzaldehyde despite a basic environment, which reduces selectivity under typical conditions. The CSNPs demonstrated a much lower activation energy than the Au-SiO2 control catalyst, 37 ± 1.9 kJ/mol and 72 ± 7.1 kJ/mol, respectively. Thiele modulus analysis indicates the CSNP pore structure does not create a mass transport limitation due to the nano-scale path of diffusion through the pore structure to the active surface. The lower activation energy and mesopore distribution together suggest the Au@SiO2 catalyst demonstrates higher activity through beneficial in-pore orientation, both reducing competitive adsorption and promoting a single, lower activation energy mechanistic pathway.

benzyl alcohol oxidation, catalysis, confinement↗

Development of thermostable carbonic anhydrases using structure-guided recombination for use in CO2 removal systems on spacecraft

Carbon capture and storage has been a research area of great interest in recent years asa method for mitigation of CO2emissions, due to the effects of climate change. The development of technologies for the efficient capture of CO2are also of great interest for human spaceflight applications. One of the most promising technologies in this area is CO2 scrubbing using liquid amines, unfortunately, liquid amines with low heats of desorption tend to have slow CO2binding kinetics. One potential solution to this problem is to use the enzyme carbonic anhydrase (CA) to enhance the kinetics of CO2binding to liquid amines, allowing the overall process to be more energy efficient. Interest in using carbonic anhydrase as a biocatalyst has led to a number of efforts to improve the thermostability and solvent tolerance of several distinct carbonic anhydrase enzymes. In the work described here, we screened through a diverse set of natural carbonic anhydrases to identify candidates for protein engineering aimed at increased stability and activity in various liquid amines. We then used SCHEMA structure-guided recombination to develop a set of chimeric carbonic anhydrases with high thermostability and activity. These chimeras were used as the starting points for further protein engineering work targeting activity in liquid amine systems. Our ultimate goal is to test the engineered enzymes in a liquid amine system for cabin air revitalization on ISS or other spacecraft.

Life Support↗

Development of Thermostable Carbonic Anhydrases Using Structure-Guided Recombination for Use in CO2 Removal Systems on Spacecraft

Carbon capture and storage has been a research area of great interest in recent years as a method for mitigation of CO2 emissions, due to the effects of climate change. The development of technologies for the efficient capture of CO2 are also of great interest for human spaceflight applications. One of the most promising technologies in this area is CO2 scrubbing using liquid amines, unfortunately, liquid amines with low heats of desorption tend to have slow CO2 binding kinetics. One potential solution to this problem is to use the enzyme carbonic anhydrase (CA) to enhance the kinetics of CO2 binding to liquid amines, allowing the overall process to be more energy efficient. Interest in using carbonic anhydrase as a biocatalyst has led to a number of efforts to improve the thermostability and solvent tolerance of several distinct carbonic anhydrase enzymes. In the work described here, we screened through a diverse set of natural carbonic anhydrases to identify candidates for protein engineering aimed at increased stability and activity in various liquid amines. We then used SCHEMA structure-guided recombination to develop a set of chimeric carbonic anhydrases with high thermostability and activity. These chimeras were used as the starting points for further protein engineering work targeting activity in liquid amine systems. Our ultimate goal is to test the engineered enzymes in a liquid amine system for cabin air revitalization on ISS or other spacecraft.

Life Support, Carbon dioxide, Carbonic anhydrase, ↗