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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Subtask 2.6 – Optimization of Aerosol Mitigation Technology for Postcombustion CO 2 Capture

Growing concerns over the impact of CO 2 emissions from combustion sources on global climate change have prompted numerous research and development projects aimed at developing cost-effective technologies for CO 2 capture. One family of technologies being demonstrated at pilot and full scale globally is postcombustion CO 2 capture (PCCC) systems that employ amine-based solvents. The captured CO 2 can be compressed and permanently stored underground or used for enhanced oil recovery (EOR). The proximity of North Dakota’s lignite-fired fleet of power plants to potential CO 2 storage options creates a unique atmosphere for PCCC within the state. However, the aerosols present in lignite flue gas present a challenge for large-scale PCCC at North Dakota power plants. Aerosols can negatively impact the long-term performance of amine-based solvents for CO 2 capture. Amine-based solvents are volatile, and aerosols provide nucleation sites where amine vapors can condense. Because aerosols cannot be easily captured at the column outlet using conventional technologies, the amine-laden aerosols escape the system and lead to accelerated solvent losses. Moreover, aerosol components can chemically react with amines to form degradation products that can permanently deactivate the amine, cause fouling, and lead to hazardous emissions. Many of the elements that have been shown to catalyze solvent degradation are present in lignite coals and can exacerbate solvent replacement economics. Understanding this issue is critical to the implementation of solvent-based CO 2 capture systems as applied to lignite-fired generation systems. The Energy & Environmental Research Center (EERC) designed and carried out this project to optimize aerosol mitigation technology for PCCC at a lignite-fired power plant. To meet the goal of this project, the following objectives were identified: Determine the effectiveness of a wet electrostatic precipitator (WESP) on collection of aerosols at a low-rank coal-fired power station. Determine the impact of aerosols on the efficiency and degradation products of amine-based carbon capture systems fired with low-rank fuels. Work was conducted at Minnkota Power Cooperative’s (MPC’s) Milton R. Young (MRY) Station Unit 2 using a slipstream of flue gas from the outlet of the plant’s flue gas desulfurization (FGD) unit. To gather initial data for sizing and specifying a WESP for this system, a temporary pilot-scale WESP was rented and installed on-site. Several different conditions were tested to examine the impact of flow rate, voltage, and current on WESP performance. The WESP was effective at removing large particulate (>200 nm) but caused an increase in fine particulate (<75 nm). Fine particulate material at the inlet and outlet of the WESP was collected, analyzed, and showed that crystalline sulfates carried over from the plant’s FGD unit were being converted to fine aerosols and SO 2 was being converted to SO 3 through the WESP. Additionally, the high moisture content of the flue gas stream at this sample location also contributed to an overall increase in aerosol mass under some of the test conditions. Using the results from the rented WESP, the project team installed a smaller-scale WESP upstream of the EERC’s slipstream CO 2 capture system. Flue gas was routed through a pilot-scale FGD unit to remove SO 2 to very low levels (~1 ppm) and then through a direct contact cooler (DCC) to further cool the gas and to remove moisture. The gas exiting the DCC was then routed through the new WESP before passing to the CO 2 absorber columns. Fluor’s amine-based solvent was used to scrub CO 2 from the slipstream through a set of two absorber columns. The rich solvent was regenerated in a stripper column by heating to drive off captured CO 2 . The system operated using a catch-and-release method where the CO 2 was separated to provide data on the process, but the captured CO 2 was released back into the host site stack. Aerosols and sulfur species were measured at multiple locations throughout the pilot-scale system. The inlet FGD and DCC removed much of the particulate matter and gaseous sulfur upstream of the WESP. With this configuration, the WESP achieved >95% particulate capture. The new WESP did not show any of the increases in SO 3 or other aerosol species that had been consistently observed with the larger-scale WESP installed immediately downstream of the plant’s full-scale FGD unit. Particulate samples captured and analyzed from the WESP inlet did not show any presence of crystalline sulfate materials, indicating that the pilot-scale FGD and DCC were efficient at reducing carryover from the plant’s full-scale FGD unit. A set of parametric tests were conducted on the new WESP to assess the impacts of flow rate, voltage, number of online WESP fields, and gas-phase sulfur content on aerosol and sulfur transformations. The results showed that the WESP performed similarly well at all sets of conditions. Sulfur and particulate matter exiting the WESP were further reduced through the absorber column as the amine-based solvent captured some of the residual contaminants. Solvent analysis showed that these species were slowly concentrating in the solvent over the duration of the test. When the WESP was taken offline and the sulfur slip through the FGD allowed to rise, the sulfate content in the solvent rose sharply, showing that the extra FGD and WESP were effective at reducing sulfate and cation uptake. This would be expected to extend amine-based solvent life by slowing the formation of heat-stable salts and other degradation products. This subtask was cofunded through the EERC–U.S. Department of Energy Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FE0024233. Nonfederal funding was provided by the North Dakota Industrial Commission and MPC.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

Mechanical and Corrosion Response of 316SS in Supercritical CO 2

The supercritical carbon dioxide (s-CO 2 ) Brayton cycle is currently being explored as a replacement for the steam Rankine cycle due to its potential for higher efficiency and lower cycle cost. 316 stainless steel is a candidate alloy for use in s-CO 2 up to roughly 600 °C, but the mechanical effects of prolonged exposure of base and welded material in s-CO 2 have not been analyzed. The potential for carburization makes this an important concern for the implementation of 316 and similar austenitic stainless steels in the s-CO 2 environment. In this study, welded and base material of two types of 316–316L and 316H–were exposed in either s-CO 2 or argon at 550 °C or 750 °C for 1000 h. 550 °C s-CO 2 exposure yielded a thin (< 1 µm) Cr oxide with occasional nodules of duplex Fe oxide and Fe–Cr spinel that were up to 5 microns thick. However, tensile results from s-CO –2 exposure matched those of 550 °C thermal aging in Ar, indicating that no mechanically detrimental carburization occurred in either 316 variant after 1000 h exposure. Conversely, 750 °C s-CO 2 exposure produced roughly 10 × the oxide thickness, with a more substantial Fe oxide (3–5 µm) on the majority of the surface and nodules of up to 40 µm thick. In comparison to aged samples, tensile testing of 750 °C CO 2 -exposed samples revealed ductility loss attributed to carburization. As a result, projections of 316L performance in s-CO 2 indicate that mechanically detrimental carburization—equal to that shown here for 750 °C, 1000 h—will likely be present after 7–14 years of service at 550 °C.

316 stainless steel↗
DOE OSTI2025

Mid-Atlantic US observations of radiocarbon in CO 2 : fossil and biogenic source partitioning and model evaluation

Accurately quantifying regional anthropogenic CO 2 fluxes is fundamental to improving our understanding of the carbon cycle and for creating effective carbon mitigation policies, and the radiocarbon to total carbon ratio in atmospheric CO 2 (Δ 14 CO 2 ) is a robust tracer of fossil fuel CO 2 that can discriminate between biogenic and fossil fuel CO 2 sources. NASA's Atmospheric Carbon and Transport-America (ACT-America) airborne mission between 2016 and 2019 aimed to improve the accuracy of regional greenhouse gas flux estimates, through refining our understanding and characterization of fluxes and flux uncertainties in models. Δ 14 CO 2 observations from 26 flights are presented for examining seasonal CO 2 source partitioning in the Mid-Atlantic USA. Observed variability in boundary layer CO 2 at timescales ranging from intra-day to seasonal was largely driven by biogenic CO 2 (CO 2bio ) variability that ranged from −19.7 ppm in summer to 16.2 ppm in fall, while fossil fuel CO 2 (CO 2ff ) variability remained at 3.3±2.0 ppm. Carbonyl sulfide uptake was well-correlated with CO 2bio uptake, and examining this relationship, as well as that between CO 2 and CO 2bio variability reinforces the seasonal extent of gross primary productivity response throughout ACT-America. We use airborne Δ 14 CO 2 flask sampling alongside in situ carbon monoxide measurements to calculate high-frequency CO 2ff and evaluate the magnitude and diurnal variability of modeled CO 2ff , deducing likely transport errors in an example flight. Although ACT-America CO 2ff signals were attenuated due to the broad source regions sampled, results illustrate the value of Δ 14 CO 2 sampling and observation-based methodologies for regional CO 2 flux attribution, evaluation and improvement of modeled CO 2 .

Baier, Bianca C. [National Oceanic and Atmospheric↗
DOE OSTI2025

Deep Learning–Assisted Multiobjective Optimization of Geological CO 2 Storage Performance under Geomechanical Risks

In geological CO 2 storage, designing the optimal well control strategy for CO 2 injection to maximize CO 2 storage while minimizing the associated geomechanical risks is not trivial. This challenge arises due to pressure buildup, CO 2 plume migration, the highly nonlinear nature of geomechanical responses to rock-fluid interaction, and the high computational cost associated with coupled flow and geomechanics simulations. In this paper, we introduce a novel optimization framework to address these challenges. The optimization problem is formulated as follows: maximize total CO 2 storage while minimizing geomechanical risks by adjusting the injection schedules within bounded constraints. The geomechanical risks are primarily driven by injection-induced pressure build-up, which is characterized by ground displacement and the induced microseismicity. We used the Fourier neural operator (FNO)-based deep learning model to construct surrogate models, replacing the time-consuming coupled flow and geomechanics simulations for evaluating the aforementioned objective functions. The developed surrogate models have been incorporated into a multiobjective optimization framework through a genetic algorithm to reduce the computational burden. The proposed optimization framework reduces the computational cost from approximately 2,400 hours, when using objective function evaluations based on physics-based simulations, to around 20 minutes. A set of Pareto-optimal solutions of the proposed workflow yields nontrivial optimal decisions, reducing the microseismicity potential and the vertical displacement. This Pareto front highlights the optimal trade-offs between CO 2 storage amount, safety, and ground displacement, emphasizing the need for careful optimization and management of injection strategies to achieve a balanced outcome. The novelty of this work is twofold. First, we demonstrate the importance of incorporating the minimization of the geomechanical risks as objective functions into the CO 2 storage optimization workflow to mitigate the potential risk of induced microseismicity and ground displacement. Second, we leverage the FNO-based surrogate models to optimize a real-field CO 2 storage operation.

42 ENGINEERING↗
DOE OSTI2020

Virtual Analysis of Gas-Diffusion-Electrode CO 2 Electrolyzers

The electrochemical reduction of CO 2 (CO2R) to value-added products is an attractive technology for tackling the rising atmospheric CO 2 levels and storing intermittent renewable energy into chemical bonds. Fundamental understanding of CO 2 R has progressed significantly in recent years and is critical in the development of CO 2 R to liquid-fuel electrolyzers, where gas-diffusion electrodes (GDEs) have been shown to be key enabling architectures. Various designs have been proposed and studied in the literature to enhance overall selectivity, rates, and maximize the conversion of CO 2 , the latter of which is only now being recognized as a critical issue. In this respect, there is a need to explore the governing phenomena inherent in these architectures to enable optimization. Mathematical modeling is ideally suited to tackle and explore these multiphysics interactions and provide virtual design analysis. In this talk, we discuss modeling methodologies and physics inherent in these devices and present our recent modeling of GDEs for CO 2 reduction. Here, we specifically examine the impacts of multiphase flow and related phenomena on overall cell performance. We then explore the performance and limitations of various cell designs guided by simulation results and examine potential methods for improving water management and tuning catalyst selectivity including the use of different anion-exchange and bipolar membranes. Finally, we discuss the disparities in local environments between aqueous and GDE devices and propose strategies to reduce the gap in knowledge between the two systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Synthetic Calcium Carbonate Production by Carbon Dioxide (CO 2 ) Mineralization of Industrial Waste Brines

The global scale of CO 2 emission has crossed 36 B tons, and the United State represents 14% of the total emissions. In light of the high cost associated with current CO 2 capture processes ($60-to-150 per ton of CO 2 ), carbon capture and utilization (CCU), wherein CO 2 is converted to beneficial products, provides a pragmatic path to overcome the economic barrier for CO 2 emissions control. In particular, CO 2 mineralization offers an attractive route as it produces high-value mineral carbonates that sequester CO 2 in a stable form. For instance, fine precipitated calcium carbonate, a valuable product with unit price in the range of $230-280/t and a global market projected to reach 99 M tons in 2020, can be produced by capturing CO 2 within aqueous Ca 2+ solution. However, two critical challenges need to be overcome—(i) the need for costly processes such as electrolysis or addition of alkali hydroxides to maintain alkalinity during mineralization, and (ii) the geographic availability of Ca-rich solutions (or brines) which often renders efficient integration with power plants impractical. To simultaneously address these challenges, this project developed two novel routes to enable carbonate production based on efficient CO 2 mineralization. In one variation, the project developed a new alkaline carbonation process to capture CO 2 and produce calcite precipitates from coal ashes. Herein, coal ash is carbonated first in a sodium carbonate solution. The carbonation reaction produces sodium hydroxide and raises the solution pH. This high-pH hydroxide solution is then used for CO 2 capture, which converts the sodium hydroxide solution back to sodium carbonate to repeat the carbonation cycle. The carbonated ash residue is refined with a CO 2 pressure swing step to produce high-purity precipitated calcium carbonate. In another variation, Ca-rich produced water brine serves as the Ca-source to mineralize CO 2 . An H + /Na + ion-exchange cycle was designed to provision alkalinity during mineralization and regenerate the ion-exchange reagent in brines with high salinity. Ca-depleted brines can then be treated within a centralized water treatment facility. Both variations beneficially utilize reject streams—such as coal ashes and brines from oil and gas extraction or CO 2 storage operations—that are available at substantial quantities in the vicinity of coal power plants within the U.S. In addition to technology development, this project included techno-economic and life-cycle analysis to identify technically and economically appropriate solutions for power plants in different geographic locations. Taken together, the project provides a unique route to integrate CO 2 emissions control and waste handling/treatment for coal power plants, while producing a high-value product to offset the economic burden associated with waste management. The developed processes utilize post-desulfurization flue gas from coal-fired power plants as is. The CO 2 conversion reactions are performed in alkaline brines at ambient pressure from the flue gas, thereby minimizing the energy burden. By beneficiation of industrial waste streams with low energy input, the processes offers significant technical advantages in energy and CO 2 footprint over the current paradigm of precipitated calcium carbonate production, which involves calcination of limestone at processing temperatures in excess of 800 °C. Overall, this project developed viable CO 2 mineralization processes while strategically maximizing the economic benefit.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2022

CO 2 hydrogenation: Selectivity control of CO versus CH 4 achieved using Na doping over Ru/m-ZrO 2 at low pressure

By doping 1%Ru/m-ZrO 2 with sodium, selectivity tuning between CO and CH 4 during CO 2 hydrogenation was achieved by controlling the relative rates of reverse water-gas shift and CO methanation. By increasing basicity through Na loading: (1) the formate C-H bond is weakened in DRIFTS of adsorbed CO, accelerating C-H bond formation of formate and promoting CO formation at the Ru/m-ZrO 2 interface; and (2) the coverage of Na increases on ensembles of Ru atoms responsible for methanation. Increasing Na content shifts selectivity from CH 4 (useful for synthetic natural gas) to CO, which can be used for Fischer-Tropsch synthesis or methanol-to-gasoline. Electronic modification of formate is likely due to enhanced basicity (strengthening bonding between catalyst and the-CO 2 function of formate and weakening C-H). In conclusion, no electron transfer from Na to Ru was detected in XANES. DRIFTS as a function of time and XPS results showed that Na exacerbates site blocking and deactivation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

NaCo 2 (SeO 3 ) 2 (OH): competing magnetic ground states of a new sawtooth structure with 3d 7 Co 2+ ions

While certain magnetic sublattices have long been known theoretically to give rise to emergent physics via competing magnetic interactions and quantum effects, finding such configurations in real materials is often deeply challenging. Here we report the synthesis and characterization of a new such material, NaCo 2 (SeO 3 ) 2 (OH) which crystallizes with a highly frustrated sublattice of sawtooth Co 2+ chains. Single crystals of NaCo 2 (SeO 3 ) 2 (OH) were synthesized using a low-temperature hydrothermal method. X-ray single crystal structure analysis reveals that the material crystallizes in orthorhombic space group of Pnma (no. 62). Its crystal structure exhibits one-dimensional chains of corner-sharing isosceles triangles that are made of two crystallographically distinct 3d 7 Co 2+ sites (Co(1) and Co(2)). The chains run along the b-axis and are interconnected via [SeO 3 ] groups to form a three-dimensional structure mediating super-exchange interactions. The temperature dependent magnetization data show a ferromagnetic-like (FM) transition at 11 K (T 1 ) followed by an antiferromagnetic (AFM) transition at about 6 K (T 2 ). Neutron-powder diffraction measurements reveal that at T 1 = 11 K only the Co(2) site orders magnetically, forming ferromagnetic zigzag chains along the b-axis. Below T 2 = 6 K, both Co(1) and Co(2) sites order in a nearly orthogonal configuration, with Co(1) moments lying inside the plane of the sawtooth chain while Co(2) moments cant out of the plane. The canting of the magnetic moments leads to a net ferromagnetic component along b-axis, parallel to the chain direction. The ordered moments are fully compensated in the ac-plane. Inelastic neutron scattering measurements reveal crystal field excitations that are consistent with the presence of a spin–orbital entangled pseudo-spin state J eff = 1/2 for the Co 2+ ions. Low-energy spin-wave excitations are observed below the second magnetic transition. The analysis of powder excitation spectrum suggests complex exchange interactions that go beyond a Heisenberg Hamiltonian model with nearest neighbor couplings. Our results demonstrate the richness of the magnetic properties of sawtooth-type structures and encourage the study of similar structures with different oxyanion groups.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Tuning the hydrogenation of CO 2 to CH 4 over mechano-chemically prepared palladium supported on ceria

CO 2 methanation reactivity, reaction mechanism, and surface structure were investigated on a mechanochemically prepared Pd/CeO 2 catalyst (PdAcCeO 2 -M), where an oxidative pretreatment (-o) increased methane yield by a factor of two compared to a reductive pretreatment (-h). Methanation rates were maintained for over 48 h and further increased upon oxidative regeneration treatments. The surface species of both PdAcCeO 2 -M-o and PdAcCeO 2 -M-h were explored via in situ CO 2 and CO hydrogenation DRIFTS, where CO hydrogenation effectively models the dissociative CO 2 mechanism (CO 2 → CO → CH 4 ). PdAcCeO 2 -M-o yielded distinct Pd-CO adsorption and the absence of monodentate carbonate at ~ 1400 cm -1 , while AP-XPS showed that PdAcCeO 2 -M-o yielded a unique Pd δ+ contribution at 335.9 eV. By gaining insights from various in situ spectroscopic techniques, and by breaking the CO 2 hydrogenation mechanism into piecewise steps, a deeper understanding of the direct CO 2 reduction towards methane and CO over mechanochemically prepared Pd/CeO 2 catalysts was obtained.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Investigation of Mass Transfer and Sorption in CO 2 /Brine/Rock Systems via In Situ FT-IR

CO 2 geological storage in deep saline formations is considered a promising method to mitigate anthropogenic CO 2 emissions and, thereby, minimize changes to the Earth’s atmosphere. A fundamental understanding of CO 2 mass transfer and sorption phenomena in brine-saturated reservoir formations is necessary to understand the long-term fate of injected CO 2 as it is subjected to different (physical, dissolution, and mineral) trapping mechanisms. In this work, we investigate CO 2 sorption in brine-saturated and dry Mt. Simon sandstone samples via in-situ Fourier Transform infrared spectroscopy (FT-IR) at elevated pressures, ranging from 0.3 MPa to 8.3 MPa, at a temperature of 50 ⁰C. The FT-IR spectra of bulk-phase CO 2 were simultaneously recorded under the same conditions. For bulk-phase CO 2 , we observed, in agreement with past studies, a doublet peak at 2361 cm -1 and 2336 cm -1 and another peak (ν 2 bending mode) at 667 cm -1 . With increasing pressure, the position of the peak at 667 cm -1 remains invariant, however, when crossing into the supercritical region the doublet peak degenerates onto a single peak at 2336 cm -1 with a barely visible shoulder at 2361 cm -1 . The bulk CO 2 data provide a perfect fit for Beer’s law for the whole range of pressure conditions. For the dry sample, the IR spectrum is experimentally indistinguishable from the bulk CO 2 spectrum, signifying that if physical adsorption occurs to any significant extent, the adsorbed CO 2 molecules are not substantially more rotationally constrained than the dense bulk CO 2 molecules. For the brine-saturated sample, we observe a strong band centered at 2342 cm -1 and a small companion peak at 2360-2361 cm -1 that degenerates into a barely visible shoulder peak at the higher pressures. The 2342 cm -1 band has been previously observed by other investigators for CO 2 dissolved in bulk water/brine as well during its adsorption on a variety of other wet natural porous media. We observe no peaks corresponding to bicarbonate or carbonate bulk species, which correlates well with the prior literature on similar low-pH aqueous solutions. The integrated peak area for the CO 2 sorbed in the brine-saturated sample correlates linearly with its solubility in the same bulk brine, as measured separately via a PVT-cell approach. Here, this validates the accuracy of both techniques, and the potential of the FT-IR method to be used in the study of mass transfer and adsorption in such systems. To that effect, a simple mathematical model is presented to analyze the FT-IR data to determine the CO 2 effective diffusivity in the brine-saturated sandstone sample.

58 GEOSCIENCES↗
DOE OSTI2021

Deep learning inversion of gravity data for detection of CO 2 plumes in overlying aquifers

In this work, we developed an effective U-Net based deep learning (DL) model for inversion of surface gravity data on a rectangular grid to predict 2-D high-resolution subsurface CO 2 distribution along a vertical cross-section due to CO 2 leakage through a wellbore within a deep CO 2 storage reservoir. We used synthetic data to model two types of CO 2 leakage scenarios: one CO 2 plume in a shallow aquifer (single plume case), and two plumes present at different depths (double plume case). The 3-D synthetic plume samples were created by sampling among predetermined CO 2 plume depths, saturations, and volumes. The corresponding surface gravity data on a rectangular grid were generated by a 3-D forward model. The U-Net model detected 72% of single-plume samples, and one or both plumes in 75% of double-plume samples. Most of the undetected single plumes have small gravity field strengths below the typical noise level of 5 μGal. This model generated reproducible, reliable predictions with acceptable errors and demonstrated improved spatial resolution over the conventional least-squares inversion. In contrast to the conventional least-squares inversion, which often overestimates the size of its target and underestimates its density, this U-Net model accurately delineated the boundary of a target. Furthermore, this DL inversion detected deep, small, or low saturation CO 2 plumes that are often more difficult to resolve with conventional gravity inversion methods. We note the limitations of this feasibility study, including the use of synthetic data with regular CO 2 plume shapes, and the prediction of a 2-D plume cross-section rather than the full 3-D plume, as well, we recognize the lower detection fraction for double-plume scenarios. Nevertheless, this study demonstrates that DL gravity inversion is a promising and potentially superior method to conventional least-squares inversion. Our U-Net based deep learning inversion approach may be adapted for inversion of other types of geophysical data. DL inversion can facilitate near real-time monitoring of geologic carbon sequestration to provide site operators with prompt information about subsurface CO 2 distribution for risk management and mitigation.

58 GEOSCIENCES↗
DOE OSTI2023

Precisely modulate interfacial Bi-O bridge bond in Co-TCPP/Bi 3 O 4 Br to trigger long-lasting charge separation for boosting CO 2 photoreduction

Insufficient charge separation and feeble CO 2 activation limit the CO 2 photoreduction efficiency. It is highly desirable to consciously construct organic–inorganic hybrid composites to simultaneously accelerate charge separation and provide favorable active sites. Herein, a defect-induced interfacial Bi-O bridge bond is constructed by grafting terminal O of cobalt porphyrin (Co-TCPP) with Bi 3 O4Br. Systematic investigations reveal that the Bi-O bridge bond as the charge migration bridge accelerates the extraction and transfer of electron from the external [Bi 3 O 4 ] layers to Co-TCPP, and the millisecond separation lifetime of electrons on Co-TCPP can be achieved. Co atoms as the active sites optimized the CO 2 adsorption and activation, thus promoting the formation of COOH*. As a result, the CO 2 photoreduction rate of 0.5% Co-TCPP/Bi 3 O4Br reaches 71.3 μmol g -1 h -1 in pure water, 2.53-fold of that on the pristine Bi 3 O4Br. This work provides atomistic insights and strategies for the construction of new organic–inorganic hybrid materials for artificial photosynthesis and CO 2 photoreduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Volatile Products of the Autoxidation of Poly(ethylenimine) in CO 2 Sorbents

Poly(ethyleneimine) (PEI)-based CO 2 sorbents are a promising material class for use in CO 2 capture applications, particularly direct air capture (DAC), due to their high amine content and CO 2 capacities. The sorbent lifetime is a key uncertainty in the deployment of these materials in such applications, as they oxidize under conditions relevant to candidate DAC process cycles. Here, in this study, we utilize thermogravimetric analysis/differential scanning calorimetry/FTIR spectroscopy to characterize the nature, rate, and quantity of volatile species formed from the oxidation of PEI when supported on mesoporous Al 2 O 3 . We show that NH 3 , CO 2 , and H 2 O are primary volatile species formed from PEI oxidation and that their production rate matches the overall oxidation rate as measured via heat flow from a differential scanning calorimeter. We show that the total quantity of NH 3 evolved is consistent with terminal primary amines being cleaved from the polymer chain and that approximately one hydrogen atom per PEI repeat unit reacts to form H 2 O during the reaction. Finally, metadynamics and quantum chemical simulations performed on a simplified system are used to highlight the likely importance of radicals in the elementary reactions that comprise the oxidation reaction set. The findings here represent the first characterization of the volatile products from the oxidation of PEI in CO 2 sorbents and lead to a greater understanding of the mechanisms behind the oxidative degradation of these materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Active Sites of Cobalt Phthalocyanine in Electrocatalytic CO 2 Reduction to Methanol

Many metal coordination compounds catalyze CO 2 electroreduction to CO, but cobalt phthalocyanine hybridized with conductive carbon such as carbon nanotubes is currently the only one that can generate methanol. The underlying structure–reactivity correlation and reaction mechanism desperately demand elucidation. Here, in this study, we report the first in situ X-ray absorption spectroscopy characterization, combined with ex situ spectroscopic and electrocatalytic measurements, to study CoPc-catalyzed CO 2 reduction to methanol. Molecular dispersion of CoPc on CNT surfaces, as evidenced by the observed electronic interaction between the two, is crucial to fast electron transfer to the active sites and multi-electron CO 2 reduction. CO, the key intermediate in the CO 2 -to-methanol pathway, is found to be labile on the active site, which necessitates a high local concentration in the microenvironment to compete with CO 2 for active sites and promote methanol production. A comparison of the electrocatalytic performance of structurally related porphyrins indicates that the bridging aza-N atoms of the Pc macrocycle are critical components of the CoPc active site that produces methanol. In situ X-ray absorption spectroscopy identifies the active site as Co(I) and supports an increasingly non-centrosymmetric Co coordination environment at negative applied potential, likely due to the formation of a Co−CO adduct during the catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Promoting electrochemical reduction of CO 2 to ethanol by B/N-doped sp 3 /sp 2 nanocarbon electrode

Electrochemical reduction of CO 2 to value-added chemicals holds promise for carbon utilization and renewable electricity storage. However, selective CO 2 reduction to multi-carbon fuels remains a significant challenge. Here, we report that B/N-doped sp 3 /sp 2 hybridized nanocarbon (BNHC), consisting of ultra-small nanoparticles with a sp 3 carbon core covered by a sp 2 carbon shell, is an efficient electrocatalyst for electrochemical reduction of CO 2 to ethanol at relatively low overpotentials. CO 2 reduction occurs with a Faradaic efficiency of 58.8%-69.1% for ethanol and acetate production at –0.5 ~ –0.6 V (vs. RHE), among which 51.6%-56.0% is for ethanol. The high selectivity for ethanol is due to the integrated effect of sp 3 /sp 2 carbon and B/N doping. Finally, both sp 3 carbon and B/N doping contribute to enhanced ethanol production with sp 2 carbon reducing the overpotential for CO 2 reduction to ethanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

A Monolithic Artificial Leaf for Solar Methanol Production from CO 2 and H 2 O

Methanol, an important liquid fuel and chemical feedstock, has yet to be produced using solar energy, H 2 O, and CO 2 as sole inputs in a standalone device. Here, this study directly addresses this longstanding challenge through presenting the first demonstration of unbiased solar methanol production from CO 2 and H 2 O with a monolithic artificial leaf design, surpassing the previous best energy efficiency in solar alcohol production by at least 1 order of magnitude. We first develop a new generation of photocathodes based on Si micropillar arrays and a cobalt tetraaminophthalocyanine molecular catalyst. By integrating a C 60 interlayer that facilitates unidirectional electron transfer through the semiconductor/catalyst interface, we realize a photovoltage of 500 mV, one of the highest recorded for single-junction Si-based photoelectrodes in aqueous CO 2 reduction, as well as unprecedented methanol formation with a Faradaic efficiency of 30% and a partial current density of 6.3 mA cm –2 . We further integrate the photocathode with a multijunction perovskite photovoltaic minimodule to afford a standalone solar fuel system, which demonstrates a light-to-methanol conversion efficiency of 0.8%, 32 times higher than the present record in light-to-alcohol conversion with an artificial leaf.

alcohols↗
DOE OSTI2022

Consistent responses of vegetation gas exchange to elevated atmospheric CO 2 emerge from heuristic and optimization models

Elevated atmospheric CO 2 concentration is expected to increase leaf CO 2 assimilation rates, thus promoting plant growth and increasing leaf area. It also decreases stomatal conductance, allowing water savings, which have been hypothesized to drive large-scale greening, in particular in arid and semiarid climates. However, the increase in leaf area could reduce the benefits of elevated CO 2 concentration through soil water depletion. The net effect of elevated CO 2 on leaf- and canopy-level gas exchange remains uncertain. To address this question, we compare the outcomes of a heuristic model based on the Partitioning of Equilibrium Transpiration and Assimilation (PETA) hypothesis and three model variants based on stomatal optimization theory. Predicted relative changes in leaf- and canopy-level gas exchange rates are used as a metric of plant responses to changes in atmospheric CO 2 concentration. Both model approaches predict reductions in leaf-level transpiration rate due to decreased stomatal conductance under elevated CO 2 , but negligible (PETA) or no (optimization) changes in canopy-level transpiration due to the compensatory effect of increased leaf area. Leaf- and canopy-level CO 2 assimilation is predicted to increase, with an amplification of the CO 2 fertilization effect at the canopy level due to the enhanced leaf area. The expected increase in vapour pressure deficit (VPD) under warmer conditions is generally predicted to decrease the sensitivity of gas exchange to atmospheric CO 2 concentration in both models. The consistent predictions by different models that canopy-level transpiration varies little under elevated CO 2 due to combined stomatal conductance reduction and leaf area increase highlight the coordination of physiological and morphological characteristics in vegetation to maximize resource use (here water) under altered climatic conditions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Probing the surface of promoted CuO-Cr 2 O 3 -Fe 2 O 3 catalysts during CO 2 activation

The influence of basic oxide promoters on copper-chromium-iron oxide catalysts was investigated to determine the nature of surface oxygen species and structure-activity relationship for the reverse water-gas shift reaction. The catalysts were characterized with in situ XRD, in situ Raman, in situ XPS, in situ HS-LEIS and H 2 -TPR. Two surface oxygen sites with different reduction characteristics were found to be present. The overall CO 2 activation rate was found to correlate with both the number and reducibility of the more active oxygen species that were likely associated with the Cu-FeO x interfacial regions for enhanced hydrogen spillover. While addition of K 2 O somewhat preserved the interfacial regions and facilitated the reduction kinetics of surface oxygen, both Na 2 O and CaO significantly suppressed the availability of metallic Cu as well as the Cu-FeO x interfaces, leading to decreased reactivity. These findings provide a direction to promote the copper-iron catalysts by creating more metal-metal oxide interfacial sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗