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DOE OSTI2021

Electrocatalytic Reduction of CO 2 to CO over Ag(110) and Cu(211) Modeled by Grand-Canonical Density Functional Theory

We report the results of modeling CO 2 reduction (CO 2 R) to CO over Ag(110) and Cu(211) surfaces at different applied potentials using grand-canonical density functional theory (GC-DFT), a method specifically designed to accurately model electrochemical systems. In addition to demonstrating GC-DFT’s ability to accurately model electrochemical processes, we also compare it with the computational hydrogen electrode (CHE) approach. GC-DFT predicts that the geometries of these reacting systems strongly depend on the applied potential and the Helmholtz free energies vary nonlinearly with the applied potential, which contradicts a central assumption of the CHE approach. The CHE approach neglects the change in the number of electrons on the electrode surface at different applied potentials, which reduces its accuracy as the potential changes from the potential of zero charge. Our results further demonstrate that the grand free energies of the reaction intermediates not only depend on the value of the applied potential but also on the metal surface type, adsorption site, and adsorbate. GC-DFT’s ability to predict the effect of the applied potential on adsorbate geometry enables it to evaluate different possible reaction mechanisms at different applied potentials. For instance, GC-DFT predicts that the first step of CO2R likely switches from proton-coupled electron transfer to sequential electron transfer and then proton transfer at more reducing potentials, a result that cannot be determined by the CHE because it assumes that all electron transfers are coupled to proton transfers and neglects the effect of the applied potential on the adsorbate geometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Theoretical Investigation of the Adsorbate and Potential–Induced Stability of Cu Facets During Electrochemical CO 2 and CO Reduction

The activity and product selectivity of electrocatalysts for reactions like the carbon dioxide reduction reaction (CO 2 RR) are intimately dependent on the catalyst's structure and composition. While engineering catalytic surfaces can improve performance, discovering the key sets of rational design principles remains challenging due to limitations in modeling catalyst stability under operating conditions. Herein, we perform first-principles density functional calculations adopting implicit solvation methods with potential control to study the influence of adsorbates and applied potential on the stability of different facets of model Cu electrocatalysts. Using coverage dependencies extracted from microkinetic models, we describe an approach for calculating potential and adsorbate-dependent contributions to surface energies under reaction conditions, where Wulff constructions are used to understand the morphological evolution of Cu electrocatalysts under CO 2 RR conditions. Here we identify that CO*, a key reaction intermediate, exhibits higher kinetically and thermodynamically accessible coverages on (100) relative to (111) facets, which can translate into an increased relative stabilization of the (100) facet during CO 2 RR. Our results support the known tendency for increased (111) faceting of Cu nanoparticles under more reducing conditions and that the relative increase in (100) faceting observed under CO 2 RR conditions is likely attributed to differences in CO* coverage between these facets.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2026

Third-body stabilization of supercritical CO 2 in CO oxidation: development and application of a ReaxFF force field for the CO/O/CO 2 system

Supercritical CO 2 (scCO 2 ) plays a crucial role as a solvent in separation processes, advanced power cycles, and materials processing. Nonetheless, the atomistic comprehension of how the dense scCO 2 matrix influences the fundamental reaction of carbon monoxide (CO) is still insufficiently explored. Experimental studies and molecular dynamics (MD) simulations frequently fail to detect the highly reactive, transient intermediates, such as atomic oxygen (O), that drive these reactions. Here, to address this issue, we have developed a novel ReaxFF reactive force field for the CO 2 /CO/O system. The force field parameters were calibrated using density functional theory and second-order Møller-Plesset calculations to model CO 2 crystal properties, intermolecular interactions, bond dissociation curves, and reaction energy barriers. The force field reproduces the cohesive energy of the CO 2 crystal, the pressure characteristics of bulk scCO 2 , the equation-of-state behavior over a wide pressure–density range, the pressure dependence of the C–O bond length under compression, and the structural properties of liquid and scCO 2 , as documented by experiments, ab-initio MD, and prominent non-reactive models. The force field was subsequently applied to study the CO + O → CO 2 reaction. In a dilute environment, the reaction is inefficient as the newly formed CO 2 rapidly dissociates due to excess kinetic and potential energy acquired from the exothermic reaction. Conversely, in a dense scCO 2 environment, the surrounding matrix acts as an efficient third body, stabilizing the emerging CO2 product via molecular collisions. Statistical analysis confirms an average excess energy dissipation of 133.9 ± 3.6 kcal/mol over 112.4 ± 17.9 ps. Kinetic energy decomposition reveals that ∼ 92% of the excess kinetic energy is stored in internal (rotational and vibrational) degrees of freedom. This ReaxFF force field establishes a mechanistic foundation for third-body stabilization in dense reactive environments.

Chowdhury, Emdadul Haque [Pennsylvania State Univ.↗

DOE OSTI2025

Hyperselective carbon membranes for precise high-temperature H 2 and CO 2 separation

More than 90% of the world’s hydrogen (H 2 ) is produced from fossil fuel sources, which requires energy-intensive separation and purification to produce high-purity H 2 fuel and to capture the carbon dioxide (CO 2 ) by-product. While membranes can decarbonize H 2 /CO 2 separation, their moderate H 2 /CO 2 selectivity requires secondary H 2 purification by pressure swing adsorption. Here, we report hyperselective carbon molecular sieve hollow fiber membranes showing H 2 /CO 2 selectivity exceeding 7000 under mixture permeation at 150°C, which is almost 30 times higher than the most selective nonmetallic membrane reported in the literature. The membrane is able to maintain an ultrahigh H 2 /CO 2 selectivity over 1400 under mixture permeation at 400°C. Pore structure characterization suggests that highly refined ultramicropores are responsible for effectively discriminating the closely sized H 2 and CO 2 molecules in the hyperselective carbon molecular sieve membrane. Modeling shows that the unprecedented H 2 /CO 2 selectivity will potentially allow one-step enrichment of fuel-grade H 2 from shifted syngas for decarbonized H 2 production.

Science & Technology - Other Topics↗

DOE OSTI2023

Sensitivity Analysis Tool for Electrochemical Conversion of CO 2 To CO: User Guide

This is the user guide for the tool described here: Development of technologies that convert carbon dioxide (CO 2 ) into products is part of the U.S. Department of Energy's Office of Fossil Energy and Carbon Management Carbon Conversion Program portfolio. One such technology under development converts CO 2 to value-added products via electrochemical reduction, where catalysts are used on the cathode to promote CO 2 conversion across the electrochemical catalyst (ECC) cell. Broadly, the ECC is integrated with balance of plant (BOP) equipment (e.g., compressors, pumps, heat exchangers, purification units) in system configurations to produce the desired product. To guide research and development (R&D) toward advancements that may make such conversion technologies economically competitive, researchers may use sensitivity analyses related to the ECC system cost and performance, including that of the cathodic and anodic catalysts. This tool is intended to inform developers and Program in assessing proposed R&D on ECC systems early in the development process. Results will guide researchers on where efforts would be best directed. The tool may be accessed here: https://www.netl.doe.gov/energy-analysis/details?id=55293cb1-6881-4181-a2b0-d00b711ce74b.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Deep mitigation of CO 2 and non-CO 2 greenhouse gases toward 1.5 °C and 2 °C futures

Stabilizing climate change well below 2 °C and towards 1.5 °C requires comprehensive mitigation of all greenhouse gases (GHG), including both CO 2 and non-CO 2 GHG emissions. Here we incorporate the latest global non-CO 2 emissions and mitigation data into a state-of-the-art integrated assessment model GCAM and examine 90 mitigation scenarios pairing different levels of CO 2 and non-CO 2 GHG abatement pathways. We estimate that when non-CO 2 mitigation contributions are not fully implemented, the timing of net-zero CO 2 must occur about two decades earlier. Conversely, comprehensive GHG abatement that fully integrates non-CO 2 mitigation measures in addition to a net-zero CO 2 commitment can help achieve 1.5 °C stabilization. While decarbonization-driven fuel switching mainly reduces non-CO 2 emissions from fuel extraction and end use, targeted non-CO 2 mitigation measures can significantly reduce fluorinated gas emissions from industrial processes and cooling sectors. Our integrated modeling provides direct insights in how system-wide all GHG mitigation can affect the timing of net-zero CO 2 for 1.5 °C and 2 °C climate change scenarios.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

On the Quantitative CO 2 Subsurface Monitoring: Rock Physics for CO 2 Storage and CO 2 EOR

Paper presented at 16th International Conference on Greenhouse Gas Control Technologies (GHGT-16), October 23–27, 2022, Lyon, France. Rock physics is key to understanding the feasibility of monitoring and the actual monitoring of the location and volume of CO 2 in the subsurface. Examples from the Broom Creek Formation of the Williston Basin in North Dakota and the Muddy Formation of the Powder River Basin in Montana and Wyoming are used to show the effect of geology and injection of CO 2 on the velocity and density of reservoir rocks.

20 FOSSIL-FUELED POWER PLANTS↗

DOE OSTI2022

In-situ investigation of the vibrational properties of H 2 O CO 2 -bearing and dry K-rich basaltic glasses at high pressure by mid infrared spectroscopy

Here, the vibrational properties of CO 2 –H 2 O-bearing and dry synthetic K-rich basaltic glasses were investigated at room temperature and pressures between 0.0001–5.5 GPa using the diamond anvil cell combined with in situ reflectance and transmittance Fourier Transform infrared micro-spectroscopy. The absorption coefficient a(v) calculated from the Kramers-Kronig relation shows that glasses are dominated by the Q 2 aluminosilicate unit followed by Q 1 , Q 3 . The variation in Q n concentration upon compression suggests that glasses undergo polymerization from ambient pressure to 2 GPa followed by less marked structural changes up to 4 GPa, above which the structure is further polymerized. Once decompressed, glasses retained a polymerized structure. Our results show that 1.03 wt% CO 2 -1.42 wt% H 2 O in a glass with 3.10 wt% K 2 O and 46.77 wt% SiO 2 prevent the formation of fully polymerized connections when cold-compressed. Our results can be used to explain the effect of volatiles and alkali on the rheology of natural basaltic magmas.

36 MATERIALS SCIENCE↗

DOE OSTI2025

CpFe(CO) 2 Radical Generated from Dinuclear [CpFe(CO) 2 ] 2 and Mononuclear (Cp)(CO) 2 Fe(H): Density Functional Theory Is Accurate for One, But Not Both

Density functional theory (DFT) methods remain the most practical approach to calculating properties and reaction mechanisms of transition metal complexes. While the accuracy of DFT methods has been evaluated for some properties of mononuclear organometallic complexes there has been a general lack of evaluation for dinuclear organometallic complexes, in particular bonding changes related to reaction mechanisms. Here, this work evaluated DFT and coupled cluster methods for the accuracy of calculating the CpFe(CO) 2 radical (Fp•) generated from dinuclear [CpFe(CO) 2 ] 2 (Fp 2 ) and mononuclear [(Cp)(CO) 2 Fe(H)] (Fp-H). This transition metal radical fragment was evaluated because dinuclear complexes built with it have recently shown a variety of unique reactions but has proven challenging to accurately calculate with DFT methods. Here we show that DFT methods provide a surprising wide range of fragmentation energies for Fp 2 and lower and mid rung DFT methods as well as DLPNO–CCSD(T) perform well for this dissociation energy. The highest rung double-hybrid methods have a large range in the Fp 2 dissociation energy, and the energy greatly depends on the amount of MP2 correlation energy included. For generating Fp• from Fp-H the lower and mid rung methods that worked well for Fp 2 showed significant error. Double-hybrid methods unfortunately are only accurate for the Fe–H bond if they are very inaccurate for the Fp 2 dissociation energy. While DLPNO–CCSD(T) is not perfect, and not close to chemically accurate for the Fe–H bond, it does provide reasonable accuracy for both Fp 2 and Fp-H dissociation energies.

density functional theory↗

DOE OSTI2022

Effect of N 2 - and CO 2 -containing shielding gases on composition modification and carbonitride precipitation in wire arc additive manufactured grade 91 steel

Additive manufacturing (AM) represents a promising technique to fabricate metallic alloys with greater control of the resulting material features as compared to traditional manufacturing routes. Recently, there is greater interest in AM research on 9 wt% Cr ferritic/martensitic (F/M) steels, which are commonly studied for use in the nuclear energy industry. This work aims to prove that wire arc AM can manufacture F/M steels with adequate mechanical properties in multiple processing atmospheres and aims to study how shielding gas composition can be leveraged during fabrication to induce specific precipitation pathways. The effect of shielding gas composition on MX (M=Nb and/or V, Xdouble bondC and/or N) carbonitride precipitation in a 9 wt% Cr ferritic/martensitic (F/M) steel alloy known as Grade 91 was studied using N 2 and CO 2 gas additions to an inert Ar shielding gas atmosphere during wire arc AM. The N and C atoms present in the processing atmospheres were absorbed into the melt pools during fabrication. Due to their differing affinities for precipitate-forming reactions, the varying levels of C and N between the samples contributed to differences in final carbonitride composition and morphologies. Such precipitate behavior is of interest as carbonitrides have been shown to contribute to increased mechanical performance. This increased performance was studied via electron microscopy and tested for strength, ductility, and fracture properties.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Storing Co 2 in Built Infrastructure: Co 2 Carbonation of Precast Concrete Products

The overall objective of the proposed study was to advance the technical understanding of CO 2 incorporation into novel cementitious materials for the development of high value products that provide a net reduction in carbon emissions. This project combined two primary phases of research that addressed technical barriers related to (i) optimizing CO 2 storage capability of cementitious materials, (ii) evaluating and enhancing physical properties of novel carbonated materials, and (iii) assessing the reductions in life cycle CO 2 emissions attributed to CO 2 carbonation of precast cementitious materials. Engineered cementitious composites (ECC) are a class of highly ductile concrete composites that have been shown to be very durable when used in the built environment. CO 2 carbonation of ECC was examined in this study and it was found that precast ECC specimens could sequester up to 35% CO 2 by cement mass after 24 hours of curing at a CO 2 pressure of 0.5 MPa and 23°C and had a strain capacity of 3%. Carbonation conditions were optimized at the bench-scale and then utilized to create full-scale CO 2 -cured ECC railroad ties that were field tested on a train track. Rail ties were selected for this initial assessment of CO 2 storage in precast concrete materials due to the large market for concrete ties in the railroad industry. Although the full-scale rail ties passed all of the required American Railway Engineering and Maintenance-of-Way Association qualifying mechanical tests, on-track testing of the CO 2 -cured ECC rail ties was unsuccessful due to fiber alignment in the ECC the during the rail tie casting process which prevented the material from achieving the expected level of strain capacity. This result highlights the challenge in scaling up bench-scale processes to full-scale product manufacturing and requires additional investigation into the casting process of large-scale infrastructure elements using ECC combined with carbonation curing. Life cycle assessment of a CO 2 -cured ECC rail tie versus a traditional concrete rail tie indicates that the ECC tie can have lifecycle carbon savings of between 11% and 51% depending on how much longer its useful lifetime is compared to traditional concrete rail ties. Both carbon and cost savings are driven by a reduction in the need to replace broken rail ties, so the key factor is the extent to which a CO 2 -cured ECC rail tie will have increased lifetime durability compared to alternative rail ties.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2025

Reductant‐ or Light‐Driven ATP‐Independent Reduction of CO 2 by Nitrogenase MoFe Protein

Nitrogenase is a versatile metalloenzyme that activates and reduces small molecules like N 2 , CO, and CO 2 into value-added chemicals at ambient conditions. Previously, it is shown that the Mo-nitrogenase could reduce CO 2 to CO, but not to hydrocarbons, in an ATP-dependent reaction. Here, it is reported that the ability of the catalytic component of Mo-nitrogenase (MoFe protein) enables ATP-independent reduction of CO 2 to up to C 4 hydrocarbons in room-temperature reactions driven by a chemical reductant (Eu II –DTPA) or visible light (via CdS@ZnS (CZS) quantum dots). Moreover, an opposite deuterium isotope effect is observed on the Eu II –DTPA driven reactions of CO 2 reduction by MoFe protein and its V-counterpart (VFe protein), in that the former displays higher activities in H 2 O, and the latter displays higher activities in D 2 O. Furthermore, these results provide an important foundation for further mechanistic exploration of the nitrogenase-enabled, atypical Fischer–Tropsch type reaction that uses CO 2 instead of CO as a substrate; moreover, they serves as a potential template for the future development of nitrogenase-based applications that effectively recycle the greenhouse gas CO 2 into valuable fuel products.

C-C coupling↗

DOE OSTI2021

Binary Atomically Dispersed Metal-Site Catalysts with Core–Shell Nanostructures for O 2 and CO 2 Reduction Reactions

Engineering atomically dispersed metal site catalysts with controlled local coordination environments and 3D nanostructures effectively improves the catalytic performance for the oxygen reduction reaction (ORR) and the carbon dioxide reduction reaction (CO 2 RR), which are critical for clean energy conversion and chemical production. Herein, an innovative approach for preparing core-shell nanostructured catalysts with different single-metal sites in the core and the shell, respectively, is developed. In particular, as the shell precursors, covalent organic polymers with a thin layered structure that is polymerized in situ and coated on a metal-doped ZIF-derived carbon core are used, followed by a controlled thermal activation. The selective combination and construction of different metal sites increase active site density in the surface layers, promote structural robustness, facilitate mass/charge transfer, and yield a possible synergy of active sites in the core and the shell. The p-FeNC(shell)@CoNC(core), consisting of a polymerized FeTPPCl-derived carbon layer (p-FeNC) on a Co-doped ZIF-derived carbon (CoNC), exhibits remarkable ORR activity and stability in acidic media along with encouraging durability in H 2 –air fuel cells. Likewise, a p-FeNC(shell)@NiNC(core) catalyst demonstrates outstanding CO 2 RR activity and stability. Hence, integrating two appropriate single-metal sites in core and shell precursors, respectively, can modulate morphological and catalytic properties for a possible synergy toward different electrocatalysis processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Joint impedance and facies inversion of time-lapse seismic data for improving monitoring of CO 2 incidentally stored from CO 2 EOR

Time-lapse seismic monitoring is an effective and proven technology for mapping the distribution of CO 2 in a subsurface reservoir. When injected CO 2 displaces other reservoir fluids, porous-medium properties are changed and thus the seismic impedance changes, causing time-lapse seismic amplitude differences in the injection zones. The analysis and interpretation of images created from these amplitude differences can provide information about reservoir architecture and the CO 2 migration within the reservoir. Incorporating seismic inversion and rock physics into the interpretation of time-lapse seismic data can considerably improve the modeling and monitoring to detect and assess the location of CO 2 over time. The joint inversion method presented in this paper has an integral representation of the geology in the inversion algorithm using elastic facies, which provides information about the spatial distribution of the geologic heterogeneities controlling the movement of fluids in the reservoir. The method was successfully applied to time-lapse seismic data from a mature oil field undergoing CO 2 enhanced oil recovery. The estimated seismic acoustic impedances and facies reflect the characteristics of individual geologic facies and fluid conditions of the reservoir subject to CO 2 injection. Finally, the probabilities estimated by the joint impedance and facies inversion for the reservoir's litho-fluid facies can be used for forecasting CO 2 saturation and pressure changes within the target reservoir.

4D seismic↗

DOE OSTI2023

Producing Greener (Lower Carbon) Oil Through CO 2 -Enhanced Oil Recovery (CO 2 -EOR)

Conference presentation at at 22nd European IOR+ Symposium, The Hague, Netherlands, October 2–4, 2023. This study explored the sensitivity of the net life cycle greenhouse gas (GHG) emissions of a CO 2 -enhanced oil recovery (CO 2 -EOR) system to three critical input parameters: i) CO 2 capture efficiency (70%, 80%, 90%, and 95%), ii) electricity grid mix emission factor (400, 500, 600, and 700 kgCO 2 e/MWh), and iii) net CO 2 utilization rate (315, 421, 526, 789, and 1052 kgCO 2 /bbl [6, 8, 10, 15, and 20 Mcf/bbl]).

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2022

Photocatalytic Aqueous CO 2 Reduction to CO and CH 4 Sensitized by Ullazine Supramolecular Polymers

There has been rapid progress on the chemistry of supramolecular scaffolds that harness sunlight for aqueous photocatalytic production of hydrogen. However, great efforts are still needed to develop similar photosynthetic systems for the great challenge of CO 2 reduction especially if they avoid the use of nonabundant metals. This work investigates the synthesis of supramolecular polymers capable of sensitizing catalysts that require more negative potentials than proton reduction. The monomers are chromophore amphiphiles based on a diareno-fused ullazine core that undergo supramolecular polymerization in water to create entangled nanoscale fibers. Under 450 nm visible light these fibers sensitize a dinuclear cobalt catalyst for CO 2 photoreduction to generate carbon monoxide and methane using a sacrificial electron donor. The supramolecular photocatalytic system can generate amounts of CH 4 comparable to those obtained with a precious metal-based [Ru(phen) 3 ](PF 6 ) 2 sensitizer and, in contrast to Ru-based catalysts, retains photocatalytic activity in all aqueous media over 6 days. Furthermore, the present study demonstrates the potential of tailored supramolecular polymers as renewable energy and sustainability materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Identifying mechanistic differences between co-fed CO 2 hydrogenation and reactive CO 2 capture using Ru and Pd dual function materials

Dual function materials (DFMs) enable reactive carbon capture (RCkeC), an intensified approach to carbon dioxide capture and utilization for cost and energy input reductions. Yet, there is a fundamental lack of understanding of mechanisms around CO 2 adsorption and subsequent conversion on these materials, hindering further development. Herein, we investigated several supported alkaline metal oxides for their CO 2 adsorption characteristics to find that Na/Al 2 O 3 had the highest CO 2 adsorption capacity, accompanied by a variety of CO 2 adsorption geometries as identified by in situ DRIFTS and computational modeling. The addition of catalytic metals (Ru, Pd) increased the adsorption capacity of Na/Al 2 O 3 without altering binding modes. In the subsequent reactive desorption step, acetate and formate intermediates were observed. Notably, this mechanistic investigation identified that the formation of acetate species was unique to RCC on a DFM, as these species were not observed in co-fed hydrogenation over the DFM or RCC over a Na-free catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Catalytic Oxygen Reduction for Deep O 2 Removal from CO 2 Streams

Streams of CO 2 from various capture processes may contain several impurities of which O 2 is often overlooked as a problematic impurity. Because of its reactivity, the National Energy Technology Laboratory has recommended a stringent limit, less than 10 ppm, for the O 2 level in treated CO 2 products for safe transport, storage, and utilization. Here, in this study, a variety of catalytic oxygen reduction approaches using commercial automotive exhaust emission catalysts are evaluated for O 2 removal from CO 2 streams using different reducing agents, including H 2 , CO, CH 3 OH, and CH 4 . When the amount of reductant added into the feed is carefully controlled, H 2 , CO, or CH 3 OH can effectively remove O 2 from 1.5% to below 10 ppm with a single-reactor design (>99.93% removal efficiency), while simultaneously meeting the impurity limits for other species. With CH 4 as a reductant, it is challenging to simultaneously meet the the O 2 and CO specifications in a single-reactor design because CH 4 also reacts with CO 2 to produce high levels of CO in the stream (at several hundred ppm). A dual-reactor design is developed to enable the use of CH 4 , a readily available and low-cost reductant, for the purification of CO 2 streams to meet the specifications for O 2 and other impurities.

CO2 purification↗