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Results for “CO electroreduction”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

NH 3 -Mediated Reactive Capture and Conversion: Integrating CO 2 Absorption from Flue Gas with CO Production via NH 4 HCO 3 Electrolysis

Efficient carbon capture and utilization require strategies that minimize energy penalties of CO 2 regeneration and compression. Reactive capture and conversion (RCC) address this challenge by integrating capture with direct electrochemical conversion. Here, we show an NH3-mediated tandem RCC system that couples capture of CO 2 from simulated flue gas (10% v/v CO 2 in N 2 ) with electroreduction of NH 4 HCO 3 to CO over a Ni single-atom catalyst (Ni-SAC). Speciation modeling and capture experiments revealed that a deep CO 2 capture with C/N ratio of 0.65 was achieved using 2.5 M NH 3 from simulated flue gas. Electrolysis of the resulting NH 4 HCO 3 on the Ni- SAC delivered an 85% CO Faradaic efficiency at 100 mA/cm 2 with excellent tolerance to NH 3 /NH 4 + as confirmed by DFT calculations and ab initio molecular dynamics (AIMD) simulations. Further, the technoeconomic analysis established a levelized total cost of CO manufacturing of $25.43/kmol, gauging the practical viability. Overall, this study holds great potential to decarbonize the chemical manufacturing industry while reducing synthetic production costs.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2021

Enhancing carbon dioxide gas-diffusion electrolysis by creating a hydrophobic catalyst microenvironment

Electroreduction of carbon dioxide (CO 2 ) over copper-based catalysts provides an attractive approach for sustainable fuel production. While efforts are focused on developing catalytic materials, it is also critical to understand and control the microenvironment around catalytic sites, which can mediate the transport of reaction species and influence reaction pathways. Here, we show that a hydrophobic microenvironment can significantly enhance CO 2 gas-diffusion electrolysis. For proof-of-concept, we use commercial copper nanoparticles and disperse hydrophobic polytetrafluoroethylene (PTFE) nanoparticles inside the catalyst layer. Consequently, the PTFE-added electrode achieves a greatly improved activity and Faradaic efficiency for CO 2 reduction, with a partial current density >250 mA cm -2 and a single-pass conversion of 14% at moderate potentials, which are around twice that of a regular electrode without added PTFE. The improvement is attributed to a balanced gas/liquid microenvironment that reduces the diffusion layer thickness, accelerates CO 2 mass transport, and increases CO 2 local concentration for the electrolysis.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Reactive capture and electrochemical conversion of CO 2 with ionic liquids and deep eutectic solvents

Ionic liquids (ILs) and deep eutectic solvents (DESs) have tremendous potential for reactive capture and conversion (RCC) of CO 2 due to their wide electrochemical stability window, low volatility, and high CO 2 solubility. There is environmental and economic interest in the direct utilization of the captured CO 2 using electrified and modular processes that forgo the thermal- or pressure-swing regeneration steps to concentrate CO 2 , eliminating the need to compress, transport, or store the gas. The conventional electrochemical conversion of CO 2 with aqueous electrolytes presents limited CO 2 solubility and high energy requirement to achieve industrially relevant products. Additionally, aqueous systems have competitive hydrogen evolution. In the past decade, there has been significant progress toward the design of ILs and DESs, and their composites to separate CO 2 from dilute streams. In parallel, but not necessarily in synergy, there have been studies focused on a few select ILs and DESs for electrochemical reduction of CO 2 , often diluting them with aqueous or non-aqueous solvents. The resulting electrode–electrolyte interfaces present a complex speciation for RCC. In this review, we describe how the ILs and DESs are tuned for RCC and specifically address the CO 2 chemisorption and electroreduction mechanisms. Critical bulk and interfacial properties of ILs and DESs are discussed in the context of RCC, and the potential of these electrolytes are presented through a techno-economic evaluation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Double sulfur vacancies by lithium tuning enhance CO2 electroreduction to n-propanol

Electrochemical CO 2 reduction can produce valuable products with high energy densities but the process is plagued by poor selectivities and low yields. Propanol represents a challenging product to obtain due to the complicated C 3 forming mechanism that requires both stabilization of *C 2 intermediates and subsequent C 1 –C 2 coupling. Herein, density function theory calculations revealed that double sulfur vacancies formed on hexagonal copper sulfide can feature as efficient electrocatalytic centers for stabilizing both CO* and OCCO* dimer, and further CO–OCCO coupling to form C 3 species, which cannot be realized on CuS with single or no sulfur vacancies. The double sulfur vacancies were then experimentally synthesized by an electrochemical lithium tuning strategy, during which the density of sulfur vacancies was well-tuned by the charge/discharge cycle number. The double sulfur vacancy-rich CuS catalyst exhibited a Faradaic efficiency toward n-propanol of 15.4 ± 1% at -1.05 V versus reversible hydrogen electrode in H-cells, and a high partial current density of 9.9 mA cm -2 at -0.85 V in flow-cells, comparable to the best reported electrochemical CO 2 reduction toward n-propanol. Our work suggests an attractive approach to create anion vacancy pairs as catalytic centers for multi-carbon-products.

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

Effects of surface diffusion in electrocatalytic CO 2 reduction on Cu revealed by kinetic Monte Carlo simulations

We report Kinetic Monte Carlo (KMC) methods are frequently used for mechanistic studies of thermally driven heterogeneous catalysis systems but are underused for electrocatalysis. Here, we develop a lattice KMC approach for electrocatalytic CO 2 reduction. The work is motivated by a prior experimental report that performed electroreduction of a mixed feed of 12 CO 2 and 13 CO on Cu; differences in the 13 C content of C2 products ethylene and ethanol (Δ 13 C) were interpreted as evidence of site selectivity. The lattice KMC model considers the effect of surface diffusion on this system. In the limit of infinitely fast diffusion (mean-field approximation), the key intermediates 12 CO* and 13 CO* would be well mixed on the surface and no evidence of site selectivity could have been observed. Using a simple two-site model and adapting a previously reported microkinetic model, we assess the effects of diffusion on the relative isotope fractions in the products using the estimated surface diffusion rate of CO* from literature reports. We find that the size of the active sites and the total surface adsorbate coverage can have a large influence on the values of Δ 13 C that can be observed. Δ 13 C is less sensitive to the CO* diffusion rate as long as it is within the estimated range. We further offer possible methods to estimate surface distribution of intermediates and to predict intrinsic selectivity of active sites based on experimental observations. This work illustrates the importance of considering surface diffusion in the study of electrochemical CO 2 reduction to multi-carbon products. Our approach is entirely based on a freely available open-source code, so will be readily adaptable to other electrocatalytic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Assessing the Long-Term Stability of Anion Exchange Membranes for Electrochemical CO 2 Reduction

Materials and cell components used in CO 2 electrolysis have largely been adapted from technologies initially developed for water electrolysis and fuel cells. However, electrochemical CO 2 reduction introduces distinct material challenges due to the unique chemical environment in this process. Here, in this study, we conducted ex-situ 1000 h stability tests on commonly used anion exchange membranes, exposing them exclusively to electrolytes and organic molecules used or produced during CO 2 electrolysis, at concentrations relevant to and compatible with postseparation processes. Notably, 15% w/w n-propanol and 5 M acetic acid caused complete dissolution or partial disintegration of the membranes unless cross-linking was present and remained stable throughout the test. When the membranes stayed physically intact, most of them exhibited excellent chemical stability in alkaline medium containing alcohols or formic acid, which was confirmed by vibrational spectroscopy and ion exchange capacity measurements. However, exposure to alcohol-and acid-containing solutions led to a substantial increase in swelling and water uptake, with potential implications for mechanical stability, ion/product crossover, and compression management of adjacent components. The potential effects of CO 2 electroreduction products on membrane stability, their subsequent impact on electrolyzer performance, and mitigation strategies are discussed.

CO2RR↗
DOE OSTI2021

Chemical upgrade of carbon monoxide to acetate on an atomically dispersed copper catalyst via CO-insertion

Electrochemical conversion of small molecules such as carbon dioxide (CO 2 ) and carbon monoxide (CO) to high-value multi-carbon products (C 2+ ) offers a chemical upgrade approach for fuels and chemical feedstock production using renewable energy, in the possible absence of the petrochemical industry under the new energy system such as hydrogen economy. Identifying robust and efficient electrocatalysts to selectively produce C 2+ products remains a challenge. In this study, we report a synthetic strategy of atomically dispersing copper atoms on nitrogen-rich porous carbon (Cu–N–C) through pyrolysis of a supramolecular assembly. Benefitting from the unsaturated coordination structure, in KOH electrolyte, the Cu–N–C with a Cu content of 6.9 wt% exhibits a maximum acetate Faradaic efficiency (FE) of 30% with an acetate partial current density as high as 48 mA cm –2 in electrochemical CO reduction. Different from the C–C coupling mechanism on metallic copper, we propose a CO insertion mechanism for the acetate production on the single site copper catalyst.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Engineering bimetallic interfaces and revealing the mechanism for carbon dioxide electroreduction to C 3+ liquid chemicals

Reduction reaction of CO 2 (CO 2 RR) to liquid C 3+ chemicals is a net-zero-carbon process and can increase local resiliency to power outages and fuel consumption. The mechanism and the catalyst design rules of CO 2 RR-to-C 3+ are unknown. Engineering bimetallic interface (e.g., Pd/Au) to tune the intermediate adsorption is promising for promoting C 3+ formation. Our density functional theory (DFT) calculations find that *CH 2 could be the key intermediate and C 1 -CH 2 coupling could be the rate-limiting step to generate C 3+ . High CO surface coverages can promote the bimetallic interfacial sites, lower the energetics of the C 1 -CH 2 coupling step, and enhance the C 3+ formation. We further construct a volcano plot of C 1 -CH 2 kinetics as a function of the binding strength of key intermediate *CH 2 via engineering the d-band center of the interfacial site. Our findings could guide the rational design of bimetallic interfaces and their near-surface microenvironment for enhancing CO 2 RR-to-C 3+ .

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

Cobalt‐Catalyzed Electroreductive Alkylation of Unactivated Alkyl Chlorides with Conjugated Olefins

Abstract Reactions of unactivated alkyl chlorides under mild and sustainable conditions are rare compared to those of alkyl bromides or iodides. As a result, synthetic methods capable of modifying the vast chemical space of chloroalkane reagents, wastes, and materials are limited. We report the cobalt‐catalyzed reductive addition of unactivated alkyl chlorides to conjugated alkenes. Co‐catalyzed activation of alkyl chlorides is performed under electroreductive conditions, and the resulting reactions constitute formal alkyl‐alkyl bond formation. In addition to developing an operationally simple methodology, detailed mechanistic studies provide insights into the elementary steps of a proposed catalytic cycle. In particular, we propose a switch in the mechanism of C−Cl bond activation from nucleophilic substitution to halogen atom abstraction, which is critical for efficiently generating alkyl radicals. These mechanistic insights were leveraged in designing ligands that enable couplings of primary, secondary, and tertiary alkyl chlorides.

Al Zubaydi, Samir↗
DOE OSTI2023

Cobalt‐Catalyzed Electroreductive Alkylation of Unactivated Alkyl Chlorides with Conjugated Olefins

Abstract Reactions of unactivated alkyl chlorides under mild and sustainable conditions are rare compared to those of alkyl bromides or iodides. As a result, synthetic methods capable of modifying the vast chemical space of chloroalkane reagents, wastes, and materials are limited. We report the cobalt‐catalyzed reductive addition of unactivated alkyl chlorides to conjugated alkenes. Co‐catalyzed activation of alkyl chlorides is performed under electroreductive conditions, and the resulting reactions constitute formal alkyl‐alkyl bond formation. In addition to developing an operationally simple methodology, detailed mechanistic studies provide insights into the elementary steps of a proposed catalytic cycle. In particular, we propose a switch in the mechanism of C−Cl bond activation from nucleophilic substitution to halogen atom abstraction, which is critical for efficiently generating alkyl radicals. These mechanistic insights were leveraged in designing ligands that enable couplings of primary, secondary, and tertiary alkyl chlorides.

Al Zubaydi, Samir↗
DOE OSTI2020

Bismuthene for highly efficient carbon dioxide electroreduction reaction

Bismuth (Bi) has been known as a highly efficient electrocatalyst for CO 2 reduction reaction. Stable free-standing two-dimensional Bi monolayer (Bismuthene) structures have been predicted theoretically, but never realized experimentally. Here, we show the first simple large-scale synthesis of free-standing Bismuthene, to our knowledge, and demonstrate its high electrocatalytic efficiency for formate (HCOO - ) formation from CO 2 reduction reaction. The catalytic performance is evident by the high Faradaic efficiency (99% at -580 mV vs. Reversible Hydrogen Electrode (RHE)), small onset overpotential (<90 mV) and high durability (no performance decay after 75 h and annealing at 400 °C). Density functional theory calculations show the structure-sensitivity of the CO2 reduction reaction over Bismuthene and thicker nanosheets, suggesting that selective formation of HCOO - indeed can proceed easily on Bismuthene (111) facet due to the unique compressive strain. This work paves the way for the extensive experimental investigation of Bismuthene in many different fields.

Science & Technology - Other Topics↗
DOE OSTI2023

Co 2 Mo 6 S 8 Catalyzes Nearly Exclusive Electrochemical Nitrate Conversion to Ammonia with Enzyme-like Activity

Electrocatalytic nitrate to ammonia conversion is a key reaction for energy and environmental sustainability. This reaction involves complex multi electron and proton transfer steps, and is impeded by the lack of catalyst for promoting both reactivity and ammonia selectivity. Here, we demonstrate active motifs based on the Chevrel phase Co 2 Mo 6 S 8 exhibit an enzyme-like high turnover frequency of ~95.1 s –1 for nitrate electroreduction to ammonia. We reveal strong synergy of multiple binding sites on this catalyst, such that the ligand effect of Co steers H ad* toward hydrogenation other than hydrogen evolution, the ensemble effect of Co, and the spatial confinement effect that promote the full hydrogenation of NO x to ammonia without N–N coupling. The catalyst exhibits almost exclusive ammonia conversion with a Faradaic efficiency of 97.1% and ammonia yielding rate of 115.5 mmol·g cat –1 ·h –1 in neutral electrolytes. The high activity was also confirmed in electrolytes with dilute nitrate and high chloride concentrations.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Dynamic Evolution of Copper Nanowires during CO 2 Reduction Probed by Operando Electrochemical 4D-STEM and X-ray Spectroscopy

Nanowires have emerged as an important family of one-dimensional (1D) nanomaterials owing to their exceptional optical, electrical, and chemical properties. In particular, Cu nanowires (NWs) show promising applications in catalyzing the challenging electrochemical CO 2 reduction reaction (CO 2 RR) to valuable chemical fuels. Despite early reports showing morphological changes of Cu NWs after CO 2 RR processes, their structural evolution and the resulting exact nature of active Cu sites remain largely elusive, which calls for the development of multimodal operando time-resolved nm-scale methods. Here, in this study, we report that well-defined 1D copper nanowires, with a diameter of around 30 nm, have a metallic 5-fold twinned Cu core and around 4 nm Cu 2 O shell. Operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM) showed that as-synthesized Cu@Cu 2 O NWs experienced electroreduction of surface Cu 2 O to disordered (spongy) metallic Cu shell (Cu@Cu S NWs) under CO 2 RR relevant conditions. Cu@Cu S NWs further underwent a CO-driven Cu migration leading to a complete evolution to polycrystalline metallic Cu nanograins. Operando electrochemical four-dimensional (4D) STEM in liquid, assisted by machine learning, interrogates the complex structures of Cu nanograin boundaries. Correlative operando synchrotron-based high-energy-resolution X-ray absorption spectroscopy unambiguously probes the electroreduction of Cu@Cu 2 O to fully metallic Cu nanograins followed by partial reoxidation of surface Cu during postelectrolysis air exposure. This study shows that Cu nanowires evolve into completely different metallic Cu nanograin structures supporting the operando (operating) active sites for the CO 2 RR.

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

Atomically Thin, Ionic–Covalent Organic Nanosheets for Stable, High–Performance Carbon Dioxide Electroreduction

The incorporation of charged functional groups is effective to modulate the activity of molecular complexes for the CO 2 reduction reaction (CO 2 RR), yet long-term heterogeneous electrolysis is often hampered by catalyst leaching. Herein, an electrocatalyst of atomically thin, cobalt-porphyrin-based, ionic–covalent organic nanosheets (CoTAP-iCONs) is synthesized via a post-synthetic modification strategy for high-performance CO 2 -to-CO conversion. The cationic quaternary ammonium groups not only enable the formation of monolayer nanosheets due to steric hindrance and electrostatic repulsion, but also facilitate the formation of a *COOH intermediate, as suggested by theoretical calculations. Consequently, CoTAP-iCONs exhibit higher CO 2 RR activity than other cobalt-porphyrin-based structures: an 870% and 480% improvement of CO current densities compared to the monomer and neutral nanosheets, respectively. Additionally, the iCONs structure can accommodate the cationic moieties. In a flow cell, CoTAP-iCONs attain a very small onset overpotential of 40 mV and a stable total current density of 212 mA cm –2 with CO Faradaic efficiency of >95% at –0.6 V for 11 h. Further coupling the flow electrolyzer with commercial solar cells yields a solar-to-CO conversion efficiency of 13.89%. Finally, this work indicates that atom-thin, ionic nanosheets represent a promising structure for achieving both tailored activity and high stability.

36 MATERIALS SCIENCE↗
DOE OSTI2026

First-Principles Insights into Proton-Coupled Electron Transfer versus Hydrogen Evolution Reaction Selectivity from a Base-Appended Cobaltocene Mediator

Performing selective proton-coupled electron transfer (PCET) to substrates such as N 2 , CO 2 , and unsaturated organic molecules under electrochemical conditions requires the suppression of the competing hydrogen evolution reaction (HER). To address this challenge, our laboratory previously demonstrated a PCET mediator strategy using a dimethylaniline-appended cobaltocene complex, [(CpCoCp NMe2 )H] + , which performs selective reductive chemistry while suppressing the HER. However, the origin of the suppressed, yet still observable, HER has not been thoroughly established. In this work, we perform density functional theory (DFT) calculations to elucidate the HER mechanism involving this redox mediator and to provide atomistic insights into the bifurcation between the PCET and HER pathways. We find that protonation of the aniline moiety to form [CpCoCp NMe2H ] + is more favorable, both kinetically and thermodynamically, than formation of the ring-protonated species [(CpCo(Cp-H) NMe2 )] + . Furthermore, PCET to acetophenone is energetically more favorable via [CpCoCp NMe2H ] + than via [(CpCo(Cp-H) NMe2 )] +1/0 . In contrast, the most favorable HER pathway involves the ring-protonated Co(I) species. These results offer mechanistic insights into HER versus PCET bifurcation and establish guiding principles for designing PCET mediators for selective electroreductive transformations.

evolution reactions↗