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Dual atom catalysts for rapid electrochemical reduction of CO to ethylene
Strong CO adsorption and facile CO dimerization are the key challenges in electrochemical CO2 reduction towards multi-carbon (C2+) products. We recently showed that CoPc immobilized on a single-walled carbon nanotube can selectively reduce CO2 to methanol. This is enabled through molecular strain, which dramatically improves the CO adsorption energy to CoPc, which in turn facilitates methanol formation. We now examine the extended Phthalocyanine (PcEx) dual atom catalyst (DAC), which is intrinsically strained and contains two catalyst centers, making it a candidate for reducing CO to C2+ products. Using Quantum Mechanics (QM), we screened 20 elements embedded in the PcEx, seeking catalysts with weak hydrogen binding, strong CO binding, and facile CO dimerization. We identi>ied Fe, Ru, Co, and Ir as the best performers and subsequently evaluated the entire CO to C2H4 mechanism (9 steps) using each of these elements as catalysts. In terms of limiting potential and overall exergonicity, we identi>ied CoPcEx as the best catalyst, followed by IrPcEx. We then examined the full CO to C2H4 mechanism on the bimetallic IrCoPcEx catalyst using grand canonical QM to obtain the reaction energetics as a function of applied potential. We conclude that the bimetallic IrCoPcEx is most promising for ef>iciently converting CO to ethylene.
Electrochemical Reductive N-Methylation with CO 2 Enabled by a Molecular Catalyst
The development of benign methylation reactions utilizing CO 2 as a one-carbon building block would enable a more sustainable chemical industry. Electrochemical CO 2 reduction has been extensively studied, but its application for reductive methylation reactions remains out of the scope of current electrocatalysis. Here, in this work, we report the first electrochemical reductive N-methylation reaction with CO 2 and demonstrate its compatibility with amines, hydroxylamines, and hydrazine. Catalyzed by cobalt phthalocyanine molecules supported on carbon nanotubes, the N-methylation reaction proceeds in aqueous media via the chemical condensation of an electrophilic carbon intermediate, proposed to be adsorbed or near-electrode formaldehyde formed from the four-electron reduction of CO 2 , with nucleophilic nitrogenous reactants and subsequent reduction. By comparing various amines, we discover that the nucleophilicity of the amine reactant is a descriptor for the C-N coupling efficacy. We extend the scope of the reaction to be compatible with cheap and abundant nitro-compounds by developing a cascade reduction process in which CO 2 and nitro-compounds are reduced concurrently to yield N-methyl amines with high mono-methylation selectivity via the overall transfer of 12 electrons and 12 protons.
Promotion and Tuning of the Electrochemical Reduction of Hetero‐ and Homobimetallic Zinc Complexes**
Abstract Compounds containing multiple metals attract significant interest due to the useful redox and reactivity properties of such species. Here, the electrochemical properties of a family of macrocyclic complexes that feature a zinc(II) center paired with a secondary redox‐inactive metal cation in heterobimetallic (Na + , Ca 2+ , Nd 3+ , Y 3+ ) motifs or homobimetallic (Zn 2+ ) motifs have been investigated. The new complexes were prepared via a divergent strategy, isolated, and structurally characterized with single‐crystal X‐ray diffraction (XRD) analysis. XRD results show that the structures of the complexes are modulated by the identity of the incorporated secondary metal ions. Cyclic voltammetry data reveal that ligand‐centered reduction is promoted in the bimetallic complexes and that the paired metal ions synergistically influence the redox properties of the complexes. Similar to prior work from our group and others, the bimetallic complexes containing stronger Lewis acids undergo more significant reduction potential shifts; contrasting with prior work on complexes containing redox‐active metals, however, the zinc(II) complexes studied here display faster electron transfer (as judged by lower reorganization energies, λ) when incorporating di‐ or tri‐valent Lewis acids in contrast to monovalent (and more weakly acidic) sodium. The quantified trends in these data offer insights that could help distinguish metal‐ versus ligand‐centered reduction of bimetallic complexes.
A Cu 2 O-derived Polymeric Carbon Nitride Heterostructured Catalyst for the Electrochemical Reduction of Carbon Dioxide to Ethylene
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Mediated Fuel Cells: Soluble Redox Mediators and their Applications to Electrochemical Reduction of O2 and Oxidation of H2, Alcohols, Biomass, and Complex Fuels
Mediated fuel cells are electrochemical devices that produce power in a manner similar to that of conventional proton exchange membrane fuel cells (PEMFCs). They differ from PEMFCs in their use of redox mediators dissolved in liquid electrolyte to conduct oxidation of the fuel or reduction of the oxidant, typically O2, in bulk solution. The mediators transport electrons (and often protons) between the electrode and the catalysts or chemical reagents in solution. This strategy can help overcome many of the challenges associated with conventional fuel cells, including managing complex multi-phase reactions (as in O2 reduction) or the use of challenging or heterogeneous fuels, such as hydrocarbons, polyols and biomass. Mediators are also commonly used in enzymatic fuel cells, where direct electron transfer from the electrode to the enzymatic active site can be slow. This review provides a comprehensive survey of historical and recent mediated fuel cell efforts, including applications using chemical and enzymatic catalysts. Our research on in this field has been exploring a number of different topics and has been supported different funding sources: the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (molecular mediators for catalytic oxygen reduction); the Great Lakes Bioenergy Research Center, DOE Office of Science DE-SC0018409 (research on biomass-based fuels; U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Catalysis Program, DE-FG02-05ER15690 (copper-catalyzed oxidation reactions); and the NIH NIGMS, R01 GM100143 and R35 GM134929 (use of molecular mediators for organic chemical synthesis).
Production of C 2 /C 3 Oxygenates from Planar Copper Nitride-Derived Mesoporous Copper via Electrochemical Reduction of CO 2
Electrochemical reduction of CO 2 provides an opportunity to produce fuels and chemicals in a carbon-neutral manner, assuming that CO 2 can be captured from the atmosphere. To do so requires efficient, selective, and stable catalysts. In this study, we report a highly mesoporous metallic Cu catalyst prepared by electrochemical reduction of thermally nitrided Cu foil. Under aqueous saturated CO 2 reduction conditions, the Cu 3 N-derived Cu electrocatalyst produces virtually no CH 4 , very little CO, and exhibits a faradaic efficiency of 68% in C 2+ products (C 2 H 4 , C 2 H 5 OH, and C 3 H 7 OH) at a current density of ~18.5 mA cm –2 and a cathode potential of -1.0 V versus the reversible hydrogen electrode. Under these conditions, the catalyst produces more oxygenated products than hydrocarbons. We show that surface roughness is a good descriptor of catalytic performance. The roughest surface reached 98% CO utilization efficiency for C 2+ product formation from CO 2 reduction and the ratio of oxygenated to hydrocarbon products correlates with the degree of surface roughness. These effects of surface roughness are attributed to the high population of undercoordinated sites as well as a high pH environment within the mesopores and adjacent to the surface of the catalyst.
Understanding the Competition between Alcohol Formation and Dimerization during Electrochemical Reduction of Aromatic Carbonyl Compounds
The electrochemical reductive dimerization of small aromatic carbonyl compounds derived from lignocellulosic biomass is a crucial C−C coupling reaction for upgrading small molecules to longchain hydrocarbons, particularly in the synthesis of drop-in sustainable aviation fuels. Although other electrochemical reduction reactions of these reactants (i.e., hydrogenation and hydrogenolysis) have undergone extensive mechanistic investigation, the understanding of dimerization remains relatively underdeveloped. Most importantly, there is a lack of understanding of the selectivity-determining step between dimerization and monomer reduction and critical factors that can affect this step. In this study, we provide a comprehensive mechanistic model to explain the competition between dimerization and monomer reduction of benzaldehyde under various conditions. Our model proposes that the selectivity between dimerization and monomer reduction depends on the competition between desorption of a ketyl radical from the electrode, necessary for dimerization, and further reduction of the ketyl radical to an alcohol on the electrode by proton-coupled electron transfer (PCET). Computationally comparing the adsorption/desorption energy and PCET activation barrier energy is challenging because conventional DFT calculations substantially underestimate the PCET kinetic barriers. In this study, we employed constrained DFTbased configuration interaction (CDFT-CI) to obtain a reliable comparison of these energies. Our mechanistic model was tested and supported by experimental results obtained with four electrodes (Cu, Pb, Bi, graphite), three pH conditions (acidic, neutral, basic), and three potentials. Our study offers a coherent mechanistic foundation that can explain how each of these conditions impacts the desorption and PCET processes and the selectivities for dimerization and alcohol production.
Process modeling, techno-economic assessment, and life cycle assessment of the electrochemical reduction of CO 2 : a review
The electrochemical reduction of CO 2 has emerged as a promising alternative to traditional fossil-based technologies for the synthesis of chemicals. Its industrial implementation could lead to a reduction in the carbon footprint of chemicals and the mitigation of climate change impacts caused by hard-to-decarbonize industrial applications, among other benefits. However, the current low technology readiness levels of such emerging technologies make it hard to predict their performance at industrial scales. During the past few years, researchers have developed diverse techniques to model and assess the electrochemical reduction of CO 2 toward its industrial implementation. The aim of this literature review is to provide a comprehensive overview of techno-economic and life cycle assessment methods and pave the way for future assessment approaches. First, we identify which modeling approaches have been conducted to extend analysis to the production scale. Next, we explore the metrics used to evaluate such systems, regarding technical, environmental, and economic aspects. Finally, we assess the challenges and research opportunities for the industrial implementation of CO 2 reduction via electrolysis.
Radiation-assisted electrochemical reduction of CO 2 to CO
Carbon monoxide (CO) is a versatile intermediate feedstock for many applications and can be produced through the electrochemical reduction of carbon dioxide (CO 2 ). However, current electrochemical CO production is hindered by high overall costs, primarily due to low conversion efficiencies and significant energy requirements. Herein, we report a unique way of enhancing the electrochemical reduction of CO 2 to CO using gamma (γ) photons. The γ-irradiation applied to the electrochemical cell setup induces the production of e˙ - , which results in an increased CO 2 ionization and production of excited CO 2 (CO$^{*}_{2}$) molecules via lower energy barrier. The ionized CO 2 ˙ - is quickly stabilized over a silver catalyst, providing an alternative low activation energy route for CO 2 reduction. In conclusion, a decrease in the overpotential barrier enhanced the electrochemical reduction of CO 2 to CO by 25%.
Electrochemical reduction of ammonia-captured CO 2 to CO over a nickel single-atom catalyst
Carbon reactive capture and conversion offers a sustainable route to valuable chemicals and fuels while aiding Green House Gas (GHG) reduction. Direct electrochemical conversion of capture solutions like bicarbonate avoids the energy demands of conventional CO 2 regeneration. Ammonium bicarbonate (NH 4 HCO 3 ) is particularly attractive due to its low decomposition temperature and ability to supply in situ CO 2 from dilute sources without requiring purified CO 2 . Meanwhile, single-atom catalysts (SACs) with nitrogen-coordinated metal sites further enhance CO 2 reduction efficiency using Earth-abundant materials. In this study, we demonstrate a nickel single-atom catalyst (Ni-SAC)-based electrolyzer that utilizes NH 4 HCO 3 as the CO 2 source, achieving significantly improved CO production performance compared to the conventional silver cathodes used in the CO 2 reduction reaction (CO 2 RR) to produce CO. The Ni-SAC cathode exhibited a Faradaic efficiency of 60.1% for CO production at −200 mA cm −2 , while the silver cathode achieved a Faradaic efficiency of only 2%, likely due to ammonium-induced poisoning. Furthermore, the integration of a customized microporous layer onto the electrode significantly increased the Faradaic efficiency from 64% to 83% at −100 mA cm −2 , emphasizing the crucial role of electrode structure optimization in enhancing CO selectivity. These findings demonstrate a sustainable and economically viable strategy for green CO production directly from CO 2 capture solutions.
Copper-Doped Tin Oxides Supported on Mesoporous Carbon Xerogel for Boosting the Electrochemical Reduction of CO 2 to Formate in Bicarbonate Solution Coupled with CO 2
The electrochemical reduction of CO 2 into valuable products at mild reaction conditions and using cheap renewable electrical energy are goals to sustain a low-carbon economy. Among the various CO 2 reduction reaction products, formic acid (FA) has received significant attention because of its low Gibbs free energy input requirement and the simple reduction reaction involving the transfer of 2 electrons and 2 protons. In this work, a copper-doped tin oxide catalyst supported on a mesoporous carbon xerogel was shown to enhance the electrochemical reduction of CO 2 to formate in a bicarbonate solution coupled with CO 2 . We observed that the synergistic SnCu oxides enhance the selectivity toward formate from 58.6% for Sn oxide and 28.7% for Cu oxide to over 71.2% for the SnCu oxides. The observed rate of formate production with SnCu oxide was 2.8 times higher compared to the rate of Cu oxide and about 1.5 times higher than with the Sn oxide catalyst. Our results reveal that selectivity for formate comes partly from the electrolysis of the bicarbonate solution and partly from continuous CO 2 gas purged into the solution. The contribution from the electrolysis of bicarbonate solution ranges from 15% to 40% when the concentration of bicarbonate solution ranges from 100 mM to 1 M. Chronoamperometric measurements for stability revealed that Cu oxide and Sn oxide showed stable current density for less than 30 h while under the same conditions, the stable current density was observed for more than 50 h with SnCu oxide catalyst. Additionally, the selectivity toward formate increased by 6% when the reactor pressure was increased from near ambient pressure to 4 psig. Our lab-scale electrochemical cell with SnCu oxide supported on the mesoporous carbon xerogel enhances the CO 2 solubility, minimizes the precipitation of salts that can degrade the catalytic performance, and suppresses the competitive hydrogen evolution reaction, demonstrating the feasibility of using our catalyst and system for the electrochemical conversion of CO 2 into formate with high selectivity, productivity, and stability. Furthermore, this could have significant implications for the mitigation of CO 2 emissions and the development of a sustainable chemical industry.
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.
Electrochemical Reduction Pathways from Goethite to Green Iron in Alkaline Solution with Silicate Additive
Energy-efficient and low-temperature iron electrolysis in alkaline solutions is a low-cost and sustainable ironmaking process with zero-carbon emissions when renewable electrical sources are involved. However, its implementation is hindered by electrochemically inert Fe 3 O 4 and parasitic H 2 gas formation during the electrochemical reduction process, resulting in the low energy efficiency of iron electrolysis. Here, we further explore the potential of electrochemical reduction of goethite (FeOOH) by employing a low concentration of silicate additive in an alkaline solution to mitigate Fe 3 O 4 accumulation and H 2 generation. Electrochemical measurements coupled with operando X-ray diffraction and X-ray absorption spectroscopy suggested FeOOH → Fe 3 O 4 → Fe(OH) 2 → Fe reduction pathways. Interestingly, a poorly crystalline or amorphous Fe(OH) 2 phase formed in the NaOH/silicate mixed electrolyte, possibly due to the inhibitive effect of silicate on water and ion transport, which eventually contributed to the improved reduction of Fe 3 O 4 , also supported by atomistic simulations. This work demonstrates the potential for silicate as a low-cost and effective electrolyte additive to improve room-temperature green iron formation via electrolysis.
Engineering Catalyst–Electrolyte Microenvironments to Optimize the Activity and Selectivity for the Electrochemical Reduction of CO 2 on Cu and Ag
We report the electrochemical reduction of carbon dioxide (CO 2 R) driven by renewably generated electricity (e.g., solar and wind) offers a promising means for reusing the CO 2 released during the production of cement, steel, and aluminum as well as the production of ammonia and methanol. If CO 2 could be removed from the atmosphere at acceptable costs (i.e., <$100/t of CO 2 ), then CO 2 R could be used to produce carbon-containing chemicals and fuels in a fully sustainable manner. Economic considerations dictate that CO 2 R current densities must be in the range of 0.1 to 1 A/cm 2 and selectivity toward the targeted product must be high in order to minimize separation costs. Industrially relevant operating conditions can be achieved by using gas diffusion electrodes (GDEs) to maximize the transport of species to and from the cathode and combining such electrodes with a solid-electrolyte membrane by eliminating the ohmic losses associated with liquid electrolytes. Additionally, high product selectivity can be attained by careful tuning of the microenvironment near the catalyst surface (e.g., the pH, the concentrations of CO 2 and H 2 O, and the identities of the cations in the double layer adjacent to the catalyst surface).
Selection of solvents for integrated CO 2 absorption and electrochemical reduction systems
Abstract Solvent‐based electrochemical CO 2 reduction (CO 2 R) enables the production of chemicals or fuels using CO 2 from a preceding absorption process. Employing previously tested CO 2 capture solvents does not ensure their suitability for either CO 2 R or integrated CO 2 absorption‐reduction. We propose solvent selection criteria that include the CO 2 solubility, kinetic constant, ionic conductivity, concentration of the bicarbonate, carbamate, and solvent cation in the CO 2 ‐loaded solution, and sustainability indicators. They are implemented for solvent selection (a) from novel, aqueous mixtures of N ‐methylcyclohexylamine (MCA) with piperazine (PZ), 2‐amino‐2‐methyl‐1‐propanol (AMP), potassium hydroxide (KOH), and potassium chloride (KCl) and (b) from aqueous monoethanolamine (MEA), AMP, KOH, MCA, and PZ solutions. Versions of a modified Kent‐Eisenberg model for strong bases, carbamate, and non‐carbamate‐forming amine solutions are developed and parameterized through experimental equilibrium measurements. CO 2 R experimental results are presented for solutions of KOH and MCA + KOH, as these indicate desired trade‐offs for CO 2 absorption and reduction.
Electrochemical Reduction of Flue Gas Carbon Dioxide to Commercially Viable C2-C4 Products (Final Report)
This is the final scientific/technical report for a DOE project focused on the electrochemical conversion of CO 2 in non-aqueous solvents to novel products. Electrochemical reduction of CO 2 provides an attractive route to produce valuable fuels and chemicals that can simultaneously lower greenhouse gas emissions when powered by renewable electricity. While recent technological advances have shown the feasibility of industrial CO 2 electroreduction, many challenges remain to improve this technology and expand the list of economically viable products. The vast majority of electrochemical CO 2 reduction research has been conducted in aqueous media under neutral to alkaline conditions, leading to commonly reported products including carbon monoxide, formic acid, methane, methanol, ethylene, acetic acid, and ethanol. In comparison, non-aqueous media for CO 2 reduction has been underexplored but represents a possible avenue to yield new products and improved operating conditions. The aim of the project was to convert waste CO 2 in the form of flue gas to a multicarbon C2 - C4 chemical product in a reactor designed to achieve economically competitive values of current density and selectivity. The project strived to advance the technology readiness of an electrochemical CO 2 reduction process in alcohol solvents from the proof-of-concept stage to a device capable of meeting performance metrics for commercial viability. In the initial plan, the University of Louisville researchers were to focus on investigating the electrochemical process and improving the faradaic efficiency for novel C2 – C4 species, while also working on a parallel effort to build a practical electrolysis reactor to markedly increase the CO 2 reduction current density. The reactor development effort also aimed to engineer a dual-electrolyte feed strategy with non-aqueous catholyte and aqueous anolyte to promote water oxidation as the coupling anodic half-reaction to enable a sustainable and economical overall process. At the outset, the University of North Dakota was to investigate the feasibility of operating directly from coal-derived flue gas without separate capture and purification. The research team sought to determine impurity effects and test mitigation strategies, as well as engineer the gaseous feed system for high reactor tolerance to lower CO 2 concentration. In the last half year of the project, the focus was planned to shift to integrating the advances in the catalysis, electrochemical conditions, reactor design, and flue gas compatibility into a fully functional device and improve it for maximum current density and faradaic efficiency for C2 – C4 species. Knowledge of the full system components, constraints, and maximum performance was then to be used as the basis for a thorough technoeconomic analysis (TEA) and life cycle analysis (LCA) at the end of the project.
Electrochemical Reduction Selectivity of Crotonaldehyde on Copper
Lignocellulosic waste is a potential feedstock for the generation of fuels and commodity chemicals, but existing conversion methods are too cost-intensive to be viable long-term solutions. Electrochemical reductions are promising for decentralized biomass valorization due to their modular scaling and capacity to run intermittently and without high temperatures or pressures. Using crotonaldehyde as a multi-functional model compound for the many partially unsaturated oxygenates found in processed biomass, we here demonstrate the production of butanal, butanol, butene, and butane (variously useful as commodity chemicals and major components of liquified petroleum gas) under ambient conditions by reductive bulk electrolysis with a copper mesh working electrode. We identify an optimum potential for reduced organic production under the reaction conditions and compare product distributions from reductions of intermediate species to further propose branching reaction pathways. Though butanal is typically the most abundant product from crotonaldehyde reduction, most of the butene and butane appear to result from a pathway involving initial reduction of the aldehyde group. We discuss evidence that selectivity is driven by interplay between crotonaldehyde reduction, local pH shifts due to the hydrogen evolution reaction, and changes in site reactivity and availability due to electrode fouling. This demonstration of model electrochemical biomass valorization also serves to inform further exploration into reduction of multi-functional molecules and electrochemical biomass processing in general.