Oxide-Derived Tin Microspheres for Efficient CO2 Electroreduction to Formic Acid
Presented by LRST at the AIChE 2020 Annual Meeting, 11/17
Nguyen-Phan, Thuy-Duong↗
SEARCH · Engineering Papers
Results for “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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Oxide Derived Tin Nanospheres for Efficient CO 2 Electroreduction to Formate
240th ECS Digital Meeting, Virtual, December 10-14, 2021
Nguyen Phan, Thuy Duong↗
Comparative Technoeconomic Analysis of Pathways for Electrochemical Reduction of CO 2 with Methanol to Produce Methyl Formate
Electrochemical CO 2 reduction has promise as a technology that could help society reach carbon neutrality while producing valuable fuels and chemicals. Herein, the electrochemical synthesis of methyl formate, a product not observed in aqueous CO 2 electrolysis, has been analyzed by a rigorous technoeconomic model to evaluate its commercial viability. Methyl formate synthesis has been demonstrated with high faradaic efficiency through the electroreduction of CO 2 in methanol. Four competing approaches were analyzed: (1) Electroreduction of captured CO 2 in a dual CH 3 OH/H 2 O electrolyzer, (2) Direct electroreduction of flue gas CO 2 in a dual CH 3 OH/H 2 O electrolyzer, (3) Electroreduction of captured CO 2 in a CH 3 OH/CH 3 OH electrolyzer, and (4) Electroreduction of captured CO 2 in a H 2 O/H 2 O electrolyzer with a downstream CH 3 OH reactor. Sensitivity analyses, cost contour plots, and comparison plots were generated. The dual methanol/water electrolysis approach was the most cost-competitive, with a levelized cost of methyl formate below the present market price. Here, the all-methanol electrolysis route was more expensive due to increased methanol consumption and greater distillation costs. Methyl formate production through aqueous CO 2 electrolysis to formic acid with a secondary esterification reaction was by far the most expensive approach, primarily due to the energy-intensive nature of distilling formic acid from water.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The impact of nitrogen oxides on electrochemical carbon dioxide reduction
The electroreduction of carbon dioxide offers a promising avenue to produce valuable fuels and chemicals using greenhouse gas carbon dioxide as the carbon feedstock. Because industrial carbon dioxide point sources often contain numerous contaminants, such as nitrogen oxides, understanding the potential impact of contaminants on carbon dioxide electrolysis is crucial for practical applications. Herein, we investigate the impact of various nitrogen oxides, including nitric oxide, nitrogen dioxide, and nitrous oxide, on carbon dioxide electroreduction on three model electrocatalysts (i.e., copper, silver, and tin). We demonstrate that the presence of nitrogen oxides (up to 0.83%) in the carbon dioxide feed leads to a considerable Faradaic efficiency loss in carbon dioxide electroreduction, which is caused by the preferential electroreduction of nitrogen oxides over carbon dioxide. The primary products of nitrogen oxides electroreduction include nitrous oxide, nitrogen, hydroxylamine, and ammonia. Despite the loss in Faradaic efficiency, the electrocatalysts exhibit similar carbon dioxide reduction performances once a pure carbon dioxide feed is restored, indicating a negligible long-term impact of nitrogen oxides on the catalytic properties of the model catalysts.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Carbon dioxide reduction in solid oxide electrolyzer cells using transition metals infiltrated into Gd 0.1 Ce 0.9 O 1.95 (GDC10) scaffolds
Here, this study reports the catalytic activity of transition metal electrocatalysts (Co, Ni, and Cu) incorporated into Gd 0.1 Ce 0.9 O 1.95 (GDC10) cathodes for the electroreduction of CO 2 in solid oxide electrolyzer cells (SOECs). CO 2 electroreduction performance of cells having porous and non-infiltrated GDC10 cathodes was compared with the performance of cells containing transition metal electrocatalysts infiltrated into porous GDC10 cathodes at 750, 800, and 850°C. Results showed that cells with Co infiltrated cathodes had the best catalytic activity towards CO 2 electroreduction. Furthermore, these cells displayed good stability towards CO electroreduction, having a faradaic efficiency value close to 100% with insignificant voltage increase when tested for 48h at 750 and 850°C under the current densities of 0.2, and 0.4Acm -2 , respectively.
25 ENERGY STORAGE↗
Organometallic catalysts for primary phosphoric acid fuel cells
A continuing effort by the U.S. Department of Energy to improve the competitiveness of the phosphoric acid fuel cell by improving cell performance and/or reducing cell cost is discussed. Cathode improvement, both in performance and cost, available through the use of a class of organometallic cathode catalysts, the tetraazaannulenes (TAAs), was investigated. A new mixed catalyst was identified which provides improved cathode performance without the need for the use of a noble metal. This mixed catalyst was tested under load for 1000 hr. in full cell at 160 to 200 C in phosphoric acid H3PO4, and was shown to provide stable performance. The mixed catalyst contains an organometallic to catalyze electroreduction of oxygen to hydrogen peroxide and a metal to catalyze further electroreduction of the hydrogen peroxide to water. Cathodes containing an exemplar mixed catalyst (e.g., Co bisphenyl TAA/Mn) operate at approximately 650 mV vs DHE in 160 C, 85% H3PO4 with oxygen as reactant. In developing this mixed catalyst, a broad spectrum of TAAs were prepared, tested in half-cell and in a rotating ring-disk electrode system. TAAs found to facilitate the production of hydrogen peroxide in electroreduction were shown to be preferred TAAs for use in the mixed catalyst. Manganese (Mn) was identified as a preferred metal because it is capable of catalyzing hydrogen peroxide electroreduction, is lower in cost and is of less strategic importance than platinum, the cathode catalyst normally used in the fuel cell.
Walsh, Fraser↗
Alkali Cation Inhibition of Imidazolium-Mediated Electrochemical CO 2 Reduction on Silver
Imidazolium-based ionic liquids have led to enhanced CO 2 electroreduction activity due to cation effects at the cathode surface, stabilizing the reaction intermediates and decreasing the activation energy. In aqueous media, alkali cations are also known to improve CO 2 reduction activity on metals such as Ag, with the enhancement attributed to electrical double layer effects and trending with the size of the alkali cation. However, the effect of a mixed catholyte solution of alkali cations in the presence of an imidazolium-based ionic liquid has not been well-explored. Herein, 1-ethyl-3-methylimidazolium tetrafluoroborate, [EMIM][BF 4 ], in water was investigated with alkali salts to unravel the interaction effects for CO 2 electroreduction on Ag. Although both [EMIM] + and alkali cations have individually improved CO 2 to CO conversion on Ag in water, electrochemical results showed that alkali cations hindered imidazolium-mediated CO 2 electroreduction in most conditions. Li + , in particular, was sharply inhibitory compared to other alkali cations and strongly redirected the selectivity to hydrogen evolution. The nature of the alkali cation inhibition was investigated with spectroscopic techniques, including in situ surface-enhanced Raman spectroscopy (SERS) and dynamic electrochemical impedance spectroscopy (DEIS). Along with computational insights from density functional theory (DFT), the electrochemical and spectroscopic data suggest that alkali cations inhibit [EMIM]-mediated CO 2 reduction by competing for surface adsorption sites, preventing the potential-dependent structural reorientation of imidazolium, and promoting hydrogen evolution by bringing solvated water to the cathode surface.
cations↗
A carbon-efficient bicarbonate electrolyzer
Carbon efficiency is one of the most pressing problems of carbon dioxide electroreduction today. While there have been studies on anion exchange membrane electrolyzers with carbon dioxide (gas) and bipolar membrane electrolyzers with bicarbonate (aqueous) feedstocks, both suffer from low carbon efficiency. In anion exchange membrane electrolyzers, this is due to carbonate anion crossover, whereas in bipolar membrane electrolyzers, the exsolution of carbon dioxide (gas) from the bicarbonate solution is the culprit. Here, we first elucidate the root cause of the low carbon efficiency of liquid bicarbonate electrolyzers with thermodynamic calculations and then achieve carbon-efficient carbon dioxide electroreduction by adopting a near-neutral-pH cation exchange membrane, a glass fiber intermediate layer, and carbon dioxide (gas) partial pressure management. We convert highly concentrated bicarbonate solution to solid formate fuel with a yield (carbon efficiency) of greater than 96%. A device test is demonstrated at 100 mA cm -2 with a full-cell voltage of 3.1 V for over 200 h.
42 ENGINEERING↗
Few-Atom Copper Catalyst for the Electrochemical Reduction of CO to Acetate: Synergetic Catalysis between Neighboring Cu Atoms
Single-atom catalysts (SACs) are gaining increasing recognition because of their superior catalytic properties for various reactions. However, the performance of SACs is often limited by the lack of neighboring metal centers to cooperate in catalysis. Herein, a synergetic interaction between neighboring Cu atoms of a few-atom catalyst (FAC) on graphdiyne is found to greatly enhance the production of acetate in CO electroreduction reaction relative to Cu SACs. In a 1.0 M KOH electrolyte, this Cu FAC exhibits an acetate Faradaic efficiency of 53.8±1.5 % and an ultrahigh relative purity of up to 97 wt% for liquid products, and excellent stability of over 23 h continuous electrolysis at -0.8 V versus reversible hydrogen electrode (RHE). Theoretical studies suggest that the intersite catalytic communication between two neighboring metal atoms confined in each pore of GDY facilitates the formation of acetic acid through either stepwise hydrogenation of CH 2 CO* or the direct reaction of H 2 O with CH 2 CO*. Our study demonstrates the unprecedented synergetic catalysis of Cu FAC in promoting the selective CO electroreduction toward acetate production.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Triggering C-N Coupling on Metal Oxide Nanocomposite for the Electrochemical Reduction of CO 2 and NO x ⁻ to Formamide
The co-electroreduction of CO 2 and NO x ⁻ (NO 3 ⁻ /NO 2 ⁻ ) to generate formamide (HCONH 2 ) offers an opportunity for downstream chemical and polymer manufacturing decarbonization; however, significant challenges lie in the C-N coupling and the associated low product selectivity. Herein, p-block metal oxides are incorporated in copper oxides to provide more accessible active sites for reactant adsorption and activation, tuning the reaction selectivity toward the formamide production. Through in situ Raman and synchrotron-based infrared spectroscopy measurements, C-N bond formation is demonstrated in real-time with the CuO x /BiO x catalyst, where the C-N bond is detected via a *CHO and *NH 2 intermediates formation, in agreement with the density functional theory calculations. When tested in a flow electrolyzer, a formamide yield rate of 134 ± 11 mmol h -1 g cat -1 is reported, the first report of co-electroreduction of CO 2 and NO x ⁻ to formamide beyond conventional H-cell measurements. These new insights on the C-N coupling mechanisms and scale-up capability provide directions for further development of electrocatalysts for the formamide production.
36 MATERIALS SCIENCE↗
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↗
Proton-Coupled Electron Transfer Mechanisms for CO 2 Reduction to Methanol Catalyzed by Surface-Immobilized Cobalt Phthalocyanine
Immobilized cobalt phthalocyanine (CoPc) is a highly promising architecture for the six-proton, six-electron reduction of CO 2 to methanol. This electroreduction process relies on proton-coupled electron transfer (PCET) reactions that can occur by sequential or concerted mechanisms. Immobilization on a conductive support such as carbon nanotubes or graphitic flakes can fundamentally alter the PCET mechanisms. We use density functional theory (DFT) calculations of CoPc adsorbed on an explicit graphitic surface model to investigate intermediates in the electroreduction of CO 2 to methanol. Our calculations show that the alignment of the CoPc and graphitic electronic states influences the reductive chemistry. These calculations also distinguish between charging the graphitic surface and reducing the CoPc and adsorbed intermediates as electrons are added to the system. This analysis allows us to identify the chemical transformations that are likely to be concerted PCET, defined for these systems as the mechanism in which protonation of a CO 2 reduction intermediate is accompanied by electron abstraction from the graphitic surface to the adsorbate without thermodynamically stable intermediates. Furthermore, this work establishes a mechanistic pathway for methanol production that is consistent with experimental observations and provides fundamental insight into how immobilization of the CoPc impacts its CO 2 reduction chemistry.
Adsorption↗
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↗
Gold-in-copper at low *CO coverage enables efficient electromethanation of CO 2
The renewable-electricity-powered CO 2 electroreduction reaction provides a promising means to store intermittent renewable energy in the form of valuable chemicals and dispatchable fuels. Renewable methane produced using CO 2 electroreduction attracts interest due to the established global distribution network; however, present-day efficiencies and activities remain below those required for practical application. Here we exploit the fact that the suppression of *CO dimerization and hydrogen evolution promotes methane selectivity: we reason that the introduction of Au in Cu favors *CO protonation vs. C-C coupling under low *CO coverage and weakens the *H adsorption energy of the surface, leading to a reduction in hydrogen evolution. We construct experimentally a suite of Au-Cu catalysts and control *CO availability by regulating CO 2 concentration and reaction rate. This strategy leads to a 1.6× improvement in the methane:H 2 selectivity ratio compared to the best prior reports operating above 100 mA cm -2 . We as a result achieve a CO 2 -to-methane Faradaic efficiency (FE) of (56 ± 2)% at a production rate of (112 ± 4) mA cm -2 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A single-site iron catalyst with preoccupied active centers that achieves selective ammonia electrosynthesis from nitrate
Isolated Fe sites achieve enhanced intrinsic activity for nitrate electroreduction to ammonia with ∼100% selectivity, which effectively inhibit water dissociation through a nitrate-preoccupation mechanism.
Li, Panpan↗
A Tandem Electrolysis Process for Multi-Carbon Chemical Production from Carbon Dioxide (Final Technical Report)
a two-step CO 2 electroreduction process for selective production of acetate and ethylene was successfully developed at the kW-scale. The CO 2 and CO electrolyzers were first investigated individually on the Watt-scale to achieve high current densities and more durable operation by using a reinforced GDL. High CO 2 conversion was obtained in the first CO 2 electrolyzer to produce a CO-dominant gas stream with minimal CO 2 , and highly pure acetate stream was produced in the second CO electrolyzer by using NiFe anode, which promoted alcohol oxidation to carboxylates. The two-step process operated stably for 200 h with acetate and ethylene as the major C 2+ products. Degradation mechanism study revealed that the flooding and the salt formation in the GDL is likely the biggest contributor to the performance degradation for both CO 2 and CO electrolyzers. A 1,000 cm 2 CO electrolyzer stack was then designed, fabricated, and operated up to a total current of 300 A along with a 500 cm 2 CO 2 electrolyzer stack which was operated up to a total current of 100 A. The CO electrolyzer stack demonstrated good stability at 300 A for at least 125 h at a carbon selectivity >96%. The impact of CO 2 , O 2 , N 2 , SO x , and NO x gas impurities on the CO electrolyzer stack was studied and a relatively high resistance to these contaminants was demonstrated. Electroreduction of CO 2 into acetic acid was also demonstrated to be environmentally favorable when compared to the traditional production of acetic acid when powered by renewable electricity. Additionally, electricity cost was identified as the primary source of cost sensitivity indicating substantial economic improvements could be achieved by continuing to drive down the cost of renewable electricity. Overall, the presented approach demonstrates the feasibility of the two-step electrochemical CO 2 reduction process for the effective production of C 2+ products at the kW-scale which should inspire future scaling efforts accelerating commercialization.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Network Optimization of the Electrosynthesis of Chemicals from CO2
Carbon dioxide electroreduction (ECO2R) is gaining attention due to its capacity to mitigate CO2 emissions while using electricity that would otherwise be curtailed. Its foreseeable industrial implementation requires of holistic methods to assess the technological and economic performance of ECO2R processes and integrate them in current chemical supply chains and power systems. Here, we combine techno-economic assessment and mathematical programming to find the optimal paths to electroreduce CO2 into valuable chemicals under variable electricity prices. The proposed approach is tested with a case study addressing the CO2 capture from flue gas or direct air and its electricity-powered reduction into carbon monoxide, formic acid or multi-carbon compounds. The results obtained demonstrate the ability of the framework to build ECO2R networks and provide operation profiles that respond to fluctuating electricity prices.
carbon dioxide↗
Accessing and Photo-Accelerating Low-Overpotential Pathways for CO 2 Reduction: A Bis-Carbene Ruthenium Terpyridine Catalyst
A ruthenium catalyst bearing a bidentate bis(carbene) ligand is prepared and studied as a catalyst for CO 2 electroreduction. The catalyst [Ru(tpy)(bis-mim)(MeCN)][PF 6 ] 2 (tpy) is 2,2′,:6′,2″-terpyridine; bis-mim is (methylenebis(N-methylimidazol-2-ylidene)) mediates reduction of CO 2 into CO with a turnover frequency of 630 s –1 and Faradaic efficiency (FE) of 30% at an overpotential of 730 mV. The strongly donating bis(carbene) ligand also enables access to a pathway operating at a lower overpotential of ca. 310 mV. While low-overpotential catalysis is slow in the dark (TOF = 0.01 s –1 ), visible light illumination increases the rate 10-fold (TOF = 0.11 s –1 ). Here, a full mechanistic picture is developed using kinetic analysis from cyclic voltammetry, spectroelectrochemistry, and computational methods, with the bis-mim ligand facilitating rapid CO 2 activation at low overpotentials. Comparisons with other ruthenium catalysts yield insight into the ability to tune the rate of chemical steps (e.g., ligand dissociation and CO 2 nucleophilic attack) and the overpotential by tailoring the primary coordination sphere while retaining the “redox-active” tpy ligand.
CO2 reduction↗