Pathways to enhance electrochemical CO2 reduction identified through direct pore-level modeling† † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3ey00122a
Ontology highlight
ABSTRACT:
SUBMITTER: Johnson E
PROVIDER: S-EPMC10483485 | biostudies-literature | 2023 Jun
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:CO2 electrochemical reduction (CO2 ER) from (bi)carbonate feed presents an opportunity to efficiently couple this process to alkaline-based carbon capture systems. Likewise, while this method of reducing CO2 currently lags behind CO2 gas-fed electrolysers in certain performance metrics, it offers a significant improvement in CO2 utilization which makes the method worth exploring. This paper presents two simple modifications to a bicarbonate-fed CO2 ER system that enhance the selectivity towards CO. Specifically, a modified hydrophilic cathode with Ag catalyst loaded through electrodeposition and the addition of dodecyltrimethylammonium bromide (DTAB), a low-cost surfactant, to the catholyte enabled the system to achieve a FECO of 85% and 73% at 100 and 200 mA·cm-2, respectively. The modifications were tested in 4 h long experiments where DTAB helped maintain FECO stable even when the pH of the catholyte became more alkaline, and it improved the CO2 utilization compared to a system without DTAB.
| S-EPMC9960053 | biostudies-literature
Project description:In this work, we employ differential electrochemical mass spectrometry (DEMS) to track the real-time evolution of CO at nanoporous gold (NpAu) catalysts with varying pore parameters (diameter and length) during the electrochemical CO2 reduction reaction (CO2RR). We show that due to the increase in the local pH with increasing catalyst roughness, NpAu catalysts suppress the bicarbonate-mediated hydrogen evolution reaction (HER) compared to a flat Au electrode. Additionally, the geometric current density for CO2RR increases with the roughness of NpAu catalysts, which we attribute to the increased availability of active sites at NpAu catalysts. Together, the enhancement of CO2RR and the suppression of competing HER results in a drastic increase in the faradaic selectivity for CO2RR with increasing pore length and decreasing pore diameter, reaching near 100% faradaic efficiency for CO in the most extreme case. Interestingly, unlike the geometric current density, the specific current density for CO2RR has a more complicated relation with the roughness of the NpAu catalysts. We show that this is due to the presence of ohmic drop effects along the length of the porous channels. These ohmic drop effects render the pores partially electrocatalytically inactive and hence, they play an important role in tuning the CO2RR activity on nanoporous catalysts.
| S-EPMC8926346 | biostudies-literature
Project description:Electrochemical CO2 reduction reaction (CO2RR) occurring at the electrode/electrolyte interface is sensitive to both the potential and concentration polarization. Compared to static electrolysis at a fixed potential, pulsed electrolysis with alternating anodic and cathodic potentials is an intriguing approach that not only reconstructs the surface structure, but also regulates the local pH and mass transport from the electrolyte side in the immediate vicinity of the cathode. Herein, via a combined online mass spectrometry investigation with sub-second temporal resolution and 1-dimensional diffusion profile simulations, we reveal that heightened surface CO2 concentration promotes CO2RR over H2 evolution for both polycrystalline Ag and Cu electrodes after anodic pulses. Moreover, mild oxidative pulses generate a roughened surface topology with under-coordinated Ag or Cu sites, delivering the best CO2-to-CO and CO2-to-C2+ performance, respectively. Surface-enhanced infrared absorption spectroscopy elucidates the potential dependence of *CO and *OCHO species on Ag as well as the gradually improved *CO consumption rate over under-coordinated Cu after oxidative pulses, directly correlating apparent CO2RR selectivity with dynamic interfacial chemistry at the molecular level.
| S-EPMC11557597 | biostudies-literature
Project description:Green synthesis of ammonia by electrochemical nitrogen reduction reaction (NRR) shows great potential as an alternative to the Haber-Bosch process but is hampered by sluggish production rate and low Faradaic efficiency. Recently, lithium-mediated electrochemical NRR has received renewed attention due to its reproducibility. However, further improvement of the system is restricted by limited recognition of its mechanism. Herein, we demonstrate that lithium-mediated NRR began with electrochemical deposition of lithium, followed by two chemical processes of dinitrogen splitting and protonation to ammonia. Furthermore, we quantified the extent to which the freshly deposited active lithium lost its activity toward NRR due to a parasitic reaction between lithium and electrolyte. A high ammonia yield of 0.410 ± 0.038 μg s-1 cm-2 geo and Faradaic efficiency of 39.5 ± 1.7% were achieved at 20 mA cm-2 geo and 10 mA cm-2 geo, respectively, which can be attributed to fresher lithium obtained at high current density.
| S-EPMC8482511 | biostudies-literature
Project description:The electrochemical CO2 reduction reaction (CO2RR) powered by excess zero-carbon-emission electricity to produce especially multicarbon (C2+) products could contribute to a carbon-neutral to carbon-negative economy. Foundational to the rational design of efficient, selective CO2RR electrocatalysts is mechanistic analysis of the best metal catalyst thus far identified, namely, copper (Cu), via quantum mechanical computations to complement experiments. Here, we apply embedded correlated wavefunction (ECW) theory, which regionally corrects the electron exchange-correlation error in density functional theory (DFT) approximations, to examine multiple C-C coupling steps involving adsorbed CO (*CO) and its hydrogenated derivatives on the most ubiquitous facet, Cu(111). We predict that two adsorbed hydrogenated CO species, either *COH or *CHO, are necessary precursors for C-C bond formation. The three kinetically feasible pathways involving these species yield all three possible products: *COH-CHO, *COH-*COH, and *OCH-*OCH. The most kinetically favorable path forms *COH-CHO. In contrast, standard DFT approximations arrive at qualitatively different conclusions, namely, that only *CO and *COH will prevail on the surface and their C-C coupling paths produce only *COH-*COH and *CO-*CO, with a preference for the first product. This work demonstrates the importance of applying qualitatively and quantitatively accurate quantum mechanical method to simulate electrochemistry in order ultimately to shed light on ways to enhance selectivity toward C2+ product formation via CO2RR electrocatalysts.
| S-EPMC9636923 | biostudies-literature
Project description:The electroreduction of CO (CORR) is a promising alternative to the direct CO2 electroreduction reaction (CO2RR) to produce C2+ products. Cu-based electrocatalysts enable the formation of C-C bonds, leading to various C2+ hydrocarbon and oxygenate products. Herein, we investigated how the composition of bimetallic Cu-Ag catalysts impacted the nature of the Cu-Ag interactions and the product distribution of the CORR, aiming to improve the selectivity to C2+ products. Cu-Ag catalysts containing 1-50 mol% Ag were prepared by sol-gel synthesis. A Ag content of 10 mol% of Ag (Cu0.9Ag0.1) was optimum with respect to increasing the C2+ product selectivity and suppressing H2 evolution. Operando X-ray absorption spectroscopy and quasi-in situ X-ray photoelectron spectroscopy demonstrated the complete reduction of CuO to Cu during CORR. Electron microscopy (EM) and in situ wide-angle X-ray scattering (WAXS) revealed substantial restructuring during reduction. EM imaging showed the formation of Ag-Cu core-shell structures in Cu0.9Ag0.1, while separate Cu and Ag particles were predominant at higher Ag content. In situ WAXS revealed the formation of a Cu-Ag nanoalloy phase in the bimetallic Cu-Ag samples. The optimum Cu0.9Ag0.1 sample contained more Cu-Ag nanoalloys than samples with a higher Ag content. The Cu-Ag interfaces between the Ag-core and the Cu-shell in the bimetallic particles are thought to host the nanoalloys. The optimum CORR performance for Cu0.9Ag0.1 is likely due to the enhanced Cu-Ag interactions, as confirmed by a sample prepared with the same surface composition by galvanic exchange.
| S-EPMC11639664 | biostudies-literature
Project description:Electrochemical CO2 reduction (CO2R) is an approach to closing the carbon cycle for chemical synthesis. To date, the field has focused on the electrolysis of ambient pressure CO2. However, industrial CO2 is pressurized-in capture, transport and storage-and is often in dissolved form. Here, we find that pressurization to 50 bar steers CO2R pathways toward formate, something seen across widely-employed CO2R catalysts. By developing operando methods compatible with high pressures, including quantitative operando Raman spectroscopy, we link the high formate selectivity to increased CO2 coverage on the cathode surface. The interplay of theory and experiments validates the mechanism, and guides us to functionalize the surface of a Cu cathode with a proton-resistant layer to further the pressure-mediated selectivity effect. This work illustrates the value of industrial CO2 sources as the starting feedstock for sustainable chemical synthesis.
| S-EPMC10205702 | biostudies-literature
Project description:Polyoxometalates (POMs), representing anionic metal-oxo clusters, display diverse properties depending on their structures, constituent elements, and countercations. These characteristics position them as promising catalysts or catalyst precursors for electrochemical carbon dioxide reduction reaction (CO2RR). This study synthesized various salts-TBA+ (tetra-n-butylammonium), Cs+, Sr2+, and Ba2+-of a dipalladium-incorporated POM (Pd2, [γ-H2SiW10O36Pd2(OAc)2]4-) immobilized on a carbon support (Pd2/C). The synthesized catalysts-TBAPd2/C, CsPd2/C, SrPd2/C, and BaPd2/C-were deposited on a gas-diffusion carbon electrode, and the CO2RR performance was subsequently evaluated using a gas-diffusion flow electrolysis cell. Among the catalysts tested, BaPd2/C exhibited high selectivity toward carbon monoxide (CO) production (ca. 90%), while TBAPd2/C produced CO and hydrogen (H2) with moderate selectivity (ca. 40% for CO and ca. 60% for H2). Moreover, BaPd2/C exhibited high selectivity toward CO production over 12 h, while palladium acetate, a precursor of Pd2, showed a significant decline in CO selectivity during the CO2RR. Although both BaPd2/C and TBAPd2/C transformed into Pd nanoparticles and WO x nanospecies during the CO2RR, the influence of countercations on their product selectivity was significant. These results highlight that POMs and their countercations can effectively modulate the catalytic performance of POM-based electrocatalysts in CO2RR.
| S-EPMC11342151 | biostudies-literature
Project description:We report here on the electrochemical reduction of S-nitrosothiol species (RSNO). Nitric oxide (NO) is the reported common product from electrochemically reduced RSNOs at physiological pH. However, studies here at pH 7.4 show that during the reduction of RSNOs (-0.6 V to -0.9 V, vs. Ag/AgCl), no significant amount of NO is detected. Gas analysis suggests RSNO are reduced to nitrous oxide (N2O) at pH 7.4 and can only be converted back to NO at more oxidizing voltages. Interestingly, at pH 4.0, a direct one-electron reduction of RSNOs appears to occur and generates significant amounts of NO from RSNO species.
| S-EPMC4390089 | biostudies-literature
Project description:Among the possible products of CO2 electrochemical reduction, CO plays a unique and vital role, which can be an ideal feedstock for further reduction to C2+ products, and also the important component of syngas that can be used as feedstock for value-added chemicals and fuels. However, it is still a challenge to tune the CO selectivity on Cu electrode. Here we newly construct an ultrasound-assisted electrochemical method for CO2 reduction, which can tune the selectivity of CO2 to CO from less than 10% to >80% at -1.18 V versus (vs.) reversible hydrogen electrode (RHE). The partial current density of CO production is significantly improved by 15 times. By in-situ Raman study, the dominating factor for the improved CO production is attributed to the accelerated desorption of *CO intermediate. This work provides a facile method to tune the product selectivity in CO2 electrochemical reduction.
| S-EPMC8213958 | biostudies-literature