Among the electrolyzers under development for CO2 electroreduction at practical reaction rates, gas-fed approaches that use gas diffusion electrodes (GDEs) as cathodes are the most promising. However, the insufficient long-term stability of these technologies precludes their commercial deployment. The structural deterioration of the catalyst material is one possible source of device durability issues. Unfortunately, this issue has been insufficiently studied in systems using actual technical electrodes. Herein, we make use of a morphologically tailored Ag-based model nanocatalyst [Ag nanocubes (NCs)] assembled on a zero-gap GDE electrolyzer to establish correlations between catalyst structures, experimental environments, electrocatalytic performances, and morphological degradation mechanisms in highly alkaline media. The morphological evolution of the Ag–NCs on the GDEs induced by the CO2 electrochemical reduction reaction (CO2RR), as well as the direct mechanical contact between the catalyst layer and anion-exchange membrane, is analyzed by identical location and post-electrolysis scanning electron microscopy investigations. We find that at low and mild potentials positive of −1.8 V versus Ag/AgCl, the Ag–NCs undergo no apparent morphological alteration induced by the CO2RR, and the device performance remains stable. At more stringent cathodic conditions, device failure commences within minutes, and catalyst corrosion leads to slightly truncated cube morphologies and the appearance of smaller Ag nanoparticles. However, comparison with complementary CO2RR experiments performed in H-cell configurations in a neutral environment clearly proves that the system failure typically encountered in the gas-fed approaches does not stem solely from the catalyst morphological degradation. Instead, the observed CO2RR performance deterioration is mainly due to the local high alkalinity that inevitably develops at high current densities in the zero-gap approach and leads to the massive precipitation of carbonates which is not observed in the aqueous environment (H-cell configuration).
The most promising strategy to up-scale the electrochemical CO2 reduction reaction (ec-CO2RR) is based on the use of gas diffusion electrodes (GDEs) that allow current densities close to the range of 1 A/cm2 to be reached. At such high current densities, however, the flooding of the GDE cathode is often observed in CO2 electrolysers. Flooding hinders the access of CO2 to the catalyst, and by thus leaving space for (unwanted) hydrogen evolution, it usually leads to a decrease of the observable Faradaic efficiency of CO2 reduction products. To avoid flooding as much as possible has thus become one of the most important aims of to-date ec-CO2RR engineering, and robust analytical methods that can quantitatively assess flooding are now in demand. As flooding is very closely related to the formation of carbonate salts within the GDE structure, in this paper we use alkali (in particular, potassium) carbonates as a tracer of flooding. We present a novel analytical approach —based on the combination of cross-sectional energy-dispersive X-ray (EDX) mapping and inductively coupled plasma mass spectrometry (ICP--MS) analysis— that can not only visualise, but can also quantitatively describe the electrolysis time dependent flooding in GDEs, leading to a better understanding of electrolyser malfunctions.
The advantage of employing gas diffusion electrodes (GDEs) in carbon dioxide reduction electrolyzers is that they allow CO2 to reach the catalyst in gaseous state, enabling current densities that are orders of magnitude larger than what is achievable in standard H‐type cells. The gain in the reaction rate comes, however, at the cost of stability issues related to flooding that occurs when excess electrolyte permeates the micropores of the GDE, effectively blocking the access of CO2 to the catalyst. For electrolyzers operated with alkaline electrolytes, flooding leaves clear traces within the GDE in the form of precipitated potassium (hydrogen)carbonates. By analyzing the amount and distribution of precipitates, and by quantifying potassium salts transported through the GDE during operation (electrolyte perspiration), important information can be gained with regard to the extent and means of flooding. In this work, a novel combination of energy dispersive X‐ray and inductively coupled plasma mass spectrometry based methods is employed to study flooding‐related phenomena in GDEs differing in the abundance of cracks in the microporous layer. It is concluded that cracks play an important role in the electrolyte management of CO2 electrolyzers, and that electrolyte perspiration through cracks is paramount in avoiding flooding‐related performance drops.
After complete transection of the thoracic spinal segment, neonatal rats exhibit spontaneous locomotor recovery of hindlimbs, but this recovery is not found in adult rats after similar injury. The potential mechanism related to the difference in recovery of neonatal and adult rats remains unknown. In this study, 342 animals were analyzed. The vascular endothelial growth factor (VEGF) level in spinal segments below injury sites was significantly higher in postnatal day 1 rats (P1) compared with 28-day-old adult rats (P28) following a complete T9 transection. VEGF administration in P28 rats with T9 transection significantly improved the functional recovery; by contrast, treatment with VEGF receptor inhibitors in P1 rats with T9 transection slowed down the spontaneous functional recovery. Results showed more neurons reduced in the lumbar spinal cord and worse local neural network reorganization below injury sites in P28 rats than those in P1 rats. Transynaptic tracing with pseudorabies virus and double immunofluorescence analysis indicated that VEGF treatment in P28 rats alleviated the reduced number of neurons and improved their network reorganization. VEGF inhibition in neonates resulted in high neuronal death rate and deteriorated network reorganization. In in vivo studies, T9 transection induced less increase in the number of microglia in the spinal cord in P1 animals than P28 animals. VEGF treatment reduced the increase in microglial cells in P28 animals. VEGF administration in cultured spinal motoneurons prevented lipopolysaccharide (LPS)-induced neuronal death and facilitated neurite growth. Western blots of the samples of lumbar spinal cord after spinal transection and cultured spinal motoneurons showed a lower level of Erk1/2 phosphorylation after the injury or LPS induction compared with that in the control. The phosphorylation level increased after VEGF treatment. In conclusion, VEGF is a critical mediator involved in functional recovery after spinal transection and can be considered a potential target for clinical therapy.
In this work, we discuss the application of a gas diffusion electrode (GDE) setup for benchmarking electrocatalysts for the reductive conversion of CO2 (CO2 RR: CO2 reduction reaction). Applying a silver nanowire (Ag-NW) based catalyst, it is demonstrated that in the GDE setup conditions can be reached, which are relevant for the industrial conversion of CO2 to CO. This reaction is part of the so-called 'Rheticus' process that uses the CO for the subsequent production of butanol and hexanol based on a fermentation approach. In contrast to conventional half-cell measurements using a liquid electrolyte, in the GDE setup CO2 RR current densities comparable to technical cells (>100 mA cm–2) are reached without suffering from mass transport limitations of the CO2 reactant gas. The results are of particular importance for designing CO2 RR catalysts exhibiting high faradaic efficiencies towards CO at technological reaction rates.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
customersupport@researchsolutions.com
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.