Search

Electrochemical reduction of carbon dioxide (CO2RR) product distribution has been found to be dependent on several key factors, such as catalyst surface morphology, stability, and porosity. Metal-modified carbon-based materials have received a lot of attention in CO2RR. However, designing a highly active metal carbon catalyst for CO2RR utilizing low-cost chemical precursors remains a challenge. Here, a series of myristic acid-Phe-Phe peptide (MA-FF) aerogel materials containing graphene oxide (Gox) and Ag nanoparticles have been prepared for electrochemical CO2RR. The morphologies of the composites were studied by scanning electron microscopy (SEM), and their surface compositions were determined using X-ray photoelectron spectroscopy (XPS). While the peptide aerogel alone showed no catalytic activity for CO2 electroreduction, the addition of Ag nanoparticles results in a Faradaic efficiency (FE) of 46% for electroreduction of CO2 to CO at an overpotential of − 0.8 V vs. RHE. Incorporation of Gox in the aerogel increases the FE to 88% and allows CO2 reduction at a lower overpotential of − 0.7 V vs. RHE. Using highly porous peptide aerogels-Gox in addition to the metal active center provides an enhanced and new method for CO2 conversion using low environmental impact bio-based aerogels., Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., ChemE/Materials for Energy Conversion and Storage

The electrochemical CO2 reduction (ECO2R) is critical to enabling the widespread use of abundant renewable energy sources. However, in order to successfully implement such technologies on an industrial scale, necessary advancement in both the material and molecular design of electrocatalysts is required. In recent years, metal-sulfide (MS)-based nanomaterials have been explored as promising electrocatalysts for ECO2R. This article provides a systematic review of the design and development of MS-based catalysts for ECO2R, including their synthesis, characterization, reaction mechanism, catalytic performance, and strategies for future optimization. The current state-of-the-art MS-based ECO2R catalysts and their technical challenges are outlined herein with the purpose of establishing new guidelines for the rational design of next generation MS-based catalysts for CO2 electroreduction., Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., ChemE/Materials for Energy Conversion and Storage

Electrochemical reduction of CO2 presents an attractive way to store renewable energy in chemical bonds in a potentially carbon-neutral way. However, the available electrolyzers suffer from intrinsic problems, like flooding and salt accumulation, that must be overcome to industrialize the technology. To mitigate flooding and salt precipitation issues, researchers have used super-hydrophobic electrodes based on either expanded polytetrafluoroethylene (ePTFE) gas-diffusion layers (GDL’s), or carbon-based GDL’s with added PTFE. While the PTFE backbone is highly resistant to flooding, the non-conductive nature of PTFE means that without additional current collection the catalyst layer itself is responsible for electron-dispersion, which penalizes system efficiency and stability. In this work, we present operando results that illustrate that the current distribution and electrical potential distribution is far from a uniform distribution in thin catalyst layers (~50 nm) deposited onto ePTFE GDL’s. We then compare the effects of thicker catalyst layers (~500 nm) and a newly developed non-invasive current collector (NICC). The NICC can maintain more uniform current distributions with 10-fold thinner catalyst layers while improving stability towards ethylene (≥ 30%) by approximately two-fold., ChemE/Materials for Energy Conversion and Storage

The electrochemical reduction of carbon dioxide (CO2) to value-added chemicals is a promising strategy to mitigate climate change. Metalloporphyrins have been used as a promising class of stable and tunable catalysts for the electrochemical reduction reaction of CO2 (CO2RR) but have been primarily restricted to single-carbon reduction products. Here, we utilize functionalized earth-abundant manganese tetraphenylporphyrin-based (Mn-TPP) molecular electrocatalysts that have been immobilized via electrografting onto a glassy carbon electrode (GCE) to convert CO2 with overall 94 % Faradaic efficiencies, with 62 % being converted to acetate. Tuning of Mn-TPP with electron-withdrawing sulfonate groups (Mn-TPPS) introduced mechanistic changes arising from the electrostatic interaction between the sulfonate groups and water molecules, resulting in better surface coverage, which facilitated higher conversion rates than the non-functionalized Mn-TPP. For Mn-TPP only carbon monoxide and formate were detected as CO2 reduction products. Density-functional theory (DFT) calculations confirm that the additional sulfonate groups could alter the C−C coupling pathway from *CO→*COH→*COH-CO to *CO→*CO-CO→*COH-CO, reducing the free energy barrier of C−C coupling in the case of Mn-TPPS. This opens a new approach to designing metalloporphyrin catalysts for two carbon products in CO2RR., ChemE/Materials for Energy Conversion and Storage, ChemE/O&O groep, QN/Kavli Nanolab Delft

The electrochemical CO2 reduction reaction (CO2RR) is an attractive method to produce renewable fuel and chemical feedstock using clean energy sources. Formate production represents one of the most economical target products from CO2RR but is primarily produced using post-transition metal catalysts that require comparatively high overpotentials. Here a composition of bimetallic Cu–Pd is formulated on 2D Ti3C2Tx (MXene) nanosheets that are lyophilized into a highly porous 3D aerogel, resulting in formate production much more efficient than post-transition metals. Using a membrane electrode assembly (MEA), formate selectivities >90% are achieved with a current density of 150 mA cm−2 resulting in the highest ever reported overall energy efficiency of 47% (cell potentials of −2.8 V), over 5 h of operation. A comparable Cu-Pd aerogel achieves near-unity CO production without the MXene templating. This simple strategy represents an important step toward the experimental demonstration of 3D-MXenes-based electrocatalysts for CO2RR application and opens a new platform for the fabrication of macroscale aerogel MXene-based electrocatalysts., ChemE/Materials for Energy Conversion and Storage, ChemE/Catalysis Engineering, ChemE/O&O groep

The ever-growing level of carbon dioxide (CO2) in our atmosphere, is at once a threat and an opportunity. The development of sustainable and cost-effective pathways to convert CO2 to value-added chemicals is central to reducing its atmospheric presence. Electrochemical CO2 reduction reactions (CO2RRs) driven by renewable electricity are among the most promising techniques to utilize this abundant resource; however, in order to reach a system viable for industrial implementation, continued improvements to the design of electrocatalysts is essential to improve the economic prospects of the technology. This review summarizes recent developments in heterogeneous porphyrin-based electrocatalysts for CO2 capture and conversion. We specifically discuss the various chemical modifications necessary for different immobilization strategies, and how these choices influence catalytic properties. Although a variety of molecular catalysts have been proposed for CO2RRs, the stability and tunability of porphyrin-based catalysts make their use particularly promising in this field. We discuss the current challenges facing CO2RRs using these catalysts and our own solutions that have been pursued to address these hurdles., ChemE/Materials for Energy Conversion & Storage, ChemE/Product and Process Engineering

Electrochemical reduction of carbon dioxide (CO2) to valuable materials is a promising approach to suppress atmospheric CO2 levels. In order to bring this strategy to a commercial scale, the design of efficient, cost-effective, and robust catalysts is essential. Current advances in CO2 conversion technology use bimetallic components that enhance electrocatalysis via the introduction of binding site diversity. In this work, Sn-Pd bimetallic aerogels supported by carbon nanotubes (Sn-Pd/CNT) demonstrate selective electroreduction of CO2 to formate in ambient conditions. Amino substituents were introduced as an additional CO2 capture site (Sn-Pd/CNT-NH2), further enhancing the electrocatalytic activity and resulting in 91% formate selectively and a current density of -39 mA cm-2 at -0.4 V vs. RHE. The results demonstrate the potential of alloying Sn with other earth-abundant metals to promote the electrochemical conversion of CO2 to value-added materials. We believe this study provides valuable insights into the intricate relationship of bimetallic aerogels and shows the potential of the -NH2 group as a facilitator for CO2 capture and conversion that will inspire new forays into the development of competitive catalytic systems., ChemE/Materials for Energy Conversion & Storage

Despite the advances made in Virtual Reality (VR) technology, the design of VR experiences lacks sufficient focus on accessibility and inclusion as the primary requirements. These are especially important for STEM education, where engaging in experiential activities is essential. This study was conducted to investigate accessibility considerations in the design and development of Immersive VR (IVR) learning spaces for wheelchair users. The specific research question is: How can we make a VR system easier to interact with for wheelchair users needing vertical movement? A user study with thirty (30) participants in three groups was conducted: Group A (the control group, non-wheelchair users) who used natural body movement to interact with the environment, Group B (verification group, non-wheelchair users) who used software controls for accessibility, and Group C (wheelchair users) who used the same software accessibility feature. The results indicate that the accessibility feature enabled wheelchair users to complete the tasks requiring raising or lowering of the body, with almost similar levels of completion rate and accuracy., Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., ChemE/Materials for Energy Conversion and Storage

The electrochemical reduction of carbon dioxide (CO2) to value-added materials has received considerable attention. Both bulk transition-metal catalysts and molecular catalysts affixed to conductive noncatalytic solid supports represent a promising approach toward the electroreduction of CO2. Here, we report a combined silver (Ag) and pyridine catalyst through a one-pot and irreversible electrografting process, which demonstrates the enhanced CO2conversion versus individual counterparts. We find that by tailoring the pyridine carbon chain length, a 200 mV shift in the onset potential is obtainable compared to the bare silver electrode. A 10-fold activity enhancement at -0.7 V vs reversible hydrogen electrode (RHE) is then observed with demonstratable higher partial current densities for CO, indicating that a cocatalytic effect is attainable through the integration of the two different catalytic structures. We extended the performance to a flow cell operating at 150 mA/cm2, demonstrating the approach's potential for substantial adaptation with various transition metals as supports and electrografted molecular cocatalysts., ChemE/Materials for Energy Conversion and Storage, ChemE/O&O groep

The electrochemical reduction of CO2 (CO2RR) on silver catalysts has been demonstrated under elevated current density, longer reaction times, and intermittent operation. Maintaining performance requires that CO2 can access the entire geometric catalyst area, thus maximizing catalyst utilization. Here we probe the time-dependent factors impacting geometric catalyst utilization for CO2RR in a zero-gap membrane electrode assembly. We use three flow fields (serpentine, parallel, and interdigitated) as tools to disambiguate cell behavior. Cathode pressure drop is found to play the most critical role in maintaining catalyst utilization at all time scales by encouraging in-plane CO2 transport throughout the gas-diffusion layer (GDL) and around salt and water blockages. The serpentine flow channel with the highest pressure drop is then the most failure-resistant, achieving a CO partial current density of 205 mA/cm2 at 2.76 V. These findings are confirmed through selectivity measurements over time, double-layer capacitance measurements to estimate GDL flooding, and transport modeling of the spatial CO2 concentration., ChemE/Materials for Energy Conversion and Storage, ChemE/O&O groep

Integrating carbon dioxide (CO2) electrolysis with CO2 capture provides exciting new opportunities for energy reductions by simultaneously removing the energy-demanding regeneration step in CO2 capture and avoiding critical issues faced by CO2 gas-fed electrolysers. However, understanding the potential energy advantages of an integrated process is not straightforward due to the interconnected processes which require knowledge of both capture and electrochemical conversion processes. Here, we identify the upper limits of the integrated process from an energy perspective by comparing the working principles and performance of integrated and sequential approaches. Our high-level energy analyses unveil that an integrated electrolyser must show similar performance to the gas-fed electrolyser to ensure an energy benefit of up to 44% versus the sequential route. However, such energy benefits diminish if future gas-fed electrolysers resolve the CO2 utilisation issue and if an integrated electrolyser shows lower conversion efficiencies than the gas-fed system., ChemE/Materials for Energy Conversion and Storage

Carbon dioxide (CO2) electrolysis is a promising route to utilise captured CO2 as a building block to produce valuable feedstocks and fuels such as carbon monoxide and ethylene. Very recently, CO2 electrolysis has been proposed as an alternative process to replace the amine recovery unit of the commercially available amine-based CO2 capture process. This process would replace the most energy-intensive unit operation in amine scrubbing while providing a route for CO2 conversion. The key enabler for such process integration is to develop an efficient integrated electrolyser that can convert CO2 and recover the amine simultaneously. Herein, this review provides an overview of the fundamentals and recent progress in advancing integrated CO2 conversion in amine-based capture media. This review first discusses the mechanisms for both CO2 absorption in the capture medium and electrochemical conversion of the absorbed CO2. We then summarise recent advances in improving the efficiency of integrated electrolysis via innovating electrodes, tailoring the local reaction environment, optimising operation conditions (e.g., temperatures and pressures), and modifying cell configurations. This review is concluded with future research directions for understanding and developing integrated CO2 electrolysers., ChemE/Materials for Energy Conversion and Storage

The ever-growing level of carbon dioxide (CO2) in our atmosphere, is at once a threat and an opportunity. The development of sustainable and cost-effective pathways to convert CO2 to value-added chemicals is central to reducing its atmospheric presence. Electrochemical CO2 reduction reactions (CO2RRs) driven by renewable electricity are among the most promising techniques to utilize this abundant resource; however, in order to reach a system viable for industrial implementation, continued improvements to the design of electrocatalysts is essential to improve the economic prospects of the technology. This review summarizes recent developments in heterogeneous porphyrin-based electrocatalysts for CO2 capture and conversion. We specifically discuss the various chemical modifications necessary for different immobilization strategies, and how these choices influence catalytic properties. Although a variety of molecular catalysts have been proposed for CO2RRs, the stability and tunability of porphyrin-based catalysts make their use particularly promising in this field. We discuss the current challenges facing CO2RRs using these catalysts and our own solutions that have been pursued to address these hurdles., ChemE/Materials for Energy Conversion and Storage, ChemE/Product and Process Engineering

Electrochemical reduction of carbon dioxide (CO2) to valuable materials is a promising approach to suppress atmospheric CO2 levels. In order to bring this strategy to a commercial scale, the design of efficient, cost-effective, and robust catalysts is essential. Current advances in CO2 conversion technology use bimetallic components that enhance electrocatalysis via the introduction of binding site diversity. In this work, Sn-Pd bimetallic aerogels supported by carbon nanotubes (Sn-Pd/CNT) demonstrate selective electroreduction of CO2 to formate in ambient conditions. Amino substituents were introduced as an additional CO2 capture site (Sn-Pd/CNT-NH2), further enhancing the electrocatalytic activity and resulting in 91% formate selectively and a current density of -39 mA cm-2 at -0.4 V vs. RHE. The results demonstrate the potential of alloying Sn with other earth-abundant metals to promote the electrochemical conversion of CO2 to value-added materials. We believe this study provides valuable insights into the intricate relationship of bimetallic aerogels and shows the potential of the -NH2 group as a facilitator for CO2 capture and conversion that will inspire new forays into the development of competitive catalytic systems., ChemE/Materials for Energy Conversion and Storage