COPPER AND ANTIMONY BASED MATERIAL AND ELECTRODE FOR THE SELECTIVE CONVERSION OF CARBON DIOXIDE TO CARBON MONOXIDE

The present invention relates to a copper and antimony based material, and an electrode obtained from this material, useful for the electrochemical reduction of carbon dioxide to carbon monoxide with high efficiency and selectivity

Heterogeneous Electrocatalysts for CO₂ Reduction to Value Added Products

The CO2 that comes from the use of fossil fuels accounts for about 65% of the global greenhouse gas emission, and it plays a critical role in global climate changes. Among the different strategies that have been considered to address the storage and reutilization of CO2, the transformation of CO2 into chemicals and fuels with a high added-value has been considered a winning approach. This transformation is able to reduce the carbon emission and induce a “fuel switching” that exploits renewable energy sources. The aim of this chapter is to categorize different heterogeneous electrocatalysts which are being used for CO2 reduction, based on the desired products of the above mentioned reactions: from formic acid and carbon monoxide to methanol and ethanol and other possible by products. Moreover, a brief description of the kinetic and mechanism of the CO2 reduction reaction) and pathways toward different products have been discussed

Tin sulfide supported on cellulose nanocrystals-derived carbon as a green and effective catalyst for CO2 electroreduction to formate

This work reports a whole green two-step approach for the synthesis of novel catalysts for efficient CO2 conversion. A conductive carbon support was firstly obtained via pyrolysis of cellulose nanocrystals (CNCs), and the carbon surface was successively decorated with tin sulfide (SnS) through a microwave-assisted hydrothermal process. The morphology and carbon structure were characterized by field emission scanning electron microscopy and Raman spectroscopy, and the presence of SnS decoration was confirmed by X-ray photoelectron spectroscopy and X-ray diffraction analyses. The SnS supported on CNC-derived carbon shows enhanced catalytic activity for the CO2 conversion to formate (HCOO-). Good selectivity of 86% and high partial current density of 55 mA cm(-2) are reached at - 1.0 V vs. reversible hydrogen electrode in KHCO3 electrolyte. Additionally, the mass activity of the composite catalyst achieves a value as high as 262.9 mA mgSn(-1) for HCOO- formation, demonstrating good utilization efficiency of Sn metal. In this work, the low-cost CNC-derived carbon is evidenced to be easily decorated with metal species and thus shows high versatility and tailorability. Incorporating metal species with conductive high-surface carbon supports represents an effective strategy to realize active and stable electrocatalysts, allowing efficient utilization of metals especially the raw and precious ones

Optimizing the Performance of Low-Loaded Electrodes for CO2-to-CO Conversion Directly from Capture Medium: A Comprehensive Parameter Analysis

Gas-fed reactors for CO2 reduction processes are a solid technology to mitigate CO2 accumulation in the atmosphere. However, since it is necessary to feed them with a pure CO2 stream, a highly energy-demanding process is required to separate CO2 from the flue gasses. Recently introduced bicarbonate zero-gap flow reactors are a valid solution to integrate carbon capture and valorization, with them being able to convert the CO2 capture medium (i.e., the bicarbonate solution) into added-value chemicals, such as CO, thus avoiding this expensive separation process. We report here a study on the influence of the electrode structure on the performance of a bicarbonate reactor in terms of Faradaic efficiency, activity, and CO2 utilization. In particular, the effect of catalyst mass loading and electrode permeability on bicarbonate electrolysis was investigated by exploiting three commercial carbon supports, and the results obtained were deepened via electrochemical impedance spectroscopy, which is introduced for the first time in the field of bicarbonate electrolyzers. As an outcome of the study, a novel low-loaded silver-based electrode fabricated via the sputtering deposition technique is proposed. The silver mass loading was optimized by increasing it from 116 μg/cm2 to 565 μg/cm2, thereby obtaining an important enhancement in selectivity (from 55% to 77%) and activity, while a further rise to 1.13 mg/cm2 did not provide significant improvements. The tremendous effect of the electrode permeability on activity and proficiency in releasing CO2 from the bicarbonate solution was shown. Hence, an increase in electrode permeability doubled the activity and boosted the production of in situ CO2 by 40%. The optimized Ag-electrode provided Faradaic efficiencies for CO close to 80% at a cell voltage of 3 V and under ambient conditions, with silver loading of 565 μg/cm2, the lowest value ever reported in the literature so far

Microwave-assisted synthesis of N/S-doped CNC/SnO2 nanocomposite as a promising catalyst for oxygen reduction in alkaline media

In this study, we report an all-green approach for the synthesis of novel catalysts for oxygen reduction reaction (ORR) via a simple two-step procedure. In particular, conductive cellulose nanocrystals (CNCs) were obtained via pyrolysis, and a successive microwave-assisted hydrothermal process was employed to activate the carbon lattice by introducing sulfur (S) and nitrogen (N) dopants, and to decorate the surface with tin oxide (SnO2) nanocrystals. The successful synthesis of N/S-doped CNC/SnO2 nanocomposite was confirmed by X-ray Photoelectron Spectroscopy analysis, Energy Dispersive X-ray microanalysis, X-ray Diffraction and Field Emission Scanning Electron Microscopy. The synergistic effects of the dopants and SnO2 nanocrystals in modifying the catalytic performance were proved by various electrochemical characterizations. Particularly, the nanocomposite material reaches remarkable catalytic performance towards the ORR, close to the Pt/C benchmark, in alkaline environviment, showing promising potential to be implemented in alkaline fuel cell and metal-air battery applications

Engineering copper nanoparticle electrodes for tunable electrochemical reduction of carbon dioxide

The electrochemical conversion of CO2 catalyzed by copper (Cu)-based materials is widely reported to produce different valuable molecules, and the selectivity for a specific product can be achieved by tuning the characteristics of catalytic materials. Differing from these studies on materials, the present work focuses on the engineering of gas diffusion electrodes in order to properly modify the selectivity, particularly by changing the Cu nanoparticle catalyst loading of the electrodes. Low catalyst loadings (≤ 0.25 mg cm−2) favor CH4 production, and intermediate (∼ 1.0 mg cm−2) loadings shift the selectivity toward C2H4. Eventually, larger values (≥ 2.0 mg cm−2) promote CO production. Detailed analyses reveal that both bulk and local CO generation rates, and charge transfer mechanism are responsible for the observed loading-dependent selectivity. The present work provides a new strategy for steering the CO2RR selectivity by simple electrode engineering beyond material development

Electrochemical Reduction of {CO}2 With Good Efficiency on a Nanostructured Cu-Al Catalyst

Carbon monoxide (CO) and formic acid (HCOOH) are suggested to be the most convenient products from electrochemical reduction of CO2 according to techno-economic analysis. To date, tremendous advances have been achieved in the development of catalysts and processes, which make this research topic even more interesting to both academic and industrial sectors. In this work, we report nanostructured Cu-Al materials that are able to convert CO2 to CO and HCOOH with good efficiency. The catalysts are synthesized via a green microwave-assisted solvothermal route, and are composed of Cu2O crystals modified by Al. In KHCO3 electrolyte, these catalysts can selectively convert CO2 to HCOOH and syngas with H-2/CO ratios between 1 and 2 approaching one unit faradaic efficiency in a wide potential range. Good current densities of 67 and 130 mA cm(-2) are obtained at -1.0 V and -1.3 V vs. reversible hydrogen electrode (RHE), respectively. When switching the electrolyte to KOH, a significant selectivity up to 20% is observed for C2H4 formation, and the current densities achieve 146 and 222 mA cm(-2) at -1.0 V and -1.3 V vs. RHE, respectively. Hence, the choice of electrolyte is critically important as that of catalyst in order to obtain targeted products at industrially relevant current densities

Influence of binders and solvents on stability of Ru/RuOx nanoparticles on ITO nanocrystals as Li–O2 battery cathodes

Fundamental research on Li–O2 batteries remains critical, and the nature of the reactions and stability are paramount for realising the promise of the Li–O2 system. We report that indium tin oxide (ITO) nanocrystals with supported 1–2 nm oxygen evolution reaction (OER) catalyst Ru/RuOx nanoparticles (NPs) demonstrate efficient OER processes, reduce the recharge overpotential of the cell significantly and maintain catalytic activity to promote a consistent cycling discharge potential in Li–O2 cells even when the ITO support nanocrystals deteriorate from the very first cycle. The Ru/RuOx nanoparticles lower the charge overpotential compared with those for ITO and carbon-only cathodes and have the greatest effect in DMSO electrolytes with a solution-processable F-free carboxymethyl cellulose (CMC) binder (<3.5 V) instead of polyvinylidene fluoride (PVDF). The Ru/RuOx/ITO nanocrystalline materials in DMSO provide efficient Li2O2 decomposition from within the cathode during cycling. We demonstrate that the ITO is actually unstable from the first cycle and is modified by chemical etching, but the Ru/RuOx NPs remain effective OER catalysts for Li2O2 during cycling. The CMC binders avoid PVDF-based side-reactions and improve the cyclability. The deterioration of the ITO nanocrystals is mitigated significantly in cathodes with a CMC binder, and the cells show good cycle life. In mixed DMSO–EMITFSI [EMITFSI=1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide] ionic liquid electrolytes, the Ru/RuOx/ITO materials in Li–O2 cells cycle very well and maintain a consistently very low charge overpotential of 0.5–0.8 V

Biochar/Zinc Oxide Composites as Effective Catalysts for Electrochemical CO2 Reduction

Novel electrocatalysts based on zinc oxide (ZnO) and biochars are prepared through a simple and scalable route and are proposed for the electrocatalytic reduction of CO₂ (CO₂RR). Materials with different weight ratios of ZnO to biochars, namely, pyrolyzed chitosan (CTO) and pyrolyzed brewed waste coffee (CBC), are synthesized and thoroughly characterized. The physicochemical properties of the materials are correlated with the CO₂RR to CO performance in a comprehensive study. Both the type and weight percentage of biochar significantly influence the catalytic performance of the composite. CTO, which has pyridinic- and pyridone-N species in its structure, outperforms CBC as a carbon matrix for ZnO particles, as evidenced by a higher CO selectivity and an enhanced current density at the ZnO_CTO electrode under the same conditions. The study on various ZnO to CTO weight ratios shows that the composite with 40.6 wt % of biochar shows the best performance, with the CO selectivity peaked at 85.8% at −1.1 V versus the reversible hydrogen electrode (RHE) and a CO partial current density of 75.6 mA cm–² at −1.3 V versus RHE. It also demonstrates good stability during the long-term CO₂ electrolysis, showing high retention in both CO selectivity and electrode activity