Cobalt-based Catalysts Research Articles

Sulfonated Covalent Organic Frameworks Anchoring Cobalt as High-Efficient and Stable Catalysts for Peroxymonosulfate Activation.

Heterogeneous cobalt-based catalysts are highly effective in activing peroxymonosulfate (PMS) and produce free radicals to deal with recalcitrant organic pollutants in water. However, unfeasible recyclability and gradual performance degradation remain challenging due to the easy agglomeration and leaching of active cobalt species. Herein, a strategy is proposed to construct stably anchored and highly dispersed Co2+ sites on dual functional sulfonated covalent organic frameworks (COF-Co). The sulfonic acid groups are able to realize the targeted binding with cobalt ions through a two-step cation-exchange method, leading to strong combination with active Co2+ sites and utmost utilization efficiencies. Moreover, the super-hydrophility of sulfonic acid groups favors the rapid accessibility of organic molecules to the catalyst and accelerates the degradation. Remarkably, COF-Co exhibits high activity in PMS activation, effective oxidation for tetracycline degradation (92% within 30min at 30mg L-1) and other coloring contaminants, and excellent recycle stability. This work can guide the rational design of efficient and environmentally friendly PMS-activated catalyst with great potential for application in wastewater treatment.

Efficient Adsorption and Degradation of Tetracycline Hydrochloride Using Metal-Organic Framework-Derived Cobalt-Based Catalysts and Mechanism Insight.

High-performance Co-based catalysts were derived by pyrolysis using synthesized MOFs as self-sacrificial templates. Various catalytic systems were constructed by peroxymonosulfate (PMS) to degrade tetracycline hydrochloride (TC). Adsorption-degradation efficiencies, cycle performance, dynamics, and the adsorption catalytic mechanism of various catalytic systems for TC were studied. The effects of different synthetic solvents, pyrolysis temperatures, and single/bimetallic element compositions on degradation efficiency were innovatively compared. The optimal catalyst and PMS dosage for the experiment were determined to be 10 mg and 0.1 mL, respectively. The results indicated that all catalytic systems could efficiently degrade TC and have a high acid-base resistance. The catalyst activity was significantly influenced by the pyrolysis temperature. The optimum pyrolysis temperatures for Zn@Co-N-C-T, CH3OH@Co-N-C-T, and H2O@Co-N-C-T were 1000, 900 and 900 °C, respectively. More abundant pore structures and active sites were generated in Zn@Co-N-C-1000, exhibiting an excellent TC degradation efficiency and adsorption capacity, achieving 94.73% and 167.564 mg/g, respectively. Meanwhile, the total organic carbon (TOC) of TC (50 mL, 50 mg/L) achieved a removal rate (TOC/TOC0) of 50.28%. Zn@Co-N-C-1000/PMS maintained over 83.27% TC degradation after five cycles. The adsorption mechanism of the catalyst for TC was investigated through the analysis of adsorption kinetics and isotherm models. The quenching test and EPR results indicated that TC was primarily degraded through the nonradical pathway. The efficient degradation of TC is attributed to the rapid electron transfer processes occurring at the two-phase interface and the redox cycling of Co0/Co2+/Co3+. Finally, LC-MS was used to analyze the intermediate products of TC degradation in the Zn@Co-N-C-1000/PMS system, and two degradation pathways were proposed.

Adsorption Property and Morphology Evolution of C Deposited on HCP Co Nanoparticles.

Despite extensive studies of deposited carbon in Fischer-Tropsch synthesis (FTS), an atomic-level comprehension of the effect of carbon on the morphology of cobalt-based FTS catalysts remains elusive. The adsorption configurations of carbon atoms on different crystal facets of hexagonal close-packed (hcp) Co nanoparticles were studied using density functional theory (DFT) calculations to explore the interaction mechanism between C and Co surfaces. The weaker adsorption strength of C atoms on Co(0001), Co(10-10), and Co(11-20) surfaces accounted for lower diffusion energy, leading to the facile formation of C dimers. Electronic property analysis shows that more electrons are transferred from Co surfaces to C atoms on corrugated facets than on flat facets. The deposition of carbon atoms on Co nanoparticles affects surface energy by forming strong Co-C bonds, which causes the system to reach a more energetically favorable morphology with an increased proportion of exposed Co(10-12) and Co(11-20) areas as the carbon content increases slightly. This transformation in morphology implies that C deposition plays a crucial role in determining the facet proportion and stability of exposed Co surfaces, contributing to the optimization of cobalt-based catalysts with improved performance.

The impact of support selection and Co loading amount on the catalytic performance for methane combustion

Methane (CH4) is a key component of natural gas and is essential for energy production and utilization. However, due to its strong greenhouse effect, efficient catalytic combustion methods are needed to convert it into CO2 and H2O. This study systematically evaluates the catalytic performance of Co, CoO, and Co3O4 in methane catalytic combustion, particularly highlighting the superior activity of Co3O4. To improve catalytic efficiency, this paper examines the effects of SiO2, Al2O3, and CeO2 as support materials using co-precipitation and impregnation methods. The results show a significant improvement in the catalytic activity of Co3O4 supported on CeO2, attributed to CeO2's unique redox properties and high oxygen storage capacity. Additionally, the study explores the impact of different loading amounts (5%, 10%, 15%, 20%) of Co3O4(x)-CeO2 catalysts on their performance. The optimal 10%wt Co3O4–CeO2 catalyst achieves methane conversion rates of 10%, 50%, and 90% at temperatures of 376 °C, 473 °C, and 578 °C, respectively, demonstrating exceptional stability during a 20-h stability test and the ability to adapt to fluctuations in CH4 concentrations in low-oxygen environments, while also exhibiting significant catalytic activity across a range of methane concentrations from 0.5% to 2.5%. These findings provide important theoretical and experimental guidance for the application of cobalt-based catalysts in CH4 combustion, paving the way for future catalyst design and optimization.

Increasing catalytic efficiency of cobalt centers in oxygen reduction reaction - Evidence from cobalt with salen ligands polymer complex

Substantial research is performed for cobalt-based catalysts for various applications in catalysis, including oxygen reduction reaction (ORR) catalysis in nonaqueous electrolytes. Cobalt exhibits high catalytic activity due to partially filled d-orbitals, which promote the formation of chemisorption bonds with various molecules. The catalytic activity of metal centers can be influenced both by changing their immediate environment and by varying the reaction conditions. This paper investigates the influence of solvent type, electrolyte concentration, and organic framework conductivity on the efficiency of ORR catalysis in non-aqueous electrolytes as illustrated by poly-CoSal polymer complex. The findings show that the increase in the solvent donor number of and conductivity of the organic backbone leads to highly efficient cobalt catalysts, which can be potentially be applied in oxygen cathodes of Li-O2 batteries. CoSal-based catalysts increase the discharge voltage of Li-O2 cells and can operate in dry atmospheric air.

Exploring the potential of cobalt-based catalysts in the methane dry reforming for sustainable energy applications

Cobalt-based powder catalysts with different Co loadings were synthesized via wet impregnation using MgAl2O4 spinel as support. The catalytic properties of the solids were evaluated in the dry-reforming methane at different reaction temperatures and two CH4:CO2 ratios. The catalyst with higher cobalt content (13 %) presented superior performance due to increased Co0 species availability, confirmed by XPS analysis. Besides, this catalyst displayed remarkable resistance to carbon deposition at 550 °C and CH4:CO2 1: 1 ratio. In-situ DRIFT measurements demonstrated the formation and transformation of carbonate and hydrogen carbonate species during the DRM reaction, highlighting efficient CO2 and CH4 activation on the catalyst surface. Based on this data, a structured catalyst was deposited on top of the FeCrAlloy monolith, which was active, stable, selective for H2, and resistant against on/off cycles. Compared with the powder catalyst, the structured system displayed higher catalytic activity, possibly due to higher reducibility of metal species and improved heat transfer provided by the FeCrAlloy substrate. The results highlight the potential of Co-based structured catalysts for H2 or synthesis gas production processes.

Advanced electrochemical oxidation of EDTA-Ni via cobalt single-atom catalysts: Exploring indirect persulfate activation pathways

This study explores an innovative electrochemical strategy for the removal of the highly stable and toxic EDTA-Ni complex found in electroplating wastewater. Utilizing a cobalt-based single-atom catalyst (Co-NC) in an electro-enhanced system, we achieved significant activation of peroxydisulfate (PDS) for effective degradation of EDTA-Ni. Under optimal conditions of 40 mA current density and a pH range of 3–7, more than 97% of EDTA-Ni (1 mM) was successfully degraded within 90 min. Through detailed electrochemical experiments, we identified that atomic hydrogen (H*) played a crucial role in the indirect activation of PDS, facilitating the formation of reactive sulfate radicals (·SO4-). Computational analysis using density functional theory (DFT) confirmed that the H*-mediated reduction pathway had a notably low energy barrier (ΔGbs = 0.51 eV), making it the dominant activation mechanism. Gas chromatography-mass spectrometry (GC–MS) further revealed the primary degradation intermediates, providing insights into the breakdown process of EDTA-Ni. This research underscores the potential of Co-NC catalyst as a highly effective catalyst for treating persistent heavy metal complexes in advanced oxidation systems.

Ionic Liquid/Deep Eutectic Solvent-Mediated Calcining Synthesis of Cobalt-Based Electrocatalysts for Water Splitting.

The recent advancements of ionic liquids (ILs) and deep eutectic solvents (DESs) in the synthesis of cobalt-based catalysts for water splitting is reviewed. ILs and DESs possess unique physical and chemical properties, serving as solvents, templates, and reagents. Combined with calcination techniques, their advantages can be fully leveraged, enhancing the stability and activity of resulted catalysts. In these solvents, not only are they suitable for simple one-step calcination, but also applicable to more complex multi-step calcination, suitable for more complex reaction conditions. The designability of ILs and DESs allows them to participate in the reaction as reactants, providing metal and heteroatoms, simplifying the preparation system of cobalt phosphide, sulfide, and nitride. This work offers insights into design principles for electrocatalysts and practical guidance for the development of efficient and high-performance materials for hydrogen production and energy storage systems.

Enhancement of peroxymonosulfate activation through regulating electronic structure of cobalt phthalocyanine by g-C3N4 for rhodamine B degradation

The catalytic performance of cobalt-based catalysts in Fenton-like reactions is significantly influenced by the electron density of Co centers. However, precise control of the electronic structure to enhance the degradation activity remains a challenge. This paper demonstrates a method to enhance the catalytic activity of cobalt phthalocyanine (CoPc) by modulating its electronic structure via integrating with graphitic carbon nitride (g-C3N4). The electron redistribution between g-C3N4 and CoPc was observed, resulting in electron-rich Co centers. Consequently, the CoPc/g-C3N4 composites exhibit significantly enhanced peroxymonosulfate (PMS) activation capability compared to CoPc and their physical mixtures. The improved catalytic performance is due to the electron-rich Co centers, better dispersion of CoPc, and enhanced hydrophilicity. This study proposes a novel strategy for the design of efficient PMS activation catalysts.

Asymmetric oxygen vacancies of self-supporting Co3O4/CuOx on Cu foam boosts propane total oxidation

As a low-cost and environmentally friendly transition metal oxides material, the Co3O4 has good catalytic activity for volatile organic compounds (VOCs) oxidation. However, the active components of powder cobalt-based catalysts may present uneven distribution and aggregation, thus affecting the catalytic efficiency. Herein, the Co/Cu-CF monolithic catalyst with asymmetric oxygen vacancies was developed through in-situ growth of Cu(OH)2 nanoarrays on Cu foam, which exhibits excellent performance for propane oxidation (T90 at 215 ℃). It is impressive that the catalyst shows satisfactory stability in terms of long-term, cyclic and water resistance. The results indicate that the existence of nanoarrays can provide a rich load surface and better disperse the active components, which effectively facilitates the interface interaction between cobalt and copper, inducing the generation of asymmetric oxygen vacancies. And, the activity of catalyst was significantly improved owing to the double activation effect of asymmetric oxygen vacancy on molecular oxygen and lattice oxygen. Therefore, this research offers a novel approach for designing efficient nanoarray monolithic catalysts for VOCs oxidation and other environmental applications.

A highly efficient Co-based catalyst for peroxymonosulfate activation for rapid degradation of RhB over a wide pH range

Cobalt-based materials have been demonstrated to be effective heterogeneous catalysts for peroxymonosulfate activation in degrading many refractory organic pollutants. In this study, a new cobalt-based catalyst was prepared using cobalt chloride hexahydrate (CoCl2·6H2O) as the Co2+ source, 2,3-pyrazine dicarboxylic acid and 3,6-DI-4-pyridyl-1,2,4,5-tetrazine (4-PYTZ) as ligands. This catalyst was employed as a peroxymonosulfate activator for the degradation of Rhodamine B(RhB). The results indicated that the prepared Co-based catalyst can effectively degrade RhB dye in aqueous solution by activating peroxymonosulfate (PMS). Specifically, when the initial concentration of RhB was 20 mg/L, its degradation rate exceeded 98 % within merely 9 min. The factors influencing the activation of PMS by the Co-based catalyst were examined, including PMS concentration, reaction temperature, solution pH, and the concentration of organic pollutants. Stability and reusability tests demonstrated that the prepared catalyst exhibited good stability, with the degradation rate of RhB remaining above 97 % after four repetitive experiments. Free radical quenching experiments and electron paramagnetic resonance (EPR) analyses revealed that sulfate radicals (SO4−) and hydroxyl radicals (OH) are the primary reactive radicals accountable for the degradation process. Additionally, it displayed excellent adaptability over a wide pH range, particularly within the pH levels ranging from 5 to 9. This study demonstrates that the prepared Co-based catalyst can serve as a stable and effective option for degrading organic dyes in wastewater treatment applications.

Cobalt-based Single-atom Dehydrogenation Catalysts Having High Selectivity and Regenerability and Method for Producing Corresponding Olefins from Paraffins Using the Same

Cobalt-based Single-atom Dehydrogenation Catalysts Having High Selectivity and Regenerability and Method for Producing Corresponding Olefins from Paraffins Using the Same

Utilization of Cobalt and its Oxide/Hydroxide Mediated by Ionic Liquids/Deep Eutectic Solvents as Catalysts in Water Splitting.

With the ever-growing global demand for sustainable energy solutions, hydrogen has garnered significant attention as a clean, efficient, and renewable energy source. In the field of hydrogen production, catalyst research stands out as one of the foremost areas of focus. In recent years, the preparation of electrocatalysts using ionic liquids (ILs) and deep eutectic solvents (DESs) has attracted widespread attention. ILs and DESs possess unique physicochemical properties and are recognized as green media as well as functional materials. Cobalt-based catalysts have proven to be efficient electrocatalysts for water splitting. Incorporating ILs or DESs into the preparation of cobalt-based catalysts offers a remarkable advantage by allowing precise control over their structural design and composition. This control directly influences the adsorption properties of the catalyst's surface and the stability of reaction intermediates, thereby enabling enhanced control over reaction pathways and product selectivity. Consequently, the catalytic activity and stability of cobalt-based catalysts can be effectively improved. In the process of preparing cobalt-based catalysts, ILs and DESs can serve as solvents and templates. Owing to the good solubility of ILs and DESs, they can efficiently dissolve raw materials and provide a special nucleation and growth environment, obtaining catalysts with novel-structures. The main focus of this review is to provide a detailed introduction to metal cobalt and its oxide/hydroxide derivatives in the field of water splitting, with a particular emphasis on the research progress achieved through the utilization of IL and DES. The aim is to assist readers in designing and synthesizing novel and high-performance electrochemical catalysts.

Photoelectrocatalytic CO2 Reduction to Methanol by Molecular Self-Assemblies Confined in Covalent Polymer Networks.

Inspired by the porous structures of photosynthetic organelles, we report here a new type of photoelectrode based on a standalone macroporous conjugated polymer network (MCN) that converts sunlight into high-energy electrons for CO2 reduction to CH3OH. The MCN provides supramolecular cavities with sufficient functional groups that control the structures of photocatalytic assemblies, which circumvents the geometric limitations of traditional inorganic counterparts. Stabilized interfacial contact between MCN and photocatalysts is achieved by strong chemical linkages throughout the network. Solar irradiation of MCN with a cobalt-based catalyst generates highly reducing electrons for the reduction of CO2 to CH3OH at a conversion efficiency of 70%. Production of CH3OH sustains for at least 100 h, with a small decrease in yield rates. Scaling up the photoelectrode from 1 to 100 cm2 results in photocurrent generation stabilized at 0.25 A and continuous CH3OH production at a conversion efficiency of 85%, demonstrating the scalability and high performances.

Halloysite-derived hierarchical cobalt silicate hydroxide hollow nanorods assembled by nanosheets for highly efficient electrocatalytic oxygen evolution reaction

The oxygen evolution reaction (OER) is regarded as the bottleneck of electrolytic water splitting. Thus, developing robust earth-abundant electrocatalysts for efficient OER has received a great deal of attention and it is an ongoing scientific challenge. Herein, hierarchical hollow nanorods assembled with ultrathin mesoporous cobalt silicate hydroxide nanosheets (denoted as CoSi) were successfully fabricated, using the silica nanotube derived from halloysite as a sacrificial template, via a simple hydrothermal method. The resulting cobalt silicate hydroxide nanosheets stack with thicknesses ∼10 nm, as confirmed by transmission electron microscopy. The elaborated nanoarchitecture possesses a high specific surface area (SSA) allowing good exposure to the cobalt active centers exhibiting superior catalytic activity vs analogs synthesized using sodium silicate. Among all as-prepared CoSi samples, those synthesized at 150 °C (CoSi-150) exhibited the minimum overpotential of ∼347 mV at a current density of 10 mA cm–2. In addition, CoSi-150 also exhibited superior performance against typical cobalt-based catalysts, and its surface hydroxyl groups were beneficial for the enhancement of OER performance. Furthermore, the CoSi-150 showed excellent durability and stability after the 105 s chronopotentiometry test in 1 M KOH. This design concept provides a new strategy for the low-cost preparation of high-quality cobalt water splitting electrocatalysts.

Advancements in Cobalt-Based Catalysts for Enhanced CO2 Hydrogenation: Mechanisms, Applications, and Future Directions: A Short Review

In 2020, China put forward the national energy and economic development strategy goal of “carbon peak and carbon neutrality”; in this context, the hydrogenation of carbon dioxide into clean energy and high-value-added chemicals can effectively alleviate the current environmental pressure. This process represents a crucial avenue for the advancement of green energy and the realisation of a sustainable energy development strategy. Among the efficient catalysts designed for CO2 hydrogenation reactions, transition metal cobalt has garnered extensive attention from researchers due to its relatively abundant reserves and low economic cost. This paper first introduces the thermodynamic process of carbon dioxide hydrogenation and discusses methods to improve the efficiency of the catalytic reaction from a thermodynamic perspective. It then briefly describes the reaction mechanism of cobalt-based catalysts in the carbon dioxide hydrogenation reaction. Based on this understanding, this paper reviews recent research on the application of cobalt-based catalysts in the hydrogenation of carbon dioxide to produce methane, hydrocarbon chemicals, and alcohols. Finally, the methods to improve the catalytic efficiency of these catalysts are discussed, and future research directions are proposed.

Impact of various metal promoters on the propane dehydrogenation performance of cobalt-based catalysts

Large-scale exploitation of natural gas and shale gas has spurred the development of the propane dehydrogenation technology. While cobalt-based catalysts, known for their low cost and low toxicity, effectively activate C–H bonds, they are often deactivated because of coke formation. In this study, we prepared SBA-15 molecular sieves using a hydrothermal synthesis method and developed a series of Co-based catalysts supported on SBA-15 with various metal promoters (denoted Co-X/SBA-15, where X = Mn, Fe, Mg, Zn, or La) via an incipient wetness impregnation method. Characterization techniques and activity evaluation results revealed that the Co–O–Mg structure in the Co-Mg/SBA-15 catalyst stabilizes the primary Co2+ active site and hinders the reduction of the CoOx species. The incorporation of Mg enhances the total alkalinity of the catalyst, facilitating propane adsorption and propylene desorption, leading to superior activity and stability. Although the addition of La improved propylene selectivity, it did not significantly enhance propane conversion. Conversely, the introduction of Mn, Fe, and Zn into the catalyst inhibited the reaction.

Highly Efficient Peroxymonosulfate Electroactivation on Co(OH)2 Nanoarray Electrode for Pefloxacin Degradation.

The activation of PMS to produce active species is an attractive technique for antibiotic degradation but is restricted to the low reaction kinetics and high costs. In this work, a cobalt-based catalyst was prepared by in situ electrodeposition to enhance the electrically activated PMS process for the degradation of antibiotics. Almost 100% of pefloxacin (PFX) was removed within 10 min by employing Co(OH)2 as the catalyst in the electrically activated peroxymonosulfate (PMS) process, and the reaction kinetic constant reached 0.52 min-1. The redox processes of Co2+ and Co3+ in Co(OH)2 catalysts were considered to be the main pathways for PMS activation, in which 1O2 was the main active species. Furthermore, this strategy could also achieve excellent degradation efficiency for other organic pollutants. This study provides an effective and low-cost strategy with no secondary pollution for pollutant degradation.

The promotional effects of ZrO2 modification on the activity and selectivity of Co/SiC catalysts for Fischer-Tropsch synthesis

Co/SiC catalysts have exhibited excellent performance in Fischer-Tropsch synthesis reaction. However, few research focuses on investigating the effect of SiC supports surface properties of on catalyst performance. In this study, ZrO2 was utilized to modify the SiC surface, leading to the preparation of a series of Co-ZrO2/SiC catalysts. The physicochemical properties of the catalyst were comprehensively analyzed by using N2 adsorption, XRD, H2-TPR, XPS analyses. Catalytic performance was evaluated using a fixed bed reactor, shedding light on the effect of ZrO2 modified SiC support on cobalt-based Fischer-Tropsch synthesis catalysts. The results indicated that ZrO2 surface modification on SiC resulted in an enhanced reduction degree of Co/SiC catalysts. Additionally, ZrO2 exhibited strong interaction with the amorphous phase on the SiC surface, thereby weakening the interaction between Co and the amorphous phase. This led to an increase in the electron density of cobalt species, consequently improving the selectivity of Co/SiC catalysts towards long-chain hydrocarbons.

Sustainable synthesis and characterization of cobalt-based biocatalysts from olive stone waste for enhanced curing of unsaturated polyester resins

The functionalization of native olive wood shell stone for the formation of new active heterogeneous cobalt-based biocatalysts has been conducted. The resulting biocatalysts have been fully characterized using various analytical techniques, including X-ray fluorescence (XRF), elemental analysis, granulometry, X-ray photoelectron spectroscopy (XPS), Fourier-Transform Infrared Spectroscopy (FTIR), thermogravimetry (TGA), moisture content, field-emission scanning electron microscopy (FESEM) and high-angle annular dark-field imaging (HAADF) with energy dispersive X-ray spectroscopy (EDX). The catalytic performance of these new functional heterogeneous materials has been verified by gelation time measurements on a multipurpose unsaturated polyester/styrene/tert-butyl peroxybenzoate system. The results are compared with those obtained using the current workhorse of the industry, which utilizes cobalt-based catalysts, particularly cobalt octoate dissolved in a solvent solution known to have adverse environmental and human health implications.