Cobalt Surface Research Articles

Boosting Propane Dehydrogenation to Propylene via Electron Hole‐Hydrogen Coupling on Cobalt Metal Surface

AbstractNonoxidative dehydrogenation of propane is useful for the high selectivity to propylene but is suffering from the heavy coke deposition on the catalyst surface. Herein, we present a proof‐of‐concept application of a hole‐hydrogen (H) couple on a metallic cobalt surface to decrease the deactivation rate. The coupled H atoms on the Cobalt (Co) surface, partially resulting from propane dehydrogenation, enabled the desorption of propylene to avoid deep hydrogenolysis and coke deposition and realize selective and durable propylene production, while conventional Co metal‐based catalysts do not generate propylene. The optimized hole‐H coupled Co catalyst provided a low deactivation rate (0.0036 h−1) and a high turnover frequency (55.6 h−1) for propylene production with a high propane flux (48 vol.% C3H8 in gas feeds) at 550 °C.

Boosting Propane Dehydrogenation to Propylene via Electron Hole-Hydrogen Coupling on Cobalt Metal Surface.

Nonoxidative dehydrogenation of propane is useful for the high selectivity to propylene but is suffering from the heavy coke deposition on the catalyst surface. Herein, we present a proof-of-concept application of a hole-hydrogen (H) couple on a metallic cobalt surface to decrease the deactivation rate. The coupled H atoms on the Cobalt (Co) surface, partially resulting from propane dehydrogenation, enabled the desorption of propylene to avoid deep hydrogenolysis and coke deposition and realize selective and durable propylene production, while conventional Co metal-based catalysts do not generate propylene. The optimized hole-H coupled Co catalyst provided a low deactivation rate (0.0036 h-1) and a high turnover frequency (55.6 h-1) for propylene production with a high propane flux (48 vol.% C3H8 in gas feeds) at 550 °C.

Understanding the effect of adsorption sites of CO at cobalt surface on its reactivity with H2/H by DFT calculations.

Cobalt (Co) is widely used in Fischer-Tropsch synthesis (FTS), converting synthesis gas, carbon monoxide + hydrogen (CO + H2), to long-chain hydrocarbons. The adsorption of CO on the Co surface is the key step in FTS. In this work, the effect of CO adsorption sites on the reactions between CO and H2 was investigated by using density functional theory (DFT). The energetics and structures of the reactions between the adsorbed CO (CO*) and H2/adsorbed H2 (H2*)/adsorbed H atom (H*) were calculated. The results show that the reaction between CO* and H2 is initiated by the molecular adsorption of H2 on the Co surface. The reactions between CO* and H2*/H* are influenced by CO adsorption sites. For the reaction system of CO* + H2*, it has the lowest reaction barrier when CO is adsorbed at the hcp site, while for CO* + H*, it has the lowest reaction barrier when CO is adsorbed on the top site. Kinetic analysis indicates that to improve the reactivity of CO + H2 in FTS, the adsorption of CO should be controlled to favour the top and bridge sites. This article is part of the theme issue 'Celebrating the 15th anniversary of the Royal Society Newton International Fellowship'.

Role of the magnetic layer interface, roughness, and thickness in the temperature-dependent magnetic properties of Al2O3/Co/CoO thin films deposited by magnetron sputtering

Using the methods of atomic force and electron microscopy and the magneto-optical Kerr effect, the role of the interface, roughness, and thickness of the magnetic layer in the temperature-dependent magnetic properties of thin Al2O3–Co films with a naturally oxidized cobalt surface was studied. The layers were deposited by magnetron sputtering. The thickness of the cobalt layer varied from 2 to 100 nm. For the first time, the dependences of coercive forces and exchange displacements on the thickness of the cobalt film in the temperature range from 80 to 300 K were obtained and analyzed. The contribution to the coercive force and exchange displacement from the oxidized cobalt surface increases as the temperature decreases below 160 K. The magnitude of the contribution depends on the base material on which the cobalt film is deposited and is maximum for a cobalt film with a thickness of ∼20 nm in the Al2O3/Co structure. A weakly magnetic layer was found at the Al2O3/Co interface. The behavior of the exchange bias in this layer is similar to the behavior of a ferromagnetic Co core with a naturally oxidized CoO shell. The thickness of this layer depends on the speed and order of deposition of the layers. When the order of deposition of layers (Co/Al2O3) changes, the behavior of the exchange displacement of the interface becomes similar to that observed in the ferromagnet/antiferromagnet system. That is, when the deposition order changes, the value of the exchange shift changes sign when the cobalt layer thickness is below 10 nm.

Etch Characteristics of Cobalt Thin Films in High Density Plasma of Cl2/O2/Ar Gas Mixture

Inductively coupled plasma reaction ion etching (ICP-RIE) of cobalt thin films patterned with SiO2 hard masks was performed using Cl2/O2/Ar gas mixture. The etch characteristics of cobalt films in Cl2/Ar gas were examined to determine the roles of Cl2 and O2, respectively. The etch rates and etch profiles of cobalt films were investigated by varying the O2 concentration in Cl2/O2/Ar gas mixture.In the optimized Cl2/Ar gas mixture, systematic etching of cobalt films was performed by changing the etch parameters including ICP RF power, DC-bias voltage, and process pressure. As the DC-bias voltage and process pressure was increased, the etch rate increased and the etch profile improved. Through the etching parameters variation experiment, the etching properties were investigated by adding O2 to Cl2/Ar under optimized conditions. X-ray photoelectron spectroscopy and optical emission spectroscopy were used to investigate the etch mechanism in the Cl2/O2/Ar gas mixture. In addition, scanning probe microscope was used to observe roughness on the etched cobalt surface. Finally, the etching of cobalt films patterned with nanometer-scale in the optimized Cl2/O2/Ar gas mixture was successfully achieved with good etch profile.AcknowledgmentThis research was supported by the Ministry of Trade, Industry & Energy (MOTIE) (20019504) and Korea Semiconductor Research Consortium (KSRC) support program for the development of future semiconductor devices. This work was supported by Korea Institute for Advancement of Technology (KIAT) grant funded by the Korea Government (MOTIE) (P0008458, HRD Program for Industrial Innovation).

Surface Atomic Rearrangement with High Cation Ordering for Ultra‐Stable Single‐Crystal Ni‐Rich Co‐Less Cathode Materials

AbstractIt is crucial to minimize cobalt content in Ni‐rich layered single‐crystal cathodes due to their high price and limited availability, yet it will inevitably lead to cation disordering, capacity degradation, and thermal issues. Herein, to overcome the intrinsic trade‐off between performance and composition of Ni‐rich Co‐less single‐crystal cathodes, a precursor engineering strategy with an epitaxially grown cobalt enrichment on the surface is innovatively proposed. In contrast to traditional coating modifications with random orientation and rigid surface‐bulk boundary, the epitaxially enriched surface cobalt layer on the precursor undergoes rapid interdiffusion with the internal Ni3+ during the optimized sintering process. This interdiffusion eliminates the surface‐bulk boundary, promoting the uniform distribution of cobalt and synergistically addressing the Li/Ni intermixing. Moreover, an enhanced surface Li+ diffusion is obtained, thereby suppressing the Li+ concentration gradient and intragranular cracks generation. Consequently, the modified LiNi0.7Co0.07Mn0.23O2 exhibits impressive cycling stability with increased capacity retention in both coin‐type half‐cells and pouch‐type full‐cells (91% after 1000 cycles), even under the harsh condition of high‐temperature, surpassing the majority of previously reported Ni‐rich cathodes. This work opens new avenues toward the low cost, high energy density, thermal stability, and long cyclic life for Ni‐rich Co‐less cathodes and sheds light on large‐scale commercial production.

Co-occurrence of microplastics and heavy metals in a freshwater lake system in Indian Himalaya: Distribution and influencing factors

Microplastic (MP) contamination in freshwater systems is a prevalent and persistent environmental issue, yet their occurrence and distribution remain poorly constrained. The present study examines the MPs abundance in sediment and water samples and factors controlling their distribution in the Manasbal Lake, north-western (NW) Himalaya. Additionally, the study investigates the relationship between heavy metals and the distribution of MPs in sediment, as well as their potential interactions. The MPs counts in lake surface sediment and water samples varied from 840 nkg−1 to 4020 nkg−1 and 13 nL−1 to 89 nL−1, respectively. The MPs distribution in Manasbal Lake exhibited spatial heterogeneity, with the greatest abundance observed in the eastern and northeastern areas near lake inlets. Grain size and land use appear to collectively modulate the variability of MPs in Manasbal Lake sediments. Five main MPs types were identified: beads/pellets, fragments, fibres, foams, and films, with beads being the predominant type. Polypropylene, polyethylene, and polystyrene are the dominant constituents of the observed MPs, with domestic sewage suggested as the predominant source for their abundance in the lake. Furthermore, the contamination factor for heavy metals indicated a high level of lead contamination in surface sediments, while copper and cobalt showed moderate contamination near the lake inlet. The SEM-EDS analysis illustrated the presence of toxic elements such as Hg, Zn, Pb, Cr, Cd, Ni, and Cu to the surface of MPs. This study expands the baseline characterization of MPs in freshwater systems and enhances our understanding of the potential sources and factors influencing MP distribution.

Fischer-Tropsch Synthesis for the Production of Sustainable Aviation Fuel: Formation of Tertiary Amines from Ammonia Contaminants.

Fischer-Tropsch synthesis combined with product workup is a promising route toward synthetic aviation fuel from renewable hydrogen and carbon sources like biomass, CO2, and waste. Cost savings can be achieved by reducing the number of gas treatment steps in new plants, but the consequence of contaminants in the feed needs investigation. While feeding 2.6 ppmV ammonia to a Fischer-Tropsch reactor, it was shown that ammonia was predominantly chemically converted into organic amines, with most nitrogen found in the water phase (89%), followed by heavy wax (7%) and light wax (1%). The concentration difference between water and light wax was shown to be due to the post-condensation separation of amines on polarity. Amines up to a chain length of 120 were detected in the heavy wax with MALDI-FT-ICR-MS, which, in combination with the high nitrogen content, suggests that amines have a similar chain growth probability compared to the main hydrocarbon products. Detailed product analysis with three independent analytical techniques showed that tertiary N,N-dimethylalkylamines were by far the most abundant amine class. This suggests that ammonia is decomposed on the cobalt surface and, potentially as a dimethylamine fragment, incorporated in the growing chain. Further evidence was obtained from the abundance of trimethylamine and from the reconciled nitrogen product analysis up to C100, which showed that the amine product distribution followed from naphtha onward the same ASF kinetics as alkanes and oxygenates while being distinctively different from the alkene distribution. The presented findings provide further avenues for studies of the Fischer-Tropsch reaction mechanism and indicate the opportunity of cost saving on gas treatment, while further validation is required to assess the impact on hydrocracking and product quality.

Modulating CO hydrogenation activity through silane functionalization of cobalt catalysts

Cobalt oxide (CoO) nanoparticles (NPs) were modified with different silanes (tetraethoxysilane – TEOS, triphenyl ethoxysilane – TPES, or trimethyl chlorosilane - TMCS) by dispersing the as-synthesized CoO NPs in n-hexane solutions containing the silanes. Fourier-transform infrared spectroscopy (FTIR) confirmed the presence of these silanes on the cobalt surfaces even after reduction in hydrogen (H2) at 573 K. Modifying CoO-NPs with TEOS resulted in face-centred cubic (fcc)-cobalt phase upon reduction whereas TPES or TMCS modification induced a mixture of hexagonal close-packed (hcp)- and fcc-cobalt phases. The modification of cobalt surfaces with the silanes alters the adsorption properties of carbon monoxide (CO) on the catalytically active sites. Furthermore, temperature programmed desorption of CO (CO-TPD) showed that the amount of dissociatively adsorbed CO relative to amount of associatively adsorbed CO increases on silane-modified cobalt surfaces, which correlates with an improved rate of CO conversion in the Fischer-Tropsch CO hydrogenation.

Nanoengineered Cobalt Electrocatalyst for Alkaline Oxygen Evolution Reaction.

The alkaline oxygen evolution reaction (OER) remains a bottleneck in green hydrogen production owing to its slow reaction kinetics and low catalytic efficiencies of earth abundant electrocatalysts in the alkaline OER reaction. This study investigates the OER performance of hierarchically porous cobalt electrocatalysts synthesized using the dynamic hydrogen bubble templating (DHBT) method. Characterization studies revealed that electrocatalysts synthesized under optimized conditions using the DHBT method consisted of cobalt nanosheets, and hierarchical porosity with macropores distributed in a honeycomb network and mesopores distributed between cobalt nanosheets. Moreover, X-ray photoelectron spectroscopy studies revealed the presence of Co(OH)2 as the predominant surface cobalt species while Raman studies revealed the presence of the cubic Co3O4 phase in the synthesized electrocatalysts. The best performing electrocatalyst required only 360 mV of overpotential to initiate a current density of 10 mA cm-2, exhibited a Tafel slope of 37 mV dec-1, and stable OER activity over 24 h. The DHBT method offers a facile, low cost and rapid synthesis approach for preparation for highly efficient cobalt electrocatalysts.

Theoretically predicted innovative palladium stripe dopingcobalt(1 1 1) surface with excellent catalytic performance for carbon monoxide oxidative coupling to dimethyl oxalate

Pd-based catalysts are extensively employed to catalyze CO oxidative coupling to generate DMO, while the expensive price and high usage of Pd hinder its massive application in industrial production. Designing Pd-based catalysts with high efficiency and low Pd usage as well as expounding the catalytic mechanisms are significant for the reaction. In this study, we theoretically predict that Pd stripe doping Co(1 1 1) surface exhibits excellent performance than pure Pd(1 1 1), Pd monolayer supporting on Co(1 1 1) and Pd single atom doping Co(1 1 1) surface, and clearly expound the catalytic mechanisms through the density functional theory (DFT) calculation and micro-reaction kinetic model analysis. It is obtained that the favorable reaction pathway is COOCH3–COOCH3 coupling pathway over these four catalysts, while the rate-controlling step is COOCH3+CO+OCH3→2COOCH3 on Pd stripe doping Co(1 1 1) surface, which is different from the case (2COOCH3→DMO) on pure Pd(1 1 1), Pd monolayer supporting on Co(1 1 1) and Pd single atom doping Co(1 1 1) surface. This study can contribute a certain reference value for developing Pd-based catalysts with high efficiency and low Pd usage for CO oxidative coupling to DMO.

Efficient electrocatalytic nitrate reduction using 3D copper foam-supported Co hexagonal nanoparticles in a membrane electrode assembly

Electrocatalytic nitrate reduction reaction (NO3RR) provides a promising route for nitrate recycling and ammonia production. In this work, Co nanoparticle catalyst was developed on a copper foam substrate (CoNPs/CF) by electrodeposition. The CoNPs/CF catalysis exhibits a Faradaic efficiency (FE) of 92.0% at −0.2 V vs. RHE and an NH3 yield rate of 14328.65 μg h−1 cm−2 at −0.5 V vs. RHE. In-suit Raman spectroscopy and theoretical calculations demonstrated that the 3D copper foam structure of the substrate enhances the electron exchange capacity, which promotes the adsorption of nitrate on the cobalt (Co) surface. Moreover, Membrane Electrode Assembly (MEA) is employed with CoNPs/CF, contributing to 98.43 mg h−1 with FE over 80%. Coupled with an air stripping process, this configuration has enabled the successful production of high-purity gaseous NH3 products. This work suggests a practical and viable approach for the conversion of wastewater nitrate into valuable ammonia products.

Three anionic surfactants for corrosion inhibition in cobalt CMP: Research on validity and mechanism

Inhibitors are introduced into the slurry to avoid excessive metal corrosion during the chemical mechanical polishing (CMP) process. The anti-corrosion effect of surfactants in CMP was not investigated systematically in past studies. In this paper, three eco-friendly anionic surfactants, potassium laurate, potassium oleate, and dodecyl benzenesulfonic acid, were studied in depth as cobalt CMP inhibitors. Electrochemical experiments demonstrated that the three inhibitors act as anodic inhibitors. Static etching tests and surface morphology analysis proved that they can effectively inhibit the corrosion rate of cobalt and improve surface morphology. XPS results demonstrated that the inhibitor reduces corrosion by inhibiting cobalt oxidation. DFT calculations demonstrated that inhibitors adsorb on the cobalt surface through the O atoms in hydrophilic groups, while the CC double bond and benzene ring can significantly enhance the adsorption. Molecular dynamics simulations showed that the inhibitors are adsorbed on the cobalt surface in parallel. Additionally, all three surfactants improved the solution's wettability on cobalt. This report provides critical insights into the corrosion inhibition specific to cobalt CMP and offers an approach to realize the multi-functionality of a single agent in slurries.

Design of Sulfur Resistant Cobalt Catalysts by Boron Promotion: Atomic Scale Insights

The effect of boron promotion on atomic sulfur formation by hydrogen sulfide dissociation on Co(111), flat surfaces of cobalt nanoparticles, was investigated using Density Functional Theory calculations. The results show that on clean Co(111), hydrogen sulfide dissociation proceeds fast due to low activation barriers, yielding atomic sulfur on the cobalt surfaces. Boron promotion hinders the dissociation of hydrogen sulfide due to increased activation barriers. Furthermore, boron prevents the interaction of sulfur compounds with cobalt surface atoms, as these poisons bind on boron. The findings indicate that boron is an effective promoter that can be used to design sulfur resistant cobalt catalysts.

Surface immobilization mechanisms of cobalt ions on hydroxyapatite catalyst supports

Cobalt deposition in an excess of solution was used to design Co-modified hydroxyapatite materials with various Co loadings and controlled dispersion. It is rationalized how the properties of hydroxyapatite supports (more or less stoichiometric compositions, nanorod or platelet morphologies and crystalline (100) zig-zag termination or non-apatitic hydrated external layer), influence the immobilization processes of Co by operating either with slightly acidic (natural) or basic pH of the suspension media. Four cobalt immobilization mechanisms impacting the final dispersion of Co on hydroxyapatites were identified by combining structural (XRD, 1H and 31P solid-state NMR, UV-Vis, Raman and X-ray fluorescence spectroscopies), surface (XPS) characterizations of Co-modified hydroxyapatites after drying and thermal treatment at 500 °C, and monitoring of the pH and the composition of the supernatant solutions during the Co deposition step. On dried Co-modified crystalline stoichiometric hydroxyapatite nanorods, cobalt is highly dispersed through cationic exchange or strong electrostatic adsorption (SEA) at slightly acidic or basic pH, respectively. After thermal treatment at 500 °C, only cation exchange preserved atomic dispersion of Co(II) ions since Co3O4 nanoparticles were observed on samples for which Co deposition occurred via SEA. On defective hydroxyapatite platelets, cobalt deposited at acidic natural pH could diffuse in an external non-apatitic layer, whereas under basic pH media, this surface layer was hydrolysed, resulting in the formation of a cobalt-substituted hydroxyapatite layer in which only a limited fraction of the surface cobalt species could be probed by XPS.

The electronic structure of the active center of Co3Se4 electrocatalyst was adjusted by Te doping for efficient oxygen evolution

In order to enhance the energy efficiency of water electrolysis, it is imperative to devise electrocatalysts for oxygen evolution reaction that are both non-precious metal-based and highly efficient. Efficient catalyst design is generally based on electronic structural engineering. Considering the electronegativity disparity between selenium (Se) and tellurium (Te), the tunable bandgaps, and the conductive metallic nature of Te. We designed a material wherein Te atoms are uniformly doped onto the surface of Cobalt tetra selenide (Co3Se4) nanorods, leading to the synthesis of a defect-rich material. Experimental results demonstrate that Te doping in Co3Se4 increases active sites and optimizes the electronic structure of Co cations, enhancing the design of multi-defect structures. This promotes the generation of the Co(oxy) hydroxide (CoOOH) active phase, enhancing catalytic activity by maximizing the binding strength between Co sites and oxygenated intermediates. Te-Co3Se4 nanorods exhibit good catalytic activity for oxygen evolution reactions, with an overpotential of 269 mV at a driving current density of 50 mA cm−2 and excellent stability in alkaline media (over 100 h). This discovery indicates the feasibility of strategically combining various imperfect structures, thereby unlocking the latent potential of diverse catalysts in electrocatalytic reactions.

Enantioselective Adsorption on Magnetic Surfaces.

From the beginning of molecular theory, the interplay of chirality and magnetism has intrigued scientists. There is still the question if enantiospecific adsorption of chiral molecules occurs on magnetic surfaces. Enantiomer discrimination wasconjectured to arise from chirality-induced spin separation within the molecules and exchange interaction with the substrate's magnetization. Here, it is shown that single helical aromatic hydrocarbons undergo enantioselective adsorption on ferromagnetic cobalt surfaces. Spin and chirality sensitive scanning tunneling microscopy reveals that molecules of opposite handedness prefer adsorption onto cobalt islands with opposite out-of-plane magnetization. As mobility ceases in the final chemisorbed state, it is concluded that enantioselection must occur in a physisorbed transient precursor state. State-of-the-art spin-resolved ab initio simulations support this scenario by refuting enantio-dependent chemisorption energies. These findings demonstrate that van der Waals interaction should also include spin-fluctuations which are crucial for molecular magnetochiralprocesses.

Zonal activation of molecular carbon dioxide and hydrogen over dual sites Ni-Co-MgO catalyst for CO2 methanation: Synergistic catalysis of Ni and Co species

An in-depth mechanism in zonal activation of CO2 and H2 molecular over dual-active sites has not been revealed yet. Here, Ni-Co-MgO was rationally constructed to elucidate the CO2 methanation mechanism. The abundant surface nickel and cobalt components as active sites led to strong Ni-Co interaction with charge transfer from nickel to cobalt. Notably, electron-enriched Coδ− species participated in efficient chemisorption and activation of CO2 to generate monodentate carbonate. Simultaneously, plentiful available Ni0 sites facilitated H2 dissociation, thus CO2 and H2 were smoothly activated at zones of Coδ− species and Ni0, respectively. Detailed in situ DRIFTS, quasi situ XPS, TPSR, and DFT calculations substantiated a new formate evolution mechanism via monodentate carbonate instead of traditional bidentate carbonate based on synergistic catalysis of Coδ− species and Ni0. The zonal activation of CO2 and H2 by tuning electron behaviors of double-center catalysts can boost heterogeneous catalytic hydrogenation performance.

Cobalt-based core@shell catalysts for guaiacol hydro conversion: use of salicylic acid as a sacrificial modulator of the interaction between the metal phase and the silica support

Salicylic acid as a cobalt-based catalyst modifier enhances the activity with increased selectivity towards cyclohexanol. This is linked to changes induced by the modifier over the cobalt surface, allowing for tuning of the catalytic activity.

Surface deposits and intracellular concentration of atmospheric particles in foliage of urban forests in the Valley of Mexico

Foliage of urban vegetation can be used as a bioindicator of air pollution, including heavy metals. We measured surface and intracellular concentration of copper, zinc, lead, nickel, chromium, cobalt and cadmium in Fraxinus uhdei leaves from three urban forests of the Metropolitan Area of the Valley of Mexico (ZMVM) during the four seasons of the year and assessed its correlation with distance to nearest roads; we also compared obtained concentrations with the local atmospheric monitoring network. We performed a two-factor experimental design: factor forest with three levels (Naucalli Park, Forests and Tlalpan) and factor season with four levels, to analyze spatio-temporal differences in heavy metal concentration. Fifteen Fraxinus uhdei trees were selected per site and a foliage sample was taken. A t-test was applied for comparisons between deposits, while an analysis of variance and Tukey's test was used to compare between seasons and forest. Relationship between surface concentrations and distance to the streets surrounding the forests was obtained using the Stepwise method. The obtained results indicate that there are higher concentrations superficially than intracellular in all metals analyzed, except for nickel. Copper was highest in Parque Naucalli, lead, nickel, chromium and cadmium in Bosques Chapultepec and zinc in Bosques Tlalpan. Highest concentrations occurred in summer for copper, zinc, nickel and chromium and in winter for lead and cadmium. We found that the surface concentration of copper, zinc, lead and cadmium in the foliage is higher when trees are closer to avenues. Our research indicates that trees can be valuable bioindicators for air pollution, as they not only mirror the diverse pollution sources but also provide insights into pollutant exposure based on proximity to those sources.