Showing papers on "Cobalt published in 2021"

Cobalt single atom site catalysts with ultrahigh metal loading for enhanced aerobic oxidation of ethylbenzene

Abstract: The oxidation of hydrocarbons to produce high value-added compounds (ketones or alcohols) using oxygen in air as the only oxidant is an efficient synthetic strategy from both environmental and economic views. Herein, we successfully synthesized cobalt single atom site catalysts (Co SACs) with high metal loading of 23.58 wt.% supported on carbon nitride (CN), which showed excellent catalytic properties for oxidation of ethylbenzene in air. Moreover, Co SACs show a much higher turn-over frequency (19.6 h−1) than other reported non-noble catalysts under the same condition. Comparatively, the as-obtained nanosized or homogenous Co catalysts are inert to this reaction. Co SACs also exhibit high selectivity (97%) and stability (unchanged after five runs) in this reaction. DFT calculations reveal that Co SACs show a low energy barrier in the first elementary step and a high resistance to water, which result in the robust catalytic performance for this reaction.

Isolated Cobalt Centers on W18O49 Nanowires Perform as a Reaction Switch for Efficient CO2 Photoreduction.

Abstract: Isolated cobalt atoms have been successfully decorated onto the surface of W18O49 ultrathin nanowires. The Co-atom-decorated W18O49 nanowires (W18O49@Co) greatly accelerate the charge carrier separ...

Local spin-state tuning of cobalt–iron selenide nanoframes for the boosted oxygen evolution

Abstract: Hydrogen economy by water splitting is the indispensable cornerstone for sustainable energy yet it is impeded by sluggish anodic water oxidation. Hence, the rational design of highly efficient electrocatalysts for oxygen evolution is the key to unlocking its wider use. Herein, cobalt–iron selenide nanoframes are reported for the efficient water oxidation, which need only 270 mV overpotential to give a 10 mA cm−2 current density and outperforms most cobalt-based catalysts, and even the benchmarked commercial ruthenium oxides (RuO2). More profoundly, iron doping regulates the local spin state of cobalt species, which further accelerates charge transfer and formation of oxygenated intermediates, and consequently contributes to the enhanced oxygen evolution. This work demonstrates a highly efficient oxygen evolution electrocatalyst and may pioneer a promising approach which involves tuning the local electronic structure to achieve the improved electrocatalysis activities in energy conversion technologies.

Two-Dimensional Covalent Organic Frameworks with Cobalt(II)-Phthalocyanine Sites for Efficient Electrocatalytic Carbon Dioxide Reduction.

Abstract: The rapid development in synthesis methodology and applications for covalent organic frameworks (COFs) has been witnessed in recent years. However, the synthesis of highly stable functional COFs still remains a great challenge. Herein two-dimensional polyimide-linked phthalocyanine COFs (denoted as CoPc-PI-COF-1 and CoPc-PI-COF-2) have been devised and prepared through the solvothermal reaction of the tetraanhydrides of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato cobalt(II) with 1,4-phenylenediamine and 4,4'-biphenyldiamine, respectively. The resultant CoPc-PI-COFs with a four-connected sql net exhibit AA stacking configurations according to powder X-ray diffraction studies, showing permanent porosity, thermal stability above 300 °C, and excellent resistance to a 12 M HCl aqueous solution for 20 days. Current-voltage curves reveal the conductivity of CoPc-PI-COF-1 and CoPc-PI-COF-2 with the value of 3.7 × 10-3 and 1.6 × 10-3 S m-1, respectively. Due to the same Co(II) electroactive sites together with similar permanent porosity and CO2 adsorption capacity for CoPc-PI-COFs, the cathodes made up of COFs and carbon black display a similar CO2-to-CO Faradaic efficiency of 87-97% at applied potentials between -0.60 and -0.90 V (vs RHE) in 0.5 M KHCO3 solution. However, in comparison with the CoPc-PI-COF-2&carbon black electrode, the CoPc-PI-COF-1 counterpart provides a larger current density (jCO) of -21.2 mA cm-2 at -0.90 V associated with its higher conductivity. This cathode also has a high turnover number and turnover frequency, amounting to 277 000 and 2.2 s-1 at -0.70 V during 40 h of measurement. The present result clearly discloses the great potential of 2D porous crystalline solids in electrocatalysis.

18.77 % Efficiency Organic Solar Cells Promoted by Aqueous Solution Processed Cobalt(II) Acetate Hole Transporting Layer.

Abstract: A robust hole transporting layer (HTL), using the cost-effective Cobalt(II) acetate tetrahydrate (Co(OAc)2 ⋅4 H2 O) as the precursor, was simply processed from its aqueous solution followed by thermal annealing (TA) and UV-ozone (UVO) treatments. The TA treatment induced the loss of crystal water followed by oxidization of Co(OAc)2 ⋅4 H2 O precursor, which increased the work function. However, TA treatment differently realize a high work function and ideal morphology for charge extraction. The resulting problems could be circumvented easily by additional UVO treatment, which also enhanced the conductivity and lowered the resistance for charge transport. The optimal condition was found to be a low temperature TA (150 °C) followed by simple UVO, where the crystal water in Co(OAc)2 ⋅4 H2 O was removed fully and the HTL surface was anchored by substantial hydroxy groups. Using PM6 as the polymer donor and L8-BO as the electron acceptor, a record high PCE of 18.77 % of the binary blend OSCs was achieved, higher than the common PEDOT:PSS-based solar cell devices (18.02 %).

Direct Magnetic Reinforcement of Electrocatalytic ORR/OER with Electromagnetic Induction of Magnetic Catalysts

Abstract: Designing stable and efficient electrocatalysts for both oxygen reduction and evolution reactions (ORR/OER) at low-cost is challenging. Here, a carbon-based bifunctional catalyst of magnetic catalytic nanocages that can direct enhance the oxygen catalytic activity by simply applying a moderate (350 mT) magnetic field is reported. The catalysts, with high porosity of 90% and conductivity of 905 S m-1 , are created by in situ doping metallic cobalt nanodots (≈10 nm) into macroporous carbon nanofibers with a facile electrospinning method. An external magnetic field makes the cobalt magnetized into nanomagnets with high spin polarization, which promote the adsorption of oxygen-intermediates and electron transfer, significantly improving the catalytic efficiency. Impressively, the half wave-potential is increased by 20 mV for ORR, and the overpotential at 10 mA cm-2 is decreased by 15 mV for OER. Compared with the commercial Pt/C+IrO2 catalysts, the magnetic catalyzed Zn-air batteries deliver 2.5-fold of capacities and exhibit much longer durability over 155 h. The findings point out a very promising strategy of using electromagnetic induction to boost oxygen catalytic activity.

Microwave-assisted thin reduced graphene oxide-cobalt oxide nanoparticles as hybrids for electrode materials in supercapacitor

Abstract: In recent times, microwave synthetic strategies have been considered as one of the facile methods for the development of efficient supercapacitor electrodes. Reduced graphene oxide containing cobalt oxide (rGO@Co3O4/CoO) hybrids were synthesized via single-step microwave irradiation in which the uniform Co3O4/CoO nanoparticles were attached in thin layers of rGO nanosheets. During short time of single-step microwave irradiation process, three kind of phenomena occurs as (i) reduction and exfoliation of graphite oxide into rGO nanosheets, (ii) decomposition of cobalt(II) acetate into Co3O4/CoO nanoparticles and (iii) rGO nanosheets covers the Co3O4/CoO nanoparticles. The BET surface area and pore diameter range of rGO@Co3O4/CoO hybrids were 133.2 m2g−1 and 5–45 nm, respectively, which shows the mesoporous structure formation of hybrids. Electrochemical evaluations of rGO@Co3O4/CoO hybrids as electrode materials for supercapacitor shows specific capacitance of 276.1 F g−1 (scan rate of 5 mV s−1) and long-term cycling stability as 82.37% capacitance retention after 10,000 cycles (scan rate of 60 mV s−1) in 0.1 M KOH electrolyte solution. The Co3O4/CoO nanoparticles with conducting scaffolds rGO structure will pave an encouraging alternative for electrode materials and suggesting good potential for supercapacitors applications.

Hollow Porous Bowl-like Nitrogen-Doped Cobalt/Carbon Nanocomposites with Enhanced Electromagnetic Wave Absorption

Abstract: A unique hollow porous bowl-like nitrogen-doped cobalt/carbon nanocomposite (HBN-Co/C) composed of Co nanoparticles anchored in N-doped porous carbon was designed for enhancing electromagnetic micr...

Cobalt-Doping of Molybdenum Disulfide for Enhanced Catalytic Polysulfide Conversion in Lithium-Sulfur Batteries.

Abstract: Metal sulfides, such as MoS2, are widely investigated in lithium-sulfur (Li-S) batteries to suppress the shuttling of lithium polysulfides (LiPSs) due to their chemical adsorption ability and catalytic activity. However, their relatively low conductivity and activity limit the LiPS conversion kinetics. Herein, the Co-doped MoS2 is proposed to accelerate the catalytic conversion of LiPS as the Co doping can promote the transition from semiconducting 2H phase to metallic 1T phase and introduce the sulfur vacancies in MoS2. A one-step hydrothermal process is used to prepare such a Co-doped MoS2 with more 1T phase and rich sulfur vacancies, which enhances the electron transfer and catalytic activity, thus effectively improving the LiPS adsorption and conversion kinetics. The cathode using the three-dimensional graphene monolith loaded with Co-doped MoS2 catalyst as the sulfur host shows a high rate capability and long cycling stability. A high capacity of 941 mAh g-1 at 2 C and a low capacity fading of 0.029% per cycle at 1 C over 1000 cycles are achieved, suggesting the effectively suppressed LiPS shuttling and improved sulfur utilization. Good cyclic stability is also maintained under a high sulfur loading indicating the doping is an effective way to optimize the metal sulfide catalysts in Li-S batteries.

Engineering High-Spin State Cobalt Cations in Spinel Zinc Cobalt Oxide for Spin Channel Propagation and Active Site Enhancement in Water Oxidation.

Abstract: Promoting the initially deficient but cost-effective catalysts to high-performing competitors is of significance in developing better catalysts. Spinel zinc cobalt oxide (ZnCo 2 O 4 ) is not considered as a superior catalyst for the electrochemical oxygen evolution reaction (OER), which is the bottleneck reaction in water-electrolysis. Herein, taking advantage of density functional theory (DFT) calculations, we find that the existence of low-spin (LS) state cobalt cations hinders the OER activity of spinel zinc cobalt oxide, as the t 2g 6 e g 0 configuration gives rise to purely localized electronic structure and exhibits poor binding affinity to the key reaction intermediate. Increasing the spin state of cobalt cations in spinel ZnCo 2 O 4 is found to propagate a spin channel to promote spin-selected charge transport during OER and generate better active sites for intermediates adsorption. The experiments find increasing the calcination temperature a facile approach to engineer high-spin (HS) state cobalt cations in ZnCo 2 O 4 , while not working for Co 3 O 4 . The activity of the best spin-state-engineered ZnCo 2 O 4 outperforms other typical Co-based oxides. Our work pinpoints the critical influence of the spinel composition on the splitting energy of the metals and further on the feasibility of spin state engineering.

Engineering Platinum–Cobalt Nano-alloys in Porous Nitrogen-Doped Carbon Nanotubes for Highly Efficient Electrocatalytic Hydrogen Evolution

Abstract: Highly efficient electrocatalysts are essential for the production of green hydrogen from water electrolysis. Herein, a metal-organic framework-assisted pyrolysis-replacement-reorganization approach is developed to obtain ultrafine Pt-Co alloy nanoparticles (sub-10 nm) attached on the inner and outer shells of porous nitrogen-doped carbon nanotubes (NCNT) with closed ends. During the thermal reorganization, the migration of Pt-Co nano-alloys to both surfaces ensures the maximized exposure of active sites while maintaining the robust attachment to the porous carbon matrix. Density functional theory calculations suggest a nearly thermodynamically-neutral free energy of adsorption for hydrogen intermediates and diversified active sites induced by alloying, thus resulting in a great promotion in intrinsic activity towards the hydrogen evolution reaction (HER). Benefiting from the delicate structural design and compositional modulation, the optimized Pt3 Co@NCNT electrocatalyst manifests outstanding HER activity and superior stability in both acidic and alkaline media.

One-step Ethylene Purification from an Acetylene/Ethylene/Ethane Ternary Mixture by Cyclopentadiene Cobalt-Functionalized Metal-Organic Frameworks.

Abstract: The separation of ethylene (C2 H4 ) from a mixture of ethane (C2 H6 ), ethylene (C2 H4 ), and acetylene (C2 H2 ) at normal temperature and pressure is a significant challenge. The sieving effect of pores is powerless due to the similar molecular size and kinetic diameter of these molecules. We report a new modification method based on a stable ftw topological Zr-MOF platform (MOF-525). Introduction of a cyclopentadiene cobalt functional group led to new ftw-type MOFs materials (UPC-612 and UPC-613), which increase the host-guest interaction and achieve efficient ethylene purification from the mixture of hydrocarbon gases. The high performance of UPC-612 and UPC-613 for C2 H2 /C2 H4 /C2 H6 separation has been verified by gas sorption isotherms, density functional theory (DFT), and experimentally determined breakthrough curves. This work provides a one-step separation of the ternary gas mixture and can further serve as a blueprint for the design and construction of function-oriented porous structures for such applications.

Activating two-dimensional Ti3C2Tx-MXene with single-atom cobalt for efficient CO2 photoreduction

Abstract: Summary Artificial CO2 photoreduction to solar fuels represents an eco-friendly and sustainable solution to obtain “sunshine” feedstocks by using renewable energy media. Herein, we report that single cobalt atoms anchored on two-dimensional Ti3C2Tx-MXene nanosheets act as an efficient photocatalytic ensemble for visible-light CO2 reduction, wherein the Ti3C2Tx nanosheets bridge visible-light absorbers (ruthenium complex) with cobalt active sites. The single cobalt atoms build strong interactions with Ti3C2Tx by forming metal-oxygen/carbon bonds, resulting in the formation of the Co-Ti3C2Tx ensemble. As a result, the production rate of CO reaches a high value of 6.06 mmol h−1 g−1 over the optimal Co-Ti3C2Tx, which markedly exceeds previous MXene-based catalysts for CO2 photoreduction. Theoretical calculation manifests that the isolated Co atoms coordinated with Ti3C2Tx can effectively facilitate the generation of CO. This work may provide a new line of thought into the rational design of high-activity MXene-based photocatalysts toward artificial CO2 conversion.

Ultralow Ru Incorporated Amorphous Cobalt-Based Oxides for High-Current-Density Overall Water Splitting in Alkaline and Seawater Media

Abstract: Realizing efficiency and stable hydrogen production by water electrolysis under high current densities is essential to the forthcoming hydrogen economy. However, its industrial breakthrough is seriously limited by bifunctional catalysts with slow hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrocatalytic processes. Herein, an ultralow Ru incorporated amorphous cobalt-based oxide (Ru-CoOx /NF), effectively driving the electrolysis of water at high current densities in alkaline water and seawater, is designed and constructed. In 1 m KOH, to reach the current density of 1000 mA cm-2 for HER and OER, it only needs 252 and 370 mV overpotentials, respectively, beyond commercial Pt/C and RuO2 catalysts. At the high current density, it also presents outstanding electrochemical stability. Then the electrolyzer apparatus assembled with Ru-CoOx /NF, just requires the ultra-low voltage of 2.2 and 2.62 V to support the current density of 1000 mA cm-2 in alkaline water and seawater electrolysis, respectively, for hydrogen production, better than that of the commercial Pt/C and RuO2 catalysts. This work demonstrates that Ru-CoOx /NF is one of the most promising catalysts for industrial applications and provides a possibility for exploration of high-current-density water electrocatalysis by changing the crystallinity of the catalyst.

Origin of the Activity of Co–N–C Catalysts for Chemoselective Hydrogenation of Nitroarenes

Abstract: The production of functionalized anilines by chemoselective hydrogenation of nitroarenes occupies an important position in the chemical industries. Recently, cobalt and nitrogen codoped carbon (Co–...

Cobalt metal-organic framework modified carbon cloth/paper hybrid electrochemical button-sensor for nonenzymatic glucose diagnostics.

Abstract: In the growing pandemic, family healthcare is widely concerned with the increase of medical self-diagnosis away from the hospital. A cobalt metal-organic framework modified carbon cloth/paper (Co-MOF/CC/Paper) hybrid button-sensor was developed as a portable, robust, and user-friendly electrochemical analytical chip for nonenzymatic quantitative detection of glucose. Highly integrated electrochemical analytical chip was successfully fabricated with a flexible Co-MOF/CC sensing interface, effectively increasing the specific area and catalytic sites than the traditional plane electrode. Based on the button-sensor, rapid quantitative detection of glucose was achieved in multiple complex bio-matrixes, such as serum, urine, and saliva, with desired selectivity, stability, and durability. With the advantages of low cost, high environment tolerance, ease of production, our nanozyme-based electrochemical analytical chip achieved reliable nonenzymatic electrocatalysis, has great potential for the application of rapid on-site analysis in personalized diagnostic and disease prevention.