Browse
Submit Data
Databases
API
Help

Dataset Information

29 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Highly selective and active CO₂ reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures.

ABSTRACT: Electrochemical reduction of carbon dioxide with renewable energy is a sustainable way of producing carbon-neutral fuels. However, developing active, selective and stable electrocatalysts is challenging and entails material structure design and tailoring across a range of length scales. Here we report a cobalt-phthalocyanine-based high-performance carbon dioxide reduction electrocatalyst material developed with a combined nanoscale and molecular approach. On the nanoscale, cobalt phthalocyanine (CoPc) molecules are uniformly anchored on carbon nanotubes to afford substantially increased current density, improved selectivity for carbon monoxide, and enhanced durability. On the molecular level, the catalytic performance is further enhanced by introducing cyano groups to the CoPc molecule. The resulting hybrid catalyst exhibits >95% Faradaic efficiency for carbon monoxide production in a wide potential range and extraordinary catalytic activity with a current density of 15.0 mA cm^-2 and a turnover frequency of 4.1 s^-1 at the overpotential of 0.52 V in a near-neutral aqueous solution.

SUBMITTER: Zhang X

PROVIDER: S-EPMC5344970 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

CO2 electrochemical catalytic reduction with a highly active cobalt phthalocyanine.

Project description:Molecular catalysts that combine high product selectivity and high current density for CO2 electrochemical reduction to CO or other chemical feedstocks are urgently needed. While earth-abundant metal-based molecular electrocatalysts with high selectivity for CO2 to CO conversion are known, they are characterized by current densities that are significantly lower than those obtained with solid-state metal materials. Here, we report that a cobalt phthalocyanine bearing a trimethyl ammonium group appended to the phthalocyanine macrocycle is capable of reducing CO2 to CO in water with high activity over a broad pH range from 4 to 14. In a flow cell configuration operating in basic conditions, CO production occurs with excellent selectivity (ca. 95%), and good stability with a maximum partial current density of 165 mA cm-2 (at -0.92 V vs. RHE), matching the most active noble metal-based nanocatalysts. These results represent state-of-the-art performance for electrolytic carbon dioxide reduction by a molecular catalyst.

| S-EPMC6689005 | biostudies-literature

Visible-Light-Driven CO2 Reduction by Mesoporous Carbon Nitride Modified with Polymeric Cobalt Phthalocyanine.

Project description:The integration of molecular catalysts with low-cost, solid light absorbers presents a promising strategy to construct catalysts for the generation of solar fuels. Here, we report a photocatalyst for CO2 reduction that consists of a polymeric cobalt phthalocyanine catalyst (CoPPc) coupled with mesoporous carbon nitride (mpg-CNx ) as the photosensitizer. This precious-metal-free hybrid catalyst selectively converts CO2 to CO in organic solvents under UV/Vis light (AM 1.5G, 100?mW?cm-2 , ?>300?nm) with a cobalt-based turnover number of 90 for CO after 60?h. Notably, the photocatalyst retains 60?% CO evolution activity under visible light irradiation (?>400?nm) and displays moderate water tolerance. The in situ polymerization of the phthalocyanine allows control of catalyst loading and is key for achieving photocatalytic CO2 conversion.

| S-EPMC6771752 | biostudies-literature

Metal-organic-frameworks derived cobalt embedded in various carbon structures as bifunctional electrocatalysts for oxygen reduction and evolution reactions.

Project description:A series of nanocomposites of cobalt embedded in N-doped nanoporous carbons, carbon nanotubes or hollow carbon onions have been synthesized by a one-step carbonization of metal-organic-framework ZIF-67. The effect of the carbonization temperature on the structural evolution of the resulting nanocomposites has been investigated in detail. Among the as-synthesized materials, the cobalt/nanoporous N-doped carbon composites have demonstrated excellent electrocatalytic activities and durability towards oxygen reduction reaction in alkaline medium. Compared to the benchmark Pt/C catalyst, the optimized Co@C-800 (carbonized at 800?°C) exhibited high oxygen reduction reaction activity with an onset potential of 0.92?V, and a half-wave potential of 0.82?V. Moreover, the optimized Co@C-800 also showed enhanced electrocatalytic activity towards oxygen evolution reaction from water splitting, with a low onset potential of 1.43?V and a potential of 1.61?V at 10?mA?cm-2 current density. This work offered a simple solution to develop metal-organic-framework-derived materials for highly efficient electrochemical applications.

| S-EPMC5509653 | biostudies-literature

Highly efficient oxygen reduction electrocatalysts based on winged carbon nanotubes.

Project description:Developing electrocatalysts with both high selectivity and efficiency for the oxygen reduction reaction (ORR) is critical for several applications including fuel cells and metal-air batteries. In this work we developed high performance electrocatalysts based on unique winged carbon nanotubes. We found that the outer-walls of a special type of carbon nanotubes/nanofibers, when selectively oxidized, unzipped and exfoliated, form graphene wings strongly attached to the inner tubes. After doping with nitrogen, the winged nanotubes exhibited outstanding activity toward catalyzing the ORR through the four-electron pathway with excellent stability and methanol/carbon monoxide tolerance. While the doped graphene wings with high active site density bring remarkable catalytic activity, the inner tubes remain intact and conductive to facilitate electron transport during electrocatalysis.

| S-EPMC3824170 | biostudies-other

Modulating the mechanism of electrocatalytic CO2 reduction by cobalt phthalocyanine through polymer coordination and encapsulation.

Project description:The selective and efficient electrochemical reduction of CO2 to single products is crucial for solar fuels development. Encapsulating molecular catalysts such as cobalt phthalocyanine within coordination polymers such as poly-4-vinylpyridine leads to dramatically increased activity and selectivity for CO2 reduction. In this study, we use a combination of kinetic isotope effect and proton inventory studies to explain the observed increase in activity and selectivity upon polymer encapsulation. We provide evidence that axial-coordination from the pyridyl moieties in poly-4-vinylpyridine to the cobalt phthalocyanine complex changes the rate-determining step in the CO2 reduction mechanism accounting for the increased activity in the catalyst-polymer composite. Moreover, we show that proton delivery to cobalt centers within the polymer is controlled by a proton relay mechanism that inhibits competitive hydrogen evolution. These mechanistic findings provide design strategies for selective CO2 reduction electrocatalysts and serve as a model for understanding the catalytic mechanism of related heterogeneous systems.

| S-EPMC6459859 | biostudies-literature

Polymer coordination promotes selective CO2 reduction by cobalt phthalocyanine.

Project description:Cobalt phthalocyanine (CoPc) is a known electrocatalyst for the carbon dioxide reduction reaction (CO2RR) that, when adsorbed onto edge-plane graphite (EPG) electrodes, shows modest activity and selectivity for CO production along with co-generation of H2. In contrast, electrodes modified with CoPc immobilized in a poly-4-vinylpridine (P4VP) film show dramatically enhanced activity and selectivity compared to those modified with CoPc alone. CoPc-P4VP films display a faradaic efficiency of ?90% for CO, with a turnover frequency of 4.8 s-1 at just -0.75 V vs. RHE. Two properties of P4VP contribute to enhancing the activity of CoPc: (1) the ability of individual pyridine residues to coordinate to CoPc and (2) the high concentration of uncoordinated pyridine residues throughout the film which may enhance the catalytic activity of CoPc through secondary and other outer coordination sphere effects. Electrodes modified with polymer-free, five-coordinate CoPc(py) films (py = pyridine) and with CoPc catalysts immobilized in non-coordinating poly-2-vinylpyridine films were prepared to independently investigate the role that each property plays in enhancing CO2RR performance of CoPc-P4VP. These studies show that a synergistic relationship between the primary and outer coordination sphere effects is responsible for the enhanced catalytic activity of CoPc when embedded in the P4VP membrane.

| S-EPMC5477023 | biostudies-literature

Nanostructured Iron Sulfide/N, S Dual-Doped Carbon Nanotube-Graphene Composites as Efficient Electrocatalysts for Oxygen Reduction Reaction.

Project description:Nanostructured FeS dispersed onto N, S dual-doped carbon nanotube-graphene composite support (FeS/N,S:CNT-GR) was prepared by a simple synthetic method. Annealing an ethanol slurry of Fe precursor, thiourea, carbon nanotube, and graphene oxide at 973 K under N2 atmosphere and subsequent acid treatment produced FeS nanoparticles distributed onto the N, S-doped carbon nanotube-graphene support. The synthesized FeS/N,S:CNT-GR catalyst exhibited significantly enhanced electrochemical performance in the oxygen reduction reaction (ORR) compared with bare FeS, FeS/N,S:GR, and FeS/N,S:CNT with a small half-wave potential (0.827 V) in an alkaline electrolyte. The improved ORR performance, comparable to that of commercial Pt/C, could be attributed to synergy between the small FeS nanoparticles with a high activity and the N, S-doped carbon nanotube-graphene composite support providing high electrical conductivity, large surface area, and additional active sites.

| S-EPMC8122905 | biostudies-literature

Wet-Spinning Assembly of Continuous, Highly Stable Hyaluronic/Multiwalled Carbon Nanotube Hybrid Microfibers.

Project description:Effective multiwalled carbon nanotube (MWCNT) fiber manufacturing methods have received a substantial amount of attention due to the low cost and excellent properties of MWCNTs. Here, we fabricated hybrid microfibers composed of hyaluronic acid (HA) and multiwalled carbon nanotubes (MWCNTs) by a wet-spinning method. HA acts as a biosurfactant and an ionic crosslinker, which improves the dispersion of MWCNTs and helps MWCNT to assemble into microfibers. The effects of HA concentration, dispersion time, injection speed, and MWCNT concentration on the formation, mechanical behavior, and conductivity of the HA/MWCNT hybrid microfibers were comprehensively investigated through SEM, UV-Vis spectroscopy, tensile testing, and conductivity testing. The obtained HA/MWCNT hybrid microfibers presented excellent tensile properties in regard to Young's modulus (9.04 ± 1.13 GPa) and tensile strength (130.25 ± 10.78 MPa), and excellent flexibility and stability due to the superior mechanical and electrical properties of MWCNTs. This work presents an effective and easy-to-handle preparation method for high-performance MWCNT hybrid microfibers assembly, and the obtained HA/MWCNT hybrid microfibers have promising applications in the fields of energy storage, sensors, micro devices, intelligent materials, and high-performance fiber-reinforced composites.

| S-EPMC6571791 | biostudies-literature

Bimetallic Pd96Fe4 nanodendrites embedded in graphitic carbon nanosheets as highly efficient anode electrocatalysts.

Project description:A facile route to anchor a nanoalloy catalyst on graphitic carbon nanosheets (GCNs) has been developed for preparing high-performance electrode materials for application in direct alcohol fuel cells (DAFCs). Uniformly dispersed bimetallic Pd-Fe nanoparticles (NPs) with tunable composition have been immobilized on GCNs derived from mesocarbon microbeads (MCMBs) by a one-pot radiolytic reduction method. The Pd-Fe/GCN hybrid shows promising electrocatalytic activity for the methanol, ethanol, ethylene glycol, tri-ethylene glycol and glycerol oxidation reactions in alkaline medium. The as-prepared flower-shape Pd96Fe4/GCN nanohybrids have high mass activity for the ethanol oxidation reaction (EOR), which is ∼36 times (11 A per mg Pd) higher than that of their monometallic counterparts. Moreover, the onset oxidation potential for the EOR on the Pd96Fe4/GCN nanohybrids negatively shifts ca. 780 mV compared to that on commercial Pd/C electrocatalysts, suggesting fast kinetics and superior electrocatalytic activity. Additionally, chronoamperometry measurements display good long-term cycling stability of the Pd96Fe4/GCN nanohybrids for the EOR and also demonstrate only ∼7% loss in forward current density after 1000 cycles. The superior catalytic activity and stability may have originated from the modified electronic structure of the Pd-Fe nanoalloys and excellent physicochemical properties of the graphitic nanosheets. The present synthetic route using GCNs as the supporting material will contribute to further design of multimetallic nanoarchitectures with controlled composition and desired functions for fuel cell applications.

| S-EPMC9417808 | biostudies-literature

Bio-inspired Hybrid Carbon Nanotube Muscles.

Project description:There has been continuous progress in the development for biomedical engineering systems of hybrid muscle generated by combining skeletal muscle and artificial structure. The main factor affecting the actuation performance of hybrid muscle relies on the compatibility between living cells and their muscle scaffolds during cell culture. Here, we developed a hybrid muscle powered by C2C12 skeletal muscle cells based on the functionalized multi-walled carbon nanotubes (MWCNT) sheets coated with poly(3,4-ethylenedioxythiophene) (PEDOT) to achieve biomimetic actuation. This hydrophilic hybrid muscle is physically durable in solution and responds to electric field stimulation with flexible movement. Furthermore, the biomimetic actuation when controlled by electric field stimulation results in movement similar to that of the hornworm by patterned cell culture method. The contraction and relaxation behavior of the PEDOT/MWCNT-based hybrid muscle is similar to that of the single myotube movement, but has faster relaxation kinetics because of the shape-maintenance properties of the freestanding PEDOT/MWCNT sheets in solution. Our development provides the potential possibility for substantial innovation in the next generation of cell-based biohybrid microsystems.

| S-EPMC4879622 | biostudies-literature