Cobalt phthalocyanine-based conjugated polymer as efficient and exclusive electrocatalyst for CO_(2) reduction to ethanol

Electrocatalytic conversion of carbon dioxide to high value-added chemicals is a promising method for solving the energy crisis and global warming.Electrochemical active metal-containing conjugated polymers have been widely studied for heterogeneous carbon dioxide reduction.In the present contribution,we designed and synthesized a stable cobalt phthalocyanine-based conjugated polymer,named CoPPc-TFPPy-CP,and also explored its electro-catalytic application in carbon dioxide reduction to liquid products in an aqueous solution.In the catalyst,cobalt phthalocyanine acts as building blocks connected with 1,3,6,8-tetrakis(4-formyl phenyl)pyrenes via imine-linkages,leading to mesoporous formation polymers with the pore size centered at 4.1nm.And the central co-balt atoms shifted to a higher oxidation state after condensation.With these chemical and structural natures,the catalyst displayed a remarkable electrocatalytic CO_(2) reduction performance with an ethanol Faradaic efficiency of 43.25%at-1.0V vs RHE.While at the same time,the electrochemical reduction process catalyzed by cobalt phthalocyanine produced only carbon monoxide and hydrogen.To the best of our knowledge,CoPPc-TFPPy-CP is the first example among organic polymers and metal-organic frameworks that produces ethanol from CO_(2) with a remarkable selectivity.

Effect of Cobalt Phthalocyanine on Floating-Charge Performance of Nickel-Metal Hydride Battery

In Ni-MH battery, oxygen evolution causes a high inner pressure during charge and overdischarge, and an inappropriate eliminating way of the oxygen in the battery results in accumulation of heat. This is the main obstacle to develop and apply high capability and high power battery. In this paper, effect of cobalt phthalocyanine (CoPc) on the floating-charge performance of Ni-MH batteries are examined. Experimental results show that the battery with CoPc additive by appropriate adding way displayed a better capability of floating charge and discharge than the one without CoPc. The battery with CoPc added into electrolyte shows the best charging efficiency and cycleability and the slowest increasing speed of inner pressure after 2000th charge and discharge.

Didodecyldimethylammonium Bromide Films Containing Cobalt Phthalocyanine Tetrasulfonate for Electrochemical Catalysis

Electrochemistry of didodecyldimethylammonium (DDAB) films containing cobalt phthalocyanine tetrasulfonate (CoPcTS4-) was examined. CoPcTS4--DDAB film electrode showed stable cyclic voltammetric responses in buffers and could catalyze reductions of trichloroacetic acid.

Constructing S-scheme charge separation in cobalt phthalocyanine/oxygen-doped g-C_(3)N_(4) heterojunction with enhanced photothermal-assisted photocatalytic H_(2) evolution

Hydrogen acquisition from solar energy is an effective way to address energy crisis,which makes the development of efficient photocatalysts become the main direction of scientific research.Herein,cobalt phthalocyanine/oxygen-doped g-C_(3)N_(4)(CoPc/OCN) S-scheme heterojunction photocatalyst was designed by coupling multi-step calcination with solvothermal method for enhanced photothermal-assisted photocatalytic H_(2) evolution.The multistep calcined g-C_(3)N_(4) is easier for O-doping formation,and the ethanol solvothermal strategy is utilized to enhance the dispersion of CoPc on OCN nano sheet surface and forms sufficient S-scheme heterojunction through H-bonds.In addition,the active sites and excellent photothermal properties of CoPc itself further improve the integrated photocatalytic activity of CoPc/OCN S-scheme heterojunction.The optimal photocatalytic hydrogen evolution rate of CoPc/OCN S-scheme heterojunction photocatalyst reached 9.56 mmol·g^(-1)·h^(-1),which is 2.69 and 1.23 times higher than that of CN and OCN,respectively.This work provides a valuable design idea and scheme for enhancing the multi-factor co-assisted photocatalytic H_(2) evolution performance.

“Substituents optimization”and“push effect”dual strategy for design of cobalt phthalocyanine catalyst on oxygen reduction reaction

Molecular metallocycle electrocatalysts like metalloporphyrins and metallophthalocyanines were found to be effective for oxygen reduction reaction(ORR)due to their M-N_(4) active sites and large conjugated elec-tronic molecular structures.Herein,the“substituents optimization”strategy combined with“push effect”modification was innovatively employed to target a single Co-N_(4) active site in three substituted phthalo-cyaninato cobalt complexes:tetranitrophthalocyaninato cobalt(CoTNPc),tetra(4-nitrophenoxy)phthalo-cyaninato cobalt(CoTPNPc),and tetraphenoxy phthalocyaninato cobalt(CoTPPc)electrocatalyst,also with 4-phenylpyridine axial coordination on Co-N_(4) unit.Through substituents screening,the half-wave poten-tial(E_(1/2))for ORR increases in the order of CoTPNPc(0.75 V)<CoTPPc(0.80 V)<CoTNPc(0.83 V)along with decreased electron-withdrawing ability of their substituents from-OC_(6) H_(4)-NO_(2),-OC_(6) H_(5) to-NO_(2) in the three cobalt phthalocyanine derivatives.CoTNPc with the weakest electron-withdrawing substituent exhibits the best ORR performance among the three compounds.This is attributed to its higher elec-tron delocalization and lifted HOMO energy level with the lower energy barrier in the rate-determining step relative to the other two compounds,which facilitate the electron transfer and reduction of oxy-gen as evidenced by XPS,UPS,and DRS analysis combined with DFT calculations.Further coordination of 4-phenylpyridine shifts the E_(1/2) up to 0.78,0.82,and 0.85 V for CoTPNPc,CoTPPc,and CoTNPc.DFT calcu-lations demonstrate that the introduction of the electron-donating phenylpyridine ligand into the cobalt phthalocyanines breaks the symmetry of the Co-N_(4) center and also raises the electron density of Co sites,which promotes O_(2) adsorption and improves ORR performance.After comparing the two strategies,the substituents on metallophthalocyanine are more determined by the electroactivity than the axial group,which directly regulates the coordination environment and then the activation barrier of the ORR pro-cess.This work provides theoretical and experimental guidance by two coupling strategies for the design of highly active molecular CoPc-based ORR electrocatalysts in the practical application.

Coordination engineering of cobalt phthalocyanine by functionalized carbon nanotube for efficient and highly stable carbon dioxide reduction at high current density

Coordination engineering can enhance the activity and stability of the catalyst in heterogeneous catalysis.However,the axial coordination engineering between different groups on the carbon carrier and molecular catalysts in the electrocatalytic carbon dioxide reduction reaction(CO_(2)RR)has been studied rarely.Through coordination engineering strategy,a series of amino(NH_(2)),hydroxyl(OH),and carboxyl(COOH)groups functionalized carbon nanotubes(CNT)immobilized cobalt phthalocyanine(CoPc)catalysts are designed.Compared with no groups,OH groups and COOH groups,NH_(2)groups can effectively change the coordination environment of the central metal Co,thereby significantly increasing the turnover frequency(TOF)(31.4 s^(-1)at-0.6 V vs.RHE,CoPc/NH_(2)-CNT>CoPc/OH-CNT>CoPc/COOH-CN>CoPc/CNT).In the flow cell,the CoPc/NH_(2)-CNT catalyst has high carbon monoxide(CO)selectivity at high current density(~100%at-225 mA·cm^(-2),~96%at-351 mA·cm^(-2)).Importantly,the CoPc/NH_(2)-CNT catalyst can operate stably for 100 h at 225 mA·cm^(-2).Theoretical calculations reveal that CoPc/NH_(2)-CNT catalyst is beneficial to the formation of^(*)COOH and desorption of^(*)CO,thus promoting CO_(2)RR.This work provides an excellent platform for understanding the effect of coordination engineering on electrocatalytic performance and promotes a way to explore efficient and stable catalysts in other applications.

Electron-withdrawing functional ligand promotes CO2 reduction catalysis in single atom catalyst

Electrochemical carbon dioxide reduction reaction (CO2RR) powered by renewable electricity offers an attractive approach to reduce carbon emission and at the same time produce valuable chemicals/fuels.To design efficient CO2 reduction electrocatalyst,it is important to understand the structure-activity relationship.Herein,we design a series of single Co atoms electrocatalysts with well-defined active sites electronic structures,which exhibit outstanding CO2RR activity with controllable selectivity to CO.Experimental and density functional theory (DFT) calculation studies show that introducing nitro (amino) ligand next to single Co atom catalytic center with electron-withdrawing (electron-donating) capability favors (hinders) CO2 reduction catalysis.This work provides an in-depth understanding of how functional ligand affects the splitting of transition metal 3d electron orbital,thereby changing the electron transfer from transition metal active site to CO2,which is closely related to the Gibbs free energy of the rate-determining step (CO2+e^-+*→*CO2^-).

A polyoxometalate based electrochemical sensor for efficient detection of L-cysteine

L-cysteine(L-cys),as an important sulfur-containing amino acid,plays an indispensable role in biological systems.Too low and excessively high ratio of L-cys will cause harm to the function of human organs.Therefore,it is very necessary to develop efficient methods to detect it in multifarious samples.This paper has built an electrochemical sensor by combining Keggin-type polyoxometalate(PMo9V3)and cobalt tetrasulfonate(Ⅱ)phthalocyanine(CoTsPc)on indium tin oxide electrodes using the layer-level self-assembly technology for efficiently detection of L-cys.The assembly process and surface morphology of the modified electrode was characterized by ultraviolet–visible spectroscopy,X-ray photoelectron spectroscopy,scanning electron microscope,and atomic force microscopy.The conditions of electro-catalysed oxidation of L-cys were optimized by cyclic voltammetry,and the kinetic electrochemical parameters were also evaluated by electrochemical impedance spectra.Furthermore,the sensing performance of the modified electrode was explored using amperometry.The proposed electrochemical L-cys sensor was found to have superior sensing performance with a range of linear response of 2.5×10^(−7) to 1.7×10^(−4) mol·L^(−1) and 1.7×10^(−4) to 39.5×10^(−4) mol·L^(−1),the detection limit of 1.0×10^(−7) mol·L^(−1)(signal/noise=3),and satisfactory anti-interference ability.Consequently,the fabricated sensor has the potential to be applied in laboratory practices for L-cys deterimination in commercial drinks.