Synthesis and Characterization of Phthalocyanines Containing Four 11-Membered Triaza Macrocycles

Two novel series of the binuclear transition metal phthalocyanines M 2 Pc 2 C and M 2 Pc 2 HcC (M = Mn(II), Fe(II), Co(II), Ni(II) and Cu(II)) have been developed for high efficient catalysts to lithium/thionyl chloride (Li/SOCl 2 ) battery. The energy of the battery whose electrolyte contains the binuclear compounds increases by approximately 10.05-82.63% than that of the battery without them. Especially the binuclear Fe 2 Pc 2 HcC, Mn 2 Pc 2 HcC and Co 2 Pc 2 C can cause the energy of the battery to maintain steadily and increase by 82.63%, 75.87% and 69.47% respectively. A new perspective on the catalytic mechanism of the binuclear metal phthalocyanines is conjectured. In order to further study the effect on Li/SOCl 2 battery cathode of the binuclear metal phthalocyanines, the SEM analysis of carbon film, carbon cathode without Ni 2 Pc 2 C and carbon cathode with Ni 2 Pc 2 C was conducted and analyzed. This paper makes a comparison between the catalytic activity of the binuclear compounds and the corresponding mononuclear compounds. All the results indicate that the catalytic activity of binuclear compounds in electrolyte operation is related to the phthalocyanine rings and electronic structures of the metal ions which are possible active sites. Only when there is enough number of active sites in the compounds and all the sites achieve an appropriate state through the synergistic effect, can the catalytic activity of the compounds achieve a very good display.

Section: Irsupporting

confidence: 70%

Catalytic Activity of Binuclear Transition Metal Phthalocyanines in Electrolyte Operation of Lithium/Thionyl Chloride Battery

Zhang

Wang

et al. 2012

“…The two bands are in agreement with the electronic spectrum characters of the metal phthalocyanines, 28 which further demonstrate that the structures of the M 2 (PcTN) 2 O and M 2 (PcTA) 2 O are accurate from the microscopic structures. 36 To investigate the effects of peripheral substituents on the phthalocyanine ring, the absorption bands of M 2 (PcTN) 2 O and M 2 (PcTA) 2 O appear in the UV-vis spectra as shown in Fig. 4.…”

Section: Resultsmentioning

confidence: 99%

Excellent Electrocatalytic Activity of Binuclear Phthalocyanines in the Electrolyte of Lithium/Thionyl Chloride Battery

Liu¹,

Gao²,

Jiang³

et al. 2016

Binuclear nitro-phthalocyanines (M2(PcTN)2O) were synthesized and reduced to binuclear amino-phthalocyanines (M2(PcTA)2O) as high-efficiency catalysts to promote the electrochemical properties of lithium/thionyl chloride (Li/SOCl2) battery. The catalytic performances of M2(PcTN)2O and M2(PcTA)2O were evaluated by adding a small amount of catalysts into the electrolyte. Elemental analysis, Fourier transform infrared (FTIR), ultraviolet-visible (UV-vis), Thermal technique (TGA) and scanning electron microscope (SEM) were employed to characterize the final products. The discharge time of the battery catalyzed by M2(PcTN)2O and M2(PcTA)2O was lengthened by 181∼510 s and 198∼564 s, respectively. The results reveal that battery capacities had been improved approximately 16.74∼47.91% and energy increased by 14.95∼44.80% compared with the bare batteries, which should be attributed to the electronic configurations of the metal ions, the phthalocyanine rings and the synergistic effect. In addition, according to the cyclic voltammetric analysis, catalytic mechanism of the synthesized binuclear phthalocyanines in the battery was speculated.

“…The two bands are the typical absorption bands of the metal phthalocyanines. 31 The Q band of b or b is einstein shift compared with that of corresponding a or a , which means that after the tetranitro in a or a reacted to become the tetraamino in b or b , the conjugation effect of b or b is enhanced. The results demonstrate that the structures of a, a , b, b are accurate from their microscopic structures.…”

Section: Resultsmentioning

confidence: 99%

Multi-Walled Carbon Nanotubes Chemically Modified by Cobalt Tetraaminophthalocyanines with Excellent Electrocatalytic Activity to Li/SOCl₂Battery

Zhang

Wang

Luo

et al. 2014

Fluorinated Multi-walled carbon nanotubes (F-MWCNTs) are chemically modified successfully by cobalt 2, 9, 16, 23tetraaminophthalocyanine and cobalt 1, 8, 15, 22-tetraaminophthalocyanine respectively. Their structures are characterized by IR, SEM, XPS and XRD. Important in this context is that the covalent linkages between F-MWCNTs and cobalt phthalocyanines are corroborated by monitoring the diagnostic signature of the nitrogen atoms as part of the formed -NH-bonds in them by XPS. The electrocatalytic activity of the two kinds of modified F-MWCNTs to Li/SOCl 2 battery is evaluated by adding them into the electrolyte of the battery. It is found that the modified F-MWCNTs can dramatically improve the discharge voltage and lengthen the discharge time of the battery, and finally make the capacity of the battery increase by 97.5% and 103.3% than that of the battery in the absence of them. The excellent electrocatalytic performance of the modified F-MWCNTs may be owing to the fine synergistic effect between the cobalt phthalocyanines and the MWCNTs in them. A reasonable catalytic mechanism of the modified F-MWCNTs to the battery is proposed according to the CV results.