(TPP)Co 1. 1 ], [ 1, 2 ] V o l. 3 N o. 4 N ov EL ECTROCH EM ISTR Y ) ) ,, Co V V. (T PP) Co (Py) , - 1.

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1 EL ECTROCH EM ISTR Y V o l 3N o 4 N ov 1997 (TPP)Co a 3 b a a (a ) (b ) (Py) (T PP)Co 1 22 Py Co (g ) gco (g ) V (vṡ SCE) Py Co (g ) gco (g ) 0 25 V V Py Co (g ) gco (g ) Co (g ) gco (g ) V (SCE) (T PP) Co (Py) Py (T PP)Co ( ) [ 17 ] [1 2 ] [ 8 9 ] [ 1 2 ] [ ] 1 22 Py Py (T PP)Co ( (g ) ) (DCE ) CaH 2 ; ;

2 (TBA P) ( 10% ) ( ) 40 ; [ 12 (T PP)Co ] ; (Py ) 4A 1 2 : (SCE) CM BP21 ( ) Gou ld 60000X2Y 1 mm YEW 3655 ( ) mm CV Py (T PP)Co (SCE) 2 2 1Co (g ) gco (g ) DCEg(0 1 m o lgl TBA P) (T PP)Co (CV ) 1a [ 3 13 (T PP)Co (g ) DCE ] g g g g 1a Py Py 01 1ad 0 80 V (g a) 0 34 V (g a ) 0 68 V (g c) 0 25 V (g c ) V (g c ) ; 1 19 V 1 40 V 240 mv 270 mv V (g c ) Py Co (g ) gco (g ) ( 1e i ) Py (g a ) 0 1 V ( 1h g a ) Py V g c Co (g ) gco (g ) (g c ) Py 3 CV (g ) [ 5 ] Co (g ) gco (g ) (g c ) ( V ) Py Py ( 2 )

3 4 : (T PP)Co 391 (g c ) Py ( T PP ) Co ( g ) (Py) 2 Co (g ) gco (g ) (g c ) (0 25 V ) Py (g a ) 0 34 V (g c ) g c Py (T PP) Co (g ) (Py) (CV ) Py I ipagipc Py [ 9 ] Py < 6 ipag 1Py (T PP)Co ipc4 Py > 6 Py ( ): a) 0; b) 0 5; c) 0 8; d) 1 0; e) 2 2; f) 11; g) 28; h) 83; i) 275 ipagipc5 C (TPP)Co= mo lgl ; C TBA P= 0 1 mo lgl : 200 mv gs F ig 1Cyclic vo ltammogram s of (T PP)Co during Py titration (g c ) (T PP)Co (g ) (Py) Py 1 Co (g ) gco (g ) V (g c 1b d) (T PP)Co (g ) (Py) 2 Py (T PP)Co (g ) Py Py Co (g ) gco (g ) : (T PP)Co (g ) + PyΩ (T PP)Co (g ) (Py) (1) (T PP)Co (g ) Py- eω (T PP)Co (g ) (Py) E 1g2= 0 30 V (2) (T PP)Co (g ) Py+ PyΩ (T PP)Co (g ) (Py) 2 (3) (T PP)Co (g ) (Py) 2+ eω (T PP)Co (g ) (Py) 2 E pc= V (4) (T PP)Co (g ) (Py) 2 k (T PP)Co (g ) (Py) + Py (5) : (T PP)Co (g ) (Py) PyςΣ + (T PP)Co (g ) (Py) 2 E g = 0 30 V E pc = V (T PP)Co (g ) (Py) - Py (T PP)Co (g ) (Py) 2

4 Co (g ) gco (g ) Co (g ) gco (g ) : (g ) ( ( T PP)Co (g ) (T PP) Co (g ) (L ) ) CE : (T PP)Co (g ) (L ) (T PP)Co (g ) + L (6) (T PP)Co (g ) + eω (T PP)Co (g ) (7) 2 PygTBA P (T PP)Co F - C l - Co (g ) g C (TPP)Co= mo lgl ; C TBA P= 0 1 mo lgl [ 8 9 Co (g ) ] : a) 0 V ; b) V : 200 m vgs 1 Py F ig 2Cyclic vo ltammogram s of (T PP) Co in PygTBA P Co (g ) gco (g ) g c so lution V (g c ) (T PP)Co (g ) (T PP) Co (g ) (Py) Py (T PP) Co (g ) (Py) Py (g a) V V (1bi) Py m o lgl TBA P Py g a Co (g ) Py (T PP) Co (g ) (Py) Py (T PP)Co (g ) Py Co (g ) Co (g ) g Co (g ) (g a) (T PP)Co (g ) (Py) + eω (T PP)Co (g ) (Py) E PC= V (8) : (T PP)Co PyςΣ (g ) (Py) (T PP)Co (g ) ςσ + - Py (T PP)Co (g ) (Py) E pc = V (T PP)Co (g ) (Py) E g = 0 84 V

5 4 : (T PP)Co 393 Cyclic V o ltamm etric Investigation of the A x ial Coo rdination Effects of Pyridine on the R edox B ehaviou rs of (T PP)Co Yan Chuanw ei a3 L in X iangqu i b L in H aichao a Cao Chunan a (as ta te K ay L ab f or Corrosion and P rotection Insṫ of Corrosion and P rotection of M eta ls Ch inese A cad em y of S ciences sheny ang ) (bd ep ṫ of chem U n iv of S ci and T ech of Ch ina H ef ei230026) A bs tra c tt he electrochem istry of (T PP) Co in p resence of pyridine w as investi2 gated in dich lo roethane so lu tion by cyclic vo ltamm etry U pon the addition of pyridine to the so lu tion tw o reduction peak s of Co (g ) gco (g ) at 0 25 and V (SCE ) w ere ob2 served It w as infered that the peak s w ere belong to the reduction s of the com p lex com 2 pounds w ith one and tw o ax ial pyridine (T PP)Co (g ) (Py) and (T PP)Co (g ) (Py) 2 Even though the m o le ratio of added pyridine w as less than 1 the reduction of Co (g ) gco (g ) still m ain ly occu red at V w h ich eviden tly resu lted from pyridine adso rp tion on the elec2 trodeṡ Besides it w as ob served that the reduction peak of Co (g ) gco (g ) w as sh ifted to V (SCE) w ith large am oun t of added pyridine T he new reduction peak cou ld be at2 tribu ted to the direct reduction of the ax ially coo rdination com p lex (T PP)Co (g ) (Py) T he m echan ism s of the effect of pyridine on the electrochem ical redox behaviou rs of (T PP ) Co w ere given coo rdination Ke y w o rds T etraphenylpo rphyrincobalt Cyclic vo ltamm etry Pyridine A x ial Re fe re nce s 1 T ruxillo L A D avis D G E lectrochem istry of cobalt tetraphenylpo rphyrin in ap ro tic m edia A nal Chem : Kadish K M Bo ttom ley L A Bero iz D R eactions of pyridine w ith a series of para2substituted te2 traphenylpo rphyrin2cobalt and 2iron com p lexeṡ Inorg Chem : OH : 23 4L in X Q Bo isselier2coco lio s B Kadish K M dition reaction s of an easily reducib le cobalt po rphyrin E lectrochem istry spectroelectrochem istry and ligand ad2 R eaction s of ( tetracyano tetraphenylpo rph inato) cobalt (g ) ( ( (CN ) 4T PP)Co g ) in pyridine and in pyridinegm ethylene ch lo ride m ixtureṡ Inorg Chem : Kadish K M L in X Q H an B C Ch lo ride2binding reactions and electrochem istry of (T PP ) Co g and

6 (T PP)Co g C l in dich lo rom ethane Inorg Chem : M u X H Kadish K M sphere O xidative electrochem istry of cobalt tetraphenylpo rphyrin under a CO atmo2 interaction betw een carbon monoxide and electrogenerated (T PP) Co + in nonbonding m edia Inorg Chem : H u Y H an B C Bao L Y et al a carbon monoxide atmo sphere Chem : E lectrochem istry of (octaethylpo rph inato) cobalt (g ) (O EP)Co under electrogeneration and characterization of (O EP) Co g (CO ) + Inorg 8 F - (T PP)Co : g L ipkow sk i J Sto lberg L M o rin S et al P robing pyridine adso rbed at go ld electrodes by ch rono2 cou lom etry radiochem istry and R am an spectro scopy J E lectroanal Chem : C ro ss N A Pem berton J E Surface enhanced R am an scattering of pyridine on A g electrodes fo rm ed w ith con tro lled2rate ox idation2reduction cycleṡ J E lectroanal Chem : 93 12L in X Q Kadish K M V accum 2tigh t th in2layer spectroelectrochem ical cell w ith a doublet p latinum gauze w o rk ing electrode A nal Chem : (B ) : 258