23

4. 4.1 ( )

4.1.1 4.1.1 Nafion

MEA

MEA 53%

47% Nafion

Nafion Nafion

100%Nafion

MEA

MEA

4.1.2 4.1.2.1 - Pt - Pt Pt

4.1.1 Pt 11.3MHCl-0.36MH2O2

1 M

Pt

Pt

2 Pt 79 %20 % Pt

1 M -

Pt

4.1.1

/mg

Nafion

0.16 0.14

Nafion 0.00 0.30

24

Pt

HNO3 + 3HCl NOCl + Cl2 + 2H2O (4.1.1)

Pt + 2NOCl + Cl2 + 2Cl- [PtCl6]2- + 2NO (4.1.2)

Pt

. 4.1.2

Nafion

Fig. 4.1.1. Time dependence of Pt dissolution with aqua regia ( ), 1MHCl-0.36MH2O2 (), 1MHCl-10.3MH2O2 (), and 11.3MHCl-0.36MH2O2 mixture () at RT.

0

20

40

60

80

100

0 2000 4000 6000 8000 10000

Dissolved

Pt/%

t/s

aqua regia

1 MHCl-0.36 MH O

1 MHCl-10.3 MH O

11.3 MHCl-0.36 MH O

2 2

2 2

2 2

Fig. 4.1.2. Scheme of three-phase interface in PEFCs

(Nafion)

25

(4.2) Cl-

2

R = R1exp(t /1)+ R2exp(t /2) (4.1.3)

R R1R2

1 (s)2 (s)

R1 R2

R1+ R2 = 1 (4.1.4)

4.1.2 R2

R2 = 1Re / Ryy (4.1.5)

ReRyy

26 %4.2104(s) (12

) Pt

94(s) Pt

(4.1.1)

Pt Pt

4.1.2 Result of the analysis based on eq. 3.3.

R 1 R 2 1 (s) 2 (s) R 2

0.74 0.26 94 4.2104 0.886

26

- Pt 2, 3)

Pt + H2O2 + 4HCl [PtCl4]2- + 2H+ + 2H2O (4.1.6)

Pt + 2H2O2 + 6HCl [PtCl6]2- + 2H+ + 4H2O (4.1.7)

H2O2 + 2HCl Cl2 + 2H2O (4.1.8)

(4.5)(4.6) Pt (4.7)

11.3MHCl-0.36MH2O2

4.1.3

1MHCl-10.3MH2O2

Pt

Pt

4.1.2.2 Pt 1.0 M Pt Pt

4.1.4 1.0 M Pt

Pt

70 1.0 M

11.3MHCl-0.36MH2O22 Pt

4.1.3. Picture of a 11.3MHCl-0.36 MH2O2mixture solution prepared immediately.

27

72 % Pt

Pt

4.1.2.3 -

4.1.4. Time dependence of Pt dissolution with 1.0 M HCl at 25 (),

40 (), 55 (), and 70 ().

0

10

20

30

40

50

60

70

80

0 2000 4000 6000 8000

Dissolved

Pt/%

t /s

25

40

55

70

28

60

. 4.1.5 25

2104(s)(6)60

3

60

4.1.6 1 M HCl 11.3MHCl-0.36MH2O2

4.1.6. Time dependence of equilibrium potential in 1 M HCl ( ) and

11.3MHCl-0.36MH2O2 mixture () using Ta wire at RT.

0.00

0.20

0.40

0.60

0.80

1.00

1.20

0 5000 10000 15000 20000

E/V

vs.A

g|AgCl|KC

lsat.

t/s

11.3 MHCl-0.36 MH O

1 M HCl

2 2

4.1.5. Time dependence of equilibrium potential in aqua regia using Ta wire at

RT(), and 60 ().

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

0 5000 10000 15000 20000

E/V

vs.A

g|AgCl|KC

lsat.

t/s

RT

60

29

1 M HCl

11.3MHCl-0.36MH2O2

1

11.3MHCl-0.36MH2O2

4.1.2.4

nobs

4.1.7 (3.1.5)

Fitting 4.1.7

Fitting

4.1.3 25 60

40

4.1.2 Volatization rate constant estimated by

non-linear least square method.

T / 107k1 / mol-1cm2s-1

25 1.0

60 40

4.1.7 Time dependence of the amount of evaporated NOCl and Cl2

0.000

0.005

0.010

0.015

0 5000 10000 15000

n obs

/mol

t / s

1212

30

4.1.3 4.1.3.1 CV Pt Pt/C 1 M H2SO4 1 M HCl

Cyclic Voltammetry CV 4.1.8

CV Pt H2SO4

19.6cm2HCl 18.8cm2 4%

HCl CV Pt

HCl

CV Pt

. 4.1.2 Nafion Nafion

pKa 0

Pt

1 M HCl 100 mVs-1-0.15 V 1.0 V(vs.

Ag|AgCl sat. KCl) Cyclic Voltammetry CV

4.1.9 . 4.1.10 50 mVs-1100 mVs-1 CV

Pt HCl

CV Pt

1 Pt

Pt CV

CV -0.15 V

0.4 V CV Pt

4.1.8. Cyclic Voltammograms of CP-supported Pt/C catalyst at 3rd cycle on GC

in 1M H2SO4 () and 1M HCl () underN2. Scanrate is 50mVs-1.

25.0

20.0

15.0

10.0

5.0

0.0

5.0

10.0

15.0

20.0

0.4 0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2

i/m

Acm

2geom

E/Vvs.Ag|AgCl

1MHSO

1MHCl

2 4

31

4.1.11 50 mVs-1-0.15 V 0.4 V CV

-0.15 V~1.0 V

Pt CV HCl

-0.15 V~0.4 V CV Pt -0.15

V~0.4 V CV 3~5

4.1.9 Cyclic voltammograms of CP-supported Pt/C catalyst at 3rd cycle on GC in

1M HCl under N2at RT. Scan rate is 100mV/s.

40.0

30.0

20.0

10.0

0.0

10.0

20.0

30.0

0.4 0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2

i/m

Acm

2geom

E/Vvs.Ag|AgCl

cyclenum.6cyclenum.9cyclenum.15cyclenum.21cyclenum.27cyclenum.33cyclenum.45cyclenum.51

4.1.10 Time dependence of relative surface area during potential cycling by CV.

0

20

40

60

80

100

120

0 5 10 15 20 25 30 35

Relativesurfacearea/%

Cyclenumber

CV50mV/s

CV100mV/s

32

7

4.1.3.2 Pt 22, 23)

4.1.11 Cyclic voltammograms of CP-supported Pt/C catalyst at 7th cycle on GC

in 1M HCl under N2at RT. Scan rate is 50mV/s.

30.0

25.0

20.0

15.0

10.0

5.0

0.0

5.0

10.0

15.0

0.2 0.1 0.0 0.1 0.2 0.3 0.4 0.5

i/m

Acm

2geom

E/Vvs.Ag|AgCl

cyclenum.1

cyclenum.2

cyclenum.3

cyclenum.4

cyclenum.5

cyclenum.6

cyclenum.7

cyclenum.30

4.1.12 Time dependence of current generated by sawtooth wave (cathode

scan100 mVs-1anode scanstep).

0.30

0.20

0.10

0.00

0.10

0.20

0.30

0.40

0 10 20 30 40 50 60

i/A

t /s

1MHSO

1MHClO(+0.1A)

1MHCl(+0.2A)

2 4

4

33

H2SO4HClO4HCl (100

mVs-1step)-

4.1.12

0.1 V 1.2 V

11 0.1 V 1.2 V

4.1.13 1 CV

Pt CV 1

CV HCl Pt

H2SO4

HClO4

2~3 CV

4.1.12 Time dependence of current generated by sawtooth wave (cathode scan

100 mVs-1anode scanstep).

0.30

0.20

0.10

0.00

0.10

0.20

0.30

0.40

0 10 20 30 40 50 60

i/A

t /s

1MHSO

1MHClO(+0.1A)

1MHCl(+0.2A)

2 4

4

4.1.13 Cyclic voltammograms of CP-supported Pt/C catalyst on GC in 1 M

H2SO4(red line), 1 M HClO4(green line) and 1 M HCl(blue line) under N2at RT.

Scan rate is 100mV/s. Solid line is before dissolution test. And dotted line is after

dissolution test with sawtooth wave(cathode scan100 mVs-1anode scanstep)

30.0

25.0

20.0

15.0

10.0

5.0

0.0

5.0

10.0

15.0

20.0

0.4 0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2

i/m

Acm

2geom

E/Vvs.Ag|AgCl

HSObeforedissolutiontestHSOafterdissolutiontestHClObeforedissolutiontestHClOafterdissolutiontestHClbeforedissolutiontestHClafterdissolutiontest

2

2

4

4

4

4

4.1.3. Electrolyte dependence of amount of platinum dissolution.

/%

H2SO4 17

HClO4 20

HCl 94

34

. 4.1.14 Pt Pt

H2SO4, HClO4

Pt Pt Pt

0

Pt 50

Pt

4.1.3 ICP 20 Pt

(4.1.9)(4.1.10) Pt

Pt

Pt + 4Cl- [PtCl4]2 + 2e E=+0.758 V (4.1.9)

Pt + 6Cl- [PtCl6]2+ 4e E=+0.744 V (4.1.10)

4.1.3.3 Pt 0.5 M1.0 M2.0 M HCl (100 mVs-1

step)-.

4.1.15

4.1.14 Time dependence of Pt dissolution with sawtooth wave (cathode scan100

mVs-1anode scanstep) at RT in 1 M H2SO4 (), 1 M HClO4 () and 1 M HCl

().

0

20

40

60

80

100

120

0 100 200 300 400 500 600

Relativesurfacearea/%

t/s

HSO

HClO

HCl

42

4

35

4.1.16 HCl 1

CV Pt Pt

4.1.16. Cyclic voltammograms of CP-supported Pt/C catalyst on GC in 0.5 M(red

line), 1.0 M(green line) and 2.0 M HCl(blue line) under N2at RT. Scan rate is

100mV/s. Solid line is before dissolution test. And dotted line is after dissolution test

with sawtooth wave(cathode scan100 mVs-1anode scanstep) 1min.

30.0

25.0

20.0

15.0

10.0

5.0

0.0

5.0

10.0

15.0

20.0

25.0

0.4 0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2

i/m

Acm

2geom

E/Vvs.Ag|AgCl

0.5MHClbeforedissolutiontest0.5MHClafterdissolutiontest1.0MHClbeforedissolutiontest1.0MHClafterdissolutiontest2.0MHClbeforedissolutiontest2.0MHClafterdissolutiontest

4.1.15 Time dependence of current generated by sawtooth wave (cathode scan

100 mVs-1anode scanstep).

0.20

0.15

0.10

0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0 10 20 30 40 50 60

i/A

t /s

0.5MHCl

1.0MHCl(+0.1A)

2.0MHCl(+0.2A)

36

4.1.17 0.5 M1 M2 M HCl Pt

Pt

Pt

Pt

95 %(0.5 M)94 %(1 M)96 %(2 M) Pt

95 % Pt

100 % Pt Nafion

4.1.18 Pt/C

4.1.17. Time dependence of Pt dissolution with sawtooth wave (cathode scan100

mVs-1anode scanstep) at RT in 0.5 M (), 1.0 M () and 2.0 M () HCl.

0

20

40

60

80

100

120

0 100 200 300 400 500 600

Relativesurfacearea/%

t/s

0.5MHCl

1.0MHCl

2.0MHCl

4.1.18. Scheme of solid/liquid interface in CP/catalyst assembly.

(Nafion)

37

4.1.3.4 Pt (100 mVs-1) 1.0 V ~ 0.1 V

1.2 V ~ 0.1 V1.4 V ~ 0.3 V (vs. Ag|AgCl sat. KCl)Pt

- 4.1.19

Fig. 4.1.19. Time dependence of current generated by sawtooth wave (cathode

scan100 mVs-1anode scanstep).

0.30

0.25

0.20

0.15

0.10

0.05

0.00

0.05

0.10

0.15

0.20

0 10 20 30 40 50 60

i/A

t /s

0.1V1.0V

0.1V1.2V

0.3V1.4V

Fig. 4.1.20. Time dependence of Pt dissolution in 1MHCl with sawtooth wave at

RT. Scan range is -0.1 V~1.0 V (), 0.1 V~1.2 V () and 0.3V~1.4 V ().

0

20

40

60

80

100

120

0 100 200 300 400 500 600

Relativesurfacearea/%

t/s

0.1V1.0V

0.1V1.2V

0.3V1.4V

38

1.4 V

Pt 4.1.20 100mVs-1

4.1.20. Time dependence of current generated by various potential wave of

(a)~(f).

10

0

10

20

30

40

50

60

70

80

90

0 10 20 30 40 50 60

i/m

A

t /s

0.7V(a)

0.9V(b)

1.2V(c)

[A]

0.30

0.20

0.10

0.00

0.10

0.20

0.30

0 5 10 15 20

i/A

t /s

(d)

(e)

(f)

[B]

0.10

0.00

0.10

0 5 10 15 20

i/A

t /s

(g) (h)[C]

39

Pt

4.1.3.5 Pt 3.1.7 (a) ~ (h)Pt -

4.1.20 4.1.20 [A]

(a)(b)

(c)

. 4.1.20 [B][C]

(e)(h) Pt (f)(g)

1 M 3.1.7 (0.7 V (a) 0.9 V (b) 1.2 V (c)

vs. Ag|AgCl)(e)(d) Pt

Pt 4.1.21

Pt

4.1.21. Time dependence of Pt dissolution with fixed electrical potential(0.7 V

(), 0.9 V (), 1.2 V ()), sawtooth wave (d) () and rectangular waveform (e)

() in 1 M HCl at RT.

0

20

40

60

80

100

120

0 50 100 150 200 250

Relativesurfacearea/%

t/s

0.7V(a)0.9V(b)1.2V(c)Sawtoothwave(d)Rectangularwave(1.2V1s0.1V1s)(e)

40

0.8 V(vs. RHE) Pt

Pt

4.1.22 3.1.7 (e)~(h) Pt

3.1.7 Pt

(h)

(h) Pt 1 97 % Pt

(e)(f)(d)

(g) Pt 20 (h)

Pt ICP-AES 97 % Pt

4.1.22. Time dependence of Pt dissolution with sawtooth waves (d) (), (f)

(), (g) (), (h) () and rectangular waveform (e) () in 1 M HCl at RT.

0

20

40

60

80

100

120

0 100 200 300 400 500 600

Relativesurfacearea/%

t/s

SW(100mV/s)(d)

RW(e)

SW(1100mV/s)(f)

SW(1100mV/s)(0.1V1s,1.2V0s)(g)

SW(1100mV/s)(0.1V0s,1.2V1s)(h)

4.1.4 Lifetime analysis of Pt dissolution by eq. 4.1.11 using non-linear least

square method.

Potential waveform / s R 2

0.7V (a) 1006 0.95000.9V (b) 337 0.98951.2V (c) 385 0.9988

Sawtooth wave (d) 86 0.9973Rectangular wave (e) 31 0.9884

Sawtooth wave (f) 53 0.9946Sawtooth wave (g) 263 0.9897Sawtooth wave (h) 20 0.9495

41

Pt

(4.1.11)

S = S0 exp (t /) (4.1.11)

S(cm2) t(s) Pt S0(cm2)

(s)

( 4.1.4)

0.7 V 0.9 V Pt

1.2 V

Pt (h)

15

4.1.3.6 Pt Pt 4.1.23 46 Pt/C CP CV

3.1.7 (e) 3 Pt

46 Pt

CP Pt

Pt

Pt ICP 82 %

Pt 14 % Pt

4.1.23. Cyclic voltammograms of CP-supported Pt/C catalyst on GC in 1M HCl

at RT. The catalyst was dissolved by aqua regia at RT for 46h.

5.0

4.0

3.0

2.0

1.0

0.0

1.0

2.0

3.0

4.0

0.2 0.1 0 0.1 0.2 0.3 0.4 0.5

i/mAcm

2geom

E/Vvs.Ag|AgCl

Afterdissolvedbyaquaregia

AndafteraddedRW(e)3min

42

4 % Pt Pt

Nafion

Pt

Pt

4.1.3.7 Pt 4.1.24 Pt/C CP Pt

UV Pt 10 ppm H2[PtCl6](H2O)6K2[PtCl4] 3 UV

Pt H2[PtCl6](H2O)6 260nm

H2[PtCl6](H2O)6

260nm [PtCl6]2

4.1.24. UV spectra of Pt leaching solution with electrochemical method(), 10

ppm H2[PtCl4](H2O)6 (), K2[PtCl4] () and Pt standard solution ().

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

200 250 300 350 400

Abs

Wavelength/nm

electrochemicalmethod

H[PtCl](HO)

K[PtCl]

Ptstandardsolution

2 4

2 6 62

43

4.1.3.8 PtRu PtRu PtRu 4.1.25

Pt PtRu

Pt 83%Ru

79% 10

Pt Ru 80%Pt/C

(0.3 mg/cm2)Pt15%

PtRu/C 2.9 mg/cm2

Nafion

PtRu PtRu/C CP

4.1.4 LCIA Pt 4.1.5 Pt

Pt1g

(3.1.9)4 Pt

- Pt (3.1.11) 4

Pt

4.1.25. Time dependence of Pt() and Ru() dissolution with SW(e)at RT.

0

10

20

30

40

50

60

70

80

90

100

0 200 400 600 800 1000 1200

Dissolved

Ptand

Ru/%

t/s

Pt

Ru

44

-

Pt (3.1.8)(3.1.9) 1 1

- Pt

(3.1.10)(3.1.11) 1 1

1 4.1.26

-

(4.1.9)(4.1.10) Pt

4.1.5. Comparison of environmental burden of Pt dissolution method without electrical

energy.

-

IPCC-100(2001) / 10-3 1.05 1.61 4.74

() HTP_cancer / 10-7 5.65 7.68 15.3

() HTP_chronic disease / 10-9 0.842 1.15 2.28

AETP / 10-6 1.46 1.99 3.96

TETP / 10-5 3.32 4.52 8.99

DAP / 10-6 1.19 1.79 21.2

EPMC / 10-8 0.974 1.40 8.72

OECF / 10-8 3.62 4.96 22.2

m3 / 10-8 0.000862 0.00117 150

1/R(Sb) / 10-7 0.100 0.155 145

MJ / 10-2 1.35 2.44 7.75

4.1.26. Relative comparison of environmental burden of Pt dissolution method

without electrical energy.

45

(4.1.9)(4.1.6) Pt

4.1.6

Pt

4.1.5

-

50%

4.1.5 XRD . 4.1.27 25

fcc

4.1.6. Comparison of environmental burden of Pt dissolution method. -

IPCC-100(2001) / 10-3 4.17 1.61 8.28

() HTP_cancer / 10-7 32.76 7.68 46.0

() HTP_chronic disease / 10-9 4.88 1.15 6.86

AETP / 10-6 8.5 1.99 11.93

TETP / 10-5 19.27 4.52 27.06

DAP / 10-6 2.95 1.79 23.15

EPMC / 10-8 2.8 1.40 10.79

OECF / 10-8 11.69 4.96 31.38

m3 / 10-11 5.0 1.17 150473.00

1/R(Sb) / 10-8 4.976 1.55 1453.19

MJ / 10-2 5.42 2.44 12.36

4.1.27 XRD patterns of (a) reproduced Pt/MWCNT catalyst and (b) Pt (ICDD Card

No. 89-7382).

20 40 60 802 Theta / degree

Inte

nsity

/ a.

u.

(b) Pt (ICDD Card No. 89-7382)

(a) Reproduced Pt/MWCNT catalyst

46

Scherrer

Bcos9.0

Bt =

(4.1.10)

t ()() X (1.54184)B Bragg

B(rad)(2)

)22(21

21 =B (4.1.11)

1.9nm

4.1.6 4.1.6.1 0.05M NaOH

pH 1.46

0.05M NaOH

Nafion 1g 1.610-2mol Nafion

26

Nafion

5.910-3mol

4.1.6.2

Nafion

47

4.2 () 4.2.1 pH NiCoFe/C NiCoFe/C XRD Scherrer

28.6 nm

NiCoFe/C pH NiCo 4.2.1

pH5.0 NiCo Ni

pH9.0 pH7.0

pH9.0 pH7.0 pH9.0

NiCoFe/C Ni 15%pH5.07.0 1%

pH9.0 pH5.07.0 Ni pH9.0

pH

pH

pH

pH (H+)(1)

Ni Co (NiO)

Ksp=10-16 (M2)

(CoO)

26)NiCo pH

Ni Co

4.2.1 pH NiCo

0.0

0.10

0.20

0.30

0.40

4.0 5.0 6.0 7.0 8.0 9.0 10

NiCo

(pp

m)

pH

48

50 27) NiCo 28-29)

MO + 2H+ M2+ + H2O (4.2.1)

[M NiCoMO NiOCoO ]

NiCo

MINEQL+(ENVIRONMENTAL RESEARCH SOFTWARE)

MINEQL+ pH NiCo

pH

NiCo

6.00.4 ppm 3.80.1 ppm

pH

30-32) pH

/ SPARC(SPARC

Performs Automated Reasoning in Chemistry, http://sparc.chem.uga.edu/sparc/)

pH /

pH SPARC

pH

pH

pH 4.0 20)

49

4.2.2 NiCo NiCoFe/C

pH NiCo 4.2.2 4.2.3

4.2.21.010-71.010-3 (M)ppH6.2pH7.9

p=0.0088 p>0.05 pH6.2

7.9 Logistic pH6.2

7.07.9 Ni pH

4.2.3 1.010-7 1.010-3 (M)

pH6.2pH7.0ppH7.0pH7.9ppH7.0

pH7.9 1.010-3 1.010-7 (M)pH6.2

pH7.9 1.010-5 1.010-4 (M) p

50

E

D

T

A

8.0610-7(M) EDTA

pH Ni Co

FIAM BLM pH

(H+)

pH NiCo AAP

WHAM(NATURAL ENVIRONMENT RESEARCH COUNCIL)

AAP NiCo

FIAM

33)WHAM 1.010-3 (M)

pH6.27.07.9 Ni 9.8810-49.8210-48.7410-4 (M)

Co 9.8710-49.8210-49.1210-4 (M)

4.2.3 Co pH6.27.09.0

*pH6.2-7.0pH7.0-7.9 p0.29 0.39

**pH6.2-7.0pH7.0-7.9 p0.021 0.42

***pH6.2-7.0pH7.0-7.9 p0.860.012

****pH6.2-7.9 p=0.21 *****pH6.2-7.0 p=0.51

-20

0

20

40

60

80

100

120

10-8 10-7 10-6 10-5 10-4 10-3 10-2

pH6.2pH7.0pH7.9

(%

)

(M)

***

***

****

*****

51

WHAM pH

pH H+

H+ Co pH6.2 H+

pH7.0

pH7.9 H+pH7.0 pH7.9

pH6.27.07.9 1.010-3 (M)

Co 2.6410-15.2710-16.4610-1 (-)

pH6.2 pH7.07.9

Co H+

pH7.0 7.9

Ni pH

H+

pH6.27.07.9 pH6.27.07.9

1.010-3 (M) Ni 6.4510-21.0710-11.0910-1 (-)

pH6.2

Ni (H. vulgare) pH

34) Ni

pH

Co pH H+

Ni pH

H+ pH

NiCoFe/C pH 5.07.09.0

4.2.1 pH5.0

10 %pH7.09.0

100 %

pH5.07.09.0 pH7.09.0

4.2.1 pH

1.0% (%) 10 % (%) 100% (%)

pH 5.0 0 14.5 100

pH 7.0 0 0 0

pH 9.0 0 0 0

52

pH5.0 Ni

Co

EC50 940 ppm

EC50 4.25 ppm 50 %

4.2.3 TU NiCoFe/C TU(Toxicity Unit)

TU 4.2.4 4.2.4

NiCo TU

NiCo Logistic

TUNiCoFe/CNiCo

Co

20%Ni 2.2% 0.075% 11%

Co Ni 4.2.1

Co Ni Co

4.2.4 NiCo TU (

pH=7.0)

-20

0

20

40

60

80

100

120

10-4 10-3 10-2 10-1 100 101 102 103

pH 5.0pH 7.0pH 9.0NiCo

(%)

TU (-)

R2=0.77 RMSE=20.4

53

Ni NiCo

EC50

50%

Ci/Gi 1.59 (-)Ci/Gi 1 (-)

BLM Biotic Ligand

35)

36,37)