Figure captions Figure 1: CVs recorded for copper and brass in deaerated borax 0.1 mol L-1. v = 0.

02 V s-1. Figure 2: CVs recorded for copper and brass in deaerated borax 0.1 mol L-1 + NaCl 0.01 mol L-1. v = 0.02 V s-1. Figure 3: CVs for copper in stagnant (a) and 600 rpm rotation speed (b) in deaerated borax 0.1 mol L-1. v = 0.02 V s-1. Figure 4: CVs for brass in stagnant (a) and 600 rpm rotation speed (b) in deaerated borax 0.1 mol L-1. v = 0.02 V s-1. Figure 5: Differential reflectance obtained for Cu2O, CuO and OCP after 5, 5 and 24 h respectively of copper electrode inmersion in deaerated borax 0.1 mol L-1. Figure 6: Differential reflectance obtained for Cu2O, CuO after 5 h of brass electrode inmersion in deaerated borax 0.1 mol L-1 and for OCP after 24 h of inmersion in deaerated borax 0.1 mol L-1 without and with NaCl 0.01 mol L-1 added. Figure 7: X-ray photoelectron spectra of Cu2p line for copper and brass aged at OCP for 24 h in aerated (solid lines) and deaerated (dashed

lines) borax 0.1 mol L-1. Figure 8: X-ray induced CuLMM Auger spectra for copper and brass aged at OCP for 24 h in aerated borax 0.1 mol L-1. Figure 9: X-ray photoelectron spectra of Cu2p line for copper and brass aged at OCP for 24 h in aerated borax 0.1 mol L-1 + NaCl 0.01 mol L-1.

Figure 10: Survey XPS spectra for copper and brass aged at OCP for 24 h in aerated borax 0.1 mol L-1 + NaCl 0.01 mol L-1. Inset: X-ray photoelectron peak of Cl2p line. Figure 11: X-ray photoelectron spectra of Cl2p line for copper and brass aged at OCP for 24 h in aerated borax 0.1 mol L-1 + NaCl 0.01 mol L-1. Figure 12: X-ray photoelectron spectra of O1s line for copper and brass aged at OCP for 24 h in aerated borax 0.1 mol L -1 with (dashed lines) and without (dashed lines) NaCl 0.01 mol L-1. Figure 13: Raman spectrum for copper aged at OCP for 24 h in aerated borax 0.1 mol L-1. Intensities relative to the background: (I) 7153, (II) 3099, (III) 2801. Figure 14: Raman spectrum for copper aged at OCP for 24 h in aerated borax 0.1 mol L-1 + NaCl 0.01 mol L-1. Intensities relative to the background: (I) 6276, (II) 3295, (III) 2436. Figure 15: Raman spectrum for brass aged at OCP for 24 h in aerated borax 0.1 mol L-1. Intensities relative to the background: (I) 45515, (II) 32188. Figure 16: Raman spectrum for brass aged at OCP for 24 h in aerated borax 0.1 mol L-1 + NaCl 0.01 mol L-1. Intensities relative to the background: (I) 23565, (II) 14107.

0,2 A2 0,1 A0 A3*

E corr

A1

i / mA cm

-2

0,0

-0,1

C4

C2 C1

-0,2

-0,3 -1,6 -1,2 -0,8 -0,4 0,0

copper brass
0,4 0,8

E / V (vs Ref)

Figure 1

0,3 0,2 0,1 A1* A3* A0 Cu2(OH)3Cl (C1*) C2 C4 C1 A1 A2

i / mA cm

-2

0,0 -0,1 -0,2 -0,3 -0,4

+ Cl 0.01 mol L

-1

copper brass
-1,6 -1,2 -0,8 -0,4 0,0 0,4 0,8

E / V (vs Ref)

Figure 2

0,2 A1 0,1 (b) A2

(a)

i / mA cm

0,0

A0

-2

-0,1

C1

-0,2 -1,6 -1,2

C2 -0,8 -0,4 0,0

E / V (vs Ref)

Figure 3

0,3

A1
0,2 0,1

(a) (b)

A2

A3*

i / mA cm

-2

0,0 -0,1 -0,2 -0,3 -0,4 -1,6 -1,2 -0,8 -0,4 0,0 0,4

C4

C1 C2

E / V (vs Ref)

Figure 4

Copper in borax 0.1 mol L

110 100 90 80 70 60 200 300 400 500 600

-1

baseline

T/%

E Cu2O for 5 h E CuO for 5 h OCP for 24 h

700 800

/ nm

Figure 5

160 140 120 100

E Cu2O for 5 h E CuO for 5 h OCP for 24 h OCP for 24 h + Cl

Brass in borax 0.1 mol L

-1

baseline

T/%

80 60 40 20 0
Zn oxo-hydroxides dissolution by Cl ions present

Zn species contribution (low %T)

200

300

400

500

600

700

800

/ nm

Figure 6

150k

Cu/Cu2O Cu(OH)2 Cu2p3/2

100k

Cu2p

Cu2p1/2 brass

CPS

copper
50k

brass copper

920

940

960

980

BE / eV

Figure 7

80k

Cu2O
60k

Auger CuLMM

Cu CPS brass
40k

copper
20k

550

560

570

580

590

600

BE / eV

Figure 8

50k

Cu/Cu2O

Cu2p

brass
40k

CPS

Cu2p3/2
30k

Cu2p1/2

copper

+ Cl 0.01 mol L
20k 920 940 960

-1

980

BE / eV

Figure 9

900k
80k

Survey
Cl2p

800k
70k

CPS

700k 600k 500k

60k

brass copper

O1s
210

50k

198

204

Cu2p

BE / eV

CPS

400k 300k 200k 100k 0 -100k 0 200 400 600 800

C1s Cl2p + 0.01 mol L Cl

-1

copper brass
1000 1200

BE / eV

Figure 10

10k

Cl2p3/2

Cl2p1/2

Cl2p

9k

copper CPS
8k

7k

6k

brass

5k 194 196 198 200 202 204 206

BE / eV

Figure 11

50k

metal oxides
40k

O1s

O1s

CPS

30k

brass
20k

copper
10k 520 525 530 535 540

brass

545

BE / eV

Figure 12

120k

Copper
110k 100k

CuO Cu2O 535 433 150 218 644

Intensity / counts

90k 80k 70k 60k 50k 100

200

300

400

500

600

700
-1

800

900

1000

Raman shift / cm

Figure 13

60k

Copper in borax 0.1 mol L -1 + Cl 0.01 mol L

-1

796 644

Intensity / counts

50k

150 220 430

40k

531 peak due to chloro-compound

30k 100

200

300

400

500

600

700
-1

800

900

1000

Raman shift / cm

Figure 14

350k

Brass
300k

CuO Intensity / counts 531 Cu2O 630

250k

210
200k

430 289

150k 100

200

300

400

500

600

700
-1

800

900

1000

Raman shift / cm

Figure 15

200k

Brass in borax 0.1 mol L -1 + Cl 0.01 mol L

-1

Intensity / counts

150k

Cu2O 150

100k

217 430

530

630

289
100 200 300

400

500

600

700
-1

800

900

1000

Raman shift / cm

Figure 16