PCMR1 VN loading = 0.

302 g, Cathode superficial area = 8 cm2

T = 550 oC Fig.2f
Current, mA Voltage, V vs OCV
0.00 0.00
5.00 0.22
10.00 0.26
20.00 0.31
40.00 0.35
60.00 0.42
80.00 0.50
100.00 0.78
125.00 1.17
150.00 1.48

PCMR1 VN loading = 0.302 g, Cathode superficial area = 8 cm2

T = 600 oC Fig.2f
Current, mA Voltage, V vs OCV
0.00 0.00
5.00 0.21
10.00 0.26
20.00 0.30
40.00 0.34
60.00 0.39
80.00 0.45
100.00 0.63
125.00 1.01
150.00 1.33
PCMR1 VN loading = 0.302 g, Cathode superficial area = 8 cm2

T = 650 oC Fig.2f
Current, mA Voltage, V vs OCV
0.00 0.00
5.00 0.19
10.00 0.25
20.00 0.30
40.00 0.33
60.00 0.39
80.00 0.43
100.00 0.59
125.00 0.96
150.00 1.23

PCMR1 VN loading = 0.302 g, Cathode superficial area = 8 cm2

T = 600 oC Fig.2f
Current, mA Voltage, V vs OCV
0.00 0.00
5.00 0.22
10.00 0.27
20.00 0.31
40.00 0.37
60.00 0.40
80.00 0.46
100.00 0.66
125.00 1.04
150.00 1.35
 -
6.70
5.38
3.65
7.99
1.53
3.59
4.76
2.77
1.58
ng = 0.302 g, Cathode superficial area = 8 cm2 Anode flow = 15 sccm

I/F Gas Chromatograph

Membrane flux, mmolH+ h-1m-2 CH4, %
0.00 1.67
214.75 1.65
463.00 1.60
925.00 1.53
1850.00 1.45
2776.00 1.31
3550.38 1.21
4057.88 1.15
4106.31 1.14
4122.88 1.12
0.83
2.91
0.58
2.28
1.13
2.12
1.45
1.54
STANDARD DEVIATION,% 0.95
STANDARD ERROR,% 1.61

ng = 0.302 g, Cathode superficial area = 8 cm2 Anode flow = 15 sccm

I/F Gas Chromatograph

Membrane flux, mmolH+ h-1m-2 CH4, %
0.00 1.33
231.25 1.32
440.56 1.28
863.38 1.22
1751.19 1.08
2474.31 0.98
3324.31 0.81
3642.44 0.77
4076.19 0.70
4255.25 0.68
3.13
4.14
3.89
0.65
1.39
1.61
2.97
3.19
STANDARD DEVIATION,% 1.97
STANDARD ERROR,% 2.84
ng = 0.302 g, Cathode superficial area = 8 cm2 Anode flow = 15 sccm

I/F Gas Chromatograph

Membrane flux, mmolH+ h-1m-2 CH4, %
0.00 1.18
232.00 1.16
417.19 1.13
771.19 1.06
1548.19 0.94
2370.78 0.81
3046.25 0.70
3796.56 0.55
4325.31 0.49
4549.38 0.45
1.07
1.59
3.32
2.68
4.77
3.35
2.33
1.97
STANDARD DEVIATION,% 1.11
STANDARD ERROR,% 3.96

ng = 0.302 g, Cathode superficial area = 8 cm2 Anode flow = 15 sccm

I/F Gas Chromatograph

Membrane flux, mmolH+ h-1m-2 CH4, %
1.35
222.44 1.33
456.50 1.29
828.79 1.21
1671.56 1.10
2439.91 0.99
3197.16 0.82
3758.66 0.79
3999.36 0.73
4075.88 0.71
3.13
4.14
3.89
 0.65
1.39
1.61
2.97
3.19
STANDARD DEVIATION,% 1.97
STANDARD ERROR,% 2.84
1.50
0.76
0.78
0.82
1.85
1.02
1.23
2.60
4.29
4.41
 CH4 INLET = 3.01% H2O INLET = ~9% (Tsaturator = 45oC) Anode exit
Gas Chromatograph Gas Chromatograph
CH4 rate, mmol h-1m-2 CO2,% CO2 rate, mmol h-1m-2 CO,%
782.81 1.27 587.96 0.06
773.44 1.30 601.85 0.05
750.00 1.34 620.37 0.04
717.19 1.43 662.04 0.02
679.69 1.54 712.96 0.03
614.06 1.67 773.15 0.03
567.19 1.78 824.07 0.03
539.06 1.84 851.85 0.03
534.38 1.85 856.48 0.04
525.00 1.87 865.74 0.03
0.42 4.34 2.17 1.66
1.46 4.62 2.31 5.11
0.29 3.29 1.65 5.31
1.14 4.27 2.14 4.67
0.57 1.61 0.81 2.48
1.06 1.08 0.54 1.59
0.73 1.76 0.88 1.15
0.77 2.03 1.02 2.88
0.48 1.98 0.99 2.05
0.81 1.52 0.76 1.64

CH4 INLET = 3.02% H2O INLET = ~9% (Tsaturator = 45oC) Anode exit
Gas Chromatograph Gas Chromatograph
CH4 rate, mmol h-1m-2 CO2,% CO2 rate, mmol h-1m-2 CO,%
623.44 1.56 722.22 0.11
618.75 1.58 731.48 0.11
600.00 1.64 759.26 0.08
571.88 1.71 791.67 0.08
506.25 1.84 851.85 0.08
459.38 1.96 907.41 0.09
379.69 2.09 967.59 0.09
360.94 2.17 1004.63 0.07
328.13 2.24 1037.04 0.07
318.75 2.27 1050.93 0.07
1.57 1.99 0.50 2.53
2.07 2.44 0.61 3.22
1.95 2.69 0.67 2.88
0.33 3.26 0.82 2.25
0.70 1.36 0.34 1.06
0.81 1.57 0.39 1.35
1.49 1.21 0.30 1.02
1.60 1.16 0.29 0.88
0.99 1.34 0.34 1.92
1.42 1.12 0.28 1.66
 CH4 INLET =2.99% H2O INLET = ~9% (Tsaturator = 45oC) Anode exit
Gas Chromatograph Gas Chromatograph
CH4 rate, mmol h-1m-2 CO2,% CO2 rate, mmol h-1m-2 CO,%
553.13 1.71 791.67 0.13
543.75 1.73 800.93 0.12
529.69 1.78 824.07 0.11
496.88 1.85 856.48 0.11
440.63 1.99 921.30 0.10
379.69 2.11 976.85 0.10
328.13 2.23 1032.41 0.09
257.81 2.36 1092.59 0.09
229.69 2.44 1129.63 0.08
210.94 2.47 1143.52 0.08
0.54 2.84 1.42 1.96
0.80 3.33 1.67 1.03
1.66 2.11 1.06 2.01
1.34 3.95 1.98 4.08
2.39 3.24 1.62 3.96
1.68 2.77 1.39 1.65
1.17 4.70 2.35 2.32
0.99 2.74 1.37 3.11
0.56 2.21 1.11 3.07
1.98 1.93 0.97 1.18

CH4 INLET = 3.01% H2O INLET = ~9% (Tsaturator = 45oC) Anode exit
Gas Chromatograph Gas Chromatograph
CH4 rate, mmol h-1m-2 CO2,% CO2 rate, mmol h-1m-2 CO,%
632.81 1.54 712.96 0.12
623.44 1.57 726.85 0.11
604.69 1.65 763.89 0.08
567.19 1.69 782.41 0.08
515.63 1.81 837.96 0.08
464.06 1.93 893.52 0.09
384.38 2.07 958.33 0.09
370.31 2.14 990.74 0.07
342.19 2.20 1018.52 0.07
332.81 2.23 1032.41 0.07
1.57 1.99 0.50 2.53
2.07 2.44 0.61 3.22
1.95 2.69 0.67 2.88
0.33 3.26 0.82 2.25
0.70 1.36 0.34 1.06
0.81 1.57 0.39 1.35
1.49 1.21 0.30 1.02
1.60 1.16 0.29 0.88
0.99 1.34 0.34 1.92
1.42 1.12 0.28 1.66
1.28 4.55
0.63 3.64
0.61 3.75
1.17 1.25
1.63 1.25
1.53 4.44
0.96 3.33
1.38 4.71
1.79 4.29
1.76 1.43
 Anode exit stream
matograph Gas Chromatograph
CO rate, mmol h-1m-2 H2,% H2 rate, mmol h-1m-2
27.78 5.22 2447.19
23.15 5.09 2387.88
18.52 4.99 2340.53
9.26 4.79 2245.20
13.89 4.36 2041.79
13.89 3.95 1852.68
13.89 3.56 1671.17
13.89 3.28 1536.60
18.52 3.27 1531.62
13.89 3.27 1532.52
0.83 1.97 0.99
2.56 4.10 2.05
2.66 3.57 1.79
2.34 3.91 1.96
1.24 2.06 1.03
0.80 1.64 0.82
0.58 1.88 0.94
1.44 1.93 0.97
1.03 1.01 0.51
0.82 1.13 0.57

Anode exit stream

matograph Gas Chromatograph
CO rate, mmol h-1m-2 H2,% H2 rate, mmol h-1m-2
50.93 6.47 2995.37
50.93 6.31 2919.71
37.04 6.31 2921.33
37.04 6.13 2839.57
37.04 5.74 2657.12
41.67 5.50 2548.19
41.67 5.14 2381.37
32.41 5.06 2344.83
32.41 4.87 2255.01
32.41 4.79 2216.51
0.63 1.13 0.28
0.81 1.42 0.35
0.72 1.39 0.35
0.56 1.38 0.34
0.27 0.61 0.15
0.34 0.73 0.18
0.26 0.56 0.14
0.22 0.51 0.13
0.48 0.82 0.20
0.42 0.70 0.17
 Anode exit stream
matograph Gas Chromatograph
CO rate, mmol h-1m-2 H2,% H2 rate, mmol h-1m-2
60.19 7.04 3259.26
55.56 6.89 3189.81
50.93 6.88 3185.19
50.93 6.80 3147.22
46.30 6.52 3016.20
46.30 6.25 2893.52
41.67 5.94 2750.00
41.67 5.64 2611.11
37.04 5.39 2495.37
37.04 5.32 2462.50
0.98 1.13 0.28
0.52 1.42 0.35
1.01 1.39 0.35
2.04 1.38 0.34
1.98 0.61 0.15
0.83 0.73 0.18
1.16 0.56 0.14
1.56 0.51 0.13
1.54 0.82 0.20
0.59 0.70 0.17

REPEAT EXPERIMENT WITH PCMR1 AT 600 oC

Anode exit stream
matograph Gas Chromatograph
CO rate, mmol h-1m-2 H2,% H2 rate, mmol h-1m-2
53.24 6.31 2921.30
52.78 6.21 2875.00
38.43 6.16 2851.85
37.50 6.00 2779.27
36.57 5.63 2604.42
39.81 5.28 2443.34
40.28 5.08 2351.39
33.94 4.73 2190.63
33.80 4.70 2175.84
31.94 4.73 2188.70
0.63 1.13 0.28
0.81 1.42 0.35
0.72 1.39 0.35
0.56 1.38 0.34
0.27 0.61 0.15
0.34 0.73 0.18
0.26 0.56 0.14
0.22 0.51 0.13
0.48 0.82 0.20
0.42 0.70 0.17
2.47
1.53
2.38
2.12
1.98
4.11 STANDARD DEVIATION % BETWEEN THE
1.26 REPEATED EXPERIMENTS AT 600
6.58
3.51
1.25
 N2 INLET = 100%

NH3 analyzer
Error in carbon balance, % NH3, ppm
3.83 0.00
7.78 28.70
4.88 53.20
6.75 82.90
3.18 127.00
3.46 162.00
2.91 188.05
4.00 196.69
2.97 184.70
3.19 172.50
-
2.15
8.71
7.22
8.40
7.26
2.89
6.88
STANDARD DEVIATION,% 7.10
STANDARD ERROR,% 3.11

N2 INLET = 100%

NH3 analyzer
Error in carbon balance, % NH3, ppm
3.51 0.00
3.41 34.00
4.41 58.00
1.74 88.00
1.82 137.00
0.71 175.00
3.76 213.00
2.53 221.00
2.22 212.00
1.93 204.50
-
3.38
2.75
1.75
3.10
6.22
5.80
4.96
STANDARD DEVIATION,% 7.54
STANDARD ERROR,% 7.33
 N2 INLET = 100%

NH3 analyzer
Error in carbon balance, % NH3, ppm
0.83 0.00
0.16 24.50
0.98 41.20
1.25 65.50
3.08 109.40
0.51 156.18
0.40 172.80
2.49 191.23
1.06 188.90
2.40 167.70
-
1.95
6.88
2.11
3.58
5.04
6.12
5.15
STANDARD DEVIATION,% 4.34
STANDARD ERROR,% 3.89

PCMR1 AT 600 oC
N2 INLET = 100%

NH3 analyzer
Error in carbon balance, % NH3, ppm
2.29 0.00
1.96 33.00
0.95 56.00
2.88 89.00
1.92 139.00
1.48 171.00
4.06 209.00
2.39 217.00
2.10 209.00
2.07 202.00
-
6.24
4.44
 2.89
1.89
6.22
5.54
5.66
STANDARD DEVIATION,% 4.93
STANDARD ERROR,% 7.97
-
2.94
3.45
1.14
1.46
EVIATION % BETWEEN THE 2.29
XPERIMENTS AT 600 1.88
1.81
1.42
1.22
 Cathode flow = 100.0 sccm Cathode exit stream
Fig.2d Gas Chromatograph
NH3 rate, mmol h-1m-2 H2, % H2 rate, mmol h-1m-2
0.00 0.00 0.44
9.21 0.03 100.00
16.27 0.07 203.13
25.17 0.13 418.75
39.60 0.27 843.75
49.73 0.42 1312.50
57.71 0.54 1687.50
60.16 0.62 1921.88
56.25 0.60 1881.25
54.00 0.64 2000.00
- 1.94 0.97
1.43 3.33 1.67
5.81 3.14 1.57
4.81 1.82 0.91
5.60 3.12 1.56
4.84 2.28 1.14
1.93 2.76 1.38
4.59 2.86 1.43
4.73 1.02 0.51
2.07 1.26 0.63

Cathode flow = 100.0 sccm Cathode exit stream

Fig.2d Gas Chromatograph
NH3 rate, mmol h-1m-2 H2, % H2 rate, mmol h-1m-2
0.00 0.00 1.13
10.44 0.03 96.88
18.11 0.06 198.13
27.63 0.13 406.25
42.05 0.26 812.50
53.72 0.39 1218.75
66.00 0.52 1625.00
67.84 0.58 1812.50
66.61 0.66 2046.88
63.85 0.69 2140.63
- 0.98 0.25
1.95 0.84 0.21
1.59 4.34 1.09
1.01 4.70 1.17
1.79 3.73 0.93
3.59 2.20 0.55
3.35 0.35 0.09
2.86 0.80 0.20
4.35 1.38 0.35
4.23 0.26 0.06
Cathode flow = 100.0 sccm Cathode exit stream
Fig.2d Gas Chromatograph
NH3 rate, mmol h-1m-2 H2, % H2 rate, mmol h-1m-2
0.00 0.00 1.88
7.66 0.03 106.25
12.88 0.07 221.88
20.47 0.14 437.50
34.19 0.28 875.00
48.81 0.42 1296.88
54.00 0.53 1668.75
59.76 0.69 2156.25
59.03 0.72 2250.00
52.41 0.82 2562.50
- 2.56 0.64
0.65 2.60 0.65
2.29 1.11 0.28
0.70 1.10 0.28
1.19 1.72 0.43
1.68 1.01 0.25
2.04 0.90 0.23
1.72 0.75 0.19
1.45 1.72 0.43
1.30 1.53 0.38

Cathode flow = 100.0 sccm Cathode exit stream

Fig.2d Gas Chromatograph
NH3 rate, mmol h-1m-2 H2, % H2 rate, mmol h-1m-2
0.00 0.00 1.13
10.31 0.03 96.88
17.50 0.07 203.13
27.81 0.12 373.80
43.44 0.25 771.75
53.44 0.37 1140.93
65.31 0.48 1501.74
67.81 0.57 1778.74
65.31 0.61 1902.83
63.13 0.62 1944.38
- 1.85 0.46
2.08 2.91 0.73
1.48 1.55 0.39
0.96 1.01 0.25
0.63 2.07 0.52
2.07 2.19 0.55
1.85 2.97 0.74
1.89 0.91 0.23
1.64 0.56 0.14
2.66 1.64 0.41
-
0.00
2.52
7.99
5.02
6.39
7.59
1.86
7.04
9.17
 Fig.2c Fig.2a
EQUATION 6
closed -open circuit H2 rate
Electrochemical H2, mmol h-1m-2 CH4 conversion, %
0.00 44.70
40.26 45.36
96.03 47.02
216.32 49.34
437.91 51.99
717.55 56.62
911.04 59.93
1010.85 61.92
965.24 62.25
1084.89 62.91
1.96 1.64
3.72 5.73
3.36 1.14
2.87 4.49
2.59 2.23
1.96 4.18
2.32 2.86
2.40 3.03
1.02 1.87
1.20 3.17

Fig.2c Fig.2a
EQUATION 6
closed -open circuit H2 rate
Electrochemical H2, mmol h-1m-2 CH4 conversion, %
0.00 55.96
20.08 56.29
122.96 57.62
249.32 59.60
473.12 64.24
770.45 67.55
1009.87 73.18
1160.84 74.50
1305.39 76.82
1360.64 77.48
0.53 6.17
0.56 8.16
1.43 7.66
1.52 1.28
1.08 2.74
0.73 3.17
0.23 5.85
0.33 6.28
0.55 3.88
0.24 5.59
 Fig.2c Fig.2a
EQUATION 6
closed -open circuit H2 rate
Electrochemical H2, mmol h-1m-2 CH4 conversion, %
0.00 61.48
34.93 62.15
145.93 63.15
323.59 65.49
630.07 69.50
929.26 73.84
1157.62 77.51
1506.23 82.53
1484.24 84.53
1763.87 85.87
0.92 2.11
1.00 3.13
0.62 6.54
0.62 5.28
0.58 9.40
0.44 6.60
0.36 4.59
0.32 3.88
0.63 2.19
0.56 7.80

Fig.2c Fig.2a
EQUATION 6
closed -open circuit H2 rate
Electrochemical H2, mmol h-1m-2 CH4 conversion, %
0.00 55.30
49.45 55.96
132.56 57.28
230.65 59.93
453.75 63.58
661.85 67.22
930.70 72.85
1046.95 73.84
1156.26 75.83
1210.66 76.49
0.75 6.17
1.08 8.16
0.74 7.66
 0.60 1.28
0.67 2.74
0.73 3.17
0.88 5.85
0.36 6.28
0.34 3.88
0.58 5.59
- -
146.22 0.59
7.80 0.57
7.49 0.56
4.10 1.03
14.10 0.49
7.84 0.45
9.81 0.89
11.42 1.29
11.02 1.28
 Fig.2b Fig.2e
EQUATION 7 EQUATION 8
CO2 selectivity % NH3 faradaic efficiency, %
95.49 -
96.30 12.14
97.10 10.73
98.62 8.27
98.09 6.58
98.24 5.38
98.34 4.88
98.40 4.49
97.88 4.29
98.42 3.89
2.59 -
3.77 1.89
1.94 3.83
3.28 1.58
1.37 0.93
1.60 0.52
1.61 0.16
1.79 0.34
1.47 0.36
1.57 0.15

Fig.2b Fig.2e
EQUATION 7 EQUATION 8
CO2 selectivity % NH3 faradaic efficiency, %
93.41 -
93.49 13.91
95.35 12.06
95.53 9.26
95.83 7.20
95.61 6.20
95.87 5.74
96.88 5.32
96.97 4.65
97.01 4.28
2.06 -
2.68 2.60
2.62 1.06
1.14 0.34
1.04 0.31
1.20 0.41
1.79 0.29
1.89 0.22
1.32 0.30
1.70 0.28
 Fig.2b Fig.2e
EQUATION 7 EQUATION 8
CO2 selectivity % NH3 faradaic efficiency, %
92.93 -
93.51 9.75
94.18 8.01
94.39 6.56
95.22 5.54
95.48 5.34
96.12 4.63
96.33 3.99
96.83 3.79
96.86 2.98
1.96 -
2.46 0.83
2.72 1.43
3.32 0.23
4.01 0.19
3.06 0.18
3.52 0.17
2.36 0.11
1.66 0.09
2.95 0.07

Fig.2b Fig.2e
EQUATION 7 EQUATION 8
CO2 selectivity % NH3 faradaic efficiency, %
93.05 -
93.23 13.77
95.21 11.44
95.43 10.04
95.82 7.79
95.73 6.56
95.97 6.12
96.69 5.41
96.79 4.90
97.00 4.64
2.06 -
2.68 2.78
2.62 0.97
1.14 0.35
1.04 0.11
1.20 0.25
1.79 0.17
1.89 0.15
1.32 0.12
1.70 0.20
- -
0.28 1.03
0.14 5.09
0.11 8.47
0.02 8.07
0.13 5.85
0.10 6.65
0.19 1.76
0.19 5.21
0.01 8.44
 COMMENTS
A) PCMR1 MESUREMENTS WAS TESTED FOR 11 DAYS

B) OVERNIGHT THE REACTOR WAS LEFT WITH 1%h2/n2

C) AT EACH CONDITION 4 MEASUREMENTS WERE TAKEN FROM THE GC FOR CH4, CO, CO2 and H2 EVERY 10 MIN

D) AT EACH CONDITION 3 MEASUREMENTS WERE TAKEN WITH PHOTOMETRIC CALCULATIONS, WHILE NH3 WAS MONIT
WITH THE CRDS ANALYZER CONTINUOUSLY (AVERAGE OF 120 MEASUREMENTS EVERY 10 OR 20 S)

E) REACTANTS & PRODUCTS RATE CALCULATION-FLOWRATE WAS MEASURED AT 20 oC

𝑅𝑎𝑡𝑒 (𝑚𝑜𝑙/𝑠)=(𝐺𝑎𝑠 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛(%)𝑥 𝑇𝑜𝑡𝑎𝑙 𝑓𝑙𝑜𝑤𝑟𝑎𝑡𝑒(𝑠𝑐𝑐𝑚))/(24,000 (𝑠

100 (%) 𝑥 60 (𝑠/𝑚𝑖𝑛))

𝑅𝑎𝑡𝑒 (𝑚𝑚𝑜𝑙/(ℎ 𝑚2))= 𝑅𝑎𝑡𝑒(𝑚𝑜𝑙/𝑠) 𝑥 1000 (𝑚𝑚𝑜𝑙/𝑚𝑜𝑙) 𝑥 (10000/8) (cm2/

F) H2 VALUE AT I = O CORRESPONDS TO ITS LEAK FROM THE ANODE CHAMBER

H) EXPERIMENTS AT 600 oC WERE REPEATED AFTER THE END OF THE CYSLE FOR VERIFICATION
, CO, CO2 and H2 EVERY 10 MIN

ALCULATIONS, WHILE NH3 WAS MONITORED

EVERY 10 OR 20 S)

𝑜𝑤𝑟𝑎𝑡𝑒(𝑠𝑐𝑐𝑚))/(24,000 (𝑠𝑐𝑐𝑚/𝑚𝑜𝑙)𝑥

𝑜𝑙/𝑚𝑜𝑙) 𝑥 (10000/8) (cm2/m2)

VERIFICATION