Optimizations of conditions for Co(qpy)(H2O)2(ClO4)2 and Ru(bpy)3Cl2

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< Highly Efficient and Selective Photocatalytic CO2 Reduction by Iron and Cobalt Quaterpyridine Complexes
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investigation
Molecular process, Photocatalytic CO2 conversion experiments
cat cat conc [µM] PS PS conc [mM] e-D e-D conc [M] H-D H-D conc [M] solvent A solvent B solvent C solv A/B/C additives additives conc [M] feedstock gas feedstock volume intensity pH T [°C] λexc [nm] t [h] TON CO TOF CO Φ CO [%] TON CH4 TOF CH4 Φ CH4 [%] TON H2 TOF H2 Φ H2 [%] TON HCOOH TOF HCOOH Φ HCOOH [%] TON MeOH TOF MeOH Φ MeOH [%] selectivity [%] [CO;CH4;H2;HCOOH;MeOH] Φ all [%] Details include

[Co(qpy)(H2O)2][ClO4]2

0.005

Ru(bpy)3Cl2

0.3

BIH

0.1

TEOA

0.5

MeCN



460 (LED) 1.33 2660 98 23 1 35 1 97.9%; 0%; 0.8%; 1.3%; 0%

100

Yes

[Co(qpy)(H2O)2][ClO4]2

0

Ru(bpy)3Cl2

0.3

BIH

0.1

TEOA

0.5

MeCN



460 (LED) 1.33 0 0 2 67 1 33 0%; 0%; 66.7%; 33.3%; 0%

100

Yes

[Co(qpy)(H2O)2][ClO4]2

0.005

Ru(bpy)3Cl2

0.3

BIH

0.1

TEOA

0.5

MeCN



Argon atmosphere 460 (LED) 1.33 0 0 33 100 0 0 n/a

100

Yes

[Co(qpy)(H2O)2][ClO4]2

0.005

Ru(bpy)3Cl2

0.3

BIH

0.1


MeCN



460 (LED) 1.33 182 94 0 0 11 6 94.3%; 0%; 0%; 5.7%; 0%

100

Yes

[Co(qpy)(H2O)2][ClO4]2

0.005

Ru(bpy)3Cl2

0.3


TEOA

0.5

MeCN



460 (LED) 1.33 114 70 25 15 25 15 69.5%; 0%; 15.2%; 15.2%; 0%

100

Yes

[Co(qpy)(H2O)2][ClO4]2

0.01

Ru(bpy)3Cl2

0.3

BIH

0.1

TEOA

0.5

MeCN



460 (LED) 1.33 1875 98 11 1 18 1 98.5%; 0%; 0.6%; 0.9%; 0%

100

Yes

[Co(qpy)(H2O)2][ClO4]2

0.2

Ru(bpy)3Cl2

0.3

BIH

0.1

TEOA

0.5

MeCN



460 (LED) 1.33 1262 98 7 0 23 2 97.7%; 0%; 0.5%; 1.8%; 0%

100

Yes

[Co(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.3

BIH

0.1

TEOA

0.5

MeCN



460 (LED) 1.33 497 98 5 1 3 1 98.4%; 0%; 1.0%; 0.6%; 0%

100

Yes

[Co(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.3


TEOA

0.5

MeCN



460 (LED) 1.33 0 0 1 50 1 50 0%; 0%; 50.0%; 50.0%; 0%

100

Yes

[Co(qpy)(H2O)2][ClO4]2

0.1

Ru(bpy)3Cl2

0.3

BIH

0.1

TEOA

0.5

MeCN



460 (LED) 1.33 466 95 2 0 22 5 95.1%; 0%; 0.4%; 4.5%; 0%

100

Yes

[Co(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.5

BIH

0.1

TEOA

0.5

MeCN



460 (LED) 1.33 521 90 49 9 6 1 90.5%; 0%; 8.5%; 1.0%; 0%

100

Yes

[Co(qpy)(H2O)2][ClO4]2

0

Ru(bpy)3Cl2

0.5

BIH

0.1

TEOA

0.5

MeCN



460 (LED) 1.33 136 74 43 23 5 3 73.9%; 0%; 23.4%; 2.7%; 0%

100

Yes

[Co(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.2

BIH

0.1

TEOA

0.5

MeCN



460 (LED) 1.33 366 95 15 4 4 1 95.1%; 0%; 3.9%; 1.0%; 0%

100

Yes

[Co(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.2

BIH

0.1

TEOA

0.5

MeCN



Argon atmosphere 460 (LED) 1.33 0 0 3 75 1 25 0%; 0%; 75.0%; 25.0%; 0%

100

Yes

[Co(qpy)(H2O)2][ClO4]2

0

Ru(bpy)3Cl2

0.2

BIH

0.1

TEOA

0.5

MeCN



460 (LED) 1.33 0 0 6 86 1 14 0%; 0%; 85.7%; 14.3%; 0%

100

Yes

Co(ClO4)2

0.05

Ru(bpy)3Cl2

0.3

BIH

0.1

TEOA

0.5

MeCN



460 (LED) 1.33 33 65 11 21 1 14 73.3%; 0%; 24.4%; 2.2%; 0%

100

Yes

[Co(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.3


TEOA

0.5

MeCN



460 (LED) 1.33 0 0 1 50 1 50 0%; 0%; 50.0%; 50.0%; 0%

100

Yes