Table 2: Summary of Control Experiments for Photocatalysis.

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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 [mL] intensity [kW/m²] pH T [°C] λexc [nm] t [h] TON CO TOF CO [TOF/min] Φ CO [%] TON CH4 TOF CH4 [TOF/min] Φ CH4 [%] TON H2 TOF H2 [TOF/min] Φ H2 [%] TON HCOOH TOF HCOOH [TOF/min] Φ HCOOH [%] TON MeOH TOF MeOH [TOF/min] Φ MeOH [%] selectivity [%] [CO;CH4;H2;HCOOH;MeOH] Φ all [%] Details include

Mn(CN)(bpy)(CO)3

0.5

Molecule:100694

BNAH

0.1


DMF

TEOA


4:1 470 15 2.1 0.0025 1.9 0.0022 52.5%; 0%; 0%; 47.5%; 0%

0.0047

Yes

Mn(CN)(bpy)(CO)3

Molecule:100694

0.5

BNAH

0.1


DMF

TEOA


4:1 470 15 1.5 0.0018 2.8 5.7 0.0069 15.0%; 0%; 28.0%; 57.0%; 0%

0.0087

Yes

Mn(CN)(bpy)(CO)3

0.5

Molecule:100694

0.5

BNAH

0.1


DMF



470 15 5.8 0.0082 0.26 95.7%; 0%; 4.3%; 0%; 0%

0.0082

Yes

Mn(CN)(bpy)(CO)3

0.5

Molecule:100694

0.5

BNAH

0.1


DMF

TEOA


4:1 Argon gas 470 0 2.6 n/a


Yes

Mn(CN)(bpy)(CO)3

0.5

Molecule:100694

0.5

BNAH

0.1


DMF

TEOA


4:1 Argon gas 470 15 1.5 0.0018 7.8 3.8 0.0047 11.5%; 0%; 59.5%; 29.0%; 0%

0.0065

Yes

Mn(CN)(bpy)(CO)3

Molecule:100694

0.5

BNAH

0.1


DMF

TEOA


4:1 Argon gas 470 15 0.87 0.0011 1.3 3.2 0.0040 16.2%; 0%; 24.2%; 59.6%; 0%

0.0051

Yes

Mn(CN)(bpy)(CO)3

0.5

Molecule:100694

BNAH

0.1


DMF

TEOA


4:1 Argon gas 470 15 2.3 0.0030 2.2 0.0030 51.1%; 0%; 0%; 48.9%; 0%

0.006

Yes

Mn(CN)(bpy)(CO)3

0.5

Molecule:100694

0.5

BNAH

0.1


DMF



Argon gas 470 15 2.4 0.0021 1.4 63.2%; 0%; 36.8%; 0%; 0%

0.0021

Yes

Mn(CN)(bpy)(CO)3

0.5

Molecule:100694

BNAH

0.1


DMF

TEOA


4:1 470 15 2 0.0024 n/a

0.0024

Yes

Mn(CN)(bpy)(CO)3

Molecule:100694

0.5

BNAH

0.1


DMF

TEOA


4:1 470 15 0.60 0.00078 1.2 0.72 0.00093 23.8%; 0%; 47.6%; 28.6%; 0%

0.00171

Yes

Mn(CN)(bpy)(CO)3

0.5

Molecule:100694

0.5

BNAH

0.1


DMF



470 15 2.2 0.00025 n/a

0.00025

Yes

Mn(CN)(bpy)(CO)3

0.5

Molecule:100694

0.5

BNAH

0.1


DMF

TEOA


4:1 Argon gas 470 15 2.2 0.0026 4.4 0.55 0.00066 30.8%; 0%; 61.5%; 7.7%; 0%

0.00326

Yes

Mn(CN)(bpy)(CO)3

0.5

Molecule:100694

0.5

BNAH

0.1


DMF



Argon gas 470 15 2.4 0.0021 1.4 63.2%; 0%; 36.8%; 0%; 0%

0.0021

Yes