Editing Visible light driven reduction of CO2 catalyzed by an abundant manganese catalyst with zinc porphyrin photosensitizer

{{#doiinfobox: 10.1016/j.apcata.2016.04.035}}
[[Category:Photocatalytic CO2 conversion to CO]]
[[Category:Photocatalytic CO2 conversion to HCOOH]]
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=== Abstract ===

==== Summary ====
A photochemical reduction of CO<sub>2</sub> was shown using the manganese catalyst {{#moleculelink:|link=ZUZWBGQHMPVNDY-UHFFFAOYSA-M|image=false|width=300|height=200}} and the zinc photosensitizer {{#moleculelink:|link=XPVVGUHKLPZAEN-DAJBKUBHSA-N|image=false|width=300|height=200}}. Turnover numbers (TONs) of 64 and 16 were reached after 180 min of irradiation for CO and formic acid, respectively. The experiments were performed using a Xenon lamp as the light source.

==== Advances and special progress ====
Photochemical CO<sub>2</sub> conversion in an environmentally friendly and sustainable photocatalytic system using earth abundant metal complexes efficiently yielded CO and HCOOH in aqueous acetonitrile solution. 

==== Additional remarks ====
The manganese catalyst and the zinc photosensitizer were used in different ratios, resulting in different TONs for CO and HCOOH production.

=== Content of the published article in detail ===
The article contains results for the reduction of CO<sub>2</sub> to CO and HCOOH using different ratios of the catalyst and photosensitizer. The catalytic system performed best for the catalyst:photosensitizer ratio of 4:1. 

==== Catalyst====
<chemform smiles="C1C=C2C3C=CC=CN=3[Mn+]([Br-])([C-]#[O+])([C-]#[O+])([C-]#[O+])N2=CC=1" inchi="1S/C10H8N2.3CO.BrH.Mn/c1-3-7-11-9(5-1)10-6-2-4-8-12-10;3*1-2;;/h1-8H;;;;1H;/q;;;;;+1/p-1" inchikey="ZUZWBGQHMPVNDY-UHFFFAOYSA-M" height="200px" width="300px" float="none">
  -INDIGO-05172311492D

  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 20 22 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 5.25985 -3.0 0.0 0
M  V30 2 C 6.99015 -2.99959 0.0 0
M  V30 3 C 6.12664 -2.49997 0.0 0
M  V30 4 N 6.99015 -4.00053 0.0 0
M  V30 5 C 5.25985 -4.00502 0.0 0
M  V30 6 C 6.12882 -4.50003 0.0 0
M  V30 7 C 6.12882 -5.50003 0.0 0
M  V30 8 C 6.9954 -6.99769 0.0 0
M  V30 9 N 6.99566 -6.0 0.0 0
M  V30 10 C 6.12889 -7.49875 0.0 0
M  V30 11 C 5.25885 -6.00309 0.0 0
M  V30 12 C 5.26531 -7.00314 0.0 0
M  V30 13 Mn 7.8 -5.075 0.0 0 CHG=1
M  V30 14 C 7.8 -6.075 0.0 0 CHG=-1
M  V30 15 C 8.66603 -5.575 0.0 0 CHG=-1
M  V30 16 C 8.50711 -4.36789 0.0 0 CHG=-1
M  V30 17 Br 7.8 -4.075 0.0 0 CHG=-1
M  V30 18 O 7.8 -7.075 0.0 0 CHG=1
M  V30 19 O 9.53205 -6.075 0.0 0 CHG=1
M  V30 20 O 9.21421 -3.66079 0.0 0 CHG=1
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 2 3 1
M  V30 2 2 4 2
M  V30 3 1 1 5
M  V30 4 1 2 3
M  V30 5 2 5 6
M  V30 6 1 6 4
M  V30 7 1 6 7
M  V30 8 2 9 7
M  V30 9 2 10 8
M  V30 10 1 7 11
M  V30 11 1 8 9
M  V30 12 2 11 12
M  V30 13 1 12 10
M  V30 14 10 4 13
M  V30 15 10 9 13
M  V30 16 10 13 14
M  V30 17 10 13 15
M  V30 18 10 13 16
M  V30 19 10 13 17
M  V30 20 3 14 18
M  V30 21 3 15 19
M  V30 22 3 16 20
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>

====Photosensitizer ====
<chemform smiles="C1=C2/C(/C3C=CC=CC=3)=C3\N=C(/C(/C4C=CC=CC=4)=C4\[N-]/C(=C(/C5C=CC=CC=5)\C5=N/C(=C(/C6C=CC=CC=6)\C(=C1)[N-]2)/C=C5)/C=C\4)C=C\3.[Zn+2]" inchikey="XPVVGUHKLPZAEN-DAJBKUBHSA-N" inchi="1S/C44H28N4.Zn/c1-5-13-29(14-6-1)41-33-21-23-35(45-33)42(30-15-7-2-8-16-30)37-25-27-39(47-37)44(32-19-11-4-12-20-32)40-28-26-38(48-40)43(31-17-9-3-10-18-31)36-24-22-34(41)46-36;/h1-28H;/q-2;+2/b41-33-,41-34-,42-35-,42-37-,43-36-,43-38-,44-39-,44-40-;" float="none" width="200" height="200">
  -INDIGO-11302313082D

  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 49 56 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 4.26444 -2.19264 0.0 0
M  V30 2 N 4.95066 -3.60797 0.0 0 CHG=-1
M  V30 3 C 5.13521 -2.6936 0.0 0
M  V30 4 C 3.97264 -3.70955 0.0 0
M  V30 5 C 3.534 -2.85356 0.0 0
M  V30 6 C 8.00662 -2.02009 0.0 0
M  V30 7 C 8.51658 -3.52705 0.0 0
M  V30 8 C 8.82814 -2.59525 0.0 0
M  V30 9 N 7.4976 -3.55292 0.0 0
M  V30 10 C 7.19098 -2.61274 0.0 0
M  V30 11 N 5.15903 -5.24596 0.0 0
M  V30 12 C 4.67909 -6.74346 0.0 0
M  V30 13 C 5.47557 -6.15555 0.0 0
M  V30 14 C 3.86667 -6.18575 0.0 0
M  V30 15 C 4.14196 -5.291 0.0 0
M  V30 16 N 7.74715 -5.30724 0.0 0 CHG=-1
M  V30 17 C 9.09989 -6.11388 0.0 0
M  V30 18 C 8.67727 -5.20374 0.0 0
M  V30 19 C 8.35684 -6.73786 0.0 0
M  V30 20 C 7.47905 -6.1624 0.0 0
M  V30 21 C 3.54011 -4.53811 0.0 0
M  V30 22 C 6.51552 -6.63012 0.0 0
M  V30 23 C 9.15199 -4.36492 0.0 0
M  V30 24 C 6.13275 -2.19316 0.0 0
M  V30 25 C 6.51552 -7.63012 0.0 0
M  V30 26 C 7.38209 -9.12778 0.0 0
M  V30 27 C 7.38235 -8.13015 0.0 0
M  V30 28 C 6.51559 -9.62883 0.0 0
M  V30 29 C 5.64555 -8.13318 0.0 0
M  V30 30 C 5.65201 -9.13323 0.0 0
M  V30 31 C 2.54011 -4.53811 0.0 0
M  V30 32 C 1.04245 -5.40469 0.0 0
M  V30 33 C 2.04009 -5.40495 0.0 0
M  V30 34 C 0.541399 -4.53818 0.0 0
M  V30 35 C 2.03706 -3.66814 0.0 0
M  V30 36 C 1.037 -3.67461 0.0 0
M  V30 37 C 10.152 -4.36492 0.0 0
M  V30 38 C 11.6496 -3.49834 0.0 0
M  V30 39 C 10.652 -3.49808 0.0 0
M  V30 40 C 12.1507 -4.36485 0.0 0
M  V30 41 C 10.655 -5.23489 0.0 0
M  V30 42 C 11.6551 -5.22843 0.0 0
M  V30 43 C 6.13275 -1.19316 0.0 0
M  V30 44 C 5.26618 0.304505 0.0 0
M  V30 45 C 5.26592 -0.693131 0.0 0
M  V30 46 C 6.13268 0.805557 0.0 0
M  V30 47 C 7.00272 -0.690101 0.0 0
M  V30 48 C 6.99626 0.309953 0.0 0
M  V30 49 Zn 6.4 -4.425 0.0 0 CHG=2
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 1 1 5
M  V30 2 1 2 3
M  V30 3 2 3 1
M  V30 4 1 4 2
M  V30 5 2 5 4
M  V30 6 1 6 10
M  V30 7 1 7 8
M  V30 8 2 8 6
M  V30 9 2 9 7
M  V30 10 1 10 9
M  V30 11 1 11 15
M  V30 12 1 12 13
M  V30 13 2 13 11
M  V30 14 2 14 12
M  V30 15 1 15 14
M  V30 16 1 16 20
M  V30 17 1 17 18
M  V30 18 1 18 16
M  V30 19 2 19 17
M  V30 20 1 20 19
M  V30 21 1 4 21
M  V30 22 2 21 15
M  V30 23 1 13 22
M  V30 24 2 22 20
M  V30 25 2 18 23
M  V30 26 1 23 7
M  V30 27 2 10 24
M  V30 28 1 24 3
M  V30 29 1 22 25
M  V30 30 2 27 25
M  V30 31 2 28 26
M  V30 32 1 25 29
M  V30 33 1 26 27
M  V30 34 2 29 30
M  V30 35 1 30 28
M  V30 36 1 21 31
M  V30 37 2 33 31
M  V30 38 2 34 32
M  V30 39 1 31 35
M  V30 40 1 32 33
M  V30 41 2 35 36
M  V30 42 1 36 34
M  V30 43 1 23 37
M  V30 44 2 39 37
M  V30 45 2 40 38
M  V30 46 1 37 41
M  V30 47 1 38 39
M  V30 48 2 41 42
M  V30 49 1 42 40
M  V30 50 1 24 43
M  V30 51 2 45 43
M  V30 52 2 46 44
M  V30 53 1 43 47
M  V30 54 1 44 45
M  V30 55 2 47 48
M  V30 56 1 48 46
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>

====Investigation====
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}

==== Sacrificial electron donor ====
In this study, triethylamine ({{#moleculelink:|link=ZMANZCXQSJIPKH-UHFFFAOYSA-N|image=false|width=300|height=200}}) was used as sacrificial electron donor. 

==== Additives ====
In this study, no additives were used.