Editing A Dinuclear Cobalt Cryptate as a Homogeneous Photocatalyst for Highly Selective and Efficient Visible-Light Driven CO2 Reduction to CO in CH3CN-H2O Solution

{{#doiinfobox: 10.1002/ange.201610607}}
[[Category:Photocatalytic CO2 conversion to CO]]
{{BaseTemplate}}

=== Abstract ===

==== Summary ====
In this article CO<sub>2</sub> was reduced to CO by using the dinuclear cobalt catalyst {{#moleculelink:|link=PWANXUIOGIXQEQ-UHFFFAOYSA-J|image=false|width=300|height=200}} along with the photosensitizer {{#moleculelink:|link=YRYUXGTVQZIGNQ-UHFFFAOYSA-N|image=false|width=300|height=200}}. The photoreaction displayed a high TON of 16896 under 450 nm LED irradiation in 10 h. These good results are attributed to the synergetic effect of the two close cobalt atoms.

==== Advances and Special progress ====
This new catalyst displays high efficiency and a very good selectivity of 98% towards CO.

==== Additional remarks ====

=== Content of the published article in detail ===
This article emphasizes on the efficiency and selectivity of this new dinuclear complex as it is the first one with such good properties in photocatalysis, especially as it works in water containing conditions and shows good results also with only 10% CO<sub>2</sub> in atmosphere.

==== Catalyst ====
<chemform smiles="[Co+](O)123N4CC5=CC(CN6[Co+2]78N9CCN7(CC6)CCN8CC6C=CC=C(C=6)CN1CCN2(CCN3CC1C=C(C9)C=CC=1)CC4)=CC=C5.Cl([O-])(=O)(=O)=O.Cl([O-])(=O)(=O)=O.Cl([O-])(=O)(=O)=O" inchi="1S/C36H54N8.3ClHO4.2Co.H2O/c1-4-31-22-32(5-1)26-38-11-17-44-19-13-40-28-34-7-2-6-33(23-34)27-39-12-18-43(16-10-37-25-31)20-14-41-29-35-8-3-9-36(24-35)30-42-15-21-44;3*2-1(3,4)5;;;/h1-9,22-24,37-42H,10-21,25-30H2;3*(H,2,3,4,5);;;1H2/q;;;;2*+2;/p-4" inchikey="PWANXUIOGIXQEQ-UHFFFAOYSA-J" height="200px" width="300px" float="none">
  -INDIGO-07262317532D

  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 62 69 0 0 0
M  V30 BEGIN ATOM
M  V30 1 Co 5.825 -5.75 0.0 0 CHG=1
M  V30 2 N 4.825 -5.75 0.0 0
M  V30 3 C 4.325 -4.88397 0.0 0
M  V30 4 C 5.03211 -4.17687 0.0 0
M  V30 5 N 6.03211 -4.17687 0.0 0
M  V30 6 C 4.325 -6.61603 0.0 0
M  V30 7 C 4.825 -7.48205 0.0 0
M  V30 8 N 6.125 -7.45705 0.0 0
M  V30 9 C 3.95897 -6.25 0.0 0
M  V30 10 C 4.975 -6.75 0.0 0
M  V30 11 N 6.4 -6.725 0.0 0
M  V30 12 C 6.78395 -3.51752 0.0 0
M  V30 13 C 7.73088 -3.53896 0.0 0
M  V30 14 C 8.5946 -2.03965 0.0 0
M  V30 15 C 7.73049 -2.53825 0.0 0
M  V30 16 C 9.46178 -2.53954 0.0 0
M  V30 17 C 8.60152 -4.04085 0.0 0
M  V30 18 C 9.46436 -3.53523 0.0 0
M  V30 19 C 10.4644 -3.53523 0.0 0
M  V30 20 N 11.3304 -4.03523 0.0 0
M  V30 21 C 7.27264 -7.21336 0.0 0
M  V30 22 C 8.27264 -7.21336 0.0 0
M  V30 23 C 6.725 -8.39808 0.0 0
M  V30 24 C 7.875 -8.42308 0.0 0
M  V30 25 C 9.13637 -5.71405 0.0 0
M  V30 26 C 8.27226 -6.21264 0.0 0
M  V30 27 C 10.0035 -6.21394 0.0 0
M  V30 28 C 9.14329 -7.71525 0.0 0
M  V30 29 C 10.0061 -7.20962 0.0 0
M  V30 30 C 9.6053 -8.42143 0.0 0
M  V30 31 C 9.60597 -9.42237 0.0 0
M  V30 32 C 7.87567 -9.42802 0.0 0
M  V30 33 C 8.74498 -9.92245 0.0 0
M  V30 34 C 11.0061 -7.20962 0.0 0
M  V30 35 C 10.7053 -8.39643 0.0 0
M  V30 36 N 11.4053 -7.60541 0.0 0
M  V30 37 N 11.9632 -6.57752 0.0 0
M  V30 38 C 8.74145 -7.92239 0.0 0
M  V30 39 O 6.825 -5.75 0.0 0
M  V30 40 C 12.3304 -4.03523 0.0 0
M  V30 41 C 13.0375 -4.74233 0.0 0
M  V30 42 N 12.5375 -5.60836 0.0 0
M  V30 43 C 13.2375 -6.47438 0.0 0
M  V30 44 C 12.8537 -7.51531 0.0 0
M  V30 45 C 12.7132 -6.57752 0.0 0
M  V30 46 C 13.4203 -5.84541 0.0 0
M  V30 47 Co 11.5375 -5.60836 0.0 0 CHG=2
M  V30 48 Cl 15.242 -2.4 0.0 0
M  V30 49 O 16.108 -1.9 0.0 0
M  V30 50 O 14.376 -1.9 0.0 0
M  V30 51 O 15.242 -3.4 0.0 0
M  V30 52 O 16.108 -2.9 0.0 0 CHG=-1
M  V30 53 Cl 16.05 -5.25 0.0 0
M  V30 54 O 16.916 -4.75 0.0 0
M  V30 55 O 15.184 -4.75 0.0 0
M  V30 56 O 16.05 -6.25 0.0 0
M  V30 57 O 16.916 -5.75 0.0 0 CHG=-1
M  V30 58 Cl 15.525 -7.875 0.0 0
M  V30 59 O 16.391 -7.375 0.0 0
M  V30 60 O 14.659 -7.375 0.0 0
M  V30 61 O 15.525 -8.875 0.0 0
M  V30 62 O 16.391 -8.375 0.0 0 CHG=-1
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 10 1 2
M  V30 2 1 2 3
M  V30 3 1 3 4
M  V30 4 1 4 5
M  V30 5 1 2 6
M  V30 6 1 6 7
M  V30 7 1 7 8
M  V30 8 1 2 9
M  V30 9 1 9 10
M  V30 10 1 10 11
M  V30 11 10 5 1
M  V30 12 10 1 11
M  V30 13 10 1 8
M  V30 14 1 5 12
M  V30 15 1 12 13
M  V30 16 2 15 13
M  V30 17 2 16 14
M  V30 18 1 13 17
M  V30 19 1 14 15
M  V30 20 2 17 18
M  V30 21 1 18 16
M  V30 22 1 18 19
M  V30 23 1 19 20
M  V30 24 1 11 21
M  V30 25 1 21 22
M  V30 26 1 8 23
M  V30 27 1 23 24
M  V30 28 2 26 22
M  V30 29 2 27 25
M  V30 30 1 22 28
M  V30 31 1 25 26
M  V30 32 2 28 29
M  V30 33 1 29 27
M  V30 34 2 31 30
M  V30 35 1 24 32
M  V30 36 2 32 33
M  V30 37 1 33 31
M  V30 38 1 29 34
M  V30 39 1 30 35
M  V30 40 1 35 36
M  V30 41 1 34 37
M  V30 42 1 30 38
M  V30 43 2 38 24
M  V30 44 1 1 39
M  V30 45 1 20 40
M  V30 46 1 40 41
M  V30 47 1 41 42
M  V30 48 1 42 43
M  V30 49 1 43 44
M  V30 50 1 36 44
M  V30 51 1 37 45
M  V30 52 1 45 46
M  V30 53 1 46 42
M  V30 54 10 42 47
M  V30 55 10 20 47
M  V30 56 10 47 37
M  V30 57 10 47 36
M  V30 58 2 48 49
M  V30 59 2 48 50
M  V30 60 2 48 51
M  V30 61 1 48 52
M  V30 62 2 53 54
M  V30 63 2 53 55
M  V30 64 2 53 56
M  V30 65 1 53 57
M  V30 66 2 58 59
M  V30 67 2 58 60
M  V30 68 2 58 61
M  V30 69 1 58 62
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>

==== Photosensitizer ====
<chemform smiles="C1=CC=N2[Ru+2]3(N4=CC=CC5C=CC6=C(C=54)N3=CC=C6)3(N4=CC=CC5C=CC6=C(C=54)N3=CC=C6)N3=CC=CC4C=CC1=C2C=43.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F" inchi="1S/3C12H8N2.2F6P.Ru/c3*1-3-9-5-6-10-4-2-8-14-12(10)11(9)13-7-1;2*1-7(2,3,4,5)6;/h3*1-8H;;;/q;;;2*-1;+2" inchikey="YRYUXGTVQZIGNQ-UHFFFAOYSA-N" height="200px" width="300px" float="none">
  -INDIGO-07262318002D

  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 57 66 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 4.68485 -4.10007 0.0 0
M  V30 2 C 6.41515 -4.09959 0.0 0
M  V30 3 C 5.55164 -3.59997 0.0 0
M  V30 4 N 6.41515 -5.10053 0.0 0
M  V30 5 C 4.68485 -5.10502 0.0 0
M  V30 6 C 5.55382 -5.60003 0.0 0
M  V30 7 C 5.5532 -2.6054 0.0 0
M  V30 8 C 6.4177 -2.10702 0.0 0
M  V30 9 C 7.2831 -3.59922 0.0 0
M  V30 10 C 7.27797 -2.60224 0.0 0
M  V30 11 C 8.13649 -2.1014 0.0 0
M  V30 12 C 9.00281 -2.59531 0.0 0
M  V30 13 N 8.15289 -4.09511 0.0 0
M  V30 14 C 9.01012 -3.58727 0.0 0
M  V30 15 C 11.8953 -4.00653 0.0 0
M  V30 16 C 11.0287 -5.50858 0.0 0
M  V30 17 C 11.895 -5.00946 0.0 0
M  V30 18 N 10.1599 -5.007 0.0 0
M  V30 19 C 11.0231 -3.50294 0.0 0
M  V30 20 C 10.158 -4.00911 0.0 0
M  V30 21 C 12.7575 -5.50921 0.0 0
M  V30 22 C 12.7568 -6.50928 0.0 0
M  V30 23 C 11.028 -6.51265 0.0 0
M  V30 24 C 11.8959 -7.0078 0.0 0
M  V30 25 C 11.9004 -8.00392 0.0 0
M  V30 26 C 11.0376 -8.50834 0.0 0
M  V30 27 N 10.1618 -7.01909 0.0 0
M  V30 28 C 10.173 -8.01759 0.0 0
M  V30 29 C 8.20163 -10.1467 0.0 0
M  V30 30 C 7.33414 -8.64517 0.0 0
M  V30 31 C 7.33321 -9.64502 0.0 0
M  V30 32 N 8.20291 -8.14359 0.0 0
M  V30 33 C 9.07387 -9.64315 0.0 0
M  V30 34 C 9.06806 -8.64087 0.0 0
M  V30 35 C 6.4692 -10.142 0.0 0
M  V30 36 C 5.60343 -9.64145 0.0 0
M  V30 37 C 6.46491 -8.14258 0.0 0
M  V30 38 C 5.60216 -8.64663 0.0 0
M  V30 39 C 4.73725 -8.15245 0.0 0
M  V30 40 C 4.73181 -7.15303 0.0 0
M  V30 41 N 6.45946 -7.13916 0.0 0
M  V30 42 C 5.58912 -6.64962 0.0 0
M  V30 43 Ru 8.15618 -6.05053 0.0 0 CHG=2
M  V30 44 P 15.092 -3.15 0.0 0 CHG=-1
M  V30 45 F 15.958 -2.65 0.0 0
M  V30 46 F 14.226 -2.65 0.0 0
M  V30 47 F 15.092 -4.15 0.0 0
M  V30 48 F 15.958 -3.65 0.0 0
M  V30 49 F 15.092 -2.15 0.0 0
M  V30 50 F 14.226 -3.65 0.0 0
M  V30 51 P 15.65 -6.15 0.0 0 CHG=-1
M  V30 52 F 16.516 -5.65 0.0 0
M  V30 53 F 14.784 -5.65 0.0 0
M  V30 54 F 15.65 -7.15 0.0 0
M  V30 55 F 16.516 -6.65 0.0 0
M  V30 56 F 15.65 -5.15 0.0 0
M  V30 57 F 14.784 -6.65 0.0 0
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 1 3 1
M  V30 2 1 4 2
M  V30 3 2 1 5
M  V30 4 2 2 3
M  V30 5 1 5 6
M  V30 6 2 6 4
M  V30 7 2 8 7
M  V30 8 1 2 9
M  V30 9 1 7 3
M  V30 10 2 9 10
M  V30 11 1 10 8
M  V30 12 2 12 11
M  V30 13 1 9 13
M  V30 14 1 11 10
M  V30 15 2 13 14
M  V30 16 1 14 12
M  V30 17 1 17 15
M  V30 18 1 18 16
M  V30 19 2 15 19
M  V30 20 2 16 17
M  V30 21 1 19 20
M  V30 22 2 20 18
M  V30 23 2 22 21
M  V30 24 1 16 23
M  V30 25 1 21 17
M  V30 26 2 23 24
M  V30 27 1 24 22
M  V30 28 2 26 25
M  V30 29 1 23 27
M  V30 30 1 25 24
M  V30 31 2 27 28
M  V30 32 1 28 26
M  V30 33 1 31 29
M  V30 34 1 32 30
M  V30 35 2 29 33
M  V30 36 2 30 31
M  V30 37 1 33 34
M  V30 38 2 34 32
M  V30 39 2 36 35
M  V30 40 1 30 37
M  V30 41 1 35 31
M  V30 42 2 37 38
M  V30 43 1 38 36
M  V30 44 2 40 39
M  V30 45 1 37 41
M  V30 46 1 39 38
M  V30 47 2 41 42
M  V30 48 1 42 40
M  V30 49 10 4 43
M  V30 50 10 43 13
M  V30 51 10 43 18
M  V30 52 10 43 27
M  V30 53 10 43 32
M  V30 54 10 43 41
M  V30 55 1 44 45
M  V30 56 1 44 46
M  V30 57 1 44 47
M  V30 58 1 44 48
M  V30 59 1 44 49
M  V30 60 1 44 50
M  V30 61 1 51 52
M  V30 62 1 51 53
M  V30 63 1 51 54
M  V30 64 1 51 55
M  V30 65 1 51 56
M  V30 66 1 51 57
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>

==== Investigation ====
{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Best result and control experiments}}

==== Sacrificial electron donor ====
In this study, the experiments were done with the sacrificial electron donor TEOA {{#moleculelink:|link=GSEJCLTVZPLZKY-UHFFFAOYSA-N|image=false|width=300|height=200}}.