Exploring the Full Potential of Photocatalytic Carbon Dioxide Reduction Using a Dinuclear Re2Cl2 Complex Assisted by Various Photosensitizers: Difference between revisions
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[[Category:Photocatalytic CO2 conversion to CO]] | [[Category:Photocatalytic CO2 conversion to CO]] | ||
{{ | {{DOI|doi=10.1002/cptc.202100034}} | ||
===Abstract=== | |||
=== | ==== Summary ==== | ||
{{#moleculelink:|link= | A photochemical reduction of CO<sub>2</sub> to CO was shown using the dirhenium complex {{#moleculelink:|link=RNNNRBGABJVOGO-UHFFFAOYSA-L|image=false|width=300|height=200}} in combination with the ruthenium and copper photosensitizers {{#moleculelink:|link=GJHHESUUYZNNGV-UHFFFAOYSA-N|image=false|width=300|height=200}} and {{#moleculelink:|link=RLYPDFWLVSLBDF-UHFFFAOYSA-N|image=false|width=300|height=200}}. Turnover numbers (TONs) of up to 270 were reached after 4 h of irradiation (λ > 400 nm) in DMF. | ||
=== | ==== Advances and special progress ==== | ||
<chemform smiles=" | One of very few studies where a dinuclear catalytic system able to activate CO<sub>2</sub> is used in combination with photosensitizers. | ||
-INDIGO- | |||
==== Additional remarks ==== | |||
The experiments were performed using the rhenium complex (50 μM in DMF) as the catalyst in combination with different loadings of the sensitizers and sacrificial electron donors under 4 h of irradiation with λ > 400 nm. | |||
===Content of the published article in detail=== | |||
The article contains results of a detailed study on the influence of additional photosensitizers on the catalytic performance of the dinuclear rhenium catalyst {{#moleculelink:|link=RNNNRBGABJVOGO-UHFFFAOYSA-L|image=false|width=300|height=200}} for the reduction of CO<sub>2</sub> to CO. The catalytic system performs best (referring to the TON of CO production) for the combination of the above mentioned catalyst with the iridium complex {{#moleculelink:|link=GJHHESUUYZNNGV-UHFFFAOYSA-N|image=false|width=300|height=200}} as the photosensitizer in the presence of BIH/TEA as sacrificial electron donors. | |||
==== Catalyst ==== | |||
<chemform smiles="C(C)(C)1C2C=C(C(C)(C)C)C=C(C3C=N4[Re+]([C-]#[O+])([C-]#[O+])([Cl-])([C-]#[O+])N5=CC=CC=C5C4=CC=3)C=2OC2C(C3C=CC4C5C=CC=CN=5[Re+]([C-]#[O+])([C-]#[O+])([C-]#[O+])([Cl-])N=4C=3)=CC(C(C)(C)C)=CC1=2" inchi="1S/C43H42N4O.6CO.2ClH.2Re/c1-41(2,3)29-21-31(27-15-17-37(46-25-27)35-13-9-11-19-44-35)39-33(23-29)43(7,8)34-24-30(42(4,5)6)22-32(40(34)48-39)28-16-18-38(47-26-28)36-14-10-12-20-45-36;6*1-2;;;;/h9-26H,1-8H3;;;;;;;2*1H;;/q;;;;;;;;;2*+1/p-2" inchikey="RNNNRBGABJVOGO-UHFFFAOYSA-L" height="200px" width="300px" float="none"> | |||
-INDIGO-01112411252D | |||
0 0 0 0 0 0 0 0 0 0 0 V3000 | |||
M V30 BEGIN CTAB | |||
M V30 COUNTS 64 72 0 0 0 | |||
M V30 BEGIN ATOM | |||
M V30 1 C 2.55001 -5.94999 0.0 0 | |||
M V30 2 C 3.05001 -6.81603 0.0 0 | |||
M V30 3 C 4.05001 -6.81604 0.0 0 | |||
M V30 4 O 4.54999 -5.95001 0.0 0 | |||
M V30 5 C 4.04999 -5.08397 0.0 0 | |||
M V30 6 C 3.04999 -5.08396 0.0 0 | |||
M V30 7 C 2.5521 -4.22028 0.0 0 | |||
M V30 8 C 3.05197 -3.35393 0.0 0 | |||
M V30 9 C 4.55186 -4.21416 0.0 0 | |||
M V30 10 C 4.04694 -3.35174 0.0 0 | |||
M V30 11 C 4.5479 -7.67972 0.0 0 | |||
M V30 12 C 4.04803 -8.54607 0.0 0 | |||
M V30 13 C 2.54814 -7.68584 0.0 0 | |||
M V30 14 C 3.05306 -8.54826 0.0 0 | |||
M V30 15 C 1.68398 -5.44999 0.0 0 | |||
M V30 16 C 1.68398 -6.44999 0.0 0 | |||
M V30 17 C 5.55185 -4.21098 0.0 0 | |||
M V30 18 C 5.5479 -7.67991 0.0 0 | |||
M V30 19 C 2.5509 -2.48852 0.0 0 | |||
M V30 20 C 3.04983 -1.62188 0.0 0 | |||
M V30 21 C 1.5509 -2.48976 0.0 0 | |||
M V30 22 C 2.0509 -1.62249 0.0 0 | |||
M V30 23 C 2.55665 -9.41635 0.0 0 | |||
M V30 24 C 1.55665 -9.42048 0.0 0 | |||
M V30 25 C 3.06022 -10.2803 0.0 0 | |||
M V30 26 C 2.05665 -10.2824 0.0 0 | |||
M V30 27 N 7.04951 -3.34441 0.0 0 | |||
M V30 28 C 6.05188 -3.34415 0.0 0 | |||
M V30 29 C 7.55057 -4.21092 0.0 0 | |||
M V30 30 C 6.05491 -5.08096 0.0 0 | |||
M V30 31 C 7.05496 -5.07449 0.0 0 | |||
M V30 32 C 8.55056 -4.20928 0.0 0 | |||
M V30 33 C 10.0468 -3.34026 0.0 0 | |||
M V30 34 N 9.04917 -3.34163 0.0 0 | |||
M V30 35 C 10.5493 -4.20595 0.0 0 | |||
M V30 36 C 9.05504 -5.07843 0.0 0 | |||
M V30 37 C 10.0551 -5.07034 0.0 0 | |||
M V30 38 C 7.04556 -6.81333 0.0 0 | |||
M V30 39 C 6.04792 -6.81307 0.0 0 | |||
M V30 40 C 7.54661 -7.67984 0.0 0 | |||
M V30 41 C 6.05096 -8.54988 0.0 0 | |||
M V30 42 N 7.05101 -8.54342 0.0 0 | |||
M V30 43 C 8.54661 -7.67821 0.0 0 | |||
M V30 44 C 10.0429 -6.80919 0.0 0 | |||
M V30 45 C 9.04522 -6.81056 0.0 0 | |||
M V30 46 C 10.5453 -7.67488 0.0 0 | |||
M V30 47 N 9.05109 -8.54736 0.0 0 | |||
M V30 48 C 10.0511 -8.53926 0.0 0 | |||
M V30 49 Re 8.00662 -2.4123 0.0 0 CHG=1 | |||
M V30 50 Re 8.02601 -9.43444 0.0 0 CHG=1 | |||
M V30 51 Cl 6.48162 -2.4373 0.0 0 CHG=-1 | |||
M V30 52 C 9.40662 -2.3873 0.0 0 CHG=-1 | |||
M V30 53 C 6.97451 -1.3802 0.0 0 CHG=-1 | |||
M V30 54 C 9.06373 -1.3552 0.0 0 CHG=-1 | |||
M V30 55 C 9.72601 -9.43444 0.0 0 CHG=-1 | |||
M V30 56 Cl 6.55101 -9.45944 0.0 0 CHG=-1 | |||
M V30 57 C 6.8939 -10.6666 0.0 0 CHG=-1 | |||
M V30 58 C 9.03312 -10.5666 0.0 0 CHG=-1 | |||
M V30 59 O 6.26741 -0.673089 0.0 0 CHG=1 | |||
M V30 60 O 9.77083 -0.648089 0.0 0 CHG=1 | |||
M V30 61 O 10.4066 -2.3873 0.0 0 CHG=1 | |||
M V30 62 O 6.1868 -11.3737 0.0 0 CHG=1 | |||
M V30 63 O 9.74022 -11.2737 0.0 0 CHG=1 | |||
M V30 64 O 10.726 -9.43444 0.0 0 CHG=1 | |||
M V30 END ATOM | |||
M V30 BEGIN BOND | |||
M V30 1 1 1 6 | |||
M V30 2 1 1 2 | |||
M V30 3 2 2 3 | |||
M V30 4 1 3 4 | |||
M V30 5 1 4 5 | |||
M V30 6 2 5 6 | |||
M V30 7 2 8 7 | |||
M V30 8 1 5 9 | |||
M V30 9 1 7 6 | |||
M V30 10 2 9 10 | |||
M V30 11 1 10 8 | |||
M V30 12 2 12 11 | |||
M V30 13 1 2 13 | |||
M V30 14 1 11 3 | |||
M V30 15 2 13 14 | |||
M V30 16 1 14 12 | |||
M V30 17 1 1 15 | |||
M V30 18 1 1 16 | |||
M V30 19 1 9 17 | |||
M V30 20 1 11 18 | |||
M V30 21 1 8 19 | |||
M V30 22 1 19 20 | |||
M V30 23 1 19 21 | |||
M V30 24 1 19 22 | |||
M V30 25 1 14 23 | |||
M V30 26 1 23 24 | |||
M V30 27 1 23 25 | |||
M V30 28 1 23 26 | |||
M V30 29 2 28 17 | |||
M V30 30 2 29 27 | |||
M V30 31 1 17 30 | |||
M V30 32 1 27 28 | |||
M V30 33 2 30 31 | |||
M V30 34 1 31 29 | |||
M V30 35 1 29 32 | |||
M V30 36 2 34 32 | |||
M V30 37 2 35 33 | |||
M V30 38 1 32 36 | |||
M V30 39 1 33 34 | |||
M V30 40 2 36 37 | |||
M V30 41 1 37 35 | |||
M V30 42 2 39 18 | |||
M V30 43 2 40 38 | |||
M V30 44 1 18 41 | |||
M V30 45 1 38 39 | |||
M V30 46 2 41 42 | |||
M V30 47 1 42 40 | |||
M V30 48 1 40 43 | |||
M V30 49 2 45 43 | |||
M V30 50 2 46 44 | |||
M V30 51 1 43 47 | |||
M V30 52 1 44 45 | |||
M V30 53 2 47 48 | |||
M V30 54 1 48 46 | |||
M V30 55 10 27 49 | |||
M V30 56 10 49 34 | |||
M V30 57 10 42 50 | |||
M V30 58 10 50 47 | |||
M V30 59 10 49 51 | |||
M V30 60 10 49 52 | |||
M V30 61 10 49 53 | |||
M V30 62 10 49 54 | |||
M V30 63 10 50 55 | |||
M V30 64 10 50 56 | |||
M V30 65 10 50 57 | |||
M V30 66 10 50 58 | |||
M V30 67 3 53 59 | |||
M V30 68 3 54 60 | |||
M V30 69 3 52 61 | |||
M V30 70 3 57 62 | |||
M V30 71 3 58 63 | |||
M V30 72 3 55 64 | |||
M V30 END BOND | |||
M V30 END CTAB | |||
M END | |||
</chemform> | |||
==== Photosensitizer ==== | |||
<chemform smiles="C(F)1C2C3C=CC=CN=3[Ir+3]3(N4C=CC=CC=4C4=[C-]3C=C(F)C=C4F)3(N4C=CC=CC=4C4=[C-]3C=C(F)C=C4F)[C-]=2C=C(F)C=1" inchi="1S/3C11H6F2N.Ir/c3*12-8-4-5-9(10(13)7-8)11-3-1-2-6-14-11;/h3*1-4,6-7H;/q3*-1;+3" inchikey="GJHHESUUYZNNGV-UHFFFAOYSA-N" height="200px" width="300px" float="none"> | |||
-INDIGO-11272314332D | |||
0 0 0 0 0 0 0 0 0 0 0 V3000 | 0 0 0 0 0 0 0 0 0 0 0 V3000 | ||
Line 14: | Line 175: | ||
M V30 COUNTS 43 51 0 0 0 | M V30 COUNTS 43 51 0 0 0 | ||
M V30 BEGIN ATOM | M V30 BEGIN ATOM | ||
M V30 1 C | M V30 1 C 6.33485 -0.200074 0.0 0 | ||
M V30 2 C | M V30 2 C 8.06515 -0.199589 0.0 0 | ||
M V30 3 C | M V30 3 C 7.20164 0.300033 0.0 0 | ||
M V30 4 C | M V30 4 C 8.06515 -1.20053 0.0 0 | ||
M V30 5 C | M V30 5 C 6.33485 -1.20502 0.0 0 | ||
M V30 6 C | M V30 6 C 7.20382 -1.70003 0.0 0 CHG=-1 | ||
M V30 7 C | M V30 7 C 5.46882 -1.70502 0.0 0 | ||
M V30 8 | M V30 8 C 4.6051 -3.20433 0.0 0 | ||
M V30 9 | M V30 9 N 5.46921 -2.70573 0.0 0 | ||
M V30 10 C | M V30 10 C 3.73792 -2.70444 0.0 0 | ||
M V30 11 C | M V30 11 C 4.59818 -1.20313 0.0 0 | ||
M V30 12 C | M V30 12 C 3.73534 -1.70875 0.0 0 | ||
M V30 13 | M V30 13 F 5.4689 0.30005 0.0 0 | ||
M V30 14 | M V30 14 F 8.93141 0.300008 0.0 0 | ||
M V30 15 C | M V30 15 C 10.7482 -4.56624 0.0 0 | ||
M V30 16 C | M V30 16 C 9.88344 -6.06497 0.0 0 | ||
M V30 17 C | M V30 17 C 10.7479 -5.56696 0.0 0 | ||
M V30 18 | M V30 18 C 9.0166 -5.5645 0.0 0 | ||
M V30 19 C 9. | M V30 19 C 9.87787 -4.06377 0.0 0 | ||
M V30 20 C | M V30 20 C 9.01469 -4.56881 0.0 0 CHG=-1 | ||
M V30 21 C | M V30 21 C 9.87787 -3.06377 0.0 0 | ||
M V30 22 C | M V30 22 C 9.01129 -1.56611 0.0 0 | ||
M V30 23 | M V30 23 N 9.01103 -2.56374 0.0 0 | ||
M V30 24 C | M V30 24 C 9.8778 -1.06505 0.0 0 | ||
M V30 25 C | M V30 25 C 10.7478 -2.56071 0.0 0 | ||
M V30 26 C | M V30 26 C 10.7414 -1.56066 0.0 0 | ||
M V30 27 | M V30 27 F 11.6143 -4.06637 0.0 0 | ||
M V30 28 | M V30 28 F 9.88298 -7.06497 0.0 0 | ||
M V30 29 C | M V30 29 C 4.66173 -6.18724 0.0 0 | ||
M V30 30 C | M V30 30 C 3.79616 -4.689 0.0 0 | ||
M V30 31 | M V30 31 C 3.79523 -5.68664 0.0 0 | ||
M V30 32 C | M V30 32 C 4.663 -4.18853 0.0 0 | ||
M V30 33 C | M V30 33 C 5.53204 -5.68477 0.0 0 | ||
M V30 34 C | M V30 34 C 5.52625 -4.68471 0.0 0 CHG=-1 | ||
M V30 35 C | M V30 35 C 6.39806 -6.18477 0.0 0 | ||
M V30 36 C | M V30 36 C 8.12836 -6.18312 0.0 0 | ||
M V30 37 | M V30 37 N 7.26452 -5.68408 0.0 0 | ||
M V30 38 | M V30 38 C 8.12903 -7.18407 0.0 0 | ||
M V30 39 | M V30 39 C 6.39874 -7.18971 0.0 0 | ||
M V30 40 | M V30 40 C 7.26804 -7.68414 0.0 0 | ||
M V30 41 F | M V30 41 F 4.66158 -7.18724 0.0 0 | ||
M V30 42 F | M V30 42 F 2.93037 -4.1886 0.0 0 | ||
M V30 43 Ir 7. | M V30 43 Ir 7.21023 -3.58073 0.0 0 CHG=3 | ||
M V30 END ATOM | M V30 END ATOM | ||
M V30 BEGIN BOND | M V30 BEGIN BOND | ||
Line 65: | Line 226: | ||
M V30 5 2 5 6 | M V30 5 2 5 6 | ||
M V30 6 1 6 4 | M V30 6 1 6 4 | ||
M V30 7 2 9 7 | M V30 7 1 5 7 | ||
M V30 | M V30 8 2 9 7 | ||
M V30 | M V30 9 2 10 8 | ||
M V30 | M V30 10 1 7 11 | ||
M V30 | M V30 11 1 8 9 | ||
M V30 | M V30 12 2 11 12 | ||
M V30 | M V30 13 1 12 10 | ||
M V30 | M V30 14 1 1 13 | ||
M V30 | M V30 15 1 2 14 | ||
M V30 16 2 17 15 | |||
M V30 17 2 | M V30 17 2 18 16 | ||
M V30 18 1 | M V30 18 1 15 19 | ||
M V30 19 | M V30 19 1 16 17 | ||
M V30 20 2 | M V30 20 2 19 20 | ||
M V30 21 1 | M V30 21 1 20 18 | ||
M V30 22 1 | M V30 22 1 19 21 | ||
M V30 23 2 23 | M V30 23 2 23 21 | ||
M V30 24 | M V30 24 2 24 22 | ||
M V30 25 | M V30 25 1 21 25 | ||
M V30 26 | M V30 26 1 22 23 | ||
M V30 27 | M V30 27 2 25 26 | ||
M V30 28 1 26 | M V30 28 1 26 24 | ||
M V30 29 | M V30 29 1 15 27 | ||
M V30 30 1 | M V30 30 1 16 28 | ||
M V30 31 | M V30 31 2 31 29 | ||
M V30 32 | M V30 32 2 32 30 | ||
M V30 33 | M V30 33 1 29 33 | ||
M V30 34 | M V30 34 1 30 31 | ||
M V30 35 | M V30 35 2 33 34 | ||
M V30 36 | M V30 36 1 34 32 | ||
M V30 37 1 | M V30 37 1 33 35 | ||
M V30 38 | M V30 38 2 37 35 | ||
M V30 39 | M V30 39 2 38 36 | ||
M V30 40 1 | M V30 40 1 35 39 | ||
M V30 41 1 | M V30 41 1 36 37 | ||
M V30 42 | M V30 42 2 39 40 | ||
M V30 43 1 | M V30 43 1 40 38 | ||
M V30 44 1 29 41 | M V30 44 1 29 41 | ||
M V30 45 1 | M V30 45 1 30 42 | ||
M V30 46 | M V30 46 10 9 43 | ||
M V30 47 | M V30 47 10 6 43 | ||
M V30 48 | M V30 48 10 43 34 | ||
M V30 49 | M V30 49 10 43 37 | ||
M V30 50 | M V30 50 10 43 20 | ||
M V30 51 | M V30 51 10 43 23 | ||
M V30 END BOND | M V30 END BOND | ||
M V30 END CTAB | M V30 END CTAB | ||
M END | M END | ||
</chemform><chemform smiles=" | </chemform><chemform smiles="C1C=C2C(C3C=CC=CC=3)=CC=N3[Cu+]4(P(C5C=CC=CC=5)(C5C=CC=CC=5)C5C6OC7C(P4(C4C=CC=CC=4)C4C=CC=CC=4)=CC=CC=7C(C)(C)C=6C=CC=5)N4=CC=C(C5C=CC=CC=5)C=1C4=C23.[P-](F)(F)(F)(F)(F)F" inchi="1S/C39H32OP2.C24H16N2.Cu.F6P/c1-39(2)33-25-15-27-35(41(29-17-7-3-8-18-29)30-19-9-4-10-20-30)37(33)40-38-34(39)26-16-28-36(38)42(31-21-11-5-12-22-31)32-23-13-6-14-24-32;1-3-7-17(8-4-1)19-13-15-25-23-21(19)11-12-22-20(14-16-26-24(22)23)18-9-5-2-6-10-18;;1-7(2,3,4,5)6/h3-28H,1-2H3;1-16H;;/q;;+1;-1" inchikey="RLYPDFWLVSLBDF-UHFFFAOYSA-N" height="200px" width="300px" float="none"> | ||
-INDIGO- | -INDIGO-11272314442D | ||
0 0 0 0 0 0 0 0 0 0 0 V3000 | 0 0 0 0 0 0 0 0 0 0 0 V3000 | ||
M V30 BEGIN CTAB | M V30 BEGIN CTAB | ||
M V30 COUNTS | M V30 COUNTS 76 88 0 0 0 | ||
M V30 BEGIN ATOM | M V30 BEGIN ATOM | ||
M V30 1 C 4. | M V30 1 C 4.75985 -5.47507 0.0 0 | ||
M V30 2 C 6. | M V30 2 C 6.49015 -5.47459 0.0 0 | ||
M V30 3 C 5. | M V30 3 C 5.62664 -4.97497 0.0 0 | ||
M V30 4 | M V30 4 C 6.49015 -6.47553 0.0 0 | ||
M V30 5 C 4. | M V30 5 C 4.75985 -6.48002 0.0 0 | ||
M V30 6 C 5. | M V30 6 C 5.62882 -6.97503 0.0 0 | ||
M V30 7 C 5. | M V30 7 C 5.6282 -3.9804 0.0 0 | ||
M V30 8 C | M V30 8 C 6.4927 -3.48202 0.0 0 | ||
M V30 9 | M V30 9 N 7.3581 -4.97422 0.0 0 | ||
M V30 10 C | M V30 10 C 7.35297 -3.97724 0.0 0 | ||
M V30 11 N | M V30 11 N 7.35042 -6.97074 0.0 0 | ||
M V30 12 C | M V30 12 C 7.35263 -7.96665 0.0 0 | ||
M V30 13 C | M V30 13 C 5.63103 -7.97493 0.0 0 | ||
M V30 14 C | M V30 14 C 6.49673 -8.46554 0.0 0 | ||
M V30 15 C | M V30 15 C 4.76217 -3.4804 0.0 0 | ||
M V30 16 C | M V30 16 C 3.03187 -3.48205 0.0 0 | ||
M V30 17 C | M V30 17 C 3.89572 -3.98109 0.0 0 | ||
M V30 18 C | M V30 18 C 3.0312 -2.4811 0.0 0 | ||
M V30 19 C | M V30 19 C 4.7615 -2.47545 0.0 0 | ||
M V30 20 C | M V30 20 C 3.8922 -1.98102 0.0 0 | ||
M V30 21 | M V30 21 C 4.765 -8.47493 0.0 0 | ||
M V30 22 C | M V30 22 C 3.90128 -9.97424 0.0 0 | ||
M V30 23 C | M V30 23 C 4.76539 -9.47564 0.0 0 | ||
M V30 24 C | M V30 24 C 3.0341 -9.47435 0.0 0 | ||
M V30 25 C | M V30 25 C 3.89436 -7.97304 0.0 0 | ||
M V30 26 C | M V30 26 C 3.03152 -8.47866 0.0 0 | ||
M V30 27 C | M V30 27 C 13.925 -6.05001 0.0 0 | ||
M V30 28 C | M V30 28 C 13.425 -5.18397 0.0 0 | ||
M V30 29 C | M V30 29 C 12.425 -5.18396 0.0 0 | ||
M V30 30 | M V30 30 O 11.925 -6.04999 0.0 0 | ||
M V30 31 | M V30 31 C 12.425 -6.91603 0.0 0 | ||
M V30 32 | M V30 32 C 13.425 -6.91604 0.0 0 | ||
M V30 33 C | M V30 33 C 11.9271 -4.32028 0.0 0 | ||
M V30 34 C | M V30 34 C 12.427 -3.45393 0.0 0 | ||
M V30 35 C | M V30 35 C 13.9269 -4.31416 0.0 0 | ||
M V30 36 C | M V30 36 C 13.4219 -3.45174 0.0 0 | ||
M V30 37 C | M V30 37 C 13.9229 -7.77972 0.0 0 | ||
M V30 38 C | M V30 38 C 13.423 -8.64607 0.0 0 | ||
M V30 39 C | M V30 39 C 11.9231 -7.78584 0.0 0 | ||
M V30 40 C | M V30 40 C 12.4281 -8.64826 0.0 0 | ||
M V30 41 | M V30 41 P 10.9271 -4.32009 0.0 0 | ||
M V30 42 | M V30 42 P 10.9231 -7.78902 0.0 0 | ||
M V30 43 C | M V30 43 C 11.1859 -3.35416 0.0 0 | ||
M V30 44 C | M V30 44 C 10.7365 -1.68325 0.0 0 | ||
M V30 45 C 10. | M V30 45 C 10.478 -2.64682 0.0 0 | ||
M V30 46 C | M V30 46 C 11.7032 -1.42354 0.0 0 | ||
M V30 47 C | M V30 47 C 12.1564 -3.09341 0.0 0 | ||
M V30 48 C | M V30 48 C 12.409 -2.12576 0.0 0 | ||
M V30 49 C | M V30 49 C 10.0611 -3.82009 0.0 0 | ||
M V30 50 C | M V30 50 C 8.33077 -3.82174 0.0 0 | ||
M V30 51 C | M V30 51 C 9.19462 -4.32078 0.0 0 | ||
M V30 52 C | M V30 52 C 8.3301 -2.82079 0.0 0 | ||
M V30 53 C | M V30 53 C 10.0604 -2.81514 0.0 0 | ||
M V30 54 C | M V30 54 C 9.1911 -2.32071 0.0 0 | ||
M V30 55 C | M V30 55 C 11.182 -8.75494 0.0 0 | ||
M V30 56 C | M V30 56 C 10.0571 -8.28902 0.0 0 | ||
M V30 57 C | M V30 57 C 12.4066 -9.9773 0.0 0 | ||
M V30 58 C | M V30 58 C 12.1487 -9.01358 0.0 0 | ||
M V30 59 C | M V30 59 C 11.6993 -10.6855 0.0 0 | ||
M V30 60 C 9. | M V30 60 C 10.4718 -9.46602 0.0 0 | ||
M V30 61 C 10. | M V30 61 C 10.7369 -10.4303 0.0 0 | ||
M V30 62 C | M V30 62 C 9.1934 -9.78832 0.0 0 | ||
M V30 63 C | M V30 63 C 10.0575 -9.28973 0.0 0 | ||
M V30 64 C 8. | M V30 64 C 8.32622 -9.28843 0.0 0 | ||
M V30 65 C | M V30 65 C 9.18648 -7.78713 0.0 0 | ||
M V30 66 C 8. | M V30 66 C 8.32364 -8.29275 0.0 0 | ||
M V30 67 C | M V30 67 C 14.6321 -5.3429 0.0 0 | ||
M V30 68 C | M V30 68 C 14.6321 -6.75712 0.0 0 | ||
M V30 69 | M V30 69 Cu 8.52413 -5.87422 0.0 0 CHG=1 | ||
M V30 70 | M V30 70 P 15.625 -2.175 0.0 0 CHG=-1 | ||
M V30 71 | M V30 71 F 15.625 -1.175 0.0 0 | ||
M V30 72 F 14.759 -2.675 0.0 0 | |||
M V30 73 F 16.491 -2.675 0.0 0 | |||
M V30 74 F 16.491 -1.675 0.0 0 | |||
M V30 75 F 15.625 -3.175 0.0 0 | |||
M V30 76 F 14.759 -1.675 0.0 0 | |||
M V30 END ATOM | M V30 END ATOM | ||
M V30 BEGIN BOND | M V30 BEGIN BOND | ||
Line 200: | Line 366: | ||
M V30 6 1 6 4 | M V30 6 1 6 4 | ||
M V30 7 2 8 7 | M V30 7 2 8 7 | ||
M V30 8 1 | M V30 8 1 2 9 | ||
M V30 9 1 7 | M V30 9 1 7 3 | ||
M V30 10 2 9 10 | M V30 10 2 9 10 | ||
M V30 11 1 10 8 | M V30 11 1 10 8 | ||
M V30 12 2 12 11 | M V30 12 2 12 11 | ||
M V30 13 1 | M V30 13 1 6 13 | ||
M V30 14 1 11 | M V30 14 1 11 4 | ||
M V30 15 2 13 14 | M V30 15 2 13 14 | ||
M V30 16 1 14 12 | M V30 16 1 14 12 | ||
M V30 17 2 17 15 | M V30 17 1 7 15 | ||
M V30 | M V30 18 2 17 15 | ||
M V30 | M V30 19 2 18 16 | ||
M V30 | M V30 20 1 15 19 | ||
M V30 | M V30 21 1 16 17 | ||
M V30 | M V30 22 2 19 20 | ||
M V30 23 1 20 18 | |||
M V30 24 1 21 | M V30 24 1 13 21 | ||
M V30 25 2 | M V30 25 2 23 21 | ||
M V30 26 | M V30 26 2 24 22 | ||
M V30 27 1 | M V30 27 1 21 25 | ||
M V30 28 | M V30 28 1 22 23 | ||
M V30 29 | M V30 29 2 25 26 | ||
M V30 30 1 | M V30 30 1 26 24 | ||
M V30 31 | M V30 31 1 27 32 | ||
M V30 32 1 28 | M V30 32 1 27 28 | ||
M V30 33 | M V30 33 2 28 29 | ||
M V30 34 1 | M V30 34 1 29 30 | ||
M V30 35 1 | M V30 35 1 30 31 | ||
M V30 36 | M V30 36 2 31 32 | ||
M V30 37 | M V30 37 2 34 33 | ||
M V30 38 | M V30 38 1 28 35 | ||
M V30 39 | M V30 39 1 33 29 | ||
M V30 40 | M V30 40 2 35 36 | ||
M V30 41 1 34 | M V30 41 1 36 34 | ||
M V30 42 2 37 | M V30 42 2 38 37 | ||
M V30 43 1 | M V30 43 1 31 39 | ||
M V30 44 1 | M V30 44 1 37 32 | ||
M V30 45 | M V30 45 2 39 40 | ||
M V30 46 | M V30 46 1 40 38 | ||
M V30 47 1 41 | M V30 47 1 33 41 | ||
M V30 48 | M V30 48 1 39 42 | ||
M V30 49 1 43 | M V30 49 1 41 43 | ||
M V30 50 2 | M V30 50 2 45 43 | ||
M V30 51 | M V30 51 2 46 44 | ||
M V30 52 1 | M V30 52 1 43 47 | ||
M V30 53 1 | M V30 53 1 44 45 | ||
M V30 54 | M V30 54 2 47 48 | ||
M V30 55 | M V30 55 1 48 46 | ||
M V30 56 1 | M V30 56 1 41 49 | ||
M V30 57 2 51 | M V30 57 2 51 49 | ||
M V30 58 | M V30 58 2 52 50 | ||
M V30 59 | M V30 59 1 49 53 | ||
M V30 60 1 | M V30 60 1 50 51 | ||
M V30 61 2 54 | M V30 61 2 53 54 | ||
M V30 62 1 | M V30 62 1 54 52 | ||
M V30 63 | M V30 63 1 42 55 | ||
M V30 64 1 | M V30 64 1 42 56 | ||
M V30 65 2 58 | M V30 65 2 58 55 | ||
M V30 66 | M V30 66 2 59 57 | ||
M V30 67 | M V30 67 1 55 60 | ||
M V30 68 1 | M V30 68 1 57 58 | ||
M V30 69 2 61 | M V30 69 2 60 61 | ||
M V30 70 1 | M V30 70 1 61 59 | ||
M V30 71 2 63 | M V30 71 2 63 56 | ||
M V30 72 | M V30 72 2 64 62 | ||
M V30 73 | M V30 73 1 56 65 | ||
M V30 74 1 | M V30 74 1 62 63 | ||
M V30 75 2 66 | M V30 75 2 65 66 | ||
M V30 76 1 | M V30 76 1 66 64 | ||
M V30 77 | M V30 77 1 27 67 | ||
M V30 78 1 | M V30 78 1 27 68 | ||
M V30 79 | M V30 79 10 9 69 | ||
M V30 80 | M V30 80 10 11 69 | ||
M V30 81 | M V30 81 10 69 42 | ||
M V30 82 | M V30 82 10 69 41 | ||
M V30 83 | M V30 83 1 70 71 | ||
M V30 84 | M V30 84 1 70 72 | ||
M V30 85 1 70 73 | |||
M V30 86 1 70 74 | |||
M V30 87 1 70 75 | |||
M V30 88 1 70 76 | |||
M V30 END BOND | M V30 END BOND | ||
M V30 END CTAB | M V30 END CTAB | ||
M END | M END | ||
</chemform> | </chemform> | ||
=== Investigation=== | ==== Investigation ==== | ||
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name= | {{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Optimizations of the conditions}} | ||
===Sacrificial electron donor === | ==== Sacrificial electron donor ==== | ||
{{#moleculelink:|link=ZMANZCXQSJIPKH-UHFFFAOYSA-N|image= | In this study, TEA ({{#moleculelink:|link=ZMANZCXQSJIPKH-UHFFFAOYSA-N|image=false|width=300|height=200}}) and BIH ({{#moleculelink:|link=VDFIVJSRRJXMAU-UHFFFAOYSA-N|image=false|width=300|height=200}}) were used as sacrificial electron donors.[[Category:Publication]] |
Latest revision as of 09:33, 10 May 2024
Abstract[edit | edit source]
Summary[edit | edit source]
A photochemical reduction of CO2 to CO was shown using the dirhenium complex (tBuxant)-(Re(bpy)(CO)3Cl)2 in combination with the ruthenium and copper photosensitizers Ir(fppy)3 and [Cu(bcp)(xant)][PF6]. Turnover numbers (TONs) of up to 270 were reached after 4 h of irradiation (λ > 400 nm) in DMF.
Advances and special progress[edit | edit source]
One of very few studies where a dinuclear catalytic system able to activate CO2 is used in combination with photosensitizers.
Additional remarks[edit | edit source]
The experiments were performed using the rhenium complex (50 μM in DMF) as the catalyst in combination with different loadings of the sensitizers and sacrificial electron donors under 4 h of irradiation with λ > 400 nm.
Content of the published article in detail[edit | edit source]
The article contains results of a detailed study on the influence of additional photosensitizers on the catalytic performance of the dinuclear rhenium catalyst (tBuxant)-(Re(bpy)(CO)3Cl)2 for the reduction of CO2 to CO. The catalytic system performs best (referring to the TON of CO production) for the combination of the above mentioned catalyst with the iridium complex Ir(fppy)3 as the photosensitizer in the presence of BIH/TEA as sacrificial electron donors.
Catalyst[edit | edit source]
Photosensitizer[edit | edit source]
Ir(fppy)3 [Cu(bcp)(xant)][PF6]
Investigation[edit | edit source]
cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | solvent A | additives | . | λexc [nm] | . | TON CO | . | |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
1. | 0.05 | 0.05 | 0.36 | > 400 | 52 | ||||||||
2. | 0.05 | 0.05 | 0.005 | TEA | > 400 | 78 | |||||||
3. | 0.05 | 0.05 | 0.01 | TEA | > 400 | 195 | |||||||
4. | 0.05 | 0.05 | 0.01 | TEA | > 400 | 154 | |||||||
5. | 0.05 | 0.05 | 0.01 | TEA | > 400 | 131 | |||||||
6. | 0.05 | 0.05 | 0.02 | TEA | > 400 | 134 | |||||||
7. | 0.05 | 0.05 | 0.02 | TEA | > 400 | 193 | |||||||
8. | 0.05 | 0.05 | 0.5 | TEA | > 400 | 255 | |||||||
9. | 0.05 | 0.01 | TEA | > 400 | 63 | ||||||||
10. | 0.05 | 0.005 | 0.01 | TEA | > 400 | 124 | |||||||
11. | 0.05 | 0.0125 | 0.01 | TEA | > 400 | 144 | |||||||
12. | 0.05 | 0.025 | 0.01 | TEA | > 400 | 149 | |||||||
13. | 0.05 | 0.1 | 0.05 | TEA | > 400 | 270 | |||||||
14. | 0.05 | 0.05 | 0.01 | TEA | > 400 | 169 |
Sacrificial electron donor[edit | edit source]
In this study, TEA (TEA) and BIH (BIH) were used as sacrificial electron donors.
Investigations
- Optimizations of the conditions (Molecular process, Photocatalytic CO2 conversion experiments)