Photochemical Reduction of Carbon Dioxide to Formic Acid using Ruthenium(II)-Based Catalysts and Visible Light: Difference between revisions

From ChemWiki
publication
About
DOI 10.1002/cctc.201500494
Authors Alonso Rosas-Hernández, Henrik Junge, Matthias Beller,
Submitted 26.08.2015
Published online 26.08.2015
Licenses http://doi.wiley.com/10.1002/tdm_license_1.1,
Subjects Inorganic Chemistry, Organic Chemistry, Physical and Theoretical Chemistry, Catalysis
Go to literature page
(Added the Catalyst molecules)
No edit summary
 
(62 intermediate revisions by 8 users not shown)
Line 1: Line 1:
{{BaseTemplate}}
[[Category:Photocatalytic CO2 conversion to HCOOH]]
[[Category:Photocatalytic CO2 conversion to HCOOH]]
{{#literature:|doi=http://dx.doi.org/10.1002/cctc.201500494}}
{{DOI|doi=10.1002/cctc.201500494 }}
=== Abstract ===


<chemform smiles="C1C=CN2~[Ru](~[*])(~[*])3(~N4C=CC=CC=4C4N~3=CC=CC=4)~N3C=CC=CC=3C=2C=1" inchi="" inchikey="" height="200px" width="300px" float="none" r1="Cl,Cl,H" r2="Cl,CO,CO">
==== Summary ====
   -INDIGO-12122214162D
A photochemical reduction of CO<sub>2</sub> to formic acid was shown using a system containing an iridium-based photosensitizer, ruthenium photocatalyst and triethanolamine as the electron donor. Turnover numbers up to 526 and a selectivity of 80% towards formic acid were observed if the reaction was performed with [Ir(ppy)<sub>2</sub>(bpy)]PF<sub>6</sub> ({{#moleculelink:|link=RJJGJTKSOSSNNL-UHFFFAOYSA-N|image=false|width=300|height=200}}) as the photosensitizer and [Ru(bpy)<sub>2</sub>(Cl)(CO)]PF<sub>6</sub> ({{#moleculelink: |link=WUXWMOMXGWJDBM-UHFFFAOYSA-M|image=false|width=300|height=200}}) as the catalyst.  The experiments were conducted under irradiation with Hg-lamp equipped with a ''λ''=400–700 nm filter.
 
==== Advances and special progress ====
The employed photocatalytic system showed activity for the photoreduction of Na<sub>2</sub>CO<sub>3</sub> to formic acid as well. A TON of 53 was observed after 5h reaction time.
 
==== Additional remarks ====
Experiments using different electron and proton donors such as triethylamine (TEA) and 1-benzyl-1,4-dihydronicotinamide (BNAH) were unsuccessful as the observed activities were lower than those obtained in the presence of TEOA.
 
=== Content of the published article in detail ===
The article contains results for the reduction of CO2 to formic under visible-light catalysis using ruthenium complexes as catalysts, the iridium complex [Ir(ppy)<sub>2</sub>(bpy)]PF<sub>6</sub> ({{#moleculelink:|link=RJJGJTKSOSSNNL-UHFFFAOYSA-N|image=false|width=300|height=200}}) as a photosensitizer and triethanolamine as the electron donor. The catalytic system performs best (referring to the TON of HCOOH production) with [Ru(bpy)<sub>2</sub>(Cl)(CO)]PF<sub>6</sub> ({{#moleculelink: |link=WUXWMOMXGWJDBM-UHFFFAOYSA-M|image=false|width=300|height=200}}) as photocatalyst.
 
==== Catalysts ====
<chemform smiles="C1C=CN2[Ru+2]([Cl-])([Cl-])3(N4C=CC=CC=4C4C=CC=CN=43)N3=CC=CC=C3C=2C=1" inchi="1S/2C10H8N2.2ClH.Ru/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;;;/h2*1-8H;2*1H;/q;;;;+2/p-2" inchikey="MGAJEYXQYJBLQL-UHFFFAOYSA-L" height="200px" width="300px" float="none">
   -INDIGO-01122412122D


   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 9: Line 24:
M  V30 COUNTS 27 32 0 0 0
M  V30 COUNTS 27 32 0 0 0
M  V30 BEGIN ATOM
M  V30 BEGIN ATOM
M  V30 1 C 4.42164 -3.4051 0.0 0
M  V30 1 C 6.66563 -3.83182 0.0 0
M  V30 2 C 6.16573 -3.41315 0.0 0
M  V30 2 C 8.16176 -3.83141 0.0 0
M  V30 3 C 5.23126 -2.93902 0.0 0
M  V30 3 C 7.41512 -3.3994 0.0 0
M  V30 4 N 6.24607 -4.34967 0.0 0
M  V30 4 N 8.16176 -4.69689 0.0 0
M  V30 5 C 4.43988 -4.2752 0.0 0
M  V30 5 C 6.66563 -4.70077 0.0 0
M  V30 6 C 5.33647 -4.80741 0.0 0
M  V30 6 C 7.417 -5.12879 0.0 0
M  V30 7 C 7.1536 -2.01998 0.0 0
M  V30 7 C 8.91079 -3.39942 0.0 0
M  V30 8 C 8.69562 -2.15033 0.0 0
M  V30 8 C 9.65823 -2.10337 0.0 0
M  V30 9 C 7.97052 -1.65293 0.0 0
M  V30 9 C 8.91086 -2.53414 0.0 0
M  V30 10 C 8.6606 -3.11885 0.0 0
M  V30 10 C 10.4079 -2.53595 0.0 0
M  V30 11 C 7.04069 -2.96795 0.0 0
M  V30 11 N 9.66341 -3.83374 0.0 0
M  V30 12 N 7.81868 -3.57293 0.0 0
M  V30 12 C 10.4097 -3.3969 0.0 0
M  V30 13 C 5.6923 -5.52361 0.0 0
M  V30 13 C 6.68725 -6.40421 0.0 0
M  V30 14 C 6.93663 -6.52444 0.0 0
M  V30 14 N 8.18338 -6.40379 0.0 0
M  V30 15 N 6.60503 -5.6549 0.0 0
M  V30 15 C 7.43673 -5.97179 0.0 0
M  V30 16 C 6.34029 -7.29343 0.0 0
M  V30 16 C 8.18338 -7.26927 0.0 0
M  V30 17 C 5.12026 -6.37657 0.0 0
M  V30 17 C 6.68725 -7.27316 0.0 0
M  V30 18 C 5.48652 -7.18714 0.0 0
M  V30 18 C 7.43862 -7.70118 0.0 0
M  V30 19 C 7.64521 -6.74796 0.0 0
M  V30 19 C 8.93262 -7.70089 0.0 0
M  V30 20 C 9.23795 -6.29939 0.0 0
M  V30 20 C 10.4288 -7.69803 0.0 0
M  V30 21 N 8.25086 -6.00768 0.0 0
M  V30 21 N 9.6814 -7.26724 0.0 0
M  V30 22 C 9.43514 -7.33957 0.0 0
M  V30 22 C 10.4302 -8.56351 0.0 0
M  V30 23 C 7.96229 -7.64558 0.0 0
M  V30 23 C 8.93404 -8.56983 0.0 0
M  V30 24 C 8.77162 -7.93243 0.0 0
M  V30 24 C 9.68611 -8.99663 0.0 0
M  V30 25 R# 8.45093 -4.23617 0.0 0 RGROUPS=(1 1)
M  V30 25 Ru 9.65664 -5.53338 0.0 0 CHG=2
M  V30 26 R# 8.54195 -5.09895 0.0 0 RGROUPS=(1 2)
M  V30 26 Cl 10.9874 -4.79065 0.0 0 CHG=-1
M  V30 27 Ru 7.51723 -4.8062 0.0 0
M  V30 27 Cl 10.9874 -6.28831 0.0 0 CHG=-1
M  V30 END ATOM
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 BEGIN BOND
Line 44: Line 59:
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 2 7
M  V30 8 2 10 8
M  V30 8 2 9 7
M  V30 9 1 7 11
M  V30 9 2 10 8
M  V30 10 1 8 9
M  V30 10 1 7 11
M  V30 11 2 11 12
M  V30 11 1 8 9
M  V30 12 1 12 10
M  V30 12 2 11 12
M  V30 13 2 15 13
M  V30 13 1 12 10
M  V30 14 2 16 14
M  V30 14 2 15 13
M  V30 15 1 13 17
M  V30 15 2 16 14
M  V30 16 1 14 15
M  V30 16 1 13 17
M  V30 17 2 17 18
M  V30 17 1 14 15
M  V30 18 1 18 16
M  V30 18 2 17 18
M  V30 19 2 21 19
M  V30 19 1 18 16
M  V30 20 2 22 20
M  V30 20 1 16 19
M  V30 21 1 19 23
M  V30 21 2 21 19
M  V30 22 1 20 21
M  V30 22 2 22 20
M  V30 23 2 23 24
M  V30 23 1 19 23
M  V30 24 1 24 22
M  V30 24 1 20 21
M  V30 25 1 2 11
M  V30 25 2 23 24
M  V30 26 1 14 19
M  V30 26 1 24 22
M  V30 27 8 4 27
M  V30 27 10 11 25
M  V30 28 8 12 27
M  V30 28 10 25 21
M  V30 29 8 15 27
M  V30 29 10 25 14
M  V30 30 8 21 27
M  V30 30 10 25 4
M  V30 31 8 27 26
M  V30 31 10 26 25
M  V30 32 8 27 25
M  V30 32 10 27 25
M  V30 END BOND
M  V30 END BOND
M  V30 END CTAB
M  V30 END CTAB
M  END
M  END
</chemform><chemform smiles="C12C3N(~[Ru]4(~OC(=O)O~4)(~N=1C=CC=C2)1~N2C=CC=CC=2C2C=CC=CN=2~1)=CC=CC=3" inchi="1S/2C10H8N2.CH2O3.Ru/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;2-1(3)4;/h2*1-8H;(H2,2,3,4);" inchikey="IFHMCSXTESYUKW-UHFFFAOYSA-N" height="200px" width="300px" float="none">
</chemform><chemform smiles="C1C=CN2[Ru]3(OC(=O)O3)3(N4C=CC=CC=4C4C=CC=CN=43)N3=CC=CC=C3C=2C=1" inchi="1S/2C10H8N2.CH2O3.Ru/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;2-1(3)4;/h2*1-8H;(H2,2,3,4);/q;;;+2/p-2" inchikey="BEIFWAYVOBNDMH-UHFFFAOYSA-L" height="200px" width="300px" float="none">
   -INDIGO-12122214192D
   -INDIGO-07282310362D


   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 80: Line 95:
M  V30 COUNTS 29 35 0 0 0
M  V30 COUNTS 29 35 0 0 0
M  V30 BEGIN ATOM
M  V30 BEGIN ATOM
M  V30 1 C 6.56741 -6.68319 0.0 0
M  V30 1 C 4.20985 -3.82507 0.0 0
M  V30 2 C 8.11231 -6.66374 0.0 0
M  V30 2 C 5.94015 -3.82459 0.0 0
M  V30 3 N 7.27159 -6.16192 0.0 0
M  V30 3 C 5.07664 -3.32497 0.0 0
M  V30 4 C 8.03707 -7.70884 0.0 0
M  V30 4 N 5.94015 -4.82553 0.0 0
M  V30 5 C 6.56426 -7.64408 0.0 0
M  V30 5 C 4.20985 -4.83002 0.0 0
M  V30 6 C 7.25438 -8.11292 0.0 0
M  V30 6 C 5.07882 -5.32503 0.0 0
M  V30 7 C 4.53118 -5.87604 0.0 0
M  V30 7 C 6.80641 -3.32499 0.0 0
M  V30 8 C 5.94132 -6.45732 0.0 0
M  V30 8 C 7.67083 -1.82609 0.0 0
M  V30 9 N 5.62526 -5.32717 0.0 0
M  V30 9 C 6.80649 -2.32428 0.0 0
M  V30 10 C 5.3951 -7.26705 0.0 0
M  V30 10 C 8.53778 -2.32638 0.0 0
M  V30 11 C 4.21463 -6.83191 0.0 0
M  V30 11 N 7.67682 -3.82729 0.0 0
M  V30 12 C 4.663 -7.38484 0.0 0
M  V30 12 C 8.5399 -3.32207 0.0 0
M  V30 13 C 4.1135 -3.04669 0.0 0
M  V30 13 C 4.23485 -6.80007 0.0 0
M  V30 14 C 5.67958 -3.31686 0.0 0
M  V30 14 N 5.96515 -6.79959 0.0 0
M  V30 15 C 4.90041 -2.7337 0.0 0
M  V30 15 C 5.10164 -6.29997 0.0 0
M  V30 16 N 5.75336 -4.35759 0.0 0
M  V30 16 C 5.96515 -7.80053 0.0 0
M  V30 17 C 4.01212 -3.97499 0.0 0
M  V30 17 C 4.23485 -7.80502 0.0 0
M  V30 18 C 4.86237 -4.70365 0.0 0
M  V30 18 C 5.10382 -8.30003 0.0 0
M  V30 19 C 6.35435 -2.08934 0.0 0
M  V30 19 C 6.83166 -8.2997 0.0 0
M  V30 20 C 7.92555 -2.17068 0.0 0
M  V30 20 C 8.56196 -8.29639 0.0 0
M  V30 21 C 7.10211 -1.68986 0.0 0
M  V30 21 N 7.69763 -7.79818 0.0 0
M  V30 22 C 8.00648 -3.2044 0.0 0
M  V30 22 C 8.56359 -9.29733 0.0 0
M  V30 23 C 6.41645 -3.04684 0.0 0
M  V30 23 C 6.8333 -9.30464 0.0 0
M  V30 24 N 7.24402 -3.65388 0.0 0
M  V30 24 C 7.70308 -9.79824 0.0 0
M  V30 25 Ru 7.016 -4.96602 0.0 0
M  V30 25 Ru 7.72682 -5.67729 0.0 0
M  V30 26 O 7.88207 -4.26835 0.0 0
M  V30 26 O 9.20801 -4.93397 0.0 0
M  V30 27 O 7.92258 -5.58581 0.0 0
M  V30 27 C 9.70801 -5.8 0.0 0
M  V30 28 C 8.60103 -4.9236 0.0 0
M  V30 28 O 9.20801 -6.66603 0.0 0
M  V30 29 O 9.63033 -4.89734 0.0 0
M  V30 29 O 10.708 -5.8 0.0 0
M  V30 END ATOM
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 BEGIN BOND
Line 117: Line 132:
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 2 7
M  V30 8 2 10 8
M  V30 8 2 9 7
M  V30 9 1 7 11
M  V30 9 2 10 8
M  V30 10 1 8 9
M  V30 10 1 7 11
M  V30 11 2 11 12
M  V30 11 1 8 9
M  V30 12 1 12 10
M  V30 12 2 11 12
M  V30 13 2 15 13
M  V30 13 1 12 10
M  V30 14 2 16 14
M  V30 14 2 15 13
M  V30 15 1 13 17
M  V30 15 2 16 14
M  V30 16 1 14 15
M  V30 16 1 13 17
M  V30 17 2 17 18
M  V30 17 1 14 15
M  V30 18 1 18 16
M  V30 18 2 17 18
M  V30 19 2 21 19
M  V30 19 1 18 16
M  V30 20 2 22 20
M  V30 20 1 16 19
M  V30 21 1 19 23
M  V30 21 2 21 19
M  V30 22 1 20 21
M  V30 22 2 22 20
M  V30 23 2 23 24
M  V30 23 1 19 23
M  V30 24 1 24 22
M  V30 24 1 20 21
M  V30 25 1 14 23
M  V30 25 2 23 24
M  V30 26 1 8 1
M  V30 26 1 24 22
M  V30 27 8 16 25
M  V30 27 10 11 25
M  V30 28 8 24 25
M  V30 28 10 25 21
M  V30 29 8 9 25
M  V30 29 10 25 14
M  V30 30 8 3 25
M  V30 30 10 25 4
M  V30 31 1 26 28
M  V30 31 1 26 27
M  V30 32 1 27 28
M  V30 32 1 27 28
M  V30 33 2 28 29
M  V30 33 2 27 29
M  V30 34 8 26 25
M  V30 34 1 26 25
M  V30 35 8 27 25
M  V30 35 1 28 25
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform><chemform smiles="C1C=CN2[Ru+2]([C-]#[O+])([Cl-])3(N4C=CC=CC=4C4C=CC=CN=43)N3=CC=CC=C3C=2C=1.F[P-](F)(F)(F)(F)F" inchikey="QJMAHGUIKKRXBN-UHFFFAOYSA-M" inchi="1S/2C10H8N2.CO.ClH.F6P.Ru/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;1-2;;1-7(2,3,4,5)6;/h2*1-8H;;1H;;/q;;;;-1;+2/p-1" float="none" width="200" height="200">
  -INDIGO-02262411182D
 
  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 35 39 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 7.92242 -4.28512 0.0 0
M  V30 2 C 9.3939 -4.28472 0.0 0
M  V30 3 C 8.65956 -3.85983 0.0 0
M  V30 4 N 9.3939 -5.13594 0.0 0
M  V30 5 C 7.92242 -5.13976 0.0 0
M  V30 6 C 8.66141 -5.56073 0.0 0
M  V30 7 C 10.1306 -3.85985 0.0 0
M  V30 8 C 10.8657 -2.58515 0.0 0
M  V30 9 C 10.1307 -3.00882 0.0 0
M  V30 10 C 11.603 -3.0106 0.0 0
M  V30 11 N 10.8708 -4.28701 0.0 0
M  V30 12 C 11.6048 -3.85737 0.0 0
M  V30 13 C 7.94368 -6.81514 0.0 0
M  V30 14 N 9.41516 -6.81473 0.0 0
M  V30 15 C 8.68081 -6.38984 0.0 0
M  V30 16 C 9.41516 -7.66595 0.0 0
M  V30 17 C 7.94368 -7.66977 0.0 0
M  V30 18 C 8.68267 -8.09074 0.0 0
M  V30 19 C 10.1521 -8.09046 0.0 0
M  V30 20 C 11.6236 -8.08764 0.0 0
M  V30 21 N 10.8885 -7.66395 0.0 0
M  V30 22 C 11.625 -8.93887 0.0 0
M  V30 23 C 10.1535 -8.94508 0.0 0
M  V30 24 C 10.8931 -9.36485 0.0 0
M  V30 25 Ru 10.8641 -5.90948 0.0 0 CHG=2
M  V30 26 Cl 12.2323 -4.95054 0.0 0 CHG=-1
M  V30 27 C 12.2815 -6.62253 0.0 0 CHG=-1
M  V30 28 O 13.1332 -7.1143 0.0 0 CHG=1
M  V30 29 F 13.8741 -4.45053 0.0 0
M  V30 30 P 14.7258 -3.95877 0.0 0 CHG=-1
M  V30 31 F 15.5776 -4.45053 0.0 0
M  V30 32 F 14.7258 -2.97524 0.0 0
M  V30 33 F 13.8741 -3.46701 0.0 0
M  V30 34 F 15.5776 -3.46701 0.0 0
M  V30 35 F 14.7258 -4.9423 0.0 0
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 2 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 2 15 13
M  V30 15 2 16 14
M  V30 16 1 13 17
M  V30 17 1 14 15
M  V30 18 2 17 18
M  V30 19 1 18 16
M  V30 20 1 16 19
M  V30 21 2 21 19
M  V30 22 2 22 20
M  V30 23 1 19 23
M  V30 24 1 20 21
M  V30 25 2 23 24
M  V30 26 1 24 22
M  V30 27 10 11 25
M  V30 28 10 25 21
M  V30 29 10 25 14
M  V30 30 10 25 4
M  V30 31 10 25 26
M  V30 32 10 25 27
M  V30 33 3 27 28
M  V30 34 1 29 30
M  V30 35 1 30 31
M  V30 36 1 30 32
M  V30 37 1 30 33
M  V30 38 1 30 34
M  V30 39 1 30 35
M  V30 END BOND
M  V30 END BOND
M  V30 END CTAB
M  V30 END CTAB
M  END
M  END
</chemform><chemform smiles="C1C=CN2~[Ru](~C#O)(~O([H])[H])3(~N4C=CC=CC=4C4N~3=CC=CC=4)~N3C=CC=CC=3C=2C=1" inchi="1S/2C10H8N2.CHO.H2O.Ru/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;1-2;;/h2*1-8H;1H;1H2;" inchikey="FMDXTMDWVPGKIR-UHFFFAOYSA-N" height="200px" width="300px" float="none">
</chemform><chemform smiles="C1C=CN2[Ru+2]([C-]#[O+])(O([H])[H])3(N4C=CC=CC=4C4C=CC=CN=43)N3=CC=CC=C3C=2C=1.F[P-](F)(F)(F)(F)F.F[P-](F)(F)(F)(F)F" inchi="1S/2C10H8N2.CO.2F6P.H2O.Ru/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;1-2;2*1-7(2,3,4,5)6;;/h2*1-8H;;;;1H2;/q;;;2*-1;;+2" inchikey="CPFZZAZNEQBLAC-UHFFFAOYSA-N" height="200px" width="300px" float="none">
   -INDIGO-12122214222D
   -INDIGO-02152416342D


   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 30 35 0 0 0
M  V30 COUNTS 44 47 0 0 0
M  V30 BEGIN ATOM
M  V30 BEGIN ATOM
M  V30 1 C 4.88353 -4.01367 0.0 0
M  V30 1 C 5.62242 -3.98512 0.0 0
M  V30 2 C 6.49467 -4.14508 0.0 0
M  V30 2 C 7.0939 -3.98472 0.0 0
M  V30 3 C 5.65227 -3.62021 0.0 0
M  V30 3 C 6.35956 -3.55983 0.0 0
M  V30 4 N 6.59022 -5.14567 0.0 0
M  V30 4 N 7.0939 -4.83594 0.0 0
M  V30 5 C 4.85996 -4.97527 0.0 0
M  V30 5 C 5.62242 -4.83976 0.0 0
M  V30 6 C 5.77142 -5.58913 0.0 0
M  V30 6 C 6.36141 -5.26073 0.0 0
M  V30 7 C 7.02354 -2.8684 0.0 0
M  V30 7 C 7.83059 -3.55985 0.0 0
M  V30 8 C 8.59272 -2.82698 0.0 0
M  V30 8 C 8.56572 -2.28515 0.0 0
M  V30 9 C 7.73189 -2.39265 0.0 0
M  V30 9 C 7.83066 -2.70882 0.0 0
M  V30 10 C 8.69857 -3.84084 0.0 0
M  V30 10 C 9.30303 -2.7106 0.0 0
M  V30 11 C 7.09288 -3.79375 0.0 0
M  V30 11 N 8.57081 -3.98701 0.0 0
M  V30 12 N 8.03247 -4.33342 0.0 0
M  V30 12 C 9.3048 -3.55737 0.0 0
M  V30 13 C 7.38633 -7.34736 0.0 0
M  V30 13 C 5.64368 -6.51514 0.0 0
M  V30 14 C 5.9367 -7.55656 0.0 0
M  V30 14 N 7.11516 -6.51473 0.0 0
M  V30 15 C 6.74404 -7.90844 0.0 0
M  V30 15 C 6.38081 -6.08984 0.0 0
M  V30 16 C 5.83442 -6.56452 0.0 0
M  V30 16 C 7.11516 -7.36595 0.0 0
M  V30 17 N 7.19184 -6.19665 0.0 0
M  V30 17 C 5.64368 -7.36977 0.0 0
M  V30 18 C 6.56743 -5.9679 0.0 0
M  V30 18 C 6.38267 -7.79074 0.0 0
M  V30 19 C 8.07224 -7.64104 0.0 0
M  V30 19 C 7.85206 -7.79046 0.0 0
M  V30 20 C 9.73101 -7.40193 0.0 0
M  V30 20 C 9.32359 -7.78764 0.0 0
M  V30 21 N 8.69266 -7.00028 0.0 0
M  V30 21 N 8.5885 -7.36395 0.0 0
M  V30 22 C 9.81611 -8.45063 0.0 0
M  V30 22 C 9.32497 -8.63887 0.0 0
M  V30 23 C 8.18872 -8.58778 0.0 0
M  V30 23 C 7.85346 -8.64508 0.0 0
M  V30 24 C 9.00146 -8.99698 0.0 0
M  V30 24 C 8.59314 -9.06485 0.0 0
M  V30 25 Ru 7.94968 -5.63386 0.0 0
M  V30 25 Ru 8.56415 -5.60948 0.0 0 CHG=2
M  V30 26 O 9.14992 -5.06621 0.0 0
M  V30 26 O 9.93229 -4.65054 0.0 0
M  V30 27 C 8.91539 -6.04352 0.0 0
M  V30 27 C 9.98149 -6.32253 0.0 0 CHG=-1
M  V30 28 O 9.8811 -6.45318 0.0 0
M  V30 28 O 10.8332 -6.8143 0.0 0 CHG=1
M  V30 29 H 9.37348 -4.08653 0.0 0
M  V30 29 H 10.8388 -5.07273 0.0 0
M  V30 30 H 9.92585 -5.60144 0.0 0
M  V30 30 H 9.84466 -3.65439 0.0 0
M  V30 31 F 11.5741 -4.15053 0.0 0
M  V30 32 P 12.4258 -3.65877 0.0 0 CHG=-1
M  V30 33 F 13.2776 -4.15053 0.0 0
M  V30 34 F 12.4258 -2.67524 0.0 0
M  V30 35 F 11.5741 -3.16701 0.0 0
M  V30 36 F 13.2776 -3.16701 0.0 0
M  V30 37 F 12.4258 -4.6423 0.0 0
M  V30 38 F 12.709 -7.35 0.0 0
M  V30 39 P 13.5749 -6.85 0.0 0 CHG=-1
M  V30 40 F 14.441 -7.35 0.0 0
M  V30 41 F 13.5749 -5.84999 0.0 0
M  V30 42 F 12.709 -6.35 0.0 0
M  V30 43 F 14.441 -6.35 0.0 0
M  V30 44 F 13.5749 -7.85001 0.0 0
M  V30 END ATOM
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 BEGIN BOND
Line 194: Line 309:
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 2 7
M  V30 8 2 10 8
M  V30 8 2 9 7
M  V30 9 1 7 11
M  V30 9 2 10 8
M  V30 10 1 8 9
M  V30 10 1 7 11
M  V30 11 2 11 12
M  V30 11 1 8 9
M  V30 12 1 12 10
M  V30 12 2 11 12
M  V30 13 2 15 13
M  V30 13 1 12 10
M  V30 14 2 16 14
M  V30 14 2 15 13
M  V30 15 1 13 17
M  V30 15 2 16 14
M  V30 16 1 14 15
M  V30 16 1 13 17
M  V30 17 2 17 18
M  V30 17 1 14 15
M  V30 18 1 18 16
M  V30 18 2 17 18
M  V30 19 2 21 19
M  V30 19 1 18 16
M  V30 20 2 22 20
M  V30 20 1 16 19
M  V30 21 1 19 23
M  V30 21 2 21 19
M  V30 22 1 20 21
M  V30 22 2 22 20
M  V30 23 2 23 24
M  V30 23 1 19 23
M  V30 24 1 24 22
M  V30 24 1 20 21
M  V30 25 1 13 19
M  V30 25 2 23 24
M  V30 26 1 2 11
M  V30 26 1 24 22
M  V30 27 8 4 25
M  V30 27 10 11 25
M  V30 28 8 12 25
M  V30 28 10 25 21
M  V30 29 8 17 25
M  V30 29 10 25 14
M  V30 30 8 21 25
M  V30 30 10 25 4
M  V30 31 8 25 26
M  V30 31 10 25 26
M  V30 32 8 25 27
M  V30 32 10 25 27
M  V30 33 3 27 28
M  V30 33 3 27 28
M  V30 34 1 26 29
M  V30 34 1 26 29
M  V30 35 1 26 30
M  V30 35 1 26 30
M  V30 36 1 31 32
M  V30 37 1 32 33
M  V30 38 1 32 34
M  V30 39 1 32 35
M  V30 40 1 32 36
M  V30 41 1 32 37
M  V30 42 1 38 39
M  V30 43 1 39 40
M  V30 44 1 39 41
M  V30 45 1 39 42
M  V30 46 1 39 43
M  V30 47 1 39 44
M  V30 END BOND
M  V30 END BOND
M  V30 END CTAB
M  V30 END CTAB
M  END
M  END
</chemform><chemform smiles="C1C=CC2C3C=CC=CN=3~[Ru](~O=C(C)C)(~O=C(C)C)(~N=2C=1)1~N2C=CC=CC=2C2=N~1C=CC=C2" inchi="1S/2C10H8N2.2C3H6O.Ru/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;2*1-3(2)4;/h2*1-8H;2*1-2H3;" inchikey="XKWYLOQQGBAKSH-UHFFFAOYSA-N" height="200px" width="300px" float="none">
</chemform><chemform smiles="C1C=CN2[Ru+2](O=C(C)C)(O=C(C)C)3(N4C=CC=CC=4C4C=CC=CN=43)N3=CC=CC=C3C=2C=1.F[P-](F)(F)(F)(F)F.F[P-](F)(F)(F)(F)F" inchi="1S/2C10H8N2.2C3H6O.2F6P.Ru/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;2*1-3(2)4;2*1-7(2,3,4,5)6;/h2*1-8H;2*1-2H3;;;/q;;;;2*-1;+2" inchikey="MVHJANUNBKMKDC-UHFFFAOYSA-N" height="200px" width="300px" float="none">
   -INDIGO-12122214242D
   -INDIGO-02262411282D


   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 33 38 0 0 0
M  V30 COUNTS 47 50 0 0 0
M  V30 BEGIN ATOM
M  V30 BEGIN ATOM
M  V30 1 C 5.50573 -7.17225 0.0 0
M  V30 1 F 12.1174 -3.75053 0.0 0
M  V30 2 N 6.9043 -7.15427 0.0 0
M  V30 2 P 12.9691 -3.25877 0.0 0 CHG=-1
M  V30 3 C 6.25586 -6.82978 0.0 0
M  V30 3 F 13.8209 -3.75053 0.0 0
M  V30 4 C 6.71695 -8.15589 0.0 0
M  V30 4 F 12.9691 -2.27524 0.0 0
M  V30 5 C 5.33916 -7.91747 0.0 0
M  V30 5 F 12.1174 -2.76701 0.0 0
M  V30 6 C 5.91415 -8.44484 0.0 0
M  V30 6 F 13.8209 -2.76701 0.0 0
M  V30 7 C 7.21625 -8.56484 0.0 0
M  V30 7 F 12.9691 -4.2423 0.0 0
M  V30 8 C 8.63947 -8.85859 0.0 0
M  V30 8 F 12.0523 -6.85 0.0 0
M  V30 9 N 8.10539 -8.15209 0.0 0
M  V30 9 P 12.9182 -6.35 0.0 0 CHG=-1
M  V30 10 C 8.35907 -9.69478 0.0 0
M  V30 10 F 13.7843 -6.85 0.0 0
M  V30 11 C 7.06492 -9.39434 0.0 0
M  V30 11 F 12.9182 -5.34999 0.0 0
M  V30 12 C 7.62204 -9.91148 0.0 0
M  V30 12 F 12.0523 -5.85 0.0 0
M  V30 13 C 5.16785 -4.55363 0.0 0
M  V30 13 F 13.7843 -5.85 0.0 0
M  V30 14 C 6.51757 -4.39553 0.0 0
M  V30 14 F 12.9182 -7.35001 0.0 0
M  V30 15 C 5.78824 -4.09545 0.0 0
M  V30 15 C 4.96571 -3.48512 0.0 0
M  V30 16 N 6.77993 -5.43252 0.0 0
M  V30 16 C 6.43719 -3.48472 0.0 0
M  V30 17 C 5.28775 -5.36582 0.0 0
M  V30 17 C 5.70285 -3.05983 0.0 0
M  V30 18 C 6.08144 -5.77947 0.0 0
M  V30 18 N 6.43719 -4.33594 0.0 0
M  V30 19 C 6.75408 -3.2373 0.0 0
M  V30 19 C 4.96571 -4.33976 0.0 0
M  V30 20 C 8.12511 -3.00621 0.0 0
M  V30 20 C 5.7047 -4.76073 0.0 0
M  V30 21 C 7.36697 -2.72554 0.0 0
M  V30 21 C 7.17388 -3.05985 0.0 0
M  V30 22 C 8.36806 -3.8652 0.0 0
M  V30 22 C 7.90901 -1.78515 0.0 0
M  V30 23 C 7.00126 -4.13112 0.0 0
M  V30 23 C 7.17395 -2.20882 0.0 0
M  V30 24 N 7.89367 -4.47269 0.0 0
M  V30 24 C 8.64632 -2.2106 0.0 0
M  V30 25 Ru 8.41026 -6.26132 0.0 0
M  V30 25 N 7.9141 -3.48701 0.0 0
M  V30 26 O 9.24511 -5.12874 0.0 0
M  V30 26 C 8.64809 -3.05737 0.0 0
M  V30 27 O 9.35312 -7.066 0.0 0
M  V30 27 C 4.98697 -6.01514 0.0 0
M  V30 28 C 10.4996 -4.95962 0.0 0
M  V30 28 N 6.45845 -6.01473 0.0 0
M  V30 29 C 10.811 -3.86385 0.0 0
M  V30 29 C 5.7241 -5.58984 0.0 0
M  V30 30 C 11.3172 -5.67688 0.0 0
M  V30 30 C 6.45845 -6.86595 0.0 0
M  V30 31 C 10.0768 -7.51261 0.0 0
M  V30 31 C 4.98697 -6.86977 0.0 0
M  V30 32 C 10.9279 -7.12955 0.0 0
M  V30 32 C 5.72596 -7.29074 0.0 0
M  V30 33 C 10.103 -8.67227 0.0 0
M  V30 33 C 7.19535 -7.29046 0.0 0
M  V30 34 C 8.66688 -7.28764 0.0 0
M  V30 35 N 7.93179 -6.86395 0.0 0
M  V30 36 C 8.66826 -8.13887 0.0 0
M  V30 37 C 7.19675 -8.14508 0.0 0
M  V30 38 C 7.93643 -8.56485 0.0 0
M  V30 39 Ru 7.90744 -5.10948 0.0 0 CHG=2
M  V30 40 O 9.27558 -4.15054 0.0 0
M  V30 41 O 9.32346 -5.80948 0.0 0
M  V30 42 C 10.1416 -3.65054 0.0 0
M  V30 43 C 10.1416 -2.65054 0.0 0
M  V30 44 C 11.0076 -4.15054 0.0 0
M  V30 45 C 10.1895 -6.30948 0.0 0
M  V30 46 C 11.0555 -5.80948 0.0 0
M  V30 47 C 10.1895 -7.30948 0.0 0
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 1 1 2
M  V30 2 1 2 3
M  V30 3 1 2 4
M  V30 4 1 2 5
M  V30 5 1 2 6
M  V30 6 1 2 7
M  V30 7 1 8 9
M  V30 8 1 9 10
M  V30 9 1 9 11
M  V30 10 1 9 12
M  V30 11 1 9 13
M  V30 12 1 9 14
M  V30 13 2 17 15
M  V30 14 2 18 16
M  V30 15 1 15 19
M  V30 16 1 16 17
M  V30 17 2 19 20
M  V30 18 1 20 18
M  V30 19 1 16 21
M  V30 20 2 23 21
M  V30 21 2 24 22
M  V30 22 1 21 25
M  V30 23 1 22 23
M  V30 24 2 25 26
M  V30 25 1 26 24
M  V30 26 2 29 27
M  V30 27 2 30 28
M  V30 28 1 27 31
M  V30 29 1 28 29
M  V30 30 2 31 32
M  V30 31 1 32 30
M  V30 32 1 30 33
M  V30 33 2 35 33
M  V30 34 2 36 34
M  V30 35 1 33 37
M  V30 36 1 34 35
M  V30 37 2 37 38
M  V30 38 1 38 36
M  V30 39 10 25 39
M  V30 40 10 39 35
M  V30 41 10 39 28
M  V30 42 10 39 18
M  V30 43 10 39 40
M  V30 44 10 39 41
M  V30 45 2 40 42
M  V30 46 1 42 43
M  V30 47 1 42 44
M  V30 48 2 41 45
M  V30 49 1 45 46
M  V30 50 1 45 47
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform><chemform smiles="C1C=CN2[Ru+2]([C-]#[O+])([H-])3(N4C=CC=CC=4C4C=CC=CN=43)N3=CC=CC=C3C=2C=1.F[P-](F)(F)(F)(F)F" inchi="1S/2C10H8N2.CO.F6P.Ru.H/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;1-2;1-7(2,3,4,5)6;;/h2*1-8H;;;;/q;;;-1;+2;-1" inchikey="HJTHNVDYVJWKQG-UHFFFAOYSA-N" height="200px" width="300px" float="none">
  -INDIGO-02262411182D
 
  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 35 39 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 4.57242 -3.91012 0.0 0
M  V30 2 C 6.0439 -3.90972 0.0 0
M  V30 3 C 5.30956 -3.48483 0.0 0
M  V30 4 N 6.0439 -4.76094 0.0 0
M  V30 5 C 4.57242 -4.76476 0.0 0
M  V30 6 C 5.31141 -5.18573 0.0 0
M  V30 7 C 6.78059 -3.48485 0.0 0
M  V30 8 C 7.51572 -2.21015 0.0 0
M  V30 9 C 6.78066 -2.63382 0.0 0
M  V30 10 C 8.25303 -2.6356 0.0 0
M  V30 11 N 7.52081 -3.91201 0.0 0
M  V30 12 C 8.2548 -3.48237 0.0 0
M  V30 13 C 4.59368 -6.44014 0.0 0
M  V30 14 N 6.06516 -6.43973 0.0 0
M  V30 15 C 5.33081 -6.01484 0.0 0
M  V30 16 C 6.06516 -7.29095 0.0 0
M  V30 17 C 4.59368 -7.29477 0.0 0
M  V30 18 C 5.33267 -7.71574 0.0 0
M  V30 19 C 6.80206 -7.71546 0.0 0
M  V30 20 C 8.27359 -7.71264 0.0 0
M  V30 21 N 7.5385 -7.28895 0.0 0
M  V30 22 C 8.27497 -8.56387 0.0 0
M  V30 23 C 6.80346 -8.57008 0.0 0
M  V30 24 C 7.54314 -8.98985 0.0 0
M  V30 25 Ru 7.51415 -5.53448 0.0 0 CHG=2
M  V30 26 H 8.88229 -4.57554 0.0 0 CHG=-1
M  V30 27 C 8.93149 -6.24753 0.0 0 CHG=-1
M  V30 28 O 9.78318 -6.7393 0.0 0 CHG=1
M  V30 29 F 10.5241 -4.07553 0.0 0
M  V30 30 P 11.3758 -3.58377 0.0 0 CHG=-1
M  V30 31 F 12.2276 -4.07553 0.0 0
M  V30 32 F 11.3758 -2.60024 0.0 0
M  V30 33 F 10.5241 -3.09201 0.0 0
M  V30 34 F 12.2276 -3.09201 0.0 0
M  V30 35 F 11.3758 -4.5673 0.0 0
M  V30 END ATOM
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 BEGIN BOND
Line 274: Line 512:
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 2 7
M  V30 8 2 10 8
M  V30 8 2 9 7
M  V30 9 1 7 11
M  V30 9 2 10 8
M  V30 10 1 8 9
M  V30 10 1 7 11
M  V30 11 2 11 12
M  V30 11 1 8 9
M  V30 12 1 12 10
M  V30 12 2 11 12
M  V30 13 2 15 13
M  V30 13 1 12 10
M  V30 14 2 16 14
M  V30 14 2 15 13
M  V30 15 1 13 17
M  V30 15 2 16 14
M  V30 16 1 14 15
M  V30 16 1 13 17
M  V30 17 2 17 18
M  V30 17 1 14 15
M  V30 18 1 18 16
M  V30 18 2 17 18
M  V30 19 2 21 19
M  V30 19 1 18 16
M  V30 20 2 22 20
M  V30 20 1 16 19
M  V30 21 1 19 23
M  V30 21 2 21 19
M  V30 22 1 20 21
M  V30 22 2 22 20
M  V30 23 2 23 24
M  V30 23 1 19 23
M  V30 24 1 24 22
M  V30 24 1 20 21
M  V30 25 1 14 23
M  V30 25 2 23 24
M  V30 26 1 4 7
M  V30 26 1 24 22
M  V30 27 2 26 28
M  V30 27 10 11 25
M  V30 28 1 28 29
M  V30 28 10 25 21
M  V30 29 1 28 30
M  V30 29 10 25 14
M  V30 30 2 27 31
M  V30 30 10 25 4
M  V30 31 1 31 32
M  V30 31 10 25 26
M  V30 32 1 31 33
M  V30 32 10 25 27
M  V30 33 8 24 25
M  V30 33 3 27 28
M  V30 34 8 16 25
M  V30 34 1 29 30
M  V30 35 8 2 25
M  V30 35 1 30 31
M  V30 36 8 9 25
M  V30 36 1 30 32
M  V30 37 8 27 25
M  V30 37 1 30 33
M  V30 38 8 26 25
M  V30 38 1 30 34
M  V30 39 1 30 35
M  V30 END BOND
M  V30 END BOND
M  V30 END CTAB
M  V30 END CTAB
Line 311: Line 550:
</chemform>
</chemform>


{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}
==== Photosensitizer ====
<chemform smiles="C1C=C[C-]2[Ir+3]3([C-]4C=CC=CC=4C4C=CC=CN=43)3(N4=CC=CC=C4C4C=CC=CN=43)N3=CC=CC=C3C=2C=1.[P-](F)(F)(F)(F)(F)F" inchi="1S/2C11H8N.C10H8N2.F6P.Ir/c2*1-2-6-10(7-3-1)11-8-4-5-9-12-11;1-3-7-11-9(5-1)10-6-2-4-8-12-10;1-7(2,3,4,5)6;/h2*1-6,8-9H;1-8H;;/q2*-1;;-1;+3" inchikey="RJJGJTKSOSSNNL-UHFFFAOYSA-N" height="200px" width="300px" float="none">
  -INDIGO-08012317142D
 
  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 44 51 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 4.03485 -3.90007 0.0 0
M  V30 2 C 5.76515 -3.89959 0.0 0
M  V30 3 C 4.90164 -3.39997 0.0 0
M  V30 4 C 5.76515 -4.90053 0.0 0 CHG=-1
M  V30 5 C 4.03485 -4.90502 0.0 0
M  V30 6 C 4.90382 -5.40003 0.0 0
M  V30 7 C 6.63141 -3.39999 0.0 0
M  V30 8 C 7.49583 -1.90109 0.0 0
M  V30 9 C 6.63149 -2.39928 0.0 0
M  V30 10 C 8.36278 -2.40138 0.0 0
M  V30 11 N 7.50182 -3.90229 0.0 0
M  V30 12 C 8.3649 -3.39706 0.0 0
M  V30 13 C 4.08485 -6.82507 0.0 0
M  V30 14 C 5.81515 -6.82459 0.0 0 CHG=-1
M  V30 15 C 4.95164 -6.32497 0.0 0
M  V30 16 C 5.81515 -7.82553 0.0 0
M  V30 17 C 4.08485 -7.83002 0.0 0
M  V30 18 C 4.95382 -8.32503 0.0 0
M  V30 19 C 6.68166 -8.3247 0.0 0
M  V30 20 C 8.41196 -8.32139 0.0 0
M  V30 21 N 7.54763 -7.82318 0.0 0
M  V30 22 C 8.41359 -9.32233 0.0 0
M  V30 23 C 6.6833 -9.32964 0.0 0
M  V30 24 C 7.55308 -9.82324 0.0 0
M  V30 25 C 9.35985 -3.77507 0.0 0
M  V30 26 C 11.0902 -3.77459 0.0 0
M  V30 27 C 10.2266 -3.27497 0.0 0
M  V30 28 C 11.0902 -4.77553 0.0 0
M  V30 29 N 9.35985 -4.78002 0.0 0
M  V30 30 C 10.2288 -5.27503 0.0 0
M  V30 31 C 10.2327 -6.27503 0.0 0
M  V30 32 C 11.105 -7.76933 0.0 0
M  V30 33 C 11.1014 -6.7717 0.0 0
M  V30 34 C 10.2405 -8.27372 0.0 0
M  V30 35 N 9.36465 -6.78143 0.0 0
M  V30 36 C 9.37498 -7.78146 0.0 0
M  V30 37 Ir 7.55 -5.775 0.0 0 CHG=3
M  V30 38 P 13.517 -3.7 0.0 0 CHG=-1
M  V30 39 F 14.383 -3.2 0.0 0
M  V30 40 F 12.651 -3.2 0.0 0
M  V30 41 F 13.517 -4.7 0.0 0
M  V30 42 F 14.383 -4.2 0.0 0
M  V30 43 F 13.517 -2.7 0.0 0
M  V30 44 F 12.651 -4.2 0.0 0
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 2 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 2 15 13
M  V30 15 2 16 14
M  V30 16 1 13 17
M  V30 17 1 14 15
M  V30 18 2 17 18
M  V30 19 1 18 16
M  V30 20 1 16 19
M  V30 21 2 21 19
M  V30 22 2 22 20
M  V30 23 1 19 23
M  V30 24 1 20 21
M  V30 25 2 23 24
M  V30 26 1 24 22
M  V30 27 2 27 25
M  V30 28 2 28 26
M  V30 29 1 25 29
M  V30 30 1 26 27
M  V30 31 2 29 30
M  V30 32 1 30 28
M  V30 33 1 30 31
M  V30 34 2 33 31
M  V30 35 2 34 32
M  V30 36 1 31 35
M  V30 37 1 32 33
M  V30 38 2 35 36
M  V30 39 1 36 34
M  V30 40 10 11 37
M  V30 41 10 37 29
M  V30 42 10 35 37
M  V30 43 10 37 21
M  V30 44 10 14 37
M  V30 45 10 37 4
M  V30 46 1 38 39
M  V30 47 1 38 40
M  V30 48 1 38 41
M  V30 49 1 38 42
M  V30 50 1 38 43
M  V30 51 1 38 44
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>
 
==== Investigations ====
{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=CO2 reduction experiments}}
 
{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Optimization of concentrations}}
 
{{#experimentlist:|form=Cyclic_Voltammetry_experiments|name=Table 3 - CV}}
 
==== Sacrificial electron donor ====
In this study, the experiments were done with the sacrificial electron donor TEOA ([[Molecule:100507|100507]]).
 
==== Additives ====
No additives were used in the described experiments.[[Category:Publication]]

Latest revision as of 15:15, 5 July 2024


Abstract[edit | edit source]

Summary[edit | edit source]

A photochemical reduction of CO2 to formic acid was shown using a system containing an iridium-based photosensitizer, ruthenium photocatalyst and triethanolamine as the electron donor. Turnover numbers up to 526 and a selectivity of 80% towards formic acid were observed if the reaction was performed with [Ir(ppy)2(bpy)]PF6 ([Ir(ppy)2(bpy)][PF6]) as the photosensitizer and [Ru(bpy)2(Cl)(CO)]PF6 (100837) as the catalyst. The experiments were conducted under irradiation with Hg-lamp equipped with a λ=400–700 nm filter.

Advances and special progress[edit | edit source]

The employed photocatalytic system showed activity for the photoreduction of Na2CO3 to formic acid as well. A TON of 53 was observed after 5h reaction time.

Additional remarks[edit | edit source]

Experiments using different electron and proton donors such as triethylamine (TEA) and 1-benzyl-1,4-dihydronicotinamide (BNAH) were unsuccessful as the observed activities were lower than those obtained in the presence of TEOA.

Content of the published article in detail[edit | edit source]

The article contains results for the reduction of CO2 to formic under visible-light catalysis using ruthenium complexes as catalysts, the iridium complex [Ir(ppy)2(bpy)]PF6 ([Ir(ppy)2(bpy)][PF6]) as a photosensitizer and triethanolamine as the electron donor. The catalytic system performs best (referring to the TON of HCOOH production) with [Ru(bpy)2(Cl)(CO)]PF6 (100837) as photocatalyst.

Catalysts[edit | edit source]

Ru(bpy)2Cl2 Ru(bpy)2CO3 [Ru(bpy)2ClCO][PF6] [Ru(bpy)(H2O)(CO)][PF6] [Ru(bpy)(AcMe)2][PF6] [Ru(bpy)2HCO][PF6]

Photosensitizer[edit | edit source]

[Ir(ppy)2(bpy)][PF6]

Investigations[edit | edit source]

catcat conc [µM]PSPS conc [mM]e-Dsolvent A.λexc [nm]TON COTON H2TON HCOOH.
1.

Ru(bpy)2Cl2

25

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7001213
2.

Ru(bpy)2CO3

25

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7002421
3.

[Ru(bpy)2ClCO][PF6]

25

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 70013862
4.

[Ru(bpy)2HCO][PF6]

25

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7008834
5.

[Ru(bpy)(H2O)(CO)][PF6]

25

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7007940
6.

[Ru(bpy)(AcMe)2][PF6]

25

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7003427
Investigation-Name: CO2 reduction experiments
catcat conc [µM]PSPS conc [mM]e-Dsolvent A.λexc [nm]TON COTON H2TON HCOOH.
1.

Ru(bpy)2Cl2

6.2

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7003926
2.

Ru(bpy)2CO3

6.2

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 70031139
3.

[Ru(bpy)2ClCO][PF6]

6.2

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7001919117
4.

[Ru(bpy)2HCO][PF6]

6.2

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7002116107
5.

[Ru(bpy)(H2O)(CO)][PF6]

6.2

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 700211475
6.

[Ru(bpy)(AcMe)2][PF6]

6.2

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 70041264
7.

[Ru(bpy)2ClCO][PF6]

3.1

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7003633296
8.

[Ru(bpy)2HCO][PF6]

3.1

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7001629145
9.

[Ru(bpy)(H2O)(CO)][PF6]

3.1

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7003428211
10.

[Ru(bpy)2ClCO][PF6]

1.6

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7004067419
11.

[Ru(bpy)2HCO][PF6]

1.6

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7002562225
12.

[Ru(bpy)(H2O)(CO)][PF6]

1.6

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7004565335
13.

[Ru(bpy)(AcMe)2][PF6]

1.6

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 70044475
Investigation-Name: Optimization of concentrations
analytereduction potentialsolventelectrolyte..WE..RE.
1.

Ru(bpy)2Cl2

0,-2.11

MeCN

TBABF4

glassy carbonAg/AgNO3 in MeCN
2.

Ru(bpy)2CO3

0.45,-1.97

MeCN

TBABF4

glassy carbonAg/AgNO3 in MeCN
3.

[Ru(bpy)2ClCO][PF6]

1.22,-1.75

MeCN

TBABF4

glassy carbonAg/AgNO3 in MeCN
4.

[Ru(bpy)2HCO][PF6]

1.20,-1.61

MeCN

TBABF4

glassy carbonAg/AgNO3 in MeCN
Investigation-Name: Table 3 - CV

Sacrificial electron donor[edit | edit source]

In this study, the experiments were done with the sacrificial electron donor TEOA (100507).

Additives[edit | edit source]

No additives were used in the described experiments.

Investigations

Retrieved from "https://chemwiki.scc.kit.edu/main/mediawiki/index.php?title=Photochemical_Reduction_of_Carbon_Dioxide_to_Formic_Acid_using_Ruthenium(II)-Based_Catalysts_and_Visible_Light&oldid=8257"
Powered by MediaWiki
Powered by Semantic MediaWiki