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

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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
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{{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 ===


=== Catalysts ===
==== Summary ====
<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">
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.
   -INDIGO-12122214162D
 
==== 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 ====
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   -INDIGO-01122412122D


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   -INDIGO-12122214192D
   -INDIGO-07282310362D


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   -INDIGO-12122214222D
   -INDIGO-02262411182D


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M  V30 END ATOM
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M  V30 BEGIN BOND
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M  V30 END BOND
M  V30 END CTAB
M  END
</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-02152416342D
 
  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 44 47 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 5.62242 -3.98512 0.0 0
M  V30 2 C 7.0939 -3.98472 0.0 0
M  V30 3 C 6.35956 -3.55983 0.0 0
M  V30 4 N 7.0939 -4.83594 0.0 0
M  V30 5 C 5.62242 -4.83976 0.0 0
M  V30 6 C 6.36141 -5.26073 0.0 0
M  V30 7 C 7.83059 -3.55985 0.0 0
M  V30 8 C 8.56572 -2.28515 0.0 0
M  V30 9 C 7.83066 -2.70882 0.0 0
M  V30 10 C 9.30303 -2.7106 0.0 0
M  V30 11 N 8.57081 -3.98701 0.0 0
M  V30 12 C 9.3048 -3.55737 0.0 0
M  V30 13 C 5.64368 -6.51514 0.0 0
M  V30 14 N 7.11516 -6.51473 0.0 0
M  V30 15 C 6.38081 -6.08984 0.0 0
M  V30 16 C 7.11516 -7.36595 0.0 0
M  V30 17 C 5.64368 -7.36977 0.0 0
M  V30 18 C 6.38267 -7.79074 0.0 0
M  V30 19 C 7.85206 -7.79046 0.0 0
M  V30 20 C 9.32359 -7.78764 0.0 0
M  V30 21 N 8.5885 -7.36395 0.0 0
M  V30 22 C 9.32497 -8.63887 0.0 0
M  V30 23 C 7.85346 -8.64508 0.0 0
M  V30 24 C 8.59314 -9.06485 0.0 0
M  V30 25 Ru 8.56415 -5.60948 0.0 0 CHG=2
M  V30 26 O 9.93229 -4.65054 0.0 0
M  V30 27 C 9.98149 -6.32253 0.0 0 CHG=-1
M  V30 28 O 10.8332 -6.8143 0.0 0 CHG=1
M  V30 29 H 10.8388 -5.07273 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 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 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 275: 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
M  END
M  END
</chemform>
</chemform>
{| class="wikitable"
|+
!Table 1
!2
!3
!4
!5
!6
!7
|-
|cat
|100610
|100607
|100611
|100612
|100608
|100609
|-
|cat c
|0.025
|0.025
|0.025
|0.025
|0.025
|0.025
|-
|PS
|100487
|100487
|100487
|100487
|100487
|100487
|-
|PS c
|0.025
|0.025
|0.025
|0.025
|0.025
|0.025
|-
|e-D
|TEOA (100507)
|TEOA
|TEOA
|TEOA
|TEOA
|TEOA
|-
|Solv A
|NMP (100532)
|NMP
|NMP
|NMP
|NMP
|NMP
|-
|T
|25
|25
|25
|25
|25
|25
|-
|exc
|400 - 700
|400 - 700
|400 - 700
|400 - 700
|400 - 700
|400 - 700
|-
|TON CO
|1
|2
|13
|8
|7
|3
|-
|TON H2
|2
|4
|8
|8
|9
|4
|-
|TON HCOOH
|13
|21
|62
|34
|40
|27
|}


=== Photosensitizer ===
==== Photosensitizer ====
<chemform smiles="C1C2C3C=CC=CC=3~[Ir]3(~C4C=CC=CC=4C4C=CC=CN=4~3)3(~N4=C(C5N~3=CC=CC=5)C=CC=C4)~N=2C=CC=1.P(F)(F)(F)(F)(F)F" inchi="1S/2C11H9N.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*1-9H;1-8H;;" inchikey="YLYRMTZQAOANTD-UHFFFAOYSA-N" height="200px" width="300px" float="none">
<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-12122214422D
   -INDIGO-08012317142D


   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 418: Line 558:
M  V30 COUNTS 44 51 0 0 0
M  V30 COUNTS 44 51 0 0 0
M  V30 BEGIN ATOM
M  V30 BEGIN ATOM
M  V30 1 C 6.86521 -4.85135 0.0 0
M  V30 1 C 4.03485 -3.90007 0.0 0
M  V30 2 C 8.41771 -4.69374 0.0 0
M  V30 2 C 5.76515 -3.89959 0.0 0
M  V30 3 C 7.49611 -4.29588 0.0 0
M  V30 3 C 4.90164 -3.39997 0.0 0
M  V30 4 C 8.59253 -5.83511 0.0 0
M  V30 4 C 5.76515 -4.90053 0.0 0 CHG=-1
M  V30 5 C 7.08033 -5.78282 0.0 0
M  V30 5 C 4.03485 -4.90502 0.0 0
M  V30 6 N 8.11488 -6.23567 0.0 0
M  V30 6 C 4.90382 -5.40003 0.0 0
M  V30 7 C 4.87789 -6.03109 0.0 0
M  V30 7 C 6.63141 -3.39999 0.0 0
M  V30 8 C 6.55161 -6.17412 0.0 0
M  V30 8 C 7.49583 -1.90109 0.0 0
M  V30 9 C 5.65652 -5.63903 0.0 0
M  V30 9 C 6.63149 -2.39928 0.0 0
M  V30 10 C 6.70386 -7.1489 0.0 0
M  V30 10 C 8.36278 -2.40138 0.0 0
M  V30 11 C 4.86086 -7.04446 0.0 0
M  V30 11 N 7.50182 -3.90229 0.0 0
M  V30 12 C 5.78608 -7.65601 0.0 0
M  V30 12 C 8.3649 -3.39706 0.0 0
M  V30 13 C 8.0594 -9.2927 0.0 0
M  V30 13 C 4.08485 -6.82507 0.0 0
M  V30 14 C 9.54214 -8.78128 0.0 0
M  V30 14 C 5.81515 -6.82459 0.0 0 CHG=-1
M  V30 15 N 8.79341 -8.63647 0.0 0
M  V30 15 C 4.95164 -6.32497 0.0 0
M  V30 16 C 9.81309 -9.84419 0.0 0
M  V30 16 C 5.81515 -7.82553 0.0 0
M  V30 17 C 8.29341 -10.2043 0.0 0
M  V30 17 C 4.08485 -7.83002 0.0 0
M  V30 18 C 9.12893 -10.5036 0.0 0
M  V30 18 C 4.95382 -8.32503 0.0 0
M  V30 19 C 9.10181 -5.24617 0.0 0
M  V30 19 C 6.68166 -8.3247 0.0 0
M  V30 20 C 10.8976 -5.28114 0.0 0
M  V30 20 C 8.41196 -8.32139 0.0 0
M  V30 21 C 10.0549 -4.75542 0.0 0
M  V30 21 N 7.54763 -7.82318 0.0 0
M  V30 22 C 10.8699 -6.15407 0.0 0
M  V30 22 C 8.41359 -9.32233 0.0 0
M  V30 23 N 9.1085 -6.4053 0.0 0
M  V30 23 C 6.6833 -9.32964 0.0 0
M  V30 24 C 10.0024 -6.72701 0.0 0
M  V30 24 C 7.55308 -9.82324 0.0 0
M  V30 25 C 10.2008 -7.25568 0.0 0
M  V30 25 C 9.35985 -3.77507 0.0 0
M  V30 26 C 11.7569 -8.07717 0.0 0
M  V30 26 C 11.0902 -3.77459 0.0 0
M  V30 27 C 11.2664 -7.30936 0.0 0
M  V30 27 C 10.2266 -3.27497 0.0 0
M  V30 28 C 11.2618 -8.93626 0.0 0
M  V30 28 C 11.0902 -4.77553 0.0 0
M  V30 29 N 9.55862 -7.95889 0.0 0
M  V30 29 N 9.35985 -4.78002 0.0 0
M  V30 30 C 10.1287 -8.92474 0.0 0
M  V30 30 C 10.2288 -5.27503 0.0 0
M  V30 31 Ir 8.17869 -7.44217 0.0 0
M  V30 31 C 10.2327 -6.27503 0.0 0
M  V30 32 C 5.79321 -8.64181 0.0 0
M  V30 32 C 11.105 -7.76933 0.0 0
M  V30 33 C 7.16286 -8.04741 0.0 0
M  V30 33 C 11.1014 -6.7717 0.0 0
M  V30 34 C 6.53603 -7.81358 0.0 0
M  V30 34 C 10.2405 -8.27372 0.0 0
M  V30 35 C 7.38389 -9.10258 0.0 0
M  V30 35 N 9.36465 -6.78143 0.0 0
M  V30 36 C 6.06915 -9.51366 0.0 0
M  V30 36 C 9.37498 -7.78146 0.0 0
M  V30 37 C 6.79378 -9.63661 0.0 0
M  V30 37 Ir 7.55 -5.775 0.0 0 CHG=3
M  V30 38 P 14.3 -3.6 0.0 0
M  V30 38 P 13.517 -3.7 0.0 0 CHG=-1
M  V30 39 F 14.3 -2.6 0.0 0
M  V30 39 F 14.383 -3.2 0.0 0
M  V30 40 F 15.3 -3.6 0.0 0
M  V30 40 F 12.651 -3.2 0.0 0
M  V30 41 F 13.3 -3.6 0.0 0
M  V30 41 F 13.517 -4.7 0.0 0
M  V30 42 F 14.3 -4.6 0.0 0
M  V30 42 F 14.383 -4.2 0.0 0
M  V30 43 F 15.0071 -4.30711 0.0 0
M  V30 43 F 13.517 -2.7 0.0 0
M  V30 44 F 13.5929 -2.89289 0.0 0
M  V30 44 F 12.651 -4.2 0.0 0
M  V30 END ATOM
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 BEGIN BOND
Line 470: Line 610:
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 2 27 25
M  V30 25 2 23 24
M  V30 26 2 28 26
M  V30 26 1 24 22
M  V30 27 1 25 29
M  V30 27 2 27 25
M  V30 28 1 26 27
M  V30 28 2 28 26
M  V30 29 2 29 30
M  V30 29 1 25 29
M  V30 30 1 30 28
M  V30 30 1 26 27
M  V30 31 1 8 5
M  V30 31 2 29 30
M  V30 32 1 24 25
M  V30 32 1 30 28
M  V30 33 8 6 31
M  V30 33 1 30 31
M  V30 34 8 10 31
M  V30 34 2 33 31
M  V30 35 8 15 31
M  V30 35 2 34 32
M  V30 36 8 31 29
M  V30 36 1 31 35
M  V30 37 8 23 31
M  V30 37 1 32 33
M  V30 38 2 34 32
M  V30 38 2 35 36
M  V30 39 2 35 33
M  V30 39 1 36 34
M  V30 40 1 32 36
M  V30 40 10 11 37
M  V30 41 1 33 34
M  V30 41 10 37 29
M  V30 42 2 36 37
M  V30 42 10 35 37
M  V30 43 1 37 35
M  V30 43 10 37 21
M  V30 44 1 35 13
M  V30 44 10 14 37
M  V30 45 8 33 31
M  V30 45 10 37 4
M  V30 46 1 38 39
M  V30 46 1 38 39
M  V30 47 1 38 40
M  V30 47 1 38 40
Line 520: Line 660:
</chemform>
</chemform>


=== Electron donor ===
==== Investigations ====
<chemform smiles="N(CCO)(CCO)CCO" inchi="1S/C6H15NO3/c8-4-1-7(2-5-9)3-6-10/h8-10H,1-6H2" inchikey="GSEJCLTVZPLZKY-UHFFFAOYSA-N" height="200px" width="300px" float="none">
{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=CO2 reduction experiments}}
  -INDIGO-12122214492D


  0  0  0  0  0  0  0  0  0  0  0 V3000
{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Optimization of concentrations}}
M  V30 BEGIN CTAB
M  V30 COUNTS 10 9 0 0 0
M  V30 BEGIN ATOM
M  V30 1 N 8.45 -5.25 0.0 0
M  V30 2 C 9.31603 -4.75 0.0 0
M  V30 3 C 10.1821 -5.25 0.0 0
M  V30 4 C 8.70882 -6.21593 0.0 0
M  V30 5 C 8.20882 -7.08195 0.0 0
M  V30 6 C 7.45 -5.25 0.0 0
M  V30 7 C 6.975 -4.43397 0.0 0
M  V30 8 O 5.97501 -4.43751 0.0 0
M  V30 9 O 11.0481 -4.74998 0.0 0
M  V30 10 O 8.70882 -7.94798 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 1 4
M  V30 4 1 4 5
M  V30 5 1 1 6
M  V30 6 1 6 7
M  V30 7 1 7 8
M  V30 8 1 3 9
M  V30 9 1 5 10
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>
{| class="wikitable"
|+
test123
!Table 2
!1
!2
!3
!4
!5
!6
!7
!8
!9
!10
!11
!12
!13
|-
|cat
|100610
|100607
|100611
|100612
|100608
|100609
|100611
|100612
|100608
|100611
|100612
|100608
|100609
|-
|cat c
|0.0062
|0.0062
|0.0062
|0.0062
|0.0062
|0.0062
|0.0031
|0.0031
|0.0031
|0.0016
|0.0016
|0.0016
|0.0016
|-
|PS
|100487
|100487
|100487
|100487
|100487
|100487
|100487
|100487
|100487
|100487
|100487
|100487
|100487
|-
|PS c
|0.025
|0.025
|0.025
|0.025
|0.025
|0.025
|0.025
|0.025
|0.025
|0.025
|0.025
|0.025
|0.025
|-
|e-D
|TEOA
|TEOA
|TEOA
|TEOA
|TEOA
|TEOA
|TEOA
|TEOA
|TEOA
|TEOA
|TEOA
|TEOA
|TEOA
|-
|Solv A
|NMP
|NMP
|NMP
|NMP
|NMP
|NMP
|NMP
|NMP
|NMP
|NMP
|NMP
|NMP
|NMP
|-
|T
|25
|25
|25
|25
|25
|25
|25
|25
|25
|25
|25
|25
|25
|-
|exc
|400 - 700
|400 - 700
|400 - 700
|400 - 700
|400 - 700
|400 - 700
|400 - 700
|400 - 700
|400 - 700
|400 - 700
|400 - 700
|400 - 700
|400 - 700
|-
|TON CO
|3
|3
|19
|21
|21
|4
|36
|16
|34
|40
|25
|45
|4
|-
|TON H2
|9
|11
|19
|16
|14
|12
|33
|29
|28
|67
|62
|65
|44
|-
|TON HCOOH
|26
|39
|117
|107
|75
|64
|296
|145
|211
|419
|225
|335
|75
|}


=== Investigations ===
{{#experimentlist:|form=Cyclic_Voltammetry_experiments|name=Table 3 - CV}}
''Kleine Erklärung: Aus der obenstehenden normalen Tabelle 1, wie sie auch im Paper zu finden ist, wird mit dem Investigationform die untenstehende schlaue Tabelle.''


''Tabelle 2'' ''soll genauso hinzugefügt werden, jede Spalte entspricht einem Experiment im Form.''
==== Sacrificial electron donor ====
In this study, the experiments were done with the sacrificial electron donor TEOA ([[Molecule:100507|100507]]).


''Alle Molekülspalten sollen abfragen, ob es eine Abkürzung gibt und diese dann anzeigen. Idealerweise ist die Abkürzung auch der Linbk zur Molekülseite. Funktioniert schon bei cat und e-D, noch hinzuzufügen bei PS und Solvent.''{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}
==== 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