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-02262411182D
 
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   -INDIGO-12122214222D
   -INDIGO-02152416342D


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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 195: 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 CTAB
M  END
</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-02262411282D
  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 47 50 0 0 0
M  V30 BEGIN ATOM
M  V30 1 F 12.1174 -3.75053 0.0 0
M  V30 2 P 12.9691 -3.25877 0.0 0 CHG=-1
M  V30 3 F 13.8209 -3.75053 0.0 0
M  V30 4 F 12.9691 -2.27524 0.0 0
M  V30 5 F 12.1174 -2.76701 0.0 0
M  V30 6 F 13.8209 -2.76701 0.0 0
M  V30 7 F 12.9691 -4.2423 0.0 0
M  V30 8 F 12.0523 -6.85 0.0 0
M  V30 9 P 12.9182 -6.35 0.0 0 CHG=-1
M  V30 10 F 13.7843 -6.85 0.0 0
M  V30 11 F 12.9182 -5.34999 0.0 0
M  V30 12 F 12.0523 -5.85 0.0 0
M  V30 13 F 13.7843 -5.85 0.0 0
M  V30 14 F 12.9182 -7.35001 0.0 0
M  V30 15 C 4.96571 -3.48512 0.0 0
M  V30 16 C 6.43719 -3.48472 0.0 0
M  V30 17 C 5.70285 -3.05983 0.0 0
M  V30 18 N 6.43719 -4.33594 0.0 0
M  V30 19 C 4.96571 -4.33976 0.0 0
M  V30 20 C 5.7047 -4.76073 0.0 0
M  V30 21 C 7.17388 -3.05985 0.0 0
M  V30 22 C 7.90901 -1.78515 0.0 0
M  V30 23 C 7.17395 -2.20882 0.0 0
M  V30 24 C 8.64632 -2.2106 0.0 0
M  V30 25 N 7.9141 -3.48701 0.0 0
M  V30 26 C 8.64809 -3.05737 0.0 0
M  V30 27 C 4.98697 -6.01514 0.0 0
M  V30 28 N 6.45845 -6.01473 0.0 0
M  V30 29 C 5.7241 -5.58984 0.0 0
M  V30 30 C 6.45845 -6.86595 0.0 0
M  V30 31 C 4.98697 -6.86977 0.0 0
M  V30 32 C 5.72596 -7.29074 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 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]([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-12122214242D
   -INDIGO-02262411182D


   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 35 39 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 C 4.57242 -3.91012 0.0 0
M  V30 2 N 6.9043 -7.15427 0.0 0
M  V30 2 C 6.0439 -3.90972 0.0 0
M  V30 3 C 6.25586 -6.82978 0.0 0
M  V30 3 C 5.30956 -3.48483 0.0 0
M  V30 4 C 6.71695 -8.15589 0.0 0
M  V30 4 N 6.0439 -4.76094 0.0 0
M  V30 5 C 5.33916 -7.91747 0.0 0
M  V30 5 C 4.57242 -4.76476 0.0 0
M  V30 6 C 5.91415 -8.44484 0.0 0
M  V30 6 C 5.31141 -5.18573 0.0 0
M  V30 7 C 7.21625 -8.56484 0.0 0
M  V30 7 C 6.78059 -3.48485 0.0 0
M  V30 8 C 8.63947 -8.85859 0.0 0
M  V30 8 C 7.51572 -2.21015 0.0 0
M  V30 9 N 8.10539 -8.15209 0.0 0
M  V30 9 C 6.78066 -2.63382 0.0 0
M  V30 10 C 8.35907 -9.69478 0.0 0
M  V30 10 C 8.25303 -2.6356 0.0 0
M  V30 11 C 7.06492 -9.39434 0.0 0
M  V30 11 N 7.52081 -3.91201 0.0 0
M  V30 12 C 7.62204 -9.91148 0.0 0
M  V30 12 C 8.2548 -3.48237 0.0 0
M  V30 13 C 5.16785 -4.55363 0.0 0
M  V30 13 C 4.59368 -6.44014 0.0 0
M  V30 14 C 6.51757 -4.39553 0.0 0
M  V30 14 N 6.06516 -6.43973 0.0 0
M  V30 15 C 5.78824 -4.09545 0.0 0
M  V30 15 C 5.33081 -6.01484 0.0 0
M  V30 16 N 6.77993 -5.43252 0.0 0
M  V30 16 C 6.06516 -7.29095 0.0 0
M  V30 17 C 5.28775 -5.36582 0.0 0
M  V30 17 C 4.59368 -7.29477 0.0 0
M  V30 18 C 6.08144 -5.77947 0.0 0
M  V30 18 C 5.33267 -7.71574 0.0 0
M  V30 19 C 6.75408 -3.2373 0.0 0
M  V30 19 C 6.80206 -7.71546 0.0 0
M  V30 20 C 8.12511 -3.00621 0.0 0
M  V30 20 C 8.27359 -7.71264 0.0 0
M  V30 21 C 7.36697 -2.72554 0.0 0
M  V30 21 N 7.5385 -7.28895 0.0 0
M  V30 22 C 8.36806 -3.8652 0.0 0
M  V30 22 C 8.27497 -8.56387 0.0 0
M  V30 23 C 7.00126 -4.13112 0.0 0
M  V30 23 C 6.80346 -8.57008 0.0 0
M  V30 24 N 7.89367 -4.47269 0.0 0
M  V30 24 C 7.54314 -8.98985 0.0 0
M  V30 25 Ru 8.41026 -6.26132 0.0 0
M  V30 25 Ru 7.51415 -5.53448 0.0 0 CHG=2
M  V30 26 O 9.24511 -5.12874 0.0 0
M  V30 26 H 8.88229 -4.57554 0.0 0 CHG=-1
M  V30 27 O 9.35312 -7.066 0.0 0
M  V30 27 C 8.93149 -6.24753 0.0 0 CHG=-1
M  V30 28 C 10.4996 -4.95962 0.0 0
M  V30 28 O 9.78318 -6.7393 0.0 0 CHG=1
M  V30 29 C 10.811 -3.86385 0.0 0
M  V30 29 F 10.5241 -4.07553 0.0 0
M  V30 30 C 11.3172 -5.67688 0.0 0
M  V30 30 P 11.3758 -3.58377 0.0 0 CHG=-1
M  V30 31 C 10.0768 -7.51261 0.0 0
M  V30 31 F 12.2276 -4.07553 0.0 0
M  V30 32 C 10.9279 -7.12955 0.0 0
M  V30 32 F 11.3758 -2.60024 0.0 0
M  V30 33 C 10.103 -8.67227 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
 
{{#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]]).


  0  0  0  0  0  0  0  0  0  0  0 V3000
==== Additives ====
M  V30 BEGIN CTAB
No additives were used in the described experiments.[[Category:Publication]]
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
|}
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}

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

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