Editing Photochemical CO2 Reduction Driven by Water-Soluble Copper(I) Photosensitizer with the Catalysis Accelerated by Multi-Electron Chargeable Cobalt Porphyrin

{{DOI|doi=10.1021/acscatal.9b04023}}
[[Category:Topic]][[Category:Publication]]
{{BaseTemplate}}

=== Abstract ===
This study introduces a fully aqueous photochemical CO₂ reduction system that uses a water-soluble copper(I) photosensitizer (CuPS){{#moleculelink:|link=PDVCFPPNDZGLBQ-UHFFFAOYSA-L|image=false|width=300|height=200}} and a cobalt porphyrin catalyst (CoTMPyP). The system achieves high turnover numbers and selectivity for CO₂-to-CO conversion, outperforming other aqueous systems. The multi-electron chargeable property of CoTMPyP is key to its catalytic efficiency and selectivity.
[[Category:Publication]]
=== Summary ===
A cop
[[Category:Publication]]
per(I) diimine complex serves as an efficient, water-soluble photosensitizer, enabling visible-light-driven CO₂-to-CO conversion in aqueous media. This system incorporates CoTMPyP, a cobalt porphyrin catalyst, achieving unprecedented catalytic performance. Key advances include a high turnover number (TON) and fast catalytic rates due to the multi-electron redox properties of CoTMPyP. The study demonstrates the potential of combining earth-abundant materials for sustainable photochemical CO₂ reduction.

=== Additional Remarks ===
The research underscores the importance of designing water-compatible, earth-abundant photocatalytic systems. CoTMPyP's multi-electron storage capability enables rapid intramolecular electron transfer, improving CO release. The CuPS-CoTMPyP system provides insights into addressing challenges like H₂ competition in aqueous CO₂ reduction systems.

=== Content of the Published Article in Detail ===

* Design and preparation of the copper(I) photosensitizer CuPS.
* Photochemical studies demonstrating the CO₂ reduction mechanism in aqueous systems.
* Role of the multi-electron chargeable CoTMPyP in accelerating catalysis.
* Experimental results showing high TON and TOF under optimized conditions.
* Discussion of reaction selectivity, including negligible formation of undesired byproducts such as HCOOH.

=== Catalysts Tested in This Study ===

* '''CoTMPyP:''' A cobalt porphyrin catalyst with high catalytic efficiency (right).
* '''CoTPPS:''' Another cobalt porphyrin derivative used for comparison, with lower activity and selectivity compared to CoTMPyP (left) {{#moleculelink: |link=LKGFMTVNMUURDY-UHFFFAOYSA-N|image=false|width=300|height=200}}.


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  -INDIGO-01102515312D

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</chemform>

=== Photosensitizer ===
The copper(I) photosensitizer CuPS ([Cu(L1)(L2)]BF4), where L1 and L2 are ligands, features long-lived excited states, making it highly efficient in driving photochemical CO₂ reduction in aqueous media.

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  -INDIGO-12112415042D

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M  V30 28 C 4.9251 -0.870721 0.0 0
M  V30 29 C 5.3391 -1.31346 0.0 0
M  V30 30 C 6.1671 -1.31346 0.0 0
M  V30 31 C 6.5811 -0.870721 0.0 0
M  V30 32 C 7.16617 -0.345865 0.0 0
M  V30 33 C 7.29824 0.27137 0.0 0
M  V30 34 P 4.0971 0.902292 0.0 0
M  V30 35 P 4.0971 -0.870721 0.0 0
M  V30 36 C -3.27829 2.07581 0.0 0
M  V30 37 C -3.27829 2.90039 0.0 0
M  V30 38 C -3.99269 3.31302 0.0 0
M  V30 39 C -4.70641 2.90039 0.0 0
M  V30 40 C -4.70641 2.07581 0.0 0
M  V30 41 C -3.99269 1.66387 0.0 0
M  V30 42 C -3.27829 -2.0635 0.0 0
M  V30 43 C -3.99269 -1.65155 0.0 0
M  V30 44 C -4.70641 -2.0635 0.0 0
M  V30 45 C -4.70641 -2.88807 0.0 0
M  V30 46 C -3.99269 -3.3007 0.0 0
M  V30 47 C -3.27829 -2.88807 0.0 0
M  V30 48 C 3.51134 1.48737 0.0 0
M  V30 49 C 3.72484 2.28389 0.0 0
M  V30 50 C 3.14182 2.86691 0.0 0
M  V30 51 C 2.3453 2.65341 0.0 0
M  V30 52 C 2.1318 1.85689 0.0 0
M  V30 53 C 2.71482 1.27387 0.0 0
M  V30 54 C 4.5111 1.61944 0.0 0
M  V30 55 C 5.33568 1.61944 0.0 0
M  V30 56 C 5.74762 2.33315 0.0 0
M  V30 57 C 5.33568 3.04756 0.0 0
M  V30 58 C 4.5111 3.04756 0.0 0
M  V30 59 C 4.09847 2.33315 0.0 0
M  V30 60 C 3.51134 -1.45579 0.0 0
M  V30 61 C 2.71482 -1.24229 0.0 0
M  V30 62 C 2.1318 -1.826 0.0 0
M  V30 63 C 2.3453 -2.62183 0.0 0
M  V30 64 C 3.14182 -2.83534 0.0 0
M  V30 65 C 3.72484 -2.25232 0.0 0
M  V30 66 C 4.31128 -1.67066 0.0 0
M  V30 67 C 3.72826 -2.25368 0.0 0
M  V30 68 C 3.94176 -3.05021 0.0 0
M  V30 69 C 4.73829 -3.26302 0.0 0
M  V30 70 C 5.32131 -2.68 0.0 0
M  V30 71 C 5.10781 -1.88348 0.0 0
M  V30 72 S 6.75046 1.92839 0.0 0
M  V30 73 O 6.16951 2.50935 0.0 0
M  V30 74 O 7.33141 1.34744 0.0 0
M  V30 75 O 7.33141 2.50935 0.0 0 CHG=-1
M  V30 76 S 6.75046 -1.89682 0.0 0
M  V30 77 O 7.33141 -1.31587 0.0 0
M  V30 78 O 6.16951 -2.47778 0.0 0
M  V30 79 O 7.33141 -2.47778 0.0 0 CHG=-1
M  V30 80 S -3.99275 0.833017 0.0 0
M  V30 81 O -4.40356 0.121507 0.0 0
M  V30 82 O -3.58194 1.54453 0.0 0
M  V30 83 O -4.70426 1.24383 0.0 0 CHG=-1
M  V30 84 S -3.99275 -0.820015 0.0 0
M  V30 85 O -3.58194 -1.53153 0.0 0
M  V30 86 O -4.40356 -0.108505 0.0 0
M  V30 87 O -4.70426 -1.23083 0.0 0 CHG=-1
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 2 40 41
M  V30 2 1 39 40
M  V30 3 2 38 39
M  V30 4 1 37 38
M  V30 5 2 36 37
M  V30 6 1 36 41
M  V30 7 1 1 36
M  V30 8 2 46 47
M  V30 9 1 45 46
M  V30 10 2 44 45
M  V30 11 1 43 44
M  V30 12 2 42 43
M  V30 13 1 42 47
M  V30 14 1 11 42
M  V30 15 2 52 53
M  V30 16 1 51 52
M  V30 17 2 50 51
M  V30 18 1 49 50
M  V30 19 2 48 49
M  V30 20 1 48 53
M  V30 21 1 34 48
M  V30 22 2 58 59
M  V30 23 1 57 58
M  V30 24 2 56 57
M  V30 25 1 55 56
M  V30 26 2 54 55
M  V30 27 1 54 59
M  V30 28 1 34 54
M  V30 29 2 64 65
M  V30 30 1 63 64
M  V30 31 2 62 63
M  V30 32 1 61 62
M  V30 33 2 60 61
M  V30 34 1 60 65
M  V30 35 1 35 60
M  V30 36 2 70 71
M  V30 37 1 69 70
M  V30 38 2 68 69
M  V30 39 1 67 68
M  V30 40 2 66 67
M  V30 41 1 66 71
M  V30 42 1 35 66
M  V30 43 2 72 73
M  V30 44 2 72 74
M  V30 45 1 72 75
M  V30 46 1 25 72
M  V30 47 2 76 77
M  V30 48 2 76 78
M  V30 49 1 76 79
M  V30 50 1 30 76
M  V30 51 2 80 81
M  V30 52 2 80 82
M  V30 53 1 80 83
M  V30 54 1 7 80
M  V30 55 2 84 85
M  V30 56 2 84 86
M  V30 57 1 84 87
M  V30 58 1 8 84
M  V30 59 2 1 2
M  V30 60 1 2 3
M  V30 61 2 3 4
M  V30 62 1 4 5
M  V30 63 2 5 6
M  V30 64 1 6 1
M  V30 65 1 2 7
M  V30 66 2 7 8
M  V30 67 1 8 9
M  V30 68 2 9 10
M  V30 69 1 10 3
M  V30 70 1 9 11
M  V30 71 2 11 12
M  V30 72 1 12 13
M  V30 73 2 13 14
M  V30 74 1 14 10
M  V30 75 1 5 15
M  V30 76 1 13 16
M  V30 77 1 18 19
M  V30 78 1 19 20
M  V30 79 1 20 21
M  V30 80 1 21 22
M  V30 81 1 22 23
M  V30 82 1 23 18
M  V30 83 2 19 24
M  V30 84 1 24 25
M  V30 85 2 25 26
M  V30 86 1 26 27
M  V30 87 2 27 20
M  V30 88 2 22 28
M  V30 89 1 28 29
M  V30 90 2 29 30
M  V30 91 1 30 31
M  V30 92 2 31 23
M  V30 93 1 18 32
M  V30 94 1 18 33
M  V30 95 1 27 34
M  V30 96 1 28 35
M  V30 97 8 34 17
M  V30 98 8 35 17
M  V30 99 8 4 17
M  V30 100 8 14 17
M  V30 END BOND
M  V30 BEGIN SGROUP
M  V30 1 SUP 1 ATOMS=(6 36 37 38 39 40 41) BRKXYZ=(9 0.000000 0.000000 0.0000-
M  V30 00 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000) BRKXYZ=(9 0.-
M  V30 000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 -
M  V30 0.000000) LABEL=Ph
M  V30 2 SUP 2 ATOMS=(6 42 43 44 45 46 47) BRKXYZ=(9 0.000000 0.000000 0.0000-
M  V30 00 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000) BRKXYZ=(9 0.-
M  V30 000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 -
M  V30 0.000000) LABEL=Ph
M  V30 3 SUP 3 ATOMS=(6 48 49 50 51 52 53) BRKXYZ=(9 0.000000 0.000000 0.0000-
M  V30 00 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000) BRKXYZ=(9 0.-
M  V30 000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 -
M  V30 0.000000) LABEL=Ph
M  V30 4 SUP 4 ATOMS=(6 54 55 56 57 58 59) BRKXYZ=(9 0.000000 0.000000 0.0000-
M  V30 00 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000) BRKXYZ=(9 0.-
M  V30 000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 -
M  V30 0.000000) LABEL=Ph
M  V30 5 SUP 5 ATOMS=(6 60 61 62 63 64 65) BRKXYZ=(9 0.000000 0.000000 0.0000-
M  V30 00 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000) BRKXYZ=(9 0.-
M  V30 000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 -
M  V30 0.000000) LABEL=Ph
M  V30 6 SUP 6 ATOMS=(6 66 67 68 69 70 71) BRKXYZ=(9 0.000000 0.000000 0.0000-
M  V30 00 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000) BRKXYZ=(9 0.-
M  V30 000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 -
M  V30 0.000000) LABEL=Ph
M  V30 7 SUP 7 ATOMS=(4 72 73 74 75) BRKXYZ=(9 0.000000 0.000000 0.000000 0.0-
M  V30 00000 0.000000 0.000000 0.000000 0.000000 0.000000) BRKXYZ=(9 0.000000-
M  V30  0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.0000-
M  V30 00) LABEL="SO3-"
M  V30 8 SUP 8 ATOMS=(4 76 77 78 79) BRKXYZ=(9 0.000000 0.000000 0.000000 0.0-
M  V30 00000 0.000000 0.000000 0.000000 0.000000 0.000000) BRKXYZ=(9 0.000000-
M  V30  0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.0000-
M  V30 00) LABEL="SO3-"
M  V30 9 SUP 9 ATOMS=(4 80 81 82 83) BRKXYZ=(9 0.000000 0.000000 0.000000 0.0-
M  V30 00000 0.000000 0.000000 0.000000 0.000000 0.000000) BRKXYZ=(9 0.000000-
M  V30  0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.0000-
M  V30 00) LABEL="SO3-"
M  V30 10 SUP 10 ATOMS=(4 84 85 86 87) BRKXYZ=(9 0.000000 0.000000 0.000000 0-
M  V30 .000000 0.000000 0.000000 0.000000 0.000000 0.000000) BRKXYZ=(9 0.0000-
M  V30 00 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.00-
M  V30 0000) LABEL="SO3-"
M  V30 END SGROUP
M  V30 END CTAB
M  END
</chemform>

=== Investigation ===
The study involved kinetic analysis of CO and H₂ production under various conditions. Control experiments confirmed the roles of CuPS, CoTMPyP, and ascorbate. The performance was evaluated by quantum yield and CO selectivity metrics, with additional insights provided by structural characterization of intermediates.

{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Tabel 1|importFile=Photocatalytic_CO2_conversion_Template_New.xlsx|description=}}

=== Further Information ===
The findings highlight the influence of ligand design in CuPS and the impact of peripheral groups in CoTMPyP. Future applications might involve integrating such catalysts into hybrid systems or scaling them for industrial CO₂ reduction.

=== Sacrificial Electron Donor ===
In this study, the sacrificial electron donor was sodium ascorbate (AscHNa), which facilitated efficient electron transfer to drive the CO₂ reduction reaction.

=== Additives ===
Additives such as bicarbonate buffer were used to maintain the pH and reaction environment, ensuring stability and efficiency of the photocatalytic system.
[[Category:Photocatalytic CO2 conversion]]