An integrated Re(I) photocatalyst and sensitizer that activates the formation of formic acid from reduction of CO2: Difference between revisions

Latest revision as of 10:37, 11 April 2024

A photochemical reduction of CO₂ to formic acid was shown using the rhenium catalyst and sensitizer [Re(bpy)2(CO)2][OTf] in combination with the supplemental photosensitizer [Ru(bpy)3][PF6]. Turnover numbers (TONs) up to 2750 for formic acid were reached in dimethylacetamide. The experiments were conducted under visible-light irradiation (λ = 405 nm) with TEOA (see section SEDs below) as sacrificial electron donor.

Advances and special progress[edit | edit source]

A unprecedented rhenium complex was used as an integrated photosensitizer/catalyst to generate formic acid from CO₂; other rhenium catalysts only allow for the formation of CO as the reduction product.

Additional remarks[edit | edit source]

The complex [Re(bpy)2(CO)2][OTf] can act both as a photocatalyst and sensitizer, but its performance is considerably enhanced by the addition of [Ru(bpy)3][PF6] as supplemental photosensitizer. The variation of the catalyst concentration also showed a drastic influence on the performance of the catalytic system.

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

The article contains results for the reduction of CO₂ to formic acid under visible-light catalysis using a rhenium complex as a catalyst. The catalytic system performs best (referring to the TON of formic acid production) in dimethylacetamide.

Catalyst[edit | edit source]

[Re(bpy)2(CO)2][OTf]

Photosensitizer[edit | edit source]

[Ru(bpy)3][PF6]

Investigations[edit | edit source]

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	solvent A	λexc [nm]	TON H2	TON HCOOH
1.			[Ru(bpy)3][PF6]	0.8	TEOA	DMA	405 nm	1.75	12.5
2.			[Ru(bpy)3][PF6]	0.8	TEOA	DMF	405 nm	2	15
3.			[Ru(bpy)3][PF6]	0.8	TEOA	MeCN	405 nm	1.5	2.5
4.	[Re(bpy)2(CO)2][OTf]	0.8			TEOA	DMA	405 nm		10.3
5.	[Re(bpy)2(CO)2][OTf]	0.8	[Ru(bpy)3][PF6]	0.8	TEOA	DMA	405 nm	1.5	52
6.	[Re(bpy)2(CO)2][OTf]	0.8			TEOA	DMF	405 nm	0.8	10.8
7.	[Re(bpy)2(CO)2][OTf]	0.8	[Ru(bpy)3][PF6]	0.8	TEOA	DMF	405 nm	2.8	66
8.	[Re(bpy)2(CO)2][OTf]	0.8	[Ru(bpy)3][PF6]	0.8	TEOA	MeCN	405 nm
9.	[Re(bpy)2(CO)2][OTf]	0.8	[Ru(bpy)3][PF6]	0.8	TEOA	MeCN	405 nm	2.8	11.5

Investigation-Name: Solvent effect study between DMA DMF and acetonitrile

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	solvent A	λexc [nm]	TON H2	TON HCOOH
1.	[Re(bpy)2(CO)2][OTf]	0.2	[Ru(bpy)3][PF6]	0.2	TEOA	DMF	405 nm	0	0
2.	[Re(bpy)2(CO)2][OTf]	0.2	[Ru(bpy)3][PF6]	0.2	TEOA	DMF	405 nm	1	12.5
3.	[Re(bpy)2(CO)2][OTf]	0.2	[Ru(bpy)3][PF6]	0.2	TEOA	DMF	405 nm	2.5	19.5
4.	[Re(bpy)2(CO)2][OTf]	0.2	[Ru(bpy)3][PF6]	0.2	TEOA	DMF	405 nm	4.5	50.5
5.	[Re(bpy)2(CO)2][OTf]	0.2	[Ru(bpy)3][PF6]	0.2	TEOA	DMF	405 nm	6	59.5
6.	[Re(bpy)2(CO)2][OTf]	0.2	[Ru(bpy)3][PF6]	0.2	TEOA	DMF	405 nm	8.5	69.25

Investigation-Name: Time profile in DMF

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	solvent A	λexc [nm]	TON H2	TON HCOOH
1.	[Re(bpy)2(CO)2][OTf]	1			TEOA	DMA	405		10.3
2.	[Re(bpy)2(CO)2][OTf]	1	[Ru(bpy)3][PF6]	1	TEOA	DMA	405	1.5	52
3.	[Re(bpy)2(CO)2][OTf]	0.5	[Ru(bpy)3][PF6]	1	TEOA	DMA	405	15	115
4.	[Re(bpy)2(CO)2][OTf]	0.2	[Ru(bpy)3][PF6]	1	TEOA	DMA	405	24	275
5.	[Re(bpy)2(CO)2][OTf]	0.1	[Ru(bpy)3][PF6]	1	TEOA	DMA	405	38	428
6.	[Re(bpy)2(CO)2][OTf]	0.05	[Ru(bpy)3][PF6]	1	TEOA	DMA	405	50	535
7.	[Re(bpy)2(CO)2][OTf]	0.02	[Ru(bpy)3][PF6]	1	TEOA	DMA	405	225	1480
8.	[Re(bpy)2(CO)2][OTf]	0.01	[Ru(bpy)3][PF6]	1	TEOA	DMA	405	375	2750

Investigation-Name: Study on the concentration of catalyst

	cat	PS	e-D	solvent A	additives	λexc [nm]	TON H2	TON HCOOH
1.	[Re(bpy)2(CO)2][OTf]	[Ru(bpy)3][PF6]	TEOA	DMF	water	405 nm	4.25	25
2.	[Re(bpy)2(CO)2][OTf]	[Ru(bpy)3][PF6]	TEOA	DMF	water	405 nm	5.75	25.75
3.	[Re(bpy)2(CO)2][OTf]	[Ru(bpy)3][PF6]	TEOA	DMF	phenol	405 nm	5.25	27
4.	[Re(bpy)2(CO)2][OTf]	[Ru(bpy)3][PF6]	TEOA	DMF	phenol	405 nm	5.75	19
5.	[Re(bpy)2(CO)2][OTf]	[Ru(bpy)3][PF6]	TEA	DMF	water	405 nm	2	12.5
6.	[Re(bpy)2(CO)2][OTf]	[Ru(bpy)3][PF6]	TEA	DMF	water	405 nm	2.75	14.5
7.	[Re(bpy)2(CO)2][OTf]	[Ru(bpy)3][PF6]	TEA	DMF	phenol	405 nm	1	10.25
8.	[Re(bpy)2(CO)2][OTf]	[Ru(bpy)3][PF6]	TEA	DMF	phenol	405 nm	16.25	11.25
9.	[Re(bpy)2(CO)2][OTf]	[Ru(bpy)3][PF6]	TEOA	DMA	water	405 nm	3.25	20.5
10.	[Re(bpy)2(CO)2][OTf]	[Ru(bpy)3][PF6]	TEOA	DMA	water	405 nm	3.5	24
11.	[Re(bpy)2(CO)2][OTf]	[Ru(bpy)3][PF6]	TEOA	DMA	phenol	405 nm	7.75	30
12.	[Re(bpy)2(CO)2][OTf]	[Ru(bpy)3][PF6]	TEOA	DMA	phenol	405 nm	9	34.75

Investigation-Name: Effect of proton donor

Sacrificial electron donor[edit | edit source]

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

Additives[edit | edit source]

In this study, the experiments were done with the additives water (H2O) and phenol (PhOH).

Investigations

Effect of proton donor (Molecular process, Photocatalytic CO2 conversion experiments)
Solvent effect study between DMA DMF and acetonitrile (Molecular process, Photocatalytic CO2 conversion experiments)
Study on the concentration of catalyst (Molecular process, Photocatalytic CO2 conversion experiments)
Time profile in DMF (Molecular process, Photocatalytic CO2 conversion experiments)

DOI	10.1039/c9cc03943k
Authors	Yasmeen Hameed, Patrick Berro, Bulat Gabidullin, Darrin Richeson,
Submitted	16.08.2019
Published online	2019
Licenses	http://rsc.li/journals-terms-of-use,
Subjects	Materials Chemistry, Metals and Alloys, Surfaces, Coatings and Films, General Chemistry, Ceramics and Composites, Electronic, Optical and Magnetic Materials, Catalysis
Go to literature page

@@ Line 1: / Line 1: @@
-{{#doiinfobox: 10.1039/c9cc03943k}}
+{{DOI|doi=10.1039/c9cc03943k}}
 [[Category:Photocatalytic CO2 conversion to HCOOH]]
 {{BaseTemplate}}
-=== Investigation ===
+===Abstract===
-=== Catalyst ===
+====Summary====
-=== Photosensitizer ===
+A photochemical reduction of CO<sub>2</sub> to formic acid was shown using the rhenium catalyst and sensitizer {{#moleculelink:|link=SQEHJZNRDJMTCB-UHFFFAOYSA-M|image=false|width=300|height=200}} in combination with the supplemental photosensitizer {{#moleculelink:|link=KLDYQWXVZLHTKT-UHFFFAOYSA-N|image=false|width=300|height=200}}. Turnover numbers (TONs) up to 2750 for formic acid were reached in dimethylacetamide. The experiments were conducted under visible-light irradiation (λ = 405 nm) with TEOA (see section SEDs below) as sacrificial electron donor.
-=== Sacrificial electron donor ===
+====Advances and special progress====
+A unprecedented rhenium complex was used as an integrated photosensitizer/catalyst to generate formic acid from CO<sub>2</sub>; other rhenium catalysts only allow for the formation of CO as the reduction product.
+====Additional remarks====
+The complex {{#moleculelink:|link=SQEHJZNRDJMTCB-UHFFFAOYSA-M|image=false|width=300|height=200}} can act both as a photocatalyst and sensitizer, but its performance is considerably enhanced by the addition of {{#moleculelink:|link=KLDYQWXVZLHTKT-UHFFFAOYSA-N|image=false|width=300|height=200}} as supplemental photosensitizer. The variation of the catalyst concentration also showed a drastic influence on the performance of the catalytic system.
+=== Content of the published article in detail ===
+The article contains results for the reduction of CO<sub>2</sub> to formic acid under visible-light catalysis using a rhenium complex as a catalyst. The catalytic system performs best (referring to the TON of formic acid production) in dimethylacetamide.
+=== Catalyst===
+<chemform smiles="C1C=C2C3C=CC=CN=3[Re+]([C-]#[O+])([C-]#[O+])3(N4C=CC=CC=4C4N3=CC=CC=4)N2=CC=1.S(C(F)(F)F)([O-])(=O)=O" inchi="1S/2C10H8N2.CHF3O3S.2CO.Re/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;2-1(3,4)8(5,6)7;2*1-2;/h2*1-8H;(H,5,6,7);;;/q;;;;;+1/p-1" inchikey="SQEHJZNRDJMTCB-UHFFFAOYSA-M" height="200px" width="300px" float="none">
+  -INDIGO-05192310272D
+  0  0  0  0  0  0  0  0  0  0 V3000
+M  V30 BEGIN CTAB
+M  V30 COUNTS 37 41 0 0 0
+M  V30 BEGIN ATOM
+M  V30 1 C 4.88485 -4.72507 0.0 0
+M  V30 2 C 6.61515 -4.72459 0.0 0
+M  V30 3 C 5.75164 -4.22497 0.0 0
+M  V30 4 N 6.61515 -5.72553 0.0 0
+M  V30 5 C 4.88485 -5.73002 0.0 0
+M  V30 6 C 5.75382 -6.22503 0.0 0
+M  V30 7 C 5.75382 -7.22503 0.0 0
+M  V30 8 C 6.6204 -8.7227 0.0 0
+M  V30 9 N 6.62066 -7.72506 0.0 0
+M  V30 10 C 5.75389 -9.22375 0.0 0
+M  V30 11 C 4.88385 -7.72809 0.0 0
+M  V30 12 C 4.89031 -8.72814 0.0 0
+M  V30 13 C 7.35985 -8.97507 0.0 0
+M  V30 14 C 9.09015 -8.97459 0.0 0
+M  V30 15 N 8.22664 -8.47497 0.0 0
+M  V30 16 C 9.09015 -9.97553 0.0 0
+M  V30 17 C 7.35985 -9.98002 0.0 0
+M  V30 18 C 8.22882 -10.475 0.0 0
+M  V30 19 C 9.95618 -8.47459 0.0 0
+M  V30 20 C 10.8199 -6.97528 0.0 0
+M  V30 21 N 9.95579 -7.47387 0.0 0
+M  V30 22 C 11.6871 -7.47517 0.0 0
+M  V30 23 C 10.8268 -8.97648 0.0 0
+M  V30 24 C 11.6897 -8.47085 0.0 0
+M  V30 25 Re 8.175 -6.775 0.0 0 CHG=1
+M  V30 26 C 8.175 -5.3 0.0 0 CHG=-1
+M  V30 27 C 9.56603 -5.975 0.0 0 CHG=-1
+M  V30 28 O 8.175 -4.3 0.0 0 CHG=1
+M  V30 29 O 10.4321 -5.475 0.0 0 CHG=1
+M  V30 30 S 14.2464 -6.03834 0.0 0
+M  V30 31 O 15.1125 -5.53834 0.0 0
+M  V30 32 O 14.7464 -6.90437 0.0 0
+M  V30 33 O 13.3804 -6.53834 0.0 0 CHG=-1
+M  V30 34 C 13.7464 -5.17232 0.0 0
+M  V30 35 F 14.4536 -4.46521 0.0 0
+M  V30 36 F 13.2464 -4.30629 0.0 0
+M  V30 37 F 12.8804 -5.67232 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 6 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 14 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 4 25
+M  V30 28 10 9 25
+M  V30 29 10 15 25
+M  V30 30 10 21 25
+M  V30 31 10 25 26
+M  V30 32 10 25 27
+M  V30 33 3 26 28
+M  V30 34 3 27 29
+M  V30 35 2 30 31
+M  V30 36 2 30 32
+M  V30 37 1 30 33
+M  V30 38 1 30 34
+M  V30 39 1 34 35
+M  V30 40 1 34 36
+M  V30 41 1 34 37
+M  V30 END BOND
+M  V30 END CTAB
+M  END
+</chemform>
+===Photosensitizer===
+<chemform smiles="" inchi="" inchikey="KLDYQWXVZLHTKT-UHFFFAOYSA-N" height="200px" width="300px" float="none"></chemform>
+===Investigations===
+{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Solvent effect study between DMA DMF and acetonitrile|importFile=}}
+{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Time profile in DMF|importFile=}}{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Study on the concentration of catalyst}}
+{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Effect of proton donor|importFile=}}
+====Sacrificial electron donor====
+In this study, the experiments were done with the sacrificial electron donor TEOA ([[Molecule:100507|100507]]).
+====Additives====
+In this study, the experiments were done with the additives water ({{#moleculelink:|link=XLYOFNOQVPJJNP-UHFFFAOYSA-N|image=false|width=300|height=200}}) and phenol ({{#moleculelink:|link=ISWSIDIOOBJBQZ-UHFFFAOYSA-N|image=false|width=300|height=200}}).[[Category:Publication]]

An integrated Re(I) photocatalyst and sensitizer that activates the formation of formic acid from reduction of CO2: Difference between revisions

Latest revision as of 10:37, 11 April 2024

Contents

Abstract[edit | edit source]

Summary[edit | edit source]

Advances and special progress[edit | edit source]

Additional remarks[edit | edit source]

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

Catalyst[edit | edit source]

Photosensitizer[edit | edit source]

Investigations[edit | edit source]

Sacrificial electron donor[edit | edit source]

Additives[edit | edit source]

Investigations

Topics

An integrated Re(I) photocatalyst and sensitizer that activates the formation of formic acid from reduction of CO2: Difference between revisions

Latest revision as of 10:37, 11 April 2024

Abstract[edit | edit source]

Summary[edit | edit source]

Advances and special progress[edit | edit source]

Additional remarks[edit | edit source]

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

Catalyst[edit | edit source]

Photosensitizer[edit | edit source]

Investigations[edit | edit source]

Sacrificial electron donor[edit | edit source]

Additives[edit | edit source]

Investigations

Current site

Topics