Toward Visible-Light Photochemical CO2‑to-CH4 Conversion in Aqueous Solutions Using Sensitized Molecular Catalysis: Difference between revisions

Latest revision as of 14:36, 5 September 2024

A photochemical reduction of CO₂ was achieved using an iron porphyrin catalyst and an iridium complex as the photosensitizer. Carbon monoxide, produced with a TON of 178 under optimized conditions, was the main product, methane was produced in a substantial amount with the TON of 32, while hydrogen was formed as a minor byproduct. The experiments were performed under irradiation with λ > 420 nm in acetonitrile and in the presence of various amines as sacrificial electron donors.

Advances and special progress[edit | edit source]

The catalytic reduction of CO₂ could also be realized under aqueous conditions (acetonitrile/water 3:7 v:v), yielding carbon monoxide as the main product while methane was produced with selectivity up to 10% (TON of 3).

Additional remarks[edit | edit source]

Among the various amines employed as sacrificial electron donors, TEA appeared as the best choice to maximize CO₂ product formation.

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

The article contains results for the reduction of CO₂ to CO as the main product under visible-light irradiation using iron porphyrin complex Fe(pTMAPP)Cl₅ (Fe(pTMAPP)Cl5) as the catalysts, an iridium complex as the photosensitizer and various amines as the sacrificial electron donor. The catalytic system performs best (referring to the TON of CO production) with Ir(ppy)₃ (Ir(ppy)3) as the photosensitizer and TEA as the sacrificial electron donor.

Catalyst[edit | edit source]

Fe(pTMAPP)Cl5

Photosensitizer[edit | edit source]

[Ir(ppy)2(bpy)][PF6] Ir(ppy)3

Investigation[edit | edit source]

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	e-D conc [M]	solvent A	additives	λexc [nm]	TON CO	TON CH4	TON H2
1.	Fe(pTMAPP)Cl5	0.002	[Ir(ppy)2(bpy)][PF6]	0.2	TEA	0.05	MeCN		> 420	178	32	103
2.	Fe(pTMAPP)Cl5	0.002	[Ir(ppy)2(bpy)][PF6]	0.2	TEOA	0.05	MeCN		> 420	134	23	67
3.	Fe(pTMAPP)Cl5	0.002	[Ir(ppy)2(bpy)][PF6]	0.2	DIPEA	0.05	MeCN		> 420	151	24	77
4.	Fe(pTMAPP)Cl5	0.002	[Ir(ppy)2(bpy)][PF6]	0.2	TEA	0.05	MeCN		> 420	24	3	5
5.	Fe(pTMAPP)Cl5	0.002	[Ir(ppy)2(bpy)][PF6]	0.2	TEOA	0.05	MeCN		> 420	19	3	4
6.	Fe(pTMAPP)Cl5	0.002	[Ir(ppy)2(bpy)][PF6]	0.2	DIPEA	0.05	MeCN		> 420	20	3	4
7.	Fe(pTMAPP)Cl5	0.002	Ir(ppy)3	0.2	TEA	0.05	MeCN		> 420	198	31	24
8.	Fe(pTMAPP)Cl5	0.002	Ir(ppy)3	0.2	TEA	0.05	MeCN		> 420		89	18
9.	Fe(pTMAPP)Cl5	0.002	Ir(ppy)3	0.2	TEA	0.05	MeCN	TFE	> 420		100	19
10.	Fe(pTMAPP)Cl5	0.002	Ir(ppy)3	0.2	TEA	0.05	MeCN	TFE	> 420		195	45

Investigation-Name: Photocatalytic reduction of CO2: conditions optimization

	analyte	anl conc [mM]	reduction potential	solvent	electrolyte	gas	WE	RE
1.	[Ir(ppy)2(bpy)][PF6]	0.5	-2.0 , -1.4	MeCN	TBAPF6	argon	glassy carbon	SCE
2.	[Ir(ppy)2(bpy)][PF6]	0.5	-2.0, -1.4	MeCN	TBAPF6	CO	glassy carbon	SCE
3.	[Ir(ppy)2(bpy)][PF6]	0.5	-2.0, -1.4	MeCN	TBAPF6	CO	glassy carbon	SCE
4.	[Ir(ppy)2(bpy)][PF6]	0.5	-2.0, -1.4	MeCN	TBAPF6	CO	glassy carbon	SCE
5.	[Ir(ppy)2(bpy)][PF6]	0.5	-2.0	MeCN	TBAPF6	CO	glassy carbon	SCE

The results show an increase in current when the solution is irradiated and triethylamine (TEA) is added (see condition column).

Investigation-Name: Cyclic voltammetry in various conditions

Sacrificial electron donor[edit | edit source]

In this study, the experiments were conducted with TEA (TEA), TEOA (TEOA), and DIPEA (DIPEA) as sacrificial electron donors.

Additives[edit | edit source]

In some experiments described in this study, TFE (TFE) was used as an additive.

Investigations

Cyclic voltammetry in various conditions (Assay, Cyclic Voltammetry experiments)
Photocatalytic reduction of CO2: conditions optimization (Molecular process, Photocatalytic CO2 conversion experiments)

DOI	10.1021/acs.jpcc.8b00950
Authors	Heng Rao, Julien Bonin, Marc Robert,
Submitted	28.04.2018
Published online	28.04.2018
Licenses	-
Subjects	Surfaces, Coatings and Films, Physical and Theoretical Chemistry, General Energy, Electronic, Optical and Magnetic Materials
Go to literature page

@@ Line 1: / Line 1: @@
 {{BaseTemplate}}
-{{#doiinfobox: 10.1021/acs.jpcc.8b00950}}{{MissingSIData}}
+{{DOI|doi=10.1021/acs.jpcc.8b00950}}
+=== Abstract ===
+==== Summary====
+A photochemical reduction of CO<sub>2</sub> was achieved using an iron porphyrin catalyst and an iridium complex as the photosensitizer. Carbon monoxide, produced with a TON of 178 under optimized conditions, was the main product, methane was produced in a substantial amount with the TON of 32, while hydrogen was formed as a minor byproduct. The experiments were performed under irradiation with ''λ >'' 420 nm in acetonitrile and in the presence of various amines as sacrificial electron donors.
+==== Advances and special progress====
+The catalytic reduction of CO<sub>2</sub> could also be realized under aqueous conditions (acetonitrile/water 3:7 v:v), yielding carbon monoxide as the main product while methane was produced with selectivity up to 10% (TON of 3).
+==== Additional remarks====
+Among the various amines employed as sacrificial electron donors, TEA appeared as the best choice to maximize CO<sub>2</sub> product formation.
+=== Content of the published article in detail ===
+The article contains results for the reduction of CO<sub>2</sub> to CO as the main product under visible-light irradiation using iron porphyrin complex Fe(pTMAPP)Cl<sub>5</sub> ({{#moleculelink:|link=LKNRTBVZMCBYCY-NGWNFTKISA-I|image=false|width=300|height=200}}) as the catalysts, an iridium complex as the photosensitizer and various amines as the sacrificial electron donor. The catalytic system performs best (referring to the TON of CO production) with Ir(ppy)<sub>3</sub> ({{#moleculelink: |link=NSABRUJKERBGOU-UHFFFAOYSA-N|image=false|width=300|height=200}}) as the photosensitizer and TEA as the sacrificial electron donor.
 ==== Catalyst====
-{{#moleculelink:|link=NRVILUOLTIKJEU-NGWNFTKISA-I|image=true}}
+{{#moleculelink:|link=LKNRTBVZMCBYCY-NGWNFTKISA-I|image=true|width=300|height=200}}
 ====Photosensitizer====
-<chemform smiles="C1C=C2C3C([Ir+]4(N5C(C6N4=CC=CC=6)=CC=CC=5)4(N5C(C6C4=CC=CC=6)=CC=CC=5)N2=CC=1)=CC=CC=3" inchi="1S/2C11H9N.C10H8N2.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;/h2*1-9H;1-8H;/q;;;+1" inchikey="WEEPMIZXGXTKSO-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-01262315082D
+   -INDIGO-08012317332D
   0  0  0  0  0  0  0  0  0  0 V3000
 M  V30 BEGIN CTAB
-M  V30 COUNTS 37 45 0 0 0
+M  V30 COUNTS 44 51 0 0 0
 M  V30 BEGIN ATOM
-M  V30 1 C 4.45797 -3.44045 0.0 0
+M  V30 1 C 4.03485 -3.90007 0.0 0
-M  V30 2 C 5.96133 -3.36319 0.0 0
+M  V30 2 C 5.76515 -3.89959 0.0 0
-M  V30 3 C 5.12223 -3.03828 0.0 0
+M  V30 3 C 4.90164 -3.39997 0.0 0
-M  V30 4 N 6.18456 -4.17527 0.0 0
+M  V30 4 C 5.76515 -4.90053 0.0 0 CHG=-1
-M  V30 5 C 4.46811 -4.21322 0.0 0
+M  V30 5 C 4.03485 -4.90502 0.0 0
-M  V30 6 C 5.26148 -4.65508 0.0 0
+M  V30 6 C 4.90382 -5.40003 0.0 0
-M  V30 7 C 4.51917 -5.73215 0.0 0
+M  V30 7 C 6.63141 -3.39999 0.0 0
-M  V30 8 C 6.22384 -5.76587 0.0 0
+M  V30 8 C 7.49583 -1.90109 0.0 0
-M  V30 9 C 5.27077 -5.2974 0.0 0
+M  V30 9 C 6.63149 -2.39928 0.0 0
-M  V30 10 C 6.0193 -6.57651 0.0 0
+M  V30 10 C 8.36278 -2.40138 0.0 0
-M  V30 11 C 4.5162 -6.49701 0.0 0
+M  V30 11 N 7.50182 -3.90229 0.0 0
-M  V30 12 C 5.18205 -6.90334 0.0 0
+M  V30 12 C 8.3649 -3.39706 0.0 0
-M  V30 13 C 7.51732 -7.30385 0.0 0
+M  V30 13 C 4.08485 -6.82507 0.0 0
-M  V30 14 C 8.97092 -7.39426 0.0 0
+M  V30 14 C 5.81515 -6.82459 0.0 0 CHG=-1
-M  V30 15 C 8.09356 -6.79102 0.0 0
+M  V30 15 C 4.95164 -6.32497 0.0 0
-M  V30 16 C 8.96182 -8.29372 0.0 0
+M  V30 16 C 5.81515 -7.82553 0.0 0
-M  V30 17 C 7.6068 -8.20544 0.0 0
+M  V30 17 C 4.08485 -7.83002 0.0 0
-M  V30 18 C 8.27229 -8.63762 0.0 0
+M  V30 18 C 4.95382 -8.32503 0.0 0
-M  V30 19 N 9.48753 -6.07146 0.0 0
+M  V30 19 C 6.68166 -8.3247 0.0 0
-M  V30 20 C 11.0499 -6.53021 0.0 0
+M  V30 20 C 8.41196 -8.32139 0.0 0
-M  V30 21 C 10.3685 -5.88703 0.0 0
+M  V30 21 N 7.54763 -7.82318 0.0 0
-M  V30 22 C 10.9588 -7.31958 0.0 0
+M  V30 22 C 8.41359 -9.32233 0.0 0
-M  V30 23 C 9.51277 -7.13327 0.0 0
+M  V30 23 C 6.6833 -9.32964 0.0 0
-M  V30 24 C 10.258 -7.63524 0.0 0
+M  V30 24 C 7.55308 -9.82324 0.0 0
-M  V30 25 C 7.60897 -1.47271 0.0 0
+M  V30 25 C 9.35985 -3.77507 0.0 0
-M  V30 26 C 9.01802 -1.50872 0.0 0
+M  V30 26 C 11.0902 -3.77459 0.0 0
-M  V30 27 C 8.3457 -1.08144 0.0 0
+M  V30 27 C 10.2266 -3.27497 0.0 0
-M  V30 28 C 8.89639 -2.52314 0.0 0
+M  V30 28 C 11.0902 -4.77553 0.0 0
-M  V30 29 C 7.45099 -2.43365 0.0 0
+M  V30 29 N 9.35985 -4.78002 0.0 0
-M  V30 30 N 8.05713 -3.03115 0.0 0
+M  V30 30 C 10.2288 -5.27503 0.0 0
-M  V30 31 C 9.48728 -2.84506 0.0 0
+M  V30 31 C 10.2327 -6.27503 0.0 0
-M  V30 32 C 10.8821 -2.79881 0.0 0
+M  V30 32 C 11.105 -7.76933 0.0 0
-M  V30 33 C 10.2032 -2.4236 0.0 0
+M  V30 33 C 11.1014 -6.7717 0.0 0
-M  V30 34 C 10.9119 -3.6346 0.0 0
+M  V30 34 C 10.2405 -8.27372 0.0 0
-M  V30 35 N 9.37872 -3.98759 0.0 0
+M  V30 35 N 9.36465 -6.78143 0.0 0
-M  V30 36 C 10.1731 -4.23891 0.0 0
+M  V30 36 C 9.37498 -7.78146 0.0 0
-M  V30 37 Ir 7.92552 -4.9583 0.0 0 CHG=1
+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
@@ Line 58: / Line 78: @@
 M  V30 5 2 5 6
 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 2 33 31
+M  V30 31 2 29 30
-M  V30 32 2 34 32
+M  V30 32 1 30 28
-M  V30 33 1 31 35
+M  V30 33 1 30 31
-M  V30 34 1 32 33
+M  V30 34 2 33 31
-M  V30 35 2 35 36
+M  V30 35 2 34 32
-M  V30 36 1 36 34
+M  V30 36 1 31 35
-M  V30 37 1 28 31
+M  V30 37 1 32 33
-M  V30 38 1 14 23
+M  V30 38 2 35 36
-M  V30 39 1 6 9
+M  V30 39 1 36 34
-M  V30 40 10 4 37
+M  V30 40 10 11 37
-M  V30 41 10 8 37
+M  V30 41 10 37 29
-M  V30 42 10 15 37
+M  V30 42 10 35 37
-M  V30 43 10 19 37
+M  V30 43 10 37 21
-M  V30 44 10 35 37
+M  V30 44 10 14 37
-M  V30 45 10 30 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>{{#moleculelink:|link=UEEXRMUCXBPYOV-UHFFFAOYSA-N|image=true}}
+</chemform>
+{{#moleculelink: |link=NSABRUJKERBGOU-UHFFFAOYSA-N|image=true}}
 ====Investigation====
-{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}
+{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Photocatalytic reduction of CO2: conditions optimization}}
-{{#experimentlist:|form=Cyclic_Voltammetry_experiments|name=Table 2 - CV}}
+{{#experimentlist: |form=Cyclic_Voltammetry_experiments|name=Cyclic voltammetry in various conditions}}
 ====Sacrificial electron donor====
-{{#moleculelink:|link=GSEJCLTVZPLZKY-UHFFFAOYSA-N|image=true}}{{#moleculelink:|link=ZMANZCXQSJIPKH-UHFFFAOYSA-N|image=true}}{{#moleculelink:|link=JGFZNNIVVJXRND-UHFFFAOYSA-N|image=true}}
+In this study, the experiments were conducted with TEA ({{#moleculelink:|link=ZMANZCXQSJIPKH-UHFFFAOYSA-N|image=false|width=300|height=200}}), TEOA ({{#moleculelink:|link=GSEJCLTVZPLZKY-UHFFFAOYSA-N|image=false|width=300|height=200}}), and DIPEA ({{#moleculelink:|link=JGFZNNIVVJXRND-UHFFFAOYSA-N|image=false|width=300|height=200}}) as sacrificial electron donors.
 ====Additives====
-{{#moleculelink:|link=RHQDFWAXVIIEBN-UHFFFAOYSA-N|image=true}}
+In some experiments described in this study, TFE ({{#moleculelink:|link=RHQDFWAXVIIEBN-UHFFFAOYSA-N|image=false|width=300|height=200}}) was used as an additive.
-[[Category:Photocatalytic CO2 conversion to CH4]]
+[[Category:Photocatalytic CO2 conversion to CH4]][[Category:Publication]]

Toward Visible-Light Photochemical CO2‑to-CH4 Conversion in Aqueous Solutions Using Sensitized Molecular Catalysis: Difference between revisions

Latest revision as of 14:36, 5 September 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]

Investigation[edit | edit source]

Sacrificial electron donor[edit | edit source]

Additives[edit | edit source]

Investigations

Topics

Toward Visible-Light Photochemical CO2‑to-CH4 Conversion in Aqueous Solutions Using Sensitized Molecular Catalysis: Difference between revisions

Latest revision as of 14:36, 5 September 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]

Investigation[edit | edit source]

Sacrificial electron donor[edit | edit source]

Additives[edit | edit source]

Investigations

Current site

Topics