Photocatalytic CO2 conversion to HCOOH

CO₂ conversion to formic acid[Pro21]

Formic acid (FA) is a simple chemical with many uses. Its applications include use as a preservative, in the leather and dyeing industry and chemical providing a C1 building block. It is also an important H₂ carrier, because of its qualities as non-toxic, easily storable liquid. This also makes it directly usable in fuel cells.[Fas16] The global production is currently estimated at 870.000 metric tons in 2021 with a CAGR (Compound Annual Growth Report) of 3.87% in volume terms during the period 2022-2027.[https://www.mordorintelligence.com/industry-reports/formic-acid-market]

Industrial production of formic acid is done mainly by carbonylation of methanol and subsequent hydrolysation of methyl formate to formic acid.[FA00]

A direct approach of synthesis by hydrogenation of CO₂ and using renewable energy, such as sunlight in photocatalysis, in a homogeneous environment, is the focus of this page.

Sacrificial electron donors

TEOA TEA BI(OH)H BIH BNAH

Ruthenium Catalysts

Ru(bpy)2CO3

Photosensitizers

Experiments

TON > 100

Cobalt Catalysts

Organic and semiconductor photosensitizer

3,7-Di((1,1'-biphenyl)-4-yl)-10-(naphthalen-1-yl)-10H-phenoxazine

Experiments

Literature

[Pro21] Photochemical reduction of carbon dioxide to formic acid. Robin Cauwenbergh, Shoubhik Das, Green Chemistry 2021, Vol. 23, Pages 2553-2574. DOI2: 10.1039/d0gc04040a

[Fas16] Formic acid synthesis using CO2 as raw material: Techno-economic and environmental evaluation and market potential. Mar Pérez-Fortes, Jan C. Schöneberger, Aikaterini Boulamanti, Gillian Harrison, Evangelos Tzimas, International Journal of Hydrogen Energy 2016, Vol. 41, Pages 16444-16462. DOI2: 10.1016/j.ijhydene.2016.05.199

[FA00] Formic Acid. Werner Reutemann, Heinz Kieczka, Ullmann's Encyclopedia of Industrial Chemistry 2000. DOI2: 10.1002/14356007.a12_013

[VLP20] Visible-Light Photocatalytic Conversion of Carbon Dioxide by Ni(II) Complexes with N4S2 Coordination: Highly Efficient and Selective Production of Formate. Sung Eun Lee, Azam Nasirian, Ye Eun Kim, Pegah Tavakoli Fard, Youngmee Kim, Byeongmoon Jeong, Sung-Jin Kim, Jin-Ook Baeg, Jinheung Kim, Journal of the American Chemical Society 2020, Vol. 142, Pages 19142-19149. DOI2: 10.1021/jacs.0c08145
Publication: Visible-Light Photocatalytic Conversion of Carbon Dioxide by Ni(II) Complexes with N4S2 Coordination: Highly Efficient and Selective Production of Formate

[PCR20] Photocatalytic CO ₂ Reduction under Visible‐Light Irradiation by Ruthenium CNC Pincer Complexes. Yasuhiro Arikawa, Itoe Tabata, Yukari Miura, Hiroki Tajiri, Yudai Seto, Shinnosuke Horiuchi, Eri Sakuda, Keisuke Umakoshi, Chemistry – A European Journal 2020, Vol. 26, Pages 5603-5606. DOI2: 10.1002/chem.201905840
Publication: Photocatalytic CO2 Reduction under Visible-Light Irradiation by Ruthenium CNC Pincer Complexes

[AiR19] An integrated Re(i) photocatalyst/sensitizer that activates the formation of formic acid from reduction of CO₂. Yasmeen Hameed, Patrick Berro, Bulat Gabidullin, Darrin Richeson, Chemical Communications 2019, Vol. 55, Pages 11041-11044. DOI2: 10.1039/c9cc03943k
Publication: An integrated Re(I) photocatalyst and sensitizer that activates the formation of formic acid from reduction of CO2

[PCR20] Photocatalytic CO₂ Reduction Using a Robust Multifunctional Iridium Complex toward the Selective Formation of Formic Acid. Kenji Kamada, Jieun Jung, Taku Wakabayashi, Keita Sekizawa, Shunsuke Sato, Takeshi Morikawa, Shunichi Fukuzumi, Susumu Saito, Journal of the American Chemical Society 2020, Vol. 142, Pages 10261-10266. DOI2: 10.1021/jacs.0c03097
Publication: Photocatalytic CO2 Reduction Using a Robust Multifunctional Iridium Complex toward the Selective Formation of Formic Acid

[HEa16] Highly Efficient and Selective Photocatalytic CO₂ Reduction by Iron and Cobalt Quaterpyridine Complexes. Zhenguo Guo, Siwei Cheng, Claudio Cometto, Elodie Anxolabéhère-Mallart, Siu-Mui Ng, Chi-Chiu Ko, Guijian Liu, Lingjing Chen, Marc Robert, Tai-Chu Lau, Journal of the American Chemical Society 2016, Vol. 138, Pages 9413-9416. DOI2: 10.1021/jacs.6b06002
Publication: Highly Efficient and Selective Photocatalytic CO2 Reduction by Iron and Cobalt Quaterpyridine Complexes

[PRo15] Photochemical Reduction of Carbon Dioxide to Formic Acid using Ruthenium(II)-Based Catalysts and Visible Light. Alonso Rosas-Hernández, Henrik Junge, Matthias Beller, ChemCatChem 2015, Vol. 7, Pages 3316-3321. DOI2: 10.1002/cctc.201500494
Publication: Photochemical Reduction of Carbon Dioxide to Formic Acid using Ruthenium(II)-Based Catalysts and Visible Light

[VLP19] Visible‐Light Photocatalytic Reduction of CO ₂ to Formic Acid with a Ru Catalyst Supported by N , N ′‐Bis(diphenylphosphino)‐2,6‐diaminopyridine Ligands. Yasmeen Hameed, Gyandshwar Kumar Rao, Jeffrey S. Ovens, Bulat Gabidullin, Darrin Richeson, ChemSusChem 2019, Vol. 12, Pages 3453-3457. DOI2: 10.1002/cssc.201901326
Publication: Visible-Light Photocatalytic Reduction of CO2 to Formic Acid with a Ru Catalyst Supported by N,N’- Bis(diphenylphosphino)-2,6-diaminopyridine Ligands

[Rtr16] Rhenium(i) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO₂ reduction. Jana Rohacova, Osamu Ishitani, Chemical Science 2016, Vol. 7, Pages 6728-6739. DOI2: 10.1039/c6sc01913g
Publication: Rhenium(I) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO2 reduction

[PCr14] Photocatalytic CO₂reduction using a Mn complex as a catalyst. Hiroyuki Takeda, Hiroki Koizumi, Kouhei Okamoto, Osamu Ishitani, Chem. Commun. 2014, Vol. 50, Pages 1491-1493. DOI2: 10.1039/c3cc48122k
Publication: Photocatalytic CO2 reduction using a Mn complex as a catalyst

[HEa18] Highly Efficient and Robust Photocatalytic Systems for CO₂ Reduction Consisting of a Cu(I) Photosensitizer and Mn(I) Catalysts. Hiroyuki Takeda, Hiroko Kamiyama, Kouhei Okamoto, Mina Irimajiri, Toshihide Mizutani, Kazuhide Koike, Akiko Sekine, Osamu Ishitani, Journal of the American Chemical Society 2018, Vol. 140, Pages 17241-17254. DOI2: 10.1021/jacs.8b10619
Publication: Highly Efficient and Robust Photocatalytic Systems for CO2 Reduction Consisting of a Cu(I) Photosensitizer and Mn(I) Catalysts

[PRo16] Photocatalytic Reduction of Carbon Dioxide to CO and HCO₂H Using fac-Mn(CN)(bpy)(CO)₃. Po Ling Cheung, Charles W. Machan, Aramice Y. S. Malkhasian, Jay Agarwal, Clifford P. Kubiak, Inorganic Chemistry 2016, Vol. 55, Pages 3192-3198. DOI2: 10.1021/acs.inorgchem.6b00379
Publication: Photocatalytic Reduction of Carbon Dioxide to CO and HCO2H Using fac-Mn(CN)(bpy)(CO)3

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	e-D conc [M]	solvent A	additives	TON CO	TON H2	TON HCOOH	lit
1.	Ni(pbi)(pyS)2	0.004	Eosin Y	2	TEOA	0.4	H2O				14000	[VLP20]
2.	Ni(pbt)(pyS)2	0.004	Eosin Y	2	TEOA	0.4	H2O				13100	[VLP20]
3.	[Ru(bpy)(py)-(MeNHC)2CO][PF6]2	0.01	[Ru(dmb)3][PF6]2	0.05	BI(OH)H	0.1	DMA		300	1897	5634	[PCR20]
4.	[Ru(bpy)(py)-(MeNHC)2(MeCN)][PF6]2	0.01	[Ru(dmb)3][PF6]2	0.05	BI(OH)H	0.1	DMA		224	1438	4593	[PCR20]
5.	[Ru(bpy)(py)-(tBuNHC)2CO][PF6]2	0.01	[Ru(dmb)3][PF6]2	0.05	BI(OH)H	0.1	DMA		129	505	3792	[PCR20]
6.	[Ru(bpy)(py)-(tBuNHC)2(MeCN)][PF6]2	0.01	[Ru(dmb)3][PF6]2	0.05	BI(OH)H	0.1	DMA		129	556	3296	[PCR20]
7.	[Re(bpy)2(CO)2][OTf]	0.01	[Ru(bpy)3][PF6]	1	TEOA		DMA			375	2750	[AiR19]
8.	[Ir(mesbpy-(PCy2)2)][BPh4]	0.02			BIH	0.2	DMA		470	15	2080	[PCR20]
9.	[Re(bpy)2(CO)2][OTf]	0.02	[Ru(bpy)3][PF6]	1	TEOA		DMA			225	1480	[AiR19]
10.	[Re(bpy)2(CO)2][OTf]	0.05	[Ru(bpy)3][PF6]	1	TEOA		DMA			50	535	[AiR19]
11.	[Fe(qpy)(H2O)2][ClO4]2	0.005	Ru(bpy)3Cl2	0.2	BIH	0.1	MeCN		3844	118	534	[HEa16]
12.	[Re(bpy)2(CO)2][OTf]	0.1	[Ru(bpy)3][PF6]	1	TEOA		DMA			38	428	[AiR19]
13.	[Ru(bpy)2ClCO][PF6]	1.6	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		40	67	419	[PRo15]
14.	[Ru(bpy)2ClCO][PF6]	0.0016	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		40	67	419	[PRo15]
15.	Ru(py)-(MeNdpp)2(CO)2Cl	0.025	[Ru(bpy)3][PF6]	0.025	TEOA		DMF				380	[VLP19]
16.	Ru(py)-(MeNdpp)2(CO)2Cl	0.1	[Ru(bpy)3][PF6]	0.1	TEOA		DMF			57.5	363	[VLP19]
17.	[Ru(bpy)(H2O)(CO)][PF6]	0.0016	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		45	65	335	[PRo15]
18.	[Ru(bpy)(H2O)(CO)][PF6]	1.6	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		45	65	335	[PRo15]
19.	[Ru(bpy)2ClCO][PF6]	0.0031	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		36	33	296	[PRo15]
20.	[Ru(bpy)2ClCO][PF6]	3.1	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		36	33	296	[PRo15]
21.	Ru(dtBubpy)(CO)2Cl2	0.05	Molecule:100877	0.05			DMF		20	72	290	[Rtr16]
22.	Ru(dtBubpy)(CO)2Cl2	0.05	Molecule:100877	0.05	BI(OH)H	0.03	DMF		16	49	280	[Rtr16]
23.	[Re(bpy)2(CO)2][OTf]	0.2	[Ru(bpy)3][PF6]	1	TEOA		DMA			24	275	[AiR19]
24.	[Ru(bpy)2HCO][PF6]	0.0016	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		25	62	225	[PRo15]
25.	[Ru(bpy)2HCO][PF6]	1.6	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		25	62	225	[PRo15]
26.	[Ru(bpy)(H2O)(CO)][PF6]	0.0031	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		34	28	211	[PRo15]
27.	[Ru(bpy)(H2O)(CO)][PF6]	3.1	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		34	28	211	[PRo15]
28.	Ru(py)-(MeNdpp)2(CO)2Cl	0.05	[Ru(bpy)3][PF6]	0.05	TEOA		DMF				210	[VLP19]
29.	[Co(qpy)(H2O)2][ClO4]2	0.005	purpurin	2	BIH	0.1	DMF	Argon atmosphere	0	226	167	[HEa16]
30.	Ru(py)-(MeNdpp)2(CO)2Cl	0.5	[Ru(bpy)3][PF6]	1	TEOA		DMF			14	162	[VLP19]
31.	Mn(bpy)(CO)3Br	0.05	Ru(bpy)3	0.05	BNAH	0.1	DMF		12	8	157	[PCr14]
32.	Mn(bpy)(CO)3Br	0.05	[Cu(phen)-(dPPh-Bu)2]2[PF6]2	0.25	BIH	0.01	MeCN		50	4	157	[HEa18]
33.	Mn(bpy)(CO)3Br	0.05	[Ru(dmb)3][PF6]2	0.05	BNAH	0.1	DMF		12	14	149	[PCr14]
34.	[Ru(bpy)2HCO][PF6]	0.0031	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		16	29	145	[PRo15]
35.	[Ru(bpy)2HCO][PF6]	3.1	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		16	29	145	[PRo15]
36.	Mn(CN)(bpy)(CO)3	0.1	[Ru(dmb)3][PF6]2	1	BNAH	0.1	DMF		7.1	1.6	130	[PRo16]
37.	Mn(CN)(bpy)(CO)3	0.1	[Ru(dmb)3][PF6]2	0.5	BNAH	0.1	DMF		9.1	1.2	130	[PRo16]
38.	[Ru(bpy)2ClCO][PF6]	0.0062	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		19	19	117	[PRo15]
39.	[Ru(bpy)2ClCO][PF6]	6.2	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		19	19	117	[PRo15]
40.	[Re(bpy)2(CO)2][OTf]	0.5	[Ru(bpy)3][PF6]	1	TEOA		DMA			15	115	[AiR19]
41.	[Fe(qpy)(H2O)2][ClO4]2	0.005	Ru(bpy)3Cl2	0.02	BIH	0.1	DMF		1365	0	115	[HEa16]
42.	[Ru(bpy)2HCO][PF6]	0.0062	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		21	16	107	[PRo15]
43.	[Ru(bpy)2HCO][PF6]	6.2	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		21	16	107	[PRo15]

Photocatalytic CO2 conversion to HCOOH

Contents

CO₂ conversion to formic acid[Pro21]

Sacrificial electron donors

Ruthenium Catalysts

Photosensitizers

Experiments

Cobalt Catalysts

Organic and semiconductor photosensitizer

Experiments

Literature

Topics

Photocatalytic CO2 conversion to HCOOH

CO2 conversion to formic acid[Pro21]

Sacrificial electron donors

Ruthenium Catalysts

Photosensitizers

Experiments

Cobalt Catalysts

Organic and semiconductor photosensitizer

Experiments

Literature

Current site

Topics

CO₂ conversion to formic acid[Pro21]