Photocatalytic CO2 conversion to HCOOH

CO₂ conversion to formic acid[Pro21][edit | edit source]

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[edit | edit source]

TEOA (100507) TEA (100505) BI(OH)H (100526) BIH (100508) BNAH (100509)

Ruthenium Catalysts[edit | edit source]

Ru(bpy)2CO3 (100482)

Photosensitizers[edit | edit source]

Experiments[edit | edit source]

Table of all the experiments that have a turnover number for HCOOH greater than 100, sorted by catalyst and in descending order. TON > 100

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	e-D conc [M]	solvent A	λexc [nm]	TON CO	TON H2	TON HCOOH
1.	Ni(pbi)(pyS)2	4	Eosin Y	2	TEOA	0.4	H2O				14000
2.	Ni(pbt)(pyS)2	4	Eosin Y	2	TEOA	0.4	H2O				13100
3.	[Ru(bpy)(py)-(MeNHC)2CO][PF6]2	0.01	[Ru(dmb)3][PF6]2	0.05	BI(OH)H	0.1	DMA	450 W Hg lamp, K2CrO4 filter	300	1897	5634
4.	[Ru(bpy)(py)-(MeNHC)2(MeCN)][PF6]2	0.01	[Ru(dmb)3][PF6]2	0.05	BI(OH)H	0.1	DMA	450 W Hg lamp, K2CrO4 filter	224	1438	4593
5.	[Ru(bpy)(py)-(tBuNHC)2CO][PF6]2	0.01	[Ru(dmb)3][PF6]2	0.05	BI(OH)H	0.1	DMA	450 W Hg lamp, K2CrO4 filter	129	505	3792
6.	[Ru(bpy)(py)-(tBuNHC)2(MeCN)][PF6]2	0.01	[Ru(dmb)3][PF6]2	0.05	BI(OH)H	0.1	DMA	450 W Hg lamp, K2CrO4 filter	129	556	3296
7.	[Re(bpy)2(CO)2][OTf]	10	[Ru(bpy)3][PF6]	1	TEOA		DMA	405		375	2750
8.	[Ir(mesbpy-(PCy2)2)][BPh4]	20			BIH	0.2	DMA	>400	470	15	2080
9.	[Re(bpy)2(CO)2][OTf]	20	[Ru(bpy)3][PF6]	1	TEOA		DMA	405		225	1480
10.	[Re(bpy)2(CO)2][OTf]	50	[Ru(bpy)3][PF6]	1	TEOA		DMA	405		50	535
11.	[Fe(qpy)(H2O)2][ClO4]2	5	Ru(bpy)3Cl2	0.2	BIH	0.1	MeCN	460 (LED)	3844	118	534
12.	[Re(bpy)2(CO)2][OTf]	100	[Ru(bpy)3][PF6]	1	TEOA		DMA	405		38	428
13.	[Ru(bpy)2ClCO][PF6]	0.0016	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP	400 - 700	40	67	419
14.	[Ru(bpy)2ClCO][PF6]	1.6	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP	400 - 700	40	67	419
15.	Ru(py)-(MeNdpp)2(CO)2Cl	25	[Ru(bpy)3][PF6]	0.025	TEOA		DMF	405			380
16.	Ru(py)-(MeNdpp)2(CO)2Cl	100	[Ru(bpy)3][PF6]	0.1	TEOA		DMF	405		57.5	363
17.	[Ru(bpy)(H2O)(CO)][PF6]	0.0016	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP	400 - 700	45	65	335
18.	[Ru(bpy)(H2O)(CO)][PF6]	1.6	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP	400 - 700	45	65	335
19.	[Ru(bpy)2ClCO][PF6]	3.1	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP	400 - 700	36	33	296
20.	[Ru(bpy)2ClCO][PF6]	0.0031	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP	400 - 700	36	33	296
21.	Ru(dtBubpy)(CO)2Cl2	50	Molecule:100877	0.05			DMF	436	20	72	290
22.	Ru(dtBubpy)(CO)2Cl2	50	Molecule:100877	0.05	BI(OH)H	0.03	DMF	436	16	49	280
23.	[Re(bpy)2(CO)2][OTf]	200	[Ru(bpy)3][PF6]	1	TEOA		DMA	405		24	275
24.	[Ru(bpy)2HCO][PF6]	1.6	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP	400 - 700	25	62	225
further results hidden...

Table of all the experiments that have a turnover number for HCOOH lower than 100, sorted by catalyst and in descending order. TON < 100

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	e-D conc [M]	solvent A	additives	λexc [nm]	TON CO	TON H2	TON HCOOH
1.	Mn(bpy)(CO)3Br	50	[Ru(dmb)3][PF6]2	0.05	BNAH	0.1	DMA		480	9	14	98
2.	Ru(py)-(MeNdpp)2(CO)2Cl	1000	[Ru(bpy)3][PF6]	1	TEOA		DMF		405		13.3	90.5
3.	[Co(qpy)(H2O)2][ClO4]2	0	purpurin	2	BIH	0.1	DMF		460 (LED)	0	0	90
4.	[Fe(qpy)(H2O)2][ClO4]2	5	Ru(bpy)3Cl2	0.02	BIH	0.1	DMF	Argon atmosphere	460 (LED)	0	52	88
5.	[Mn(dtBubpy)(CO)3(MeCN)][PF6]	50	Molecule:100877	0.05			DMF		436	32		85
6.	[MoO(2Hqpdt)2][NBu4]	50	Ru(bpy)3Cl2	0.5	BIH	0.1	MeCN		400	40	89	83
7.	[MoO(qpdt)2][NBu4]2	50	Ru(bpy)3Cl2	0.5	BIH	0.1	MeCN		400	73	670	80
8.	Mn(bpy)(CO)3Br	50	[Ru(dmb)3][PF6]2	0.05	BNAH	0.1	MeCN		480	40	17	78
9.	[Co(qpy)(H2O)2][ClO4]2	5	purpurin	2	BIH	0.1	DMF		460 (LED)	790	11	78
10.	[Ru(bpy)(H2O)(CO)][PF6]	6.2	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		400 - 700	21	14	75
11.	[Ru(bpy)(H2O)(CO)][PF6]	0.0062	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		400 - 700	21	14	75
12.	[Ru(bpy)(AcMe)2][PF6]	1.6	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		400 - 700	4	44	75
13.	[Ru(bpy)(AcMe)2][PF6]	0.0016	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		400 - 700	4	44	75
14.	Ru(py)-(HNdpp)2(CO)2Cl	500	[Ru(bpy)3][PF6]	1	TEOA		DMF		405		14	70.5
15.	Mn(bpy)(CO)3Br	50	[Ru(dmb)3][PF6]2	0.05	BNAH	0.1	DMF		480	8	1	67
16.	Molecule:100845	50	[Cu(phen)-(dPPh-Bu)2]2[PF6]2	0.25	BIH	0.01	MeCN		436	164	1	65
17.	[Ru(bpy)(AcMe)2][PF6]	0.0062	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		400 - 700	4	12	64
18.	[Ru(bpy)(AcMe)2][PF6]	6.2	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		400 - 700	4	12	64
19.	[Ru(bpy)2ClCO][PF6]	0.025	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		400 - 700	13	8	62
20.	[Ru(bpy)2ClCO][PF6]	25	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA		NMP		400 - 700	13	8	62
21.	[Mn(dtBubpy)(CO)3(MeCN)][PF6]	50	Molecule:100877	0.05	BI(OH)H	0.03	DMF		436	80		60
22.	Mn(phdk)(CO)3(MeCN)	100	Ru(bpy)3Cl2	100	BNAH	0.1	MeCN		480	15		58
23.	Mn(phdk)(CO)3Br	100	Ru(bpy)3Cl2	100	BNAH	0.1	MeCN		480	8		52
24.	Mn(phdk)(CO)3(MeCN)	100	Ru(bpy)3Cl2	200	BNAH	0.1	MeCN		480	8		52
further results hidden...

Cobalt Catalysts[edit | edit source]

Organic and semiconductor photosensitizer[edit | edit source]

3,7-Di((1,1'-biphenyl)-4-yl)-10-(naphthalen-1-yl)-10H-phenoxazine (100493)

Experiments[edit | edit source]

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

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Photocatalytic CO2 conversion to HCOOH

Contents

CO₂ conversion to formic acid[Pro21][edit | edit source]

Sacrificial electron donors[edit | edit source]

Ruthenium Catalysts[edit | edit source]

Photosensitizers[edit | edit source]

Experiments[edit | edit source]

Cobalt Catalysts[edit | edit source]

Organic and semiconductor photosensitizer[edit | edit source]

Experiments[edit | edit source]

Literature

Topics

Photocatalytic CO2 conversion to HCOOH

CO2 conversion to formic acid[Pro21][edit | edit source]

Sacrificial electron donors[edit | edit source]

Ruthenium Catalysts[edit | edit source]

Photosensitizers[edit | edit source]

Experiments[edit | edit source]

Cobalt Catalysts[edit | edit source]

Organic and semiconductor photosensitizer[edit | edit source]

Experiments[edit | edit source]

Literature

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Topics

CO₂ conversion to formic acid[Pro21][edit | edit source]