Photocatalytic CO2 conversion to HCOOH

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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 TEA BI(OH)H BIH BNAH

Ruthenium Catalysts[edit | edit source]

Ru(bpy)2CO3

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.

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

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

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
[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
[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
[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
[PRD18] Pyranopterin Related Dithiolene Molybdenum Complexes as Homogeneous Catalysts for CO 2 Photoreduction. Thibault Fogeron, Pascal Retailleau, Lise‐Marie Chamoreau, Yun Li, Marc Fontecave, Angewandte Chemie International Edition 2018, Vol. 57, Pages 17033-17037. DOI2: 10.1002/anie.201809084
Publication: Pyranopterin Related Dithiolene Molybdenum Complexes as Homogeneous Catalysts for CO2 Photoreduction
[FIR18] Function-Integrated Ru Catalyst for Photochemical CO2 Reduction. Sze Koon Lee, Mio Kondo, Masaya Okamura, Takafumi Enomoto, Go Nakamura, Shigeyuki Masaoka, Journal of the American Chemical Society 2018, Vol. 140, Pages 16899-16903. DOI2: 10.1021/jacs.8b09933
Publication: Function-Integrated Ru Catalyst for Photochemical CO2 Reduction