A Highly Durable, Self-Photosensitized Mononuclear Ruthenium Catalyst for CO₂ Reduction

Abstract

A novel mononuclear ruthenium (Ru) complex bearing a PNNP-type tetradentate ligand is introduced here as a self-photosensitized catalyst for the reduction of carbon dioxide (CO₂). When the pre-activation of the Ru complex by reaction with a base was carried out, an induction period of catalyst almost disappeared and the catalyst turnover numbers (TONs) over a reaction time of 144 h reached 307 and 489 for carbon monoxide (CO) and for formic acid (HCO₂H), respectively. The complex has a long lifespan as a dual photosensitizer and reduction catalyst, due to the sterically bulky and structurally robust (PNNP)Ru framework. Isotope-labeling experiments under ¹³CO₂ atmosphere indicate that CO and HCO₂H were both produced from CO₂.

Key words

CO₂ reduction - photocatalyst - ruthenium complex - carbon monoxide - formic acid

Publication History

Received: 30 August 2021

Accepted after revision: 29 November 2021

Accepted Manuscript online:
29 November 2021

Article published online:
05 January 2022

• References and Notes

• 1a Fukuzumi S. Joule 2017; 1: 689
• 1b Fukuzumi S, Lee Y.-M, Nam W. ChemPhotoChem 2018; 2: 121
• 1c El-Khouly ME, El-Mohsnawy E, Fukuzumi S. J. Photochem. Photobiol., C 2017; 31: 36
• 1d Mase K, Yoneda M, Yamada Y, Fukuzumi S. ACS Energy Lett. 2016; 1: 913
• 1e Yoshioka S, Jung J, Saito S. J. Synth. Org. Chem., Jpn. 2020; 78: 856
• 2a Aoi S, Mase K, Ohkubo K, Suenobu T, Fukuzumi S. ACS Energy Lett. 2017; 2: 532
• 2b Aoi S, Mase K, Ohkubo K, Fukuzumi S. Chem. Commun. 2015; 51: 10226
• 2c Rintjema J, Kleij AW. Synthesis 2016; 48: 3863
• 2d O’Brien CJ, Nicewicz DA. Synlett 2021; 32: 814
• 2e Luo Y, Chan B, Fukuda T, Onodera G, Kimura M. Synlett 2021; 32: 1551
• 2f Azzouz R, Moreno VC, Herasme-Grullon C, Levacher V, Estel L, Ledoux A, Derrouiche S, Marsais F, Bischoff L. Synlett 2020; 31: 183
• 2g Matsuo H, Fujii A, Choi J.-C, Fujitani T, Fujita K. Synlett 2019; 30: 1914
• 2h Doi R, Okano T, Abdullah I, Sato Y. Synlett 2019; 30: 1048
• 2i Cokoja M, Bruckmeier C, Rieger B, Herrmann WA, Kühn FE. Angew. Chem. Int. Ed. 2011; 50: 8510
• 2j Saravanan A, Senthil Kumar P, Vo D.-VN, Jeevanantham S, Bhuvaneswari V, Anantha Narayanan V, Yaashikaa PR, Swetha S, Reshma B. Chem. Eng. Sci. 2021; 236: 116515
• 2k Batrice RJ, Gordon JC. RSC Adv. 2021; 11: 87
• 3a Fukuzumi S, Lee Y.-M, Ahn HS, Nam W. Chem. Sci. 2018; 9: 6017
• 3b Aresta M, Dibenedetto A. Dalton Trans. 2007; 2975
• 3c Benson EE, Kubiak CP, Sathrum AJ, Smieja JM. Chem. Soc. Rev. 2009; 38: 89
• 3d Perazio A, Lowe G, Gobetto R, Bonin J, Robert M. Coord. Chem. Rev. 2021; 443: 214018
• 3e Le QV, Nguyen V.-H, Nguyen TD, Sharma A, Rahman G, Nguyen DL. T. Chem. Eng. Sci. 2021; 237: 116547
• 3f Cauwenbergh R, Das S. Green. Chem. 2021; 23: 2553
• 3g Pan H, Heagy MD. Nanomaterials 2020; 10: 2422
• 3h Li X, Yu J, Jaroniec M, Chen X. Chem. Rev. 2019; 119: 3962
• 4a Aoi S, Mase K, Ohkubo K, Fukuzumi S. Catal. Sci. Technol. 2016; 6: 4077
• 4b Zhuo T.-C, Song Y, Zhuang G.-L, Chang L.-P, Yao S, Zhang W, Wang Y, Wang P, Lin W, Lu T.-B, Zhang Z.-M. J. Am. Chem. Soc. 2021; 143: 6114
• 4c Nakada A, Kumagai H, Robert M, Ishitani O, Maeda K. Acc. Mater. Res. 2021; 2: 458
• 4d Ma B, Chen G, Fave C, Chen L, Kuriki R, Maeda K, Ishitani O, Lau T.-C, Bonin J, Robert M. J. Am. Chem. Soc. 2020; 142: 6188
• 4e Chen W.-P, Liao P.-Q, Jin P.-B, Zhang L, Ling B.-K, Wang S.-C, Chan Y.-T, Chen X.-M, Zheng Y.-Z. J. Am. Chem. Soc. 2020; 142: 4663
• 5 Koppenol WH, Rush JD. J. Phys. Chem. 1987; 91: 4429
• 6 Seo H, Katcher MH, Jamison TF. Nat. Chem. 2017; 9: 453
• 7a Yamazaki Y, Takeda H, Ishitani O. J. Photochem. Photobiol., C 2015; 25: 106
• 7b Elgrishi N, Chambers MB, Wang X, Fontecave M. Chem. Soc. Rev. 2017; 46: 761
• 7c Sahara G, Ishitani O. Inorg. Chem. 2015; 54: 5096
• 8a Yuan H, Cheng B, Lei J, Jiang L, Han Z. Nat. Commun. 2021; 12: 1835
• 8b Lee SE, Nasirian A, Kim YE, Fard PT, Kim Y, Jeong B, Kim S.-J, Baeg J.-O, Kim J. J. Am. Chem. Soc. 2020; 142: 19142
• 8c Hong D, Tsukakoshi Y, Kotani H, Ishizuka T, Kojima T. J. Am. Chem. Soc. 2017; 139: 6538
• 8d Hong D, Kawanishi T, Tsukakoshi Y, Kotani H, Ishizuka T, Kojima T. J. Am. Chem. Soc. 2019; 141: 20309
• 8e Zhang X, Cibian M, Call A, Yamauchi K, Sakai K. ACS Catal. 2019; 9: 11263
• 8f Rao H, Schmidt LC, Bonin J, Robert M. Nature 2017; 548: 74
• 8g Guo Z, Cheng S, Cometto C, Anxolabéhère-Mallart E, Ng S.-M, Ko C.-C, Liu G, Chen L, Robert M, Lau T.-C. J. Am. Chem. Soc. 2016; 138: 9413
• 9a Call A, Cibian M, Yamamoto K, Nakazono T, Yamauchi K, Sakai K. ACS Catal. 2019; 9: 4867
• 9b Rodrigues RR, Boudreaux CM, Papish ET, Delcamp JH. ACS Appl. Energy Mater. 2019; 2: 37
• 9c Rao H, Bonin J, Robert M. ChemSusChem 2017; 10: 4447
• 10 Yoshioka S, Nimura S, Naruto M, Saito S. Sci. Adv. 2020; 6: eabc0274
• 11a Miura T, Held IE, Oishi S, Naruto M, Saito S. Tetrahedron Lett. 2013; 54: 2674
• 11b Miura T, Naruto M, Toda K, Shimomura T, Saito S. Sci. Rep. 2017; 7: 1586
• 12a Costentin C, Drouet S, Robert M, Savéant J.-M. Science 2012; 338: 90
• 12b Costentin C, Passard G, Robert M, Savéant J.-M. J. Am. Chem. Soc. 2014; 136: 11821
• 12c Haviv E, Azaiza-Dabbah D, Carmieli R, Avram L, Martin JM. L, Neumann R. J. Am. Chem. Soc. 2018; 140: 12451
• 13 Kamada K, Jung J, Wakabayashi T, Sekizawa K, Sato S, Morikawa T, Fukuzumi S, Saito S. J. Am. Chem. Soc. 2020; 142: 10261
• 14a Takeda H, Koike K, Inoue H, Ishitani O. J. Am. Chem. Soc. 2008; 130: 2023
• 14b Sampson MD, Froehlich JD, Smieja JM, Benson EE, Sharp ID, Kubiak CP. Energy Environ. Sci. 2013; 6: 3748
• 14c Maurin A, Ng C.-O, Chen L, Lau T.-C, Robert M, Ko C.-C. Dalton Trans. 2016; 45: 14524
• 14d Hameed Y, Berro P, Gabidullin B, Richeson D. Chem. Commun. 2019; 55: 11041
• 14e Talukdar K, Roy SS, Amatya E, Sleeper EA, Magueres PL, Jurss JW. Inorg. Chem. 2020; 59: 6087
• 15a Sato S, Morikawa T, Kajino T, Ishitani O. Angew. Chem. Int. Ed. 2013; 52: 988
• 15b Garg K, Matsubara Y, Ertem MZ, Lewandowska-Andralojc A, Sato S, Szalda DJ, Muckerman JT, Fujita E. Angew. Chem. Int. Ed. 2015; 54: 14128
• 15c Genoni A, Chirdon DN, Boniolo M, Sartorel A, Bernhard S, Bonchio M. ACS Catal. 2017; 7: 154
• 15d Sato S, Morikawa T. ChemPhotoChem 2018; 2: 207
• 15e Qi X, Zhong R, Chen M, Sun C, You S, Gu J, Shan G, Cui D, Wang X, Su Z. ACS Catal. 2021; 11: 7241
• 16a Chauvin J, Lafolet F, Chardon-Noblat S, Deronzier A, Jakonen M, Haukka M. Chem. Eur. J. 2011; 17: 4313
• 16b Castillo CE, Armstrong J, Laurila E, Oresmaa L, Haukka M, Chauvin J, Chardon-Noblat S, Deronzier A. ChemCatChem 2016; 8: 2667
• 17a Rao H, Bonin J, Robert M. Chem. Commun. 2017; 53: 2830
• 17b Bonin J, Chaussemier M, Robert M, Routier M. ChemCatChem 2014; 6: 3200
• 17c Behar D, Dhanasekaran T, Neta P, Hosten CM, Ejeh D, Hambright P, Fujita E. J. Phys. Chem. A 1998; 102: 2870
• 18a Das S, Rodrigues RR, Lamb RW, Qu F, Reinheimer E, Boudreaux CM, Webster CE, Delcamp JH, Papish ET. Inorg. Chem. 2019; 58: 8012
• 18b Lee SK, Kondo M, Okamura M, Enomoto T, Nakamura G, Masaoka S. J. Am. Chem. Soc. 2018; 140: 16899
• 18c Hawecker J, Lehn J.-M, Ziessel R. J. Chem. Soc., Chem. Commun. 1985; 56
• 19 Experimental Conditions Photocatalytic reactions were performed at atmospheric pressure in 8 mL test tubes containing 4 mL of a DMA/TEOA (5:1 v/v) solution purged with CO₂ for 10 min, a Ru complex (0.1 mM), and BIH (0.10 M). The solutions were irradiated in a turntable irradiation apparatus at room temperature using a Xe lamp (300 W) combined with a UV-cut filter having a cutoff wavelength of below 400 nm and a UV- and IR-cut filter ranging from 385 nm to 740 nm. The gaseous reaction products were analyzed using a micro-GC (Agilent 490) equipped with a thermal conductivity detector (column: MS5A 10-m BF column; isothermal at 80 °C; carrier gas: Ar), and the products in the solution were analyzed using Prominence Organic Acid Analysis System (SCR-102H column; column temp: 40 °C; cell temp: 43 °C). The reaction set-up is shown in Figure S11 (see the Supporting­ Information).
• 20 Pre-activation of Ru-1 with a 2–8 equiv of KOt-Bu gave UV/Vis absorption spectra almost identical with one another, indicating that the photoactive complex is stable in the presence of excess KOt-Bu (Figure S3). Although ¹H NMR (CD₃CN) measurements of Ru-1·2KOt-Bu showed a RuH signal (J _P–H = 26.4 Hz, triplet) at –16.3 ppm, it was difficult to determine the exact structure due to the overall intractable/inscrutable spectrum (Figures S19). In Figure S2, the structure of the pre-activated Ru complex was proposed merely on the basis of ESI-(HR)MS measurement.
• 21 Zhang J, Leitus G, Ben-David Y, Milstein D. Angew. Chem. Int. Ed. 2006; 45: 1113
• 22a Suna Y, Himeda Y, Fujita E, Muckerman JT, Ertem MZ. ChemSusChem 2017; 10: 4535
• 22b Hufziger KT, Thowfeik FS, Charboneau DJ, Nieto I, Dougherty WG, Kassel WS, Dudley TJ, Merino EJ, Papish ET, Paul JJ. J. Inorg. Biochem. 2014; 130: 103
• 22c Tawarah KM, Abu-Shamleh HM. Dyes Pigm. 1991; 16: 241
• 23 DFT calculations of the HOMO–LUMO gaps of Ru-1 and the proposed structure of the pre-activated Ru complex which lost Cl^– and a bipyridyl CH₂P hydrogen also suggest that the complex which has a quinoid structure could absorb longer wavelengths than Ru-1 (Figure S12).
• 24 Hatchard CG, Parker CA. Proc. R. Soc. London, Ser. A 1956; 235: 518