Selective photocatalytic reduction of CO2 to CO mediated by a [FeFe]-hydrogenase model with a 1,2-phenylene S-to-S bridge

doi:10.1016/S1872-2067(20)63644-0

Abstract

Abstract:

Photocatalytic reduction of CO₂ to CO is a promising approach for storing solar energy in chemicals and mitigating the greenhouse effect of CO₂. Our recent studies revealed that [(μ-bdt)Fe₂(CO)₆] (1, bdt = benzene-1,2-dithiolato), a [FeFe]-hydrogenase model with a rigid and conjugate S-to-S bridge, was catalytically active for the selective photochemical reduction of CO₂ to CO, while its analogous complex [(μ-edt)Fe₂(CO)₆] (2, edt = ethane-1,2-dithiolato) was inactive. In this study, it was found that the turnover number of 1 for CO evolution reached 710 for the 1/[Ru(bpy)₃]²⁺/BIH (BIH = 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]-imidazole) system under optimal conditions over 4.5 h of visible-light irradiation, with a turnover frequency of 7.12 min^-1 in the first hour, a high selectivity of 97% for CO, and an internal quantum yield of 2.8%. Interestingly, the catalytic selectivity of 1 can be adjusted and even completely switched in a facile manner between the photochemical reductions of CO₂ to CO and of protons to H₂ simply by adding different amounts of triethanolamine to the catalytic system. The electron transfer in the photocatalytic system was studied by steady-state fluorescence and transient absorption spectroscopy, and a plausible mechanism for the photocatalytic reaction was proposed.

Key words: Catalytic selectivity, Carbon dioxide reduction, Carbon monoxide, Diiron complex, Hydrogenase model, Photocatalysis

Minglun Cheng, Xiongfei Zhang, Yong Zhu, Mei Wang. Selective photocatalytic reduction of CO₂ to CO mediated by a [FeFe]-hydrogenase model with a 1,2-phenylene S-to-S bridge[J]. Chinese Journal of Catalysis, 2021, 42(2): 310-319.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63644-0

https://www.cjcatal.com/EN/Y2021/V42/I2/310

Figures/Tables 13

Fig. 1. Structures of the diiron dithiolate complexes 1 and 2 used in the present work.

Table 1 Photochemical CO2 reduction in the presence of 1 and 2 under different conditions.

Catalyst	Additive	CO (μmol)	H₂ (μmol)	TON CO / H₂	CO selectivity (%)
1	—	25.6	0.07	256/0.7	> 99
2	—	0.06	0.03	0.6/0.3	—
1	0.5 M CH₃OH	25.3	0.2	253/2	> 99
1	1.5 M CH₃OH	38.9	2.5	389/25	94
1	2% TEOA	9.8	12.4	98/124	44
1	20% TEOA	0.9	102	9/1020	< 2

Fig. 2. Time-dependent evolution of CO and H2 during photocatalytic CO2 reduction with the system of 1 (20 μM), [Ru(bpy)3](PF6)2 (0.2 mM), and BIH (20 mM), in dry CH3CN or CH3CN/CH3OH (1.5 M); the solution was saturated with CO2 and irradiated by visible light (λ ＞ 420 nm).

Table 2 Control experiments under different conditions.

Entry	[1] (μM)	[{Ru(bpy)₃}²⁺] (mM)	[BIH] (mM)	TON_CO	TON_H2
1	20	0.2	20	255	0.7
2	0	0.2	20	0.7	1.2
3	20	0.2	0	1.5	0
4	20	0	20	0	0
5^a	20	0.2	20	0	0
6 ^b	20	0.2	20	0.3	0.8

Fig. 3. (a) Mass spectrum of CO obtained from the system of 1 (20 μM), [Ru(bpy)3]2+ (0.2 mM), and BIH (20 mM) in 13CO2-saturated MeCN solution after 2 h of irradiation. (b) Time-dependent evolution of CO and H2 during the photocatalytic CO2 reduction with the systems of 1 (20 μM), [Ru(bpy)3]2+ (0.2 mM), and BIH (20 mM) in dry MeCN in the absence and presence of Hg (20 μL); the solutions were saturated with CO2 and irradiated by visible light.

Fig. 4. Time-dependent evolution of CO and H2 detected in the photocatalytic CO2 reduction carried out by the irradiation of the CO2-saturated CH3CN solution of 1 (20 μM), [Ru(bpy)3](PF6)2 (0.2 mM), and BIH (20 mM) containing 2% (v/v) (a) and 20% (v/v) (b) TEOA.

Fig. 5. (a) Time evolution of CO evolved from the system of [Ru(bpy)3]2+ (0.4 mM) and BIH (20 mM) with varied concentrations of 1 in CO2-saturated CH3CN/CH3OH (1.5 M) under irradiation (λ ＞ 420 nm) over 3.5 h; (b) Plot of the CO evolution rate (kobs(CO)) versus [1] in the first 90 min of irradiation.

Fig. 6. Time-dependent evolution of CO and H2 from different photocatalytic systems. (a) 1 (20 μM) and BIH (20 mM) with varied concentration of [Ru(bpy)3]2+; (b) 1 (20 μM) and [Ru(bpy)3]2+ (0.6 mM) with varied concentration of BIH in CO2-saturated CH3CN/CH3OH (1.5 M) under irradiation.

Table 3 Results for the photocatalytic CO2 reduction with different concentrations of 1, [Ru(bpy)3]2+, and BIH.

Entry	[1] (μM)	[{Ru(bpy)₃}²⁺] (mM)	[BIH] (mM)	TON CO / H₂	TOF_CO^a (min^-1)	CO selectivity (%)
1	5	0.4	20	464/9	5.16	98
2	10	0.4	20	549/42	5.16	93
3	20	0.4	20	557/36	4.63	94
4	20	0.2	20	395/27	3.54	94
5	20	0.6	20	556/23	6.73	96
6	20	0.6	40	710/21	7.12	97

Fig. 7. Plot of TONCO versus time for the photocatalytic system containing 1 (20 μM), [Ru(bpy)3]2+ (0.2 mM), and BIH (20 mM) in CO2-saturated CH3CN/CH3OH (1.5 M); after 150 min of irradiation when CO evolution ceased, 1 or [Ru(bpy)3]2+ equal to the initial quantity was added to the catalytic system.

Fig. 8. Phosphorescence spectra of [Ru(bpy)3]2+ (10 μM) in CH3CN containing different concentrations of 1 (a) or BIH (b), excited by monochromatic light at 450 nm. Kinetic traces of (c) transient bleaching recovery monitored at 450 nm for [Ru(bpy)3]2+ (5.0 × 10-5 M) only, [Ru(bpy)3]2+/1 (2.5 × 10-5 M), and [Ru(bpy)3]2+/BIH (2.0 × 10-4 M) and (d) transient decay monitored at 520 nm for [Ru(bpy)3]2+/BIH and [Ru(bpy)3]2+/BIH/1 in deoxygenated CH3CN solutions.

Fig. 9. Microsecond transient absorption spectra of [Ru(bpy)3]2+ (5.0 × 10-5 M), [Ru(bpy)3]2+ with BIH (2.0 × 10-4 M), and [Ru(bpy)3]2+ with BIH and 1 (2.5 × 10-5 M) in deoxygenated CH3CN solution.

Scheme 1. Proposed mechanism for the photocatalytic reduction of CO2 to CO by the 1/[Ru(bpy)3]2+/BIH system.

References

[1]	M. Halmann, Nature, 1978,275, 115-116.
[2]	T. Inoue, A. Fujishima, S. Konishi, K. Honda, Nature, 1979,277, 637-638.
[3]	J. Bonin, A. Maurin, M. Robert, Coord. Chem. Rev., 2017,334, 184-198.
[4]	H. Takeda, C. Cometto, O. Ishitani, M. Robert, ACS Catal., 2017,7, 70-88.
[5]	N. Elgrishi, M. B. Chambers, X. Wang, M. Fontecave, Chem. Soc. Rev., 2017,46, 761-796.
[6]	K. E. Dalle, J. Warnan, J. J. Leung, B. Reuillard, I. S. Karme, E. Reisner, Chem. Rev., 2019,119, 2752-2875.
[7]	H. Takeda, H. Koizumi, K. Okamoto, O. Ishitani, Chem. Commun., 2014,50, 1491-1493.
[8]	E. Torralba-Peñalver, Y. Luo, J.-D. Compain, S. Chardon-Noblat, B. Fabre, ACS Catal., 2015,5, 6138-6147.
[9]	P. L. Cheung, C. W. Machan, A. Y. S. Malkhasian, J. Agarwal, C. P. Kubiak, Inorg. Chem., 2016,55, 3192-3198.
[10]	J.-X. Zhang, C.-Y. Hu, W. Wang, H Wang, Z.-Y. Bian, Appl. Catal. A, 2016,522, 145-151.
[11]	J. Bonin, M. Chaussemier, M. Robert, M. Routier, ChemCatChem, 2014,6, 3200-3207.
[12]	H. Takeda, K. Ohashi, A. Sekine, O. Ishitani, J. Am. Chem. Soc., 2016,138, 4354-4357.
[13]	P. G. Alsabeh, A. Rosas-Hernández, E. Barsch, H. Junge, R. Ludwig, M. Beller, Catal. Sci. Technol., 2016,6, 3623-3630.
[14]	A. Rosas-Hernández, P. G. Alsabeh, E. Barsch, H. Junge, R. Ludwig, M. Beller, Chem. Commun., 2016,52, 8393-8396.
[15]	H. Rao, J Bonin, M. Robert, ChemSusChem, 2017,10. 4447-4450.
[16]	H. Rao, L. C. Schmidt, J. Bonin, M. Robert, Nature, 2017,548, 74-77.
[17]	J. Bonin, M. Robert, M. Routier, J. Am. Chem. Soc., 2014,136, 16768-16771.
[18]	A. Rosas-Hernández, C. Steinlechner, H. Junge, M. Beller, Green Chem., 2017,19, 2356-2360.
[19]	H. Rao, J. Bonin, M. Robert, Chem. Commun., 2017,53, 2830-2833.
[20]	Z. Guo, S. Cheng, C. Cometto, E. Anxolabéhère-Mallart, S.-M. Ng, C.-C. Ko, G. Liu, L. Chen, M. Robert, T.-C. Lau, J. Am. Chem. Soc., 2016,138, 9413-9416.
[21]	J. Grodkowski, T. Dhanasekaran, P. Neta, P. Hambright, B. S. Brunschwig, K. Shinozaki, E. Fujita, J. Phys. Chem. A, 2000,104, 11332-11339.
[22]	L. Chen, Z. Guo, X.-G. Wei, C. Gallenkamp, J. Bonin, E. Anxolabéhère-Mallart, K.-C. Lau, T.-C. Lau, M. Robert, J. Am. Chem. Soc., 2015,137, 10918-10921.
[23]	J. Grodkowski, P. Neta, E. Fujita, A. Mahammed, L. Simkhovich, Z. Gross, J. Phys. Chem. A, 2002,106, 4772-4778.
[24]	S. L.-F. Chan, T. L. Lam, C. Yang, S.-C. Yan, N. M. Cheng, Chem. Commun., 2015,51, 7799-7801.
[25]	M. Zhang, M. El-Roz, H. Frei, J. L. Mendoza-Cortes, M. Head-Gordon, D. C. Lacy, J. C. Peters, J. Phys. Chem. C, 2015,119, 4645-4654.
[26]	C. Yang, F. Mehmood, T. L. Lam, S. L.-F. Chan, Y. Wu, C.-S. Yeung, X. Guan, K. Li, C. Y.-S. Chung, C.-Y. Zhou, T. Zou, C.-M. Che, Chem. Sci., 2016,7, 3123-3136.
[27]	F. Wang, B. Cao, W.-P. To, C.-W. Tse, K. Li, X.-Y. Chang, C. Zang, S. L.-F. Chan, C.-M. Che, Catal. Sci. Technol., 2016,6, 7408-7420.
[28]	D.-C. Liu, H.-J. Wang, J.-W. Wang, D.-C. Zhong, L. Jiang, T.-B. Lu, Chem. Commun., 2018,54, 11308-11311.
[29]	C.-Y. Zhu, Y.-Q. Zhang, R.-Z. Liao, W. Xia, J.-C. Hu, J. Wu, H. Liu, F. Wang, Dalton Trans., 2018,47, 13142-13150.
[30]	J. J. Leung, J. Warnan, K. H. Ly, N. Heidary, D. H. Nam, M. F. Kuehnel, E. Reisner, Nat. Catal., 2019,2, 354-365.
[31]	T. Ouyang, C. Hou, J.-W. Wang, W.-J. Liu, D.-C. Zhong, Z.-F. Ke, T.-B. Lu, Inorg. Chem., 2017,56, 7307-7311.
[32]	T. Ouyang, H.-H. Huang, J.-W. Wang, D.-C. Zhong, T.-B. Lu, Angew. Chem. Int. Ed., 2017,56, 738-743.
[33]	T. Ouyang, H.-J. Wang, H.-H. Huang, J.-W. Wang, S. Guo, W.-J. Liu, D.-C. Zhong, T.-B. Lu, Angew. Chem. Int. Ed., 2018,57, 16480-16485.
[34]	V. S. Thoi, N. Kornienko, C. G. Margarit, P. Yang, C. J. Chang, J. Am. Chem. Soc., 2013,135, 14413-14424.
[35]	H. Shirley, X. Su, H. Sanjanwala, K. Talukdar, J. W. Jurss, J. H. Delcamp, J. Am. Chem. Soc., 2019,141, 6617-6622.
[36]	D. Hong, Y. Tsukakoshi, H. Kotani, T. Ishizuka, T. Kojima, J. Am. Chem. Soc., 2017,139, 6538-6541.
[37]	M. F. Kuehnel, K. L. Orchard, K. E. Dalle, E. Reisner, J. Am. Chem. Soc., 2017,139, 7217-7223.
[38]	G. Neri, M. Forster, J. J. Walsh, C. M. Robertson, T. J. Whittles, P. Farràs, A. J. Cowan, Chem. Commun., 2016,52, 14200-14203.
[39]	Z. Guo, F. Yu, Y. Yang, C.-F. Leung, S.-M. Ng, C.-C. Ko, C. Cometto, T.-C. Lau, M. Robert, ChemSusChem, 2017,10, 4009-4013.
[40]	D. Hong, T. Kawanishi, Y. Tsukakoshi, H. Kotani, T. Ishizuka, T. Kojima, J. Am. Chem. Soc., 2019,141, 20309-20317.
[41]	C. Steinlechner, A. F. Roesel, E. Oberem, A. Päpcke, N. Rockstroh, F. Gloaguen, S. Lochbrunner, R. Ludwig, A. Spannenberg, H. Junge, R. Francke, M. Beller, ACS Catal. 2019,9, 2091-2100.
[42]	J.-H. Jeoung, H. Dobbek, Science, 2007,318, 1461-1464.
[43]	C. Bruckmeier, M. W. Lehenmeier, R. Reithmeier, B. Rieger, J. Herranz, C. Kavakli, Dalton Trans., 2012,41, 5026-5037.
[44]	R. O. Reithmeier, S. Meister, B. Rieger, A. Siebel, M. Tschurl, U. Heiz, E. Herdtweck, Dalton Trans., 2014,43, 13259-13269.
[45]	K. Mochizuki, S. Manaka, I. Takeda, T. Kondo, Inorg. Chem., 1996,35, 5132-5136.
[46]	M. Cheng, Y. Yu, X. Zhou, Y. Luo, M. Wang, ACS Catal., 2018,9, 768-774.
[47]	J. A. Cabeza, M. A. Martínez-García, V. Riera, D. Ardura, S. García-Granda, Organometallics, 1998,17, 1471-1477.
[48]	F. Gloaguen, J. D. Lawrence, M. Schmidt, S. R. Wilson, T. B. Rauchfuss, J. Am. Chem. Soc., 2001,123, 12518-12527.
[49]	A. Juris, V. Balzani, P. Belser, A. von Zelewsky, Helv. Chim. Acta, 1981,64, 2175-2182.
[50]	C. K. Prier, D. A. Rankic, D. W. C. MacMillan, Chem. Rev., 2013,113, 5322-5363.
[51]	Y. Tamaki, K. Koike, T. Morimoto, O. Ishitani, J. Catal., 2013,304, 22-28.
[52]	E. Hasegawa, S. Takizawa, T. Seida, A. Yamaguchi, N. Yamaguchi, N. Chiba, T. Takahashi, H. Ikeda, K. Akiyama, Tetrahedron, 2006,62, 6581-6588.
[53]	G. A. N. Felton, A. K. Vannucci, J. Chen, L. T. Lockett, N. Okumura, B. J. Petro, U. I. Zakai, D. H. Evans, R. S. Glass, D. L. Lichtenberger, J. Am. Chem. Soc., 2007,129, 12521-12530.
[54]	R. J. Wright, W. Zhang, X. Yang, M. Fasulo, T. D. Tilley, Dalton Trans., 2012,41, 73-82.
[55]	K. T. Ngo, M. McKinnon, B. Mahanti, R. Narayanan, D. C. Grills, M. Z. Ertem, J. Rochford, J. Am. Chem. Soc., 2017,139, 2604-2618.
[56]	E. Haviv, D. Azaiza-Dabbah, R. Carmieli, L. Avram, J. M. L. Martin, R. Neumann, J. Am. Chem. Soc., 2018,140, 12451-12456.
[57]	Y.-C. Liu, K.-T. Chu, R.-L. Jhang, G.-H. Lee, M.-H. Chiang, Chem. Commun., 2013,49, 4743-4745.
[58]	B. Probst, A. Rodenberg, M. Guttentag, P. Hamm, R. Alberto, Inorg. Chem., 2010,49, 6453-6460.

Selective photocatalytic reduction of CO₂ to CO mediated by a [FeFe]-hydrogenase model with a 1,2-phenylene S-to-S bridge

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