1,2-亚苯基二硫桥[FeFe]-氢化酶模拟物选择性光催化还原CO2至CO

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

摘要/Abstract

摘要：

利用基于非贵金属的分子催化剂通过光驱动催化CO₂还原生成CO是将太阳能储存为化学能和缓解CO₂温室效应的有效途径之一, 具有重要的科学意义和潜在的应用前景. 已报道的非贵金属分子催化剂, 大多数对于光驱动CO₂还原表现出缓慢的催化反应速率和/或对CO产物的低选择性, 反应常常伴随着质子还原产氢反应, 只有很少几种非贵金属分子催化剂对光催化CO₂还原生成CO表现出高催化反应速率(> 100 h^-1)和高选择性. 研究表明, 双核过渡金属配合物由于分子中邻近的两个金属中心的协同催化作用, 对于CO₂还原生成CO的催化活性明显高于相应的单核配合物. 因此, 具有两个邻近的金属离子的非贵金属双核配合物有望作为CO₂选择性还原的高效分子催化剂.
我们最近的研究发现, 具有刚性、共轭亚苯基二硫桥结构的[FeFe]-氢化酶模拟物[(μ-bdt)Fe₂(CO)₆] (1, bdt = 苯-1,2-二巯基)能够高活性、高选择性地光化学还原CO₂至CO, 而与其类似的模拟物[(μ-edt)Fe₂(CO)₆] (2, edt = 乙烷-1,2-巯基)则不具有光催化还原CO₂活性, 表明铁铁氢化酶模拟物中硫-硫桥的结构是影响模拟物的催化性能的重要结构因素之一. 可见光照射1/[Ru(bpy)₃]²⁺/BIH (BIH = 1,3-二甲基-2-苯基-2,3-二氢-1H-苯并[d]-咪唑)体系4.5 h, 1催化生成CO的循环数(TON)为710, 在初始1 h的转化率(TOF)为7.12 min^-1, CO的选择性达到97%, 内量子效率为2.8%. 有趣的是, 向体系中加入TEOA时可以调节1的催化选择性, 光化学反应能够在CO₂还原产生CO和质子还原产生H₂之间进行切换. 此外, 采用稳态荧光和瞬态吸收光谱研究了光催化体系中的电子转移, 提出可能的光催化反应机理. 该研究结果揭示了刚性硫-硫桥结构的氢化酶模拟物对光化学CO₂还原至CO的特殊催化活性, 拓展了铁铁氢化酶模拟物的催化多功能性.

关键词: 催化选择性, 二氧化碳还原, 一氧化碳, 双核铁配合物, 氢化酶模拟物, 光催化

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

程明伦, 张雄飞, 朱勇, 王梅. 1,2-亚苯基二硫桥[FeFe]-氢化酶模拟物选择性光催化还原CO₂至CO[J]. 催化学报, 2021, 42(2): 310-319.

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

图/表 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.

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1,2-亚苯基二硫桥[FeFe]-氢化酶模拟物选择性光催化还原CO₂至CO

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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