金属有机框架载体内Ru(bda)L2催化剂微环境的调控实现高效光驱动水氧化

doi:10.1016/S1872-2067(23)64411-0

摘要/Abstract

摘要：

人工光合作用研究中, 因涉及多个电子和质子的转移而具有缓慢动力学特征的产氧半反应, 是实现水全分解的关键. 作为一类高效水氧化催化剂, Ru(bda)L₂(H₂bda = 2,2'-联吡啶-6,6'-二羧酸, L=配体)分子催化剂被广泛应用于化学驱动的水氧化研究, 其中O-O键的形成是水氧化反应的决速步骤. 相比之下, 因光敏剂和牺牲试剂的参与, 光驱动水氧化反应的决速步骤为高价Ru物种的形成, 且存在光敏剂自身氧化分解与光敏剂氧化催化中心成为高价Ru物种之间的竞争. 因此, 促进分子催化剂向光敏剂的多步非等价电子转移, 是提高光催化水氧化性能的关键. 自然光合作用中, 水氧化过程中高效的质子传输和电子转移与光系统PSII中[Mn₄CaO₅]簇活性位点周围复杂的蛋白质微环境密切相关. 因此, 利用多孔载体实现Ru分子催化剂的固载, 在多相化提高其稳定性的同时, 为Ru催化剂周围微环境的调控提供了可能.
基于本课题组前期发展的配位辅助自组装策略, 本文将Ru(bda)L₂分子催化剂固载到金属-有机框架UiO-66载体中(Ru(bda)L₂@UiO-66), 作为孤立的催化位点用于化学驱动和光驱动水氧化反应研究. 在Ce⁴⁺化学驱动水氧化反应中, Ru(bda)L₂@UiO-66表现出比均相体系更高的活性和稳定性. 在以Ru(bpy)₃Cl₂为光敏剂, Na₂S₂O₈为牺牲剂的光催化体系, Ru(bda)L₂@UiO-66在磷酸盐缓冲水溶液中光驱动水氧化催化转化数高达566, 比相同条件下的均相催化剂高出近20倍. 进一步对比磷酸盐缓冲水溶液、硼酸盐缓冲水溶液和纯水三种溶剂中的光驱动水氧化性能, 发现水氧化性能越高, 因光敏剂氧化分解而产生的CO₂量越低. 通过紫外-可见漫反射光谱、红外光谱、X射线粉末衍射和X射线光电子能谱等技术对反应前后催化剂的组成和结构进行研究, 结果表明, 在化学驱动水氧化反应前后Ru(bda)L₂@UiO-66结构保持不变; 而光驱动水氧化反应中, 高的产氧性能伴随着UiO-66骨架结构在高浓度硫酸盐存在下的逐步坍塌. 动力学同位素效应(KIE)揭示了水氧化过程中存在质子参与. 质子库存实验与氢核磁证实, 在光催化过程中载体因磷酸盐的摄入而在催化剂周边构建了含水的氢键网络. 结合水氧化亲核进攻反应机制中质子的参与以及可能的质子耦合电子转移, 提出载体摄入的磷酸盐作为质子中继体与水分子的氢键网络相耦合, 促进了光驱动水分解产氧性能, 同时抑制了与之相竞争的光敏剂的氧化分解机理. 综上, 本工作提供了一种运用多相化载体来模拟催化剂类酶微环境的思路, 对于实现高效人工光合作用具有一定参考价值.

关键词: Ru(bda)L₂催化剂, 隔离位点, 光驱动水氧化, 质子介质, 微环境

Abstract:

A Ru(bda)L₂ molecular catalyst (H₂bda = 2,2′-bipyridine-6,6′-dicarboxylic acid, L represents ligands) was incorporated into a UiO-66 metal-organic framework (MOF) as isolating sites for chemical- and photo-driven water oxidation with the water nucleophilic attack mechanism. An impressive turn-over number of 566 was obtained for photo-driven water oxidation in the phosphate buffer saline, which was nearly 20 times that of the homogenous counterpart in the presence of ruthenium tris(bipyridine) and sodium persulfate. Infrared spectroscopy, X-ray diffraction and X-ray spectroscopy techniques were used to characterize the composition and structure of the catalysts. Kinetic isotope effect (KIE), proton inventory experiment and proton nuclear magnetic resonance were conducted to understand the photo-driven O₂ evolution mechanism. It was observed that the protons participated in O₂ evolution with a normal KIE value, and the uptake of phosphates by UiO-66 matrix improved the affinity towards H₂O via hydrogen bonding. The high O₂ output and the limited photosensitizer oxidative decomposition in PBS suggest that the phosphate acted as a proton mediator to assist proton and/or proton-couple electron transfer through a hydrogen-bonded network of water molecules. This study uses a heterogenous matrix to emulate an enzyme-like microenvironment capable of achieving efficient artificial photosynthesis.

Key words: Ru(bda)L₂ catalyst, Isolating site, Photo-driven water oxidation, Proton mediator, Microenvironment

冯坚信, 李轩, 罗宇成, 苏志芳, 钟茂灵, 余宝蓝, 石建英. 金属有机框架载体内Ru(bda)L₂催化剂微环境的调控实现高效光驱动水氧化[J]. 催化学报, 2023, 48: 127-136.

Jianxin Feng, Xuan Li, Yucheng Luo, Zhifang Su, Maoling Zhong, Baolan Yu, Jianying Shi. Microenvironment regulation of Ru(bda)L₂ catalyst incorporated in metal-organic framework for effective photo-driven water oxidation[J]. Chinese Journal of Catalysis, 2023, 48: 127-136.

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https://www.cjcatal.com/CN/Y2023/V48/I5/127

图/表 10

Scheme 1. Illustration showing the incorporation of the Ru(bda)L2 molecular catalyst into the UiO-66 framework.

Fig. 1. HAADF-STEM images and corresponding elemental maps of Ru(bda)L2@UiO-66.

Fig. 2. Three reaction cycles (20 min in every run) driven by low concentration of CeIV (0.1 mol L-1) (a) and single-pass reaction driven by the high concentration of CeIV (0.3 mol L-1) (b) in Ru(bda)L2@UiO-66, Ru(bda)L2 and Ru(bda)L2/UiO-66 catalyzing chemical water oxidation for oxygen evolution in 5 mL of HNO3 aqueous solution (0.1 mol L-1). In the recycling experiment, Ce(NH4)2(NO3)6 solid was directly added into the previous reaction solution to restart the following cycles.

Fig. 3. Photocatalytic oxygen evolution (a) and TON (3 h) (b) comparison for Ru(bda)L2@UiO-66 (5 mg), Ru(bda)L2/UiO-66 (5 mg) and Ru(bda)L2 (equivalent) in PBS solution. TON = n(O2)/n(Ru(bda)L2); (c) Photocatalytic oxygen evolution in PBS solution with different amounts of Ru(bda)L2@UiO-66. (d) The dependence of the initial O2 evolution rate (10 min) on the Ru(bda)L2@UiO-66 concentration. Reaction condition: Ru(bpy)32+ (2.6 mmol L-1), Na2S2O8 (0.12 mol L-1), PBS solution (5 mL), visible light (λ > 420 nm) irradiated at 100 mW cm-2 intensity.

Fig. 4. Oxygen evolution (a) and CO2 evolution (b) against time in photocatalytic water oxidation by Ru(bda)L2@UiO-66 in three different solvents of PBS, BBS and H2O. Reaction conditions: 5 mg of catalyst dispersed in 5 mL of solution, in the presence of Ru(bpy)32+ (2.6 mmol L-1) and Na2S2O8 (0.12 mol L-1), visible light (λ > 420 nm) irradiated at 100 mW cm-2 intensity.

Fig. 5. UV-vis diffuse reflectance spectra of Ru(bda)L2@UiO-66, Ru(bda)L2/UiO-66, UiO-66 and Ru(bda)L2.

Fig. 6. XRD patterns (a,b) and IR spectra (c,d) of pristine catalysts of UiO-66, Ru(bda)L2@UiO-66 and Ru(bda)L2/UiO-66 (a,c), and recycled Ru(bda)L2@UiO-66 catalysts (b,d) after chemical-driven oxidation in Ce4+ solution and photo-driven oxidation in H2O, BBS, and PBS solutions. Terephthalic acid (TA) was added to the recycled samples (b,d) for comparison.

Fig. 7. Ru 3p (a), S 2p (b) and P 2p (c) XPS spectra of pristine Ru(bda)L2@UiO-66 and recycled Ru(bda)L2@UiO-66 after photo-driven oxidation in H2O, BBS, PBS solutions and chemical-driven oxidation in Ce4+ solution.

Fig. 8. (a) The kinetic isotope effect of Ru(bda)L2@UiO-66 (5 mg) in 5 mL of non-deuterated and deuterated PBS solution in the presence of Ru(bpy)32+ (PS, 2.6 mmol L-1) and Na2S2O8 (SA, 0.12 mol L-1), visible light (λ > 420 nm) irradiated at 100 mW cm-2 intensity. (b) The dependence of rate constant ratio (kn/k0) in non-deuterated and deuterated mixed solvent (kn) and in non-deuterated solvent (k0) on D2O molar fractions (n). (c) 1H NMR spectra of water molecules in CDCl3 before and after the addition of Ru(bda)L2@UiO-66 and Ru(bda)L2@UiO-66 (P).

Fig. 9. Illustration of the derived microenvironment (left panel) with the phosphate proton-mediator and preorganized water-networks around Ru(bda)L2 catalysts (middle panel) to promote proton transport and/or electron transfer during photo-driven O2 evolution with the WNA mechanism (right panel).

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金属有机框架载体内Ru(bda)L₂催化剂微环境的调控实现高效光驱动水氧化

Microenvironment regulation of Ru(bda)L₂ catalyst incorporated in metal-organic framework for effective photo-driven water oxidation

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