第二配位层的氧化还原活性二茂铁促使铁卟啉在氧存在下发生质子还原

doi:10.1016/S1872-2067(20)63761-5

摘要/Abstract

摘要：

采用洁净、可持续的替代能源以解决化石燃料的过度消耗及因其燃烧而导致的日益加剧的全球变暖问题已经成为当务之急. 其中, 如何实现在大气含氧条件下的析氢反应成为需要攻克的重大挑战. 氧还原在热力学上比质子还原更容易进行, 并且氧气部分还原时通常产生活性氧物种, 致使催化剂失活. 因此, 需要开发在氧气存在情况下能够有效还原质子的催化剂. 本文设计了一种四苯基铁卟啉分子, 该分子通过三氮唑将四个二茂铁连接在苯基邻位, 并证明该催化剂能够在有氧气的情况下高效还原质子, 产生氢气. 作为铁卟啉类化合物催化质子还原的活性物种, Fe(0)发生质子还原比发生O₂还原的动力学速率快得多, 从而为氧气存在下的选择性质子还原奠定了基础.

关键词: 铁卟啉, 析氢反应, 耐氧性, 电催化, 动力学

Abstract:

Hydrogen evolution in the presence of atmospheric level of oxygen is a significant barrier in the quest for an alternative, sustainable and green source of energy to counter the depleting fossil fuel sources and increasing global warming due to fossil fuel burning. Oxygen reduction is thermodynamically more favourable than proton reduction and it often produces reactive oxygenated species upon partial reduction which deactivates the catalyst. Thus, catalyst development is required for efficient proton reduction in the presence of oxygen. Here, we demonstrate an iron porphyrin having triazole containing 2 ^nd sphere hydrogen bonding residues appended with redox active ferrocene moieties (α₄-Tetra-2-(3-ferrocenyl-1,2,3-triazolyl)phenylporphyrin (FeFc₄)) as a bifunctional catalyst for fast and selective oxygen reduction to water and thus, preventing the proton reduction by the same catalyst from oxidative stress. Fe(0) is the active species for proton reduction in these iron porphyrin class of complexes and it is observed that the kinetics of proton reduction at Fe(0) state occurs at much faster rate than O₂ reduction and thus, paving the way for selective proton reduction in the presence of oxygen.

Key words: Iron porphyrin, Hydrogen evolution reaction, Oxygen tolerance, Electrocatalysis, Kinetics

Biswajit Mondal, Pritha Sen, Abhishek Dey. 第二配位层的氧化还原活性二茂铁促使铁卟啉在氧存在下发生质子还原[J]. 催化学报, 2021, 42(8): 1327-1331.

Biswajit Mondal, Pritha Sen, Abhishek Dey. Proton reduction in the presence of oxygen by iron porphyrin enabled with 2 ^nd sphere redox active ferrocenes[J]. Chinese Journal of Catalysis, 2021, 42(8): 1327-1331.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63761-5

https://www.cjcatal.com/CN/Y2021/V42/I8/1327

图/表 6

Scheme 1. (a) Strategies to obtain oxygen-tolerant proton reduction catalytic system; (b) The iron porphyrin (FeFc4) used in this study; (c) Chemical structure of FeFc4. Usually, the oxygen reduction starts at MIII/II state whereas, hydrogen evolution occurs either at MI or M0 depending on the metal and ligand environment.

Fig. 1. Heterogeneous electrocatalysis: (a) Linear sweep voltammetry (LSV) of FeFc4. LSV of FeFc4 in the presence of air with catalyst physisorbed on pyrolytic graphite electrode; (b) Rotating ring disk electrochemistry (RRDE) of FeFc4 in the presence of Air. RRDE of FeFc4 in the presence of air with catalyst physisorbed on pyrolytic graphite electrode, Pt and AgCl/Ag are used as counter and reference electrodes, respectively. Scan rate = 50 mV s-1, rotation speed is 300 rpm and Pt is held at 1.1 V.

Fig. 2. Rotating ring disk electrochemistry (RRDE) of FeEs4 in the Presence of Air. RRDE of FeEs4 in the presence of air with catalyst physiadsorbed on pyrolytic graphite electrode, Pt and AgCl/Ag are used as counter and reference electrodes, respectively. Scan rate = 50 mV s-1, rotation speed is 300 rpm and Pt is held at 1.1 V.

Fig. 3. Charge vs. time plot for HER with FeFc4 at varied N2:O2 mixtures and the corresponding FY values are tabulated. Charge vs. time plot for FeFc4 at different ratios of N2 and O2 mixtures; catalyst physisorbed on pyrolytic graphite and applied a constant -1.3 V at the working electrode, Pt and AgCl/Ag are used counter and reference electrode, respectively.

Fig. 4. Reaction of Fe(0)Fc4 with weak acid, PhOH and the corresponding UV-Vis kinetics. (a) UV-Vis spectra of Fe(0)Fc4 (green) and its reaction with PhOH (red); (b) UV-Vis kinetics of the reaction of Fe(0)Fc4 with weak acid PhOH, 1M (red dots).

Scheme 2. Proposed pathway for O2-tolerant proton reduction.

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