电极表面第二配位环境对水氧化分子催化剂O-O键形成机理的调控

doi:10.1016/S1872-2067(20)63671-3

催化学报 ›› 2021, Vol. 42 ›› Issue (3): 460-469.DOI: 10.1016/S1872-2067(20)63671-3

电极表面第二配位环境对水氧化分子催化剂O-O键形成机理的调控

卓启明^a,†, 詹绍琦^b,†, 段乐乐^a^,^c, 刘畅^a, 吴秀娟^a, Mårten S.G. Ahlquist^b, 李福胜^a^,^*(), 孙立成^a^,^d

^a大连理工大学精细化工国家重点实验室人工光合作用研究所,辽宁大连116024,中国
^b瑞典皇家理工学院,化学工程学院理论化学与生物学系,斯德哥摩10691,瑞典
^c南方科技大学化学,系格拉布斯研究院,广东深圳518055,中国
^d瑞典皇家理工学院,化学工程学院化学系,斯德哥摩10044,瑞典

收稿日期:2020-05-09 接受日期:2020-06-15 出版日期:2021-03-18 发布日期:2021-01-23
通讯作者: 李福胜
作者简介:^†共同第一作者.
基金资助:
大连理工大学基本科研业务费(DUT19LK16);国家自然科学基金(21120102036);国家自然科学基金(91233201);国家自然科学基金(21771098);国家自然科学基金(2014CB239402);精细化工重点实验室开放课题(KF1802);瑞典研究理事会(2017-00935);瑞典能源署

Tuning the O-O bond formation pathways of molecular water oxidation catalysts on electrode surfaces via second coordination sphere engineering

Qiming Zhuo^a,†, Shaoqi Zhan^b,†, Lele Duan^a^,^c, Chang Liu^a, Xiujuan Wu^a, Mårten S. G. Ahlquist^b, Fusheng Li^a^,^*(), Licheng Sun^a^,^d

^aState Key Laboratory of Fine Chemicals,Institute of Artificial Photosynthesis,DUT-KTH Joint Education and Research Centre on Molecular Devices,Institute for Energy Science and Technology,Dalian University of Technology,Dalian 116024,Liaoning,China
^bDepartment of Theoretical Chemistry and Biology,School of Engineering Sciences in Chemistry,Biotechnology and Health,KTH Royal Institute of Technology,Stockholm 10691,Sweden
^cDepartment of Chemistry and Shenzhen Grubbs Institute,Southern University of Science and Technology (SUSTech),Shenzhen 518055,Guangdong,China
^dDepartment of Chemistry,School of Engineering Sciences in Chemistry,Biotechnology and Health,KTH Royal Institute of Technology,Stockholm 10044,Sweden

Received:2020-05-09 Accepted:2020-06-15 Online:2021-03-18 Published:2021-01-23
Contact: Fusheng Li
About author:^*Tel/Fax:+86-411-84986494; E-mail:fusheng@dlut.edu.cn
First author contact:^†These authors contributed equally to this work.
Supported by:
Fundamental Research Funds for the Central Universities(DUT19LK16);the Natural Science Foundation of China(21120102036);the Natural Science Foundation of China(91233201);the Natural Science Foundation of China(21771098);the Natural Science Foundation of China(2014CB239402);the State Key Laboratory of Fine Chemicals(KF1802);the Swedish Research Council(2017-00935);A Wallenberg Foundation

摘要/Abstract

摘要：

水氧化反应可以提供四个电子和四个质子,反应产物是可以资源化的氧气,因而,水氧化反应是大规模能源转化和存储技术理想的阳极反应. 但是,由于水氧化反应具有较高的热力学能垒,涉及四个电子和四个质子的转移过程以及氧-氧键(O-O)的形成,是一个耗能高且动力学缓慢的复杂反应. 因此,开发高效的水氧化催化剂来加速水氧化反应速率,对于能源转化和存储相关技术至关重要. 然而,人们对水氧化催化剂的合理设计和在催化反应中提高反应活性的方法了解甚少,在温和条件下促进O-O键的有效形成仍然是一个根本性的挑战. 迄今为止,关于水氧化分子催化剂的研究主要集中在催化剂的配位结构(第一配位环境)和催化效率之间的关系上,水氧化分子催化剂的第二配位环境对其催化活性的影响尚未得到充分研究. 将催化剂引入到电极表面时,其催化环境和均相反应时完全不同. 因此,水氧化催化剂在电极表面的催化反应动力学、质子耦合电子转移过程以及其O-O键形成机理可能发生改变.
本文以4-乙烯基吡啶为轴向配体的[Ru(bda)](络合物1,bda = 2,2’-联吡啶-6,6’-二羧酸)水氧化分子催化剂,通过电化学聚合的方法将络合物1固载在玻璃碳电极表面,用于研究第二配位环境对电极表面水氧化分子催化剂催化机理的影响. 通过直接聚合络合物1在玻璃碳表面得到电极材料poly-1@GC; 将4-三氟甲基苯乙烯和苯乙烯作为限制单元分别与络合物1共聚,得到电极材料poly-1+P3F@GC和poly-1+PSt@GC. 通过一系列电极表面动力学方法和DFT计算分别求出催化剂在三种电极材料中的反应级数ρ_cata、催化剂的溶液质子-原子转移性质、催化剂的水氧化氘动力学同位素效应KIEs_H/D,以及[Ru(bda)]催化剂在不同材料中的偶极矩的变化. 通过对比催化剂在不同电极材料中的催化行为和相关关键参数发现,电极表面催化剂的第二层配位环境对其水氧化反应过程中的O-O键形成机制和质子耦合电子转移过程有着显著的影响. [Ru(bda)]在直接聚合的电极材料poly-1@GC中,通过自由基耦合机理(I2M)形成O-O键. 而当[Ru(bda)]与4-三氟甲基苯乙烯和苯乙烯共聚时,由于[Ru(bda)]催化剂被分散,不利于自由基耦合机理的发生,[Ru(bda)]在电极材料poly-1+P3F@GC和poly-1+PSt@GC中主要通过水分子亲核进攻机理进行(WNA)催化水氧化. 同时,具有强偶极矩的4-三氟甲基苯基能够稳定[Ru(bda)]在催化过程的中间体,可以使引发O-O键生成的关键物种Ru^V=O的氧化电位发生明显的负向移动,使得[Ru(bda)]在poly-1+P3F@GC可以更容易触发水氧化反应,进而加快了[Ru(bda)]采用水分子亲核进攻机理时的催化反应速率.

关键词: 水氧化催化剂, 第二配位环境, 偶极矩, O-O键形成, 反应动力学

Abstract:

A molecular [Ru(bda)]-type (bda = 2,2’-bipyridine-6,6’-dicarboxylate) water oxidation catalyst with 4-vinylpyridine as the axial ligand (Complex 1) was immobilized or co-immobilized with 1-(trifluoromethyl)-4-vinylbenzene (3F) or styrene (St) blocking units on the surface of glassy carbon (GC) electrodes by electrochemical polymerization,in order to prepare the corresponding poly-1@GC,poly-1+P3F@GC,and poly-1+PSt@GC functional electrodes. Kinetic measurements of the electrode surface reaction revealed that [Ru(bda)] triggers the O-O bond formation via (1) the radical coupling interaction between the two metallo-oxyl radicals (I2M) in the homo-coupling polymer (poly-1),and (2) the water nucleophilic attack (WNA) pathway in poly-1+P3F and poly-1+PSt copolymers. The comparison of the three electrodes revealed that the second coordination sphere of the water oxidation catalysts plays vital roles in stabilizing their reaction intermediates,tuning the O-O bond formation pathways and improving the water oxidation reaction kinetics without changing the first coordination structures.

Key words: Water oxidation catalyst, Second coordination sphere, Dipole moment, O-O bond formation, Reaction kinetics

卓启明, 詹绍琦, 段乐乐, 刘畅, 吴秀娟, Mårten S.G. Ahlquist, 李福胜, 孙立成. 电极表面第二配位环境对水氧化分子催化剂O-O键形成机理的调控[J]. 催化学报, 2021, 42(3): 460-469.

Qiming Zhuo, Shaoqi Zhan, Lele Duan, Chang Liu, Xiujuan Wu, Mårten S. G. Ahlquist, Fusheng Li, Licheng Sun. Tuning the O-O bond formation pathways of molecular water oxidation catalysts on electrode surfaces via second coordination sphere engineering[J]. Chinese Journal of Catalysis, 2021, 42(3): 460-469.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63671-3

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图/表 6

Scheme 1 Overview of oxo-oxo coupling (I2M) and water nucleophilic attack (WNA) mechanisms for O-O bond formation by WOCs.

Scheme 2 Schematic diagrams of electrodes prepared via electrochemical polymerization.

Fig. 1. Pourbaix diagrams of poly-1@GC (a),poly-1+PSt@GC (b),and poly-1+P3F@GC (c) electrodes; (d) simulated Pourbaix diagrams of the three electrodes.

Fig.2. (a) LSV curves of poly-1@GC at various catalyst coverages (Γ). The inset plot shows the logarithm of the current density at selected potentials against the logarithm of the corresponding peak current of the RuIII/II couple; the slopes of the linear fitting curves reflect the reaction orders in catalyst coverage (ρΓ). (b) LSV curves of poly-1@GC in D2O and H2O (electrolyte: Na2SO4 anhydrous,50 mM). The inset plot shows the KIE values as a function of the potential. (c) LSV curves of poly-1@GC at various phosphate buffer concentrations ([Pi]). The inset plot shows the logarithm of the current density at selected potentials against the logarithm of the phosphate concentration; the slopes of the linear fitting curves reflect the reaction orders in [Pi]. (d) TOF values of poly-1@GC with a catalyst coverage of 5.1 × 10-11 mol cm-2,measured by the chronoamperometric method.

Fig.3. (a) LSV curves of poly-1+PSt@GC at various catalyst coverages Γ. The inset plot shows the logarithm of the current density at selected potentials as a function of the logarithm of the corresponding peak current of the RuIII/II couple; the slopes of the linear fitting curves reflect the reaction orders in catalyst coverage (ρΓ). (b) LSV curves of poly-1+PSt@GC in D2O and H2O (electrolyte: Na2SO4 anhydrous,50 mM). The plot inset shows the KIE values as a function of the potential. (c) LSV curves of poly-1+PSt@GC at various phosphate buffer concentrations. The inset plot shows the logarithm of the current density at selected potentials as a function of the logarithm of the phosphate concentration; the slopes of the linear fitting curves reflect the reaction orders in [Pi]. (d) TOF values of poly-1+PSt@GC with a catalyst coverage of 7.2 × 10-11 mol cm-2,measured by the chronoamp erometric method.

Fig.4. (a) LSV curves of poly-1+P3F@GC at various catalyst coverages Γ. The inset plot shows the logarithm of the current density at selected potentials against the logarithm of the corresponding peak current of the RuIII/II couple; the slopes of the linear fitting curves reflect the reaction orders in catalyst coverage (ρΓ). (b) LSV curves of poly-1+P3F@GC in D2O and H2O (electrolyte: anhydrous Na2SO4,50 mM). The inset shows the KIE values as a function of the potential. (c) LSV curves of poly-1+P3F@GC at various phosphate buffer concentrations. The inset plot shows the logarithm of the current density at selected potentials as a function of the logarithm of the phosphate concentration; the slopes of the linear fitting curves reflect the reaction orders in [Pi]. (d) TOFs of poly-1+P3F@GC with a catalyst coverage of 5.6 × 10-11 mol cm-2,measured by the chronoamperometric method.

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电极表面第二配位环境对水氧化分子催化剂O-O键形成机理的调控

Tuning the O-O bond formation pathways of molecular water oxidation catalysts on electrode surfaces via second coordination sphere engineering

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