氧化还原活性联吡啶N-杂环卡宾供体负载的钴配合物在低过电位下电催化水析氢

doi:10.1016/S1872-2067(22)64151-2

摘要/Abstract

摘要：

本文研究了三种可调的、具有氧化还原活性联吡啶-N-杂环卡宾(NHC)配体的钴配合物水溶液的电催化析氢性能. 考察了在整个催化剂体系中结构修饰对配体框架的影响, 其中包括非大环衍生物(1-Co)和16(2-Co)和15元大环(3-Co). 结构-活性关系研究结果表明, 大环-环状络合物的活性高于非大环络合物, 其中最刚性的15元大环负载的催化剂整体性能最佳. 在330 mV的低过电位下, 3-Co催化pH=4的醋酸盐缓冲液析氢反应的法拉第效率为97%. 机理研究与钴氢化物物种的形成相吻合, 钴氢化物会质子化, 并通过杂化方式放出H₂.

关键词: 氧化还原活性联吡啶, N-杂环卡宾供体, 钴配合物, 电催化, 水分解, 析氢反应

Abstract:

Three cobalt complexes bearing tunable, redox-active bipyridyl N-heterocyclic carbene (NHC)-based ligands have been studied for electrocatalytic hydrogen evolution from aqueous solutions. The effect of structural modifications to the ligand framework is investigated across the catalyst series, which includes a non-macrocyclic derivative (1-Co) and 16-(2-Co) and 15-(3-Co) membered macrocycles. A structure-activity relationship is demonstrated, in which the macrocyclic complexes have greater activity compared to their non-macrocyclic counterpart with the most rigid catalyst, supported by the 15-membered macrocycle, performing best overall. Indeed, 3-Co catalyzes H₂ evolution from aqueous pH 4 acetate buffer with a Faradaic efficiency of 97% at a low overpotential of 330 mV. Mechanistic studies are consistent with formation of a cobalt-hydride species that is subsequently protonated to evolve H₂ via a heterolytic pathway.

Key words: Redox-active bipyridyl, N-heterocyclic carbene donors, Cobalt complex, Electrocatalysis, Water splitting, Hydrogen evolution

Lizhu Chen, Xiaojun Su, Jonah W. Jurss. 氧化还原活性联吡啶N-杂环卡宾供体负载的钴配合物在低过电位下电催化水析氢[J]. 催化学报, 2022, 43(12): 3187-3194.

Lizhu Chen, Xiaojun Su, Jonah W. Jurss. Electrocatalytic hydrogen evolution from water at low overpotentials with cobalt complexes supported by redox-active bipyridyl-NHC donors[J]. Chinese Journal of Catalysis, 2022, 43(12): 3187-3194.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(22)64151-2

https://www.cjcatal.com/CN/Y2022/V43/I12/3187

图/表 6

Scheme 1. Cobalt(II) catalysts (1-Co, 2-Co, and 3-Co) supported by tunable redox-active bipyridyl-NHC ligands.

Fig. 1. (a) CVs of 0.5 mmol L?1 1-Co, 2-Co, and 3-Co in aqueous 0.5 mol L?1 acetate buffer (pH = 4) under N2 (ν = 100 mV s?1, glassy carbon disk). (b) CVs of 5 μmol L?1 1-Co, 2-Co, and 3-Co in aqueous 1.0 mol L?1 pH 4 acetate buffer under N2 (ν = 100 mV s?1, Hg pool (4 cm dia). (c) CVs under same conditions as graph (a), but immediately following a 60 s electrolysis at ?0.8 V vs. NHE. (d) CVs under same conditions as graph (b), but immediately following a 60 s electrolysis at ca. ?0.6 V vs. NHE. CVs of electrode background and 0.5 mmol L?1 CoCl2 under the same conditions are shown as gray and dashed gray curves, respectively.

Fig. 2. (a) Charge vs. time plots from CPEs with 5 μmol L?1 1-Co, 2-Co, and 3-Co in 1.0 mol L?1 pH 4 acetate buffer under N2, applied potential (Eappl) = -0.57 V vs. NHE, Hg pool (4 cm dia). Electrolyses of bare electrode and 0.5 mmol L?1 CoCl2 under the same conditions are shown as gray and dashed gray curves, respectively. (b) Controlled potential electrolyses with (red) and without (gray) 5 μmol L?1 3-Co at Eappl = -0.57 V vs. NHE (same conditions, different CPE run than in Fig. 2(a)). The maximum theoretical H2 production is plotted (line) from accumulated charge. Blue squares are quantified H2 at different times points.

Table 1 Experimental results for 1-Co, 2-Co, and 3-Co from cyclic voltammetry and 2-h controlled potential electrolyses (Eappl = -0.57 V vs. NHE) in 1.0 mol L-1 pH 4 acetate buffer under N2 at a Hg pool electrode (4 cm dia).

Catalyst	E_cat^a(V)	E_cat^b(V)	Charge (C)	FE (%)	TON ^c	TOF (h^-1)
1-Co	-0.66	-0.55	23.4	100	295	147
2-Co	-0.64	-0.53	28.4	97	358	179
3-Co	-0.58	-0.47	37.7	97	472	236

Fig. 3. (a) CVs of 5 μmol L-1 3-Co in 1.0 mol L-1 buffered aqueous solutions at different pH under N2 at ν = 100 mV s-1, Hg pool electrode. (b) Plot of the catalytic potential at icat = 1 mA (black) as a function of pH.

Fig. 4. (a) CVs of 1 mmol L-1 3-Co in anhydrous CH3CN/0.1 mol L-1 Bu4NPF6 solution with various concentrations of dichloroacetic acid (glassy carbon disk, ν = 100 mV s-1). (b) Plot of catalytic current vs. acid concentration.

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