Electrocatalytic hydrogen evolution from water at low overpotentials with cobalt complexes supported by redox-active bipyridyl-NHC donors

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

Abstract

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. 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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64151-2

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

Figures/Tables 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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