Interfacial engineering of heterogeneous molecular electrocatalysts using ionic liquids towards efficient hydrogen peroxide production

doi:10.1016/S1872-2067(21)63946-3

Abstract

Abstract:

Efficient and selective oxygen reduction reaction (ORR) electrocatalysts are critical to realizing decentralized H₂O₂ production and utilization. Here we demonstrate a facile interfacial engineering strategy using a hydrophobic ionic liquid (IL, i.e., [BMIM][NTF₂]) to boost the performance of a nitrogen coordinated single atom cobalt catalyst (i.e., cobalt phthalocyanine (CoPc) supported on carbon nanotubes (CNTs). We find a strong correlation between the ORR performance of CoPc/CNT and the thickness of its IL coatings. Detailed characterization revealed that a higher O₂ solubility (2.12 × 10^-3 mol/L) in the IL compared to aqueous electrolytes provides a local O₂ enriched surface layer near active catalytic sites, enhancing the ORR thermodynamics. Further, the hydrophobic IL can efficiently repel the as-synthesized H₂O₂ molecules from the catalyst surface, preventing their fast decomposition to H₂O, resulting in improved H₂O₂ selectivity. Compared to CoPc/CNT without IL coatings, the catalyst with an optimal ~8 nm IL coating can deliver a nearly 4 times higher mass specific kinetic current density and 12.5% higher H₂O₂ selectivity up to 92%. In a two-electrode electrolyzer test, the optimal catalyst exhibits an enhanced productivity of 3.71 mol_H2O2 g_cat^-1 h^-1, and robust stability. This IL-based interfacial engineering strategy may also be extended to many other electrochemical reactions by carefully tailoring the thickness and hydrophobicity of IL coatings.

Key words: Hydrogen peroxide, Ionic liquid, Oxygen reduction reaction, Single-atom catalyst, Heterogeneous molecular catalyst

Zixun Yu, Chang Liu, Yeyu Deng, Mohan Li, Fangxin She, Leo Lai, Yuan Chen, Li Wei. Interfacial engineering of heterogeneous molecular electrocatalysts using ionic liquids towards efficient hydrogen peroxide production[J]. Chinese Journal of Catalysis, 2022, 43(5): 1238-1246.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63946-3

https://www.cjcatal.com/EN/Y2022/V43/I5/1238

Figures/Tables 5

Fig. 1. Catalyst synthesis and characterization. (a) Schematic illustration of the synthesis of IL coated CoPc/CNT catalysts; (b) HAADF-STEM image of the CoPc/CNT catalyst; BF-STEM (c), STEM-EDX mapping result (d), and HAADF-STEM image (e) of the IL coated CoPc/CNT-1 catalyst; XPS survey scans (f), and N 1s (g) and Co 2p (h) high-resolution XPS spectra of different catalysts.

Fig. 2. Electrochemical performance of CoPc/CNT catalysts. LSV curves of the CoPc/CNT and CoPc/CNT-x catalysts collected in O2 saturated electrolyte (a), and the calculated H2O2 selectivity (λH2O2) and electron transfer number (n) (b); (c) The mass kinetic current density (jK-mass) of different catalysts toward H2O2 production. Inset shows the jK-mass at 0.2 V vs. RHE.

Table 1 ORR performance of CoPc/CNT catalysts. Performance parameters were collected at 0.2 V.

Catalyst	U_disk/ V	U_ring/ V	n	H₂O₂ (%)	FE_H2O2 (%)	j_K/ mA cm^-2
CoPc/CNT	0.55	0.54	2.39	80	67	16.45
CoPc/CNT-0.2	0.59	0.58	2.33	83	71	18.46
CoPc/CNT-1	0.64	0.62	2.15	92	86	22.51
CoPc/CNT-1.5	0.66	0.64	2.18	91	84	31.41
CoPc/CNT-2	0.65	0.62	2.30	85	74	22.18

Fig. 3. (a) Relationship between the half-wave potential increment (ΔE1/2) and the H2O2 selectivity differences to the x value in CoPc/CNT-x catalysts; (b) O2 solubility measurement.

Fig. 4. H2O2 production performance of two-electrode electrolyzers assembled using CoPc/CNT-1.5 and CoPc/CNT. Electrolyzer voltage responses (a), and H2O2 selectivity (b) at different current densities; (c) Chronopotentiometry test results and the amount of H2O2 produced.

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