Nitrogen-doped Carbon Pyrolyzed from ZIF-8 for Electrocatalytic Oxygen Reduction to Hydrogen Peroxide

doi:10.6023/A22010030

Abstract

Electrochemical production of H₂O₂ from O₂ via the two-electron reduction reaction (2e-ORR) is a green and safe process that is being heavily investigated. Zeolitic imidazolate frameworks (ZIF) as a subclass of metal-organic frameworks (MOFs) have attracted enormous scientific interests due to their high porosity, excellent mechanical stability, tunable surface properties, and exceptional chemical and thermal stabilities. Herein, a series of pyrolyzed ZIF catalysts (p-ZIF) were synthesized by treating 2-methylimidazole zinc salt (ZIF-8) at high temperatures (900, 950 and 1000 ℃). During pyrolysis, zinc was vaporized, leaving the metal-free nitrogen-doped porous graphitic carbon materials. The effects of the pyrolysis temperature on the structure and catalytic performance of the p-ZIF catalysts in 2e-ORR were systematically studied. In 2e-ORR in an acidic electrolyte, the p-ZIF catalysts displayed low overpotential, low Tafel slope, and negligible activity loss after 3000 cycles of accelerated durability testing (ADT). In particular, the p-ZIF-950 catalyst possessed the highest H₂O₂ partial current of 0.185 mA at 0 V vs. RHE, followed by the p-ZIF-900 (0.146 mA) and p-ZIF-1000 (0.135 mA) catalysts. The H₂O₂ selectivity over the p-ZIF-950 catalyst was also constantly higher than those over the other two p-ZIF catalysts across the potential range investigated and maximized at 89.2%. Highly efficient and durable H₂O₂ production was demonstrated on the p-ZIF-950 catalyst by the linear accumulation of H₂O₂ to 522 mmol•g_cat^-1 within 6 h, translating to an H₂O₂ production rate of 87 mmol•g_cat^-1•h^-1. The morphology, composition, carbon defect, texture, and surface chemical state were characterized by techniques such as transmission electron microscopy (TEM), elemental analysis, Raman spectroscopy, N₂ physisorption, and X-ray photoelectron spectroscopy (XPS). The p-ZIF catalysts not only nicely carried over the regular rhombic dodecahedral morphology of ZIF-8, but also possessed abundant amount of nitrogen, high specific surface area, and hierarchical pore structure. According to the characterization results, the specific surface area and carbon defect are unlikely the key factors that determine the catalytic performance, while the evolutions of the average pore size and surface content of graphitic N mimicked those of the H₂O₂ partial current and selectivity on the p-ZIF catalysts. In light of the literature works, the large pore size is proposed to facilitate the in-diffusion of O₂ and out-diffusion of H₂O₂, while the graphitic N is able to enhance the activation of O₂ and desorption of H₂O₂, both of which are beneficial to the kinetics of the 2e-ORR reaction.

Key words: hydrogen peroxide, ZIF-8, pyrolysis, electrocatalysis, oxygen reduction reaction

Cite this article

Dan Wang, Bo Feng, Xiaoxin Zhang, Yanan Liu, Yan Pei, Minghua Qiao, Baoning Zong. Nitrogen-doped Carbon Pyrolyzed from ZIF-8 for Electrocatalytic Oxygen Reduction to Hydrogen Peroxide[J]. Acta Chimica Sinica, 2022, 80(6): 772-780.

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Fig. & Tab. 12

Figure 1. RRDE ORR results of the p-ZIF catalysts in the O2-saturated 0.1 mol•L-1 HClO4 electrolyte. (a) Linear sweep voltammograms (LSV), (b) H2O2 selectivity and (c) electron transfer number Reaction conditions: 40 µg of catalyst, scan rate of 10 mV•s-1, and rotation speed of 1600 r•min-1. The Pt ring was potentiostated at 1.2 V vs. RHE for H2O2 detection

Figure 2. Tafel slopes of the p-ZIF catalysts in the O2-saturated 0.1 mol•L-1 HClO4 electrolyte Reaction conditions: scan rate of 10 mV•s-1 and rotation speed of 1600 r•min-1

Figure 3. Stability performance under accelerated durability testing (ADT) conditions in the O2-saturated 0.1 mol•L-1 HClO4 electrolyte. (a) p-ZIF-900, (b) p-ZIF-950, and (c) p-ZIF-1000 Reaction conditions: 40 µg of catalyst and scan rate of 200 mV•s-1

Figure 4. The current (left) and the photometrically determined amount of H2O2 normalized by the mass of the p-ZIF-950 catalyst (right) as a function of the reaction time Reaction conditions: catalyst loading of 200 μg•cmgeo-2, rotation speed of the working electrode of 1600 r•min-1, and the working voltage of 0.1 V vs. RHE. The 0.1 mol•L-1 HClO4 electrolyte was continuously bubbled with O2

Catalyst	Bulk composition^a(w)/%				S_BET^b/ (m²•g^-1)	V_pore^b/ (cm³•g^-1)	d_pore^b/ nm
Catalyst	C	H	O	N	S_BET^b/ (m²•g^-1)	V_pore^b/ (cm³•g^-1)	d_pore^b/ nm
p-ZIF-900	62.10	3.71	23.12	11.05	870(610)	0.61(0.32)	5.6
p-ZIF-950	73.11	3.89	14.42	8.56	913(636)	0.85(0.34)	9.9
p-ZIF-1000	83.22	4.96	6.85	4.94	1190(761)	0.83(0.41)	5.1

Table 1. The bulk compositions and textural properties of the p-ZIF catalysts

Figure 5. XRD patterns of the p-ZIF catalysts

Figure 6. TEM images and EDS mapping of the C, N, and O elements on the p-ZIF catalysts. (a), (d) p-ZIF-900; (b), (e) p-ZIF-950; (c), (f) p-ZIF-1000

Figure 7. Raman spectra of the p-ZIF catalysts

Figure 8. (a) N2 adsorption-desorption isotherms and (b) pore size distributions of the p-ZIF catalysts

Figure 9. (a) C 1s and (b) N 1s spectra of the p-ZIF-900, p-ZIF-950, and p-ZIF-1000 catalysts

Catalyst	Surface N/at%	Fraction in surface N				Surface graphitic N/at%
Catalyst	Surface N/at%	Pyridinic N	Pyrrolic N	Graphitic N	Oxidic N	Surface graphitic N/at%
p-ZIF-900	12.0	0.645	0.203	0.119	0.033	1.43
p-ZIF-950	8.5	0.562	0.113	0.263	0.062	2.23
p-ZIF-1000	4.7	0.414	0.255	0.294	0.037	1.38

Table 2. Total surface content of nitrogen and the relative fraction of various surface nitrogen species on the p-ZIF catalysts determined by XPS

Figure 10. Cyclic voltammograms in the non-Faradic potential region at varying scan rates of 5, 10, 15, 20, and 25 mV•s-1 in the N2-saturated 0.1 mol•L-1 HClO4 electrolyte for the (a) p-ZIF-900, (c) p-ZIF-950, and (e) p-ZIF-1000 catalysts. (b), (d), and (f) are the corresponding plots of average current density vs. scan rate

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基于热解ZIF-8的氮掺杂碳电化学氧还原合成过氧化氢催化剂