Polyvinylpyrrolidone-Assisted Synthesis of Metal-organic Framework-Derived Hierarchically Porous Carbon for Bifunctional Electrocatalysis

doi:10.6023/A25060236

Abstract

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) occurring at bifunctional oxygen electrodes are fundamental to numerous electrochemical energy storage and conversion technologies, including fuel cells and water electrolysis. However, both ORR and OER involve multi-step proton-coupled electron transfers, resulting in sluggish reaction kinetics and requiring high activation overpotentials. Consequently, developing efficient electrocatalysts to lower the reaction energy barriers and accelerate electron transfer is critical for enhancing energy conversion efficiency. This work presents a synergistic strategy integrating bimetallic catalysis with interface engineering. Specifically, a cobalt/nickel bimetallic metal-organic framework (MOF) precursor undergoes polyvinylpyrrolidone (PVP)-assisted pyrolysis, transforming into a hierarchically porous nitrogen-doped carbon matrix embedded with cobalt-nickel alloy nanoparticles (P-CoNi-N-C). Electrochemical characterization reveals that P-CoNi-N-C exhibits ORR performance rivaling commercial Pt/C (onset potential of 1.053 V, half-wave potential of 0.825 V, and electron transfer number of 3.96) and exceptional OER activity (E_j₌₁₀ of 1.609 V, low overpotential of 0.379 V, and mass activity of P-CoNi-N-C at 1.60 V is five times that of Co-N-C). Similarly, P-CoNi-N-C has remarkable long-term stability with a current attenuation rate of only 0.84%•h^-1. Comprehensive material characterization confirms that the superior bifunctional performance of P-CoNi-N-C stems from the synergistic interplay of its hierarchically porous architecture, optimized adsorption energy for oxygen intermediates, and unique heterointerface structure. Furthermore, the P-CoNi-N-C catalyst exhibits excellent electrochemical performance (charge current density of 127 mA•cm^-2 and power density of 127.3 mW•cm^-2) and cycling stability (capacity retention rate of 92% after 80 h) in rechargeable zinc-air batteries.

Key words: oxygen reduction reactions, oxygen evolution reaction, metal-organic frameworks, graded porous, heterogeneous interfacial structure

Cite this article

Ziyi Shui, Shurui Yin, Jintao Deng, Liuyun Xu, Li Guo. Polyvinylpyrrolidone-Assisted Synthesis of Metal-organic Framework-Derived Hierarchically Porous Carbon for Bifunctional Electrocatalysis[J]. Acta Chimica Sinica, 2026, 84(1): 53-63.

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Fig. & Tab. 11

Figure 1. Synthesis schema of (a) Co-N-C and (b) P-CoNi-N-C

Figure 2. SEM images of (a) ZIF-67 and (b) Co-N-C catalysts, (c) P-ZIF-67 and (d) P-Co-N-C catalysts; (e) TEM image, (f) HRTEM image, (g) SAED pattern and (h) EDS elemental distribution mappings of P-Co-N-C

Figure 3. SEM images of (a) P-Ni-ZIF-67 and (b) P-CoNi-N-C catalysts; (c) TEM image, (d) HRTEM image, (e) SAED pattern and (f) EDS elemental distribution mappings of P-CoNi-N-C

Figure 4. (a) XRD patterns, (b) N2 adsorption/desorption curves, (c) Raman spectra, (d) TGA curves of Co-N-C, P-Co-N-C and P-CoNi-N-C catalysts

Figure 5. High-resolution (a) N 1s spectra, (b) Co 2p spectra and (c) and C 1s spectra of Co-N-C, P-Co-N-C and P-CoNi-N-C

	S_BET/ (m²•g^-1)	S_Micro/ (m²•g^-1)	S_Meso/ (m²•g^-1)	V_Pore/ (cm³•g^-1)
Co-N-C	188	46	142	0.19
P-Co-N-C	285	54	231	0.32
P-CoNi-N-C	296	58	238	0.34

Table 1. Summary of the porous properties

Figure 6. (a) Oxygen reduction polarization curve, (b) Eonset and E1/2 collected on catalysts, (c) Tafel plot and (d) ORR stability measured by chronoamperometric technique of Co-N-C, P-Co-N-C, P-CoNi-N-C and Pt/C catalysts

Figure 7. ORR polarization curves at various speeds and the Koutecky-Levich plots of (a) Co-N-C, (b) P-Co-N-C, (c) P-CoNi-N-C and (d) Pt/C catalysts; (e) The electron transfer numbers in the range of 0.2~0.8 V and (f) the corresponding kinetic current density at 0.4 V of four catalytic materials

Figure 8. (a) Oxygen evolution polarization curve; (b) Tafel plot; (c) Mass-activity comparison, (d) double-layer capacitance (Cdl) as determined by electrochemically active surface area (ECSA), (e) EIS plot and (f) OER stability measured by chronoamperometric technique of Co-N-C, P-Co-N-C, P-CoNi-N-C and RuO2 catalysts

Figure 9. Bifunctional property of Co-N-C, P-Co-N-C, P-CoNi-N-C, Pt/C and RuO2 catalysts at ORR/OER potential window

Figure 10. (a) Diagram of rechargeable zinc air battery, (b) Charge-discharge polarization curve and (c) its corresponding discharge power density curve, (d) Constant current charge-discharge cycle stability test

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