用于高效的氧还原反应的钴原子锚定氮-掺杂多孔碳电催化剂的制备与表征

doi:10.19894/j.issn.1000-0518.250165

摘要/Abstract

摘要：

由于贵金属（PMG）电催化剂的高成本、稀缺性和低稳定性限制了其在氧还原反应（ORR）中的广泛应用，因此开发高性能的非贵金属电催化剂至关重要。本文以2-甲基咪唑和乙酰丙酮钴（Ⅱ）［Co（acac）₂］为原料，制备了乙酰丙酮钴（Ⅱ）@沸石咪唑框架-8［Co（acac）₂@ZIF-8］。然后，通过热解Co（acac）₂@ZIF-8，合成了一种高稳定、高性能的钴基催化剂Co-N-C。研究发现，所合成的Co-N-C具有明确的十二面体结构、较大的表面积和孔体积，对ORR表现出优异的电催化活性。在0.1 mol/L KOH溶液中的起始电位（E_onset）和半波电位（E_1/2）分别为1.028 V和0.844 V（vs.RHE）。当向溶液中注入5 mL 1.0 mol/L甲醇时，E_1/2几乎没有变化。在5000次循环后，E_1/2仅降低约15 mV。

关键词: 氧还原反应, 钴原子, 氮-掺杂, 多孔碳

Abstract:

Due to the high cost， scarcity and low stability limiting the widespread application of the precious metal group （PMG） electrocatalysts toward oxygen reduction reaction （ORR）， it is of vital importance to develop outstanding non-precious transition metal alternatives. Herein， a highly stable and efficient cobalt-based catalyst， Co-N-C， was synthesized via the pyrolysis of a precursor of Co（acac）₂@ZIF-8， originating from Co（acac）₂ and zeolitic imidazolate frameworks （ZIF-8）. The as-synthesized Co-N-C not only possesses well-defined dodecahedral shape with large surface area and pore volume but also shows the excellent electrocatalytic activity towards ORR. The E_onset and E_1/2 in 0.1 mol/L KOH solution are 1.028 and 0.844 V（vs.RHE）， respectively. When injecting 5 mL of 1.0 mol/L methanol into the solution， there was almost no change in E_1/2. After 5000 cycles， E_1/2 has a slight decrease of about 15 mV.

Key words: Oxygen reduction reaction, Cobalt atom, Nitrogen-doped, Porous carbon

中图分类号:

O643.3

柴瑞涛, 张国. 用于高效的氧还原反应的钴原子锚定氮-掺杂多孔碳电催化剂的制备与表征[J]. 应用化学, 2026, 43(2): 226-234.

Rui-Tao CHAI, Guo ZHANG. Preparation and Characterization of the Electrocatalysts of Cobalt Atom Anchored on Nitrogen-Doped Porous Carbon for Efficient Oxygen Reduction Reaction[J]. Chinese Journal of Applied Chemistry, 2026, 43(2): 226-234.

图/表 9

图1 Co-N-C的合成及电催化ORR示意图

Fig.1 Schematic illustration of the synthesis of Co-N-C for ORR electrocatalysis

图2 Co-N-C的（A）SEM图、（B、C）TEM图、（D、E）XPS谱和（F）N2吸附-解吸等温线图

Fig.2 （A） SEM image，（B， C） TEM images，（D， E） XPS spectra and （F） N2 adsorption-desorption isotherms plot of Co-N-C

图3 Co-N-C的（A）HAADF-STEM元素分布图（Co-蓝色、C-红色和N-绿色）和（B）EDX光谱

Fig.3 （A） Element maps of HAADF-STEM （Co-blue， C-red， and N-green） and （B） EDX spectrum of Co-N-C

图4 （A） Co-N-C在Ar/O2饱和的0.1 mol/L KOH中以50 mV/s的速度扫描的CV图；（B） Co-N-C和Ni-N-C分别在O2 饱和0.1 mol/L KOH中以1600 r/min的速度和5 mV/s扫速的LSV曲线

Fig.4 （A） Cyclic voltammetry curves of Co-N-C in Ar/O2-saturated 0.1 mol/L KOH at a speed of 50 mV/s；（B） Linear sweep voltammetry curve of Co-N-C and Ni-N-C in O2-saturated 0.1 mol/L KOH at a speed of 1600 r/min at a scanning rate of 5 mV/s， respectively

图5 Co-N-C在O2饱和的0.1 mol/L KOH和0.1 mol/L KOH/1.0 mol/L CH3OH中的LSV曲线，甲醇的体积分别为（A） 5、（B） 10、（C） 15和（D） 20 mL

Fig.5 Linear sweep voltammetry curves of Co-N-C in O2-saturated 0.1 mol/L KOH and 0.1 mol/L KOH/1.0 mol/L CH3OH with methanol：（A） 5，（B） 10，（C） 15 and （D） 20 mL

图6 Co-N-C在O2饱和的0.1 mol/L KOH中循环扫描5000次前后的LSV图

Fig. 6 Linear sweep voltammetry curves of Co-N-C in O2-saturated 0.1 mol/L KOH before and after 5000 potential cycles

表1 Co-N-C氧还原反应的电子转移数（n）

Table 1 Number of electron transfer （n） of Co-N-C towards ORR

E/V（vs.RHE）	0.2	0.3	0.4	0.5	0.6	0.7	0.8
n	3.64	3.67	3.69	3.72	3.76	3.82	3.91

图7 Co-N-C和 Ni-N-C的过氧化氢产率曲线

Fig.7 Curves of hydrogen peroxide yield for Co-N-C and Ni-N-C

表2 不同钴基催化剂对ORR的电催化活性的比较

Table 2 Comparison of electrocatalytic activity toward ORR with different Co-based catalysts

Catalyst	E_onset/V（vs.RHE）	E_1/2/V（vs.RHE）	Ref.
aFP-TCoP/C	0.76	0.80	［17］
CoL （mass ratios 2∶1）	0.936	0.84	［3］
ZL 600 （mass ratio 3∶1）	0.91	0.79	［2］
ZIF-67@CoTMPP （800）	0.854	0.784	［21］
Co-NC （Zn₁₂-SiO₂［20］）-900	0.875	0.835	［13］
Co/NHCS-BCNT	0.941	0.814	［20］
BCTFCo-phen（OH）	0.89	0.80	［28］
Pt/C	0.98	0.81	［2］
Co-N-C	1.028	0.844	This work

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