氮掺杂碳包埋钴纳米粒子电催化合成过氧化氢

doi:10.1016/S1872-2067(21)63804-4

摘要/Abstract

摘要：

电催化还原氧是一种新兴的可持续生产过氧化氢(H₂O₂)的合成技术, 寻找低成本、高活性和高选择性的电催化剂是该技术实际应用的关键. 钴氮掺杂的碳材料因含有钴氮(Co-N_x)催化活性位, 成为一类新兴的可促进H₂O₂电化学合成的材料.

本文采用低能耗干式球磨外加控制热解的方法来制备包含许多Co-N_x结构的钴氮掺杂碳材料. 该方法使用材料廉价, 即将醋酸钴、2-甲基咪唑和Ketjenblack EC-600JD高纯度且导电的碳黑分别作为金属、氮和碳的前体. 在酸性介质中的电化学测试结果表明, 该材料的氧还原反应电流密度明显增加, 同时起始电位向正方向移动. 该催化剂在较大电位范围内对H₂O₂的选择性约为90%. H₂O₂整体电解实验表明, H₂O₂产率达到100 mmol g_cat^-1 h^-1, H₂O₂法拉第效率达到85% (0.3 V vs. RHE条件下2 h). 耐久性测试(在0.3 V vs. RHE条件下6 h)表明, 催化剂表现出相对稳定的性能, 且在整个测试循环中, 法拉第效率达到约85%, 表明催化剂在实际应用中具有良好的耐久性. 催化剂表现出较高的电催化合成H₂O₂活性和选择性可能是由于形成了Co-N_x活性位, 以及酸性环境和应用电位等其它因素的影响.

关键词: 过氧化氢, 双电子氧还原, 碳催化剂, 电催化

Abstract:

Electrocatalytic reduction of oxygen is a growing synthetic technique for the sustainable production of hydrogen peroxide (H₂O₂). The current challenges concern seeking low-cost, highly active, and selective electrocatalysts. Cobalt-nitrogen-doped carbon containing catalytically active cobalt-nitrogen (Co-N_x) sites is an emerging class of materials that can promote the electrochemical generation of H₂O₂. Here, we report a straightforward method for the preparation of cobalt-nitrogen-doped carbon composed of a number of Co-N_x moieties using low-energy dry-state ball milling, followed by controlled pyrolysis. This scalable method uses inexpensive materials containing cobalt acetate, 2-methylimidazole, and Ketjenblack EC-600JD as the metal, nitrogen, and carbon precursors, respectively. Electrochemical measurements in an acidic medium show the present material exhibits a significant increase in the oxygen reduction reaction current density, accompanied by shifting the onset potential into the positive direction. The current catalyst has also demonstrated an approximate 90 % selectivity towards H₂O₂ across a wide range of potential. The H₂O₂ production rate, as measured by H₂O₂ bulk electrolysis, has reached 100 mmol g_cat.^-1 h^-1 with high H₂O₂ faradaic efficiency close to 85% (for 2 h at 0.3 V vs. RHE). Lastly, the catalyst durability has been tested (for 6 h at 0.3 V vs. RHE). The catalyst has shown relatively consistent performance, while the overall faradic efficiency reaches approximate 85% throughout the test cycle indicating the promising catalyst durability for practical applications. The formed Co-N_x moieties, along with other parameters, including the acidic environment and the applied potential, likely are the primary reasons for such high activity and selectivity to H₂O₂ production.

Key words: Hydrogen peroxide, Two-electron oxygen reduction, Carbon catalyst, Electrocatalysis

Basil Sabri Rawah, 李文震. 氮掺杂碳包埋钴纳米粒子电催化合成过氧化氢[J]. 催化学报, 2021, 42(12): 2296-2305.

Basil Sabri Rawah, Wenzhen Li. Electrocatalytic generation of hydrogen peroxide on cobalt nanoparticles embedded in nitrogen-doped carbon[J]. Chinese Journal of Catalysis, 2021, 42(12): 2296-2305.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63804-4

https://www.cjcatal.com/CN/Y2021/V42/I12/2296

图/表 18

Fig. 1. Synthesis scheme of the Co-N-KB catalyst.

Fig. 2. SEM images of Co-N-KB (a), N-KB (b), and KB (c).

Fig. 3. TEM image (a), cobalt nanoparticles particle size distribution calculated from TEM images (b), and HR-TEM image (c) of Co-N-KB catalyst.

Fig. 4. XRD patterns of KB (bottom), N-KB (middle) and Co-N-KB (top) catalysts.

Fig. 5. XPS survey spectra of N-KB (bottom) and Co-N-KB (top).

Fig. 6. High-resolution XPS spectra of N 1s (a) and Co 2P3/2 (b) of the Co-N-KB catalyst.

Table 1 Elemental composition of the Co-N-KB catalyst from high-resolution XPS spectra of N 1s.

Catalyst	Binding energy (eV)	Atomic percentage (%)
Pyridinic-N	398.24	32.67
Co-N_x	398.84	25.08
Pyrrolic-N	400.24	20.87
Graphite-N	401.34	21.39

Fig. 7. Ring currents measured on the Pt-ring at 1.2 VRHE (top) the disk current density (bottom) of KB, N-KB and Co-N-KB catalysts with the same catalyst loading measured by RRDE at 1600 rpm in O2 saturated 0.5 M H2SO4.

Fig. 8. High-resolution XPS spectra of N 1s of the N-KB catalyst.

Table 2 Elemental composition of the Co-N-KB catalyst from high-resolution XPS spectra of Co 2p3/2.

Catalyst	Binding energy (eV)	Atomic percentage (%)
Co	778.21	—
CoO	779.21	27.01
Co-N_x	780.31	72.98

Fig. 9. H2O2 selectivity and the number of transferred electrons (n) profiles of Co-N-KB (a) and N-KB (b) catalysts with the same catalyst loading measured by RRDE at 1600 rpm in O2 saturated 0.5 M H2SO4 at different potential range.

Fig. 10. H2O2 selectivity and the number of transferred electrons of N-KB and Co-N-KB catalysts with the same catalyst loading measured by RRDE with 1600 rpm in O2 saturated 0.5 M H2SO4 at 0.2 and 0.3 VRHE.

Fig. 11. TEM image of Acid-W/Co-N-KB sample.

Fig. 12. H2O2 selectivity of Co-N-KB and Acid-W/Co-N-KB catalysts with the same catalyst loading measured by RRDE with 1600 rpm in O2 saturated 0.5 M H2SO4.

Fig. 13. Ring currents measured on the Pt-ring at 1.2 VRHE (top), the disk current (bottom) of N-KB, and commercial Co-NPs on N-KB with loading of 2 and 50 μgCo cm-2 by RRDE at 1600 rpm in O2 saturated 0.5 M H2SO4.

Fig. 14. H2O2 accumulated concentration standardized by catalyst loading over time (left) and H2O2 faradaic efficiency (right) of Co-N-KB catalyst in O2 saturated 0.5 M H2SO4 at 0.3 VRHE with 250 rpm.

Table 3 Comparison of H2O2 production rate and faradic efficiency at acidic pH.

Catalyst	pH	Potential (V_RHE)	H₂O₂ (mmol g_cat.^-1 h^-1)	H₂O₂faradic efficiency (%)	Ref.
N-doped-CMK-3	0.3	0.2	~101.66	~73	[38]
Co-N-C	0.3	0.3	~84.2	~60	[39]
Co-NC-im	1	0.5	~49	>95	[37]
Co/carbon	0	0.25	~5	~80	[41]
Co-N-KB	0.3	0.3	~100	~85	This work

Fig. 15. Durability test: ORR reduction current (left) and H2O2 faradaic efficiency (right) of Co-N-KB catalyst in O2 saturated 0.5 M H2SO4 at 0.3 VRHE with 250 rpm for 6 h.

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