自掺杂污泥碳的制备及其电催化氧还原的性能

doi:10.13208/j.electrochem.180630

摘要/Abstract

摘要： 开发低成本、高性能的阴极催化剂是燃料电池商业化应用的关键. 本文以剩余污泥为前驱体，在碳化前通过连续添加苯酚来对污泥进行驯化，热解后得到自模板、自活化及N、P、Fe自掺杂的多孔类石墨烯碳材料. 结果表明，污泥经苯酚驯化后，微生物得到富集，含碳量显著提高，N、P、Fe等元素大大增加. 热解温度升高能提高材料的石墨化程度，但过高的温度会使杂原子掺杂量减少，从而降低氧还原催化活性. 其中，800 ℃下煅烧得到的污泥碳（PSC-800）比表面积为402.4 m²·g^-1，远高于未驯化污泥碳（SC-800）的262.4 m²·g^-1. 光电子能谱（XPS）数据表明，PSC-800具有较高的杂原子掺杂量及含铁量，形成了吡啶氮、石墨氮等氧还原活性位点. 在碱性条件下催化4电子的氧还原反应，初始电位为0.93 V，高于SC-800的0.89 V及其他温度煅烧的污泥碳（PSC-600：0.75 V，PSC-700：0.87 V， PSC-900：0.91 V）. 极限电流密度与商业铂碳相当，具有良好的稳定性及抗甲醇毒性.

关键词: 污泥碳, 氧还原, 苯酚驯化, 杂原子掺杂, 电催化

Abstract: The development of low-cost, high-performance cathode catalysts is critical for practical application of fuel cells. Here, the N, P-doped porous graphene-like carbon with outstanding oxygen reduction reaction (ORR) performance was synthesized by pyrolysis of surplus sludge, which functioned as a self-doped, self-activated, and self-templated precursor by acclimation with continuous feedings of phenol. The results show that the amounts of microorganisms were enriched after acclimation, with increasing contents of N, P, Fe, as well as C atoms. The increasing pyrolysis temperature resulted in the formation of an ordered graphitic structure, however, the excessively high temperature induced the drop in the amounts of the heteroatoms that are doped in the carbon framework. The phenol-acclimated sludge pyrolyzed at 800 ℃(PSC-800) featured a BET surface area as high as 402.4 m²·g^-1, which was much higher than that of the raw sludge carbon (SC-800) (262.4 m²·g^-1). X-ray photoelectron spectroscopic (XPS) data suggests that the PSC-800 had higher levels of heteroatom doping, which was conductive to the formation of oxygen reduction active sites such as pyridinic nitrogen and graphitic nitrogen. The obtained PSC-800 exhibited excellent ORR activity in alkaline media with the onset potential of 0.93 V, higher than 0.75, 0.87, 0.91, and 0.89 V for PSC-600, PSC-700, PSC-900 and SC-800, respectively. In comparison to the commercial Pt/C catalyst, the PSC-800 showed comparable catalytic activity in terms of the close onset potential, kinetic-limiting current and four-electron transfer process, and higher tolerance to methanol toxicity and superior stability.

Key words: sludge carbon, oxygen reduction reaction, phenol acclimation, heteroatoms doping, electrocatalysis

中图分类号:

O646

叶雅丽, 冯伟明, 李格, 雷振超, 冯春华. 自掺杂污泥碳的制备及其电催化氧还原的性能[J]. 电化学（中英文）, 2019, 25(2): 270-279.

YE Ya-li, FENG Wei-ming, LI Ge, LEI Zhen-chao, FENG Chun-hua. Preparation and Electrocatalytic Oxygen Reduction Performance of Self-Doped Sludge-Derived Carbon[J]. Journal of Electrochemistry, 2019, 25(2): 270-279.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.180630

https://electrochem.xmu.edu.cn/CN/Y2019/V25/I2/270

参考文献

[1] Basu S. Fuel cell science and technology[M]. New Delhi, India: Anamaya Publishers, 2007. 356-364.
[2] Park S, Shao Y, Liu J, et al. Oxygen electrocatalysts for water electrolyzers and reversible fuel cells: status and perspective[J]. Energy & Environmental Science, 2012, 5(11): 9331-9344.
[3] He D, Kou Z K, Xiong Y L, et al. Simultaneous sulfonation and reduction of graphene oxide as highly efficient supports for metal nanocatalysts[J]. Carbon, 2014, 66: 312-319.
[4] Ding W(丁炜), Zhang X(张雪), Li L(李莉), et al. Recent progress in heteroatoms doped carbon materials as a catalyst for oxygen reduction reaction[J]. Journal of Electrochemistry(电化学), 2014, 20(5): 426-438.
[5] Li R, Wei Z D, Gou X L. Nitrogen and phosphorus dual-doped graphene/carbon nanosheets as bifunctional electrocatalysts for oxygen reduction and evolution[J]. ACS Catalysis, 2015, 5(7): 4133-4142.
[6] Zitolo A, Goellner V, Armel V, et al. Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials[J]. Nature Materials, 2015, 14(9): 937-942.
[7] Aijaz A, Fujiwara N, Xu Q. From metal-organic framework to nitrogen-decorated nanoporous carbons: high CO₂ uptake and efficient catalytic oxygen reduction[J]. Journal of the American Chemical Society, 2014, 136(19): 6790-6793.
[8] Ferrero G A, Preuss K, Marinovic A, et al. Fe-N-doped carbon capsules with outstanding electrochemical performance and stability for the oxygen reduction reaction in both acid and alkaline conditions[J]. ACS Nano, 2016, 10(6): 5922-5932.
[9] Kundu S, Nagaiah T C, Xia W, et al. Electrocatalytic activity and stability of nitrogen-containing carbon nanotubes in the oxygen reduction reaction[J]. The Journal of Physical Chemistry C, 2009, 113(32): 14302-14310.
[10] Liu L, Xiong Q, Li C G, et al. Conversion of straw to nitrogen doped carbon for efficient oxygen reduction catalysts in microbial fuel cells[J]. RSC Advances, 2015, 5(109): 89771-89776.
[11] Borghei M, Laocharoen N, Kibena-Põldsepp E, et al. Porous N, P-doped carbon from coconut shells with high electrocatalytic activity for oxygen reduction: Alternative to Pt-C for alkaline fuel cells[J]. Applied Catalysis B: Environmental, 2017, 204: 394-402.
[12] Yuan H R, Deng L F, Cai X X, et al. Nitrogen-doped carbon sheets derived from chitin as non-metal bifunctional electrocatalysts for oxygen reduction and evolution[J]. RSC Advances, 2015, 5(69): 56121-56129.
[13] Li Z, Xu Z W, Tan X H, et al. Mesoporous nitrogen-rich carbons derived from protein for ultra-high capacity battery anodes and supercapacitors[J]. Energy & Environmental Science, 2013, 6(3): 871-878.
[14] Zhou K, Zhou W J, Du Y P, et al. High-performance supercapacitors based on nitrogen-doped porous carbon from surplus sludge[J]. Science of Advanced Materials, 2015, 7(3): 571-578.
[15] Tan Y M, Xu C F, Chen G X, et al. Facile synthesis of manganese-oxide-containing mesoporous nitrogen-doped carbon for efficient oxygen reduction[J]. Advanced Functional Materials, 2012, 22(21): 4584-4591.
[16] Shen Y F, Xiang F, Veenstra T D, et al. High-resolution capillary isoelectric focusing of complex protein mixtures from lysates of microorganisms[J]. Analytical Chemistry, 1999, 71(23): 5348-5353.
[17] Cosgrove D J. Plant expansins: diversity and interactions with plant cell walls[J]. Current Opinion in Plant Biology, 2015, 25: 162-172.
[18] Meunier B, de Visser S P, Shaik S. Mechanism of oxidation reactions catalyzed by cytochrome P450 enzymes[J]. Chemical Reviews, 2004, 104(9): 3947-3980.
[19] Terano H, Nomoto K, Takase S. Siderophore production and induction of iron-regulated proteins by a microorganism from rhizosphere of barley[J]. Bioscience, Biotechnology, and Biochemistry, 2002, 66(11): 2471-2473.
[20] Thipkhunthod P, Meeyoo V, Rangsunvigit P, et al. Describing sewage sludge pyrolysis kinetics by a combination of biomass fractions decomposition[J]. Journal of Analytical and Applied Pyrolysis, 2007, 79(1/2): 78-85.
[21] Biagini E, Barontini F, Tognotti L. Devolatilization of biomass fuels and biomass components studied by TG/FTIR technique[J]. Industrial & Engineering Chemistry Research, 2006, 45(13): 4486-4493.
[22] Liang H W, Wei W, Wu Z S, et al. Mesoporous metal-nitrogen-doped carbon electrocatalysts for highly efficient oxygen reduction reaction[J]. Journal of the American Chemical Society, 2013, 135(43): 16002-16005.
[23] Meng F L, Wang Z L, Zhong H X, et al. Reactive multifunctional template-induced preparation of Fe-N-doped mesoporous carbon microspheres towards highly efficient electrocatalysts for oxygen reduction[J]. Advanced Materials, 2016, 28(36): 7948-7955.
[24] Ye D X, Wang L, Zhang R, et al. Facile preparation of N-doped mesocellular graphene foam from sludge flocs for highly efficient oxygen reduction reaction[J]. Journal of Materials Chemistry A, 2015, 3(29): 15171-15176.
[25] Zhou K, Zhou W J, Liu X J, et al. Nitrogen self-doped porous carbon from surplus sludge as metal-free electrocatalysts for oxygen reduction reactions[J]. ACS Applied Materials & Interfaces, 2014, 6(17): 14911-14918.
[26] Li Y J, Wang G L, Wei T, et al. Nitrogen and sulfur co-doped porous carbon nanosheets derived from willow catkin for supercapacitors[J]. Nano Energy, 2016, 19: 165-175.
[27] Fan X H, Kong F T, Kong A G, et al. Covalent porphyrin framework-derived Fe₂P@Fe₄N-coupled nanoparticles embedded in N-doped carbons as efficient trifunctional electrocatalysts[J]. ACS Applied Materials & Interfaces, 2017, 9(38): 32840-32850.
[28] Men B, Sun Y Z, Li M J, et al. Hierarchical metal-free nitrogen-doped porous graphene/carbon composites as an efficient oxygen reduction reaction catalyst[J]. ACS Applied Materials & Interfaces, 2016, 8(2): 1415-1423.
[29] Sun M, Davenport D, Liu H J, et al. Highly efficient and sustainable non-precious-metal Fe-N-C electrocatalysts for the oxygen reduction reaction[J]. Journal of Materials Chemistry A, 2018, 6, 2527-2539
[30] Wu Z Y, Xu X X, Hu B C, et al. Iron carbide nanoparticles encapsulated in mesoporous Fe-N-doped carbon nanofibers for efficient electrocatalysis[J]. Angewandte Chemie International Edition, 2015, 54(28): 8297-8301.
[31] Li C, Chen Z, Ni Y, et al. Coordination compound-derived ordered mesoporous N-free Fe-P_x-C material for efficient oxygen electroreduction[J]. Journal of Materials Chemistry A, 2016, 4(37): 14291-14297.
[32] Yang D S, Bhattacharjya D, Inamdar S, et al. Phosphorus-doped ordered mesoporous carbons with different lengths as efficient metal-free electrocatalysts for oxygen reduction reaction in alkaline media[J]. Journal of the American Chemical Society, 2012, 134(39): 16127-16130.
[33] Fu P, Zhou L H, Sun L H, et al. Nitrogen-doped porous activated carbon derived from cocoon silk as a highly efficient metal-free electrocatalyst for the oxygen reduction reaction[J]. RSC Advances, 2017, 7(22): 13383-13389.
[34] Chen C(陈驰), Zhou Z Y(周志有), Zhang X S(张新胜) , et al. Synthesis of Fe, N-doped graphene/carbon black composite with high catalytic activity for oxygen reduction reaction[J]. Journal of Electrochemistry(电化学), 2016, 22(1): 25-31.
[35] Zhou L H, Yang C L, Wen J, et al. Soft-template assisted synthesis of Fe/N-doped hollow carbon nanospheres as advanced electrocatalysts for the oxygen reduction reaction in microbial fuel cells[J]. Journal of Materials Chemistry A, 2017, 5(36): 19343-19350.
[36] Xiao M L, Zhu J B, Feng L G, et al. Meso/macroporous nitrogen-doped carbon architectures with iron carbide encapsulated in graphitic layers as an efficient and robust catalyst for the oxygen reduction reaction in both acidic and alkaline solutions[J]. Advanced Materials, 2015, 27(15): 2521-2527.
[37] Lai L F, Potts J R, Zhan D, et al. Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction[J]. Energy & Environmental Science, 2012, 5(7): 7936-7942.
[38] Guo D H, Shibuya R, Akiba C, et al. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts[J]. Science, 2016, 351(6271): 361-365.
[39] Wang R F, Wang H, Zhou T B, et al. The enhanced electrocatalytic activity of okara-derived N-doped mesoporous carbon for oxygen reduction reaction[J]. Journal of Power Sources, 2015, 274: 741-747.
[40] Zhao C Y(赵灿云), Huang L(黄林), You Y(尤勇), et al. Recycling MF solid waste into mesoporous nitrogen-doped carbon with iron carbide complex in graphitic layers as an efficient catalyst for oxygen reduction reaction[J]. Journal of Electrochemistry (电化学), 2016, 22(2): 176-184.
[41] Singh K P, Bae E J, Yu J S. Fe-P: a new class of electroactive catalyst for oxygen reduction reaction[J]. Journal of the American Chemical Society, 2015, 137(9): 3165-3168.