磷掺杂的介孔碳材料作为高效氧还原电催化剂

doi:10.1016/S1872-2067(19)63363-2

摘要/Abstract

摘要： 化学改性的碳材料由于其可控的理化性能、可设计的微纳结构以及优良的稳定性，在可再生能源储存和转换领域得到了极大的关注.将杂原子例如N，P，B和S掺杂到碳材料的骨架结构可以显著改善其电催化活性，这是因为杂原子掺杂可以打破相邻碳原子的电中性，创造活性位点，从而有利于氧气分子的吸附和氧还原反应的进行.早期报道比较多的是氮掺杂的碳材料，后续的研究发现，与氮掺杂相比，磷掺杂能够更有效地对碳的结构和性能进行改性，因为磷原子比氮原子具有更大的共价半径和更低的电负性，磷掺杂的碳材料也表现出更为优异的催化活性.此外，氧还原反应活性极大地依赖于碳材料的结构性质诸如导电性，稳定性和活性位点的分散程度等.基于这种考虑，构建具有高比表面积以及发达孔隙率的多孔碳材料有利于对活性位点的充分利用，并改善催化反应过程的物质传输.但是制备磷掺杂多孔碳材料的方法一般都比较复杂且危险，为此，本课题组发展了一种有机-有机自组装的软模板法，以有机膦酸为磷源制备了磷掺杂的介孔碳材料用于电催化氧还原反应，所得到的材料具有较高的磷掺杂率和较大的比表面积，然而，该催化剂的表观活性与商业Pt/C相比仍有很大差距，而且磷掺杂量对介孔碳材料结构和活性的影响也不甚清楚.基于此，本文采用有机膦酸羟基乙叉二膦酸（HEDP）为磷源，酚醛树脂为碳源，并加入适量的铁物种制备得到了介观结构良好的碳材料，其中，制备过程中铁物种可以作为石墨化催化剂，增强材料的石墨化程度，随后的酸洗将其去除，所得碳材料比表面积大，孔径分布窄，导电性能良好.此外，进一步探讨了磷的掺杂量对电催化活性的影响.
XRD和TEM结果表明，适量磷掺杂所制备的催化剂（P-MC-4）具有有序的蠕虫状孔结构；EDS图谱表明，磷原子已经均匀的掺杂到碳材料的骨架结构中；N₂吸附-脱附测试表明，适量的磷掺杂有利于改善碳材料的孔性，较高的磷掺杂量会导致碳材料较差的织构性质.Raman光谱结果表明，铁物种的引入增强了碳材料的石墨化程度并提高了导电性，而磷掺杂导致其缺陷位点增多，磷掺杂量越多，缺陷也就越多.我们进一步研究了P-MC-4的表面化学性质，XPS结果表明，磷掺杂量为0.47 at%的HEDP可以作为一种极有潜力的磷源来合成磷掺杂的介孔碳材料，此外，HEDP的引入量决定了磷的掺杂量，也极大的影响了碳材料的催化活性.电催化反应测试表明，P-MC-4的氧还原活性与商业Pt/C是可比的，其遵循的是4电子的反应路径，而且其抗甲醇氧化能力和稳定性优于Pt/C.其原因主要归结于以下几点：（1）磷掺杂提供了催化反应的活性位点，磷能够改善碳材料的给电子能力，进而提高电催化活性；磷的掺杂量极大的影响了碳材料的结构性质并进一步影响催化活性，适量的磷掺杂能够显著提升碳材料的电催化活性；（2）加入铁物种作为石墨化试剂，能显著提高碳材料的石墨化程度，从而增大其导电性，有利于催化反应中的电子传输；（3）相比微孔和大孔介孔结构更有利于活性位点的暴露和物质传输，而且P-MC-4具有相对有序的孔结构和较高的比表面积，也有助于催化反应中的介质传输.值得注意的是，最终得到的催化剂并不含有铁，所以该材料是一个无金属的催化活性良好的电催化剂，有望替代Pt/C催化剂应用于燃料电池中.

关键词: 磷掺杂, 介孔碳, 电催化剂, 氧还原反应

Abstract: hemically modified carbonaceous materials have attained utmost attention in the fields of renewable energy storage and conversion, due to the controllable physicochemical properties, tailorable micro-/nanostructures, and respectable stability. Herein, P-doped mesoporous carbons were synthesized by using F127 as the soft template, organophosphonic acid as the P source and phenolic resin as the carbon source. Small amounts of iron species were introduced to act as a graphitization catalyst. The synthesized carbons exhibit the well-defined wormhole-like pore structure featuring high specific surface area and homogenously doped P heteroatoms. Notably, introducing iron species during the synthesis process can optimize the textural properties and the degree of graphitization of carbon materials. The doping amount of P has an important effect on the porous structure and the defect degree, which correspondingly influence the active sites and the oxygen reduction reaction (ORR) activity. The resultant material presents superior catalytic activity for the ORR, together with remarkably enhanced durability and methanol tolerance in comparison with the commercial Platinum catalyst, demonstrating the possibility for its use in electrode materials and electronic nanodevices for metal-air batteries and fuel cells.

Key words: P-doping, Mesoporous carbons, Electrocatalyst, Oxygen reduction reaction

赵挥, 胡忠攀, 朱运培, 葛丽, 袁忠勇. 磷掺杂的介孔碳材料作为高效氧还原电催化剂[J]. 催化学报, 2019, 40(9): 1366-1374.

Hui Zhao, Zhong-Pan Hu, Yun-Pei Zhu, Li Ge, Zhong-Yong Yuan. P-doped mesoporous carbons for high-efficiency electrocatalytic oxygen reduction[J]. Chinese Journal of Catalysis, 2019, 40(9): 1366-1374.

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https://www.cjcatal.com/CN/Y2019/V40/I9/1366

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