有机膦酸盐衍生的氮掺杂的磷酸钴/碳纳米管杂化材料作为高效氧还原电催化剂

引用本文: 赵挥, 翁晨晨, 任金涛, 葛丽, 刘玉萍, 袁忠勇. 有机膦酸盐衍生的氮掺杂的磷酸钴/碳纳米管杂化材料作为高效氧还原电催化剂[J]. 催化学报, 2020, 41(2): 259-267. doi: S1872-2067(19)63455-8 shu

Citation: Hui Zhao, Chen-Chen Weng, Jin-Tao Ren, Li Ge, Yu-Ping Liu, Zhong-Yong Yuan. Phosphonate-derived nitrogen-doped cobalt phosphate/carbon nanotube hybrids as highly active oxygen reduction reaction electrocatalysts[J]. Chinese Journal of Catalysis, 2020, 41(2): 259-267. doi: S1872-2067(19)63455-8 shu

有机膦酸盐衍生的氮掺杂的磷酸钴/碳纳米管杂化材料作为高效氧还原电催化剂

a 南开大学材料科学与工程学院, 国家新材料研究院, 天津 300350;
b 聊城大学材料科学与工程学院, 山东聊城 252000;
c 南开大学化学学院, 教育部先进能源材料化学重点实验室, 天津 300071
基金项目:
国家自然科学基金（21421001，21573115）.

摘要: 随着环境污染和能源危机的日益严重，探索高效的非贵金属氧还原电催化剂来替代商业Pt/C迫在眉睫.其中，报道比较多的是具有钴基活性物种和氮掺杂碳的复合材料例如Co-N_x-C，Co₃O₄/GO，Co-N/CNT等，该复合材料具有高导电性、良好的稳定性和优异的催化活性.与其他钴基催化剂相比，磷酸钴由于其成本低廉，对环境友好，多功能的优良特性，已被广泛应用于催化、吸附、分离及储能等领域，在电催化方面也有极大的应用潜力.研究表明，磷酸基团不仅可以充当质子受体，也会诱导局部钴原子的几何结构发生扭曲，从而有利于水分子的吸附并促进析氧反应的发生.此外，磷酸钴也被证实具有一定的氧还原活性.尽管磷酸钴电催化剂的研究已经取得了一定进展，磷酸根有利于质子传输，但是其导电性很差，不利于电荷的转移和传输，使得其电催化活性不高.将磷酸钴和导电碳材料复合是解决问题的有效方法.而且，磷酸钴在碱性溶液中并不稳定，极大限制了其在电催化氧还原中的应用.金属有机膦酸盐是一类包含金属离子和有机膦酸配体的杂化材料，通过简单的焙烧便可以很容易地得到金属无机磷酸盐，并且在焙烧过程中氮掺杂的碳也会原位产生，并包覆在磷酸钴的表面，使得其导电性和催化活性大大提高.为此，本研究组制备了有机膦酸钴衍生的磷酸钴和氮磷掺杂的石墨烯的复合材料并用于电催化氧还原和析氧反应，所得到的材料导电性和稳定性良好，然而，该催化剂的表观活性与商业Pt/C相比仍有较大差距，且使用有机膦酸钴作为前驱体对活性的影响也不甚清楚.因此，本文采用含氮的有机膦酸配体乙二胺四亚甲基膦酸钠（EDTMPS）为磷源制备了氮掺杂的磷酸钴/碳纳米管杂化材料（CoPiC-N/CNT-3），其催化活性和稳定性良好，并进一步探讨了各种不同因素对电催化活性的影响.
XRD和TEM结果表明，用这种方法得到的磷酸钴（CoPiC）为Co₂P₂O₇物相，与磷酸二氢钠为磷源制备得到的CoPi相比，CoPiC的表面有石墨化碳层的存在，EDS图谱表明，Co，P，C，N均匀地掺杂到复合材料的骨架结构中.Raman光谱结果表明，石墨化碳层的存在和适量的碳纳米管的引入均可以增强复合材料的石墨化程度并提高了导电性，而氮掺杂导致其缺陷位点增多.XPS结果进一步表明，有机膦酸钴可以作为前驱体可制得氮掺杂的磷酸钴/碳纳米管杂化材料.电催化反应测试表明，CoPiC-N/CNT-3的氧还原活性与商业Pt/C相当，其遵循的是4电子的反应路径，而且抗甲醇氧化能力和稳定性均优于Pt/C.原因主要归结于以下几点：（1）磷酸钴颗粒与氧化碳纳米管的协同作用可以显著增强氧还原催化活性，引入的碳纳米管可以克服磷酸钴导电性差的缺陷；（2）磷酸钴在复合材料中分散均匀，使得可以充分利用催化剂的活性位点；（3）氮掺杂可以调变材料的电子结构，从而改善催化活性；（4）石墨化碳层的存在可以改善材料的电子导电性和稳定性，有利于电子转移并可以保护磷酸钴颗粒在催化氧还原反应过程中不被电解液腐蚀.可见，所制有机膦酸衍生的氮掺杂的磷酸钴/碳纳米管杂化材料有望替代Pt/C催化剂，并推动清洁可再生能源领域的相关研究.

关键词:

English

Phosphonate-derived nitrogen-doped cobalt phosphate/carbon nanotube hybrids as highly active oxygen reduction reaction electrocatalysts

a National Institute for Advanced Materials, School of Materials Science and Engineering, Nankai University, Tianjin 300350, China;
b School of Materials Science and Engineering, Liaocheng University, Liaocheng 252000, Shandong, China;
c Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China
Received Date: 18 May 2019
Revised Date: 16 July 2019
Fund Project:
This work was supported by the National Natural Science Foundation of China (21421001, 21573115).

Abstract: The exploration of cost-effective non-noble-metal electrocatalysts is highly imperative to replace the state-of-the-art platinum-based catalysts for oxygen reduction reaction (ORR). Here, we prepared cobalt phosphonate-derived N-doped cobalt phosphate/carbon nanotube hybrids (CoPiC-N/CNTs) by hydrothermal treatment of N-containing cobalt phosphonate and oxidized carbon nanotubes (o-CNT) followed by high-temperature calcination under nitrogen atmosphere. The resultant CoPiC-N/CNT exhibits a superior electrocatalytic performance for the ORR in alkaline media, which is equal to the commercial Pt/C catalyst in the aspect of half-wave potential, onset potential and diffuse limiting current density. Furthermore, the excellent tolerance to methanol and strong durability outperform those of commercial Pt/C. It is found that cobalt phosphonate-derived N-doped cobalt phosphate and the in-situ formed graphitic carbons play key roles on the activity enhancement. Besides, introducing a suitable amount of CNTs enhances the electronic conductivity and further contributes to the improved ORR performance.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

有机膦酸盐衍生的氮掺杂的磷酸钴/碳纳米管杂化材料作为高效氧还原电催化剂

English

Phosphonate-derived nitrogen-doped cobalt phosphate/carbon nanotube hybrids as highly active oxygen reduction reaction electrocatalysts

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

有机膦酸盐衍生的氮掺杂的磷酸钴/碳纳米管杂化材料作为高效氧还原电催化剂

English

Phosphonate-derived nitrogen-doped cobalt phosphate/carbon nanotube hybrids as highly active oxygen reduction reaction electrocatalysts

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs