射频等离子制备石墨烯负载Co3O4催化剂及其析氧性能研究

摘要/Abstract

摘要： 氢能的引入能有效提升配电网的供电可靠性,而电解水制氢是实现低碳转型的关键技术,开发高效的电解水催化剂势在必行。过渡金属氧化物储量大、催化活性高,是具有广阔应用前景的析氧反应催化剂。本文通过射频等离子体处理制备石墨烯上负载Co₃O₄析氧催化剂,XRD、Raman和XPS测试结果显示,二维结构石墨烯的引入加速表面电子迁移,增大了反应面积。等离子体处理促进了纳米粒子在石墨烯上的负载,利用等离子体刻蚀作用在催化剂表面制造出大量碳结构缺陷和氧空位结构,改善了活性位点分布,有效调控Co₃O₄电子结构,提高析氧催化活性。电化学测试表明,本文中合成的Co₃O₄@rGO在电流密度为50 mA·cm^-2时的过电位为410 mV,动力学反应速率较快,表现出优于商业IrO₂的析氧催化活性。

关键词: 等离子体, 石墨烯, CO₃O₄, 氧空位, 电催化, 析氧反应

Abstract: The introduction of hydrogen energy can effectively improve the power supply reliability of the distribution network, and hydrogen production from water electrolysis is a key technology to achieve low-carbon transformation, so it is imperative to develop efficient electrolysis water catalysts. Transition metal oxides have large reserves and high catalytic activity, and are regarded as promising oxygen evolution reaction catalysts. In this work, the oxygen evolution catalyst of graphene which supports Co₃O₄ was prepared by radio frequency plasma. The test results of XRD, Raman and XPS show that the introduction of two-dimensional graphene accelerates the surface electron migration and increases the reaction area. Plasma treatment facilitates the loading of nanoparticle on graphene, and plasma etching is used on the surface of catalyst to create a large number of graphene structural defects and oxygen vacancies, which improves the distribution of active sites, effectively regulates the electronic structure of Co₃O₄ and improves the catalytic activity of oxygen evolution. Electrochemical tests show that the overpotential of Co₃O₄@rGO synthesized in this experiment is 410 mV at a current density of 50 mA·cm^-2, the kinetic reaction rate is fast, and exhibits a catalytic activity of oxygen evolution that is superior to that of commercial IrO₂.

Key words: plasma, graphene, Co₃O₄, oxygen vacancy, electrocatalysis, oxygen evolution reaction

中图分类号:

TQ151

敖刚, 李冬东, 朱倩钰, 刘昊橙, 李昊澄, 史毅, 罗庆亮, 杨庆. 射频等离子制备石墨烯负载Co₃O₄催化剂及其析氧性能研究[J]. 人工晶体学报, 2022, 51(8): 1406-1412.

AO Gang, LI Dongdong, ZHU Qianyu, LIU Haocheng, LI Haocheng, SHI Yi, LUO Qingliang, YANG Qing. Preparation of Graphene Supported Co₃O₄ Catalyst by Radio Frequency Plasma and Its Oxygen Evolution Performance[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2022, 51(8): 1406-1412.

参考文献

[1] 张晓君,马梁,孙迎辉.基于电催化析氧反应的硫化物催化剂研究进展[J].材料导报,2021,35(23):23040-23049.
ZHANG X J, MA L, SUN Y H. Advances in sulfide-based electrocatalysts for oxygen evolution reaction[J]. Materials Reports, 2021, 35(23): 23040-23049(in Chinese).
[2] 韩斌,冯思琛,徐俊,等.Fe掺杂NiCo-LDH的制备及OER催化性能[J].材料导报,2021,35(14):14001-14006.
HAN B, FENG S C, XU J, et al. Preparation of Fe-doped NiCo-LDH and its OER performance[J]. Materials Reports, 2021, 35(14): 14001-14006(in Chinese).
[3] LI S S, HAO X G, ABULITI A, et al. Nanostructured Co-based bifunctional electrocatalysts for energy conversion and storage: current status and perspectives[J]. Journal of Materials Chemistry, A Materials for Energy and Sustainability, 2019, 7(32): 18674-18707.
[4] MAO S, WEN Z H, HUANG T Z, et al. High-performance bi-functional electrocatalysts of 3D crumpled graphene-cobalt oxide nanohybrids for oxygen reduction and evolution reactions[J]. Energy Environ Sci, 2014, 7(2): 609-616.
[5] TONG Y, CHEN P Z, ZHOU T P, et al. A bifunctional hybrid electrocatalyst for oxygen reduction and evolution: cobalt oxide nanoparticles strongly coupled to B, N-decorated graphene[J]. Angewandte Chemie, 2017, 56(25): 7121-7125.
[6] DOU S, WANG X, WANG S Y. Rational design of transition metal-based materials for highly efficient electrocatalysis[J]. Small Methods, 2019, 3(1): 1800211.
[7] WANG S P, BENDT G, SADDELER S, et al. Synergistic effects of Mo₂C-NC@Co_xFe_y core-shell nanoparticles in electrocatalytic overall water splitting reaction[J]. Energy Technology, 2019, 7(6): 1801121.
[8] HUANG H W, YU C, YANG J, et al. Strongly coupled architectures of cobalt phosphide nanoparticles assembled on graphene as bifunctional electrocatalysts for water splitting[J]. ChemElectroChem, 2016, 3(5): 719-725.
[9] CHEN H L, ZHAO Q D, GAO L G, et al. Water-plasma assisted synthesis of oxygen-enriched Ni-Fe layered double hydroxide nanosheets for efficient oxygen evolution reaction[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(4): 4247-4254.
[10] DENG S J, CHEN N, DENG D Y, et al. Meso- and macroporous coral-like Co₃O₄ for VOCs gas sensor[J]. Ceramics International, 2015, 41(9): 11004-11012.
[11] RASHAD M, RÜSING M, BERTH G, et al. CuO and Co₃O₄ nanoparticles: synthesis, characterizations, and Raman spectroscopy[J]. Journal of Nanomaterials, 2013, 2013: 714853.
[12] HONG X D, LI S L, TANG X N, et al. Self-supporting porous CoS₂/rGO sulfur host prepared by bottom-up assembly for lithium-sulfur batteries[J]. Journal of Alloys and Compounds, 2018, 749: 586-593.
[13] 张芸秋,梁勇明,周建新.石墨烯掺杂的研究进展[J].化学学报,2014,72(3):367-377.
ZHANG Y Q, LIANG Y M, ZHOU J X. Recent progress of graphene doping[J]. Acta Chimica Sinica, 2014, 72(3): 367-377(in Chinese).
[14] PIMENTA M A, DRESSELHAUS G, DRESSELHAUS M S, et al. Studying disorder in graphite-based systems by Raman spectroscopy[J]. Physical Chemistry Chemical Physics: PCCP, 2007, 9(11): 1276-1291.
[15] KIM M, MIN N K, YUN S J, et al. On the etching mechanism of ZrO₂ thin films in inductively coupled BCl₃/Ar plasma[J]. Microelectronic Engineering, 2008, 85(2): 348-354.
[16] YANG C, YU Y, XIE Y J, et al. One-step synthesis of size-tunable gold nanoparticles/reduced graphene oxide nanocomposites using argon plasma and their applications in sensing and catalysis[J]. Applied Surface Science, 2019, 473: 83-90.
[17] JIN M T, JIAO N, ZHANG C X, et al. Reduction mechanism of hydroxyl group from graphene oxide with and without-NH₂ agent[J]. Physica B: Condensed Matter, 2015, 477: 70-74.
[18] LIU P, LIU J N, ZHANG B B, et al. Enhanced electroluminescent performance by doping organic conjugated ionic compound into graphene oxide hole-injecting layer[J]. Journal of Materials Science, 2019, 54(19): 12688-12697.
[19] WU S L, ZHANG C, CUI X Y, et al. Facile synthesis of nitrogen-doped and boron-doped reduced graphene oxide using radio-frequency plasma for supercapacitors[J]. Journal of Physics D: Applied Physics, 2021, 54(26): 265501.
[20] LIU L, JIANG Z Q, FANG L, et al. Probing the crystal plane effect of Co₃O₄ for enhanced electrocatalytic performance toward efficient overall water splitting[J]. ACS Applied Materials & Interfaces, 2017, 9(33): 27736-27744.
[21] ZHANG X, FAN Q Y, QU N, et al. Ultrathin 2D nitrogen-doped carbon nanosheets for high performance supercapacitors: insight into the effects of graphene oxides[J]. Nanoscale, 2019, 11(17): 8588-8596.
[22] ZHANG J, CHEN J W, LUO Y, et al. Sandwich-like electrode with tungsten nitride nanosheets decorated with carbon dots as efficient electrocatalyst for oxygen reduction[J]. Applied Surface Science, 2019, 466: 911-919.
[23] ZHU Y S, ZHANG T R, LEE J Y. Nitrogenated-graphite-encapsulated carbon black as a metal-free electrocatalyst for the oxygen evolution reaction in acid[J]. ChemElectroChem, 2018, 5(4): 583-588.
[24] LIU D L, ZHANG C, YU Y F, et al. Hydrogen evolution activity enhancement by tuning the oxygen vacancies in self-supported mesoporous spinel oxide nanowire arrays[J]. Nano Research, 2018, 11(2): 603-613.
[25] ZHUANG L, GE L, YANG Y, et al. Ultrathin iron-cobalt oxide nanosheets with abundant oxygen vacancies for the oxygen evolution reaction[J]. Advanced Materials, 2017, 29(17): 1606793.
[26] ZHU Y M, LIU X, JIN S G, et al. Anionic defect engineering of transition metal oxides for oxygen reduction and evolution reactions[J]. Journal of Materials Chemistry A, 2019, 7(11): 5875-5897.
[27] DOU S, TAO L, HUO J, et al. Etched and doped Co₉S₈/graphene hybrid for oxygen electrocatalysis[J]. Energy & Environmental Science, 2016, 9(4): 1320- 1326.
[28] SUN S C, MA F X, LI Y, et al. Sulfur vacancies promoting Fe-doped Ni₃S₂ nanopyramid arrays as efficient bifunctional electrocatalysts for overall water splitting[J]. Sustainable Energy & Fuels, 2020, 4(7): 3326-3333.

射频等离子制备石墨烯负载Co₃O₄催化剂及其析氧性能研究

Preparation of Graphene Supported Co₃O₄ Catalyst by Radio Frequency Plasma and Its Oxygen Evolution Performance

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	李佩漩, 郭凤梅, 张迎九. 双向有序Ti₃C₂T_x/rGO复合气凝胶的制备及其电化学性能的研究[J]. 人工晶体学报, 2022, 51(7): 1241-1247.
[2]	胡慧敏, 邢向英, 韩宇静, 王会香, 吕宝亮. Co₃O₄在多相催化反应中的晶面效应[J]. 人工晶体学报, 2022, 51(7): 1309-1319.
[3]	齐越, 王俊强, 朱泽华, 武晨阳, 李孟委. 石墨烯及石墨烯/氮化硼的电子结构特性研究[J]. 人工晶体学报, 2022, 51(4): 620-627.
[4]	蔡英, 钏定泽, 陈庆华, 刘继涛. 氨基酸/氧化石墨烯/羟基磷灰石复合材料在酸蚀人牙釉质体外再矿化中的应用[J]. 人工晶体学报, 2022, 51(3): 516-522.
[5]	黄强, 孙兵, 徐文莉, 丛野, 陈永婷, 朱辉, 李轩科, 张琴. 铁基氮化物在储能及电催化领域中的研究进展[J]. 人工晶体学报, 2022, 51(2): 344-359.
[6]	刘权, 展红全, 袁梦磊, 李芾, 谢志鹏, 汪长安. 自掺杂SnO₂微球的水热合成及其可见光催化性能[J]. 人工晶体学报, 2022, 51(1): 139-147.
[7]	范兴其, 姚梦琴, 刘飞, 王晓丹, 曹建新. 制备方法对Al₂O₃-CeO₂物化性质及CO₂加氢制甲醇催化性能的影响[J]. 人工晶体学报, 2021, 50(9): 1745-1755.
[8]	张君, 熊迁, 吴振海, 龙蛟, 赵军普, 郑建刚, 张雄军, 郑奎兴, 魏晓峰. 等离子体电极普克尔盒研究进展[J]. 人工晶体学报, 2021, 50(8): 1593-1601.
[9]	葛薛豪, 吴静, 邢栋梁, 潘闻景, 张宇林, 蒋青松. NiCoSe₄薄膜制备及其在染料敏化太阳能电池中的应用[J]. 人工晶体学报, 2021, 50(6): 1062-1069.
[10]	张众, 杨琳, 李晓慧, 王梓兰, 王静怡. 草酸配体修饰的锆取代型硅钨-氧簇合物的合成、结构和电化学性质研究[J]. 人工晶体学报, 2021, 50(5): 884-888.
[11]	张杰. 氢氧化镍/还原氧化石墨烯复合材料的制备及其电化学性能[J]. 人工晶体学报, 2021, 50(5): 915-919.
[12]	由甲川, 赵雷, 刁宏伟, 王文静. 沉积温度对等离子体化学气相沉积制备硅氧薄膜微结构的影响[J]. 人工晶体学报, 2021, 50(3): 509-515.
[13]	许森, 方宁象, 张善伟, 张虹, 林文松. 还原氧化石墨烯增强碳化硼陶瓷的制备与表征[J]. 人工晶体学报, 2021, 50(3): 572-577.
[14]	林晓霞, 李慧, 付德刚. 还原氧化石墨烯/TiO₂纳米线复合膜的制备及对Cu²⁺吸附性的影响[J]. 人工晶体学报, 2021, 50(2): 318-324.
[15]	刘晓晨, 郁鑫鑫, 葛新岗, 姜龙, 李义锋, 安晓明, 郭辉. 氮掺杂对氢终端金刚石射频器件特性的影响[J]. 人工晶体学报, 2021, 50(11): 2045-2052.