Co3O4/Ti电催化膜电极制备及其苯甲醇催化氧化性能

doi:10.13208/j.electrochem.170407

电化学（中英文） ›› 2018, Vol. 24 ›› Issue (2): 122-128. doi: 10.13208/j.electrochem.170407

Co₃O₄/Ti电催化膜电极制备及其苯甲醇催化氧化性能

郑玉梅^{1, 2}，尹振^{1, 2*}，王虹^{1, 3}，李建新^{1, 3*}

1. 天津工业大学分离膜与膜过程国家重点实验室/分离膜科学与技术国际联合研究中心，天津 300387; 2. 天津工业大学环境与化学工程学院，天津 300387; 3. 天津工业大学材料科学与工程学院，天津 300387

收稿日期:2017-04-07 修回日期:2017-05-11 出版日期:2018-04-28 发布日期:2017-05-12
通讯作者: 尹振,李建新 E-mail:yinzhen@tjpu.edu.cn, jxli@tjpu.edu.cn
基金资助:
国家自然科学基金项目（No. 21576208, No. 21676200）、天津市应用基础与前沿技术研究计划（No. 15JCQNJC05300）及天津市科技计划项目(No. 15PTSYJC00240)资助

Preparation of Co₃O₄/Ti Electrocatalytic Membrane Electrode for Catalytic Oxidation of Benzyl Alcohol

ZHENG Yu-mei^{1, 2}, YIN Zhen^{1, 2}*, WANG Hong^{1, 3}, LI Jian-xin^{1, 3*}

1. State Key Laboratory of Separation Membranes and Membrane Processes/Separation Membrane Science and Technology International Joint Research Centre, Tianjin Polytechnic University, Tianjin 300387, China; 2. School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, China; 3. School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300387, China

Received:2017-04-07 Revised:2017-05-11 Published:2018-04-28 Online:2017-05-12
Contact: YIN Zhen, LI Jian-xin E-mail:yinzhen@tjpu.edu.cn, jxli@tjpu.edu.cn

摘要/Abstract

摘要：

本文采用浸渍涂覆法成功制备出多孔Ti负载纳米Co₃O₄电催化膜电极（Co₃O₄/Ti），以该膜电极为阳极，辅助电极为阴极，构建电催化膜反应器（electrocatalytic membrane reactor,ECMR）用于可控催化氧化苯甲醇制备苯甲醛和苯甲酸，并考察了 Co₃O₄/Ti 膜电极结构、电化学性能以及ECMR不同操作参数对苯甲醇转化率、苯甲醛和苯甲酸选择性的影响. 结果表明，负载Co₃O₄纳米颗粒可以显著提高Ti膜电极的电化学性能和催化活性. 在常温常压下，当反应物苯甲醇浓度为10 mmol·L^-1，pH为7.0，停留时间为5.0 min，电流密度为2.5 mA·cm^-2，苯甲醇的转化率达到49.8%，苯甲醛选择性为51.5%，苯甲酸选择性为23.6%.

关键词: 电催化氧化, 电催化膜反应器, 四氧化三钴, 苯甲醇氧化

Abstract:

The cobalt oxide(Co₃O₄) nanoparticles were loaded on microporous Ti membrane to prepare Co₃O₄/Ti electrocatalytic membrane electrode by dip-coating method. The microstructures and electrochemical properties of Co₃O₄/Ti electrocatalytic membrane were investigated. The Co₃O₄/Ti electrocatalytic membrane reactor (ECMR) assembled by using the Co₃O₄/Ti electrocatalytic membrane as an anode was adopted for catalytic oxidation of benzyl alcohol to produce benzaldehyde and benzoic acid.The effects of different operation parameters on benzyl alcohol conversion, and selectivity to benzaldehyde and benzoic acid of ECMR were studied. The results indicated that the electrochemical performance and catalytic activity of Co₃O₄/Ti membrane were improved significantly. The values of 49.8% for the conversion of benzyl alcohol, 51.5% for the selectivity to benzaldehyde and 23.6% for the selectivity to benzoic acid were obtained under the operating conditions with the benzyl alcohol concentration of 10 mmol·L^-1, pH of 7.0, residence time of 5.0 min, current density of 2.5 mA·cm^-2 at ambient temperature and pressure.

Key words: electrocatalytic oxidation, elctrocatalytic membrane reactor, cobalt oxide, benzyl alcohol oxidation

中图分类号:

O646

郑玉梅，尹振，王虹，李建新. Co₃O₄/Ti电催化膜电极制备及其苯甲醇催化氧化性能[J]. 电化学（中英文）, 2018, 24(2): 122-128.

ZHENG Yu-mei, YIN Zhen, WANG Hong, LI Jian-xin. Preparation of Co₃O₄/Ti Electrocatalytic Membrane Electrode for Catalytic Oxidation of Benzyl Alcohol[J]. Journal of Electrochemistry, 2018, 24(2): 122-128.

参考文献

[1] Parmeggiani C, Cardona F. Transition metal based catalysts in the aerobic oxidation of alcohols[J]. Green Chem- istry, 2012, 14(3): 547-564.

[2] Enache D I, Edward J K, Landon P, et al. Solvent-free oxidation of primary alcohols to aldehydes using Au-Pd/TiO₂ catalysts[J]. Science, 2006, 311(5759): 362-365.

[3] Liu J, Yang H Q, Kleitz F, et al. Yolk-shell hybrid materials with a periodic mesoporous organosilica shell: Ideal nanoreactors for selective alcohol oxidation[J]. Advanced Functional Materials, 2012, 22(3): 591-599.

[4] Watanabe H, Asano S, Fujita S, et al. Nitrogen-doped, metal-free activated carbon catalysts for aerobic oxidation of alcohols[J]. ACS Catalysis, 2015, 5(5): 2886-2894.

[5] Adam W, Gelalcha F G, Saha-Möller C R, et al. Chemoselective C-H oxidation of alcohols to carbonyl compounds with iodosobenzene catalyzed by (salen) chromium complex[J]. The Journal of Organic Chemistry, 2000, 65 (7):1915-1918.

[6] Menger F M, Lee C. Synthetically useful oxidations at solid sodium permanganate surfaces [ J ] . Tetrahedron Letters ,1981, 22(18): 1655-1656.

[7] Sato K, Aoki M, Takagi J , et al. Organic solvent- and halide-free oxidation of alcohols with aqueous hydrogen peroxide [J]. Journal of the American Chemical Society,1997, 119(50): 12386-12387.

[8] Abad A, Almela C, Corma A, et al. Efficient chemoselective alcohol oxidation using oxygen as oxidant. Superior performance of gold over palladium catalysts[J]. Tetrahedron, 2006, 62(28): 6666-6672.

[9] Teng Y, Song L X, Wang L B, et al. Face-raised octahedral Co3O4nanocrystals and their catalytic activity in the selective oxidation of alcohols[J]. The Journal of Physical Chemistry C, 2014, 118(9): 4767-4773.

[10] Zhu J, Kailasam K, Fischer A, et al. Supported cobalt oxide nanoparticles as catalyst for aerobic oxidation of alcohols in liquid phase[J]. ACS Catalysis, 2011, 1(4): 342-347.

[11] Kowal A, Port S N, Nichols R J. Nickel hydroxide electrocatalysts for alcohol oxidation reactions: An evalua- tion by infrared spectroscopy and electrochemical methods[J]. Catalysis Today, 1997, 38(4):483-492.

[12] Li J, Li J, Wang H, et al. Electrocatalytic oxidation of n-propanol to produce propionic acid using an electro- catalytic membrane reactor[J]. Chemical Communications, 2013, 49(40): 4501-4503.

[13] Tian W J（田文杰）Wang H(王虹), Yin Z(尹振), et al.Preparation of nano-manganite loaded titanium electo- catalytic membrane for the catalytic oxidation of benzyl alcohol[J]. Acta Physico-ChimicaSinica(物理化学学报),2015, 31(8): 1567-1574.

[14] Fang X, Yin Z, Wang H, et al. Controllable oxidation of cyclohexane to cyclohexanol and cyclohexanone by a nano-MnOx/Ti electrocatalytic membrane reactor[J]. Journal of Catalysis, 2015, 329: 187-194.

[15] Wöltinger J, Drauz K, Bommarius A S. The membrane reactor in the fine chemicals industry[J]. Applied Catalysis A: General, 2001, 221(1): 171-185.

[16] Ketchie W C, Fang Y L, Wong M S, et al. Influence of gold particle size on the aqueous-phase oxidation of carbon monoxide and glycerol[J]. Journal of Catalysis, 2007, 250(1): 94-101.

[17] Wang H, Wang H, Li J, et al. An electrocatalytic reactor for the high selectivity production of sodium 2, 2, 3, 3-tetrafluoropropionate from 2, 2, 3, 3-tetrafluoro-1-propanol [J]. Electrochimica Acta, 2014, 123: 33-41.

[18] Niu D F(钮东方), Yu C K(俞程凯), Zhang X S(张新胜).Preparation of benzoquinone from phenol by electrooxidation[J]. Journal of Electrochemistry(电化学), 2013, 19(5): 477-481.

[19] Liu H, Vecitis C D. Reactive transport mechanism for organic oxidation during electrochemical filtration: Mass-transfer , physical adsorption , and electron-transfer [J]. Journal of Physical Chemistry C, 2012, 116(1):374-383.

[20] Camara G A, Iwasita T. Parallel pathways of ethanol oxidation: The effect of ethanol concentration[J]. Journal of Electroanalytical Chemistry, 2005, 578(2): 315-321.

[21] Enache D I, Edwards J K, Landon P, et al. Solvent-free oxidation of primary alcohols to aldehydes using Au-Pd/TiO₂ catalysts[J]. Science, 2006, 311(5759): 362-365.

[22] Dijksman A, Marino-González A, Payeras A M I, et al. Efficient and selective aerobic oxidation of alcohols into aldehydes and ketones using ruthenium/TEMPO as the catalytic system[J]. Journal of the American Chemical Society,2001, 123(28): 6826-6833.

Co₃O₄/Ti电催化膜电极制备及其苯甲醇催化氧化性能

Preparation of Co₃O₄/Ti Electrocatalytic Membrane Electrode for Catalytic Oxidation of Benzyl Alcohol

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

Metrics

[1]	孙齐, 韩严和, 付晓璐. 改性钛基PbO₂电极的制备及其对COD的快速检测[J]. 电化学（中英文）, 2021, 27(5): 558-569.
[2]	周雪, 王虹, 尹振, 张玉军, 李建新. 间歇电沉积法制备纳米MnO_x/Ti膜电极及其催化氧化环己烷性能[J]. 电化学（中英文）, 2020, 26(3): 397-405.
[3]	李乐，王虹，马荣花，惠洪森，梁小平，李建新. 纳米氧化锰负载钛基电催化膜制备及处理含酚废水性能研究[J]. 电化学（中英文）, 2018, 24(4): 309-318.
[4]	林晓东，陈杜宏，田中群. 壳层厚度可调控的Ag@Pd@Pt纳米粒子的合成和甲酸电催化研究[J]. 电化学（中英文）, 2016, 22(6): 570-576.
[5]	周文，卢雪峰，吴明娒，李高仁. 模板法合成NiO@Co₃O₄空心多孔小球及其储电性能的研究[J]. 电化学（中英文）, 2016, 22(5): 513-520.
[6]	王霞，胡俊，李永军*. 电化学制备二维“花状”Pt纳米结构及其对甲醇的电催化氧化[J]. 电化学（中英文）, 2014, 20(4): 365-369.
[7]	马永钧*，田玉秀，刘婧，周敏，丁静，金芝梅，王向梅. Nd-Fe-MoO₄^2-氰桥混配聚合物修饰铂电极的丙三醇电催化氧化[J]. 电化学（中英文）, 2014, 20(2): 150-155.
[8]	王彬，王崇太*，华英杰，刘津媛，郑良飞. Keggin型钴取代杂多阴离子PW₁₁O₃₉Co(II)(H₂O)^5-的电催化性能[J]. 电化学（中英文）, 2013, 19(5): 488-492.
[9]	苏静，林海波*，徐红，黄卫民，何亚鹏. 草酸在Ti/IrO₂-Ta₂O₅阳极圆柱形电解槽中的电催化氧化降解动力学[J]. 电化学（中英文）, 2013, 19(4): 293-299.
[10]	刘晓蕾，丹媛媛，陆海彦，林海波*，欧阳明丽，袁传军. 不同掺杂元素的钛基PbO₂电极对苯酚电催化氧化性能的影响[J]. 电化学（中英文）, 2013, 19(1): 59-64.
[11]	胡光辉, 曾海霞, 魏志钢, 潘湛昌, 谢署光, 邹燕娣. Ni-P-TiO2化学复合镀层电极的乙醇电催化氧化[J]. 电化学（中英文）, 2012, 18(2): 186-190.
[12]	陈野, 赵文丽, 温青. 阳极电沉积Ti/MnO2电极及其苯酚降解的电催化性能[J]. 电化学（中英文）, 2011, 17(2): 199-203.
[13]	褚道葆, 查龙武, 王树西, 王建, 肖英, 侯源源, 何建国, 张雪娇, . 离子液体中CNT/nanoTiO_2-Pt膜电极电催化氧化葡萄糖[J]. 电化学（中英文）, 2009, 15(3): 299-303.
[14]	崔艳萍, 杨昌柱, 黄健, 濮文虹, 张敬东, . 新型纳米金修饰玻碳电极对水杨酸的电催化氧化[J]. 电化学（中英文）, 2008, 14(3): 298-303.
[15]	初园园, 邬冰, 唐亚文, 陆天虹, 高颖, . 甲醇在Pt/C和Pt/WO_3/C电极上的电氧化[J]. 电化学（中英文）, 2008, 14(2): 155-158.