间歇电沉积法制备纳米MnOx/Ti膜电极及其催化氧化环己烷性能

doi:10.13208/j.electrochem.190312

电化学（中英文） ›› 2020, Vol. 26 ›› Issue (3): 397-405. doi: 10.13208/j.electrochem.190312

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

周雪¹, 王虹¹^,³, 尹振², 张玉军¹, 李建新¹^*()

1. 天津工业大学材料科学与工程学院,分离膜与膜过程国家重点实验室,天津 300387
2. 天津工业大学化学与化工学院,天津 300387
3. 南开大学先进能源材料化学教育部重点实验室,天津 300071

收稿日期:2019-03-12 修回日期:2019-04-18 出版日期:2020-06-28 发布日期:2019-04-25
通讯作者: 李建新 E-mail:jxli@tiangong.edu.cn
基金资助:
国家自然科学基金（No. 21676200，No. 21576208）、教育部创新团队发展计划（No. IRT-17R80）和天津科学支撑计划（No. 17JCYBJC19800）

Preparations of Nano-MnO_x/Ti Electrocatalytic Membrane Electrode for Catalytic Oxidation of Cyclohexane Using Intermittent Electrodeposition

ZHOU Xue¹, WANG Hong¹^,³, YIN Zhen², ZHANG Yu-jun¹, LI Jian-xin¹^*()

1. State Key Laboratory of Separation Membranes and Membrane Processes, School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300387, P. R. China
2. Chemistry and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, P. R. China
3. Key Laboratory of Advanced Energy Materials Chemistry, Ministry of Education, Nankai University, Tianjin 300071, P. R. China

Received:2019-03-12 Revised:2019-04-18 Published:2020-06-28 Online:2019-04-25
Contact: LI Jian-xin E-mail:jxli@tiangong.edu.cn

摘要/Abstract

摘要：

高选择性氧化环己烷（CHA）制备环己酮和环己醇（KA油）具有重要的工业价值和应用前景. 本文提出采用间歇电沉积法制备纳米MnO_x催化剂负载多孔管式钛膜,构建电催化膜反应器（ECMR）催化氧化环己烷制备环己醇和环己酮. 利用场发射扫描电子显微镜（FESEM）、X射线衍射仪（XRD）和电化学工作站等表征手段对催化剂的结构与性能进行表征. 结果表明,间歇电沉积法制备的催化剂为纳米花球状γ-MnO₂. 与基体钛膜相比,MnO_x/Ti膜电极具有更优的电化学性能和传质性能. 此外,以MnO_x/Ti电催化膜为阳极,不锈钢网为阴极构建ECMR. 当环己烷初始浓度30 mmol·L^-1、反应温度30^oC、停留时间34.3 min、电流密度2.3 mA·cm^-2等条件下,ECMR环己烷转化率达25.6%,KA油总选择性高于99%. 同时,ECMR重复使用8次后表现较高催化稳定性.

关键词: 间歇电沉积, MnO_x/Ti电催化膜, 电催化膜反应器, 环己烷氧化, 环己醇和环己酮

Abstract:

Cyclohexanone and cyclohexanol (KA oil) obtained from highly selective oxidation of cyclohexane (CHA) show important industrial value and application prospects. In this work, the intermittent electrodeposition was developed to prepare nano-MnO_x catalyst loading porous tubular titanium membrane electrode (MnO_x/Ti), which was employed to constitute an electro-catalytic membrane reactor (ECMR) for the oxidation of cyclohexane to produce cyclohexanol and cyclohexanone. The surface morphology, crystal structure and electrochemical property of the catalysts were characterized by FESEM, XRD and electrochemical workstation, respectively. The results show that the catalyst prepared by the intermittent electrodeposition displayed nano-flower-like γ-MnO₂. Compared with titanium membrane, the MnO_x/Ti electrocatalytic membrane exhibited better electrochemical performance and mass transfer performance. Furthermore, the ECMR was constructed by using the MnO_x/Ti electrocatalytic membrane as the anode and the stainless steel mesh as the cathode. When the initial concentration of cyclohexane was 30 mmol·L^-1, the reaction temperature was 30^oC, the residence time was 34.3 min and the current density was 2.3 mA·cm^-2. The cyclohexane conversion rate reached 25.6% and the total selectivity of KA oil exceeded 99%. Simultaneously, the ECMR with MnO_x/Ti electrode showed a good stability during the oxidation of cyclohexane.

Key words: intermittent electrodeposition, MnO_x/Ti electrocatalytic membrane, electrocatalytic membrane reactor, cyclohexane oxidation, cyclohexanol and cyclohexanone

中图分类号:

O646

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.

ZHOU Xue, WANG Hong, YIN Zhen, ZHANG Yu-jun, LI Jian-xin. Preparations of Nano-MnO_x/Ti Electrocatalytic Membrane Electrode for Catalytic Oxidation of Cyclohexane Using Intermittent Electrodeposition[J]. Journal of Electrochemistry, 2020, 26(3): 397-405.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.190312

https://electrochem.xmu.edu.cn/CN/Y2020/V26/I3/397

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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

Preparations of Nano-MnO_x/Ti Electrocatalytic Membrane Electrode for Catalytic Oxidation of Cyclohexane Using Intermittent Electrodeposition

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间歇电沉积法制备纳米MnOx/Ti膜电极及其催化氧化环己烷性能

Preparations of Nano-MnOx/Ti Electrocatalytic Membrane Electrode for Catalytic Oxidation of Cyclohexane Using Intermittent Electrodeposition

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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

Preparations of Nano-MnO_x/Ti Electrocatalytic Membrane Electrode for Catalytic Oxidation of Cyclohexane Using Intermittent Electrodeposition