石墨化介孔碳包裹WC纳米粒子的构建及其氧还原性能研究

doi:10.15541/jim20170305

无机材料学报 ›› 2018, Vol. 33 ›› Issue (2): 213-220.DOI: 10.15541/jim20170305 CSTR: 32189.14.10.15541/jim20170305

所属专题：电催化研究；乘风破浪的新能源材料

石墨化介孔碳包裹WC纳米粒子的构建及其氧还原性能研究

崔香枝¹, 张琳琳¹, 曾黎明^1,2, 张晓华^1,2, 陈航榕¹, 施剑林¹

1. 中国科学院上海硅酸盐研究所高性能陶瓷和超微结构国家重点实验室, 上海 200050
2. 中国科学院大学, 北京 100049

收稿日期:2017-06-21 修回日期:2017-10-12 出版日期:2018-02-26 网络出版日期:2018-01-26
作者简介:崔香枝(1979),女,副研究员.E-mail:cuixz@mail.sic.ac.cn
基金资助:
基金项目: 国家重大科技基础研究发展计划(973)(2013CB933200);上海市自然科学基金(16ZR1440600)

Fabrication of Tungsten Carbide Nanoparticle-encased Graphite-like Mesoporous Carbon as a Precious Metal-free Electrocatalyst for Oxygen Reduction

CUI Xiang-Zhi¹, ZHANG Lin-Lin¹, ZENG Li-Ming^1,2, ZHANG Xiao-Hua^1,2, CHEN Hang-Rong¹, SHI Jian-Lin¹

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. University of the Chinese Academy of Sciences, Beijing 100049, China

Received:2017-06-21 Revised:2017-10-12 Published:2018-02-26 Online:2018-01-26
Supported by:
National Key Basic Research Program of China (2013CB933200); Natural Science Foundation of Shanghai (16ZR1440600)

摘要/Abstract

摘要：

采用模板复型辅助的化学气相沉积法(CVD)成功制备出一种非贵金属的氧还原反应(ORR)催化剂材料—包裹碳化钨纳米粒子的石墨化介孔碳(WC/MG)复合物。制备的介孔结构WC/MG复合材料不仅具有高氧还原反应电化学催化活性, 还表现出良好的电化学稳定性。在O₂饱和的0.1 mol/L KOH电解质溶液中, 900℃制备的样品WC/ MG-900其半波电势(E_1/2)和极限电流密度仅比商用贵金属催化剂Pt/C分别低50 mV 和 0.2 mA/cm²。Koutecky- Levich曲线和旋转环盘电极实验均表明, 该介孔结构的WC/MG复合材料表现出近似4电子的ORR反应途径, 具有可与Pt/C催化剂相比拟的ORR催化活性, 以及比Pt/C更优越的电化学稳定性和耐甲醇性能, 使得该介孔结构WC/MG复合物在氧还原电极材料中表现出良好的应用前景。

关键词: 碳化钨, 石墨化, 介孔, 氧还原反应

Abstract:

Tungsten carbide nanoparticle-encased graphite-like mesoporous carbon (WC/MG), as a precious metal- free cathode catalyst for oxygen reduction reaction, was successfully synthesized by a template replicating-assisted chemical vapor deposition (CVD) method. The obtained mesostructured WC/MG composite possesses high oxygen reduction reaction catalytic activity and stable electrochemical property. In O₂-staturated 0.1 mol/L KOH solution, the half-wave potential (E_1/2) and limiting current density of the sample WC/MG-900 annealed at 900℃ were only 50 mV and 0.2 mA/cm² lower than those of commercial Pt/C catalyst, respectively. Koutecky-Levich (K-L) plots and rotating ring-disk electrode (RDE) measurements indicated that the mesostructured WC/MG exhibited an approximate 4 e^- transfer pathway during the ORR process. The comparable ORR performance to Pt/C, long-lived electrochemical stability and excellent methanol tolerance make the synthesized mesostructured WC/MG composite a potential electrode catalyst in oxygen reduction reaction.

Key words: tungsten carbide, graphitization, mesoporous, ORR

中图分类号:

TQ174

崔香枝, 张琳琳, 曾黎明, 张晓华, 陈航榕, 施剑林. 石墨化介孔碳包裹WC纳米粒子的构建及其氧还原性能研究[J]. 无机材料学报, 2018, 33(2): 213-220.

CUI Xiang-Zhi, ZHANG Lin-Lin, ZENG Li-Ming, ZHANG Xiao-Hua, CHEN Hang-Rong, SHI Jian-Lin. Fabrication of Tungsten Carbide Nanoparticle-encased Graphite-like Mesoporous Carbon as a Precious Metal-free Electrocatalyst for Oxygen Reduction[J]. Journal of Inorganic Materials, 2018, 33(2): 213-220.

图/表 8

图1 (a)样品的广角XRD图谱, 内嵌图为WC/MG-900在2θ =20o~30o的XRD图谱和(b)相对应的小角XRD图谱

Fig. 1 (a) Wide-angle XRD patterns of the prepared samples with inset showing the XRD pattern (2θ =20°-30°) of WC/MG- 900, and (b) the corresponding small-angle XRD patterns

图2 样品的SEM照片WC/MG-800 (a), WC/MG-900 (b, e), WC/MG-1000 (c); 样品WC/MG-900的EDX谱(d)以及相应的元素分布图(e-1)和(e-2)

Fig. 2 SEM images of sample WC/MG-800 (a), WC/MG-900 (b) and (e), and WC/MG-1000 (c); EDX pattern of WC/MG-900 (d) and its corresponding element mappings (e-1) and (e-2)

图3 WC/MG-800(a)、WC/MG-900(b)、WC/MG-1000(c)样品的TEM照片, (b)中方块区域的HRTEM照片(b-1)和(b-2)

Fig. 3 TEM images of sample WC/MG-800 (a), WC/MG-900 (b), and WC/MG-1000 (c); HRTEM images (b-1, b-2) of the squared area in Fig.3(b) with the inset showing the squared area in (b-1)

图4 所制备样品的Raman图谱

Fig. 4 Raman spectra of the prepared samples

图5 (a)样品的N2吸脱附曲线, (b)相对应的BJH孔径分布曲线

Fig. 5 (a) N2 sorption isotherms of the prepared samples and (b) the corresponding BJH pore size distribution curves

图6 (a)样品的CV曲线, (b)电流密度和循环时间相对应的柱状图, (c)样品在1600 r/min的LSV曲线, (d)WC/MG-900在不同转速下的LSV曲线和相对应的K-L曲线, (e)样品的RRDE曲线, (f)样品的电子转移数

Fig. 6 (a) Current-voltage curves of different samples in 0.1 mol/L KOH solutions; (b) Current density vs. cycling times histograms; (c) LSV curves of samples at a rotating rate of 1600 r/min; (d) LSV curves of sample WC/MG-900 at varied rotating rates and the corresponding K-L plots in the inset; (e) Ring-disc current density curves; (f) Electron transfer number curve

表1 样品的孔结构参数和电子转移数

Table 1 Pore structural parameters and electron-transfer number of prepared composites

Sample	S_BET^[a]/ (m²•g^-1)	D_BJH^[b]/ nm	V_BJH^[c]/ (cm³•g^-1)	J_L^[d]/ (mA•cm^-2)	n^[e]
SBA-15	738	7.5	1.36	-	-
WC	98	9.2	0.13	3.6	3.2
WC/MG-800	113	5.8	0.23	3.8	3.4
WC/MG-900	118	6.4	0.25	4.5	3.7
WC/MG-1000	124	8.4	0.34	4.6	3.5
20wt%Pt/C	185	-	-	4.7	3.9

图7 样品在0.75V (a) O2饱和的0.1 mol/L KOH电解质溶液, (b) O2饱和的0.1 mol/L KOH+3 mol/L CH3OH电解质溶液中的电流-时间曲线

Fig. 7 Chronoamperometric responses of samples at 0.75 V (vs. RHE) in O2-saturated (a) 0.1 mol/L KOH solution, and (b) 0.1 mol/L KOH with 3 mol/L CH3OH solution added at ca.5 min

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石墨化介孔碳包裹WC纳米粒子的构建及其氧还原性能研究

Fabrication of Tungsten Carbide Nanoparticle-encased Graphite-like Mesoporous Carbon as a Precious Metal-free Electrocatalyst for Oxygen Reduction

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