铂/聚邻甲基苯胺/碳材料掺杂碳糊电极对甲醇的催化氧化

doi:10.7503/cjcu20170093

摘要/Abstract

摘要：

以石墨和液体石蜡油为主要原料, 分别制备了掺杂不同量多壁碳纳米管(MWCNT)、石墨烯(GRA)、电容活性炭(YEC)和电池活性炭(YBC)的多种碳糊底电极Y-CPE(Y代表各种掺杂碳材料, CPE代表纯碳糊电极). 采用恒电位法在-0.10 V(vs. Ag/AgCl)电位下将铂电沉积到这些电极上. 结果表明, 当电池碳的含量为14%时, Pt/YBC-CPE(14%)复合电极对甲醇具有最好的电催化氧化活性. 采用恒电位方法在0.85 V(vs. Ag/AgCl)电位下将聚邻甲基苯胺(POT)电聚合沉积到纯碳糊电极CPE和含有电池碳的YBC-CPE(14%)电极上, 得到复合电极POT/CPE和POT/YBC-CPE(14%), 再通过恒电位方法将铂电沉积到这2个复合电极上. 扫描电镜(SEM)观察结果表明, 在Pt/CPE, Pt/YBC-CPE(14%), Pt/POT(6.5 mC)/CPE和Pt/POT(6.5 mC)/YBC-CPE(14%)4个复合电极中, 在Pt/POT/YBC-CPE(14%)复合电极上的铂粒子的尺寸最小, 并且Pt/POT(6.5 mC)/YBC-CPE(14%)复合电极电催化氧化甲醇活性最高. 在POT(6.5 mC)/CPE和POT(6.5 mC)/YBC-CPE(14%)上Pt纳米颗粒的电沉积过程是一个近似的3D成核过程. 研究还发现, 复合电极Pt/POT/CPE和Pt/POT/YBC-CPE电催化氧化甲醇的活性随POT膜厚度的增加先增大后减少, 存在一个最佳的膜厚度.

关键词: 碳糊电极, 活性炭, 聚邻甲基苯胺, 铂纳米颗粒, 电催化氧化甲醇

Abstract:

Various liquid oil-bound carbon paste electrodes were prepared from the mixtures of graphite powders and paraffin(CPE), multi-walled carbon nanotubes and graphite powders and paraffin(MWCNT-CPE), graphene and graphite powders and paraffin(GRA-CPE), activated capacitors carbon and graphite powders and paraffin(YEC-CPE), activated batteries carbon and graphite powders and paraffin(YBC-CPE), respectively. Poly(o-toluidine)(POT) film was prepared by constant potential deposition at 0.85 V(vs. Ag|AgCl) in monomer solution at the surface of CPE and YBC-CPE(14%)(14% refers to the mass fraction of YBC in the carbon mixture materials) with various film growth charges. Platinum nanoparticles were successfully electrodeposited on Y-CPE(Y refers to the various carbon materials mentioned above except graphite powders), POT/CPE, POT/YBC-CPE(14%) at a fixed potential of -0.10 V(vs. Ag|AgCl) in 0.5 mol/L H₂SO₄ solution containing 3.0 mmol/L H₂PtCl₆. In order to learn about the instantaneous or progressive nucleation process of platinum on composite electrodes, non-dimensional plots of (I/I_m)² vs. t/t_m of the experimental were compared with theory through the expressions. The morphologies of platinum nanoparticles were char-acterized by scanning electron microscopy(SEM). The SEM images reveal that the presence of YBC and POT influences the size of platinum nanoparticle. The electrocatalytic activities of as-formed Pt/CPE, Pt/POT/CPE, Pt/YBC-CPE and Pt/POT/YBC-CPE(14%) towards the electrooxidation of methanol were evaluated by cyclic voltammetry(CV). The experimental results indicate that compared with other POT/Y-CPE, Pt/POT/YBC-CPE(14%) has the best electrocatalytic activity towards methanol oxidation in an acidic medium.

Key words: Carbon paste electrode, Activated carbon, Poly(o-toluidine), Platinum nanoparticles, Electrocatalytic oxidation methan

中图分类号:

O646

TrendMD:

张园园, 李芬培, 刘香晴, 陈海燕, 骆荧, 井利红, 陆嘉星, 张贵荣. 铂/聚邻甲基苯胺/碳材料掺杂碳糊电极对甲醇的催化氧化. 高等学校化学学报, 2017, 38(12): 2320.

ZHANG Yuanyuan, LI Fenpei, LIU Xiangqing, CHEN Haiyan, LUO Ying, JING Lihong, LU Jiaxing, ZHANG Guirong. Methanol Electrocatalytic Oxidation on Pt/Poly(o-toluidine) Film/Activated Carbon Doped Graphite Carbon Paste Electrode^†. Chem. J. Chinese Universities, 2017, 38(12): 2320.

图/表 8

Fig.1 CVs of Pt/CPE and CPE in 1.0 mol/L CH3OH+0.5 mol/L H2SO4 and -0.10—0.85 V at 100 mV/s

Fig.2 jF peak current density as a function of w for Pt/MWCNT-CPE(A), Pt/GRA-CPE(B), Pt/YEC-CPE(C) and Pt/YBC-CPE(D), respectively, in 0.5 mol/L H2SO4+1 mol/L CH3OH and -0.10—0.85 V at 100 mV/s

Fig.3 Current vs. time transient plot obtained during the potentiostatic experiment(at -0.10 V) of CPE, POT(6.5 mC)/CPE, YBC-CPE(14%) and POT(6.5 mC)/YBC-CPE(14%) in a 0.5 mol/L H2SO4+3 mmol/L H2PtCl6 solution

Fig.4 Plots of the experimental data and the theoretical models for 3D nucleation of the platinum deposition on CPE(A), POT(6.5 mC)/CPE(B), YBC-CPE(14%)(C) and POT(6.5 mC)/YBC-CPE(14%)(D)

Fig.5 SEM IMAGES of Pt/CPE(A), Pt/POT(6.5 mC)/CPE(B), Pt/YBC-CPE(14%)(C) and Pt/POT(6.5 mC)/YBC-CPE(14%)(D)

Fig.6 CVs of Pt/CPE, Pt/POT(6.5 mC)/CPE, Pt/ YBC-CPE(14%) and Pt/POT(6.5 mC)/YBC-CPE(14%) in 0.5 mol/L H2SO4+1.0 mol/L CH3OH and -0.10—0.85 V at 100 mV/s(A)and in 0.5 mol/L H2SO4 and -0.25—0.85 V at 50 mV/s(B)

Fig.7 jF peak current density and EASA as a function of POT film charge(QPOT) for Pt/POT/CPE(A) and Pt/POT/YBC-CPE(14%)(B) in 0.5 mol/L H2SO4 + 1 mol/L CH3OH solution and -0.10—0.85 V at 100 mV/s

Table 1 Parameters related to the electrooxidation of 1 mol/L CH3OH at Pt/POT/CPE and Pt/POT/YBCPE(14%)

Electrode	Q_POT/mC	j_F/(A·g^-1)	E_F/V	$I F / R$	E_onset/V
Pt/POT/CPE	0	121.26	0.730	1.03	0.225
	4.5	140.36	0.744	1.04	0.290
	6.5	176.46	0.742	1.08	0.337
	10.5	144.37	0.733	1.12	0.469
	15.5	129.63	0.734	1.12	0.492
Pt/POT/YBCPE(14%)	0	161.00	0.722	0.99	0.242
	4.5	163.84	0.717	1.04	0.238
	6.5	200.17	0.714	1.07	0.264
	10.5	159.83	0.718	1.10	0.413
	15.5	135.53	0.728	1.13	0.465

Table 1 Parameters related to the electrooxidation of 1 mol/L CH3OH at Pt/POT/CPE and Pt/POT/YBCPE(14%)

Electrode	Q_POT/mC	j_F/(A·g^-1)	E_F/V	$I F / R$	E_onset/V
Pt/POT/CPE	0	121.26	0.730	1.03	0.225
	4.5	140.36	0.744	1.04	0.290
	6.5	176.46	0.742	1.08	0.337
	10.5	144.37	0.733	1.12	0.469
	15.5	129.63	0.734	1.12	0.492
Pt/POT/YBCPE(14%)	0	161.00	0.722	0.99	0.242
	4.5	163.84	0.717	1.04	0.238
	6.5	200.17	0.714	1.07	0.264
	10.5	159.83	0.718	1.10	0.413
	15.5	135.53	0.728	1.13	0.465

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