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Temperature-Dependence of Methanol Oxidation Rates at PtRu and Pt Electrodes

机译:PtRu和Pt电极上甲醇氧化速率的温度依赖性

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High temperature operation of direct methanol fuel cells is essential from the viewpoint of achieving a high performance with reduced amounts of Pt electrocatalysts used. A thin-layer flow cell of 0.1 mm gap is applied to evaluate the activity of PtRu (46 atom percent Ru) allay and Pt electrodes for methanol oxidation reaction (MOR) in a wide temperature range from 20 to 120 deg C in 1 M CH_3OH + 0.1 M HclO_4 solution under pressurized operation. The steady electrocatalytic activity could be evaluated by linear potential-sweep voltammetry under a certain electrolyte flow rate (>0.2mLl/s), which eliminated an effect of the oxidation current of hydrogen evolved at the proximate counter cathode. Onset potentials [vs. reversible hydrogen electrode (RHE)] far the MOR shifted linearly to less positive potentials with elevating temperature, e.g., from 0.45 V (at 20 deg C) to 0.34 V (at 120 deg C) on the PtRu electrode and from 0.66 to 0.52 V on the Pt electrode, respectively. A low apparent activation energy of 16 kJ/mol for the MOR was found on PtRu at 0.45 to 0.55 V, which was smaller than that of 24 kJ/mol an Pt at 0.70 V.
机译:从减少使用的Pt电催化剂的量实现高性能的观点出发,直接甲醇燃料电池的高温操作是必不可少的。应用间隙为0.1 mm的薄层流通池在1 M CH_3OH中从20到120摄氏度的宽温度范围内评估PtRu(46%原子百分比的Ru)合金和Pt电极对甲醇氧化反应(MOR)的活性+在加压操作下的0.1 M HclO_4溶液。稳定的电催化活性可以通过线性电位扫描伏安法在一定的电解液流速(> 0.2mLl / s)下进行评估,从而消除了在邻近的​​反阴极产生的氢的氧化电流的影响。发作电位[vs.可逆氢电极(RHE)]随温度升高,MOR线性地移动到较小的正电位,例如,PtRu电极上的0.45 V(在20℃时)到0.34 V(在120℃时),从0.66到0.52 V在铂电极上。在0.45至0.55 V的PtRu上发现MOR的表观活化能很低,为16 kJ / mol,比在0.70 V的PtRu的表观活化能低24 kJ / mol。

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