Catalytic performance of bimetallic PtCo supported on nanosheets MoS2 in aqueous-phase reforming of methanol to hydrogen
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摘要: 采用水热法合成了层数只有六层的纳米片层二硫化钼（MoS2），并进一步负载Pt和PtM双金属（M=Ru、Pd、Co和Ni），用于催化甲醇水相重整制氢反应。结果表明，PtCo/MoS2对于甲醇水相重整具有最优异的催化性能，在220℃下产氢转换频率（TOF）为37142 h-1。氮气吸附-脱附等温线、透射电子显微镜（TEM）、程序升温还原（H2-TPR）以及X射线光电子能谱（XPS）等表征结果表明，PtCo/MoS2中金属还原程度高，且Pt与载体MoS2形成了强电子相互作用，使缺电子的Pt有利于吸附活化甲醇，并进一步促进甲醇重整反应。Abstract: Nanosheets MoS2 with only 6 layers have been successfully synthesized by hydrothermal method and used as support to prepare a series of Pt and PtM (M=Ru, Pd, Co and Ni) bimetallic catalysts for low temperature aqueous-phase reforming of methanol (APRM) to produce hydrogen. Among those catalysts, PtCo supported on MoS2 nanosheets catalyst exhibited the best performance, and its turnover frequency (TOF) of H2 formation reached 37142 h-1 at 220℃. The N2 adsorption-desorption, TEM, H2-TPR and XPS results showed that PtCo/MoS2 performed the highest reduction degree, and the strong electronic interaction between Pt and MoS2 enhanced the adsorption and activation of methanol on the electron-deficient Pt, thus promoted the methanol reforming.
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图 1 (a) 纳米片层MoS2的XRD谱图；(b)纳米片层MoS2的SEM照片；(c)纳米片层MoS2的TEM照片
Figure 1 (a) XRD patterns of the nanosheets MoS2; (b) SEM image of the nanosheets MoS2; (c) TEM image of the nanosheets MoS2
图 2 纳米片层MoS2负载双金属催化剂的XRD谱图
Figure 2 XRD patterns of the nanosheets MoS2 supported bimetallic catalysts
图 3 纳米片层MoS2负载双金属催化剂的TEM照片
Figure 3 TEM images of the nanosheets MoS2 supported bimetallic catalysts
(a): PtRu/MoS2; (b): PtPd/MoS2; (c): PtCo/MoS2; (d): PtNi/MoS2
图 4 纳米片层MoS2负载双金属催化剂的H2-TPR谱图
Figure 4 H2-TPR profiles of the nanosheets MoS2 supported bimetallic catalysts
图 5 纳米片层MoS2负载双金属催化剂中Pt 4f的XPS谱图
Figure 5 Pt 4f XPS profiles of the nanosheets MoS2 supported bimetallic catalysts
表 1 不同金属催化剂的催化性能及反应条件的优化
Table 1 Performance of the catalysts under the optimized reaction conditions
Entry Catalyst Pt loading w/% ABET /(m2·g-1) Temperature t/ ℃ TOF (mol H2 per mol Pt per hour) NaOH m/g 1 Pt/MoS2 0.2 37.2 190 860 0.0 2 Pd/MoS2 0.2 - 190 23 0.0 3 Ru/MoS2 0.2 - 190 701 0.0 4 Pt/MoS2 0.2 37.2 220 3054 0.0 5 Pt/MoS2 0.2 37.2 220 8057 0.1 6 Pt/MoS2 0.2 37.2 220 11217 0.3 reaction conditions: 1 h, 0.1 g catalyst, 15 g mixture of methanol and water(n(CH3OH):n(H2O)=1:3), 2 MPa N2 
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表 2 纳米片层MoS2负载双金属催化剂的性能评价
Table 2 Evaluation results of nanosheets MoS2 supported catalysts with different bimetal loadings
Entry Catalyst ABET/ (m2·g-1) Temperature t/℃ TOF (mol H2 per mol Pt per hour) 1 PtRu/MoS2 27.0 220 23360 2 PtPd/MoS2 24.5 220 18162 3 PtCo/MoS2 26.7 220 37142 4 PtNi/MoS2 26.1 220 17800 reaction conditions: 1 h, 0.1 g catalyst, 15 g mixture of methanol and water(n(CH3OH):n(H2O) =1:3), 2 MPa N2
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