Effect of calcination temperature of LaNiO3 on CuO/LaNiO3 catalyst for hydrogen production via methanol steam reforming
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摘要: 采用溶胶凝胶法合成了LaNiO3钙钛矿型氧化物载体，再采用浸渍法制备了CuO/LaNiO3催化剂，并通过XRF、XRD、BET、H2-TPR和XPS等手段对催化剂进行了表征，考察了LaNiO3钙钛矿的焙烧温度对CuO/LaNiO3催化剂结构及其催化甲醇水蒸气重整制氢性能的影响。结果表明，载体焙烧温度主要影响了催化剂的表面晶格氧缺位，活性组分和载体间的相互作用。当载体焙烧温度为800℃时，催化剂表面氧空穴较多，活性组分与载体间相互作用较强，因此，催化甲醇水蒸气重整制氢活性较好。Abstract: The LaNiO3 perovskite support was synthesized by sol-gel method. The CuO/LaNiO3 catalyst was prepared by impregnation method. The catalyst was characterized by XRF, XRD, BET, H2-TPR and XPS. The effect of calcination temperature of LaNiO3 perovskite on the structure of CuO/LaNiO3 catalyst and its catalytic performance for methanol steam reforming were investigated. The results show that the calcination temperature of the support mainly affects the surface oxygen vacancy of the catalyst, the interaction between the active component and the support. When the calcination temperature of the support is 800℃, the surface of the catalyst has more oxygen vacancy, and the interaction between the active component and the support is stronger. Therefore, the hydrogenation activity of methanol steam reforming is higher.
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Key words:
- perovskite /
- methanol steam reforming /
- hydrogen /
- calcination temperature
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图 1 不同焙烧温度下制备的钙钛矿载体的XRD谱图
Figure 1 XRD patterns of the perovskite support prepared at different calcination temperatures
a: LaNiO3-600; b: LaNiO3-700; c: LaNiO3-800; d: LaNiO3-900
■: La2O3; : ▼: NiO; Δ: La2NiO4; ▲: La2Ni2O5; ◆: perovskite
图 2 不同焙烧温度下制备的LaNiO3钙钛矿催化材料的XRD谱图
Figure 2 XRD patterns of the LaNiO3 perovskite catalytic materials prepared at different calcination temperatures
a: CuO/LaNiO3-600; b: CuO/LaNiO3-700; c: CuO/LaNiO3-800; d: CuO/LaNiO3-900
●: CuO; ▼: NiO; ■: La2O3; Δ: La2NiO4; ▲: La2Ni2O5; ◆: perovskite
图 3 不同焙烧温度下制备的CuO/LaNiO3-t催化剂的H2-TPR谱图
Figure 3 H2-TPR profiles of the CuO/LaNiO3-t catalysts prepared at different calcination temperatures
a: CuO/LaNiO3-600; b: CuO/LaNiO3-700; c: CuO/LaNiO3-800; d: CuO/LaNiO3-900
图 4 不同焙烧温度下制备的钙钛矿催化剂的La 3d的XPS谱图
Figure 4 XPS spectra of La 3d of the catalysts prepared at different calcination temperatures
a: CuO/LaNiO3-600; b: CuO/LaNiO3-700; c: CuO/LaNiO3-800; d: CuO/LaNiO3-900
图 5 不同焙烧温度下制备的钙钛矿催化剂的Ni 2p的XPS谱图
Figure 5 XPS profiles of the Ni 2p of the perovskite catalyst prepared at different calcination temperatures
a: CuO/LaNiO3-600; b: CuO/LaNiO3-700; c: CuO/LaNiO3-800; d: CuO/LaNiO3-900
图 6 不同焙烧温度下制备的钙钛矿催化剂的Cu 2p的XPS谱图
Figure 6 XPS spectra of Cu 2p of the perovskite catalysts prepared at different calcination temperatures
a: CuO/LaNiO3-600; b: CuO/LaNiO3-700; c: CuO/LaNiO3-800; d: CuO/LaNiO3-900
图 7 不同焙烧温度下制备的钙钛矿催化剂的Cu俄歇谱图
Figure 7 Cu Auger spectra of the perovskite catalysts prepared at different calcination temperatures
a: CuO/LaNiO3-600; b: CuO/LaNiO3-700; c: CuO/LaNiO3-800; d: CuO/LaNiO3-900
图 8 不同焙烧温度下制备钙钛矿催化剂的O 1s的XPS谱图
Figure 8 XPS spectra of O 1s of the perovskite catalysts prepared at different calcination temperatures
a: CuO/LaNiO3-600; b: CuO/LaNiO3-700; c: CuO/LaNiO3-800; d: CuO/LaNiO3-900
图 9 反应温度对催化剂活性的影响
Figure 9 Effects of the reaction temperature on the catalytic performance
(reaction conditions: atmospheric pressure, GHSV=800 h-1, W/M=1.2:1, no carrier gas)
a: CuO/LaNiO3-600; b: CuO/LaNiO3-700; c: CuO/LaNiO3-800; d: CuO/LaNiO3-900
图 10 反应温度对催化剂CO体积分数的影响
Figure 10 Effect of reaction temperature on the CO content in tail gas
(reaction conditions: atmospheric, GHSV=800 h-1, W/M=1.2:1, no carrier gas)
a: CuO/LaNiO3-600; b: CuO/LaNiO3-700; c: CuO/LaNiO3-800; d: CuO/LaNiO3-900表 1 不同焙烧温度下制备的钙钛矿催化材料的元素含量
Table 1 Elemental content of perovskite catalytic materials prepared at different calcination temperatures
Catalyst Content of element w/% Cu La Ni O CuO/LaNiO3-600 8.1 53.2 21.7 17.0 CuO/LaNiO3-700 8.2 50.0 24.4 17.4 CuO/LaNiO3-800 8.5 51.2 23.0 17.3 CuO/LaNiO3-900 8.3 50.1 24.3 17.3 Normal value 9.0 51.4 21.7 17.9 
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表 2 催化剂的物化性质及其用于催化甲醇水蒸气重整反应中氢气产率
Table 2 Physicochemical properties and catalytic performance of the catalysts
Catalyst ABET /(m2·g-1) Pore volume v/(cm3·g-1) Bore diameter d/nm dCuO /nm Cu surface areaa A/(m2·gcat-1) H2 production rateb /(cm3·kg-1·s-1) LaNiO3-600 11.5 0.03 3.86 - - - LaNiO3-700 7.9 0.03 3.36 - - - LaNiO3-800 7.4 0.02 3.06 - - - LaNiO3-900 5.3 0.01 3.37 - - - CuO/LaNiO3-600 12.4 0.04 3.79 26.1 0.8 218.0 CuO/LaNiO3-700 10.8 0.02 3.41 30.1 1.0 372.9 CuO/LaNiO3-800 7.5 0.02 3.03 20.2 1.2 1007.2 CuO/LaNiO3-900 7.6 0.02 3.85 23.6 1.1 491.6 a: determined by N2O experiments; b: reaction conditions: atmospheric pressure, 240 ℃, W/M=1.2:1, GHSV=800 h-1, no carrier gas
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表 3 不同焙烧温度下催化剂和O 1s XPS曲线拟合
Table 3 O 1s XPS curve-fitting results of the catalysts calcined at various temperatures
Catalyst Oads/(Oads+O-OH+Olatt) CuO/LaNiO3-600 0.20 CuO/LaNiO3-700 0.24 CuO/LaNiO3-800 0.31 CuO/LaNiO3-900 0.21
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