Effect of the metal-support interaction in the Cu/ZnO catalyst on its performance in the hydrogenation of furfural to furfuryl alcohol
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摘要: 采用共沉淀法制备了系列Cu/Zn比不同的Cu/ZnO催化剂,研究了Cu/Zn比与金属载体强相互作用(SMSI)的关系及其对糠醛气相加氢制糠醇催化反应性能的影响。XRD、H2-TPR、SEM、HRTEM和XPS等表征结果显示,Cu/ZnO催化剂中的金属载体强相互作用改变了催化剂的微观结构。ZnO载体对活性金属Cu颗粒具有不同程度的几何修饰,影响了Cu表面的电子状态。不同Cu/Zn比的Cu/ZnO催化剂的SMSI作用顺序为:20Cu/ZnO > 40Cu/ZnO > 60Cu/ZnO > 80Cu/ZnO。在同一反应条件下,20Cu/ZnO催化剂的糠醛转化率高于80%的时间仅为5 h,而60Cu/ZnO催化剂的糠醛转化率高于80%的时间可以达到28 h,表明适当的SMSI作用有利于提升Cu/ZnO催化剂在糠醛加氢反应中的稳定性,而过强的SMSI作用会抑制其催化活性。Abstract: A series of Cu/ZnO catalysts were prepared by the coprecipitation method and the effect of Cu/Zn ratio on the strong metal support interaction (SMSI) as well as its relation to the catalytic performance of Cu/ZnO in the gaseous hydrogenation of furfural to furfuryl alcohol was investigated. The H2-TPR, XRD, SEM, TEM and XPS characterization results reveal that there exists the SMSI effect in the Cu/ZnO catalyst that influences the catalyst microstructure. ZnO support, acting as a geometric modifier on the active metal Cu particles, has a significant influence on the electronic state of the surface Cu species. The strength of SMSI is related to the Cu/Zn ratio and the SMSI strength of various Cu/ZnO catalysts follows the order of 20Cu/ZnO > 40Cu/ZnO > 60Cu/ZnO > 80Cu/ZnO. Under the same reaction conditions, the lifetime of the 20Cu/ZnO catalyst with a furfural conversion of above 80% is only 5 h, in comparison with the lifetime of 28 h for the 60Cu/ZnO catalyst. That is, appropriate SMSI can enhance the stability of the Cu/ZnO catalyst in the hydrogenation of furfural to furfuryl alcohol, whereas excessive SMSI is detrimental to the catalyst activity.
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表 1 新鲜Cu/ZnO催化剂的物理化学性质
Table 1 Physicochemical properties of fresh Cu/ZnO catalysts
Catalyst SBETa/(m2·g−1) vtotala/(cm3·g−1) dporea/nm dCub/nm dparticlesb/nm dCud/nm DCud/% SCud/(m2·g−1) 20Cu/ZnO 22.9 0.14 24.1 9.3 25.0 8.3 12.1 13.1 40Cu/ZnO 42.5 0.17 18.8 10.6 26.0 13.6 7.4 15.9 60Cu/ZnO 28.5 0.17 24.2 14.4 28.0 21.0 4.8 15.4 80Cu/ZnO 24.2 0.18 24.3 20.2 29.0 16.3 6.1 26.5 a: Determined by nitrogen adsorption; b: Average Cu particle size was calculated using the Scherrer equation; c: Determined by TEM; d: Copper particle size, copper dispersion and exposed metallic copper surface area were determined using N2O-titration. 表 2 催化剂还原峰及酸量
Table 2 Reduction temperature and acidity distribution of different catalysts
Catalyst α β Relative area Acidity/
(mmol·g−1)Acid site density/
(mmol·m−2)t/℃ fraction/% t/℃ fraction/% 20Cu/ZnO 229.7 28.0 246.9 72.0 2765.8 0.059 0.0025 40Cu/ZnO 240.1 40.6 254.1 59.4 6349.5 0.197 0.0046 60Cu/ZnO 247.0 46.4 261.3 53.6 9424.3 0.113 0.0039 80Cu/ZnO 257.1 49.0 273.2 51.0 10944.3 0.072 0.0029 表 3 还原态Cu/ZnO催化剂表面金属物种在XPS中的分布
Table 3 Distribution of various metal species on the surface of reduced Cu/ZnO catalysts determined by XPS
Catalyst BE/eV KE/eV Cu0/ (Cu++ Cu0)a Cu 2p3/2 Zn 2p3/2 Cu+ Cu0 Zn2+ Zn0 20Cu/ZnO 932.4 1020.8 916.96 919.40 989.7 − 33.58% 40Cu/ZnO 932.3 1020.6 917.00 918.85 990.1 − 23.55% 60Cu/ZnO 932.4 1020.5 916.98 918.90 990.3 − 29.16% 80Cu/ZnO 932.5 1020.6 916.83 918.67 988.9 992.4 32.83% a: Ratio of Cu0 to (Cu++Cu0) was obtained by deconvolution of the Cu LMM spectra. 表 4 使用后Cu/ZnO催化剂的物理化学性质
Table 4 Physicochemical properties of the spent Cu/ZnO catalysts after the reaction test
Catalyst dCua/nm dparticles b/nm △wc/% 20Cu/ZnO-spent 5.2 24.22 5.6 40Cu/ZnO-spent 6.0 − 9.2 60Cu/ZnO-spent 14.4 − 9.2 80Cu/ZnO-spent 20.5 33.70 12.66 a: Average Cu particle size was calculated from the XRD patterns by using the Scherrer equation; b: Mean particle size was determined by TEM; c: The coke deposition was determined by TGA. -
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