Effect of metal support interaction in Cu/ZnO catalyst on the hydrogenation of furfural to furfuryl alcohol
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摘要: 本研究考察了共沉淀法制备的Cu/ZnO催化剂中Cu/Zn比例对金属载体强相互作用以及其催化糠醛气相加氢制糠醇反应性能的影响。XRD、H2-TPR、SEM、HRTEM、XPS表征结果表明，Cu/ZnO催化剂体系中存在金属载体强相互作用（SMSI），改变了催化剂的微观结构。ZnO载体对活性金属Cu颗粒形成了不同程度的几何修饰，影响了Cu表面电子状态。Cu/Zn比例影响催化剂SMSI作用，SMSI作用顺序是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，表明过强的SMSI作用会抑制催化剂的活性，适当的SMSI作用使Cu/ZnO催化剂在糠醛加氢反应中的稳定性得到提升。Abstract: Cu/ZnO catalysts were prepared by coprecipitation method and the effect of Cu/Zn ratio on the strong metal support interaction was investigated. The effect of SMSI on the performance of furfural hydrogenation to furfuryl alcohol was also studied. The Cu/ZnO catalysts were characterized by H2-TPR, XRD, SEM, TEM and XPS. The results showed that there is strong metal-support interaction (SMSI) in the Cu/ZnO catalyst, which changes the microstructure of the catalyst. ZnO support played the role of geometric modification on the active metal Cu particles, and it changed electronic state of the Cu on the surface. SMSI was affected by the change of Cu/Zn ratio, the order of SMSI action is 20Cu/ZnO> 40Cu/ZnO> 60Cu/ZnO> 80Cu/ZnO. Under the same reaction conditions, the furfural conversion rate of the 20Cu/ZnO was higher than 80% catalyst for only 5 h, while the time of the 60Cu/ZnO catalyst reached 28 h. The results show that the activity of the Cu/ZnO catalyst in the furfural hydrogenation reaction was inhibited by the over-strong SMSI action, and the stability of catalysts in the reaction was improved by appropriate SMSI effect.
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图 1 催化剂（a）焙烧后（b）还原后的XRD谱图
Figure 1 XRD patterns of calcined catalysts (a) and reduced catalysts (b)
图 2 还原后催化剂的SEM和TEM图像
Figure 2 SEM images of reduced catalysts: (a, e) 20Cu/ZnO; (b, f) 40Cu/ZnO; (c, g) 60Cu/ZnO; (d, h) 80Cu/ZnO
图 4 催化剂的（a）H2-TPR （b）NH3-TPD谱图
Figure 4 (a)H2-TPR and (b)NH3-TPD profiles of catalysts
图 5 还原后催化剂的HRTEM图像
Figure 5 HRTEM images of reduced catalysts (a) 20Cu/ZnO; (b) 40Cu/ZnO; (c) 60Cu/ZnO; (d) 80Cu/ZnO
图 6 还原后催化剂的XPS谱图
Figure 6 XPS spectra of catalyst after reduction (a) Cu 2p; (b) Zn 2p; (c) Cu LMM; (d) Zn LMM
图 7 Cu/ZnO催化剂上（a）糠醛的转化率和（b）糠醇的选择性
Figure 7 The conversion of furfural (a) and the selectivity of furfuryl alcohol (b) over Cu/ZnO catalysts Reaction conditions: t=190 ℃, p=0.1 MPa, H2/FUR=9.7, WHSV=1.7 h−1.
图 8 使用10 h后Cu/ZnO催化剂的（(a)、(b)）TEM图像以及（c）XRD、（d）TG谱图
Figure 8 ((a)、(b))TEM images and (c)XRD、(d)TG spectra of used Cu/ZnO catalysts
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 dparticlesc/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. 
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表 2 催化剂还原峰及酸量
Table 2 Reduction and acidity distribution of different catalysts
Catalyst α峰 β峰 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
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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 metal species on the surface of reduced Cu/ZnO catalysts in XPS
Catalysts BE/eV KE/eV KE/eV x(Cu0)a/% Cu 2p3/2 Zn 2p3/2 Cu+ Cu0 Zn2+ Zn0 Cu0/ (Cu++ Cu0) 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) obtained by deconvolution of Cu LMM spectra.
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表 4 使用后Cu/ZnO催化剂的物理化学性质
Table 4 Physicochemical properties of used Cu/ZnO catalysts
Catalyst dCua/nm dparticles b/nm △Wc/% 20Cu/ZnO-ed 5.2 24.22 5.6 40Cu/ZnO-ed 6.0 − 9.2 60Cu/ZnO-ed 14.4 − 9.2 80Cu/ZnO-ed 20.5 33.70 12.66 a: Average Cu particle size was calculated using the Scherrer equation; b: Determined by TEM; c: Determined by TG.
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