Characterization of Ni/N-rGO catalyst and study on the hydrogenation performance of phenol
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摘要: 以325目鳞片石墨为原料，采用改进Hummers法合成氧化石墨(GO)，再以尿素为氮源，通过水热法制备了氮掺杂还原氧化石墨烯(N-rGO)载体，然后通过浸渍法制备出负载型Ni/N-rGO催化剂。通过N2吸附-脱附、XRD、SEM、H2-TPR等测试方法对所制备的催化剂进行表征分析。以苯酚选择性加氢制备环己酮为反应体系，在反应温度150 ℃、压力0.4 MPa、时间2.0 h的条件下，对比了N-rGO、还原氧化石墨烯(rGO)、活性炭(AC)等载体负载Ni催化剂的加氢性能。结果表明，N-rGO载体不但具有较大的比表面积和适宜的孔结构，而且N-rGO和金属镍之间有较好的协同作用，Ni/N-rGO催化剂展现出优异的催化活性和选择性。Abstract: Using 325 mesh flake graphite as raw material, graphite oxide (GO) was synthesized by improved Hummers method. Nitrogen-doped reduced graphene oxide (N-rGO) carrier was prepared by hydrothermal method using urea as nitrogen source, and then supported Ni/N-rGO catalyst was prepared by impregnation method. The prepared catalysts were characterized and analyzed by N2 adsorption-desorption, XRD, SEM, H2-TPR and other methods. The hydrogenation performance of Ni catalysts supported by N-rGO, reduced graphene oxide (rGO) and activated carbon (AC) were compared under the reaction conditions of 150 ℃, 0.4 MPa and 2.0 h with selective hydrogenation of phenol to cyclohexanone as probe reaction. The results show that the N-rGO support not only has a large specific surface area and suitable pore structure, but also has good synergistic effect with nickel metal, and the Ni/N-rGO catalyst thus shows excellent catalytic activity and selectivity.
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Key words:
- N-rGO carrier /
- catalytic hydrogenation /
- phenol /
- cyclohexanone /
- reaction mechanism
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图 1 GO、rGO、N(X)-rGO的FT-IR谱图
Figure 1 FT-IR spectra of GO, rGO and N(X)-rGO
a: GO; b: rGO; c: N(10)-rGO; d: N(20)-rGO; e: N(30)-rGO; f: N(40)-rGO; g: N(50)-rGO
图 2 N-rGO和Ni/N-rGO的N2吸附-脱附等温线及孔径分布
Figure 2 N2 adsorption-desorption isotherms and pore size distributions of N-rGO and Ni/N-rGO
图 4 GO、rGO、N-rGO、Ni/GO、Ni/rGO、Ni/N-rGO的SEM照片
Figure 4 SEM images of GO, rGO, N-rGO, Ni/GO, Ni/rGONi/N-rGO
(a): GO; (b): rGO; (c): N-rGO; (d): 20%Ni/GO; (e): 20%Ni/rGO; (f): 20%Ni/ N-rGO
图 5 系列镍基催化剂的H2-TPR谱图
Figure 5 H2-TPR patterns of series nickel-based catalysts
a: 20%Ni/rGO; b: 10%Ni/N-rGO; c: 20%Ni/N-rGO; d: 30%Ni/N-rGO
图 6 Ni/N-rGO催化苯酚加氢的可能机理图
Figure 6 Ni/N-rGO the possible mechanism of catalytic phenol hydrogenation
表 1 各催化剂的物理结构性质
Table 1 Physical structural properties of each catalyst
Sample Specific surface
area/（m2·g−1）Average pore size/nm Pore volume
/（cm3·g−1）GO 70 2.0 0.03 N-rGO 352 4.8 0.42 rGO 315 4.5 0.40 AC 483 1.9 0.33 Ni/N-rGO 273 5.4 0.37 Ni/rGO 215 5.1 0.35 Ni/AC 348 2.1 0.27 
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表 2 不同镍基催化剂的活性和选择性
Table 2 Activity and selectivity of different nickel-based catalysts
Sample Phenol conversion rate/% Cyclohexanone selectivity/% rGO 48.1 30.6 N(30)-rGO 59.7 39.9 10%Ni/N(30)-rGO 81.2 47.3 20%Ni/N(30)-rGO 91.9 61.8 30%Ni/N(30)-rGO 86.2 55.2 20%Ni/rGO 82.7 45.4 20%Ni/AC 67.2 32.6
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