Boron-functionalized reduced graphene oxide as carbocatalysts with enhanced activity for hydrogenation of anthracene
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摘要: 制备了一系列硼掺杂的还原氧化态石墨烯催化剂并应用于蒽加氢反应。结果表明，随着催化剂处理温度的升高，催化剂中有序碳结构会发生变化，硼会取代材料骨架中的碳，进而影响蒽和氢气的吸附活化。经硼改性后，催化剂对蒽加氢反应表现出了很高的加氢活性，蒽的最高转化率可达97%，深度加氢产物八氢蒽的最高选择性可达19%。Abstract: A series of boron doped reduced graphene oxide catalysts were prepared and applied to anthracene hydrogenation. The results show that, with the change of the treatment temperature of the catalyst, the ordered carbon structure in the catalyst changed and boron replaced the carbon in the material skeleton, which affected the adsorption and activation of anthracene and hydrogen. After boron doping, the catalyst showed higher activity for anthracene hydrogenation reaction, the highest conversion of anthracene was up to 97%, and the highest selectivity of deep hydrogenation product octahydroanthracene was up to 19%.
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Key words:
- reduced graphene oxide /
- boron doped /
- anthracene hydrogenation
1) #:共同第一作者 -
图 1 催化剂的SEM照片和EDX图片：BrGO650 (a)、BrGO800 (b)、BrGO900 (c)、BrGO1000 (d)和BrGO1100 (e)
Figure 1 SEM images and EDX pictures of BrGO650 (a), BrGO800 (b), BrGO900 (c), BrGO1000 (d) and BrGO1100 (e)
图 2 催化剂BrGO650 (a)、BrGO800 (b)、BrGO900 (c)、BrGO1000 (d)和BrGO1100 (e)的TEM、SAED照片，BrGO650 (a1)、BrGO800 (b1)、BrGO900 (c1)、BrGO1000 (d1)和BrGO1100 (e1)的HRTEM照片
Figure 2 TEM and the SAED images of BrGO650 (a), BrGO800 (b), BrGO900 (c), BrGO1000 (d), BrGO1100 (e) and HRTEM images of BrGO650 (a1), BrGO800 (b1), BrGO900 (c1), BrGO1000 (d1), BrGO1100 (e1)
图 3 催化剂BrGO650、BrGO800、BrGO900、BrGO1000和BrGO1100的XRD谱图
Figure 3 XRD patterns of BrGO650, BrGO800, BrGO900, BrGO1000 and BrGO1100
图 4 催化剂BrGO650、BrGO800、BrGO900、BrGO1000和BrGO1100的拉曼光谱谱图
Figure 4 Raman spectra of BrGO650, BrGO800, BrGO900, BrGO1000 and BrGO1100
图 5 催化剂BrGO650、BrGO800、BrGO900、BrGO1000和BrGO1100的XPS谱图(a)和C 1s高分辨图(b)
Figure 5 XPS spectra (a) and high resolution C 1s XPS spectra (b) of BrGO650, BrGO800, BrGO900, BrGO1000, and BrGO1100
图 6 催化剂BrGO650 (a)、BrGO800 (b)、BrGO900 (c)、BrGO1000 (d)和BrGO1100 (e)的C 1s分峰拟合谱图
Figure 6 C 1s spectra of BrGO650 (a), BrGO800 (b), BrGO900 (c), BrGO1000 (d) and BrGO1100 (e)
图 7 催化剂BrGO650 (a)、BrGO800 (b)、BrGO900 (c)、BrGO1000 (d)和BrGO1100 (e)的B 1s分峰拟合谱图
Figure 7 B 1s spectra of BrGO650 (a), BrGO800 (b), BrGO900 (c), BrGO1000 (d) and BrGO1100 (e)
图 8 催化剂BrGO650、BrGO800、BrGO900、BrGO1000和BrGO1100的FT-IR谱图
Figure 8 FT-IR spectra of BrGO650, BrGO800, BrGO900, BrGO1000, and BrGO1100
图 9 催化剂BrGO650、BrGO800、BrGO900、BrGO1000和BrGO1100的蒽转化率和产物选择性
Figure 9 Anthracene conversion and products distribution over BrGO650, BrGO800, BrGO900, BrGO1000 and BrGO1100
reaction conditions: t=350 ℃, pH2=4 MPa, H2/feed=600(cm3/cm3), LHSV=2.5 h-1
图 10 催化剂BrGO650、BrGO800、BrGO900、BrGO1000、BrGO1100、rGO450、rGO650、rGO900、rGO1100的氢转移能力
Figure 10 Hydrogen transfer capability over BrGO650 (■), BrGO800 (●), BrGO900 (▲), BrGO1000 (▼), BrGO1100 (◆), rGO450 ($ \triangleright $), rGO650 (□), rGO900 (△) and rGO1100 (◇)
表 1 XPS中催化剂表面C、B、O的相对含量和拉曼中催化剂的D/G面积比
Table 1 Surface species concentration of C, B, O from XPS and the area ratio (D/G) from Raman
Sample Content wat/% D/G C B O BrGO650 71.70 9.27 19.03 2.21 BrGO800 82.51 5.31 12.18 2.29 BrGO900 81.74 6.41 11.85 2.36 BrGO1000 82.27 6.92 10.81 2.42 BrGO1100 82.58 7.11 10.31 2.27 
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表 2 催化剂BrGO650、BrGO800、BrGO900、BrGO1000和BrGO1100的表面C 1s和B 1s物种的种类及相对含量
Table 2 Relative surface concentration of carbon species and boron species obtained by fitting the C 1s and B 1s spectra for all samples
Samples Fitting of C 1s peak
(relative atomic percentage /%)Fitting of B 1s peak
(relative atomic percentage /%)C-C C-B C-O-C C=O BC3 BC2O BCO2 B2O3 BrGO650 33.31 34.15 18.71 13.83 - - - 100 BrGO800 33.79 41.91 12.59 11.70 - - 15.77 84.23 BrGO900 32.33 43.35 10.01 14.31 - 3.47 17.73 78.80 BrGO1000 36.51 41.14 7.87 14.48 0.26 3.62 23.68 72.44 BrGO1100 38.31 39.94 7.13 14.61 3.41 3.70 24.08 68.81
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