Plasmon-enhanced photocatalytic selective hydrogenation of phenylacetylene over Ni/TiO2 catalysts
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摘要: 研究采用浸渍还原法制备了碳修饰的二氧化钛负载的Ni纳米颗粒催化剂，在苯乙炔选择性加氢反应中表现出良好的光催化性能。Ni纳米颗粒在可见光激发下产生高能“热电子”促进了反应底物的解离和活化。富电子态的Ni纳米颗粒抑制了苯乙烯在Ni/TiO2表面的吸附，提高了苯乙烯的选择性。本工作为光催化苯乙炔选择性加氢反应提供了一种绿色且高效的方法。Abstract: It is a great challenge for the selective hydrogenation of phenylacetylene to styrene over non-noble metal catalyst under mild reaction conditions. Carbon-modified TiO2 supported nickel nanoparticles catalyst was prepared using impregnation-reduction method, which exhibited excellent photocatalytic performance in selective hydrogenation of phenylacetylene under visible light irradiation. The photo-excited hot electrons over Ni nanoparticles promoted the activation of reactants. The electron-rich Ni nanoparticles inhibit the adsorption of phenylethylene on the surface of Ni/TiO2, which increased the selectivity of phenylethylene. This work provides an environmentally-benign and efficient method for photocatalytic hydrogenation of phenylacetylene.
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Key words:
- Ni nanoparticles /
- phenylacetylene /
- photocatalysis /
- selective hydrogenation /
- hot electrons
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图 1 Ni/TiO2、Ni/Al2O3和Ni/SiO2催化剂的XRD谱图
Figure 1 XRD patterns of Ni/TiO2, Ni/Al2O3 and Ni/SiO2 catalyst
图 2 (a) Ni/TiO2的TEM照片, (b) Ni/TiO2的HRTEM照片和 (c) TiO2表面的碳物种
Figure 2 (a) TEM image of Ni/TiO2, (b) HRTEM image of Ni/TiO2 and (c) carbon species on the surface of TiO2
图 4 (a)Ni/TiO2、Ni/Al2O3和Ni/SiO2催化剂的Ni 2p XPS谱图 (b)Ni/TiO2和TiO2的Ti 2pXPS谱图
Figure 4 (a) Ni 2p XPS spectra of Ni/TiO2, Ni/Al2O3 and Ni/SiO2 catalyst and (b) Ti 2p XPS spectra of Ni/TiO2 and TiO2
图 6 催化剂的N2吸附-脱附等温线(a)和催化剂的孔径分布(b)
Figure 6 (a) N2 adsorption-desorption isotherms of catalysts and (b) pore size distribution lines ofcatalysts
图 7 (a)暗反应和(b)光反应苯乙炔选择性加氢反应动力学曲线
Figure 7 Kinetic curves for the selective hydrogenation of phenylacetylenein the dark (a) and under light irradiation (b)
图 8 光强、温度、波长对Ni/TiO2催化苯乙炔选择性加氢反应的影响及催化剂的循环稳定性
Figure 8 Effect of intensity (a), wavelength (b), reaction temperature (c) on catalytic activity of the selective hydrogenation of phenylacetylene and (d) catalytic stability of Ni/TiO2catalyst
图 9 苯乙炔和苯乙烯共吸附在Ni/TiO2催化剂上的原位DRIFTS谱图
Figure 9 In-situ DRIFTS of co-adsorption of phenylacetylene and styrene on the Ni/TiO2 catalyst
图 10 暗反应和光照条件下Ni/TiO2催化剂表面H2活化的原位漫反射傅里叶变换红外光谱谱图
Figure 10 DRIFTS of the H2 activation process over Ni/TiO2 catalyst in the dark and under visible light irradiation
图 11 可见光下Ni/TiO2催化苯乙炔选择性加氢的反应机理
Figure 11 Reaction mechanism for the selective hydrogenation of phenylacetylene to styrene over Ni/TiO2catalyst under visible light irradiation
表 1 不同样品的物理化学参数
Table 1 Physicochemical parameters of varioussamples
Entry Sample SBET /(m2·g−1) vPore /(cm3·g−1) dPore /nm 1 TiO2 82.30 0.35 15.21 2 Ni/TiO2 62.35 0.32 19.13 3 Al2O3 188.89 0.67 12.86 4 Ni/Al2O3 167.15 0.66 16.91 5 SiO2 170.55 0.71 21.05 6 Ni/SiO2 144.43 0.75 24.95 
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表 2 光催化苯乙炔选择性加氢活性
Table 2 Comparison of photocatalytic selective hydrogenation of phenylacetylene
Entry Catalyst Irradiation Time /h Con. /% Sel. /% 1a 1.5% Ni/TiO2 light 5 33.2 97.6 dark 5 − − 2 a 3.0% Ni/TiO2 light 5 70.7 98.0 dark 5 5.3 96.1 3 a 4.5% Ni/TiO2 light 5 87.6 97.5 dark 5 12.1 96.4 4 a 5.5% Ni/TiO2 light 5 62.2 98.4 dark 5 7.1 95.9 5 Ni/Al2O3 light 6 39.7 93.0 dark 6 6.9 95.8 6 Ni/SiO2 light 6 7.9 96.0 dark 6 3.1 99.9 7 a TiO2 light 5 − − 8b no catalyst light 5 − − 9c 4.5% Ni/TiO2 light 5 − − 10d Ni/TiO2 light 4 66.9 98.2 11e 4.5% Ni/TiO2 light 3 81.9 98.6 dark 3 48.7 99.9 a: Reaction conditions: phenylacetylene (0.1 mmol), catalyst (20 mg), isopropanol (2 mL), H2 (1 atm), 60 ℃, 5 h, LED lamp (wavelength 430−720 nm, light intensity 0.5 W/cm2); b: Without catalyst; c: Ar (1 atm); d: Prepared using Ni(OH)2 as precursor; e A mixture of phenylacetylene (0.05 mmol) and styrene (0.05 mmol) was used as reactant
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表 3 Ni基催化剂在苯乙炔选择性加氢中的性能
Table 3 Performance comparison of various Ni based catalysts for the selective hydrogenation of phenylacetylene
Catalyst Solvent Phenylacetylene /mmol t /℃ p /MPa Con. /% Sel. /% Ref Ni NSs ethanol 1.0 50 0.1 98 89 [3] Ni/2D BP tetrahydrofuran/toluene (3∶1) 0.3 80 1.0 93.2 92.8 [26] Ni-fructose@SiO2-800 acetonitrile 1.0 110 1.0 − 88a [27] Ni/C-400-6 ethanol 10 50 1.0 >99 77.3 [28] Ni-CNFs(1)/MS 2-propanol 1.7 80 0.1 90.8 ~ 90 [29] H350-Ni/COF methanol 0.4 100 1.0 >99 85 [30] Ni2P/MZSM-5-2 ethanol 45.6 100 1.0 ~ 99 ~ 85 [31] Ni2P/Al2O3 2-propanol 9.1 100 0.3 98.6 88.2 [32] Ni2Si/SiO2 ethanol 10 80 1.0 79.0 87.7 [33] 450-NiSix ethanol 10 50 0.41 79.9 87.7 [34] NiCo0.09/ SiO2 ethanol 49.0 60 0.5 >99 88 [2] NiZn3/Al2O3 methanol 49.0 60 0.5 >99 92 [35] Pre-NiCu/MMO toluene 5.0 100 0.4 95.8 90.3 [23] Ni3Sn/MgAl2O4 hexane 1.0 40 0.5 >99 89 [36] Ni5Mg4Ga3-700 2-propanol 9.1 40 0.3 95.1 92.2 [37] Ni/TiO2 2-propanol 0.1 60 0.1 >99 93.5 this work
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