Study on catalytic combustion of chlorobenzene over TiO2-supported V-W composite bimetallic catalysts
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摘要: 本研究采用等体积浸渍法制备了一系列TiO2负载V-W双金属氧化物催化剂，考察了V/W比例对于氯苯催化燃烧活性和HCl选择性的影响。结果表明，适量W的掺杂（5V5W-Ti 和3V7W-Ti）提高了氯苯催化燃烧活性和HCl选择性。结合BET、XRD、XPS、H2-TPR、NH3-TPD和Py-FTIR等表征，说明其高的活性是由于其高活性组分分散度和丰富的催化剂表面吸附氧；适量W的掺杂显著增强了催化剂表面酸性，尤其是强酸和Brønsted酸，从而提高了产物中HCl的选择性。Abstract: A series of TiO2-supported V-W bimetallic catalysts were prepared by incipient wetness impregnation method. The effects of V/W ratios on the catalytic combustion performance for chlorobenzene were investigated. The results showed that proper W doping (5V5W-Ti and 3V7W-Ti) improved the catalytic combustion activity of chlorobenzene and the selectivity of HCl. In combination with BET, XRD, XPS, H2-TPR, NH3-TPD and Py-FTIR characterizations, it indicated that higher activity for chlorobenzene oxidation was attributed to the high dispersion of the active species and the abundant surface adsorbed oxygen. In addition, moderate doping of W significantly enhanced the surface acidity of catalysts, especially strong acids and Brønsted acids, and thus improved the selectivity to HCl in the products.
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Key words:
- chlorobenzene /
- catalytic combustion /
- bimetallic catalysts /
- selectivity to HCl
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图 1 xV(10−x)W-Ti催化剂的XRD谱图
Figure 1 XRD patterns of xV(10−x )W-Ti catalysts ( x =1, 3, 5, 9 and 10)
图 2 xV(10−x)W-Ti催化剂的H2-TPR谱图
Figure 2 H2-TPR profiles of xV(10−x )W-Ti catalysts ( x =1, 3, 5, 9 and 10)
图 3 xV(10−x)W-Ti催化剂的NH3-TPD谱图
Figure 3 NH3-TPD profiles of xV(10−x)W-Ti catalysts ( x =1, 3, 5, 9 and 10)
图 4 10V-Ti、5V5W-Ti和1V9W-Ti催化剂的Py-FTIR谱图
Figure 4 Py-FTIR profiles of 10V-Ti, 5V5W-Ti and 1V9W-Ti catalysts
图 5 10V-Ti、5V5W-Ti和1V9W-Ti催化剂的(a) Ti 2p, (b) V 2p, (c) W 4f和(d) O 1s轨道的XPS谱图
Figure 5 XPS spectra of (a) Ti 2 p , (b) V 2 p, (c) W 4 f and (d) O 1 s for 10V-Ti, 5V5W-Ti and 1V9W-Ti catalysts
图 6 xV(10−x)W-Ti催化剂对（a）CB转化率和（b）HCl生成率的影响
Figure 6 Effect of xV(10−x)W-Ti catalysts on (a) CB conversion and (b) HCl production ( x =1, 3, 5, 9 and 10; GHSV=20000 h−1, CB=100 μg/mL)
图 7 （a）10V-Ti催化剂的氯苯催化氧化活性曲线；（b）分别在300和325 ℃下对10V-Ti催化剂进行长期稳定性实验
Figure 7 (a) Activity curve of chlorobenzene catalytic oxidation of 10V-Ti catalyst; (b) long-term stability of 10V-Ti catalyst at 300 and 325 ℃, respectively (GHSV=20000 h−1, CB=1000 μg/mL)
表 1 xV(10−x)W-Ti催化剂的比表面积和孔容
Table 1 Specific surface area and pore volume of xV(10−x)W-Ti catalysts ( x =1, 3, 5, 9 and 10)
Sample SBET/（m2·g−1） Pore volume/（mL·g−1） α-TiO2 89.73 0.26 10V-Ti 33.04 0.18 9V1W-Ti 54.71 0.16 5V5W-Ti 50.35 0.20 3V7W-Ti 51.96 0.22 1V9W-Ti 69.81 0.23 
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表 2 10V-Ti、5V5W-Ti和1V9W-Ti催化剂的酸量
Table 2 Acid amount of 10V-Ti, 5V5W-Ti and 1V9W-Ti catalysts
Sample B acid/ (μmol·g−1) L acid/ (μmol·g−1) Total acidity/ (μmol·g−1) 1V9W-Ti 51.03 28.29 79.32 5V5W-Ti 50.83 61.21 112.03 10V-Ti 14.26 59.37 73.63
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表 3 10V-Ti、5V5W-Ti和1V9W-Ti催化剂表面元素价态及不同氧物种含量
Table 3 Surface elemental valence states and oxygen species content of 10V-Ti, 5V5W-Ti and 1V9W-Ti catalysts
Sample V5+/(V5++V4+) Oβ/(Oα+Oβ+Oγ) Oγ/(Oα+Oβ+Oγ) 1V9W-Ti 0.65 0.14 0.06 5V5W-Ti 0.73 0.16 0.06 10V-Ti 0.64 0.12 0.05
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