Effect of crystal structure of ZrO2 catalyst on isobutene synthesis from CO hydrogenation
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摘要:
不同晶型结构的ZrO2在CO加氢制异丁烯反应中表现出不同的催化性能。尽管单斜相ZrO2在合成气制异丁烯反应中具有最优异的催化性能，但是对于其异构化活性位仍缺乏深入认识。通过研究ZrO2晶型结构对反应性能的影响差异，有利于深入认识ZrO2催化剂上合成气制异丁烯反应的关键影响因素。因此，本研究制备了一系列不同晶型结构的ZrO2催化剂，研究了它们在结构性质及催化CO加氢制异丁烯反应性能方面的差异。相对于四方相和无定型ZrO2，在单斜相ZrO2催化剂表面，有较多的配位不饱和的Zr位点和O位点。配位不饱和的Zr位点是CO吸附活化的位点，有利于CO的转化。而较多的不饱和配位的O位点，为异丁烯的生成提供了更多的碱性位。此外，在单斜相ZrO2催化剂表面，配位不饱和的Zr位点和O位点的存在，抑制了电子向反应中生成的甲酸盐物种转移，因此，甲酸盐物种在催化剂表面吸附较弱，有利于CO加氢生成异丁烯。
Abstract:ZrO2 catalysts with different crystal structures show different catalytic performance in isobutene synthesis from CO hydrogenation reaction. Although monoclinic ZrO2 has the best catalytic performance in isobutene synthesis from syngas, its isosynthesis active sites are still not well understood. To better understand the critical parameters that influence syngas to isobutene reactions over ZrO2 catalysts, we prepared a series of ZrO2 catalysts with distinct crystal structures and investigated their catalytic performance of CO hydrogenation to isobutene. Compared with tetragonal and amorphous ZrO2 catalysts, there are more coordinatively unsaturated Zr and O sites on the surface of monoclinic ZrO2 catalyst. The coordinatively unsaturated Zr sites are the active sites of CO adsorption and activation, which is beneficial to CO conversion. The coordinatively unsaturated O sites provide more basic sites for isobutene formation. Furthermore, the coordinatively unsaturated Zr and O sites on monoclinic ZrO2 catalyst surface may inhibit electron transfer to formate species formed during reaction, resulting in weak adsorption on catalyst surface of formate species. The weakly adsorbed formate species on the surface of monoclinic ZrO2 catalyst is favorable for the synthesis of isobutene from CO hydrogenation reaction.
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Key words:
- CO hydrogenation /
- isobutene /
- ZrO2 /
- crystal structures
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图 1 不同晶型结构ZrO2催化剂的（a）XRD谱图和（b）Raman谱图
Figure 1 (a) XRD patterns and (b) Raman spectra of ZrO2 catalysts with varied crystal phase
图 2 不晶型结构ZrO2催化剂的NH3-TPD-MS谱图
Figure 2 NH3-TPD-MS patterns of ZrO2 catalysts with varied crystal phase
图 3 不同晶型结构ZrO2催化剂的CO2-TPD-MS谱图
Figure 3 CO2-TPD-MS patterns of ZrO2 catalysts with varied crystal phase
图 6 ZrO2样品（a）O 1s和（b）Zr 3d的XPS谱图
Figure 6 XPS spectra of (a) O 1s and (b) Zr 3d of the ZrO2 samples
图 7 不同晶型结构ZrO2样品在400 ℃，0.1 MPa下CO吸附30 min的红外光谱谱图
Figure 7 In-situ CO DRIFTS analysis of CO adsorption under atmosphere at 400 ℃ for 30 min on ZrO2 catalysts with varied crystal phase: (a) 4000–2500 cm−1; (b) 1800–1100 cm−1
表 1 不同晶型结构ZrO2催化剂上CO加氢制异丁烯催化性能a
Table 1 Catalytic performance of CO hydrogenation to isobutene over ZrO2 catalysts with different crystal phase a
Catalyst CO Conv.
/%bSel. Cmol/% Products distribution in CHn CHnb DME CO2 C1 ${\rm{C} }_{{2}}^=$ ${\rm{C}}_{{3}}^= $ ${ {n} }{\text{-} }{\rm{C} }_{{4} }^{= \;{\rm{c} } }$ ${ {i} }{\text{-} }{\rm{C} }_{{4} }^{= \;{\rm{c} } }$ C5 + m-ZrO2 31.9 32.1 3.9 64.0 3.3 8.6 (1.7) 3.0 (2.5) 3.6 (2.1)d 50.2 25.0 t-ZrO2 24.7 36.1 6.7 57.2 14.9 5.1 (5.0) 2.0 (2.7) 6.7 (3.1) 38.4 22.1 am-ZrO2 31.1 35.1 0.0 64.9 32.5 6.6 (12.4) 6.1 (4.7) 9.3 (7.9) 6.5 14.0 a: Reaction conditions: H2/CO=1, 400 ℃, 5.0 MPa, GHSV=430 h−1, catalysts were pretreated in a stream of H2/N2=1∶10 at 400 ℃ for 6 h before reaction;
b: CHn means the hydrocarbons products except for oxygenated chemicals and CO2;
c: ${{n}}{\text{-}}{\rm{C}}_{{4}}^{=} $ and ${{i}}{\text{-}}{\rm{C}}_{{4}}^{=} $ stand for the linear butenes and isobutene, respectively;
d: data in parentheses mean the selectivity of alkane (Cn) in total hydrocarbons
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表 2 不同晶型结构ZrO2样品的织构性质参数
Table 2 Textural properties of the resulting ZrO2 samples
Sample SBET/(m2∙g−1) a vpore/(cm3∙g−1) b dave/nm c m-ZrO2 125.6 0.26 8.2 t-ZrO2 85.8 0.09 4.3 am-ZrO2 215.0 0.16 3.1 a: BJH desorption cumulative surface area of pores between 1.7 and 300 nm width;
b: BJH desorption cumulative volume of pores between 1.7 and 300 nm width;
c: BJH desorption average pore width (4V/A)
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表 3 ZrO2样品的XPS拟合
Table 3 XPS fitting results of ZrO2 samples
Sample Binding energy /eV Area/% Zr 3d5/2 Zr 3d3/2 OLattice ODefect OOH OLattice ODefect OOH OLattice/
(ODefect + OOH)m-ZrO2 181.86 184.23 529.74 531.40 532.94 70.8 25.7 3.6 0.41 t-ZrO2 181.99 184.38 529.84 531.46 532.94 69.1 26.5 4.4 0.45 am-ZrO2 182.23 184.60 530.16 531.79 533.00 70.0 26.1 3.9 0.43
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