催化学报 ›› 2021, Vol. 42 ›› Issue (3): 470-481.DOI: 10.1016/S1872-2067(20)63678-6
谭媛a,b, 刘晓艳a,*(), 张磊磊a, 刘菲a, 王爱琴a, 张涛a,c
收稿日期:
2020-05-19
接受日期:
2020-06-23
出版日期:
2021-03-18
发布日期:
2021-01-23
通讯作者:
刘晓艳
基金资助:
Yuan Tana,b, Xiaoyan Liua,*(), Leilei Zhanga, Fei Liua, Aiqin Wanga, Tao Zhanga,c
Received:
2020-05-19
Accepted:
2020-06-23
Online:
2021-03-18
Published:
2021-01-23
Contact:
Xiaoyan Liu
About author:
*Tel:+86-411-84379416;Fax:+86-411-84691570; E-mail: xyliu2003@dicp.ac.cnSupported by:
摘要:
α,β-不饱和醛/酮选择加氢生成不饱和醇是化学工业中一类重要反应,在精细化工生产中具有广泛应用,近年来吸引了研究者的广泛关注. 该类反应因涉及不饱和官能团和碳氧双键的选择加氢而颇具挑战性: 以肉桂醛选择加氢生成肉桂醇反应为例,肉桂醛分子中同时含有共轭的C=C双键和C=O双键,从热力学角度上看,C=O双键键能比C=C双键键能大,因而碳碳双键比碳氧双键更容易被活化从而加氢得到饱和醛; 从动力学角度上看,C=C双键也比C=O双键更容易加氢. 对于传统的铂族贵金属催化剂,其应用于该类反应时往往存在选择性低,容易深度加氢等问题. 负载型金催化剂此前被报道在该类反应中表现出高选择性,然而在反应物接近完全转化时,目标产物也容易发生过度加氢生成饱和醇.
前期的研究结果发现用锌铝水滑石作载体,硫醇稳定的金原子团簇(Au25)作为金的前驱体制备负载型金催化剂时,其在不饱和芳香硝基化合物的选择加氢反应中表现出很高的选择性. 考虑到在肉桂醛分子中C=O双键的加氢相比于C=C双键更加困难,因此,本工作尝试将上述催化剂应用于以肉桂醛为代表的不饱和醛/酮选择加氢反应中. 考察了反应温度、氢气压力以及溶剂效应对反应活性的影响,结果发现升高温度或提高压力都能明显提升反应速率,然而不同的溶剂对催化性能影响很大,当以具备氢转移能力的异丙醇和乙醇作为反应溶剂时,催化活性和选择性最优,在反应温度为130oC,氢气压力为15 atm,异丙醇为溶剂时反应5 h,肉桂醛的转化率和肉桂醇的选择性可以达到98.3%和95.4%,并且延长反应时间至15 h,目标产物也不会发生过度加氢生成苯丙醇,其选择性可以维持在95%以上.
为了研究该催化剂高活性和高选择性的原因,制备了不同粒径大小和不同载体负载的金催化剂,结果发现相比于其它负载型金催化剂,以锌铝水滑石负载的Au25团簇作为催化剂前体制得的催化剂在肉桂醛选择加氢制肉桂醇反应中表现出最优的活性和选择性. 对照实验和原位漫反射红外光谱测试表明上述催化剂对碳碳双键的加氢表现为惰性,对目标产物的吸附也相对较弱.27Al固体核磁共振结果表明配位不饱和的五配位Alp物种可能为C=O双键的优先吸附提供所需的氧空位,这可能是该催化剂具有较高选择性的原因. 综上,推测小尺寸的金颗粒具有较多低配位的金原子,可以活化氢气,而反应物和产物的吸脱附性质与载体密切相关,在以锌铝水滑石为前驱体制备的金催化剂表面,C=C双键吸附较弱,C=O双键优先吸附,产物较容易脱附,不容易发生过度加氢反应,因此该催化剂在肉桂醛选择加氢反应中表现出高活性和高选择性. 上述工作可以为设计制备高选择性的负载型金催化剂提供参考.
谭媛, 刘晓艳, 张磊磊, 刘菲, 王爱琴, 张涛. 纳米金催化肉桂醛选择加氢制肉桂醇[J]. 催化学报, 2021, 42(3): 470-481.
Yuan Tan, Xiaoyan Liu, Leilei Zhang, Fei Liu, Aiqin Wang, Tao Zhang. Producing of cinnamyl alcohol from cinnamaldehyde over supported gold nanocatalyst[J]. Chinese Journal of Catalysis, 2021, 42(3): 470-481.
Fig. 3. The catalytic performances over the 1.0% Au25/ZnAl-300 catalyst with different solvents. Reaction conditions: cinnamaldehyde 0.25 mmol,catalyst 50 mg (Au 1.0 mol%),H2 pressure 15 atm,130 °C,5 h.
Entry | Catalyst | Size (nm) | Conv. (%) | Sel. (%) | ||||
---|---|---|---|---|---|---|---|---|
COL | HCAL | HCOL | ||||||
1 | 1.1%Au25/ZnAl-300 | 1.7 b | 98.3 | 95.4 | 0 | 4.5 | ||
2 | 1.0%Au25/MgAl-300 | 2.2 b | 99.2 | 39.5 | 13.6 | 38.4 | ||
3 | 1.0%Au25/NiAl-300 | 3.2 b | 100 | 0 | 0 | 86.7 | ||
4 | 1.0%Au/ZnAl-300(DP) a | 2.6 b | 61.5 | 85.9 | 3.7 | 3.6 | ||
5 | 1.0%Au/ZrO2 c | 3.3 | 75.7 | 50.0 | 17.3 | 16.8 | ||
6 | 0.8%Au/Fe2O3 c | 1.8 | 93.0 | 45.4 | 4.9 | 3.6 | ||
7 | 1.5%Au/TiO2 d | 4.1 | 51.9 | 14.6 | 0 | 0 | ||
8 | 1.1%Au25/ZnAl-HT | 1.4 | 26.8 | 43.6 | 1.6 | 0 | ||
9 | ZnAl-300 | — | 9.6 | 23.9 | 3.1 | 0 | ||
10 | 1.1%Au25/ZnAl-300 e | 1.7 | 28.4 | 35.2 | 0 | 0 |
Table 1 Catalytic results for the hydrogenation of CAL over the gold catalysts in this work.
Entry | Catalyst | Size (nm) | Conv. (%) | Sel. (%) | ||||
---|---|---|---|---|---|---|---|---|
COL | HCAL | HCOL | ||||||
1 | 1.1%Au25/ZnAl-300 | 1.7 b | 98.3 | 95.4 | 0 | 4.5 | ||
2 | 1.0%Au25/MgAl-300 | 2.2 b | 99.2 | 39.5 | 13.6 | 38.4 | ||
3 | 1.0%Au25/NiAl-300 | 3.2 b | 100 | 0 | 0 | 86.7 | ||
4 | 1.0%Au/ZnAl-300(DP) a | 2.6 b | 61.5 | 85.9 | 3.7 | 3.6 | ||
5 | 1.0%Au/ZrO2 c | 3.3 | 75.7 | 50.0 | 17.3 | 16.8 | ||
6 | 0.8%Au/Fe2O3 c | 1.8 | 93.0 | 45.4 | 4.9 | 3.6 | ||
7 | 1.5%Au/TiO2 d | 4.1 | 51.9 | 14.6 | 0 | 0 | ||
8 | 1.1%Au25/ZnAl-HT | 1.4 | 26.8 | 43.6 | 1.6 | 0 | ||
9 | ZnAl-300 | — | 9.6 | 23.9 | 3.1 | 0 | ||
10 | 1.1%Au25/ZnAl-300 e | 1.7 | 28.4 | 35.2 | 0 | 0 |
Fig. 4. Time courses of the yield of cinnamaldehyde and cinnamyl alcohol over the Au25/ZnAl-300 catalyst. Reactions conditions: 130 °C,H2 15 atm,isopropanol as the solvent,cinnamaldehyde 0.25 mmol.
Catalyst | Reaction conditions | Conv. (%) | Sel. (%) | Ref. | ||||
---|---|---|---|---|---|---|---|---|
Solvent | Au (mol%) | Tem. (°C) | PH2 (MPa) | t (h) | ||||
Au25/ZnAl-300 | isopropanol | 1.0 | 130 | 1.5 | 5 15 | 98.3 100 | 95.4 95.7 | This work |
Au/ZnO-CP | isopropanol | 1.0 | 110 | 2 | 0.8 | 100 | ~92 | [ |
Au/MgAlO | ethanol | 2.4 | 120 | 1 | 5 | 96 | 40 | [ |
Au/meso-CeO2 | H2O/ethanol | 1.0 | 100 | 1 | 0.5 | 48 | 97 | [ |
Au25/Fe2O3 Au25/TiO2 | toluene/ethanol | 5.1 | 0 | 0.1 | 3 | 49 46 | 100 100 | [ |
Au/DMF | amide | 1.0 | 60 | 4 | 56 | 94 | 94 | [ |
Au/Mg2AlO | ethanol | 0.2 | 120 | 1 | 2 | 78 | 85 | [ |
Au/5FeAl Au/HDAE | isopropanol | 0.7 0.6 | 100 | 1 | 3 | 20 28 | 67 88 | [ |
Au/TiO2 | ethanol | 6.3 | 60 | 0.1 | — | 50 | 47 | [ |
Au/FeOOH | ethanol | 14.8 | 60 | 0.1 | — | 50 | 91 | [ |
Au/Al2O3 | ethanol | 0.1 | 100 | 8.5 | 2.8 | 94 | 89 | [ |
Table 2 Catalytic results reported recently for hydrogenation of CAL to COL over the supported gold catalysts.
Catalyst | Reaction conditions | Conv. (%) | Sel. (%) | Ref. | ||||
---|---|---|---|---|---|---|---|---|
Solvent | Au (mol%) | Tem. (°C) | PH2 (MPa) | t (h) | ||||
Au25/ZnAl-300 | isopropanol | 1.0 | 130 | 1.5 | 5 15 | 98.3 100 | 95.4 95.7 | This work |
Au/ZnO-CP | isopropanol | 1.0 | 110 | 2 | 0.8 | 100 | ~92 | [ |
Au/MgAlO | ethanol | 2.4 | 120 | 1 | 5 | 96 | 40 | [ |
Au/meso-CeO2 | H2O/ethanol | 1.0 | 100 | 1 | 0.5 | 48 | 97 | [ |
Au25/Fe2O3 Au25/TiO2 | toluene/ethanol | 5.1 | 0 | 0.1 | 3 | 49 46 | 100 100 | [ |
Au/DMF | amide | 1.0 | 60 | 4 | 56 | 94 | 94 | [ |
Au/Mg2AlO | ethanol | 0.2 | 120 | 1 | 2 | 78 | 85 | [ |
Au/5FeAl Au/HDAE | isopropanol | 0.7 0.6 | 100 | 1 | 3 | 20 28 | 67 88 | [ |
Au/TiO2 | ethanol | 6.3 | 60 | 0.1 | — | 50 | 47 | [ |
Au/FeOOH | ethanol | 14.8 | 60 | 0.1 | — | 50 | 91 | [ |
Au/Al2O3 | ethanol | 0.1 | 100 | 8.5 | 2.8 | 94 | 89 | [ |
Catalyst | Size (nm) | Conv. (%) | ||||
---|---|---|---|---|---|---|
Styrene a | Styrene b | Benzaldehyde b | ||||
1.1% Au25/ZnAl-300 | 1.7 | 3.8 | 5.1 | 77.7 | ||
1.0% Au25/MgAl-300 | 2.2 | 67.5 | 58.2 | 95.1 | ||
1.0% Au/ZrO2 | 3.1 | 71.4 | 97.2 | 100 |
Table 3 Control experiments with styrene and benzaldehyde as the substrates over Au catalysts.
Catalyst | Size (nm) | Conv. (%) | ||||
---|---|---|---|---|---|---|
Styrene a | Styrene b | Benzaldehyde b | ||||
1.1% Au25/ZnAl-300 | 1.7 | 3.8 | 5.1 | 77.7 | ||
1.0% Au25/MgAl-300 | 2.2 | 67.5 | 58.2 | 95.1 | ||
1.0% Au/ZrO2 | 3.1 | 71.4 | 97.2 | 100 |
Fig. 5. ATR-IR spectra of the liquid cinnamyl aldehyde (a) and in-situ DRIFTS of the adsorbed CAL over the catalysts: (b) Au25/NiAl-300; (c) Au25/MgAl-300; (d) Au25/ZnAl-300 at 25 °C.
Entry | Peak position (cm-1) | Group | Intensity | Vibration type | Ref. |
---|---|---|---|---|---|
1 | 3666 | -OH | strong | Free -OH | [ |
2 | 3082 3061 | =CH- | weak | -CH stretching vibration in aromatic or olefin | [ |
3 | 3025 | | weak | -CH stretching vibration in benzene ring | [ |
4 | 2928 2856 | -CH2 | strong | -CH asymmetric and symmetrical stretching vibration in saturated alkane | [ |
5 | 2812 2741 | -CHO | strong | -CH asymmetric and symmetrical stretching vibration in aldehyde | [ |
6 | 1688 | C=O | strong | C=O stretching vibration in unsaturated aldehyde | [ |
7 | 1626 | C=C | medium | C=C stretching vibration in conjugate alkene | [ |
8 | 1604 1576 1494 | | weak | skeleton stretching vibration in benzene ring | [ |
9 | 1452 1392 | =CH- | weak | -CH asymmetric and symmetrical bending vibration in olefin | [ |
10 | 1293 1250 | =CH- | weak | -CH in-plane bending vibration in olefin | [ |
11 | 1072 | | weak | -CH in-plane bending vibration in benzene ring | [ |
12 | 976 | =CH- | weak | -CH out-of-plane bending vibration in olefin | [ |
Table 4 The attribution of peaks in FTIR spectra of the hydrogenation process of CAL over the Au25/NiAl-300 catalyst.
Entry | Peak position (cm-1) | Group | Intensity | Vibration type | Ref. |
---|---|---|---|---|---|
1 | 3666 | -OH | strong | Free -OH | [ |
2 | 3082 3061 | =CH- | weak | -CH stretching vibration in aromatic or olefin | [ |
3 | 3025 | | weak | -CH stretching vibration in benzene ring | [ |
4 | 2928 2856 | -CH2 | strong | -CH asymmetric and symmetrical stretching vibration in saturated alkane | [ |
5 | 2812 2741 | -CHO | strong | -CH asymmetric and symmetrical stretching vibration in aldehyde | [ |
6 | 1688 | C=O | strong | C=O stretching vibration in unsaturated aldehyde | [ |
7 | 1626 | C=C | medium | C=C stretching vibration in conjugate alkene | [ |
8 | 1604 1576 1494 | | weak | skeleton stretching vibration in benzene ring | [ |
9 | 1452 1392 | =CH- | weak | -CH asymmetric and symmetrical bending vibration in olefin | [ |
10 | 1293 1250 | =CH- | weak | -CH in-plane bending vibration in olefin | [ |
11 | 1072 | | weak | -CH in-plane bending vibration in benzene ring | [ |
12 | 976 | =CH- | weak | -CH out-of-plane bending vibration in olefin | [ |
Fig. 6. In-situ DRIFTS of the hydrogenation process of CAL with increasing temperature after introducing 1.5 MPa of hydrogen over the catalysts of Au25/NiAl-300 (a),Au25/MgAl-300 (b),and Au25/ZnAl-300
Fig. 8. The HAADF-STEM images of Au25/ZnAl-300 catalyst before and after using three times in hydrogenation of cinnamaldehyde. Reaction conditions: 130 °C,H2 pressure 15 atm,cinnamaldehyde 0.25 mmol,solvent 5 mL isopropanol,catalyst 50 mg.
Fig. 9. The conversion of CAL and the selectivity of COL with the recycle times. Reactions conditions: 130 °C,H2 pressure 15 atm,cinnamaldehyde 0.25 mmol,solvent 5 mL isopropanol,catalyst 50 mg. After each test,the catalyst was washed with isopropanol and separated by centrifugation. Then,the new reactant mixture added to the reactor and moved to a next run.
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