2-乙基蒽醌在双金属整体式催化剂上的氢化反应:实验和DFT研究

doi:10.1016/S1872-2067(18)63035-9

摘要/Abstract

摘要：

过氧化氢（H₂O₂）是一种绿色化工原料和环境友好氧化剂.目前，超过98%的H₂O₂是通过蒽醌法生产.蒽醌法主要包括2-乙基蒽醌氢化生成2-乙基氢蒽醌和2-乙基氢蒽醌氧化生成2-乙基蒽醌和H₂O₂的过程.其中，2-乙基蒽醌氢化是关键步骤.在氢化过程中，生成的2-乙基氢蒽醌和四氢-2-乙基氢蒽醌是目标产物，同时生成许多副产物.目前，Pd颗粒催化剂是广泛使用的催化剂，但是蒽醌氢化过程中，质量传递是主要的控制因素.与颗粒催化剂对比，整体式催化剂可以减弱整个反应的内外扩散，提高反应速率.很多研究结果显示，整体式催化剂的传质优于颗粒催化剂，可以提高催化效率.近期许多研究显示，双金属颗粒催化剂在很多氢化反应中体现出优异的催化性能.本工作制备了双金属整体式催化剂，考察了其在蒽醌氢化过程中的催化性能.
首先，通过浸渍法制备了4种双金属整体式催化剂Pd-M/SiO₂/COR （M=Ni，Fe，Mn和Cu）以及Pd/SiO₂/COR和Ni/SiO₂/COR两种单金属整体式催化剂.催化活性结果显示，Ni/SiO₂/COR的H₂O₂产量低于Pd/SiO₂/COR，而且在700℃还原的Pd-Ni/SiO₂/COR整体式催化剂在Pd/M=2时取得了最高选择性（95.3%）和H₂O₂产量（7.5g/L）.然后，考察了金属负载量的影响.结果显示，在金属负载量低于0.4%时，随着金属负载量增加，选择性和H₂O₂产量增加，在金属负载量高于0.4%时，随着金属负载量增加，选择性和H₂O₂产量降低.
TEM结果表明，添加第二种金属后，双金属整体式催化剂颗粒尺寸变小，分布更均匀.EDS结果显示，双金属形成了合金.H₂-TPR结果显示，随着Pd/M比率增加，还原温度降低，说明Pd有助于第二种金属氧化物的还原.这可能是由于Pd表面的氢溢流到第二种金属（Ni，Fe，Mn和Cu）表面.此外，文献结果表明，合金的形成能够抑制PdH的形成.本工作表明添加第二种金属（Ni，Fe，Mn和Cu）后，PdH的峰强度减弱或者峰消失，也说明形成了合金.XPS结果显示，添加第二种金属后，在336.3±0.1和341.4±0.1eV出现了新的Pd3d_5/2和Pd3d_3/2峰，说明形成了合金.H₂-O₂滴定结果表明，Pd-Ni/SiO₂/COR的Pd分散度和Pd比表面积都高于其他双金属催化剂，说明第二种金属Ni更有利于促进Pd的分散，减弱颗粒集聚，揭示了Q#8197；Pd和Ni之间强烈的相互作用.
DFT计算结果显示，Pd₃M₁（M=Ni，Fe，Mn和Cu）双金属整体式催化剂和2-乙基蒽醌之间的结合能低于Pd/SiO₂/COR和2-乙基蒽醌之间的结合能，但是Pd₃M₁（M=Ni，Fe和Mn）双金属催化剂和2-乙基氢蒽醌之间的结合能减小得很少，这可能是由于2-乙基蒽醌的C=O和第二种金属之间具有强烈相互作用的缘故.Pd₃Cu₁双金属催化剂和2-乙基氢蒽醌之间的结合能减小很多，主要是由于Pd₃Cu₁表面不利于2-乙基氢蒽醌的吸附.
因此，Pd-Ni/SiO₂/COR比Pd/SiO₂/COR，Ni/SiO₂/COR和其他的双金属整体式催化剂具有更高的选择性和H₂O₂产量，主要是由于合金的形成以及2-乙基氢蒽醌的C=O双键和2-乙基氢蒽醌强烈的相互作用.

关键词: 双金属整体式催化剂, 合金, 2-乙基氢蒽醌, DFT计算, 协同作用

Abstract:

We studied the hydrogenation of 2-ethylanthraquinone (eAQ) over Pd/SiO₂/COR (COR=cordierite) monometallic and Pd-M/SiO₂/COR (M=Ni, Fe, Mn, and Cu) bimetallic monolithic catalysts, which were prepared by the co-impregnation method. Detailed investigations showed that the particle sizes and structures of the Pd-M (M=Ni, Fe, Mn, and Cu) bimetallic monolithic catalysts were greatly affected by the second metal M and the mass ratio of Pd to the second metal M. By virtue of the small particle size and the strong interaction between Pd and Ni of Pd-Ni alloy, Pd-Ni bimetallic monolithic catalysts with the mass ratio of Pd/Ni=2 achieved the highest H₂O₂ yield (7.5 g/L) and selectivity (95.3%). Moreover, density functional theory calculations were performed for eAQ adsorption to gain a better mechanistic understanding of the molecule-surface interactions between eAQ and the Pd(1 1 1) or PdM(1 1 1) (M=Ni, Fe, Mn, and Cu) surfaces. It was found that the high activity of the bimetallic Pd-Ni catalyst was a result of strong chemisorption between Pd₃Ni₁ (1 1 1) and the carbonyl group of eAQ.

Key words: Bimetallic monolithic catalyst, Alloy, 2-Ethylanthraquinone hydrogenation, DFT calculation, Synergistic effect

郭燕燕, 代成娜, 雷志刚. 2-乙基蒽醌在双金属整体式催化剂上的氢化反应:实验和DFT研究[J]. 催化学报, 2018, 39(6): 1070-1080.

Yanyan Guo, Chengna Dai, Zhigang Lei. Hydrogenation of 2-ethylanthraquinone with bimetallic monolithic catalysts: An experimental and DFT study[J]. Chinese Journal of Catalysis, 2018, 39(6): 1070-1080.

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参考文献

[1] C. Samanta, Appl. Catal. A, 2008, 350, 133-149.
[2] E. Santacesaria, M. D. Serio, R. Velotti, U. Leone, Ind. Eng. Chem. Res., 1994, 33, 277-284.
[3] H. Shang, H. J. Zhou, Z. H. Zhu, W. H. Zhang, J. Ind. Eng. Chem., 2012, 18, 1851-1857.
[4] J. M. Campos-Martin, G. Blanco-Brieva, J. L. G. Fierro, Angew. Chem. Int. Ed., 2006, 45, 6962-6984.
[5] V. Paunovic, V. Ordomsky, M. F. N. D'Angelo, J. C. Schouten, T. A. Nijhuis, J. Catal., 2014, 309, 325-332.
[6] L. K. Ouyang, G. J. Da, P. F. Tian, T. Y. Chen, G. D. Liang, J. Xu, Y. F. Han, J. Catal., 2014, 311, 129-136.
[7] R. Ciriminna, L. Albanese, F. Meneguzzo, M. Pagliaro, ChemSusChem, 2016, 9, 3374-3374.
[8] R. B. Rankin, J. Greeley, ACS Catal., 2012, 2, 2664-2672.
[9] H. M. Chen, D. P. Huang, X. Y. Su, J. L. Huang, X. L. Jing, M. M. Du, D. H. Sun, L. S. Jia, Q. B. Li, Chem. Eng. J., 2015, 262, 356-363.
[10] Y. Y. Guo, C. N. Dai, Z. G. Lei, Chem. Eng. Sci., 2017, 172, 370-384.
[11] A. Drelinkiewicz, A. Waksmundzka-Góra, J. Mol. Catal. A, 2006, 258, 1-9.
[12] R. Kosydar, A. Linkiewicz, E. Lalik, J. Gurgul, Appl. Catal. A, 2011, 402, 121-131.
[13] C. Shen, Y. J. Wang, J. H. Xu, Y. C. Lu, G. S. Luo, Chem. Eng. J., 2011, 173, 226-232.
[14] Y. C. Zhu, L. Y. Yu, X. F. Wang, Y. H. Zhou, H. Q. Ye, Catal. Commun., 2013, 40, 98-102.
[15] A. Drelinkiewicz, M. Hasik, J. Mol. Catal. A, 2001, 177, 149-164.
[16] J. G. Zhang, D. F. Li, Y. J. Zhao, Q. D. Kong, S. D. Wang, Catal. Commun., 2008, 9, 2565-2569.
[17] X. T. Li, H. J. Su, G. Y. Ren, S. D. Wang, RSC Adv., 2015, 5, 100968-100977.
[18] Y. Nakagawa, K. Tomishige, Catal. Commun., 2010, 12, 154-156.
[19] A. A. Shesterkina, O. A. Kirichenko, L. M. Kozlova, G. I. Kapustin, I. V. Mishin, A. A. Strelkova, L. M. Kustov, Mendeleev Commun., 2016, 26, 228-230.
[20] P. Insorn, B. Kitiyanan, Catal. Today, 2015, 256, 223-230.
[21] K. Fulajtárova, T. Soták, M. Hronec, I. Vohra, E. Dobrocka, M. Omastová, Appl. Catal. A, 2015, 502, 78-85.
[22] E. X. Yuan, C. Wu, X. Hou, M. B. Dou, G. Z. Liu, G. Z. Li, L. Wang, J. Catal., 2017, 347, 79-88.
[23] J. T. Feng, H. Y. Wang, D. G. Evans, X. Duan, D. Q. Li, Appl. Catal. A, 2010, 382, 240-245.
[24] Y. Y. Guo, C. N. Dai, Z. G. Lei, B. H. Chen, X. C. Fang, Catal. Today, 2016, 276, 36-45.
[25] R. Car, M. Parrinello, Phys. Rev. Lett., 1985, 55, 2471-2474.
[26] M. C. Payne, J. D. Joannopoulos, D. C. Allan, M. P. Teter, D. H. Vanderbilt, Phys. Rev. Lett., 1986, 56, 2656.
[27] J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[28] G. Kresse, D. Joubert, Phys. Rev. B, 1999, 59, 1758-1775.
[29] F. Cinquini, F. Delbecq, P. Sautet, Phys. Chem. Chem. Phys., 2009, 11, 11546-11556.
[30] N. Pino, S. Sitthisa, Q. H. Tan, T. Souza, D. López, D. E. Resasco, J. Catal., 2017, 350, 30-40.
[31] E. Povoden-Karadeniz, P. Lang, F. Moszner, S. Pogatscher, A. V. Ruban, P. J. Uggowitzer, E. Kozeschnik, Calphad, 2015, 51, 314-333.
[32] S. Sitthisa, T. Pham, T. Prasomsri, T. Sooknoi, R. G. Mallinson, D. E. Resasco, J. Catal., 2011, 280, 17-27.
[33] O. Sanz, F. J. Echave, M. Sánchez, A. Monzon, M. Montes, Appl. Catal. A, 2008, 340, 125-132.
[34] B. Yuan, B. Zhang, Z. L. Wang, S. M. Liu, J. Li, Y. Liu, C. Li, Chin. J. Catal., 2017, 38, 440-446.
[35] M. Q. Chai, X. Y. Liu, L. Li, G. X. Pei, Y. J. Ren, Y. Su, H. K. Cheng, A. Q. Wang, T. Zhang, Chin. J. Catal., 2017, 38, 1338-1346.
[36] B. Y. Bai, Q. Qiao, J. H. Li, J. M. Hao, Chin. J. Catal., 2016, 37, 102-122.
[37] G. Agostini, C. Lamberti, R. Pellegrini, G. Leofanti, F. Giannici, A. Longo, E. Groppo, ACS Catal., 2014, 4, 187-194.
[38] E. Groppo, G. Agostini, A. Piovano, N. B. Muddada, G. Leofanti, R. Pellegrini, G. Portale, A. Longo, C. Lamberti, J. Catal., 2012, 287, 44-54.
[39] G. X. Pei, X. Y. Liu, M. Q. Chai, A. Q. Wang, T. Zhang, Chin. J. Catal., 2017, 38, 1540-1548.
[40] S. Sitthisa, T. Pham, T. Prasomsri, T. Sooknoi, R. G. Mallinson, D. E. Resasco, J. Catal., 2011, 280, 17-27.
[41] R. R. Hong, Y. F. He, J. T. Feng, D. Q. Li. AIChE J., 2017, 63, 3955-3965.
[42] Y. N. Liu, Y. F. He, D. R. Zhou, J. T. Feng, D. Q. Li, Catal. Sci. Technol., 2016, 6, 3027-3037.
[43] J. Sá, G. D. Arteaga, R. A. Daley, J. Bernardi, J.A. Anderson, J. Phys. Chem. B, 2006, 110, 17090-17095.
[44] S. Karski, I. Witońska, J. Rogowski, J. Gonuchowska. J. Mol. Catal. A, 2005, 240, 155-163.
[45] S. Karski, I. Witońska. J. Mol. Catal. A, 2003, 191, 87-92.
[46] Q. Zhang, J. Li, X. X. Liu, Q. M. Zhu. Appl. Catal. A, 2000, 197, 221-228.
[47] A. S. Ivanova, E. M. Slavinskaya, R. V. Gulyaev, V. I. Zaikovskii, O. A. Stonkus, I. G. Danilova, L. M. Plyasova, I. A. Polukhina, A. I. Boronin, Appl. Catal. B, 2010, 97, 57-71.
[48] V. Johánek, I. Stará, V. Matoln, Surf. Sci., 2002, 507-510, 92-98.
[49] S. Maheswari, S. Karthikeyan, P. Murugan, P. Sridhar, S. Pitchumani, Phys. Chem. Chem. Phys., 2012, 14, 9683-9695.
[50] N. Lopez, J. K. Nørskov, Surf. Sci., 2001, 477, 59-75.
[51] T. Kamachi, T. Ogata, E. Mori, K. Iura, N. Okuda, M. Nagata, K. Yoshizawa, J. Phys. Chem. C, 2015, 119, 8748-8754.
[52] M. K. Bradley, J. bin Roson, D. P. Woodruff, Surf. Sci., 2010, 604, 920-925.