负载型Pd-Ni双金属纳米颗粒在无溶剂苯甲醇氧化中有效抑制甲苯的生成

引用本文: 车建伟, 郝梦佳, 易武中, Hisyoshi Koyshi, 周宇恒, 肖丽萍, 范杰. 负载型Pd-Ni双金属纳米颗粒在无溶剂苯甲醇氧化中有效抑制甲苯的生成[J]. 催化学报, 2017, 38(11): 1870-1879. doi: 10.1016/S1872-2067(17)62904-8 shu

Citation: Jianwei Che, Mengjia Hao, Wuzhong Yi, Hisayoshi Kobayashi, Yuheng Zhou, Liping Xiao, Jie Fan. Selective suppression of toluene formation in solvent-free benzyl alcohol oxidation using supported Pd-Ni bimetallic nanoparticles[J]. Chinese Journal of Catalysis, 2017, 38(11): 1870-1879. doi: 10.1016/S1872-2067(17)62904-8 shu

负载型Pd-Ni双金属纳米颗粒在无溶剂苯甲醇氧化中有效抑制甲苯的生成

a 浙江大学化学系浙江省应用化学重点实验室, 浙江杭州 310027;
b 京都工艺纤维大学, 日本京都606-8585
基金项目:
国家自然科学基金（21271153，21373181，21222307，U1402233）；国家自然科学基金重大研究计划（91545113）；中央高校基本科研业务费专项资金（2014XZZX003-02）.

摘要: 醇类化合物的选择性氧化是实验室和工业应用中一类重要的官能团转化反应.以分子氧为氧化剂，在液相无溶剂条件下温和氧化符合绿色化学的要求.负载型Pd基催化剂因其优异的催化活性而在该反应中得到广泛应用.但是，单金属Pd催化剂对反应目标产物醛类化合物的选择性还有待提高.例如，在苯甲醇液相无溶剂氧化中，甲苯是在单金属Pd催化剂上的主要副产物.针对这一问题，除了对载体进行改性和修饰外，开发双金属Pd基催化剂也是一种有效的选择性调控策略.虽然已有的Pd-Au双金属催化剂可以在一定程度上降低甲苯的选择性，但是在较高温度和较高转化率下仍然难以控制甲苯的大量生成.
本文采用固相合金化法合成了负载型Pd-Ni双金属纳米颗粒.该方法首先以硝酸镍为镍的前驱体浸渍介孔二氧化硅，然后负载钯纳米颗粒.在高温固相还原条件下，作为种子的钯纳米颗粒和镍通过原子迁移和生长，形成Pd-Ni双金属纳米颗粒.扫描透射电镜、能量色散X射线光谱、X射线衍射和X射线光电子能谱等表征证实了Pd-Ni双金属纳米颗粒的生成.上述催化剂用于苯甲醇液相无溶剂氧化，催化结果显示Ni的加入可以抑制副产物甲苯的生成，并且随Ni负载量增加，甲苯的选择性（在80%等转化率下）由22.6%（单金属Pd）降低至1.6%（双金属Pd₁Ni₂₀）.尽管Ni的加入降低了单金属Pd的活性，但是由于提高了目标产物苯甲醛的选择性，醛的最终产率得到提升.进一步催化研究表明，Ni的加入可以抑制无氧氛围下甲苯的生成，说明Ni可以抑制歧化反应和降低表面氢浓度.这种作用可归结于Pd-Ni双金属的协同效应.该效应得到了CO吸附的傅里叶变换漫反射红外光谱和密度泛函理论研究的证实.双金属的几何效应和电子效应均减弱了苯甲醇在双金属纳米颗粒表面的解离吸附和相互作用，导致苯甲醇的吸附减弱，同时C-O键断裂不易进行.另外，由于Ni的亲氧性，双金属纳米颗粒表面有利于氧的吸附，降低吸附氢的浓度，减少C-H键生成，从而抑制甲苯的生成.

关键词:

English

Selective suppression of toluene formation in solvent-free benzyl alcohol oxidation using supported Pd-Ni bimetallic nanoparticles

a Key Lab of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang, China;
b Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Kyoto 606-8585, Kyoto Prefecture, Japan
Received Date: 12 July 2017
Revised Date: 13 August 2017
Fund Project:
This work was supported by National Natural Science Foundation of China (21271153, 21373181, 21222307, U1402233), Major Research Plan of National Natural Science Foundation of China (91545113), and the Fundamental Research Funds for the Central Universities (2014XZZX003-02).

Abstract: The solvent-free oxidation of benzyl alcohol was studied using supported Pd-Ni bimetallic nanopar-ticles. Compared with monometallic Pd, the addition of Ni to Pd was found to be effective in sup-pressing the nondesired product toluene, thereby enhancing the selectivity towards benzaldehyde. This result was attributed to a dual effect of Ni addition:the weakening of dissociative adsorption of benzyl alcohol and the promotion of oxygen species involved in the oxidation pathway.

Key words:

1. [1] T. Mallat, A. Baiker, Chem. Rev., 2004, 104, 3037-3058.
2. [2] S. E. Davis, M. S. Ide, R. J. Davis, Green Chem., 2013, 15, 17-45.
3. [3] K. Mori, T. Hara, T. Mizugaki, K. Ebitani, K. Kaneda, J. Am. Chem. Soc., 2004, 126, 10657-10666.
4. [4] H. L. Wu, Q. H. Zhang, Y. Wang, Adv. Synth. Catal., 2005, 347, 1356-1360.
5. [5] F. Li, Q. H. Zhang, Y. Wang, Appl. Catal. A, 2008, 334, 217-226.
6. [6] P. F. Zhang, Y. T. Gong, H. R. Li, Z. R. Chen, Y. Wang, Nat. Commun., 2013, 4, 1593.
7. [7] Z. A. Qiao, P. F. Zhang, S. H. Chai, M. F. Chi, G. M. Veith, N. C. Gallego, M. Kidder, S. Dai, J. Am. Chem. Soc., 2014, 136, 11260-11263.
8. [8] N. Dimitratos, J. A. Lopez-Sanchez, D. Morgan, A. Carley, L. Prati, G. J. Hutchings, Catal. Today, 2007, 122, 317-324.
9. [9] M. Sankar, E. Nowicka, R. Tiruvalam, Q. He, S. H. Taylor, C. J. Kiely, D. Bethell, D. W. Knight, G. J. Hutchings, Chem. Eur. J., 2011, 17, 6524-6532.
10. [10] T. Homma, T. Kitaoka, Chem. Eng. J., 2016, 285, 467-476.
11. [11] B. Wang, M. Lin, T. P. Ang, J. Chang, Y. H. Yang, A. Borgna, Catal. Commun., 2012, 25, 96-101.
12. [12] Y. T. Chen, Z. Guo, T. Chen, Y. H. Yang, J. Catal., 2010, 275, 11-24.
13. [13] Y. B. Yan, Y. T. Chen, X. L. Jia, Y. H. Yang, Appl. Catal. B, 2014, 156-157, 385-397.
14. [14] Y. M. Lu, H. Z. Zhu, J. W. Liu, S. H. Yu, ChemCatChem, 2015, 7, 4131-4136.
15. [15] D. I. Enache, J. K. Edwards, P. Landon, B. Solsona-Espriu, A. F. Car-ley, A. A. Herzing, M. Watanabe, C. J. Kiely, D. W. Knight, G. J. Hutchings, Science, 2006, 311, 362-365.
16. [16] D. I. Enache, D. Barker, J. K. Edwards, S. H. Taylor, D. W. Knight, A. F. Carley, G. J. Hutchings, Catal. Today, 2007, 122, 407-411.
17. [17] Q. He, P. J. Miedziak, L. Kesavan, N. Dimitratos, M. Sankar, J. A. Lopez-Sanchez, M. M. Forde, J. K. Edwards, D. W. Knight, S. H. Tay-lor, C. J. Kiely, G. J. Hutchings, Faraday Discuss., 2013, 162, 365-378.
18. [18] R. Ferrando, J. Jellinek, R. L. Johnston, Chem. Rev., 2008, 108, 845-910.
19. [19] A. K. Singh, Q. Xu, ChemCatChem, 2013, 5, 652-676.
20. [20] Y. Xu, L. Chen, X. C. Wang, W. T. Yao, Q. Zhang, Nanoscale, 2015, 7, 10559-10583.
21. [21] J. K. A. Clarke, Chem. Rev., 1975, 75, 291-305.
22. [22] F. Gao, D. W. Goodman, Chem. Soc. Rev., 2012, 41, 8009-8020.
23. [23] N. Tsubaki, S. L. Sun, K. Fujimoto, J. Catal., 2001, 199, 236-246.
24. [24] A. Yarulin, I. Yuranov, F. Cárdenas-Lizana, D. T. L. Alexander, L. Kiwi-Minsker, Appl. Catal. A, 2014, 478, 186-193.
25. [25] K. A. Goulas, S. Sreekumar, Y. Y. Song, P. Kharidehal, G. Gunbas, P. J. Dietrich, G. R. Johnson, Y. C. Wang, A. M. Grippo, L. C. Grabow, A. A. Gokhale, F. D. Toste, J. Am. Chem. Soc., 2016, 138, 6805-6812.
26. [26] D. J. Childers, N. M. Schweitzer, S. M. K. Shahari, R. M. Rioux, J. T. Miller, R. J. Meyer, J. Catal., 2014, 318, 75-84.
27. [27] M. Armbrüster, M. Behrens, F. Cinquini, K. Föttinger, Y. Grin, A. Haghofer, B. Klötzer, A. Knop-Gericke, H. Lorenz, A. Ota, S. Penner, J. Prinz, C. Rameshan, Z. Révay, D. Rosenthal, G. Rupprechter, P. Sautet, R. Schlögl, L. D. Shao, L. Szentmiklósi, D. Teschner, D. Torres, R. Wagner, R. Widmer, G. Wowsnick, ChemCatChem, 2012, 4, 1048-1063.
28. [28] S. J. Freakley, Q. He, J. H. Harrhy, L. Lu, D. A. Crole, D. J. Morgan, E. N. Ntainjua, J. K. Edwards, A. F. Carley, A. Y. Borisevich, C. J. Kiely, G. J. Hutchings, Science, 2016, 351, 965-968.
29. [29] T. Komatsu, K. Inaba, T. Uezono, A. Onda, T. Yashima, Appl. Catal. A, 2003, 251, 315-326.
30. [30] G. C. Ma, X. Q. Yan, Y. L. Li, L. P. Xiao, Z. J. Huang, Y. P. Lu, J. Fan, J. Am. Chem. Soc., 2010, 132, 9596-9597.
31. [31] R. Sato, M. Kanehara, T. Teranishi, Small, 2011, 7, 469-473.
32. [32] Y. Tang, S. D. Xu, Y. H. Dai, X. Q. Yan, R. H. Li, L. P. Xiao, J. Fan, Chem. Commun., 2014, 50, 213-215.
33. [33] M. C. Payne, M. P. Teter, D. C. Allan, T. A. Arias, J. D. Joannopoulos, Rev. Mod. Phys., 1992, 64, 1045-1097.
34. [34] V. Milman, B. Winkler, J. A. White, C. J. Pickard, M. C. Payne, E. V. Akhmatskaya, R. H. Nobes, Int. J. Quantum Chem., 2000, 77, 895-910.
35. [35] J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
36. [36] J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1997, 78, 1396.
37. [37] D. Vanderbilt, Phys. Rev. B, 1990, 41, 7892-7895.
38. [38] J. Saha, K. Bhowmik, I. Das, G. De, Dalton Trans., 2014, 43, 13325-13332.
39. [39] C. Y. Du, M. Chen, W. G. Wang, G. P. Yin, ACS Appl. Mater. Interfaces, 2011, 3, 105-109.
40. [40] J. Zhao, A. Sarkar, A. Manthiram, Electrochim. Acta, 2010, 55, 1756-1765.
41. [41] K. S. Kim, N. Winograd, Chem. Phys. Lett., 1975, 30, 91-95.
42. [42] S. M. Foiles, M. I. Baskes, M. S. Daw, Phys. Rev. B, 1986, 33, 7983-7991.
43. [43] M. F. Zhou, L. Andrews, C. W. Bauschlicher, Chem. Rev., 2001, 101, 1931-1961.
44. [44] M. A. Matin, J. H. Jang, Y. U. Kwon, J. Power Sources, 2014, 262, 356-363.
45. [45] D. M. Meier, A. Urakawa, A. Baiker, J. Phys. Chem. C, 2009, 113, 21849-21855.
46. [46] N. Dimitratos, J. A. Lopez-Sanchez, D. Morgan, A. F. Carley, R. Tiru-valam, C. J. Kiely, D. Bethell, G. J. Hutchings, Phys. Chem. Chem. Phys., 2009, 11, 5142-5153.
47. [47] A. Savara, C. E. Chan-Thaw, I. Rossetti, A. Villa, L. Prati, Chem-CatChem, 2014, 6, 3464-3473.
48. [48] P. Liu, J. K. Nørskov, Phys. Chem. Chem. Phys., 2001, 3, 3814-3818.
49. [49] B. Hammer, J. K. Nørskov, Adv. Catal., 2000, 45, 71-129.
50. [50] R. J. Hou, W. T. Yu, M. D. Porosoff, J. G. Chen, T. F. Wang, J. Catal., 2014, 316, 1-10.
51. [51] A. Villa, D. Ferri, S. Campisi, C. E. Chan-Thaw, Y. Lu, O. Kröcher, L. Prati, ChemCatChem, 2015, 7, 2534-2541.
52. [52] S. Y. Shan, V. Petkov, L. F. Yang, J. Luo, P. Joseph, D. Mayzel, B. Pra-sai, L. Y. Wang, M. Engelhard, C. J. Zhong, J. Am. Chem. Soc., 2014, 136, 7140-7151.

扫一扫看文章

计量

PDF下载量: 3
文章访问数: 817
HTML全文浏览量: 44

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

负载型Pd-Ni双金属纳米颗粒在无溶剂苯甲醇氧化中有效抑制甲苯的生成

English

Selective suppression of toluene formation in solvent-free benzyl alcohol oxidation using supported Pd-Ni bimetallic nanoparticles

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

负载型Pd-Ni双金属纳米颗粒在无溶剂苯甲醇氧化中有效抑制甲苯的生成

English

Selective suppression of toluene formation in solvent-free benzyl alcohol oxidation using supported Pd-Ni bimetallic nanoparticles

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs