Palladium-based Nanocatalysts Supported on Polybenzoxazine for Aromatic Alcohol Oxidation †

doi:10.7503/cjcu20190594

Abstract

Abstract:

Carbon supported palladium-based nanocatalysts were synthesized via an impregnation-pyrolysis method, based on a spherical polybenzoxazine as support, owing to the interaction between nitrogen groups and metal nanoparticles. Transmission electron microscope(TEM) images of Pd/C catalyst showed that palladium nanoparticles were uniformly distributed over the support with an average size of about 3.5 nm. The cha-racterization results of Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS) and temperature programmed desorption(CO₂-TPD) analysis, showed that a mount of nitrogen and oxygen functional groups existed on the support. The nitrogen and oxygen atoms might have interactions with Pd atoms, which could effectively immobilize palladium nanoparticles and obtain well dispersed palladium-carbon nanocatalysts. The bimetallic Pd-Au/C and Pd-Pt/C catalysts were prepared via the same method to further enhance the catalytic activity. The average particle size of Pd-Au and Pd-Pt nanoparticles were 4.3 and 4.2 nm, respectively, without an obvious agglomeration, which demonstrated the effective immobilization role of polybenzoxazine support. The catalysts were evaluated by the benzyl alcohol oxidation reaction at 80 ℃ and water as solvent. The Pd₁-Au₁/C catalyst exhibited the highest conversion of >98% within 2 h and the selectivity to benzaldehyde of >99%, revealing the excellent catalytic performances. Moreover, the catalyst could be used for several runs and easily regenerated by calcination. Furthermore, the catalyst could also oxidize aromatic alcohols with different substituents into corresponding aldehydes, such as 4-methyl benzyl alcohol, 4-methoxybenzyl alcohol, 2-methyl benzyl alcohol and so on, providing an excellent catalyst for aromatic alcohol oxidation.

Key words: Pd, Carbon material, Dispersion, Aromatic alcohol oxidation

CLC Number:

O643.36

TrendMD:

HAO Yan, YANG Hua, WANG Xiang, LI Qingyang, ZHAO Pan, TANG Qinghu, SONG Shili, XI Guoxi. Palladium-based Nanocatalysts Supported on Polybenzoxazine for Aromatic Alcohol Oxidation ^†[J]. Chem. J. Chinese Universities, 2020, 41(4): 757.

Figures/Tables 7

Fig.1 Schematic process of the Pd/C catalyst via an impregnation pyrolysis method

Fig.2 FTIR spectra of polybenzoxazine(a) and Pd/polybenzoxazine(b)(A) , XPS spectra of N1s(B) and CO2-TPD spectrum(C) of carbon support, XPS spectra of Pd3d(D) , XRD pattern(E) , and TEM and HRTEM images(inset)(F) of Pd/C catalyst

Fig.3 TEM image(A), HRTEM image(B), SAED image(C), XPS spectra of Pd3d and Au4f(D) of Pd1-Au1/C catalyst

Fig.4 TEM image(A), HRTEM image(B), SAED image(C), XPS spectra of Pd3d and Pt4f(D) of Pd2-Pt1/C catalyst

Fig.5 Catalytic activities of various catalysts in the benzyl alcohol oxidation reaction (A) n(Pd)/n(Pd+Pt): a. 0; b. 1/6; c. 1/5; d. 1/3; e. 1/2; f. 2/3; g. 4/5; h. 5/6; i. 1. (B) n(Pd)/n(Pd+Au): a. 0; b. 1/6; c. 1/5; d. 1/3; e. 1/2; f. 2/3; g. 4/5; h. 5/6; i. 1.

Catalyst	Metal loading(%)	Reaction time/h	Conversion(%)	Selectivity(%)	Ref.
Pd-Au/C	2	2	98	95	This work
Pd/Fe@C	1	25	93	99	[29]
Au/ZnCuO	4	5	93	99	[30]
Pd/CeO₂	3	2	93	99	[31]
Pd/FMOF	3	12	89	99	[32]
Au-Pd/Fe-Gr	5	4	96.2	89.9	[33]

Substrate	Product	Conversion(%)	Selectivity(%)
4-Methylbenzyl alcohol	4-Methylbenzaldehyde	32	>99
4-Methoxybenzyl alcohol	4-Methoxybenzaldehyde	37	>99
2-Methylbenzyl alcohol	2-Methylbenzaldehyde	13	>99
4-Nitrobenzyl alcohol	4-Nitrobenzaldehyde	4	>99

References 34

[1]	Song Y. C., Ding X. S., Yan Y. H., Wang S. F., Wang Y. J., J. Chem. Industry Engin., 2019, 70 4), 1401— 1408
	( 宋宇淙,丁晓墅,闫亚辉,王淑芳,王延吉.化工学报, 2019, 70(4), 1401— 1408)
[2]	Chen Z. Y., Mao J. X., Zhou R. X., Appl. Surf. Sci., 2019, 465, 25— 22
[3]	Cui W. H., Li S. D., Wang D. D., Deng Y. Z., Chen Y. F., Catal. Commun., 2019, 119, 86— 90
[4]	Lin Z. C., Huang Q. X., Lei M., Chem. J. Chinese Universities, 2019, 40 5), 1013— 1018
	( 林周晨,黄巧茜,雷鸣.高等学校化学学报, 2019, 40(5), 1013— 1018)
[5]	Liu J. J., Zou S. H., Wu J. C., Kobayashi H., Zhao H. T., Fan J., Chinese J. Catal., 2018, 39( 6), 1081— 1089
[6]	Li J. W., Li P. P., Li J. B., Tian Z. Q., Yu F ., Catalysts, 2019, 9( 6), 1— 12
[8]	Naik G. K., Majhi S. M., Jeong K. U., Lee I. H., Yu Y. T., J. Alloy. Compd., 2019, 771, 505— 512
	Li T. J., Lin H. F., Ouyang X. P., Qu X. Q., Wan Z. C., ACS Catal., 2019, 9( 7), 5828— 5836
[9]	Li Y., Yao L., Zhang L. Q., Liu A. R., Zhang Y. J., Liu S. Q., J. Electroanal. Chem., 2014, 730, 65— 68
[10]	Lv Q., Si W. Y., He J. J., Sun L., Zhang C. F., Wang N., Yang Z., Li X. D., Wang X., Deng W. Q., Long Y. Z., Huang C. S., Li Y. L., Nat. Commun., 2018, 9, 3376— 3386
[11]	Zhou J., Wu K., Wang W. J., Xu Z. Y., Wan H. Q., Zheng S. R., Appl. Catal. A-Gen, 2017, 470, 336— 343
[12]	Ravat V., Nongwe I., Meijboom R., Bepete G., Coville N. J., J. Catal., 2013, 305, 36— 45
[13]	Ma X. B., Feng Y. Y., Li Y., Han Y. S., Lu G. P., Yang H. F., Kong D. S., Chinese J. Catal., 2015, 36( 7), 943— 951
[14]	Wang S., Li W. C., Hao G. P., Hao Y., Sun Q., Zhang X. Q., Lu A. H., J. Am. Chem. Soc., 2011, 133, 15304— 15307
[15]	Luo J., Peng F., Wang H. J., Yu H., Catal. Commun., 2013, 39, 44— 49
[16]	Huang C. L., Zhong W., Wen J. J., Zhang M. Y., Huang H. M., Fu M. L., Wu J. L., Ye D. Q., Chen L. M., Acta Scien. Circum., 2019, 39 6), 1942— 1951
	( 黄春蕾,钟雯,文进军,张明远,黄皓旻,付名利,吴军良,叶代启,陈礼敏.环境科学学报, 2019, 39(6), 1942— 1951)
[17]	Liu J., Zhou W. Y., Wu Z., Sun F. A., He M. Y., Chen Q., Chinese J. Appl. Chem., 2015, 32 9), 1033— 1039
	( 刘杰,周维友,吴中,孙富安,何明阳,陈群.应用化学, 2015, 32(9), 1033— 1039)
[18]	Lu A H., . Li W . C., Hou Z . S, Schüth F. Chem. Commun., 2007, ( 10), 1038— 1040
[19]	Ruiz-García C., Heras F., Calvo L., Alonso-Morales N., Rodriguez J. J., Gilarranz M. A., Ind. Eng. Chem. Res., 2019, 58, 4355— 4363
[20]	Yan X. H., Ge X., Zhang L., Qi L. J., Li Y., Wei S. H., Zhu X. S., Tang Y. W., Chem. J. Chinese Universities, 2017, 38 9), 1619— 1626
	( 闫晓红,葛霞,张琳,齐丽娟,刘洋,魏少华,朱晓舒,唐亚文.高等学校化学学报, 2017, 38(9), 1619— 1626)
[21]	Han F. Y., Xia J. W., Zhang X. L., Fu Y. S., RSC Advances, 2019, 9, 17812— 17823
[22]	Nassiri H., Hayes R. E., Semagina N., Chem. Eng. Sci., 2018, 186, 44— 51
[23]	Hong W., Wang J., Wang E. K., ACS Appl. Mater. Inter., 2014, 6, 9481— 9487
[24]	Hong W., Shang C. S., Wang J., Wang E. K., Energy Environ. Sci., 2015, 8, 2910— 2915
[25]	Wang Z. T., Song Y. X., Zou J. H., Li L. Y., Yu Y., Wu L., Catal. Sci. Technol., 2018, 8, 268— 275
[26]	Hao Y., Hao G. P., Guo D. C., Guo C. Z., Li W. C., Li M. Y., Lu A. H ., ChemCatChem, 2012, 4, 1595— 1602
[27]	Zhu X. J., Guo Q. S., Sun Y. F., Chen S. J., Wang J. Q., Wu M. M., Fu W. Z., Tang Y. Q., Duan X. Z., Chen D., Wan Y., Nat. Commun., 2019, 10, 1428— 1438
[28]	Yan Y. B., Jia X. L., Yang Y. H., Catal. Today, 2016, 259, 292— 302
[29]	Zhang H., Liu Y., Zhang X. G., Chinese J. Catal., 2011, 32, 1693— 1701
[30]	Wang W., Xie Y., Zhang S.H ., Liu X., Zhang L. Y.,Zhang B. S, Haruta M., Huang J. H ., Chin. J. Catal.,2019, 40, 1924— 1933
[31]	Zheng H., Wei Z. H., Hu X. Q., Xu J., Xue B., Chemistry Select, 2019, 4, 5470— 5475
[32]	Liu J. Y., Yu H. J., Wang L., Deng Z., Vatsadze S. Z., J. Mol. Struc., 2019, 1198, 126895
[33]	Sun J. Y., Tong X. L., Liu Z. H., Liao S. Y., Zhuang X. L., Xue S., Catal. Commun., 2016, 85, 70— 74
[34]	Tang Q. H., Liu T., Yang Y. H., Catal. Commun., 2008, 9( 15), 2570— 2573

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