杂环化聚丙烯亚胺树状聚合物负载钌铑双金属纳米粒子的制备及在催化丁腈橡胶氢化中的应用

doi:10.7503/cjcu20150797

摘要/Abstract

摘要：

以十五元三烯氮杂大环改性的不同代数聚丙烯亚胺树状聚合物(Gn-M, n=2, 3, 4)为模板, 通过共络合-还原方法制备了一系列钌/铑双金属纳米粒子[Gn-M(Ru_xRh_100-_x) DTNs, x为Ru摩尔分数], 并将其应用于丁腈橡胶(NMR)的催化氢化. 用紫外-可见光谱(UV-Vis)、 X射线衍射分析(XRD)及X射线能谱(EDS)表征DTNs的金属组成和结构, 结果表明, DTNs上的双金属离子被还原成金属单质并负载于Gn-M上; 粒度分析结果表明, G2-M(Ru₅₀Rh₅₀), G3-M(Ru₅₀Rh₅₀)和G4-M(Ru₅₀Rh₅₀) DTNs的平均粒径分别为7.5, 8.1和4.5 nm. 凝胶测试及核磁共振波谱(¹H NMR)结果表明, Ru/Rh DTNs催化剂对丁腈橡胶的催化氢化反应具有良好的选择性. 当以G4-M(Ru₃₀Rh₇₀) DTNs为催化剂时, NBR的氢化度最高可达99.51%, 循环使用2次后, 丁腈橡胶的氢化度仍可达到90.58%.

关键词: 杂环, 树状聚丙烯亚胺, 钌铑双金属纳米粒子, 丁腈橡胶, 氢化反应

Abstract:

A series of Ru/Rh bimetallicdendrimer-stabilized nanoparticles[Gn-M(Ru_xRh_100-_x) DTNs, x: mole molar fraction of Ru] was prepared by complexing-reducing method with the 15-membered azamacrocycles-terminated poly(propylene imine) dendrimer(Gn-M, n=2, 3, 4) as template. These bimetallic DTNs were used as catalysts for the hydrogenation of nitrile-butadiene rubber(NBR). The results of UV-Vis spectroscopy(UV-Vis), X-ray diffraction(XRD) and energy dispersive spectrum(EDS) indicated that bimetallic ions were successful reduced and stabilized by Gn-M. Particle size analysis showed that the average size of G2-M(Ru₅₀Rh₅₀), G3-M(Ru₅₀Rh₅₀) and G4-M(Ru₅₀Rh₅₀) DTNs were 7.5, 8.1 and 4.5 nm, respectively. G4-M(Ru₃₀Rh₇₀) DTNs catalyst reached the maximum hydrogenation degree(HD) of 99.51%, and the results of gel fraction measurement and ¹H nuclear magnetic resonance(¹H NMR) indicated that Ru/Rh DTNs were highly selective for the catalytic hydrogenation of NBR. Moreover, the HD can still reach 90.58% after twice recycle.

Key words: Heterocycle, Poly(propylene imine) dendrimer, Ru/Rh bimetallic nanoparticles, Nitrile-butadiene rubber, Hydrogenation

中图分类号:

O631
O643.36

TrendMD:

萧烨, 王洋, 周为, 彭晓宏. 杂环化聚丙烯亚胺树状聚合物负载钌铑双金属纳米粒子的制备及在催化丁腈橡胶氢化中的应用. 高等学校化学学报, 2016, 37(4): 786.

XIAO Ye, WANG Yang, ZHOU Wei, PENG Xiaohong. Preparation of Ru/Rh Bimetallic Nanoparticles Stabilized by Heterocyclic Poly(propylene imine) Dendrimer and Their Application for Catalytic Hydrogenation of Nitrile-Butadiene Rubber^†. Chem. J. Chinese Universities, 2016, 37(4): 786.

图/表 9

Fig.1 UV-Vis spectra of G2-M(A), G3-M(B) and G4-M(C) bimetallic nanoparticles with various Ru/Rh molar ratios^(A) a. G2-M; b. G2-M(Ru); c. G2-M(Ru70Rh30); d. G2-M(Ru50Rh50); e. G2-M(Ru30Rh70); f. G2-M(Rh). (B) a. G3-M; b. G3-M(Ru); c. G3-M(Ru70Rh30); d. G3-M(Ru50Rh50); e. G3-M(Ru30Rh70); f. G3-M(Rh). (C) a. G4-M; b. G4-M(Ru); c. G4-M(Ru70Rh30); d. G4-M(Ru50Rh50); e. G4-M(Ru30Rh70); f. G4-M(Rh).

Fig.2 High-resolution TEM images(A—C) and the corresponding size distribution histograms(A'—C') of G2-M(Ru50Rh50)(A, A'), G3-M(Ru50Rh50)(B, B') and G4-M(Ru50Rh50)(C, C') nanoparticles

Table 1 Comparison of the calculated value and the measured value of Gn-M(Ru50Rh50) bimetallic DTNs size

Gn-M(R $u 5 0$ R $h 5 0$ DTNs)	10^-3 Atom number	d_calculated/nm	d_Measured/nm
G2-M	8.20	6.4	7.5±0.8
G3-M	10.32	6.9	8.1±1.1
G4-M	1.77	3.6	4.5±1.5

Table 1 Comparison of the calculated value and the measured value of Gn-M(Ru50Rh50) bimetallic DTNs size

Gn-M(R $u 5 0$ R $h 5 0$ DTNs)	10^-3 Atom number	d_calculated/nm	d_Measured/nm
G2-M	8.20	6.4	7.5±0.8
G3-M	10.32	6.9	8.1±1.1
G4-M	1.77	3.6	4.5±1.5

Fig.3 EDS analysis for G4-M(Ru50Rh50) bimetallic nanoparticles

Fig.4 XRD patterns of G4-M(Rh)(a), G4-M(Ru30Rh70)(b), G4-M(Ru50Rh50)(c), G4-M(Ru70Rh30)(d) and G4-M(Ru)(e) DTNs

Fig.5 Hydrogenation degree(HD) of NBR as various molar ratio of rhodium in G2-M(RuxRh100-x)(a), G3-M(RuxRh100-x)(b) and G4-M(RuxRh100-x)(c) bimetallic nanoparticles^Conditions: NBR 3.6 g, mDTNs/mNBR=0.35%, mDTNs/mTPP=10%, 800 r/min of agitation, 100 ℃, 5.5 MPa of H2, reaction time: 9 h.

Fig.6 1H NMR spectra of NBR(A) and HNBR(B)^ Conditions: NBR 3.6 g, mDTNs/mNBR=0.35%, mDTNs/mTPP=10%, 800 r/min of agitation, 100 ℃, 5.5 MPa of H2, reaction time: 9 h.

Fig.7 Representative FTIR spectra of NBR(a) and HNBR(b—d) with different extent of hydrogenation^HD(%): b. 65.85; c. 89.74; d. 99.51.

Fig.8 Hydrogenation degrees of NBR catalyzed by G4-M(Ru30Rh70) in different cycles^Conditions: NBR 3.6 g, mDTNs/mNBR=0.35%, mcatalysis/mTPP=10%, 800 r/min of agitation, 100 ℃, 5.5 MPa of H2, reaction time: 9 h.

参考文献 17

[1]	Hansmann M. M., Pernpointner M., Doepp R., Hashmi A. S. K., Chem. Eur. J., 2013, 19(45), 15290—15303
[2]	Shaabani A., Mahyari M., Catal. Lett., 2013, 143(12), 1277—1284
[3]	Xiao Q., Sarina S., Jaatinen E., Jia J. F., Arnold D. P., Liu H. W., Zhu H. Y., Green Chem., 2014, 16, 4272—4285
[4]	Chen L. G., Zhu Y. L., Hongyan Z., Zheng H. Y., Zhang C. H., Li Y. W., Appl. Catal. A Gen., 2012, 411/412, 95—104
[5]	Cardenas-Lizana F., Gomez-Quero S., Amorim C., Keane M. A., Appl. Catal. A Gen., 2014, 473, 41—50
[6]	Scholten J. D., Curr. Org. Chem., 2013, 17(4), 348—363
[7]	Knecht M. R., Garcia-Martinez J. C., Crooks R. M., Chem. Mater., 2006, 18(21), 5039—5044
[8]	Chung Y. M., Rhee H. J., Colloid Interface Sci., 2004, 271(1), 131—135
[9]	Chung Y. M., Rhee H. K., J. Mol. Catal. A, Chem., 2003, 206, 291—298
[10]	Zhang W., Li L., Du Y. K., Wang X. M., Yang P., Catal. Lett., 2009, 127, 429—436
[11]	deBrabander-van den Berg E. M. M., Meijer E. W., Angew. Chem. Int. Ed. Engl., 1993, 32, 1308—1311
[12]	Wang Y., Peng X. H., Nano-Micro. Lett., 2014, 6(1), 55—62
[13]	Martin P., McManus N. T., Rempel G. L., J. Mol. Catal. A: Chem., 1997, 126(2/3), 115—131
[14]	Cao P., Ni Y. Q., Zou R., Yue D. M., RSC Adv., 2015, 5, 3417—3424
[15]	Fideler P., Process for the Selective Hydrogenation of Unsatuated Compounds, US 4978771, 1990-12-18
[16]	Peng X., Pan M., Lu X., J. Appl. Polym. Sci., 2011, 122, 334—341
[17]	Crooks R. M., Zhao M., Sun L., Chechik V., Yeung L. K., Acc. Chem. Res., 2001, 34(3), 181—190