氮化碳负载钯催化剂的制备及对SBS选择性催化加氢性能的研究

doi:10.11949/0438-1157.20221307

摘要/Abstract

摘要：

苯乙烯-丁二烯-苯乙烯嵌段共聚物（SBS）选择性催化加氢是保留链段中苯环不被加氢而CC双键选择性加氢，从而得到具有更优异性能的高附加值氢化产物SEBS。为了消除反应物大分子孔内扩散限制问题，采用胶体SiO₂亚微米球为模板，通过氰胺热缩合成功合成了三维有序超大孔氮化碳（3DOM g-C₃N₄），以其为载体采用化学还原负载法得到了具有超大孔结构的Pd/3DOM g-C₃N₄催化剂，并将其用于SBS的选择性催化加氢反应。结果表明，Pd/3DOM g-C₃N₄催化剂具有超大孔-大孔-介孔多级孔三维贯穿结构且Pd颗粒尺寸小、分散均匀，该催化剂在较为温和的反应条件下，即表现出极为优异的加氢活性和选择性。根据红外表征计算得到其对SBS的 1,2-CC和1,4-CC总加氢度达到98%，而对苯环没有加氢，选择性为100%。其优异的催化性能主要归功于载体独特的超大孔-大孔-介孔多级孔三维贯穿结构可以有效消除大分子在孔隙中的扩散限制，从而提高了对活性位点的可接近性；Pd和载体氮化碳中的吡啶N之间存在强相互作用，有利于Pd的锚定，进而获得颗粒尺寸小且分散度和稳定性高的Pd纳米颗粒。

关键词: g-C₃N₄, 超大孔载体, 负载型 Pd基催化剂, SBS, 加氢

Abstract:

The selective catalytic hydrogenation of styrene-butadiene-styrene block copolymer (SBS) is to selectively hydrogenate the unsaturated CC in polybutadiene segment while maintaining the phenyl group in polystyrene segment intact so as to yield high-valued hydrogenated products SEBS with greatly improved performance. In order to eliminate the diffusion limitation, herein, three-dimensional ordered super-macroporous carbon nitride (3DOM g-C₃N₄) was successfully synthesized via thermal condensation of cyanamide with colloidal SiO₂sub-microspheres as the template. Afterwards, the Pd/3DOM g-C₃N₄ catalyst was obtained by chemical reduction method and applied for selective catalytic hydrogenation of SBS. The results showed that the Pd/3DOM g-C₃N₄ catalyst possessed a three-dimensional penetrating structure of super-macroporous-macroporous-mesoporous multistage pore with the small-sized and well-dispersed Pd nanoparticles over it. Such catalyst exhibited excellent hydrogenation activity and selectivity under mild reaction conditions. According to the Fourier transform infrared (FTIR) characterization, the total hydrogenation degree of 1,2-CC and 1,4-CC to SBS was 98%, while the benzene ring was not hydrogenated thus the selectivity to CC was 100%. The excellent catalytic performance is mainly attributed to the unique three-dimensional penetrating structure of super-macroporous-macroporous-mesoporous multistage pore of the support, which can effectively eliminate the macromolecules diffusion limitation in pores, thereby greatly improving the accessibility to the active sites. The strong interaction between Pd and pyridinic N in the g-C₃N₄support is beneficial to anchoring Pd²⁺ during impregnation process, and then obtains Pd nanoparticles with small particle size and high dispersion and stability.

Key words: g-C₃N₄, super-macroporous support, supported Pd catalyst, SBS, hydrogenation

中图分类号:

TQ 032.4

梁梦欣, 郭艳, 王世栋, 张宏伟, 袁珮, 鲍晓军. 氮化碳负载钯催化剂的制备及对SBS选择性催化加氢性能的研究[J]. 化工学报, 2023, 74(2): 766-775.

Mengxin LIANG, Yan GUO, Shidong WANG, Hongwei ZHANG, Pei YUAN, Xiaojun BAO. Study on preparation of Pd catalyst supported on carbon nitride for the selective hydrogenation of SBS[J]. CIESC Journal, 2023, 74(2): 766-775.

图/表 11

图1 Pd/3DOM g-C3N4催化剂的合成策略示意图

Fig.1 Schematic illustration of the synthetic strategy for Pd/3DOM g-C3N4 catalyst

图2 SBS结构式

Fig.2 The structural formula of SBS

图3 SiO2、3DOM g-C3N4和Pd/3DOM g-C3N4的形貌以及Pd/3DOM g-C3N4的Pd颗粒粒径分布

Fig.3 The morphology of SiO2, 3DOM g-C3N4 and Pd/3DOM g-C3N4 and the Pd particle size distribution of Pd/3DOM g-C3N4

图4 3DOM g-C3N4载体及Pd/3DOM g-C3N4催化剂的织构图

Fig.4 Texture images of 3DOM g-C3N4 support and Pd/3DOM g-C3N4 catalyst

表1 3DOM g-C3N4载体及Pd/3DOM g-C3N4催化剂的结构参数

Table 1 Physiochemical parameters of 3DOM g-C3N4 support and Pd/3DOM g-C3N4 catalyst

Samples	BET surface area/(m²/g)	Pore volume/(cm³/g)	Pore size/nm
3DOM g-C₃N₄	21	0.03	3.7/30
Pd/3DOM g-C₃N₄	24	0.05	3.9/32

图5 3DOM g-C3N4载体和Pd/3DOM g-C3N4催化剂的XPS谱图

Fig.5 XPS spectra of 3DOM g-C3N4 and Pd/3DOM g-C3N4 catalyst

表2 3DOM g-C3N4载体和Pd/3DOM g-C3N4催化剂的XPS数据

Table 2 XPS data for 3DOM g-C3N4 and Pd/3DOM g-C3N4 catalyst

Samples	N/%	C/%	O/%	Pd/%	Binding energy/eV			Graphitic N/%	Pyrrolic N/%	Pyridinic N/%
Samples	N/%	C/%	O/%	Pd/%	Graphitic N	Pyrrolic N	Pyridinic N	Graphitic N/%	Pyrrolic N/%	Pyridinic N/%
3DOM g-C₃N₄	48.45	46.36	5.19	—	400.80	399.71	398.26	7.19	17.95	74.85
Pd/3DOM g-C₃N₄	48.20	44.23	7.02	0.54	400.85	399.70	398.47	8.13	19.39	72.84

图6 g-C3N4、Pd/g-C3N4的形貌和g-C3N4的孔结构

Fig.6 Morphology of g-C3N4 and Pd/g-C3N4 and pore structure of g-C3N4

图7 SBS原料及由Pd/3DOM g-C3N4和Pd/g-C3N4催化加氢后的氢化产物SEBS的FTIR光谱

Fig.7 The FTIR spectra of SBS and SEBS produced by Pd/3DOM g-C3N4 and Pd/g-C3N4

图8 SBS原料及由Pd/3DOM g-C3N4催化加氢后的氢化产物SEBS的1H NMR图

Fig.8 The 1H NMR spectra of SBS and SEBS produced by Pd/3DOM g-C3N4

图9 单氰胺前体的热重图、热缩聚过程及氮化碳负载Pd催化剂示意图

Fig.9 TG curve, thermal condensation process of the cyanamide precursor and schematic illustration of the carbon nitride-supported Pd catalyst

参考文献 34

1	Wang H, Rempel G L. Aqueous-phase catalytic hydrogenation of unsaturated polymers[J]. Catalysis Today, 2015, 247: 117-123.
2	Han K Y, Cao G P, Zuo H R, et al. Hydrogenation of commercial polystyrene on Pd/TiO₂monolithic ceramic foam catalysts: catalytic performance and enhanced internal mass transfer[J]. Reaction Kinetics, Mechanisms and Catalysis, 2015, 114(2): 501-517.
3	阴义轩, 成婷婷, 袁珮, 等. 丁腈橡胶非均相加氢催化剂失活原因及再生性能研究[J]. 化工学报, 2019, 70(7): 2528-2539.
	Yin Y X, Cheng T T, Yuan P, et al. Deactivation and regeneration of heterogeneous catalysts for hydrogenation of nitrile butadiene rubber[J]. CIESC Journal. 2019, 70(7): 2528-2539.
4	Wang S H, Ge B Q, Yin Y X, et al. Solvent effect in heterogeneous catalytic selective hydrogenation of nitrile butadiene rubber: relationship between reaction activity and solvents with density functional theory analysis[J]. ChemCatChem, 2020, 12(2): 663-672.
5	Zhang P, Zhang H W, Wang S H, et al. Effect of support morphology on the activity and reusability of Pd/SiO₂ for NBR hydrogenation[J]. Journal of Materials Science, 2020, 55(27): 12876-12883.
6	Zhu J Q, Birgisson B, Kringos N. Polymer modification of bitumen: advances and challenges[J]. European Polymer Journal, 2014, 54: 18-38.
7	葛冰青, 阴义轩, 王亚溪, 等. 溶剂对丁腈橡胶溶解、尺寸、结构和催化加氢的影响研究[J]. 化工学报, 2021, 72(1): 543-554.
	Ge B Q, Yin Y X, Wang Y X, et al. Study of solvent effect on the dissolution, size, structure and catalytic hydrogenation of nitrile butadiene rubber[J]. CIESC Journal. 2021, 72(1): 543-554.
8	Sun H M, Yang J T, Zhang H W, et al. Hierarchical flower-like NiCu/SiO₂ bimetallic catalysts with enhanced catalytic activity and stability for petroleum resin hydrogenation[J]. Industrial & Engineering Chemistry Research, 2021, 60(15): 5432-5442.
9	Falk J C. Lithium based coordination catalysts for the hydrogenation of diene and vinylaromatic polymers[J]. Macromolecular Chemistry and Physics, 1972, 160(1): 291-299.
10	Wei L, Jiang J Y, Wang Y H, et al. Selective hydrogenation of SBS catalyzed by Ru/TPPTS complex in polyether modified ammonium salt ionic liquid[J]. Journal of Molecular Catalysis A: Chemical, 2004, 221(1/2): 47-50.
11	贺小进, 李伟, 陈建军. 氢化SBS国内外现状及发展趋势[J]. 化工新型材料, 2008, 36(9): 10-15.
	He X J, Li W, Chen J J. The status and development trend of hydrogenated SBS at home and abroad[J]. New Chemical Materials, 2008, 36(9): 10-15.
12	于付江, 陈建军, 贺小进, 等. 苯甲酸甲酯促进茂金属催化剂催化SBS加氢反应研究[J]. 高分子学报, 2010(11): 1306-1312.
	Yu F J, Chen J J, He X J, et al. Selective catalytic hydrogenation of sbs block copolymer with metallocene catalyst accelerated by methyl benzoate[J]. Acta Polymerica Sinica, 2010(11): 1306-1312.
13	曾伟, 刘甲, 张德谨, 等. Pd-Au/1cTiO₂/SiO₂催化剂的制备及其烯烃的环氧化性能[J]. 化工学报, 2020, 71(11): 4999-5006.
	Zeng W, Liu J, Zhang D J, et al. Preparation of catalyst Pd-Au/1cTiO₂/SiO₂ and epoxidation of olefins[J]. CIESC Journal. 2020, 71(11): 4999-5006.
14	Singha N K, Sivaram S. Homogeneous catalytic hydrogenation of poly(styrene-co-butadiene) using a ruthenium based Wilkinson catalyst[J]. Polymer Bulletin, 1995, 35(1): 121-128.
15	李宇辉. 二氯二茂钛用于丁苯共聚物SBS加氢的研究[J]. 化工管理, 2021(27): 144-145.
	Li Y H. Study on titanocene dichloride used in hydrogenation of SBS copolymer[J]. Chemical Enterprise Management, 2021(27): 144-145.
16	Chen J, Ma L, Cheng T T, et al. Stable and recyclable Pd catalyst supported on modified silica hollow microspheres with macroporous shells for enhanced catalytic hydrogenation of NBR[J]. Journal of Materials Science, 2018, 53(21): 15064-15080.
17	Ai C J, Gong G B, Zhao X T, et al. Macroporous hollow silica microspheres-supported palladium catalyst for selective hydrogenation of nitrile butadiene rubber[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 77: 250-256.
18	Zou R, Li C, Zhang L Q, et al. Selective hydrogenation of nitrile butadiene rubber (NBR) with rhodium nanoparticles supported on carbon nanotubes at room temperature[J]. Catalysis Communications, 2016, 81: 4-9.
19	Luo Z H, Feng M, Lu H, et al. Nitrile butadiene rubber hydrogenation over a monolithic Pd/CNTs@Nickel foam catalysts: tunable CNTs morphology effect on catalytic performance[J]. Industrial & Engineering Chemistry Research, 2019, 58(5): 1812-1822.
20	Feng M, Luo Z H, Chen R Q, et al. Palladium supported on carbon nanotube modified nickel foam as a structured catalyst for polystyrene hydrogenation[J]. Applied Catalysis A: General, 2019, 570: 329-338.
21	Liu Q H, Yang J T, Zhang H W, et al. Tuning the properties of Ni-based catalyst via La incorporation for efficient hydrogenation of petroleum resin[J]. Chinese Journal of Chemical Engineering, 2022, 45: 41-50.
22	Wang R, Sun H M, Liang M X. Flower-like nickel phosphide catalyst for petroleum resin hydrogenation with enhanced catalytic activity, hydrodesulfurization ability and stability[J]. Chemical Engineering Science, 2022, 264(12): 118180.
23	Ge B Q, Hu Y D, Zhang H W, et al. Zirconium promoter effect on catalytic activity of Pd based catalysts for heterogeneous hydrogenation of nitrile butadiene rubber[J]. Applied Surface Science, 2021, 539(2): 148212.
24	Chang J R, Huang S M. Pd/Al₂O₃ catalysts for selective hydrogenation of polystyrene-block-polybutadiene-block-polystyrene thermoplastic elastomers[J]. Industrial & Engineering Chemistry Research, 1998, 37(4): 1220-1227.
25	Pan D, Shi G, Zhang T, et al. New understanding and controllable synthesis of silica hollow microspheres with size-tunable penetrating macroporous shells as a superior support for polystyrene hydrogenation catalysts[J]. Journal of Materials Chemistry A, 2013, 1(34): 9597-9602.
26	Chen J, Hu Y D, Cai A F, et al. The mesopore-elimination treatment and silanol-groups recovery for macroporous silica microspheres and its application as an efficient support for polystyrene hydrogenation[J]. Catalysis Communications, 2018, 111: 75-79.
27	Lin B, Li J L, Xu B R, et al. Spatial positioning effect of dual cocatalysts accelerating charge transfer in three dimensionally ordered macroporous g-C₃N₄for photocatalytic hydrogen evolution[J]. Applied Catalysis B: Environmental, 2019, 243: 94-105.
28	Lin B, Yang G D, Yang B L, et al. Construction of novel three dimensionally ordered macroporous carbon nitride for highly efficient photocatalytic activity[J]. Applied Catalysis B: Environmental, 2016, 198: 276-285.
29	Guo Y, Yang J T, Zhuang J Y, et al. Selectively catalytic hydrogenation of styrene-butadiene rubber over Pd/g-C₃N₄ catalyst[J]. Applied Catalysis A: General, 2020, 589: 117312.
30	Sun J W, Fu Y S, He G Y, et al. Green Suzuki-Miyaura coupling reaction catalyzed by palladium nanoparticles supported on graphitic carbon nitride[J]. Applied Catalysis B: Environmental, 2015, 165: 661-667.
31	Zhao R Y, Sun X X, Jin Y R, et al. Au/Pd/g-C₃N₄ nanocomposites for photocatalytic degradation of tetracycline hydrochloride[J]. Journal of Materials Science, 2019, 54(7): 5445-5456.
32	Xu X L, Luo J J, Li L P, et al. Unprecedented catalytic performance in amine syntheses via Pd/g-C₃N₄ catalyst-assisted transfer hydrogenation[J]. Green Chemistry, 2018, 20(9): 2038-2046.
33	Cheng T T, Chen J, Cai A F, et al. Synthesis of Pd/SiO₂ catalysts in various HCl concentrations for selective NBR hydrogenation: effects of H⁺ and Cl^- concentrations and electrostatic interactions[J]. ACS Omega, 2018, 3(6): 6651-6659.
34	王悦, 蒋权, 尚介坤, 等. 介孔氮化碳材料合成的研究进展[J]. 物理化学学报, 2016, 32(8): 1913-1928.
	Wang Y, Jiang Q, Shang J K, et al. Advances in the synthesis of mesoporous carbon nitride materials[J]. Acta Physico-Chimica Sinica, 2016, 32(8): 1913-1928.

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