Pd/mpg-C3N4催化剂的制备、表征及其对松香加氢反应的催化性能

doi:10.3969/j.issn.0253-2417.2019.02.011

摘要/Abstract

摘要：

以SiO₂和三聚氰胺为原料，通过高温焙烧法制得介孔类石墨相氮化碳(mpg-C₃N₄)，以浸渍法负载Pd纳米粒子制得Pd/mpg-C₃N₄，并用于催化松香加氢反应。采用XRD、FT-IR、TEM、ICP-AES、XPS、氮气吸附-脱附及GC分析对催化剂的结构、形貌特征、Pd负载量、金属价态、比表面积和孔径以及催化活性进行分析。结果表明：Pd纳米粒子成功地均匀分散在了氮化碳的层状结构中，Pd的负载并没有改变mpg-C₃N₄的骨架结构，Pd/mpg-C₃N₄仍然保持着介孔结构；但是Pd的负载使mpg-C₃N₄的比表面积、孔容和孔径均有所减小，Pd/mpg-C₃N₄的比表面积、孔容和孔径分别为47.73 m²/g、0.17 cm³/g和3.39 nm。在负载量为7.96%，5 MPa H₂、150 ℃和反应4 h的松香催化加氢优化条件下制得去氢枞酸GC含量5.99%，枞酸GC含量小于1%的氢化松香产品(其中四氢枞酸为37.12%，二氢枞酸为56.71%)。催化剂Pd/mpg-C₃N₄重复使用4次后，四氢枞酸GC含量由37.12%下降至24.71%，去氢枞酸GC含量由5.99%上升至9.76%。

关键词: 介孔类石墨相氮化碳, 纳米钯, 松香, 催化加氢

Abstract:

Using SiO₂ and melamine as raw materials, mesoporous graphitic carbon nitride(mpg-C₃N₄) was prepared by high-temperature baking method. Pd/mpg-C₃N₄ was then prepared by impregnating of Pd nanoparticles and used to catalyze the hydrogenation of rosin. XRD, FT-IR, TEM, ICP-AES, XPS, nitrogen adsorption-desorption and GC were used to analyze the structure, morphology, actual loading of Pd, metal valence, specific surface area, pore size and catalytic activity of the catalyst. The results showed that nano-Pd was successfully uniformly dispersed in the layered structure of carbon nitride. Pd/mpg-C₃N₄ still maintained the mesoporous structure after Pd loading. However, due to Pd loading, the BET surface area, pore volume and pore diameter of mpg-C₃N₄ were reduced to 47.73 m²/g, 0.17 cm³/g and 3.39 nm, respectively. Hydrogenated rosin products with 5.99% dehydroabietic acid and less than 1% abietic acid were obtained under the optimized conditions for the hydrogenation of rosin (7.96% Pd loading, 5 MPa H₂, 150 ℃, 4 h). After four cycles for the catalyst, the GC content of tetrahydroabietic acid decreased from 37.12% to 24.71%, and the GC content of dehydroabietic acid increased from 5.99% to 9.76%.

Key words: mesoporous graphitic carbon nitride, nano-palladium, rosin, catalytic hydrogenation

中图分类号:

TQ35

李晓豪,解从霞. Pd/mpg-C₃N₄催化剂的制备、表征及其对松香加氢反应的催化性能[J]. 林产化学与工业, 2019, 39(2): 73-80.

Xiaohao LI,Congxia XIE. Preparation, Characterization and Performance for Rosin Hydrogenation of Pd/mpg-C₃N₄ Catalyst[J]. Chemistry and Industry of Forest Products, 2019, 39(2): 73-80.

图/表 10

图1

图2

图3

图4

图5

图6

表1

图7

表2

图8

参考文献 15

1	王显华. 皂化松香的应用研究综述[J]. 广东化工, 2011, 38 (3): 30- 31, 46. doi: 10.3969/j.issn.1007-1865.2011.03.014
	WANG X H . Review of studies on the application of saponified rosin[J]. Guangdong Chemical, 2011, 38 (3): 30- 31, 46. doi: 10.3969/j.issn.1007-1865.2011.03.014
2	梁明远, 刘雄民, 李伟光, 等. 枞酸氧化反应及其抗氧剂的研究[J]. 应用化工, 2010, 39 (3): 314- 317, 328. doi: 10.3969/j.issn.1671-3206.2010.03.002
	LIANG M Y , LIU X M , LI W G , et al. Study on the oxidation reaction of abietic acid and antioxidants[J]. Applied Chemical Industry, 2010, 39 (3): 314- 317, 328. doi: 10.3969/j.issn.1671-3206.2010.03.002
3	韦小杰, 李前, 陈小鹏, 等. Pd/C催化剂上松香加氢制备二氢和四氢枞酸的本征动力学[J]. 高校化学工程学报, 2011, 25 (2): 269- 275. doi: 10.3969/j.issn.1003-9015.2011.02.016
	WEI X J , LI Q , CHEN X P , et al. The intrinsic kinetics of catalytic hydrogenation of rosin to abietenoic-acid and abietanoec-acid on Pd/C catalyst[J]. Journal of Chemical Engineering of Chinese Universities, 2011, 25 (2): 269- 275. doi: 10.3969/j.issn.1003-9015.2011.02.016
4	LIU Y , LI L , LIU S W , et al. The selective hydrogenation of rosin to hydroabietic content using Pd/SBA-15 as catalysts[J]. Research on Chemical Intermediates, 2017, 43 (2): 1211- 1221. doi: 10.1007/s11164-016-2693-6
5	吕先富, 于世涛, 李露, 等. 纳米Pd组装介孔分子筛MCM-41催化松香加氢反应[J]. 林产化学与工业, 2007, 27 (6): 51- 55. doi: 10.3321/j.issn:0253-2417.2007.06.011
	LÜ X F , YU S T , LI L , et al. Study on hydrogenation of rosin catalyzed by mesoporous molecular sieve MCM-41 loaded with nanometer Pd[J]. Chemistry and Industry of Forest Products, 2007, 27 (6): 51- 55. doi: 10.3321/j.issn:0253-2417.2007.06.011
6	WANG X C , MAEDA K , THOMAS A , et al. A metal-free polymeric photocatalyst for hydrogen production from water under visible light[J]. Nature Materials, 2009, 8 (1): 76- 80. doi: 10.1038/nmat2317
7	WANG X C , CHEN X , THOMAS A , et al. Metal-containing carbon nitride compounds: A new functional organic-metal hybrid material[J]. Advanced Materials, 2009, 21 (16): 1609- 1612. doi: 10.1002/adma.v21:16
8	HUANG X H , XIAO Y J , CAO Y J , et al. Enhancing both selectivity and coking-resistance of a single-atom Pd₁/C₃N₄ catalyst for acetylene hydrogenation[J]. Nano Research, 2017, 10 (4): 1302- 1312. doi: 10.1007/s12274-016-1416-z
9	ZHAO Y K , TANG R R , HUANG R . Palladium supported on graphitic carbon nitride: An efficient and recyclable heterogeneous catalyst for reduction of nitroarenes and suzuki coupling reaction[J]. Catalysis Letters, 2015, 145 (11): 1961- 1971. doi: 10.1007/s10562-015-1600-x
10	DENG D S , YANG Y , GONG Y T , et al. Palladium nanoparticles supported on mpg-C₃N₄ as active catalyst for semihydrogenation of phenylacetylene under mild conditions[J]. Green Chemistry, 2013, 15 (9): 2525- 2531. doi: 10.1039/c3gc40779a
11	WANG Y , YAO J , LI H R , et al. Highly selective hydrogenation of phenol and derivatives over a Pd@carbon nitride catalyst in aqueous media[J]. Journal of the American Chemical Society, 2011, 133 (8): 2362- 2365. doi: 10.1021/ja109856y
12	LEE A F , NAUGHTON J N , LIU Z , et al. High-pressure XPS ofcrotyl alcohol selective oxidation over metallic and oxidized Pd(111)[J]. ACS Catalysis, 2012, 2 (11): 2235- 2241. doi: 10.1021/cs300450y
13	ZHOU Z X , SHEN Y F , LI Y , et al. Chemical cleavage of layered carbon nitride with enhanced photoluminescent performances and photoconduction[J]. ACS Nano, 2015, 9 (12): 12480- 12487. doi: 10.1021/acsnano.5b05924
14	THOMMES M , KANEKO K , NEIMARK A V , et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report)[J]. Pure and Applied Chemistry, 2015, 87 (9/10): 1051- 1069.
15	俞明远, 解从霞, 刘仕伟, 等. 水溶性钯-膦配合物催化松香加氢反应的研究[J]. 林产化学与工业, 2009, 29 (6): 11- 14. doi: 10.3321/j.issn:0253-2417.2009.06.003
	YU M Y , XIE C X , LIU S W , et al. Study on hydrogenation of rosin catalyzed by thermoregulated water-soluble phosphine palladium complex[J]. Chemistry and Industry of Forest Products, 2009, 29 (6): 11- 14. doi: 10.3321/j.issn:0253-2417.2009.06.003

样品 samples	比表面积/(m²·g^-1) BET specific surface area	孔容/(cm³·g^-1) pore volume	孔径/nm pore diameter
g-C₃N₄	6.61	0.03	1.78
mpg-C₃N₄	60.31	0.21	8.88
Pd/mpg-C₃N₄	47.73	0.17	3.39

催化剂种类 catalyst type	四氢枞酸/% tetrahydroabietic acid	二氢枞酸/% dihydroabietic acid	去氢枞酸/% dehydroabietic acid	枞酸/% abietic acid
Pd/C	28.44	64.84	6.61	< 1
Ru/C	16.70	62.62	11.11	9.57
Raney-Ni	18.06	61.38	19.48	1.08
Pd/mpg-C₃N₄	37.12	56.71	5.99	< 1
Pd/g-C₃N₄	21.20	63.56	13.19	2.05

[1]	许嘉琍, 张海波, 姚姝凤, 高宏, 商士斌. 林业生物质基果蔬涂膜保鲜剂的研究进展[J]. 林产化学与工业, 2019, 39(3): 10-16.
[2]	申晨, 王亚明, 蒋丽红, 郑艳娥, 宋爽爽, 来倩. Ni-P/rGO复合催化剂的制备、表征及其松香加氢性能研究[J]. 林产化学与工业, 2019, 39(3): 57-64.
[3]	程增会,张代晖,王基夫,王春鹏,储富祥,许凤. 分散聚合法制备单分散松香基聚合物微球[J]. 林产化学与工业, 2019, 39(2): 39-45.
[4]	罗云龙,沈明贵,蔡照胜,商士斌,宋湛谦. 脱氢枞酸酰胺基-3, 4-二氢嘧啶酮衍生物的合成与抗病毒活性研究[J]. 林产化学与工业, 2019, 39(2): 46-52.
[5]	冯晓龙, 李小童, 黄灵阁, 郭凯. 紫外光固化改性松香甲基丙烯酸酯的制备及性能[J]. 林产化学与工业, 2018, 38(5): 45-52.
[6]	李兆双, 李建芳, 刘鹤, 商士斌, 宋湛谦. 松香衍生物生物活性研究进展[J]. 林产化学与工业, 2018, 38(3): 17-24.
[7]	张海波, 蒋建新, 高宏, 商士斌, 宋湛谦. 松香基聚丙烯酰胺水凝胶的药物释放性能及其动力学研究[J]. 林产化学与工业, 2018, 38(3): 25-32.
[8]	林海霞, 杨明生, 田超, 韩春蕊. 松香基叔胺盐的自组装、复配及载药性能研究[J]. 林产化学与工业, 2018, 38(2): 59-66.
[9]	李侨光, 刘鹤, 李建芳, 商士斌, 宋湛谦. 松香基交联剂的制备及其对硅橡胶性能的影响[J]. 林产化学与工业, 2018, 38(2): 87-93.
[10]	李侨光, 刘鹤, 商士斌, 宋湛谦. 松香及其衍生物改性高分子材料的研究进展[J]. 林产化学与工业, 2017, 37(4): 23-29.
[11]	巫佳, 陆有达, 杨慧, 赖熙晨, 林日辉, 陈其勇. 松香淀粉酯对苯并芘的吸附研究[J]. 林产化学与工业, 2017, 37(4): 67-72.
[12]	王红琴, 王亚明, 蒋丽红, 晋艳琼. [Rh(COD)Cl]₂催化剂的制备及催化松节油加氢反应[J]. 林产化学与工业, 2016, 36(6): 56-62.
[13]	王小燕, 于世涛, 侯胜利, 陈祥云, 解从霞. [BMIM]BF₄中钌纳米催化剂的制备及催化α-蒎烯加氢反应[J]. 林产化学与工业, 2016, 36(6): 81-86.
[14]	刘少锋, 王春鹏, 储富祥, 俞娟, 王基夫. 松香基单体的RAFT聚合和表征[J]. 林产化学与工业, 2016, 36(4): 99-104.
[15]	齐帆, 杨艳平, 商士斌, 蔡照胜, 高宏, 黄旭娟. 脱氢枞醇丁烯二酸单酯的合成及助焊性能研究[J]. 林产化学与工业, 2016, 36(2): 94-98.

Pd/mpg-C₃N₄催化剂的制备、表征及其对松香加氢反应的催化性能

Preparation, Characterization and Performance for Rosin Hydrogenation of Pd/mpg-C₃N₄ Catalyst

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 15

相关文章 15

编辑推荐

Metrics

本文评价

关于本刊

投稿指南

在线期刊

相关单位

联系我们