镁铝复合金属氧化物负载钌纳米颗粒催化HMF 选择性氧化制 FDCA

doi:10.12066/j.issn.1007-2861.2064

摘要/Abstract

摘要：

采用水热-氢气还原法合成了镁铝复合金属氧化物负载 Ru 纳米颗粒催化剂,利用 X 射线衍射(X-ray diffraction,XRD)、扫描电镜(scanning electron microscope,SEM)、透射电镜(transmission electron microscope,TEM)、N₂ 物理吸附、CO₂-程序升温脱附(CO₂-temperature programmed desorption,CO₂-TPD)、电感耦合等离子体发射光谱(inductively coupled plasma-optical emission spectroscopy,ICP-OES)等表征手段对催化剂进行结构、形貌和组成分析。结果表明,镁铝物质的量之比 n(Mg):n(Al)=5:1 的催化剂载体具有最强的碱性(142.81 mmol·g^-1)和较大的比表面积(97.0 m²·g^-1),有利于负载高分散的 Ru 纳米颗粒。在最佳反应条件(120 ℃、2 MPa O₂、5 h)下,负载量为 2.0% 的 RO-5 催化剂能够高效催化 5-羟甲基糠醛(5-hydroxymethylfurfural,HMF)氧化制备 2,5-呋喃二甲酸(2,5-furandicarboxylic acid,FDCA),HMF 转化率和 FDCA 产率分别达到 100.0% 和 99.0%。条件优化实验进一步证实,HMF 催化氧化的反应路径为生成 2,5-呋喃二甲醛(2,5-diformylfuran,DFF)和 5-甲酰基-2-呋喃甲酸(5-formyl-2-furancarboxylic acid, FFCA)中间产物的过程。

关键词: 镁铝复合氧化物, Ru 纳米颗粒, 氧化, 羟甲基糠醛, 呋喃二甲酸

Abstract:

Ru nanoparticles supported on Mg-Al mixed metal oxide catalysts have been prepared via the hydrothermal-reduction method. The structure, morphology and composition of the catalysts have been systematically analyzed using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), N₂ physisorption, CO₂-temperature programmed desorption（CO₂-TPD) and inductively coupled plasma-optical emission spectroscopy (ICP-OES). The characterization results show that the highly dispersed Ru nanoparticles benefit from the strongest alkalinity (142.81 mmol·g^-1 and the competitive specific surface area (97.0 m²·g^-1 of mixed metal oxides with n(Mg):n(Al)=5:1. The RO-5 catalyst with Ru loading of 2.0% can efficiently catalyze aerobic oxidation of 5-hydroxymethylfurfural (HMF), obtaining 100.0% HMF conversion and 99.0% 2,5-furandicarboxylic acid (FDCA) yield under the optimal reaction condition (120 ℃ , 2 MPa O₂, 5 h). According to the optimizing results, the reaction pathway for the conversion of HMF to FDCA is further confirmed for the formation of 2,5-diformylfuran,(DFF) and 5-formyl-2-furancarboxylic acid (FFCA) intermediates.

Key words: Mg-Al mixed oxide, Ru nanoparticles, oxidation, hydroxymethylfurfural, furandicarboxylic acid

中图分类号:

O643.3

王凌晨, 谌春林, 张敏. 镁铝复合金属氧化物负载钌纳米颗粒催化HMF 选择性氧化制 FDCA[J]. 上海大学学报(自然科学版), 2020, 26(4): 552-561.

WANG Lingchen, CHEN Chunlin, ZHANG Min. Ru nanoparticles supported on Mg-Al mixed metal oxide catalysts for selective oxidation of HMF methylfurfural into FDCA[J]. Journal of Shanghai University（Natural Science Edition）, 2020, 26(4): 552-561.

图/表 9

图 1

表 1

图 2

图 3

图 4

图 5

表 2

图 6

图 7

参考文献 21

[1]	Gallezot P. Conversion of biomass to selected chemical products[J]. Chemical Society Reviews, 2012,41(4):1538-1558. doi: 10.1039/c1cs15147a pmid: 21909591
[2]	Huber G W, Chheda J N, Barrett C J, et al. Production of liquid alkanes by aqueous-phase processing of biomass-derived carbohydrates[J]. Science, 2005,308(5727):1446-1450. pmid: 15933197
[3]	Corma A, Iborra S, Velty A. Chemical routes for the transformation of biomass into chemicals[J]. Chemical Reviews, 2007,107(6):2411-2502. doi: 10.1021/cr050989d pmid: 17535020
[4]	Vispute T P, Zhang H Y, Sanna A, et al. Renewable chemical commodity feedstocks from integrated catalytic processing of pyrolysis oils[J]. Science, 2010,330(6008):1222-1227. pmid: 21109668
[5]	郑路凡, 杜泽学, 宗保宁. 催化合成典型5-羟甲基糠醛衍生物的研究进展[J]. 化工进展, 2015,34(6):1511-1518. doi: 10.16085/j.issn.1000-6613.2015.06.002
[6]	Zhang Z, Deng K. Recent advances in the catalytic synjournal of 2,5-furandicarboxylic acid and its derivatives[J]. ACS Catalysis, 2015,5(11):6529-6544. doi: 10.1021/acscatal.5b01491
[7]	孙璠, 李泽龙, 刘蒲, 等. 镁铝复合金属氧化物负载纳米 Pd 催化剂的制备及其在醇胺一步合成亚胺反应中的应用[J]. 分子催化, 2014,28(5):410-417.
[8]	Ardemani L, Cibin G, Dent A J, et al. Solid base catalysed 5-HMF oxidation to 2,5-FDCA over Au/hydrotalcites: fact or fiction[J]. Chemical Science, 2015,6(8):4940-4945. doi: 10.1039/c5sc00854a pmid: 30155002
[9]	Wang Y, Yu K, Lei D, et al. Basicity-tuned hydrotalcite-supported Pd catalysts for aerobic oxidation of 5-hydroxymethyl-2-furfural under mild conditions[J]. ACS Sustainable Chemistry and Engineering, 2016,4(9):4752-4761. doi: 10.1021/acssuschemeng.6b00965
[10]	Choudhary H, Ebitani K. Hydrotalcite-supported PdPt-catalyzed aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid in water[J]. Chemistry Letters, 2016,45(6):613-615. doi: 10.1246/cl.160178
[11]	Chen C L, Li X T, Wang L C, et al. Highly porous nitrogen- and phosphorus-codoped graphene: an outstanding support for Pd catalysts to oxidize 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid[J]. ACS Sustainable Chemistry & Engineering, 2017,5(12):11300-11306.
[12]	Gorbanev Y Y, Kegn S S, Riisager A. Effect of support in heterogeneous ruthenium catalysts used for the selective aerobic oxidation of HMF in water[J]. Topics in Catalysis, 2011,54(16/18):1318-1324. doi: 10.1007/s11244-011-9754-2
[13]	Gorbanev Y Y, Kegn S S, Riisager A. Selective aerobic oxidation of 5-hydroxymethylfurfural in water over solid ruthenium hydroxide catalysts with magnesium-based supports[J]. Catalysis Letters, 2011,141(12):1752-1760. doi: 10.1007/s10562-011-0707-y
[14]	Xie J, Nie J, Liu H. Aqueous-phase selective aerobic oxidation of 5-hydroxymethylfurfural on Ru/C in the presence of base[J]. Chinese Journal of Catalysis, 2014,35(6):937-944. doi: 10.1016/S1872-2067(14)60136-4
[15]	Nagpure A S, Venugopal A K, Lucas N, et al. Renewable fuels from biomass-derived compounds: Ru-containing hydrotalcites as catalysts for conversion of HMF to 2,5-dimethylfuran[J]. Catalysis Science & Technology, 2015,5(3):1463-1472.
[16]	Millange F, Walton R I, O'hare D. Time-resolved in situ X-ray diffraction study of the liquid-phase reconstruction of Mg-Al-carbonate hydrotalcite-like compounds[J]. Journal of Materials Chemistry, 2000,10(7):1713-1720. doi: 10.1039/b002827o
[17]	杨永杰, 曾虹燕, 王亚举, 等. 镁铝物质的量之比对水滑石纳米材料及其催化性能的影响[J]. 化学反应工程与工艺, 2011,27(4):358-362.
[18]	Davis S E, Zope B N, Davis R J. On the mechanism of selective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over supported Pt and Au catalysts[J]. Green Chemistry, 2012,14(1):143-147. doi: 10.1039/c1gc16074e
[19]	Zhang Z, Zhen J, Liu B, et al. Selective aerobic oxidation of the biomass-derived precursor 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid under mild conditions over a magnetic palladium nanocatalyst[J]. Green Chemistry, 2015,17(2):1308-1317. doi: 10.1039/C4GC01833H
[20]	Lei D, Yu K, Li M R, et al. Facet effect of single-crystalline Pd nanocrystals for aerobic oxidation of 5-hydroxymethyl-2-furfural[J]. ACS Catalysis, 2017,7(1):421-432. doi: 10.1021/acscatal.6b02839
[21]	Ventura M, Lobefaro F, De Giglio E, et al. Selective aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran or 2-formyl-5-furancarboxylic acid in water by using MgOCeO$_{2}$ mixed oxides as catalysts[J]. CHEMSUSCHEM, 2018,11(8):1305-1315. doi: 10.1002/cssc.201800334 pmid: 29513920