Citation: Cai-Li WANG, Bo-Yong YE, Han WANG, Song-Lin WANG, Lei YANG, Zhao-Yin HOU. Preparation and application in the hydrogenation of dimethyl terephthalate of Ru@G-CS catalyst[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(11): 2091-2102. doi: 10.11862/CJIC.2023.174 shu

Preparation and application in the hydrogenation of dimethyl terephthalate of Ru@G-CS catalyst

Cai-Li WANG ¹ ,
Bo-Yong YE ¹ ,
Han WANG ² ,
Song-Lin WANG ² ,
Lei YANG ² ,
Zhao-Yin HOU ^{1, 2,,}

1.
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Department of Chemistry, Zhejiang University, Hangzhou 310058, China
2.
Zhejiang Hengyi Petrochemical Research Institute Co., Ltd., Hangzhou 311200, China

Corresponding author: Zhao-Yin HOU, zyhou@zju.edu.cn
Received Date: 20 May 2023
Revised Date: 17 September 2023

Figures(14)

A series of nitrogen-doped graphene-coated Ru-based catalysts (Ru@G-CS) were prepared using glucose, melamine, and RuCl₃ as raw materials in a facile one-step pyrolysis method at 700℃ with a varied mass ratio of glucose/melamine in feed. The composition, structure, and surface morphology of these catalysts were characterized with powder X-ray diffraction, Raman spectroscopy, N₂ adsorption-desorption, X-ray photoelectron spectroscopy, scanning electron microscope, and transmission electron microscope. Characterization results showed that nitrogen in the graphene skeleton can promote the dispersion of Ru, and there was also a strong interaction between nitrogen and loaded Ru. Ru@G-CS(1:4) catalyst (with the mass ratio of glucose/melamine in feed was 1:4) possesses the highest surface area (429 m²·g^-1), biggest pore volume (0.45 cm³·g^-1) and highly dispersed Ru particles (about 1 nm) that encapsulated in 1-2 layered graphene film. At the same time, the detected w_Ru⁰/w_{Ru^{4 +}} (73.6/26.4), I_D/I_G (1.30) and I_2D/I_G (0.32) reached their maximum in Ru@G-CS(1:4). These catalysts were tested in dimethyl terephthalate (DMT) hydrogenation to 1,4-cyclohexane dimethyl dicarboxylate (DMCD) under mild conditions and compared with those traditional carriers (HZSM-5, Al₂O₃, MgO, ZnO) supported Ru catalysts. Ru@G-CS(1:4) exhibited high activity and stability at 160℃, 2.5 MPa H₂, m_DMT/m_Ru=833, the detected conversion of DMT reached 100% and the selectivity of DMCD remained higher than 98.5% within 4 h. The calculated turnover frequency of each Ru was 233.4 h^-1. More importantly, Ru@G-CS(1:4) could maintain its performance at least in 10 cycles. It was concluded that the electron-structure synergistic effect might be the main reason for the excellent activity and stability of Ru@G-CS(1:4).
- dimethyl terephthalate,
- dimethyl 1,4-cyclohexanedicarboxylate,
- hydrogenation,
- graphene,
- Ru
1. [1]
  Martín A J, Mondelli C, Jaydev S D, Pérez-Ramírez J. Catalytic processing of plastic waste on the rise[J]. Chem, 2021,7(6):1487-1533. doi: 10.1016/j.chempr.2020.12.006
2. [2]
  Ellis L D, Rorrer N A, Sullivan K P, Otto M, McGeehan J E, Román-Leshkov Y, Wierckx N, Beckham G T. Chemical and biological catalysis for plastics recycling and upcycling[J]. Nat. Catal., 2021,4(7):539-556. doi: 10.1038/s41929-021-00648-4
3. [3]
  Kakadellis S, Rosetto G. Achieving a circular bioeconomy for plastics[J]. Science, 2021,373(6550):49-50. doi: 10.1126/science.abj3476
4. [4]
  Borrelle S B, Ringma J, Law K L, Cole C M, Laurent L, Alexis M, Erin M, Jenna J, George H L, Michelle A H, Marcus E, Hugh P P, Hannah D F, Leah R G, Beth P, Akbar T, Miranda B, Nicholas M, Megan B, Chelsea M R. Predicted growth in plastic waste exceeds efforts to mitigate plastic pollution[J]. Science, 2020,369(6510):1515-1518. doi: 10.1126/science.aba3656
5. [5]
  Jie X Y, Li W S, Slocombe D, Gao Y, Banerjee I, Gonzalez C S, Yao B Z, AlMegren H, Alshihri S, Dilworth J, Thomas J, Xiao T C, Edwards P. Microwave-initiated catalytic deconstruction of plastic waste into hydrogen and high-value carbons[J]. Nat. Catal., 2020,3(11):902-912. doi: 10.1038/s41929-020-00518-5
6. [6]
  Lee S S, Yee A F. Temperature-dependent transition of deformation mode in poly(1,4-cyclohexylenedimethylene terephthalate)/poly(ethylene terephthalate) copolymers[J]. Macromolecules, 2003,36(18):6791-6796. doi: 10.1021/ma034660a
7. [7]
  Colonna M, Berti C, Binassi E, Celli A, Fiorini M, Marchese P, Messori M, Brunelle D J. Poly(1,4-cyclohexylenedimethylene-1,4-cyclohexanedicarboxylate): Analysis of parameters affecting polymerization and cis-trans isomerization[J]. Polym. Int., 2011,60(11):1607-1613. doi: 10.1002/pi.3128
8. [8]
  Li Y W, Wang M, Liu X W, Hu C Q, Xiao D Q, Ma D. Catalytic transformation of PET and CO₂ into high-value chemicals[J]. Angew. Chem. Int. Ed., 2022,134(10)e202117205. doi: 10.1002/ange.202117205
9. [9]
  Shou H G, Jia K., Zhou X, Gao L Q, He X H, Zhou X F, Zhang D W, Liu X B.. Large scale synthesis of an amorphous polyester elastomer with tunable mechanoluminescence and preliminary application in optical strain sensing[J]. J. Mater. Chem. C, 2017,5(17):4134-4138. doi: 10.1039/C7TC00433H
10. [10]
  Turner S R. Development of amorphous copolyesters based on 1,4-cyclohexanedimethanol[J]. J. Polym. Sci. Part A: Polym. Chem., 2004,42(23):5847-5852. doi: 10.1002/pola.20460
11. [11]
  Wu X Y, Bruyn M D, Hulan J M, Brasil H, Sun Z H, Barta K. High yield production of 1,4-cyclohexanediol and 1,4-cyclohexanediamine from high molecular-weight lignin oil[J]. Green Chem., 2023,25(1):211-220. doi: 10.1039/D2GC03777G
12. [12]
  Zhang F A, Chen J L, Chen P, Sun Z Y, Xu S L. Pd nanoparticles supported on hydrotalcite-modified porous alumina spheres as selective hydrogenation catalyst[J]. AIChE J., 2012,58(6):1853-1861. doi: 10.1002/aic.12694
13. [13]
  Xiao X X, Xin H Y, Qi Y Y, Zhao C, Wu P, Li X H. One-pot conversion of dimethyl terephthalate to 1,4-cyclohexanedimethanol[J]. Appl. Catal. A-Gen., 2022,632118510. doi: 10.1016/j.apcata.2022.118510
14. [14]
  Yu W, Bhattacharjee S, Lu W Y, Tan C S. Synthesis of Al-modified SBA-15-supported Ru catalysts by chemical fluid deposition for hydrogenation of dimethyl terephthalate in water[J]. ACS Sustainable Chem. Eng., 2020,8(10):4058-4068. doi: 10.1021/acssuschemeng.9b05634
15. [15]
  Chen J L, Liu X, Zhang F Z. Composition regulation of bimetallic RuPd catalysts supported on porous alumina spheres for selective hydrogenation[J]. Chem. Eng. J., 2015,259:43-52. doi: 10.1016/j.cej.2014.07.049
16. [16]
  Fan Q N, Li X F, Yang Z X, Han J J, Xu S L, Zhang F Z. Double-confined nickel nanocatalyst derived from layered double hydroxide precursor: Atomic scale insight into microstructure evolution[J]. Chem. Mater., 2016,28(17):6296-6304. doi: 10.1021/acs.chemmater.6b02553
17. [17]
  Gustafson B L, Guo Y J, Tennant B A. Low pressure process for the hydrogenation of dimethyl benzenedicarboxylates to the corresponding dimethyl cyclohexanedicarboxylates: EP0703894. 1998-08-26.
18. [18]
  WANG X H, XIN J N, MA Y H, ZHANG P, WANG Y, LÜ L H. Synthesis of dimethyl 1,4-cyclohexanedicarboxylate by low pressure hydrogenation of dimethyl terephthalate[J]. Petrochemical Technology, 2007,36(5):433-436.
19. [19]
  SONG G Q, DU W B, CAO Y M. A preparation method of dimethyl cyclohexane dicarboxylate: CN1308052A. 2001-08-15.
20. [20]
  LU C S, LIU Q Q, NIE J J, ZHANG X J, ZHOU Y B, ZHAO J, FENG F, MA L, ZHANG Q F, GUO L L, XU X L, LÜ J H, CEN J, LI X N. Preparation of supported ruthenium hydrogenation catalyst and its application in catalytic hydrogenation of dimethyl terephthalate: CN109701522B. 2021-06-08.
21. [21]
  Li X F, Sun Z Y, Chen J L, Zhu Y, Zhang F Z. One-pot conversion of dimethyl terephthalate into 1,4-cyclohexanedimethanol with supported trimetallic RuPtSn catalysts[J]. Ind. Eng. Chem. Res., 2014,53(2):619-625. doi: 10.1021/ie402987c
22. [22]
  Huang Y Q, Ma Y, Cheng Y W, Wang L J, Li X. Dimethyl terephthalate hydrogenation to dimethyl cyclohexanedicarboxylates over bimetallic catalysts on carbon nanotubes[J]. Ind. Eng. Chem. Res., 2014,53(12):4604-4613. doi: 10.1021/ie500015m
23. [23]
  Deng J, Deng D H, Bao X H. Robust catalysis on 2D materials encapsulating metals: concept, application, and perspective[J]. Adv. Mater., 2017,29(43)1606967. doi: 10.1002/adma.201606967
24. [24]
  Tang L, Meng X G, Deng D H, Bao X H. Confinement catalysis with 2D materials for energy conversion[J]. Adv. Mater., 2019,31(50)1901996. doi: 10.1002/adma.201901996
25. [25]
  YUAN Q X, CHEN W M, LÜ X R. Effect of one-dimensional/two- dimensional composite carbon support on methanol oxidation performance of Pd catalysts[J]. Chinese J. Inorg. Chem., 2022,38(11):2165-2172.
26. [26]
  ZHU S, SHENG J, JIA G D, LIU H D, LI Y. Synthesis and modification of mesoporous carbon nanomaterials[J]. Chinese J. Inorg. Chem., 2022,38(1):1-13.
27. [27]
  CAO S Y, CHEN B J, YU F F, XU X W, YAO Y Y. Preparation of MoO₂@nitrogen doped carbon composites for degradation of organic pollutants[J]. Chinese J. Inorg. Chem., 2023,39(1):80-90.
28. [28]
  Yang H H, Nie R F, Xia W, Yu X L, Jin D F, Lu X H, Zhou D, Xia Q H. Co embedded within biomass-derived mesoporous N-doped carbon as an acid-resistant and chemoselective catalyst for transfer hydrodeoxygenation of biomass with formic acid[J]. Green Chem., 2017,19(23):5714-5722. doi: 10.1039/C7GC02648J
29. [29]
  Hu Y, Bai C, Li M, Hojamberdiev M, Geng D S, Li X G. Tailoring atomically dispersed cobalt-nitrogen active sites in wrinkled carbon nanosheets via "fence" isolation for highly sensitive detection of hydrogen peroxide[J]. J. Mater. Chem. A, 2022,10(6):3190-3200. doi: 10.1039/D1TA09645A
30. [30]
  Deng X D, Zhao B T, Zhu L, Shao Z P. Molten salt synthesis of nitrogen-doped carbon with hierarchical pore structures for use as high-performance electrodes in supercapacitors[J]. Carbon., 2015,93:48-58. doi: 10.1016/j.carbon.2015.05.031
31. [31]
  Barman B K, Sarkar B, Nanda K K. Pd-coated Ru nanocrystals supported on N-doped graphene as HER and ORR electrocatalysts[J]. Chem. Commun., 2019,55(92):13928-13931. doi: 10.1039/C9CC06208D
32. [32]
  Sun Y Y, Li X W, Cai Z S, Bai H Z, Tang G P, Hou Z Y. Synthesis of 3D N-doped graphene/carbon nanotube hybrids with encapsulated Ni NPs and their catalytic application in the hydrogenation of nitroarenes[J]. Catal. Sci. Technol., 2018,8(19):4858-4863. doi: 10.1039/C8CY01145A
33. [33]
  Zhang B B, Song J L, Yang G Y, Han B X. Large-scale production of high-quality graphene using glucose and ferric chloride[J]. Chem. Sci., 2014,5(12):4656-4660. doi: 10.1039/C4SC01950D
34. [34]
  CHANG Y N, LU X Y, MA Z Y, XU D D, LIU Y, BAO J C. Synthesis and hydrazine-assisted overall water splitting performance of Ru nanoclusters/MoOMoO_3-x nanobelt bifunctional catalyst[J]. Chinese J. Inorg. Chem., 2022,38(10):2037-2046.
35. [35]
  Chen B F, Dong M H, Liu S L, Xie Z B, Yang J J, Li S P, Wang Y Y, Du J, Liu H Z, Han B X. CO₂ hydrogenation to formate catalyzed by Ru coordinated with a N, P-containing polymer[J]. ACS Catal., 2020,10(15):8557-8566. doi: 10.1021/acscatal.0c01678
36. [36]
  Zhao Y F, Li W S, Rehman M U, Wang S P, Li G B, Xu Y. Roles of N on the N-doped Ru/AC catalyst in the hydrogenation of phthalate esters[J]. Res. Chem. Intermed., 2022,48(7):2987-3006. doi: 10.1007/s11164-022-04730-9
37. [37]
  Shi J J, Zhao M S, Wang Y Y, Fu J, Lu X Y, Hou Z Y. Upgrading of aromatic compounds in bio-oil over ultrathin graphene encapsulated Ru nanoparticles[J]. J. Mater. Chem. A, 2016,4(16):5842-5848. doi: 10.1039/C6TA01317A
38. [38]
  Wang Y, Ren P J, Hu J T, Tu Y C, Gong Z M, Cui Y Zheng Y P, Chen M S, Zhang W J, Ma C, Yu L, Yang F, Wang Y, Bao X H, Deng D H. Electron penetration triggering interface activity of Pt-graphene for CO oxidation at room temperature[J]. Nat. Commun., 2021,12(1)5814. doi: 10.1038/s41467-021-26089-y
39. [39]
  Deng J, Ren P J, Deng D H, Bao X H. Enhanced electron penetration through an ultrathin graphene layer for highly efficient catalysis of the hydrogen evolution reaction[J]. Angew. Chem., 2015,127(7):2128-2132. doi: 10.1002/ange.201409524
40. [40]
  Sun Y Y, Li X W, Wang J G, Ning W S, Fu J, Lu X Y, Hou Z Y. Carbon film encapsulated Pt NPs for selective oxidation of alcohols in acidic aqueous solution[J]. Appl. Catal. B-Environ., 2017,218(5):538-544.
41. [41]
  Fu H Q, Huang K T, Yang G G, Cao Y H, Wang H J, Peng F, Wang Q, Yu H. Synergistic effect of nitrogen dopants on carbon nanotubes on the catalytic selective epoxidation of styrene[J]. ACS Catal., 2020,10(1):129-137. doi: 10.1021/acscatal.9b03584
42. [42]
  He B, Liu F, Yan S K. Temperature-directed growth of highly pyridinic nitrogen doped, graphitized, ultra-hollow carbon frameworks as an efficient electrocatalyst for the oxygen reduction reaction[J]. J. Mater. Chem. A, 2017,5(34):18064-18070. doi: 10.1039/C7TA04685E
1. [1]
  Zhihuan XU , Qing KANG , Yuzhen LONG , Qian YUAN , Cidong LIU , Xin LI , Genghuai TANG , Yuqing LIAO . Effect of graphene oxide concentration on the electrochemical properties of reduced graphene oxide/ZnS. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1329-1336. doi: 10.11862/CJIC.20230447
2. [2]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Fei Liu . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 100036-. doi: 10.3866/PKU.WHXB202408004
3. [3]
  Jianding LI , Junyang FENG , Huimin REN , Gang LI . Proton conductive properties of a Hf(Ⅳ)-based metal-organic framework built by 2,5-dibromophenyl-4,6-dicarboxylic acid. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1094-1100. doi: 10.11862/CJIC.20240464
4. [4]
  Liuyun Chen , Wenju Wang , Tairong Lu , Xuan Luo , Xinling Xie , Kelin Huang , Shanli Qin , Tongming Su , Zuzeng Qin , Hongbing Ji . Soft template-induced deep pore structure of Cu/Al₂O₃ for promoting plasma-catalyzed CO₂ hydrogenation to DME. Acta Physico-Chimica Sinica, 2025, 41(6): 100054-. doi: 10.1016/j.actphy.2025.100054
5. [5]
  Tian TIAN , Meng ZHOU , Jiale WEI , Yize LIU , Yifan MO , Yuhan YE , Wenzhi JIA , Bin HE . Ru-doped Co₃O₄/reduced graphene oxide: Preparation and electrocatalytic oxygen evolution property. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 385-394. doi: 10.11862/CJIC.20240298
6. [6]
  Rui HUANG , Shengjie LIU , Qingyuan WU , Nanfeng ZHENG . Enhanced selectivity of catalytic hydrogenation of halogenated nitroaromatics by interfacial effects. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 201-212. doi: 10.11862/CJIC.20240356
7. [7]
  Jie XIE , Hongnan XU , Jianfeng LIAO , Ruoyu CHEN , Lin SUN , Zhong JIN . Nitrogen-doped 3D graphene-carbon nanotube network for efficient lithium storage. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1840-1849. doi: 10.11862/CJIC.20240216
8. [8]
  Zhuoming Liang , Ming Chen , Zhiwen Zheng , Kai Chen . Multidimensional Studies on Ketone-Enol Tautomerism of 1,3-Diketones By ¹H NMR. University Chemistry, 2024, 39(7): 361-367. doi: 10.3866/PKU.DXHX202311029
9. [9]
  Yunting Shang , Yue Dai , Jianxin Zhang , Nan Zhu , Yan Su . Something about RGO (Reduced Graphene Oxide). University Chemistry, 2024, 39(9): 273-278. doi: 10.3866/PKU.DXHX202306050
10. [10]
  Liangzhen Hu , Li Ni , Ziyi Liu , Xiaohui Zhang , Bo Qin , Yan Xiong . A Green Chemistry Experiment on Electrochemical Synthesis of Benzophenone. University Chemistry, 2024, 39(6): 350-356. doi: 10.3866/PKU.DXHX202312001
11. [11]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
12. [12]
  Zhenlin Zhou , Siyuan Chen , Yi Liu , Chengguo Hu , Faqiong Zhao . A New Program of Voltammetry Experiment Teaching Based on Laser-Scribed Graphene Electrode. University Chemistry, 2024, 39(2): 358-370. doi: 10.3866/PKU.DXHX202308049
13. [13]
  Tianqi Bai , Kun Huang , Fachen Liu , Ruochen Shi , Wencai Ren , Songfeng Pei , Peng Gao , Zhongfan Liu . 石墨烯厚膜热扩散系数与微观结构的关系. Acta Physico-Chimica Sinica, 2025, 41(3): 2404024-. doi: 10.3866/PKU.WHXB202404024
14. [14]
  Jiahao Lu , Xin Ming , Yingjun Liu , Yuanyuan Hao , Peijuan Zhang , Songhan Shi , Yi Mao , Yue Yu , Shengying Cai , Zhen Xu , Chao Gao . 基于稳态电热法的石墨烯膜导热系数的精确可靠测量. Acta Physico-Chimica Sinica, 2025, 41(5): 100045-. doi: 10.1016/j.actphy.2025.100045
15. [15]
  Zeyu XU , Anlei DANG , Bihua DENG , Xiaoxin ZUO , Yu LU , Ping YANG , Wenzhu YIN . Evaluation of the efficacy of graphene oxide quantum dots as an ovalbumin delivery platform and adjuvant for immune enhancement. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1065-1078. doi: 10.11862/CJIC.20240099
16. [16]
  Hao BAI , Weizhi JI , Jinyan CHEN , Hongji LI , Mingji LI . Preparation of Cu₂O/Cu-vertical graphene microelectrode and detection of uric acid/electroencephalogram. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1309-1319. doi: 10.11862/CJIC.20240001
17. [17]
  Shuhui Li , Rongxiuyuan Huang , Yingming Pan . Electrochemical Synthesis of 2,5-Diphenyl-1,3,4-Oxadiazole: A Recommended Comprehensive Organic Chemistry Experiment. University Chemistry, 2025, 40(5): 357-365. doi: 10.12461/PKU.DXHX202407028
18. [18]
  Yunli Xu , Xuwen Da , Lei Wang , Yatong Peng , Wanpeng Zhou , Xiulian Liu , Yao Wu , Wentao Wang , Xuesong Wang , Qianxiong Zhou . Ru(Ⅱ)-based aggregation-induced emission (AIE) agents with efficient ¹O₂ generation, photo-catalytic NADH oxidation and anticancer activity. Chinese Chemical Letters, 2025, 36(5): 110168-. doi: 10.1016/j.cclet.2024.110168
19. [19]
  Lirui Shen , Kun Liu , Ying Yang , Dongwan Li , Wengui Chang . Synthesis and Application of Decanedioic Acid-N-Hydroxysuccinimide Ester: Exploration of Teaching Reform in Comprehensive Applied Chemistry Experiment. University Chemistry, 2024, 39(8): 212-220. doi: 10.3866/PKU.DXHX202312035
20. [20]
  Ling Liu , Haibin Wang , Genrong Qiang . Curriculum Ideological and Political Design for the Comprehensive Preparation Experiment of Ethyl Benzoate Synthesized from Benzyl Alcohol. University Chemistry, 2024, 39(2): 94-98. doi: 10.3866/PKU.DXHX202304080

Get Citation

PDF

XML

Metrics

PDF Downloads(13)
Abstract views(1240)
HTML views(184)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142