Citation: Zi-Xuan WANG, Yuan-Yuan JIANG, Ru-Ru ZHOU, Ping CHEN, Zhao-Yin HOU. Preparation and Application of the Bifunctional Pd/ZrHP Catalyst for Selective Hydrogenation of Phenol[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(5): 812-820. doi: 10.11862/CJIC.2022.087 shu

Preparation and Application of the Bifunctional Pd/ZrHP Catalyst for Selective Hydrogenation of Phenol

Department of Chemistry, Zhejiang University, Hangzhou 310028, China

Corresponding author: Ping CHEN, zyhou@zju.edu.cn Zhao-Yin HOU, c224@zju.edu.cn
Received Date: 4 November 2021
Revised Date: 11 March 2022

Figures(12)

Hydrogenation of phenol to cyclohexanone is a vital step in the production of synthetic fiber (nylon). In this work, a layered-structured solid acid (zirconium hydrogen phosphate, ZrHP) supported Pd catalyst was synthe- sized in a microwave method. The structure and property of Pd/ZrHP catalyst were characterized via X-ray diffrac- tion (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), nitro- gen adsorption- desorption, X-ray photoelectron spectroscopy (XPS), and temperature-programmed desorption (TPD) technologies. It was found that Pd/ZrHP catalyst exhibited better performance than the Pd-based catalysts supported by traditional oxide (Al₂O₃, SiO₂, MgO), molecular sieve (H-Beta), and active carbon (XC-72) under the mild condi- tion (100 ℃, 1.0 MPa H₂). The specific activity of the surface Pd atom in Pd/ZrHP reached 612.2 h^-1, and it could be recycled five times without obvious deactivation. The synergistic effect between Pd metal and the acidic sites on ZrHP surface might be the main reason for the selective formation of cyclohexanone.
- phenol,
- cyclohexanone,
- hydrogenation,
- zirconium phosphate,
- Pd
1. [1]
  Lin C J, Huang S H, Lai N C, Yang C M. Efficient Room-Temperature Aqueous-Phase Hydrogenation of Phenol to Cyclohexanone Catalyzed by Pd Nanoparticles Supported on Mesoporous MMT-1 Silica with Unevenly Distributed Functionalities[J]. ACS Catal., 2015,5(7):4121-4129. doi: 10.1021/acscatal.5b00380
2. [2]
  He J, Lu X H, Shen Y, Jing R, Nie R F, Zhou D, Xia Q H. Highly Selective Hydrogenation of Phenol to Cyclohexanol over Nano Silica Supported Ni Catalysts in Aqueous Medium[J]. J. Mol. Catal., 2017,440:87-95. doi: 10.1016/j.mcat.2017.07.016
3. [3]
  Guo Q, Mo S G, Liu P X, Zheng W D, Qin R X, Xu C F, Wu Y Y Q, Wu B H, Zheng N F. Air-Promoted Selective Hydrogenation of Phenol to Cyclohexanone at Low Temperature over Pd-Based Nanocatalysts[J]. Sci. China Chem., 2017,60(11):1444-1449. doi: 10.1007/s11426-017-9095-4
4. [4]
  Gao Y N, Hensen E J M. Highly Active and Stable Spinel-Oxide Sup-ported Gold Catalyst for Gas-Phase Selective Aerobic Oxidation of Cyclohexanol to Cyclohexanone[J]. Catal. Commun., 2018,17:53-56.
5. [5]
  Liu H Z, Jiang T, Han B X, Liang S G, Zhou Y X. Selective Phenol Hydrogenation to Cyclohexanone Over a Dual Supported Pd-Lewis Acid Catalyst[J]. Science, 2009,326(5957):1250-1252. doi: 10.1126/science.1179713
6. [6]
  Jiang H, Qu Z Y, Li Y, Huang J, Chen R Z, Xing W H. One-Step Semi-Continuous Cyclohexanone Production via Hydrogenation of Phenol in a Submerged Ceramic Membrane Reactor[J]. Chem. Eng. J., 2016,284:724-732. doi: 10.1016/j.cej.2015.09.037
7. [7]
  Zhao C C, Zhang Z Y, Liu Y R, Shang N Z, Wang H J, Wang C, Gao Y J. Palladium Nanoparticles Anchored on Sustainable Chitin for Phenol Hydrogenation to Cyclohexanone[J]. ACS Sustainable Chem. Eng., 2020,8(32):12304-12312. doi: 10.1021/acssuschemeng.0c04751
8. [8]
  Shafaghat H, Rezaei P S, Daud W M A W. Catalytic Hydrogenation of Phenol, Cresol and Guaiacol over Physically Mixed Catalysts of Pd/C and Zeolite Solid Acids[J]. RSC Adv., 2015,5(43):33990-33998. doi: 10.1039/C5RA00367A
9. [9]
  Wang H J, Zhao F Y, Fujita S I, Arai M. Hydrogenation of Phenol in ScCO₂ over Carbon Nanofiber Supported Rh Catalyst[J]. Catal. Commun., 2008,9(3):362-368. doi: 10.1016/j.catcom.2007.07.002
10. [10]
  Xiang Y Z, Ma L, Lu C S, Zhang Q F, Li X N. Aqueous System for the Improved Hydrogenation of Phenol and Its Derivatives[J]. Green Chem., 2008,10(9):939-943. doi: 10.1039/b803217c
11. [11]
  Zhang Z Z, Xu M K, Ho W K, Zhang X W, Yang Z Y, Wang X X. Simultaneous Excitation of PdCl₂ Hybrid Mesoporous g-C₃N₄ Molecular/Solid-State Photocatalysts for Enhancing the Visible-Light-Induced Oxidative Removal of Nitrogen Oxides[J]. Appl. Catal. B, 2016,184:174-181. doi: 10.1016/j.apcatb.2015.11.034
12. [12]
  Yang X, Du L, Liao S J, Li Y X, Song H Y. High-Performance Gold-Promoted Palladium Catalyst towards the Hydrogenation of Phenol with Mesoporous Hollow Spheres as Support[J]. Catal. Commun., 2012,17:29-33. doi: 10.1016/j.catcom.2011.10.006
13. [13]
  Nelson N C, Manzano J S, Sadow A D, Overbury S H, Slowing I I. Selective Hydrogenation of Phenol Catalyzed by Palladium on High-Surface-Area Ceria at Room Temperature and Ambient Pressure[J]. ACS Catal., 2015,5(4):2051-2061. doi: 10.1021/cs502000j
14. [14]
  YAN R H, CAI W Q, ZHUO J L, WANG X, LI M Z. One-Pot Solvent Evaporation Induced Self-Assembly Synthesis of Pd-Ba-Zn/γ-Al ₂O₃ Catalyst with Homogeneous Distribution of the Promoters and Its Hydrogenation Performance of Anthraquinone[J]. Chemical Industry and Engineering Progress, 2018,37(3):1014-1020.
15. [15]
  Zhong J W, Chen J Z, Chen L M. Selective Hydrogenation of Phenol and Related Derivatives[J]. Catal. Sci. Technol., 2014,4(10):3555-3569. doi: 10.1039/C4CY00583J
16. [16]
  Mahata N, Vishwanathan V.. Influence of Palladium Precursors on Structural Properties and Phenol Hydrogenation Characteristics of Supported Palladium Catalysts[J]. J. Catal., 2000,196(2):262-270. doi: 10.1006/jcat.2000.3041
17. [17]
  Zhao C, Yu Y Z, Jentys A, Lercher J A.. Understanding the Impact of Aluminum Oxide Binder on Ni/HZSM-5 for Phenol Hydrodeoxygen-ation[J]. Appl. Catal. B, 2013,132:282-292.
18. [18]
  Zhao M S, Shi J J, Hou Z Y.. Selective Hydrogenation of Phenol to Cyclohexanone in Water over Pd Catalysts Supported on Amberlyst- 45[J]. Chin. J. Catal., 2016,37(2):234-239. doi: 10.1016/S1872-2067(15)60997-4
19. [19]
  Li X W, Jiang Y Y, Zhou R R, Hou Z Y.. Layered α-Zirconium Phos-phate: An Efficient Catalyst for the Synthesis of Solketal from Glycerol[J]. Appl. Clay Sci., 2019,174:120-126. doi: 10.1016/j.clay.2019.03.034
20. [20]
  Bashir A, Ahad S, Malik L A, Qureashi A, Manzoor , T , Dar G N, Pandith A H. Revisiting the Old and Golden Inorganic Material, Zir-conium Phosphate: Synthesis, Intercalation, Surface Functionaliza-tion, and Metal Ion Uptake[J]. Ind. Eng. Chem. Res., 2020,59(52):22353-22397. doi: 10.1021/acs.iecr.0c04957
21. [21]
  Li D F, Ni W X, Hou Z S. Conversion of Biomass to Chemicals over Zirconium Phosphate-Based Catalysts[J]. Chin. J. Catal., 2017,38(11):1784-1793. doi: 10.1016/S1872-2067(17)62908-5
22. [22]
  Li N, Tompsett G A, Huber G W.. Renewable High -Octane Gasoline by Aqueous-Phase Hydrodeoxygenation of C₅ and C₆ Carbohydrates over Pt/Zirconium Phosphate Catalysts.[J]. ChemSusChem, 2010,3(10):1154-1157. doi: 10.1002/cssc.201000140
23. [23]
  Gong H H, Zhou C, Cui Y, Dai S, Zhao X G, Lou R H, An P F, Li H, Wang H F, Hou Z S. Direct Transformation of Glycerol to Propanal using Zirconium Phosphate-Supported Bimetallic Catalysts[J]. ChemSusChem, 2020,13(18):4954-4966. doi: 10.1002/cssc.202001600
24. [24]
  Lou R H, Zhao X G, Gong H H, Qian W, Li D F, Chen M Y, Cui K, Wang J J, Hou Z S. Effect of Tungsten Modification on Zirconium Phosphate-Supported Pt Catalyst for Selective Hydrogenolysis of Glycerol to 1-Propanol[J]. Energy Fuels, 2020,34(7):8707-8717. doi: 10.1021/acs.energyfuels.0c00645
25. [25]
  Zhao X G, Lin Q, Xiao W D. Characterization of Pd-CeO₂/α-Alumina Catalyst for Synthesis of Dimethyl Oxalate[J]. Appl. Catal. A, 2005,284(1/2):253-257.
26. [26]
  Hu Y, Yang H M, Zhang Y C, Hou Z S, Wang X R, Qiao Y X, Li H, Feng B, Huang Q F. The Functionalized Ionic Liquid-Stabilized Pal-ladium Nanoparticles Catalyzed Selective Hydrogenation in Ionic Liquid[J]. Catal. Commun., 2009,10(14):1903-1907. doi: 10.1016/j.catcom.2009.06.025
27. [27]
  LU Z Y, HONG Y Y, DAI Y Y, LI X Q, YAN X H. Synthesis and Characterization of Palladium Nanoparticles with High Proportion of Exposed (111) Facet for Hydrogenation Performance[J]. Chinese J. Inorg. Chem., 2021,37(6):1143-1151.
28. [28]
  Zhu W W, Yang H M, Yu Y Y, Hua L, Li H, Feng B, Hou Z S. Amphiphilic Ionic Liquid Stabilizing Palladium Nanoparticles for Highly Efficient Catalytic Hydrogenation[J]. Phys. Chem. Chem. Phys., 2011,13(30):13492-13500. doi: 10.1039/c1cp20255c
29. [29]
  Jin D F, Hou Z Y, Zhang L W, Zheng X M.. Selective Synthesis of para-para'-Dimethyl Methane over H -Beta Zeolite[J]. Catal. Today, 2008,131(1/4):378-384.
30. [30]
  Nie R F, Lei H, Pan S Y, Wang L N, Fei J H, Hou Z Y. Core-Shell Structured CuO-ZnO@H-ZSM-5 Catalysts for CO Hydrogenation to Dimethyl Ether[J]. Fuel, 2012,96(1):419-425.
31. [31]
  Wang Y, Yao J, Li H R, Su D S, Antonietti M. Highly Selective Hydrogenation of Phenol and Derivatives over a Pd@Carbon Nitride Catalyst in Aqueous Media[J]. J. Am. Chem. Soc., 2011,133(8):2362-2365. doi: 10.1021/ja109856y
1. [1]
  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
2. [2]
  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
3. [3]
  Xiaoyu Zhao , Kai Gao , Sen Xue , Wei Ran , Rui Liu . Synergistic effects of oxygen vacancies and Pd single atoms on Pd@TiO_2−x for efficient HER catalysis. Chinese Chemical Letters, 2025, 36(6): 110309-. doi: 10.1016/j.cclet.2024.110309
4. [4]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
5. [5]
  Weihan Zhang , Menglu Wang , Ankang Jia , Wei Deng , Shuxing Bai . 表面硫物种对钯-硫纳米片加氢性能的影响. Acta Physico-Chimica Sinica, 2024, 40(11): 2309043-. doi: 10.3866/PKU.WHXB202309043
6. [6]
  Jingyu Cai , Xiaoyu Miao , Yulai Zhao , Longqiang Xiao . Exploratory Teaching Experiment Design of FeOOH-RGO Aerogel for Photocatalytic Benzene to Phenol. University Chemistry, 2024, 39(4): 169-177. doi: 10.3866/PKU.DXHX202311028
7. [7]
  Long Jin , Jian Han , Dongmei Fang , Min Wang , Jian Liao . Pd-catalyzed asymmetric carbonyl alkynylation: Synthesis of axial chiral ynones. Chinese Chemical Letters, 2024, 35(6): 109212-. doi: 10.1016/j.cclet.2023.109212
8. [8]
  Yanxin Jiang , Kwai Wun Cheng , Zhiping Yang , Jun (Joelle) Wang . Pd-catalyzed enantioselective and regioselective asymmetric hydrophosphorylation and hydrophosphinylation of enynes. Chinese Chemical Letters, 2025, 36(5): 110231-. doi: 10.1016/j.cclet.2024.110231
9. [9]
  Renxiao Liang , Zhe Zhong , Zhangling Jin , Lijuan Shi , Yixia Jia . A Palladium/Chiral Phosphoric Acid Relay Catalysis for the One-Pot Three-Step Synthesis of Chiral Tetrahydroquinoline. University Chemistry, 2024, 39(5): 209-217. doi: 10.3866/PKU.DXHX202311024
10. [10]
  Hongbo Zhang , Yihong Tang , Suxia Zhang , Yuanting Li . Electrochemical Monitoring of Photocatalytic Degradation of Phenol Pollutants: A Recommended Comprehensive Analytical Chemistry Experiment. University Chemistry, 2024, 39(6): 326-333. doi: 10.3866/PKU.DXHX202310013
11. [11]
  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
12. [12]
  Guan-Nan Xing , Di-Ye Wei , Hua Zhang , Zhong-Qun Tian , Jian-Feng Li . Pd-based nanocatalysts for oxygen reduction reaction: Preparation, performance, and in-situ characterization. Chinese Journal of Structural Chemistry, 2023, 42(11): 100021-100021. doi: 10.1016/j.cjsc.2023.100021
13. [13]
  Min Song , Qian Zhang , Tao Shen , Guanyu Luo , Deli Wang . Surface reconstruction enabled o-PdTe@Pd core-shell electrocatalyst for efficient oxygen reduction reaction. Chinese Chemical Letters, 2024, 35(8): 109083-. doi: 10.1016/j.cclet.2023.109083
14. [14]
  An Lu , Yuhao Guo , Yi Yan , Lin Zhai , Xiangyu Wang , Weiran Cao , Zijie Li , Zhixia Zhao , Yujie Shi , Yuanjun Zhu , Xiaoyan Liu , Huining He , Zhiyu Wang , Jian-Cheng Wang . Nanomedicine integrating the lipidic derivative of 5-fluorouracil, miriplatin and PD-L1 siRNA for enhancing tumor therapy. Chinese Chemical Letters, 2024, 35(6): 108928-. doi: 10.1016/j.cclet.2023.108928
15. [15]
  Yue Sun , Liming Yang , Yaohang Cheng , Guanghui An , Guangming Li . Pd(I)-catalyzed ring-opening arylation of cyclopropyl-α-aminoamides: Access to α-ketoamide peptidomimetics. Chinese Chemical Letters, 2024, 35(6): 109250-. doi: 10.1016/j.cclet.2023.109250
16. [16]
  Tao Yu , Vadim A. Soloshonok , Zhekai Xiao , Hong Liu , Jiang Wang . Probing the dynamic thermodynamic resolution and biological activity of Cu(Ⅱ) and Pd(Ⅱ) complexes with Schiff base ligand derived from proline. Chinese Chemical Letters, 2024, 35(4): 108901-. doi: 10.1016/j.cclet.2023.108901
17. [17]
  Mengli Xu , Zhenmin Xu , Zhenfeng Bian . Achieving Ullmann coupling reaction via photothermal synergy with ultrafine Pd nanoclusters supported on mesoporous TiO2. Chinese Journal of Structural Chemistry, 2024, 43(7): 100305-100305. doi: 10.1016/j.cjsc.2024.100305
18. [18]
  Aiyi Xin , Jiawei Li , Xinyang Ran , Chuanjiang Fu , Zhiguo Wang . Collaborative Science and Education Based Experimental Design in Organic Chemistry: A Case Study of the Nucleophilic Substitution Reaction of 2-Hydroxymethyl-4,6-Di-Tert-Butylphenol. University Chemistry, 2025, 40(5): 366-375. doi: 10.12461/PKU.DXHX202407031
19. [19]
  Xiaoxiao Huang , Zhi-Long He , Yangpeng Chen , Lei Li , Zhenyu Yang , Chunyang Zhai , Mingshan Zhu . Novel P-doping-tuned Pd nanoflowers/S,N-GQDs photo-electrocatalyst for high-efficient ethylene glycol oxidation. Chinese Chemical Letters, 2024, 35(6): 109271-. doi: 10.1016/j.cclet.2023.109271
20. [20]
  Xiaofei NIU , Ke WANG , Fengyan SONG , Shuyan YU . Self-assembly of [Pd₆(L)₄]⁸⁺-type macrocyclic complexes for fluorescent sensing of HSO₃^-. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1233-1242. doi: 10.11862/CJIC.20240057

Get Citation

PDF

XML

Metrics

PDF Downloads(11)
Abstract views(1235)
HTML views(247)

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