Citation: Li-bao WANG, Hong-hao WANG, Lei ZHANG, Shao-jun QING, Dong-mei LIU, Zhi-xian GAO, Hai-juan ZHANG, Guo-qing GUAN. Effect of citric acid content on the hydrothermal synthesis of CuO/Ce_0.8Zr_0.2O₂ catalytic water gas shift hydrogen production performance[J]. Journal of Fuel Chemistry and Technology, ;2022, 50(3): 337-345. doi: 10.19906/j.cnki.JFCT.2021078 shu

Effect of citric acid content on the hydrothermal synthesis of CuO/Ce_0.8Zr_0.2O₂ catalytic water gas shift hydrogen production performance

1.
School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, China
2.
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
3.
Energy Conversion Engineering Research Office of Regional Innovation, Hirosaki University, Matsubara 030-0813, Japan

Corresponding author: Lei ZHANG, lnpuzhanglei@163.com Zhi-xian GAO, gaozx@sxicc.ac.cn
Received Date: 6 July 2021
Revised Date: 10 August 2021

Figures(13)

Ce_0.8Zr_0.2O₂ solid solutions were synthesized by hydrothermal method, and active components were loaded by impregnation method to get CuO/Ce_0.8Zr_0.2O₂ catalysts. Effects of citric acid content on the structure, properties and hydrogen production performance of CuO/Ce_0.8Zr_0.2O₂ catalysts were investigated. CuO/Ce_0.8Zr_0.2O₂ catalysts prepared with different citric acid content are distinct in Cu surface area, reduction performance and interaction between Ce_0.8Zr_0.2O₂ solid solution and CuO. Among them, the catalyst prepared with a citric acid concentration of 0.04 mol/L has a large Cu surface area, a low CuO reduction temperature and a strong interaction between Ce_0.8Zr_0.2O₂ solid solution and CuO, which has the best catalytic activity and the highest CO conversion in the water gas shift conversion process. At 320 ℃, water/gas molar ratio n(H₂O)/n(CO) = 2, total volume velocity GHSV = 6600 h⁻¹, its CO conversion is 96.9% close to thermodynamic equilibrium value.
- hydrothermal method,
- citric acid,
- water gas shift,
- solid solution
1. [1]
  RYAN J G, KHALID A A, WILLIAM H G. Thermochemical production of hydrogen from hydrogen sulfide with iodine thermochemical cycles[J]. Int J Hydrogen Energy,2018,43(29):12939−12947. doi: 10.1016/j.ijhydene.2018.04.217
2. [2]
  JACOBSON M Z, COLELLA W, GOLDEN D. Cleaning the air and improving health with hydrogen fuel-cell vehicles[J]. Science,2005,308(5730):1901−1905. doi: 10.1126/science.1109157
3. [3]
  MASCHARAK P K. Cobaloxime-based photocatalytic devices for hydrogen production[J]. Angew Chem Int Ed,2008,47(3):564−567. doi: 10.1002/anie.200702953
4. [4]
  ZHANG Yan-jie, CHEN Chong-qi, ZHAN Ying-ying, YE Yuan-song, LOU Ben-yong, ZHENG Guo-cai, LIN Qi. CuO/ZrO₂ catalysts for the production of H₂ through the water-gas shift reaction: Effect of calcination temperature of ZrO₂[J]. J Fuel Chem Technol,2019,47(4):91−100.
5. [5]
  GOKHALE A A, DUMESIC J A, MAVRIKAKIS M. On the mechanism of low-temperature water gas shift reaction on copper[J]. J Am Chem Soc,2008,130(4):1402−1414. doi: 10.1021/ja0768237
6. [6]
  WANG X Q, RODRIGUEZ J, HANSON J, GAMARRA D. In situ studies of the active sites for the water gas shift reaction over Cu-CeO₂ catalysts: Complex interaction between metallic copper and oxygen vacancies of ceria[J]. J Phys Chem B,2006,110(1):428−34. doi: 10.1021/jp055467g
7. [7]
  MARONO M, SANCHEZ J M, RUIZ E. Hydrogen-rich gas production from oxygen pressurized gasification of biomass using a Fe-Cr water gas shift catalyst[J]. Int J Hydrogen Energy,2010,35(1):37−45. doi: 10.1016/j.ijhydene.2009.10.078
8. [8]
  REDDY G K, KIM S J, DONG J H, SMIRNIOTIS P G. Long-term WGS stability of Fe/Ce and Fe/Ce/Cr catalysts at high and low steam to CO ratios-XPS and mssbauer spectroscopic study[J]. Appl Catal A: Gen,2012,415:101−110.
9. [9]
  REDDY G K, SMIRNIOTIS P G. Effect of copper as a dopant on the water gas shift activity of Fe/Ce and Fe/Cr modified ferrites[J]. Catal Lett,2011,141(1):27−32. doi: 10.1007/s10562-010-0465-2
10. [10]
  FU W, BAO Z H, DING W Z, CHOU K. The synergistic effect of the structural precursors of Cu/ZnO/Al₂O₃ catalysts for water-gas shift reaction[J]. Catal Commun,2011,12(6):505−509. doi: 10.1016/j.catcom.2010.11.017
11. [11]
  KOWALIK P, PROCHNIAK W, BOROWIECKI T. The effect of alkali metals doping on properties of Cu/ZnO/Al₂O₃ catalyst for water gas shift[J]. Catal Today,2011,176(1):144−148. doi: 10.1016/j.cattod.2011.01.028
12. [12]
  FIGUEIREDO R T, SANTOS M S, ANDRADE H M, FIERRO J. Effect of alkali cations on the Cu/ZnO/Al₂O₃ low temperature water gas-shift catalyst[J]. Catal Today,2011,172(1):166−170. doi: 10.1016/j.cattod.2011.03.073
13. [13]
  OSA A R, LUCAS A D, ROMERO A, CASERO P. High pressure water gas shift performance over a commercial non-sulfide CoMo catalyst using industrial coal-derived syngas[J]. Fuel,2012,97(1):428−434.
14. [14]
  MUDIYANSELAGE K, SENANAYAKE S D, RAMIREZ P J, KUNDU S. Intermediates arising from the water-gas shift reaction over Cu surfaces: from UHV to near atmospheric pressures[J]. Top Catal,2015,58(4):271−280.
15. [15]
  JEONG D W, NA H S, SHIM J O, JANG W J. Hydrogen production from low temperature WGS reaction on co-precipitated Cu-CeO₂ catalysts: An optimization of Cu loading[J]. Int J Hydrogen Energy,2014,39(17):9135−9142. doi: 10.1016/j.ijhydene.2014.04.005
16. [16]
  WANG S P, WANG X Y, HUANG J, ZHANG S M. The catalytic activity for CO oxidation of CuO supported on Ce_0.8Zr_0.2O₂ prepared via citrate method[J]. Catal Commun,2007,8(3):231−236. doi: 10.1016/j.catcom.2006.06.006
17. [17]
  JIANG L, ZHU H W, RAZZAQ R, ZHU M L. Effect of zirconium addition on the structure and properties of CuO/CeO₂ catalysts for high-temperature water-gas shift in an IGCC system[J]. Int J Hydrogen Energy,2012,21(21):15914−15924.
18. [18]
  JEONG D W, NA H S, SHIM J O, JANG W J, ROH H S. A crucial role for the CeO₂-ZrO₂ support for the low temperature water gas shift reaction over Cu-CeO₂-ZrO₂ catalysts[J]. Catal Sci Technol,2015,5:3706−3713. doi: 10.1039/C5CY00499C
19. [19]
  ZHENG Yun-di, LIN Xing-yi, ZHENG Qi, ZHAN Ying-ying, LI Da-lin, WEI Ke-mei. Effects of ZrO₂ content on structure and properties of Cu CeO₂-ZrO₂ catalysts for water-gas shift reaction[J]. J Chin Rare Earth Soc,2005,6(8):679−683.
20. [20]
  GOMEZ I D, KOCEMBA I, RYNKOWSKI J M. Au/Ce_1−xZr_xO₂ as effective catalysts for low-temperature CO oxidation[J]. App Catal B: Environ,2008,83:240−241. doi: 10.1016/j.apcatb.2008.02.012
21. [21]
  VLAIC G, FORNASIERO P, GEREMIA S, KASPAR J. Relationship between the zirconia-promoted reduction in the Rh-loaded Ce_0.5Zr_0.5O₂ mixed oxide and the Zr-O local structure[J]. J Catal,1997,168(2):386−392. doi: 10.1006/jcat.1997.1644
22. [22]
  ZHANG Zeng-qing, FAN Jun, HU Xiao-yun, LIU En-zhou, ZHAO Bo, KANG Li-min. Preparation, grain growth and application of Ce_0.5Zr_0.5O₂[J]. J Chin Rare Earth Soc,2013,31(2):217−221.
23. [23]
  YANG S Q, HE J P, ZHANG N, SUI X W, ZHANG L, YANG Z X. Effect of rare-earth element modification on the performance of Cu/ZnAl catalysts derived from hydrotalcite precursor in methanol steam reforming[J]. J Fuel Chem Technol,2018,46(2):179−188. doi: 10.1016/S1872-5813(18)30010-0
24. [24]
  ZHANG Y J, CHEN C Q, ZHANG Y Y, LIN Q, LOU B Y, ZHENG G C, ZHENG Q. Highly active Y-promoted CuO/ZrO₂ catalysts for the production of hydrogen through water-gas shift reaction[J]. J Fuel Chem Technol,2017,45(9):1137−1149.
25. [25]
  XIE H M, DU Q X, LI H, ZHOU G L, CHEN S M, JIAO Z J, REN J M. Catalytic combustion of volatile aromatic compounds over CuO-CeO2 catalyst[J]. Korean J Chem Eng,2017,34(7):1944−1951.
26. [26]
  QING Shao-jun, HOU Xiao-ning, LIU Ya-jie, WANG Lei, LI Lin-dong, GAO Zhi-xian. Catalytic performance of Cu-Ni-Al spine l for methanol steam reforming to hydrogen[J]. J Fuel Chem Technol,2018,46(10):69−76.
27. [27]
  SHE W, JI T Q, CUI M X, YAN P F, WENG N S, LI W, LI G M. Catalytic performance of CeO₂-supported Ni catalyst for hydrogenation of nitroarenes fabricated via coordination-assisted strategy[J]. ACS App Mater Interfaces,2018,10(17):14698−14707. doi: 10.1021/acsami.8b01187
28. [28]
  BENNICI S, GERVASINI A, RAVASIO N, ZACCHERIA F. Optimization of tailoring of CuO_x species of silica alumina supported catalysts for the selective catalytic reduction of NO_x[J]. J Phys Chem B,2003,107(22):5168−5176. doi: 10.1021/jp022064x
29. [29]
  PENG X OMASTA T, ROLLER J, MUSTAIN W E. Highly active and durable Pd-Cu catalysts for oxygen reduction in alkaline exchange membrane fuel cells[J]. Front Energy,2017,11(3):299−309. doi: 10.1007/s11708-017-0495-1
1. [1]
  Shuting Zhuang , Lida Zhao . Teaching through Research: A Comprehensive Experiment on Carbon Quantum Dots from Microplastic Waste. University Chemistry, 2025, 40(10): 217-224. doi: 10.12461/PKU.DXHX202412010
2. [2]
  Shuting KONG , Fengshi ZHANG , Zhiyi LU , Yanling LIU , Minglang YE , Zhengfang HU , Longsheng WANG , Bing HU , Haiying WANG . Research advance of the preparation of tributyl citrate catalyzed by supported heteropolyacid catalysts. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 441-452. doi: 10.11862/CJIC.20250303
3. [3]
  Haoying ZHAI , Lanzong WEN , Wenjie LIAO , Qin LI , Wenjun ZHOU , Kun CAO . Metal-organic framework-derived sulfur-doped iron-cobalt tannate nanorods for efficient oxygen evolution reaction performance. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 1037-1048. doi: 10.11862/CJIC.20240320
4. [4]
  Huoshuai Huang , Zhidong Wei , Jiawei Yan , Jiasheng Chi , Qianxiang Su , Mingxia Chen , Zhi Jiang , Yangzhou Sun , Wenfeng Shangguan . Unveiling the mechanism of direct-to-indirect bandgap transition in the photocatalytic hydrogen evolution of Zn_xCd_1−xS solid solution. Acta Physico-Chimica Sinica, 2026, 42(1): 100141-0. doi: 10.1016/j.actphy.2025.100141
5. [5]
  Jinghua Wang , Yanxin Yu , Yanbiao Ren , Yesheng Wang . Integration of Science and Education: Investigation of Tributyl Citrate Synthesis under the Promotion of Hydrate Molten Salts for Research and Innovation Training. University Chemistry, 2024, 39(11): 232-240. doi: 10.3866/PKU.DXHX202402057
6. [6]
  Lihua Jin , Lei Tian , Chaozhan Wang , Jiawei Liu , Quan Bai , Yan Li . Teaching Exploration and Practice of the Instrumental Analysis Experiment “Distinguishing Green Plastic Bags by Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy”. University Chemistry, 2026, 41(2): 360-365. doi: 10.12461/PKU.DXHX202502089
7. [7]
  Min Hu , Yinghuan Li , Yanhong Bai , Yanping Ren , Juanjuan Song , Yongxian Fan , Dongcheng Liu , Xiuqiong Zeng , Faqiong Zhao , Wenwei Zhang , Mei Shi , Wan Li , Xiuyun Wang , Weihong Li , Xiaohang Qiu , Yong Fan , Jianrong Zhang , Shuyong Zhang . Suggestions on the Method of Hydrothermal-Solventthermal Synthesis and Their Operation Standards. University Chemistry, 2026, 41(3): 208-215. doi: 10.12461/PKU.DXHX202507034
8. [8]
  Mengxiu Li , Jiahui Mao , Jiangfeng Ni , Liang Li . Three birds with one stone: modification of Li₅FeO₄ with thermal induction of Lewis acid. Acta Physico-Chimica Sinica, 2026, 42(4): 100189-0. doi: 10.1016/j.actphy.2025.100189
9. [9]
  Huiying ZHANG , Ping LI , Weixia DONG , Zhiwen HU , Qifu BAO , Qizheng DONG , Mingmin BAI , Wenqi LI . Photocatalytic performance of spheroidal nano Bi₄Ti₃O₁₂ prepared by surfactant-assisted hydrothermal reaction. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 551-561. doi: 10.11862/CJIC.20250269
10. [10]
  Yuan Zheng , Quan Lan , Zhenggen Zha , Lingling Li , Jun Jiang , Pingping Zhu . Teaching Reform of Organic Synthesis Experiments by Introducing Reverse Thinking and Design Concepts: Taking the Synthesis of Cinnamic Acid Based on Retrosynthetic Analysis as an Example. University Chemistry, 2024, 39(6): 207-213. doi: 10.3866/PKU.DXHX202310065
11. [11]
  Yuena Yang , Xufang Hu , Yushan Liu , Yaya Kuang , Jian Ling , Qiue Cao , Chuanhua Zhou . The Realm of Smart Hydrogels. University Chemistry, 2024, 39(5): 172-183. doi: 10.3866/PKU.DXHX202310125
12. [12]
  Zhou Fang , Zhihao Zhang , Weihan Jiang , Kin Shing Chan . Warfarin: From Poison to Cure, the Remarkable Journey of a Molecule. University Chemistry, 2025, 40(4): 326-330. doi: 10.12461/PKU.DXHX202406038
13. [13]
  Zhi Zheng , Qi Ma , Feiyang Liu , Gukui Chen , Junlong Zhao . Defeating Dental Plaque with Science: Unlocking the Power of Biofilm Management. University Chemistry, 2026, 41(2): 295-300. doi: 10.12461/PKU.DXHX202502088
14. [14]
  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
15. [15]
  Yang Lv , Yingping Jia , Yanhua Li , Hexiang Zhong , Xinping Wang . Integrating the Ideological Elements with the “Chemical Reaction Heat” Teaching. University Chemistry, 2024, 39(11): 44-51. doi: 10.12461/PKU.DXHX202402059
16. [16]
  Yang ZHOU , Lili YAN , Wenjuan ZHANG , Pinhua RAO . Thermal regeneration of biogas residue biochar and the ammonia nitrogen adsorption properties. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1574-1588. doi: 10.11862/CJIC.20250032
17. [17]
  Zehua Zhao , Xiaoyan An , Jinrong Xu , Ling Yang , Hao Zhao , Zhongyun Wu . Independent Development and Application of Calorimetric Experiment Data Acquisition and Processing Software. University Chemistry, 2025, 40(11): 402-408. doi: 10.12461/PKU.DXHX202505045
18. [18]
  Qingying Gao , Tao Luo , Jianyuan Su , Chaofan Yu , Jiazhu Li , Bingfei Yan , Wenzuo Li , Zhen Zhang , Yi Liu . Refinement and Expansion of the Classic Cinnamic Acid Synthesis Experiment. University Chemistry, 2024, 39(5): 243-250. doi: 10.3866/PKU.DXHX202311074
19. [19]
  Lanjun Cheng , Xinyuan Wang , Jie An , Xiang Wu , Chengfeng Zhu , Yanming Fu , Yougui Li . Improvement of the Resolution Experiment of Racemic Tartaric Acid. University Chemistry, 2025, 40(7): 277-285. doi: 10.12461/PKU.DXHX202408010
20. [20]
  Zhi Zheng , Feiyang Liu , Junlong Zhao . D-Amino Acids and Mirror-Image Proteins. University Chemistry, 2026, 41(2): 353-359. doi: 10.12461/PKU.DXHX202505017

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(3320)
HTML views(678)

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

Effect of citric acid content on the hydrothermal synthesis of CuO/Ce0.8Zr0.2O2 catalytic water gas shift hydrogen production performance

Metrics

通讯作者: 陈斌, bchen63@163.com

Effect of citric acid content on the hydrothermal synthesis of CuO/Ce_0.8Zr_0.2O₂ catalytic water gas shift hydrogen production performance