Citation: QIN Fa-jie, LIU Ya-jie, QING Shao-jun, HOU Xiao-ning, GAO Zhi-xian. Cu-Al spinel as a sustained release catalyst for H₂ production from methanol steam reforming:Effects of different copper sources[J]. Journal of Fuel Chemistry and Technology, ;2017, 45(12): 1481-1488. shu

Cu-Al spinel as a sustained release catalyst for H₂ production from methanol steam reforming:Effects of different copper sources

1.
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: GAO Zhi-xian, gaozx@sxicc.ac.cn
Received Date: 17 July 2017
Revised Date: 27 September 2017

Fund Project: the National Natural Science Foundation of China 21673270The project was supported by the National Natural Science Foundation of China (21503254, 21673270)the National Natural Science Foundation of China 21503254

Figures(8)

Cu-Al spinel catalysts were synthesized by the solid-state reaction method using pseudo-boehmite as the Al source and hydroxides, acetates and nitrates of copper as the Cu source. Several techniques such as TG-MS, XRD, H₂-TPR, BET and XANES were employed for the exploration of the synthetic process, phase composition, reduction behaviors and surface structure of the catalysts. Moreover, the catalytic properties for methanol steam reforming (MSR) of these catalysts were evaluated. The obtained results showed that spinel solid solution can be successfully synthesized with the three different Cu sources. The synthesized spinels showed little difference in crystalline size, but their specific surface area (25.4-65.9 m²/g), pore volume (0.213-0.434 cm³/g), surface structure (distribution of Cu) and reduction properties were quite different, which led to different catalytic behavior and performance. During the methanol steam reforming reaction, active Cu species can be released from Cu-Al spinel structure. The catalyst synthesized from copper(Ⅱ) hydroxide shows excellent catalytic performance for MSR as it generates the smallest Cu particles (6.6 nm).
- solid-state reaction method,
- solid solution,
- methanol steam reforming
1. [1]
  LI Xiao-feng, WANG Jing, ZHANG Lei, LEI Yan-qiu, LIU Pan, CHEN Ran, CHEN Ke-zheng, HE Su-fang, LUO Yong-ming. Effect of cerium and praseodymium addition on Ni/Al₂O₃ catalyst to produce H₂ from methanaol steam reforming[J]. J Chin Soc Rare Earths, 2016,34(4):403-410.
2. [2]
  LIN Zi-dong, BAI Song, ZHANG Xiao-hui. Dexelopment prospect of water electrolysis hydrogen production technology[J]. Chem Defe Ships, 2014(2):48-54.
3. [3]
  WANG X, GORTE R J. A study of steam reforming of hydrocarbon fuels on Pd/ceria[J]. Appl Catal A:Gen, 2002,224(1):209-218.
4. [4]
  ILINICH O, RUETTINGER W, LIU X, FARRAUTO R. Cu-Al₂O₃-CuAl₂O₄ water-gas shift catalyst for hydrogen production in fuel cell applications:Mechanism of deactivation under start-stop operating conditions[J]. J Catal, 2007,247(1):112-118. doi: 10.1016/j.jcat.2007.01.014
5. [5]
  RARÓG-PILECKA W, SZMIGIEL D, KOWALCZYK Z, JODZIS S, ZIELINSKI J. Ammonia decomposition over the carbon-based ruthenium catalyst promoted with barium or cesium[J]. J Catal, 2003,218(2):465-469. doi: 10.1016/S0021-9517(03)00058-7
6. [6]
  WANG Gui-zhi. Technology for production hydrogen from methanol and its application in fuel cell system[J]. Chem Ind, 2008,26(1):17-22.
7. [7]
  SÁ S, SILVA H, BRANDÃO L, SOUSA J, MENDES A. Catalysts for methanol steam reforming-A review[J]. Appl Catal B:Environ, 2010,99(1/2):43-54.
8. [8]
  MATSUMURA T, TANAKA K, TODE N, YAZAWA T, HARUTA M. Catalytic methanol decomposition to carbon monoxide and hydrogen over nickel supported on silica[J]. J Mol Catal A:Chem, 2000,152(1/2):157-165.
9. [9]
  SHEN G, FUJITA S, MATSUMOTO S, TAKEZAWA N. Steam reforming of methanol on binary Cu/ZnO catalysts:Effects of preparation condition upon precursors, surface structure and catalytic activity[J]. J Mol Catal A:Chem, 1997,124(2):123-136.
10. [10]
  VELU S, SUZUKI K, OSAKI T. Selective production of hydrogen by partial oxidation of methanol over catalysts derived from CuZnAl-layered double hydroxides[J]. Catal lett, 1999,62(2/4):159-167. doi: 10.1023/A:1019023811688
11. [11]
  VELU S, SUZUKI K. Selective production of hydrogen for fuel cells via oxidative steam reforming of methanol over CuZnAl oxide catalysts:effect of substitution of zirconium and cerium on the catalytic performance[J]. Top Catal, 2003,22(3/4):235-244. doi: 10.1023/A:1023576020120
12. [12]
  MAO Li-ping, LV Gong-xuan. Hydrogen production from methanol steam reforming over nano-Cu/A1₂O₃ catalyst[J]. J Gansu Sci, 2009,21(1):77-80.
13. [13]
  PURNAMA H, GIRGSDIES F, RESSLER T, SCHATTKA J H, CARUSO R A, SCHOMÄCKER R, SCHLÖGL R. Activity and selectivity of a nanostructured CuO/ZrO₂ catalyst in the steam reforming of methanol[J]. Catal Lett, 2004,94(1/2):61-68. doi: 10.1023/B:CATL.0000019332.80287.6b
14. [14]
  SHISHIDO T, YAMAMOTO Y, MORIOKA H, TAKAKI K, TAKEHIRA K. Active Cu/ZnO and Cu/ZnO/Al₂O₃ catalysts prepare by homogeneous precipitation method in steam reforming of methanol[J]. Appl Catal A:Gen, 2004,263(2):249-253. doi: 10.1016/j.apcata.2003.12.018
15. [15]
  OGUCHI H, NISHIGUCHI T, MATSUMOTO T, KANAI H, UTANI K, MATSUMURA Y, IMAMURA S. Steam reforming of methanol over Cu/CeO₂/ZrO₂ catalysts[J]. Appl Catal A:Gen, 2005,281(1):69-73.
16. [16]
  KAMEOKA S, TANABE T, TSAI A P. Spinel CuFe₂O₄:A precursor for copper catalyst with high thermal stability and activity[J]. Catal Lett, 2005,100(1/2):89-93.
17. [17]
  MAITI S, LLORCA J, DOMINGUEZ M, COLUSSI S, TROVARELLI A, PRIOLKAR K, AQUILANTI G, GAYEN A. Combustion synthesized copper-ion substituted FeAl₂O₄ (Cu_0.1Fe_0.9Al₂O₄):A superior catalyst for methanol steam reforming compared to its impregnated analogue[J]. J Power Sources, 2016,304:319-331. doi: 10.1016/j.jpowsour.2015.11.066
18. [18]
  YONG S, OOI C, CHAI S, WU X. Review of methanol reforming-Cu-based catalysts, surface reaction mechanisms, and reaction schemes[J]. Int J Hydrogen Energy, 2013,38(22):9541-9552. doi: 10.1016/j.ijhydene.2013.03.023
19. [19]
  MATSUKATA M, UEMIYA S, KIKUCHI E. Copper-alumina spinel catalysts for steam reforming of methanol[J]. Chem Lett, 1988,5(5):761-764.
20. [20]
  FUKUNAGA T, RYUMON N, ICHIKUNI N, SHIMAZU S. Characterization of CuMn-spinel catalyst for methanol steam reforming[J]. Catal Commun, 2009,10(14):1800-1803. doi: 10.1016/j.catcom.2009.06.001
21. [21]
  PUSSANA H, KAJORNSAK F. Cu-Cr, Cu-Mn, and Cu-Fe spinel-oxide-type catalysts for reforming of oxygenated hydrocarbons[J]. J Phys Chem C, 2013,117(45):23757-23765. doi: 10.1021/jp407717c
22. [22]
  LI Guang-jun, XI Hong-juan, ZHANG Su-hong, GU Chuan-tao, QING Shao-jun, HOU Xiao-ning, GAO Zhi-xian. Catalytic characteristics of spinel CuM₂O₄ (M=Al, Fe, Cr) for the steam reforming of methanol[J]. J Fuel Chem Technol, 2012,40(12):1466-1471. doi: 10.3969/j.issn.0253-2409.2012.12.009
23. [23]
  HUANG Y H, WANG S F, TSAI A P, KAMEOKA S. Reduction behaviors and catalytic properties for methanol steam reforming of Cu-based spinel compounds CuX₂O₄ (X=Fe, Mn, Al, La)[J]. Cera Inter, 2014,40(3):4541-4551. doi: 10.1016/j.ceramint.2013.08.130
24. [24]
  XI Hong-juan, LI Guang-jun, QING Shao-jun, HOU Xiao-ning, ZHAO Jin-zhen, LIU Ya-jie, GAO Zhi-xian. Cu-Al spinel catalyst prepared by solid phase method for methanol steam reforming[J]. J Fuel Chem Technol, 2013,41(8):998-1002.
25. [25]
  XI H, HOU X, LIU Y, QING S, GAO Z. Cu-Al spinel oxide as an efficient catalyst for methanol steam reforming[J]. Angew Chem, 2014,53(44):11886-11889. doi: 10.1002/anie.201405213
26. [26]
  GRIONI M, GOEDKOOP J B, SCHOORL R, GROOT F M F, FUGGLR J C, SCHÄFERS F, KOCH E E, ROSSI G, ESTEVA J M, KARNATAK R C. Studies of copper valence states with Cu L₃ X-ray-absorption spectroscopy[J]. Phys Rev B, 1989,39(3):1541-1545. doi: 10.1103/PhysRevB.39.1541
27. [27]
  SHIMIZU K, MAESHIMA H, YOSHIDA H, SATSUMA A, HATTORI T. Spectroscopic characterisation of catalysts for selective Cu-Al₂O₃ catalytic reduction of NO with propene[J]. Phys Chem Chem Phys, 2000,2(10):2435-2439. doi: 10.1039/b000943l
28. [28]
  LUO M F, FANG P F, HE M, XIE Y L. In situ XRD, Raman, and TPR studies of CuO/Al₂O₃ catalysts for CO oxidation[J]. J Mol Catal A:Chem, 2005,239(1/2):243-248.
1. [1]
  Xue Liu , Lipeng Wang , Luling Li , Kai Wang , Wenju Liu , Biao Hu , Daofan Cao , Fenghao Jiang , Junguo Li , Ke Liu . Research on Cu-Based and Pt-Based Catalysts for Hydrogen Production through Methanol Steam Reforming. Acta Physico-Chimica Sinica, 2025, 41(5): 100049-0. doi: 10.1016/j.actphy.2025.100049
2. [2]
  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
3. [3]
  Wanmin Cheng , Juan Du , Peiwen Liu , Yiyun Jiang , Hong Jiang . Photoinitiated Grignard Reagent Synthesis and Experimental Improvement in Triphenylmethanol Preparation. University Chemistry, 2024, 39(5): 238-242. doi: 10.3866/PKU.DXHX202311066
4. [4]
  Yanhui Zhong , Ran Wang , Zian Lin . Analysis of Halogenated Quinone Compounds in Environmental Water by Dispersive Solid-Phase Extraction with Liquid Chromatography-Triple Quadrupole Mass Spectrometry. University Chemistry, 2024, 39(11): 296-303. doi: 10.12461/PKU.DXHX202402017
5. [5]
  Jian Jin , Jing Cheng , Xueping Yang . Integration Practice of Organic Chemistry Experiment and Safety Education: Taking the Synthesis of Triphenylmethanol as an Example. University Chemistry, 2024, 39(3): 345-350. doi: 10.3866/PKU.DXHX202309010
6. [6]
  Zhiwen HU , Weixia DONG , Qifu BAO , Ping LI . Low-temperature synthesis of tetragonal BaTiO₃ for piezocatalysis. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 857-866. doi: 10.11862/CJIC.20230462
7. [7]
  Jiaojiao Yu , Bo Sun , Na Li , Cong Wen , Wei Li . Improvement of Classical Organic Experiment Based on the “Reverse-Step Optimization Method”: Taking Synthesis of Ethyl Acetate as an Example. University Chemistry, 2025, 40(3): 333-341. doi: 10.12461/PKU.DXHX202405177
8. [8]
  Xiaohang JIN , Qi LIU , Jianping LANG . Room‑temperature solid‑state synthesis, structure, and third‑order nonlinear optical properties of phosphine‑ligand‑protected silver thiolate clusters. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1505-1512. doi: 10.11862/CJIC.20250125
9. [9]
  Bingliang Li , Yuying Han , Dianyang Li , Dandan Liu , Wenbin Shang . One-Step Synthesis of Benorilate Guided by Green Chemistry Principles and in vivo Dynamic Evaluation. University Chemistry, 2024, 39(6): 342-349. doi: 10.3866/PKU.DXHX202311070
10. [10]
  Zhuo Wang , Xue Bai , Kexin Zhang , Hongzhi Wang , Jiabao Dong , Yuan Gao , Bin Zhao . MOF-Templated Synthesis of Nitrogen-Doped Carbon for Enhanced Electrochemical Sodium Ion Storage and Removal. Acta Physico-Chimica Sinica, 2025, 41(3): 2405002-0. doi: 10.3866/PKU.WHXB202405002
11. [11]
  Xiaogang Liu , Mengyu Chen , Yanyan Li , Xiantao Ma . Experimental Reform in Applied Chemistry for Cultivating Innovative Competence: A Case Study of Catalytic Hydrogen Production from Liquid Formaldehyde Reforming at Room Temperature. University Chemistry, 2025, 40(7): 300-307. doi: 10.12461/PKU.DXHX202408007
12. [12]
  Kai CHEN , Fengshun WU , Shun XIAO , Jinbao ZHANG , Lihua ZHU . PtRu/nitrogen-doped carbon for electrocatalytic methanol oxidation and hydrogen evolution by water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1357-1367. doi: 10.11862/CJIC.20230350
13. [13]
  Yongmei Liu , Lisen Sun , Zhen Huang , Tao Tu . Curriculum-Based Ideological and Political Design for the Experiment of Methanol Oxidation to Formaldehyde Catalyzed by Electrolytic Silver. University Chemistry, 2024, 39(2): 67-71. doi: 10.3866/PKU.DXHX202308020
14. [14]
  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
15. [15]
  Zhen Yao , Bing Lin , Youping Tian , Tao Li , Wenhui Zhang , Xiongwei Liu , Wude Yang . Visible-Light-Mediated One-Pot Synthesis of Secondary Amines and Mechanistic Exploration. University Chemistry, 2024, 39(5): 201-208. doi: 10.3866/PKU.DXHX202311033
16. [16]
  Xingyang LI , Tianju LIU , Yang GAO , Dandan ZHANG , Yong ZHOU , Meng PAN . A superior methanol-to-propylene catalyst: Construction via synergistic regulation of pore structure and acidic property of high-silica ZSM-5 zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1279-1289. doi: 10.11862/CJIC.20240026
17. [17]
  Qingqing SHEN , Xiangbowen DU , Kaicheng QIAN , Zhikang JIN , Zheng FANG , Tong WEI , Renhong LI . Self-supporting Cu/α-FeOOH/foam nickel composite catalyst for efficient hydrogen production by coupling methanol oxidation and water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1953-1964. doi: 10.11862/CJIC.20240028
18. [18]
  Feifei Yang , Wei Zhou , Chaoran Yang , Tianyu Zhang , Yanqiang Huang . Enhanced Methanol Selectivity in CO₂ Hydrogenation by Decoration of K on MoS₂ Catalyst. Acta Physico-Chimica Sinica, 2024, 40(7): 2308017-0. doi: 10.3866/PKU.WHXB202308017
19. [19]
  Feng Han , Fuxian Wan , Ying Li , Congcong Zhang , Yuanhong Zhang , Chengxia Miao . Comprehensive Organic Chemistry Experiment: Phosphotungstic Acid-Catalyzed Direct Conversion of Triphenylmethanol for the Synthesis of Oxime Ethers. University Chemistry, 2025, 40(3): 342-348. doi: 10.12461/PKU.DXHX202405181
20. [20]
  Shi-Yu Lu , Wenzhao Dou , Jun Zhang , Ling Wang , Chunjie Wu , Huan Yi , Rong Wang , Meng Jin . Amorphous-Crystalline Interfaces Coupling of CrS/CoS₂ Few-Layer Heterojunction with Optimized Crystallinity Boosted for Water-Splitting and Methanol-Assisted Energy-Saving Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(8): 2308024-0. doi: 10.3866/PKU.WHXB202308024

Get Citation

PDF

XML

Metrics

PDF Downloads(6)
Abstract views(2829)
HTML views(448)

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

Cu-Al spinel as a sustained release catalyst for H2 production from methanol steam reforming:Effects of different copper sources

Metrics

通讯作者: 陈斌, bchen63@163.com

Cu-Al spinel as a sustained release catalyst for H₂ production from methanol steam reforming:Effects of different copper sources