Citation: YANG Shu-qian, HE Jian-ping, ZHANG Na, SUI Xiao-wei, ZHANG Lei, YANG Zhan-xu. Effect of rare-earth element modification on the performance of Cu/ZnAl catalysts derived from hydrotalcite precursor in methanol steam reforming[J]. Journal of Fuel Chemistry and Technology, ;2018, 46(2): 179-188. shu

Effect of rare-earth element modification on the performance of Cu/ZnAl catalysts derived from hydrotalcite precursor in methanol steam reforming

1.
College of Chemistry, Chemical Engineering, and Environmental Engineering, Liaoning Shihua University, Fushun 113001, China
2.
Department of Chemical Engineering, Fushun Vocational Technology Institute, Fushun 113122, China

Corresponding author: ZHANG Lei, lnpuzhanglei@163.com YANG Zhan-xu, zhanxuy@126.com
Received Date: 9 August 2017
Revised Date: 13 December 2017

Fund Project: the Doctoral Scientific Research Foundation of Liaoning Province 2016013022the National Natural Science Foundation of China 21671092the National Natural Science Foundation of China 21376237The project was supported by the National Natural Science Foundation of China (21671092, 21376237) and the Doctoral Scientific Research Foundation of Liaoning Province (2016013022)

Figures(12)

Zn-Al layered double hydroxides (ZnAl-LDHs) were prepared on γ-Al₂O₃ by an in-situ synthesis method; with ZnAl-LDHs as the supports, a series of rare-earth element M (M=Y, La, Ce, Sm and Gd) doped M/Cu/ZnAl catalysts were then obtained through sequential wet impregnation method and used in the methanol steam reforming to produce hydrogen. The M/Cu/ZnAl catalysts were characterized by XRD, SEM-EDS, N₂ sorption, H₂-TPR, XPS and N₂O titration and the effect of rare-earth metal doping on their catalytic performance in the methanol steam reforming was then investigated. The results showed that the activity of Cu/ZnAl catalyst is closely related to the copper surface area and the reducibility; larger copper surface area and lower reduction temperature lead to a higher catalytic activity in methanol steam reforming. The addition of rare-earth elements including Ce, Sm and Gd can improve the copper dispersion, surface copper area and the catalyst reducibility, which is helpful to enhance the activity of M/Cu/ZnAl catalysts. Especially, the Ce/Cu/ZnAl catalyst exhibits the highest activity; over it, the methanol conversion is 100% (about 40% higher than that over the Cu/ZnAl catalyst) and the CO concentration in the product is only 0.39%, for the methanol steam reforming at 250℃.
- rare-earth,
- hydrotalcite,
- Cu/ZnAl,
- methanol steam reforming,
- hydrogen,
- carbon monoxide
1. [1]
  JACOBSON M Z, COLELLA W G, 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
2. [2]
  FIHRI A, ARTERO V, RAZAVET M, BAFFERT C, LEIBL W, FONTECAVE M. Cobaloxime-based photocatalytic devices for hydrogen production[J]. Angew Chem Int Ed, 2008,47(3):564-567.
3. [3]
  KUC J, NEUMANN M, ARMBRUSTER M, YOON S, ZHANG Y, ERNI R, WEIDENKAFF A, MATAM S K. Methanol steam reforming catalysts derived by reduction of perovskite-type oxides LaCo_1-x-yPd_x Zn_yO_3±δ[J]. Catal Sci Technol, 2016,6:1455-1468. doi: 10.1039/C5CY01410G
4. [4]
  MA Y, GUAN G, PHANTHONG P, LI X, CAO J, HAO X, WANG Z, ABUDULA A. Steam reforming of methanol for hydrogen production over nanostructured wire-like molybdenum carbide catalyst[J]. Int J Hydrogen Energy, 2014,39(33):18803-18811. doi: 10.1016/j.ijhydene.2014.09.062
5. [5]
  SA S, SILVA H, BRANDAO L, SOUSA J M, MENDES A. Catalysts for methanol steam reforming-A review[J]. Appl Catal B:Environ, 2010,99(1/2):43-57.
6. [6]
  ZHANG Lei, PAN Li-wei, NI Chang-jun, ZHAO Sheng-sheng, WANG Shu-dong, HU Yong-kang, WANG An-jie, JIANG Kai. Optimization of methanol steam reforming for hydrogen[J]. J Fuel Chem Technol, 2013,41(1):116-122.
7. [7]
  KIM W, MOHAIDEEN K K, SEO D J, YOON L Y. Methanol-steam reforming reaction over Cu-Al-based catalysts derived from layered double hydroxides[J]. Int J Hydrogen Energy, 2017,42(4):2081-2087. doi: 10.1016/j.ijhydene.2016.11.014
8. [8]
  ZHOU J J, ZHANG Y, WU G S, MAO D S, LU G Z. Influence of the component interaction over Cu/ZrO₂ catalysts induced with fractionated precipitation method on the catalytic performance for methanol steam reforming[J]. RSC Adv, 2016,6:30176-30183. doi: 10.1039/C5RA24163D
9. [9]
  DAS D, LLORCA J, DOMINGUEZ M, COLUSSI S, TROVARELLI A, GAYEN A. Methanol steam reforming behavior of copper impregnated over CeO₂-ZrO₂ derived from a surfactant assisted coprecipitation route[J]. Int J Hydrogen Energy, 2015,40(33):10463-10479. doi: 10.1016/j.ijhydene.2015.06.130
10. [10]
  LYTKINA A A, ZHILYAEVA N A, ERMILOVA M M, OREKHOVA N V, YAROSLAVTSEO A B. Influence of the support structure and composition of Ni-Cu-based catalysts on hydrogen production by methanol steam reforming[J]. Int J Hydrogen Energy, 2015,40(31):9677-9684. doi: 10.1016/j.ijhydene.2015.05.094
11. [11]
  HUANG Y H, WANG S F, TSAI A P, KAMEOKA S. Catalysts prepared from copper-nickel ferrites for the steam reforming of methanol[J]. J Power Sources, 2015,281:138-145.
12. [12]
  BUSCA G, COSTANTINO U, MARMOTTINI F, MONTANARI T, PATRONO P, PINZARI F, RAMIS G. Methanol steam reforming over ex-hydrotalcite Cu-Zn-Al catalysts[J]. Appl Catal A:Gen, 2006,310:70-78. doi: 10.1016/j.apcata.2006.05.028
13. [13]
  YAO C Z, WANG L C, LIU Y M, WU G S, CAO Y, DAI W L, FAN K N. Effect of preparation method on the hydrogen production from methanol steam reforming over binary Cu/ZrO₂ catalysts[J]. Appl Catal A:Gen, 2006,297(2):151-158. doi: 10.1016/j.apcata.2005.09.002
14. [14]
  PATEL S, PANT K K. Influence of preparation method on performance of Cu(Zn)(Zr) -alumina catalysts for the hydrogen production via steam reforming of methanol[J]. Porous Mater, 2006,13(3):373-378.
15. [15]
  SHEN J P, SONG C S. Influence of preparation method on performance of Cu/Zn-based catalysts for low-temperature steam reforming and oxidative steam reforming of methanol for H₂ production for fuel cells[J]. Catal Today, 2002,77(1):89-98.
16. [16]
  HAMMOUD D, GENNEQUIN C, ABOUKAIS A, AAD E A. Steam reforming of methanol over x% Cu/Zn-Al 400500 based catalysts for production of hydrogen:Preparation by adopting memory effect of hydrotalcite and behavior evaluation[J]. Int J Hydrogen Energy, 2015,40(2):1283-1297. doi: 10.1016/j.ijhydene.2014.09.080
17. [17]
  CAI Y C, LIU S W, XU X L, LI S B. team reforming of methanol over CuO-ZnO-La₂O₃-Al₂O₃ catalyst[J]. Mol Catal, 2002,2(15):152-154.
18. [18]
  PATEL S, PANT K K. Activity and stability enhancement of copper-alumina catalysts using cerium and zinc promoters for the selective production of hydrogen via steam reforming of methanol[J]. J Power Sources, 2006,159(1):139-143. doi: 10.1016/j.jpowsour.2006.04.008
19. [19]
  TROVARELLI A. Catalytic properties of ceria and CeO₂-containing materials[J]. Catal Rev Sci Eng, 1996,38(4):439-520. doi: 10.1080/01614949608006464
20. [20]
  HE J P, YANG Z X, ZHANG L, LI Y, PAN L W. Cu supported on ZnAl-LDHs precursor prepared by in-situ synthesis method on γ-Al₂O₃ as catalytic material with high catalytic activity for methanol steam reforming[J]. Int J Hydrogen Energy, 2017,42(15):9930-9937. doi: 10.1016/j.ijhydene.2017.01.229
21. [21]
  XIE R F, FAN G L, YANG L, LI F. Solvent-free oxidation of ethylbenzene over hierarchical flower-like core-shell structured Co-based mixed metal oxides with significantly enhanced catalytic performance[J]. Catal Sci Technol, 2015,5(1):540-548.
22. [22]
  AGARWAL V, PATEL S, PANT K K. H₂ production by steam reforming of methanol over Cu/ZnO/Al₂O₃ catalysts:Transient deactivation kinetics modeling[J]. Appl Catal A:Gen, 2005,279(1):155-164.
23. [23]
  ZHANG L, PAN L W, NI C J, SUN T J, ZHAO S S, WANG S D, WANG A J, HU Y K. CeO₂-ZrO₂-promoted CuO/ZnO catalyst for methanol steam reforming[J]. Int J Hydrogen Energy, 2013,38(11):4397-4406. doi: 10.1016/j.ijhydene.2013.01.053
24. [24]
  ZHANG L, PAN L W, NI C J, SUN T J, WANG S D, WANG A J, HU Y K, ZHAO S S. Effect of precipitation aging time on the performance of CuO/ZnO/CeO₂-ZrO₂ for methanol steam reforming[J]. J Fuel Chem Technol, 2013,41(7):883-888. doi: 10.1016/S1872-5813(13)60038-9
25. [25]
  HURST N W, GENTRY S J, JONES A, MCNICOL B D. Temperature programmed reduction[J]. Catal Rev Sci Eng, 1982,24(2):233-309. doi: 10.1080/03602458208079654
26. [26]
  SHIM J O, NA H S, JHA A, JANG W J, JEONG D W, NAH I W, JEON B H, ROH H S. Effect of preparation method on the oxygen vacancy concentration of CeO₂-promoted Cu/γ-Al₂O₃ catalysts for HTS reactions[J]. Chem Eng J, 2016,306:908-915. doi: 10.1016/j.cej.2016.08.030
27. [27]
  WANG C, CHENG Q P, WANG X L, MA K, BAI X Q, TAN S R, TIAN Y, TONG D, ZHENG L R, ZHANG J, LI X G. Enhanced catalytic performance for CO preferential oxidation over CuO catalysts supported on highly defective CeO₂ nanocrystals[J]. Appl Surf Sci, 2017,422:932-943. doi: 10.1016/j.apsusc.2017.06.017
28. [28]
  ZHANG Lei, LEI Jun-teng, TIAN Yuan, HU Xin, BAI Jin, LIU Dan, YANG Yi, PAN Li-wei. Effect of precursor and precipitant concentration on the performance of CuO/ZnO/CeO₂-ZrO₂ catalyst for methanol steam reforming[J]. J Fuel Chem Technol, 2015,43(11):1366-1374. doi: 10.3969/j.issn.0253-2409.2015.11.012
29. [29]
  DAS D, LLORCA J, DOMINGUEZ M, COLUSSI S, TROVARELLI A, GAYEN A. Methanol steam reforming behavior of copper impregnated over CeO₂-ZrO₂ derived from a surfactant assisted coprecipitation route[J]. Int J Hydrogen Energy, 2015,40(33):10463-10479.
30. [30]
  ZHANG Guo-qiang, GUO Tian-yu, ZHENG Hua-yan, LI Zhong. Effect of calcination temperature on catalytic performance of CuCe/Ac catalysts for oxidative carbonylation of methanol[J]. J Fuel Chem Technol, 2016,44(6):674-679.
31. [31]
  XIAO S, ZHANG Y F, GAO P, ZHONG L S, LI X P, ZHANG Z Z, WANG H, WEI W, SUN Y H. Highly efficient cu-based catalysts via hydrotalcite-like precursors for CO₂ hydrogenation to methanol[J]. Catal Today, 2017,281:327-336. doi: 10.1016/j.cattod.2016.02.004
32. [32]
  LIU L J, YAO Z J, DENG Y, GAO F, LIU B, DONG L. Nanoscale ceria on the activity of CuO/CeO₂ for NO reduction by CO[J]. ChemCatChem, 2011,3(6):978-989.
33. [33]
  LIANG F L, YU Y, ZHOU W, XU X Y, ZHU Z H. Highly defective CeO₂ as a promoter for efficient and stable water oxidation[J]. J Mater Chem A, 2015,3(2):634-640. doi: 10.1039/C4TA05770H
1. [1]
  Tongtong Zhao , Yan Wang , Shiyue Qin , Liang Xu , Zhenhua Li . New Experiment Development: Upgrading and Regeneration of Discarded PET Plastic through Electrocatalysis. University Chemistry, 2024, 39(3): 308-315. doi: 10.3866/PKU.DXHX202309003
2. [2]
  Yuchen Zhou , Huanmin Liu , Hongxing Li , Xinyu Song , Yonghua Tang , Peng Zhou . Designing thermodynamically stable noble metal single-atom photocatalysts for highly efficient non-oxidative conversion of ethanol into high-purity hydrogen and value-added acetaldehyde. Acta Physico-Chimica Sinica, 2025, 41(6): 100067-. doi: 10.1016/j.actphy.2025.100067
3. [3]
  Qin Hu , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . Ni掺杂构建电子桥及激活MoS₂惰性基面增强光催化分解水产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2406024-. doi: 10.3866/PKU.WHXB202406024
4. [4]
  Xue Liu , Lipeng Wang , Luling Li , Kai Wang , Wenju Liu , Biao Hu , Daofan Cao , Fenghao Jiang , Junguo Li , Ke Liu . Cu基和Pt基甲醇水蒸气重整制氢催化剂研究进展. Acta Physico-Chimica Sinica, 2025, 41(5): 100049-. doi: 10.1016/j.actphy.2025.100049
5. [5]
  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
6. [6]
  Yaping Li , Sai An , Aiqing Cao , Shilong Li , Ming Lei . The Application of Molecular Simulation Software in Structural Chemistry Education: First-Principles Calculation of NiFe Layered Double Hydroxide. University Chemistry, 2025, 40(3): 160-170. doi: 10.12461/PKU.DXHX202405185
7. [7]
  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
8. [8]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
9. [9]
  Jinghan ZHANG , Guanying CHEN . Progress in the application of rare-earth-doped upconversion nanoprobes in biological detection. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2335-2355. doi: 10.11862/CJIC.20240249
10. [10]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-. doi: 10.3866/PKU.WHXB202406029
11. [11]
  Liang TANG , Jingfei NI , Kang XIAO , Xiangmei LIU . Synthesis and X-ray imaging application of lanthanide-organic complex-based scintillators. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1892-1902. doi: 10.11862/CJIC.20240139
12. [12]
  Changqing MIAO , Fengjiao CHEN , Wenyu LI , Shujie WEI , Yuqing YAO , Keyi WANG , Ni WANG , Xiaoyan XIN , Ming FANG . Crystal structures, DNA action, and antibacterial activities of three tetranuclear lanthanide-based complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2455-2465. doi: 10.11862/CJIC.20240192
13. [13]
  Ji-Quan Liu , Huilin Guo , Ying Yang , Xiaohui Guo . Calculation and Discussion of Electrode Potentials in Redox Reactions of Water. University Chemistry, 2024, 39(8): 351-358. doi: 10.3866/PKU.DXHX202401031
14. [14]
  Bing WEI , Jianfan ZHANG , Zhe CHEN . Research progress in fine tuning of bimetallic nanocatalysts for electrocatalytic carbon dioxide reduction. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 425-439. doi: 10.11862/CJIC.20240201
15. [15]
  Chuanming GUO , Kaiyang ZHANG , Yun WU , Rui YAO , Qiang ZHAO , Jinping LI , Guang LIU . Performance of MnO₂-0.39IrO_x composite oxides for water oxidation reaction in acidic media. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1135-1142. doi: 10.11862/CJIC.20230459
16. [16]
  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
17. [17]
  Yongpo Zhang , Xinfeng Li , Yafei Song , Mengyao Sun , Congcong Yin , Chunyan Gao , Jinzhong Zhao . Synthesis of Chlorine-Bridged Binuclear Cu(I) Complexes Based on Conjugation-Driven Cu(II) Oxidized Secondary Amines. University Chemistry, 2024, 39(5): 44-51. doi: 10.3866/PKU.DXHX202309092
18. [18]
  Wei HE , Jing XI , Tianpei HE , Na CHEN , Quan YUAN . Application of solar-driven inorganic semiconductor-microbe hybrids in carbon dioxide fixation and biomanufacturing. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 35-44. doi: 10.11862/CJIC.20240364
19. [19]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
20. [20]
  Shiyi WANG , Chaolong CHEN , Xiangjian KONG , Lansun ZHENG , Lasheng LONG . Polynuclear lanthanide compound [Ce₄^ⅢCe₆^Ⅳ(μ₃-O)₄(μ₄-O)₄(acac)₁₄(CH₃O)₆]·2CH₃OH for the hydroboration of amides to amine. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 88-96. doi: 10.11862/CJIC.20240342

Get Citation

PDF

XML

Metrics

PDF Downloads(6)
Abstract views(2474)
HTML views(369)

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