Citation: Juan YANG, Peng-yu CHEN, Jun DAI, Li-qing RONG, Da-zhao WANG. Synthesis of Co₃O₄/WO₃ composite catalysts for visible-light-driven conversion of methane to methanol[J]. Journal of Fuel Chemistry and Technology, ;2022, 50(4): 464-473. doi: 10.19906/j.cnki.JFCT.2021086 shu

Synthesis of Co₃O₄/WO₃ composite catalysts for visible-light-driven conversion of methane to methanol

Juan YANG ^{1, 2, 3} ,
Peng-yu CHEN ¹ ,
Jun DAI ^{1, 2,,} ,
Li-qing RONG ¹ ,
Da-zhao WANG ¹

1.
School of Safety Science and Engineering, Henan Polytechnic University, Jiaozuo 454003, China
2.
State Collaborative Innovation Center of Coal Work Safety and Clean-efficiency Utilization, Jiaozuo 454003, China
3.
School of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo 454003, China

Corresponding author: Jun DAI, daijun@hpu.edu.cn
Received Date: 18 August 2021
Revised Date: 27 September 2021

Figures(12)

Direct and selective conversion of methane to methanol under mild conditions still faces grand challenges. In this study, Co₃O₄/WO₃ nanocomposite catalysts were synthesized by facile hydrothermal method, combining with surface impregnation process. The structural composition and micro morphology of Co₃O₄/WO₃ composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and UV-visible absorption spectrum. The catalytic performance of Co₃O₄/WO₃ on the conversion of methane to methanol was investigated under visible light illumination at room temperature. The results show that incorporating Co₃O₄ can remarkably improve the photocatalytic performance of methane conversion. The optimal catalyst 3.0% Co₃O₄/WO₃ exhibits a methane conversion of 2041 μmol/g after visible light irradiation for 2 h, and the according methanol productivity and selectivity reach 1194 μmol/g and 58.5%, which are 4.03 and 2.39 times of single WO₃ respectively. This performance is superior to most reported heterogeneous photocatalysts for methane conversion, meanwhile possessing excellent cyclic stability. Combining the results of transient photocurrent and electron paramagnetic resonance (EPR) with the catalytic activity, the intrinsic mechanism of enhanced methane conversion via introducing Co₃O₄ is revealed, which is of theoretical significance to design light-driven catalysts for methane conversion to methanol.
- methane,
- visible light catalysis,
- methanol,
- tungsten oxide,
- Co₃O₄
1. [1]
  MCFARLAND E. Unconventional chemistry for unconventional natural gas[J]. Science,2012,338(6105):340−342. doi: 10.1126/science.1226840
2. [2]
  SCHWACH P, PAN X L, BAO X H. Direct conversion of methane to value-added chemicals over heterogeneous catalysts: Challenges and prospects[J]. Chem Rev,2017,117(13):8497−8520. doi: 10.1021/acs.chemrev.6b00715
3. [3]
  ZHAN C G, NICHOLS J A, DIXON D A. Ionization potential, electron affinity, electronegativity, hardness, and electron excitation energy: Molecular properties from density functional theory orbital energies[J]. J Phys Chem A,2003,107(20):4184−4195. doi: 10.1021/jp0225774
4. [4]
  DA SILVA M J. Synthesis of methanol from methane: Challenges and advances on the multi-step (syngas) and one-step routes (DMTM)[J]. Fuel Process Technol,2016,145:42−61. doi: 10.1016/j.fuproc.2016.01.023
5. [5]
  KWON Y, KIM T Y, KWON G, YI J, LEE H. Selective activation of methane on single-atom catalyst of rhodium dispersed on zirconia for direct conversion[J]. J Am Chem Soc,2017,139(48):17694−17699. doi: 10.1021/jacs.7b11010
6. [6]
  AGARWAL N, FREAKLEY S J, MCVICKER R U, ALTHAHBAN S M, DIMITRATOS N, HE Q, MORGAN D J, JENKINS R L, WILLOCK D J, TAYLOR S H, KIELY C J, HUTCHINGS G J. Aqueous Au-Pd colloids catalyze selective CH₄ oxidation to CH₃OH with O₂ under mild conditions[J]. Science,2017,358(6360):223−227. doi: 10.1126/science.aan6515
7. [7]
  YU Gui-yang. The study of spatial field effect on improving semiconductor photocatalytic hydrogen evolution[D]. Changchun: Jilin University, 2019.
8. [8]
  YANG J, HAO J Y, XU S Y, WANG Q, DAI J, ZHANG A C, PANG X C. InVO₄/β-AgVO₃ nanocomposite as a direct Z-Scheme photocatalyst toward efficient and selective visible-light-driven CO₂ reduction[J]. ACS Appl Mater Inter,2019,11(35):32025−32037. doi: 10.1021/acsami.9b10758
9. [9]
  LI H, SHANG J, AI Z H, ZHANG L Z. Efficient visible light nitrogen fixation with BiOBr nanosheets of oxygen vacancies on the exposed {001} facets[J]. J Am Chem Soc,2015,137(19):6393−6399. doi: 10.1021/jacs.5b03105
10. [10]
  XU Zhen-min, BIAN Zhen-feng. Photocatalytic methane conversion[J]. Acta Phys-Chim Sin,2020,36(3):1907013. doi: 10.3866/PKU.WHXB201907013
11. [11]
  ZHU W L, SHEN M K, FAN G Z, YANG A, MEYER J R, OU Y N, YIN B, FORTNER J, FOSTON M, LI Z S, ZOU Z G, SADTLER B. Facet-dependent enhancement in the activity of bismuth vanadate microcrystals for the photocatalytic conversion of methane to methanol[J]. ACS Appl Nano Mater,2018,1(12):6683−6691. doi: 10.1021/acsanm.8b01490
12. [12]
  LIU H S, SONG C J, ZHANG L, ZHANG J J, WANG H J, WILKINSON D P. A review of anode catalysis in the direct methanol fuel cell[J]. J Power Sources,2006,155(2):95−110. doi: 10.1016/j.jpowsour.2006.01.030
13. [13]
  SONG H, MENG X G, WANG S Y, ZHOU W, WANG X S, KAKO T, YE J H. Direct and selective photocatalytic oxidation of CH₄ to oxygenates with O₂ on cocatalysts/ZnO at room temperature in water[J]. J Am Chem Soc,2019,141(51):20507−20515. doi: 10.1021/jacs.9b11440
14. [14]
  LUO L H, LUO J, LI H L, REN F N, ZHANG Y F, LIU A D, LI W-X, ZENG J. Water enables mild oxidation of methane to methanol on gold single-atom catalysts[J]. Nat Commun,2021,12:1218. doi: 10.1038/s41467-021-21482-z
15. [15]
  YU L H, SHAO Y, LI D Z. Direct combination of hydrogen evolution from water and methane conversion in a photocatalytic system over Pt/TiO₂[J]. Appl Catal B: Environ,2017,204:216−223. doi: 10.1016/j.apcatb.2016.11.039
16. [16]
  ZHAN Ying-ying, KANG Liang, ZHOU Yu-chang, CAI Guo-hui, CHEN Chong-qi, JIANG Li-long. Pd/Al₂O₃ catalysts modified with Mg for catalytic combustion of methane: Effect of Mg/Al mole ratios on the supports and active PdO_x formation[J]. J Fuel Chem Technol,2019,47(10):1235−1244. doi: 10.3969/j.issn.0253-2409.2019.10.010
17. [17]
  YANG Huan, WANG Gui-yun, TIAN Wei-song, TONG Chun-jie. Hydrothermal synthesis of monoclinic WO₃ and its photocatalytic hydrogen production performance[J]. J Fuel Chem Technol,2018,46(11):1359−1369. doi: 10.3969/j.issn.0253-2409.2018.11.010
18. [18]
  VILLA K, MURCIA-LÓPEZ S, MORANTE J R, ANDREU T. An insight on the role of La in mesoporous WO₃ for the photocatalytic conversion of methane into methanol[J]. Appl Catal B: Environ,2016,187:30−36. doi: 10.1016/j.apcatb.2016.01.032
19. [19]
  VILLA K, MURCIA-LÓPEZ S, ANDREU T, MORANTE J R. Mesoporous WO₃ photocatalyst for the partial oxidation of methane to methanol using electron scavengers[J]. Appl Catal B: Environ,2015,163:150−155. doi: 10.1016/j.apcatb.2014.07.055
20. [20]
  WANG Bing, ZHAO Mei-ming, ZHOU Yong, YAN Shi-cheng, ZOU Zhi-gang. Recent progress and challenge in research of photocatalytic reduction of CO₂ to solar fuels[J]. Sci Sin Tech,2017,47(3):286−296. doi: 10.1360/N092016-00434
21. [21]
  SUN Shang-cong, ZHANG Xu-ya, LIU Xian-long, PAN Lun, ZHANG Xiang-wen, ZOU Ji-jun. Design and construction of cocatalysts for photocatalytic water splitting[J]. Acta Phys-Chim Sin,2020,36(3):1905007. doi: 10.3866/PKU.WHXB201905007
22. [22]
  CHEN Peng, ZHOU Ying, DONG Fan. Advances in regulation strategies for electronic structure and performance of two-dimensional photocatalytic materials[J]. Acta Phys-Chim Sin,2021,37(8):2010010.
23. [23]
  WANG Z D, CHU Z, DONG C W, WANG Z, YAO S Y, GAO H, LIU Z Y, LIU Y, YANG B, ZHANG H. Ultrathin BiOX (X=Cl, Br, I) nanosheets with exposed {001} facets for photocatalysis[J]. ACS Appl Nano Mater,2020,3(2):1981−1991. doi: 10.1021/acsanm.0c00022
24. [24]
  ZHOU Wen-jun, SHEN Bo-xiong, ZHANG Qin, WANG Xin-yi, LU Feng-ju. Preparation of the Ti³⁺/TiO₂ supported CuO catalyst and its photocatalytic performance in the degradation of toluene[J]. J Fuel Chem Technol,2019,47(2):249−256. doi: 10.3969/j.issn.0253-2409.2019.02.015
25. [25]
  LIU J, KE J, LI Y, LIU B J, WANG L D, XIAO H N, WANG S B. Co₃O₄ quantum dots/TiO₂ nanobelt hybrids for highly efficient photocatalytic overall water splitting[J]. Appl Catal B: Environ,2018,236:396−403. doi: 10.1016/j.apcatb.2018.05.042
26. [26]
  YANG J, WEN Z H, SHEN X X, DAI J, LI Y, LI Y J. A comparative study on the photocatalytic behavior of graphene-TiO₂ nanostructures: Effect of TiO₂ dimensionality on interfacial charge transfer[J]. Chem Eng J,2018,334:907−921. doi: 10.1016/j.cej.2017.10.088
27. [27]
  XIE J J, JIN R X, LI A, BI Y P, RUAN Q S, DENG Y C, ZHANG Y J, YAO S Y, SANKAR G, MA D, TANG J W. Highly selective oxidation of methane to methanol at ambient conditions by titanium dioxide-supported iron species[J]. Nat Catal,2018,1(11):889−896. doi: 10.1038/s41929-018-0170-x
28. [28]
  MA M, ZHANG K, LI P, JUNG M S, JEONG M J, PARK J H. Dual oxygen and tungsten vacancies on a WO₃ photoanode for enhanced water oxidation[J]. Angew Chem Int Ed,2016,55(39):11819−11823. doi: 10.1002/anie.201605247
29. [29]
  LIU D N, CHEN D Y, LI N J, XU Q F, LI H, HE J H, LU J M. ZIF-67-derived 3D hollow mesoporous crystalline Co₃O₄ wrapped by 2D g-C₃N₄ nanosheets for photocatalytic removal of nitric oxide[J]. Small,2019,15(31):1902291. doi: 10.1002/smll.201902291
30. [30]
  ZHANG H Y, GUO C F, REN J B, NING J Q, ZHONG Y J, ZHANG Z Y, HU Y. Beyond CoO_x: A versatile amorphous cobalt species as an efficient cocatalyst for visible-light-driven photocatalytic water oxidation[J]. Chem Commun,2019,55(93):14050−14053. doi: 10.1039/C9CC07835E
31. [31]
  PARK J, YOON H, CHOI S, SON J. Nanoscaffold WO₃ by kinetically controlled polymorphism[J]. Cryst Growth Des,2019,19(1):479−486. doi: 10.1021/acs.cgd.8b01551
32. [32]
  LIU H, ZHANG J, AO D. Construction of heterostructured ZnIn₂S₄@NH₂-MIL-125(Ti) nanocomposites for visible-light-driven H₂ production[J]. Appl Catal B: Environ,2018,221:433−442. doi: 10.1016/j.apcatb.2017.09.043
33. [33]
  YUAN J L, WEN J Q, GAO Q Z, CHEN S C, LI J M, LI X, FANG Y P. Amorphous Co₃O₄ modified CdS nanorods with enhanced visible-light photocatalytic H₂-production activity[J]. Dalton Trans,2015,44(4):1680−1689. doi: 10.1039/C4DT03197K
34. [34]
  MURCIA-LÓPEZ S, VILLA K, ANDREU T, MORANTE J R. Partial oxidation of methane to methanol using bismuth-based photocatalysts[J]. ACS Catal,2014,4:3013−3019. doi: 10.1021/cs500821r
35. [35]
  ZENG Y, LUO X, LI F, HUANG A H, WU H M, XU G Q, WANG S L. Noble metal-free FeOOH/Li_0.1WO₃ core-shell nanorods for selective oxidation of methane to methanol with Visible-NIR light[J]. Environ Sci Technol,2021,55(11):7711−7720. doi: 10.1021/acs.est.1c01152
36. [36]
  MURCIA-LÓPEZ S, BACARIZA M C, VILLA K, LOPES J M, HENRIQUES C, MORANTE J R, ANDREU T. Controlled photocatalytic oxidation of methane to methanol through surface modification of beta zeolites[J]. ACS Catal,2017,7:2878−2885. doi: 10.1021/acscatal.6b03535
37. [37]
  LI Y, LI J, ZHANG G K, WANG K, WU X Y. Selective photocatalytic oxidation of low concentration methane over graphitic carbon nitride-decorated tungsten bronze cesium[J]. ACS Sustainable Chem Eng,2019,7(4):4382−4389. doi: 10.1021/acssuschemeng.8b06270
38. [38]
  CHEN Z Q, CHEN P F, XING P X, HU X, LIN H J, ZHAO L H, WU Y, HE Y M. Rapid fabrication of KTa_0.75Nb_0.25/g-C₃N₄ composite via microwave heating for efficient photocatalytic H₂ evolution[J]. Fuel,2019,241:1−11. doi: 10.1016/j.fuel.2018.12.011
39. [39]
  CHENG Rong-min, XU Hong, SHAN Rui-ping, ZHAN Cong-hong. Influential factors of La-doped Calcium Titanate for photocatalytic H₂ evolution under visible light[J]. Chem J Chin Univ,2020,41(6):1345−1351. doi: 10.7503/cjcu20190644
40. [40]
  ZHAO Z W, FAN J Y, DENG X Y, LIU J. One-step synthesis of phosphorus-doped g-C₃N₄/Co₃O₄ quantum dots from vitamin B12 with enhanced visible-light photocatalytic activity for metronidazole degradation[J]. Chem Eng J,2019,360:1517−1529. doi: 10.1016/j.cej.2018.10.239
41. [41]
  TANG C N, LIU E Z, WAN J, HU X Y, FAN J. Co₃O₄ nanoparticles decorated Ag₃PO₄ tetrapods as an efficient visible-light-driven heterojunction photocatalyst[J]. Appl Catal B: Environ,2016,181:707−715. doi: 10.1016/j.apcatb.2015.08.045
42. [42]
  HE W W, KIM H K, WARNER W G, MELKA D, CALLAHAN J H, YIN J J. Photogenerated charge carriers and reactive oxygen species in ZnO/Au hybrid nanostructures with enhanced photocatalytic and antibacterial activity[J]. J Am Chem Soc,2014,136:750−757. doi: 10.1021/ja410800y
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沈阳化工大学材料科学与工程学院沈阳 110142

Synthesis of Co3O4/WO3 composite catalysts for visible-light-driven conversion of methane to methanol

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通讯作者: 陈斌, bchen63@163.com

Synthesis of Co₃O₄/WO₃ composite catalysts for visible-light-driven conversion of methane to methanol