Citation: Liping Zhou, Chunying Wang, Yaobin Li, Xiaofeng Liu, Hua Deng, Wenpo Shan, Hong He. The effect of hydrogen reduction of α-MnO₂ on formaldehyde oxidation: The roles of oxygen vacancies[J]. Chinese Chemical Letters, ;2023, 34(3): 107605. doi: 10.1016/j.cclet.2022.06.028 shu

The effect of hydrogen reduction of α-MnO₂ on formaldehyde oxidation: The roles of oxygen vacancies

Liping Zhou ^{a, b} ,
Chunying Wang ^{b, c} ,
Yaobin Li ^{b, c, *,} ,
Xiaofeng Liu ^b ,
Hua Deng ^b ,
Wenpo Shan ^{a, b, c, *,} ,
Hong He ^{b, d}

a.
College of Resources and Environmental Sciences, Fujian Agriculture and Forestry University, Fuzhou 350002, China
b.
Center for Excellence in Regional Atmospheric Environment, Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021, China
c.
Zhejiang Key Laboratory of Urban Environmental Processes and Pollution Control, Ningbo Urban Environment Observation and Research Station, Institute of Urban Environment, Chinese Academy of Sciences, Ningbo 315800, China
d.
State Key Joint Laboratory of Environment Simulation and Pollution Control, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China

ybli@iue.ac.cn

wpshan@iue.ac.cn

Received Date: 15 February 2022
Revised Date: 13 April 2022
Accepted Date: 11 June 2022
Available Online: 16 June 2022

Figures(4)

A series of α-MnO₂ catalysts with various Mn valence states were treated by hydrogen reduction for different periods of time. Their catalytic capacity for formaldehyde (HCHO) oxidation was evaluated. The results indicated that hydrogen reduction dramatically improves the catalytic performance of α-MnO₂ in HCHO oxidation. The α-MnO₂ sample reduced by hydrogen for 2 h possessed superior activity and could completely oxidize 150 ppm HCHO to CO₂ and H₂O at 70 ℃. Multiple characterization results illustrated that hydrogen reduction contributed to the production of more oxygen vacancies. The oxygen vacancies on the catalyst surface enhanced the adsorption, activation and mobility of O₂ molecules, and thereby enhanced HCHO catalytic oxidation. This study provides novel insight into the design of outstanding MnO_x catalysts for HCHO oxidation at low temperature.
- Hydrogen reduction,
- α-MnO₂,
- Formaldehyde oxidation,
- Oxygen vacancies
1. [1]
  E.L. Hult, H. Willem, P.N. Price, et al., Indoor Air 25 (2015) 523–535. doi: 10.1111/ina.12160
2. [2]
  T. Salthammer, S. Mentese, R. Marutzky, Chem. Rev. 110 (2010) 2536–2572. doi: 10.1021/cr800399g
3. [3]
  C. Ma, X. Li, T. Zhu, Carbon 49 (2011) 2869–2877. doi: 10.1016/j.carbon.2011.02.056
4. [4]
  R. Portela, I. Jansson, S. Suárez, et al., Chem. Eng. J. 310 (2017) 560–570. doi: 10.1016/j.cej.2016.06.018
5. [5]
  X. Zhu, X. Gao, R. Qin, et al., Appl. Catal. B: Environ. 170 (2015) 293–300. doi: 10.1016/j.apcatb.2015.01.032
6. [6]
  B. Bai, Q. Qiao, H. Arandiyan, J. Li, J. Hao, Environ. Sci. Technol. 50 (2016) 2635–2640. doi: 10.1021/acs.est.5b03342
7. [7]
  L. Miao, J. Wang, P. Zhang, Appl. Surf. Sci. 466 (2019) 441–453. doi: 10.1016/j.apsusc.2018.10.031
8. [8]
  J. Ma, R. Cao, Y. Dang, et al., Chin. Chem. Lett. 32 (2021) 2985–2993. doi: 10.1016/j.cclet.2021.03.031
9. [9]
  Y. Li, C. Zhang, H. He, J. Zhang, M. Chen, Catal. Sci. Technol. 6 (2016) 2289–2295. doi: 10.1039/C5CY01521A
10. [10]
  C. Wang, Y. Li, L. Zheng, et al., ACS Catal. 11 (2021) 456–465. doi: 10.1021/acscatal.0c03196
11. [11]
  W. Ahmad, E. Park, H. Lee, J.Y. Kim, Y. Oh, Appl. Surf. Sci. 538 (2021) 147504. doi: 10.1016/j.apsusc.2020.147504
12. [12]
  F. Wang, Y. Wang, K. Han, H. Yu, J. Environ. Chem. Eng. 8 (2020) 104041. doi: 10.1016/j.jece.2020.104041
13. [13]
  C. Wang, Y. Li, C. Zhang, H. He, Appl. Catal. B: Environ. 282 (2021) 119540. doi: 10.1016/j.apcatb.2020.119540
14. [14]
  K. Li, J. Ji, M. He, H. Huang, Catal. Sci. Technol. 10 (2020) 6257–6265. doi: 10.1039/D0CY01085E
15. [15]
  Y. Li, C. Wang, C. Zhang, H. He, Top. Catal. 63 (2020) 810–816. doi: 10.1007/s11244-020-01349-1
16. [16]
  S. Kang, M. Wang, N. Zhu, et al., Chin. Chem. Lett. 30 (2019) 1450–1454. doi: 10.1016/j.cclet.2019.03.023
17. [17]
  B. Chen, X. Zhu, Y. Wang, L. Yu, C. Shi, Chin. J. Catal. 37 (2016) 1729–1737. doi: 10.1016/S1872-2067(16)62470-1
18. [18]
  Z. Tang, W. Zhang, Y. Li, et al., Appl. Surf. Sci. 364 (2016) 75–80. doi: 10.1016/j.apsusc.2015.12.112
19. [19]
  B. Chen, X. Zhu, Y. Wang, et al., Catal. Today 281 (2017) 512–519. doi: 10.1016/j.cattod.2016.06.023
20. [20]
  Y. Li, X. Chen, C. Wang, C. Zhang, H. He, ACS Catal. 8 (2018) 11377–11385. doi: 10.1021/acscatal.8b03026
21. [21]
  J. Guo, C. Lin, C. Jiang, P. Zhang, Appl. Surf. Sci. 475 (2019) 237–255. doi: 10.1016/j.apsusc.2018.12.238
22. [22]
  Y. Wen, T. Xin, J. Li, et al., Catal. Commun. 10 (2009) 1157–1160. doi: 10.1016/j.catcom.2008.12.033
23. [23]
  S. Lu, K. Li, F. Huang, C. Chen, B. Sun, Appl. Surf. Sci. 400 (2017) 277–282. doi: 10.1016/j.apsusc.2016.12.207
24. [24]
  L. Ma, D. Wang, J. Li, et al., Appl. Catal. B: Environ. 148-149 (2014) 36–43. doi: 10.1016/j.apcatb.2013.10.039
25. [25]
  J. Chen, M. Huang, W. Chen, H. Tang, R. Wang, Ind. Eng. Chem. Res. 59 (2020) 18781–18789. doi: 10.1021/acs.iecr.0c03459
26. [26]
  Z. Lin, S. Rong, P. Zhang, J. Wang, Appl. Catal. B: Environ. 211 (2017) 212–221. doi: 10.1016/j.apcatb.2017.04.025
27. [27]
  J. Pei, H. Xu, L. Yi, Build. Environ. 84 (2015) 134–141. doi: 10.1016/j.buildenv.2014.11.002
28. [28]
  Y. Sekine, A. Nishimura, Atmos. Environ. 35 (2001) 2001–2007. doi: 10.1016/S1352-2310(00)00465-9
29. [29]
  H. Chen, J. He, C. Zhang, H. He, J. Phys. Chem. C 111 (2007) 18033–18038. doi: 10.1021/jp076113n
30. [30]
  L. Qi, Y. Le, C. Wang, R. Lei, T. Wu, New J. Chem. 45 (2021) 3960–3968. doi: 10.1039/D0NJ05515H
31. [31]
  H. Li, J. Cao, D. Park, Y. Huang, Environ. Sci. Technol. 53 (2019) 10906–10916. doi: 10.1021/acs.est.9b03197
32. [32]
  C. Zhang, J. Zhang, L. Wang, Y. Li, H. He, Catal. Sci. Technol. 5 (2015) 2305–2313. doi: 10.1039/C4CY01461H
33. [33]
  B. Chen, B. Wu, L. Yu, M. Crocker, C. Shi, ACS Catal. 10 (2020) 6176–6187. doi: 10.1021/acscatal.0c00459
34. [34]
  S. Rong, P. Zhang, F. Liu, Y. Yang, ACS Catal. 8 (2018) 3435–3446. doi: 10.1021/acscatal.8b00456
35. [35]
  E. Saputra, S. Muhammad, H. Sun, et al., Environ. Sci. Technol. 47 (2013) 5882–5887. doi: 10.1021/es400878c
36. [36]
  H. Deng, S. Kang, J. Ma, C. Zhang, H. He, Appl. Catal. B: Environ. 239 (2018) 214–222. doi: 10.1016/j.apcatb.2018.08.006
37. [37]
  J. Wang, D. Li, P. Zhang, Q. Xu, J. Yu, RSC Adv. 5 (2015) 100434–100442. doi: 10.1039/C5RA17018D
38. [38]
  J. Wang, J. Li, C. Jiang, et al., Appl. Catal. B: Environ. 204 (2017) 47–155.
39. [39]
  J. Wang, G. Zhang, P. Zhang, J. Mater. Chem. A 5 (2017) 5719–5725. doi: 10.1039/C6TA09793F
40. [40]
  C.M. Julien, M. Massot, C. Poinsignon, Spectrochim. Acta A 60 (2004) 689–700. doi: 10.1016/S1386-1425(03)00279-8
41. [41]
  A. Yusuf, Y. Sun, C. Snape, J. He, C. Wang, Mol. Catal. 497 (2020) 111204. doi: 10.1016/j.mcat.2020.111204
42. [42]
  B. Bai, Q. Qiao, J. Li, J. Hao, Chin. J. Catal. 37 (2016) 27–31. doi: 10.1016/S1872-2067(15)61026-9
43. [43]
  Y. Huang, Y. Liu, W. Wang, J. Cao, et al., Appl. Catal. B: Environ. 278 (2020) 119294. doi: 10.1016/j.apcatb.2020.119294
44. [44]
  X. Liu, K. Zhou, L. Wang, B. Wang, Y. Li, J. Am. Chem. Soc. 131 (2009) 3140–3141. doi: 10.1021/ja808433d
45. [45]
  H. Zhao, J. Tang, Z. Li, et al., Catal. Sci. Technol. 11 (2021) 7110–7124. doi: 10.1039/D1CY01490K
46. [46]
  L. Zhang, S. Wang, L. Lv, Y. Ding, S. Wang, Langmuir 37 (2021) 1410–1419. doi: 10.1021/acs.langmuir.0c02841
47. [47]
  P. Hu, X. Tang, Z. Huang, F. Xu, A. Zakariae, Environ. Sci. Technol. 49 (2015) 2384–2390. doi: 10.1021/es504570n
48. [48]
  X. Zeng, C. Shan, M. Sun, et al., Chin. Chem. Lett. 33 (2022) 4771–4775. doi: 10.1016/j.cclet.2021.12.085
49. [49]
  L. Li, X. Feng, N. Yao, S. Chen, M. Xia, ACS Catal. 5 (2015) 4825–4832. doi: 10.1021/acscatal.5b00320
50. [50]
  X. Li, J. Ma, L. Yang, et al., Environ. Sci. Technol. 52 (2018) 12685–12696. doi: 10.1021/acs.est.8b04294
51. [51]
  G. Zhu, J. Zhu, W. Jiang, et al., Appl. Catal. B: Environ. 209 (2017) 729–737. doi: 10.1016/j.apcatb.2017.02.068
52. [52]
  Y. Wei, L. Yan, C. Wang, X. Xu, G. Chen, J. Phys. Chem. B 108 (2004) 18547–18551. doi: 10.1021/jp0479522
53. [53]
  H. Li, F. Ren, J. Liu, et al., Appl. Catal. B: Environ. 172-173 (2015) 37–45. doi: 10.1007/s40333-014-0072-y
54. [54]
  L. Li, T. Hua, J. He, Q. Yang, J. Phys. Chem. C 120 (2016) 23660–23668. doi: 10.1021/acs.jpcc.6b08312
55. [55]
  Y. Wang, K. Liu, J. Wu, Z. Hu, L. Guo, ACS Catal. 10 (2020) 10021–10031. doi: 10.1021/acscatal.0c02310
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The effect of hydrogen reduction of α-MnO2 on formaldehyde oxidation: The roles of oxygen vacancies

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The effect of hydrogen reduction of α-MnO₂ on formaldehyde oxidation: The roles of oxygen vacancies