Please wait a minute...
Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

Postal Subscription Code 80-973

2018 Impact Factor: 3.883

Front. Environ. Sci. Eng.    2020, Vol. 14 Issue (2) : 20    https://doi.org/10.1007/s11783-019-1199-z
RESEARCH ARTICLE
In situ electron-induced reduction of NOx via CNTs activated by DBD at low temperature
Weixuan Zhao1,2, Liping Lian1,2, Xingpeng Jin1,2, Renxi Zhang1,2(), Gang Luo1,2(), Huiqi Hou1,2, Shanping Chen3, Ruina Zhang3
1. Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention (LAP3), Institute of Environmental Science, Fudan University, Shanghai 200433, China
2. National Engineering Laboratory for VOCs Pollution Control Material & Technology, University of Chinese Academy of Sciences, Beijing 100049, China
3. Shanghai Institute for Design & Research on Environmental Engineering, Shanghai 200232, China
 Download: PDF(1431 KB)   HTML
 Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks
Abstract

• An in situ electron-induced deNOx process with CNT activated by DBD was achieved.

• Carbon atoms on CNT surface were verified to be excited by plasma in DBD-CNT system.

• Reactions between NOx and excited C result in synergistic effect of DBD-CNT system.

In this study, a new in situ electron-induced process is presented with carbon nanotubes (CNTs) as a reduction agent activated by dielectric barrier discharge (DBD) for nitrogen oxide (NOx) abatement at low temperature (<407 K). Compared with a single DBD system and a DBD system with activated carbon (DBD-AC), a DBD system with carbon nanotubes (DBD-CNT) showed a significant promotion of NOx removal efficiency and N2 selectivity. Although the O2 content was 10%, the NOx conversion and N2 selectivity in the DBD-CNT system still reached 64.9% and 81.9% at a specific input energy (SIE) of 1424 J/L, and these values decreased to 16.8%, 31.9% and 43.2%, 62.3% in the single DBD system and the DBD-AC system, respectively. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were utilized to investigate surface changes in the CNTs after activation by DBD to explore the NOx reduction abatement mechanism of this new process. Furthermore, the outlet gas components were also observed via Fourier transform infrared spectroscopy (FTIR) to help reveal the NOx reduction mechanism. Experimental results verified that carbon atoms excited by DBD and the structure of CNTs contributed to the synergistic activity of the DBD-CNT system. The new deNOx process was accomplished through in situ heterogenetic reduction reactions between the NOx and carbon atoms activated by the plasma on the CNTs. In addition, further results indicated that the new deNOx process exhibited acceptable SO2 tolerance and water resistance.

Corresponding Author(s): Renxi Zhang,Gang Luo   
Issue Date: 17 December 2019
 Cite this article:   
Weixuan Zhao,Liping Lian,Xingpeng Jin, et al. In situ electron-induced reduction of NOx via CNTs activated by DBD at low temperature[J]. Front. Environ. Sci. Eng., 2020, 14(2): 20.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-019-1199-z
https://academic.hep.com.cn/fese/EN/Y2020/V14/I2/20
Fig.1  Schematic of the DBD-CNT hybrid system.
Fig.2  Effect of the O2 concentration on the NOx conversion in the DBD, DBD-AC and DBD-CNT systems.
Process Feed gas concentration of the inlet (mg/m3) Product concentration
of the outlet
(mg/m3)
N2 selectivity (%)
NO NO2 NO NO2 N2O NO3
DBD 321 123 273 93.4 7.1 75.3 31.9
DBD-AC 321 123 214 41.7 15.3 46.8 62.3
DBD-CNT 321 123 120 31.4 21.2 37.9 81.9
Tab.1  The N2 selectivity, concentration of the feed gas and the products at the outlet
Fig.3  SEM images of untreated CNTs and CNTs treated by DBD. (a), (c): Untreated CNTs and (b), (d): CNTs treated by DBD.
Element Untreated CNTs CNTs treated by DBD
Weight percentage (%) Atom percentage (%) Weight percentage (%) Atom percentage (%)
C 90.84 92.97 86.77 89.73
O 9.16 7.03 13.23 10.27
Tab.2  Surface element comparison between the SEM spectra of untreated CNTs and CNTs treated by DBD
Fig.4  Comparison between the XPS O1s spectra untreated CNTs and CNTs treated with DBD.
Fig.5  The product concentration and FTIR spectra observed in the DBD and DBD-CNT systems with different O2 concentrations and SIEs. (a), (c): DBD system, (b), (d): DBD-CNT system. Feed gas composition: (a), (b): 321 mg/m3 NO, 123 mg/m3 NO2, balance N2 and free O2. (c), (d): 321 mg/m3 NO, 123 mg/m3 NO2, balance N2 and O2 concentration from 2% to 8%.
Fig.6  Effects of SO2 and H2O on NO removal in the DBD-CNT system. Experimental conditions: 1424 J/L, 10% O2, 286 mg/m3 SO2, 10% H2O (when added), and the other conditions are the same as those in Fig. 2.
Fig.7  Reaction process of the DBD-CNT system: (a) DBD-CNT system with free O2; (b) DBD-CNT system with excess O2.
1 H Ago, T Kugler, F Cacialli, W R Salaneck, M S Shaffer, A H Windle, R H Friend (1999). Work functions and surface functional groups of multiwall carbon nanotubes. Journal of Physical Chemistry B, 103(38): 8116–8121
https://doi.org/10.1021/jp991659y
2 R Atkinson, D L Baulch, R A Cox, R F Hampson Jr, J A Kerr, M J Rossi, J Troe (2000). Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement VIII, halogen species evaluation for atmospheric chemistry. Journal of Physical and Chemical Reference Data, 29(2): 167–266
https://doi.org/10.1063/1.556058
3 I M Campbell, C N Gray (1973). Rate constants for O(3P) recombination and association with N(4S). Chemical Physics Letters, 18(4): 607–609
https://doi.org/10.1016/0009-2614(73)80479-8
4 I H Chen, C C Wang, C Y Chen (2010). Preparation of carbon nanotube (CNT) composites by polymer functionalized CNT under plasma treatment. Plasma Processes and Polymers, 7(1): 59–63
https://doi.org/10.1002/ppap.200900067
5 J X Chen, K L Pan, S J Yu, S Y Yen, M B Chang (2017). Combined fast selective reduction using Mn-based catalysts and nonthermal plasma for NOx removal. Environmental Science and Pollution Research International, 24(26): 21496–21508
https://doi.org/10.1007/s11356-017-9785-8 pmid: 28748438
6 B K Cho, J H Lee, C C Crellin, K L Olson, D L Hilden, M K Kim, P S Kim, I Heo, S H Oh, I S Nam (2012). Selective catalytic reduction of NOx by diesel fuel: Plasma-assisted HC/SCR system. Catalysis Today, 191(1): 20–24
https://doi.org/10.1016/j.cattod.2012.03.044
7 S Devahasdin, C Fan Jr, K Li, D H Chen (2003). TiO2 photocatalytic oxidation of nitric oxide: transient behavior and reaction kinetics. Journal of Photochemistry and Photobiology A Chemistry, 156(1–3): 161–170
https://doi.org/10.1016/S1010-6030(03)00005-4
8 N Fang, J Guo, S Shu, H Luo, Y Chu, J Li (2017). Enhancement of low-temperature activity and sulfur resistance of Fe0.3Mn0.5Zr0.2 catalyst for NO removal by NH3-SCR. Chemical Engineering Journal, 325: 114–123
https://doi.org/10.1016/j.cej.2017.05.053
9 A Felten, C Bittencourt, J J Pireaux, G Van Lier, J C Charlier (2005). Radio-frequency plasma functionalization of carbon nanotubes surface O2, NH3, and CF4 treatments. Journal of Applied Physics, 98(7): 074308
https://doi.org/10.1063/1.2071455
10 P Forzatti (2001). Present status and perspectives in de-NOx SCR catalysis. Applied Catalysis A-General, 222(1–2): 221–236
https://doi.org/10.1016/S0926-860X(01)00832-8
11 W D Geppert, D Reignier, T Stoecklin, C Naulin, M Costes, D Chastaing, S D Le Picard, I R Sims, I W M Smith (2000). Comparison of the cross-sections and thermal rate constants for the reactions of C(3PJ) atoms with O2 and NO. Physical Chemistry Chemical Physics, 2(13): 2873–2881
https://doi.org/10.1039/b002583f
12 X Hao, G Wang, S Chen, H Yu, X Quan (2019). Enhanced activation of peroxymonosulfate by CNT-TiO2 under UV-light assistance for efficient degradation of organic pollutants. Frontiers of Environmental Science & Engineering, 13(5): 77
https://doi.org/doi: org/10.1007/s11783-019-1161-0
13 C He, B Xu, Z Jiang, Y Xu, J Zhao, H Pan (2015). Simultaneous removal of CO, NOx, and HC emitted from gasoline engine in a nonthermal plasma-driven catalysis system. Asia-Pacific Journal of Chemical Engineering, 10(4): 633–640
https://doi.org/10.1002/apj.1899
14 H He, Y Yu (2005). Selective catalytic reduction of NOx over Ag/Al2O3 catalyst: from reaction mechanism to diesel engine test. Catalysis Today, 100(1–2): 37–47
https://doi.org/10.1016/j.cattod.2004.11.006
15 X Hu, G B Zhao, J J Zhang, L Wang, M Radosz (2004). Nonthermal-plasma reactions of dilute nitrogen oxide mixtures: NOx-in-argon and NOx+CO-in-argon. Industrial & Engineering Chemistry Research, 43(23): 7456–7464
https://doi.org/10.1021/ie0495731
16 C B Jacobs, M J Peairs, B J Venton (2010). Review: Carbon nanotube based electrochemical sensors for biomolecules. Analytica Chimica Acta, 662(2): 105–127
https://doi.org/10.1016/j.aca.2010.01.009 pmid: 20171310
17 M Kang, E D Park, J M Kim, J E Yie (2007). Manganese oxide catalysts for NOx reduction with NH3 at low temperatures. Applied Catalysis A-General, 327(2): 261–269
https://doi.org/10.1016/j.apcata.2007.05.024
18 Y J Kim, H J Kwon, I Heo, I S Nam, B K Cho, J W Choung, M S Cha, G K Yeo (2012). Mn–Fe/ZSM5 as a low-temperature SCR catalyst to remove NOx from diesel engine exhaust. Applied Catalysis B: Environmental, 126: 9–21
https://doi.org/10.1016/j.apcatb.2012.06.010
19 D Klvana, J Kirchnerová, C Tofan (1999). Catalytic decomposition of nitric oxide by perovskites. Korean Journal of Chemical Engineering, 16(4): 470–477
https://doi.org/10.1007/BF02698270
20 T Liese, E Loffler, W Grunert (2001). Selective catalytic reduction of NO by methane over CeO2–zeolite catalysts-active sites and reaction steps. Journal of Catalysis, 197(1): 123–130
https://doi.org/10.1006/jcat.2000.3074
21 H J Mick, M Burmeister, P Roth (1993). Atomic resonance absorption spectroscopy measurements on high-temperature CO dissociation kinetics. AIAA Journal, 31(4): 671–676
https://doi.org/10.2514/3.11602
22 H Miessner, K P Francke, R Rudolph (2002). Plasma-enhanced HC-SCR of NOx in the presence of excess oxygen. Applied Catalysis B: Environmental, 36(1): 53–62
https://doi.org/10.1016/S0926-3373(01)00280-6
23 C A Mitchell, J L Bahr, S Arepalli, J M Tour, R Krishnamoorti (2002). Dispersion of functionalized carbon nanotubes in polystyrene. Macromolecules, 35(23): 8825–8830
https://doi.org/10.1021/ma020890y
24 Y Nie, J Wang, K Zhong, L Wang, Z Guan (2007). Synergy study for plasma-facilitated C2H4 selective catalytic reduction of NOx over Ag/g-Al2O3 catalyst. IEEE Transactions on Plasma Science, 35(3): 663–669
https://doi.org/10.1109/TPS.2007.896764
25 J Niu, X Yang, A Zhu, L Shi, S Qi, Y Xu (2006). Plasma-assisted selective catalytic reduction of NOx by C2H2 over Co-HZSM-5 catalyst. Catalysis Communications, 7(5): 297–301
https://doi.org/10.1016/j.catcom.2005.10.016
26 H Pan, Y Guo, Y Jian, C He (2015). Synergistic effect of non-thermal plasma on NOx reduction by CH4 over an In/H-BEA catalyst at low temperatures. Energy & Fuels, 29(8): 5282–5289
https://doi.org/10.1021/acs.energyfuels.5b00864
27 M Salazar, R Becker, W Grünert (2015). Hybrid catalysts-an innovative route to improve catalyst performance in the selective catalytic reduction of NO by NH3. Applied Catalysis B: Environmental, 165: 316–327
https://doi.org/10.1016/j.apcatb.2014.10.018
28 M Salazar, S Hoffmann, V Singer, R Becker, W Grünert (2016a). Hybrid catalysts for the selective catalytic reduction (SCR) of NO by NH3. On the role of fast SCR in the reaction network. Applied Catalysis B: Environmental, 199: 433–438
https://doi.org/10.1016/j.apcatb.2016.06.043
29 M Salazar, S Hoffmann, L Tillmann, V Singer, R Becker, W Gr�nert (2017). Hybrid catalysts for the selective catalytic reduction (SCR) of NO by NH3: Precipitates and physical mixtures. Applied Catalysis B: Environmental, 218: 793–802
https://doi.org/10.1016/j.apcatb.2017.06.079
30 M Salazar, S Hoffmann, O P Tkachenko, R Becker, W Grünert (2016b). Hybrid catalysts for the selective catalytic reduction of NO by NH3: The influence of component separation on the performance of hybrid systems. Applied Catalysis B: Environmental, 182: 213–219
https://doi.org/10.1016/j.apcatb.2015.09.028
31 K Shimizu, A Satsuma (2006). Selective catalytic reduction of NO over supported silver catalysts--practical and mechanistic aspects. Physical Chemistry Chemical Physics, 8(23): 2677–2695
https://doi.org/10.1039/B601794K pmid: 16763698
32 K Shimizu, T Sugiyama, L S M Nishamani, M Kanamori (2009). Application of microplasma for NOx removal. IEEE Transactions on Industry Applications, 45(4): 1506–1512
https://doi.org/10.1109/TIA.2009.2023494
33 Y Show, N Fukuzumi (2007). Selective growth of CNT by using triode-type radio frequency plasma chemical vapor deposition method. Diamond and Related Materials, 16(4–7): 1106–1109
https://doi.org/10.1016/j.diamond.2006.11.066
34 H Siaka, C Dujardin, A Moissette, P Granger (2018). Structural induced effect of potassium on the reactivity of vanadate species in V2O5–WO3/TiO2 SCR-catalyst. Topics in Catalysis, 62(9): 56–62
35 S R Sivakkumar, J M Ko, D Y Kim, B C Kim, G G Wallace (2007). Performance evaluation of CNT/polypyrrole/MnO2 composite electrodes for electrochemical capacitors. Electrochimica Acta, 52(25): 7377–7385
https://doi.org/10.1016/j.electacta.2007.06.023
36 C E Stere, W Adress, R Burch, S Chansai, A Goguet, W G Graham, F D Rosa, V Palma, C Hardacre (2014). Ambient temperature hydrocarbon selective catalytic reduction of NOx using atmospheric pressure nonthermal plasma activation of a Ag/Al2O3 catalyst. American Chemical Society Catalysis, 4(2): 666–673
https://doi.org/10.1021/cs4009286
37 C E Stere, W R Adress, R Burch, S Chansai, A Goguet, W G Graham, C Hardacre (2015). Probing a non-thermal plasma activated heterogeneously catalyzed reaction using in situ DRIFTS-MS. ACS Catalysis, 5(2): 956–964
https://doi.org/10.1021/cs5019265
38 Q Sun, A Zhu, X Yang, J Niu, Y Xu (2003). Formation of NOx from N2 and O2 in catalyst-pellet filled dielectric barrier discharges at atmospheric pressure. Chemical Communications (Cambridge, England), 12(12): 1418–1419
https://doi.org/10.1039/b303046f pmid: 12841270
39 W Tian, H Yang, X Fan, X Zhang (2011). Catalytic reduction of NOx with NH3 over different-shaped MnO2 at low temperature. Journal of Hazardous Materials, 188(1–3): 105–109
https://doi.org/10.1016/j.jhazmat.2011.01.078 pmid: 21333446
40 S K Vashist, D Zheng, K Al-Rubeaan, J H Luong, F S Sheu (2011). Advances in carbon nanotube based electrochemical sensors for bioanalytical applications. Biotechnology Advances, 29(2): 169–188
https://doi.org/10.1016/j.biotechadv.2010.10.002 pmid: 21034805
41 V Vestreng, L Ntziachristos, A Semb, S Reis, I S A Isaksen, L Tarrason (2008). Evolution of NOx emissions in Europe with focus on road transport control measures. Atmospheric Chemistry and Physics, 8(3): 1503–1520
42 H Wang, X Li, P Chen, M Chen, X Zheng (2013). An enhanced plasma-catalytic method for DeNOx in simulated flue gas at room temperature. Chemical Communications (Cambridge, England), 49(81): 9353–9355
https://doi.org/10.1039/c3cc44217a pmid: 24003442
43 J Wang, Y Cai, J Wang, L Zhang, X Li (2011). Research on the effect of C3H6 on NO conversion rate in a NTP reactor. In: International Conference on Optoelectronics & Image Processing. Warsaw: IEEE
https://doi.org/10.1109/ICOIP.2010.216
44 P Wang, S Su, J Xiang, H You, F Cao, L Sun, S Hu, Y Zhang (2014). Catalytic oxidation of Hg0 by MnOx-CeO2/g-Al2O3 catalyst at low temperatures. Chemosphere, 101: 49–54
https://doi.org/10.1016/j.chemosphere.2013.11.034 pmid: 24332734
45 Y Wang, F Yu, M Zhu, C Ma, D Zhao, C Wang (2017). N-doping of plasma exfoliated graphene oxide via dielectric barrier discharge plasma treatment for oxygen reduction reaction. Journal of Materials Chemistry A, 6(5): 2011–2017
https://doi.org/10.1039.C7TA08607E
46 S Yang, F Qi, S Xiong, H Dang, Y Liao, P K Wong, J Li (2016). MnOx supported on Fe–Ti spinel: A novel Mn based low temperature SCR catalyst with a high N2 selectivity. Applied Catalysis B: Environmental, 181: 570–580
https://doi.org/10.1016/j.apcatb.2015.08.023
47 S A Yashnik, Z R Ismagilov (2019). Control of the NO–NH3 SCR behavior of Cu-ZSM-5 by variation of the electronic state of copper. Topics in Catalysis, 62(1–4): 179–191
https://doi.org/10.1007/s11244-018-1101-4
48 L Zhao, C Li, Y Wang, H Wu, L Gao, J Zhang, G Zeng (2016). Simultaneous removal of elemental mercury and NO from simulated flue gas using a CeO2 modified V2O5–WO3/TiO2 catalyst. Catalysis Science & Technology, 6(15): 6076–6086
https://doi.org/10.1039/C5CY01576F
49 W Zhao, Y Liu, H Wei, R Zhang, G Luo, H Hou, S Chen, R Zhang (2019). NO removal by plasma-enhanced NH3-SCR using methane as an assistant reduction agent at low temperature. Applied Sciences (Basel, Switzerland), 9(13): 2751
https://doi.org/10.3390/app9132751
50 W Zhao, F Wang, Y Liu, R Zhang, H Hou (2018). Effects of electrode structure and electron energy on abatement of NO in dielectric barrier discharge reactor. Applied Sciences (Basel, Switzerland), 8(4): 618
https://doi.org/10.3390/app8040618
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed