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Frontiers of Chemical Science and Engineering

Front. Chem. Sci. Eng.    2019, Vol. 13 Issue (3) : 444-457     https://doi.org/10.1007/s11705-019-1811-6
REVIEW ARTICLE
Review of plasma-assisted reactions and potential applications for modification of metal–organic frameworks
Tingting Zhao, Niamat Ullah, Yajun Hui, Zhenhua Li()
Key Lab for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin 300072, China
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Abstract

Plasma catalysis is drawing increasing attention worldwide. Plasma is a partially ionized gas comprising electrons, ions, molecules, radicals, and photons. Integration of catalysis and plasma can enhance catalytic activity and stability. Some thermodynamically unfavorable reactions can easily occur with plasma assistance. Compared to traditional thermal catalysis, plasma reactors can save energy because they can be operated at much lower temperatures or even room temperature. Additionally, the low bulk temperature of cold plasma makes it a good alternative for treatment of temperature-sensitive materials. In this review, we summarize the plasma-assisted reactions involved in dry reforming of methane, CO2 methanation, the methane coupling reaction, and volatile organic compound abatement. Applications of plasma for modification of metal–organic frameworks are discussed.

Keywords plasma catalysis      methane      carbon dioxide      VOCs      metal–organic frameworks     
Corresponding Authors: Zhenhua Li   
Just Accepted Date: 06 May 2019   Online First Date: 26 June 2019    Issue Date: 22 August 2019
 Cite this article:   
Tingting Zhao,Niamat Ullah,Yajun Hui, et al. Review of plasma-assisted reactions and potential applications for modification of metal–organic frameworks[J]. Front. Chem. Sci. Eng., 2019, 13(3): 444-457.
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http://journal.hep.com.cn/fcse/EN/10.1007/s11705-019-1811-6
http://journal.hep.com.cn/fcse/EN/Y2019/V13/I3/444
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Fig.1  Transmission electron microscopy images of carbon produced in the plasma dry reforming process: (a) spherical carbon nanoparticles; (b) carbon nanotubes (CH4/CO2 = 7:3, total flow rate: 51 min1, input power: 165 W). Reprinted from ref. [38], copyright (2014), with permission from Elsevier
Fig.2  Schematic representation of dry CH4 reforming on or near the surface of an Al2O3-supported metal catalyst in the presence of plasma: (a) excitation of CH4 species by gas-phase electron impact, (b) transition-metal catalyst supported on dielectric support (e.g., Al2O3) within plasma discharge zone, and (c) chemical equation of dry CH4 reforming. Reprinted from ref. [59], copyright (2016), with permission from American Chemical Society
Temperature /°C DHf° /(kJ·mol?1) DG° /(kJ·mol?1) logKp
27 ?165.101 ?113.290 19.724
127 ?170.080 ?95.265 12.440
227 ?174.803 ?76.015 7.940
327 ?179.042 ?55.844 4.86
427 ?182.757 ?35.003 2.61
527 ?185.975 ?13.677 0.893
627 ?188.720 +8.037 ?0.466
727 ?191.012 +30.012 ?1.568
Tab.1  Thermodynamic properties of CO2 methanation reaction
Fig.3  Experimental setup for plasma-catalytic methanation of CO2. Reprinted from ref. [93], copyright (2016), with permission from Elsevier
Fig.4  Components of a switching-TPE lambda probe and bidirectional ion transport through the ceramic (yttria-stabilized zirconia) ion conductor. Reprinted from ref. [104], copyright (2017), with permission from Elsevier
Material Molar ratio /%
AC
DBD
Pulsed
DBD
Pulsed
Spark
AC
Spark
Hollow
Cathode
Gliding
Arc
Rotating
Arc
H2 0.520 0.210 1.373 2.920 0.850 1.83 1.310
C2H6 0.106 0.065 0.026 0.000 0.014 ? 0.002
C2H4 0.007 0.003 0.031 0.024 0.015 ? 0.011
C3H8 0.018 0.009 0.002 0.000 0.000 ? 0.000
C3H6 0.002 0.000 0.005 0.000 0.003 ? 0.000
C2H2 0.008 0.003 0.459 0.860 0.270 0.272 0.420
CH4 conv. /% 14.76 12.375 49.405 82.930 25.772 23.72 42.170
Sel.(H2) /% 36.457 19.312 32.249 42.053 33.173 73.2 34.815
Sel.(C2H2) /% 2.243 1.104 43.124 49.171 42.149 43.52 44.649
Tab.2  Product analysis of methane coupling reaction in different plasma sources. Reprinted from ref. [111], copyright (2013), with permission from Springer
Fig.5  Schematic illustration of methane conversion under plasma over Pd-IL/γ-Al2O3. Reprinted from ref. [112], copyright (2013), with permission from Elsevier
Fig.6  Effect of energy density on CH4 conversion and C2 hydrocarbon yield. Reprinted from ref. [115], copyright (2006), with permission from Nuclear Fusion and Plasma Physics
Fig.7  Energy efficiency of CH4 coupling reaction. Reprinted from ref. [115], copyright (2006), with permission from Nuclear Fusion and Plasma Physics
Fig.8  Reactor configurations: (a) conventional reactor, (b) zeolite-hybrid reactor. Reprinted from ref. [134], copyright (2001), with permission from IEEE
Fig.9  Overview of equipment for toluene oxidation in a gas circulation system. Reprinted from ref. [136], copyright (2011), with permission from IEEE
Fig.10  CO selectivity, CO2 selectivity, and carbon balance of the three-stage system in four different conditions: DBD alone, DBD-BCD, DBD-catalyst, and DBD-BCD-catalyst. The specific input energy of DBD and BCD is fixed at 64 and 128.9 J/L, respectively. Reprinted from ref. [137], copyright (2015), with permission from American Chemical Society
Catalyst Temperature /°C Ref.
ZIF-67 500 148
ZIF-8 550 149
Co-MOF-74 450 150
Ni-MOF-74 300 151
MIL-101 330 152
MOF-5 400 153
Cu-BTC 280 154
UiO-66 500 155
Tab.3  Thermogravimetric analysis of various MOFs
Fig.11  Schematic of particle formation process on MOFs: (a) Blank MOFs; (b) Formation of seed particles (approximately 1 nm in diameter) at low metal loadings (for Pt ≈ 0.5 wt.% metal loading) by APD irradiation; (c) Particle growth up to approximately 2 nm in diameter by further APD irradiation (0.5 wt.% –1.5 wt.%); (d) Formation of nanorods by further APD irradiation (above 2 wt.%). Reprinted from ref. [156], copyright (1996), with permission from Royal Society of Chemistry
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