Plasma Catalysis

Maria Carreon
South Dakota School of Mines & Technology
ARPA-E REMEDY Workshop

October 20, 2020

Introduction/Background
Personal Background
‣ Born 3/25/1984 in Morelia, Mexico.
‣ BS Chemical Engineering (2007) at Universidad Michoacana (UMSNH), Mexico.
‣ MS Chemical Engineering (2010) at Universidad Michoacana (UMSNH), Mexico.
‣ PhD Chemical Engineering at University of Louisville 2015.
‣ Assistant Professor at the University of Tulsa, Russell School of Chemical
Engineering, Fall 2015-Spring 2019.
‣ Assistant Professor at SDSMT, Chemical & Biological Engineering Department,
Summer 2019-Present.

1
 Carreon Lab
https://mariacarreong.wixsite.com/carreon
Research interests:
• Rational design of porous materials at different length scales, including Zeolites, Mixed
Metal Oxides, Nanowires, Nanotubes, Thin Films, Graphene and MOFs (Metal Organic
Frameworks).
• Formation mechanisms of these materials to establish fundamental structure/separation,
catalytic and adsorption relationships.
Research Areas: Zeolite Membranes; Rational Design of Heterogeneous Catalysts; CO2
Conversion to Chemicals; Plasma Catalytic reactions.
Materials Design Functional Applications

CO2: 0.33nm CH4: 0.38 nm

500nm 500nm Ammonia

fast
slow

October 22, 2020 Plasma Catalysis 2

 Plasma Definition
‣ Plasma is considered as the fourth state of matter.
‣ Plasma comprise 99.9% of the visible universe.
‣ Typically, plasma is generated by driving an electrical current through gas.
‣ Plasma contains electrons, neutrals, and highly excited atomic, molecular, ionic
and radical species.
‣ Two types of Plasma: Thermal and Non-Thermal (NTP)
‣ In NTP, electrons are usually at very high temperatures because of their smaller
mass, whereas ions and background gas are at room temperature (safe to touch).
 Non-thermal plasma (NTP)
• Non-thermal plasmas exhibit higher selectivity compared to thermal plasmas.
• Non-thermal plasmas are the most commonly used plasmas for technological
applications.
• The electron temperature in NTPs range from 0.01-16 eV. Range extremely
suitable for chemical reactions as the bond dissociation and ionization energies of
atoms and molecules fall in this regime.
• The challenge: to employ successfully targeted excited species in order to form
the desired products. This can be achieved with the help of a catalyst.

Carreon, Maria L. "Plasma catalysis: a brief tutorial." Plasma Research Express 1, no. 4 (2019):
043001.
Non-thermal plasma systems motivation
Plasma reactor/ process offers advantages such as:
(1) simple one step processes,
(2) operated and stopped instantaneously – switch on and off
(3) very fast reactions – resulting in smaller units,
(4) generally non-polluting.

Plasma technology has the potential to provide a convenient route to store

renewable electricity in a flexible way and convert it into chemicals thorough
highly efficient reactions.

https://obamawhitehouse.archives.gov/blog/2015/11/13/investments-renewable-energy-are-paying-
and-paving-way-ambitious-climate-action
What we have learnt from plasma catalytic ammonia synthesis
• Under plasma environment all metals tested outperformed Fe (Haber-Bosch
catalyst).
Binding Energy on Surface (in Bulk)
Tm NH3 Yield Energy Yield Energy Cost
Catalyst (kJ/mol)
(K) (%) (g-NH3/kWh) (MJ/mol)
N H
Ni 1728 34.1 0.41 147 -446 (-376) -266 (-207)
Sn 505 28.8 0.35 174 - -
Aua 1338 19.1 0.22 263 -168 (-42) -193 (-100)
Aga 1235 18.6 0.22 271 -155 (-130) -197 (-153)
Ina 430 17.7 0.22 283 - -
Pda 1828 17.6 0.21 285 -396 (-317) -270 (-215)
Cua 1358 16.7 0.20 301 -296 (-247) -231 (-174)
Gaa 303 11.2 0.14 451 -410 (-389) -172 (-139)
Fea 1811 9.5 0.12 532 -705 (-213) -323 (-82)
aMetals also run in our previous work. (a) Ref 1 J. Shah, W. Wang, A. Bogaerts, Maria L. Carreon*, ACS Appl. Energy

Mater. 2018, 1, 4824-4839; (b) Ref 2 J. Shah, J. Harrison, Maria L. Carreon*, Catalysts 2018, 8, 437.
Data from Haber-Bosch Process
Fec,d 1811 8-15% 500 0.5 -705 (-213) -323 (-82)
cReference: H.-H. Kim, Y. Teramoto, A. Ogata, H. Takagi, T. Nanba, Plasma Chem. Plasma Process. 2016, 36, 45-72. dTo achieve such yields a minimum production
capacity of 100 ton/day is required. The process occurs at high temperature(450-600°C) & High Pressure (150-350 bar). The major limitation in this process is scaling
down & catalyst regeneration (Iron).
 Finding new materials through DFT and experimental results
Subtracted activation energy of desired reaction from the total activation energy of undesired reactions
(Activation energy of H2 recombination + Activation energy of Bulk diffusion) – Activation energy of N-
H formation.

New
material

Old material

Vacuum discharges simultaneously competing parallel reactions:

N-H formation via E-R, H2 formation via E-R and H-bulk diffusion.

Shah Javishk, Gorky, Psarras Peter, Seong Bomsaerah, Gomez-Gualdron Diego, Carreon Maria L.* Ammonia yield enhancement by
hydrogen sink effect during plasma catalysis. ChemCatChem, 2020, 12 (4), 1200-1211.
 Ammonia Sorption Capacity of MOFs in plasma
• Ni-MOF-74 displayed a decrease in ammonia yield as a function
of time.
• Behavior explained by the high ammonia sorption capacity over
Ni based MOFs.
• In our study, as the reaction proceeded, the ammonia molecules
start to fill the MOF pores reducing the ammonia detection in
the exhaust gases.
• The total ammonia loading was found to be 3.14 mmol/g-MOF.
• Microporous molecular sieve crystals composed of inorganic
(SAPO-34), hybrid (ZIF-8, and ZIF-67), and organic (CC3) walls
with uniform crystallographic limiting pore apertures (3.4-3.8 Å
range).
• ZIF-8 and ZIF-67 displayed the best catalytic performance. The
dipole-dipole interactions between the polar ammonia molecule
and the polar walls of ZIF-8 and ZIF-67 led to relatively low
ammonia uptakes and storage capacity, and to the high
observed ammonia synthesis rates.
Shah, Javishk, Wu, Ting, Lucero, Jolie, Carreon, Moises A., Carreon, Maria L.*, Nonthermal Plasma
Synthesis of Ammonia over Ni-MOF-74, ACS Sustainable Chemistry & Engineering, 7(1), 2018, 377-383.
Gorky, Fnu, Lucero, Jolie, Crawford, James, Carreon, Moises A., and Carreon, Maria L.*, Plasma
Assisted Ammonia Synthesis over Microporous Crystalline Molecular Sieves, ACS Catalysis, Under
review.
 Plasma catalysis and other environmental reactions
• The main appeal of plasma-assisted catalysis is the alternative way
to activate the “source gas” by collision with electrons. This can be exploited
to help activate strong bonds(e.g. C-H bond in CH4 and N≡N bond in N2).

• Abatement of volatile organic compounds (VOCs) emitted from various

industries by decomposing VOCs into harmless substances such as CO2 and
H2O has been performed when employing NTP.

• NTP VOCs decomposition benefits: (1) energy efficiency higher than that of
thermal oxidation. (2) operates at atmospheric pressure and room
temperature. (3) can be easily integrated with various packing materials. (4)
It can be quickly switched on/off.

• This can serve as a motivation to explore other catalytic systems such as

methane into CO2!

Khan, Faisal I., and Aloke Kr Ghoshal. "Removal of volatile organic compounds from polluted air." Journal of loss prevention in
the process industries 13, no. 6 (2000): 527-545; C. Dai, Y. Zhou, H. Peng, S. Huang, P. Qin, J. Zhang, Y. Yang, L. Luo, X. Zhang,
Current progress in remediation of chlorinated volatile organic compounds: A review, J. Ind. Eng. Chem. 62 (2018) 106–119.

October 22, 2020 Insert Presentation Name 9

Atmospheric restauration: methane removal
‣ CH4 is the most dominant anthropogenic greenhouse gas (after CO2).
‣ Methane react with nitrogen oxides leading to tropospheric ozone
pollution.
‣ Methane is 84 times more potent than CO2 over the first 20 years after
release and ~28 times more potent after a century.
‣ Methane concentrations could be restored to preindustrial levels by
removing ~3.2 of the 5.3 Gt of CH4 currently in the atmosphere.
‣ Rather than capturing and storing the methane, the CH4 could be
oxidized to CO2, a thermodynamically favorable reaction:
CH4 + 2O2 → CO2 + 2H2O; ΔHr = –803 kJ mol–1.
‣ The large activation barrier associated with splitting methane’s C–H
bond (435 kJ mol–1/4.5 eV) could in principle be overcome by the right
selection of NTP with a proper catalyst for such environment.
‣ Only plasma allows to overcome the activation barrier associated with
the N-N bond (941. 69 kJ/mol-1/9.75 eV).
Jackson, R. B., E. I. Solomon, J. G. Canadell, M. Cargnello, and C. B. Field. "Methane removal and atmospheric
restoration." Nature Sustainability 2, no. 6 (2019): 436-438; https://nvlpubs.nist.gov/nistpubs/Legacy/NSRDS/nbsnsrds31.pdf

October 22, 2020 Insert Presentation Name 10

“The synergistic effect of the right plasma-catalyst pair has been demonstrated
for the synthesis of ammonia. In principle, this remarkable synergy can be
exploited for other societal relevant reactions, including the oxidation of methane
to carbon dioxide.”

October 22, 2020 Insert Presentation Name 11

The challenges to pave the plasma catalysis future

Carreon, Maria L. "Plasma catalysis: a brief tutorial." Plasma Research Express 1, no. 4 (2019): 043001.

October 22, 2020 Insert Presentation Name 12

Acknowledgements
Personnel:
Professor Annemie Bogaerts, University of Antwerp
Professor Diego Gomez-Gualdron, CSM
Professor Moises A. Carreon, CSM

Gorky, Javishk Shah, Anthony Best, Beth Blake, Shelby

Guthrie, Peter Psarras, Bomsaerah Seong, Jolie Lucero

Funding:
South Dakota School of Mines and Technology Start-up
NSF-CBET Award No. 1947303
U.S. Department of Energy (FES Plasma Science Frontier
FOA:DE-FOA-0002260) Award No. DE-SC0021309.
 Questions?

“Plasma processing is born out of the need to access a parameter space in

materials processing unattainable by strictly chemical methods”

Lieberman and Lichtenberg