epscor/rii irg 3: nanotechnology based...

EPSCRoRESEARCH IN PUERTO RICO


Ins$tuteforFunc$onalNanomaterialsUniversityofPuertoRico h9p://www.ifn.upr.edu

EPSCoR/RII IRG 3: Nanotechnology Based Remediation

IRG 3 Leader: Dr. Arturo Hernandez [email protected]

Research Focus: IRG3 3 aims at addressing key challenges in the area of chemical and environmental remediation by combining expertise in synthesis and characterization of nanoporous materials, adsorption, catalysis, bio-electrochemistry, environmental chemistry, and computational chemistry. The group aims at developing solutions to address: (1) deep removal of CO2 from light gas mixtures, storage and conversion, (2) removal of contaminants of emerging concern (CECs) from water sources, and (3) recovery of water from human waste and subsequent production of energy in closed-volume applications.

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NASA Ames: Michael Flynn, John Hogan, Darrell Jan NASA Marshall: D. Layne Carter

Riqiang Fu

Benito Mariñas

Bryan Coughlin, Jim Watkins

Raphael G. Raptis

Randall Q. Snurr

Stra

tegi

c Pa

rtne

rs

Nelson Cardona, María Curet-Arana, Arturo Hernández-Maldonado, María Martínez-Iñesta, Yomaira Pagán-Torres, Oscar Perales, Sangchul Hwang

Harry Rivera

Cor

e G

roup

Carlos Cabrera, Rafael Rios, Zhongfang Chen

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2015-16 Postdoctoral Fellows (7)

Supported by this RII grant: •  Dr. Fajim Hossain (Water Remed) •  Dr. José Primera Pedrozo (Test Bed) •  Dr. Xiaoxuan Wei (Computational)

Supported by other grants: •  Dr. Yarylin Cedeño •  Dr. Eduardo Nicolau •  Dr. Chen Huanhao •  Dr. Moxin Yu

2015-16 PhD and Graduate Research Fellows (27)

Supported by this RII grant: •  Lisandro Cunci •  Liliana Gamez •  Yaritza Hernandez •  Isomar Latorre Supported by other grants: •  Raúl Acevedo •  Rebeca Caban •  Wilman Cabrera •  José Fonseca •  Karen Gonzalez •  Yaritza Hernández •  Jose Lopez •  Tatiana Luna •  Roberto Martínez •  Paul Meza •  Brian Montejo

•  Abdiel Oquendo •  Krisiam Ortiz-Martinez •  Oscar Oyola •  Melina Perez •  Carlos Poventud •  Angelica Quinones •  Myrna Reyes •  Ana Lucia Vega •  Angel Vega-Negron

•  Marietta Marcano •  Karina Riascos-Rodriguez •  Yohaselly Santiago

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IRG3 Research Activities Portfolio

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CO2 Storage and Delivery: Structural Expansion and Contraction of Nanoporous Coordination Polymers UPRM: K. Riascos, O. M. Garcia, J. Primera, and A. Hernández-Maldonado NASA: J. Hogan, D. Jan; NHMFL: R. Fu; U. Wisconsin: Paul Evans

Dissemination Products: •  Hernández-Maldonado, A.J.; Arrieta-Pérez, R.R.; Primera-Pedrozo, J.N.; Exley, J. Cryst. Growth Des. 2015, 15(8), 4123-4131. • Riascos-Rodríguez, K.; Schroeder, A.J.; Arend, M.R.; Evans, P; Hernández-Maldonado, A.J.. Dalton Trans. 2014, 43(28), 10877-10884. • García-Ricard, O.J.; Meza-Morales, P.; Silva-Martinez, J.C.; Curet-Arana, M.C.; Hogan, J.; Hernández-Maldonado, A.J.. Micropor. Mesopor. Mat. 2013, 177, 54-58.

CPL-n (Cu2(pzdc)2(L)) [pzdc = 2,3-pyrazinedicarboxylate, L = linear pillar ligand] coordination polymers or metal organic frameworks (MOFs) were employed for CO2 storage and delivery at low to moderate pressures. Main Conclusion: CPL-n exhibit CO2 adsorption/delivery capacities better than MOF ZIF-8 due superior diffusion kinetics and concomitant structural expansion/contraction.

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Systematic DFT calculations and Grand Canonical Monte Carlo simulations were used to analyze CPL-n materials and their interaction with CO2.

Main conclusions: (1) Strongest interaction with CO2.occurs in the vicinity of the Cu node and (2) when superimposed, adsorption equilibrium loadings calculated for different degrees of rotation of the organic ligand corroborate that the CPL-2 structure goes through local transformations during the adsorption of CO2.

CO2 Storage and Delivery: DFT Studies and Atomistic Simulations for CO2 Adsorption onto CPL-n Coordination Polymers and UPRM: P. Meza, M.C. Curet-Arana; NWU: R. Snurr

Dissemination Products: • Meza-Morales, P.; Santana-Vargas, Alberto; Curet-Arana, M.C. “Systematic DFT Study on the Properties of Porous Coordination Ligand Networks and Their Interaction with CO2”, Adsorption, 2015, DOI: 10.1007/s10450-015-9692-6 • García-Ricard, O.J.; Meza-Morales, P.; Silva-Martínez J.C.; Maria C. Curet-Arana, Hogan, J.A.; and Hernández-Maldonado A.J. Micropor. Mesopor. Mat., 2013, 177, 54-58.

Interaction Energies CO2 with CPL-2

IE < -20 kJ/mol -20 kJ/mol ≤IE ≤-10 kJ/mol IE > -10 kJ/mol

Amou

nt A

dsor

bed

[mm

ol/g

]

Pressure [atm]

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The production of methanol and dimethyl ether (DME) via CO2 hydrogenation was studied using Pd catalysts supported on α-Ga2O3, α-β-Ga2O3 and β-Ga2O3 polymorphs. The formation of a Pd2Ga intermetallic compound was observed using XRD and XPS. The catalytic activity improves with an increase in the content of the Pd2Ga intermetallic compound. The content of Pd2Ga on Pd/Ga2O3 depends on the Ga2O3 crystalline phase of the catalyst. A slight catalytic deactivation was observed for all samples studied. The Pd/α-β-Ga2O3 catalyst displayed the largest deactivation. The deactivation appears to be caused by a loss of basic sites. The selectivity to dimethyl ether is not dependent on the Pd2Ga content, but depends on the catalyst acidity. This assertion was tested by adding niobia to the catalysts, thus increasing the DME selectivity from 0 to 53 %. The content of Pd2Ga over Pd/Ga2O3 catalysts was identified to be a crucial parameter for CO2 hydrogenation to methanol.

CO2 Conversion: Hydrogenation to Methanol and Dimethyl Ether by Pd-Pd2Ga Catalysts Supported over Ga2O3 Polymorphs UPRM: O. Oyola, N. Cardona-Martínez UNL & CONICET (Argentina): M. Baltanás

Dissemination Products: •  O. Oyola-Rivera, M.A. Baltanás, N. Cardona-Martínez, CO2 hydrogenation to Methanol and Dimethyl Ether by Pd-Pd2Ga catalysts supported over Ga2O3 polymorphs, Journal of CO2 Utilization, 2015, 9, 8-15.

Sample CO2 Conversion

TOF (s-1)

DME Selectivity

3.8%Pd/α-Ga2O3 14 0.27 22

3.5%Pd/α-β-Ga2O3 12 0.23 12

2.6%Pd/β-Ga2O3 12 8.80 13

3.2%Pd/LS-Ga2O3 12 1.10 4

6 0.90 0

4.7%Pd-Nb2O5 on LS-Ga2O3

5 1.50 53

Equilibrium conversion = 20%

CO2 + 3H2 ⇄⇄ CH3OH + H2O 2CH3OH ⇄⇄ CH3OCH3 + H2O

Ga2O3

Pd2GaPd

Effect of time on stream on methanol and DME selectivity for Pd-Nb2O5/LS-Ga2O3

T = 543 K P = 1.72 MPa WHSV = 27 h-1

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The main goal of this project is to obtain a fundamental understanding of the catalytic systems that can convert CO2 back to other organic compounds.

CO2 Conversion: Quantum Mechanical Analysis of Reaction Pathways on the Catalyzed Conversion of CO2 UPRM: Y. Santiago, M.C. Curet-Arana

Dissemination Products: •  Santiago, Y.; Curet-Arana, M.C., React. Kinet. Mech. Catal., 2015, DOI: 10.1007/s11144-015-0904-6 •  Y. Santiago-Rodríguez, et al. “Atomic and Molecular Adsorption on Au(111)", Surface Science, 2014, 627, 57-69. •  Santiago-Rodríguez, Yohaselly; Curet-Arana, Maria C., “Quantum Mechanical study of CO2 and CO Hydrogenation on Metal-Doped Cu(111) Surfaces”, 249th ACS National Meeting and Exposition, Denver, CO, March, 2015

(1)

(2)

n

L

+ + CO2

L

L

L+ C2H4

H2 + CO2

CH3OH + H2O

HCOOH

CH3OCH3 + H2O

CH2O HCOOH CH3OH CH3O2 CH2O2

•  Challenges: CO2 is a highly stable molecule, and its efficient and selective conversion still remains a challenge.

•  Main Conclusions: The axial ligand of the salen complexes impacts the electronic properties of the catalyst, and the reaction energies for the formation of CO2-epoxide-metal(salen) complexes.

Preliminary results of key intermediates adsorbed onto Cu-Ga surface suggest that Cu-Ga might outperform Cu catalyst for CO/CO2 hydrogenation.

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Rising concerns of carbon dioxide emissions to the atmosphere have led researchers to study the direct reduction of CO2 to methanol, a fuel and chemical feedstock. Methanol is industrially produced over CuZnO/Al2O3 catalyst using a mixture of CO/H2/CO2 at high pressures (e.g., 50-100 bar). Here the development of a catalytic process for the direct reduction of CO2 at atmospheric pressure to chemicals and fuels is envisioned.

• Challenges: Development of an active and selective heterogeneous catalyst for the conversion of CO2 to methanol and ethers at low pressures.

• Path to innovation: Studies have demonstrated supported bimetallic particles are promising catalysts for the selective conversion of CO2 to methanol at atmospheric pressure. However, catalysts synthesis strategies employed lack control over the composition and size of the nanostructured atomic ensembles formed, factors which ultimately control catalyst activity and selectivity. The Pagán-Torres research group is working on the development of controlled synthesis methods to produce supported bimetallic nanostructured particles with finite composition and size, for the conversion of CO2 to methanol. Furthermore, functionalization of synthesized catalysts with metal oxide overcoats containing acidic moieties will enable the cascading production of ethers from CO2.

IRG 3 Start-up: Atomically Controlled Design and Synthesis of Nanostructured Catalysts for the Conversion of CO2 to Chemicals and Fuels UPRM: Yomaira J. Pagán-Torres; Sandra Albarracín Suazo; Wella Vidal Urquiza

Innovative Catalyst Synthesis Approach

*SEA: Strong electrostatic adsorption; ALD: Atomic Layer Deposition

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Path to Innovation: •  Combined experimental and theoretical effort for the design of

metal exchanged zeolites for the activation of CO2 and CH4.

Exploratory Research Work: CO2 and CH4 Conversion in Zn-Modified FAU UPRM: Curet-Arana, Pagán-Torres, Martínez-Iñesta, Sandra Albarracín (GS), Karen Weintraub (UG), Lorelis González (UG)

CO2

CH4

Adsorbed CH4 (kJ/mol)

CH3_Zn / O-H Intermediate (kJ/mol)

Aluminum Configuration 1 -38.73 69.75

Aluminum Configuration 2 -141.02 -80.42

Si

Zn

Al 1 2 3 4 5 6 7 8

Al-configurations in the six-membered ring of FAU

Adsorbed CH4 CH3_Zn/ OH Intermediate

Overview: Design of catalytic materials for the activation of green house gases, CO2 and CH4, for acetic acid production.

Results: •  Computational studies demonstrate Zn2+ in FAU facilitate C-H bond cleavage of CH4 via electrostatic and

electron transfer interactions and that the location of aluminum atoms affects reaction energies for CH4 activation. These data is necessary to understand the reaction of CO2 with adsorbed CH4.

•  Experimentally, zeolites mordenite (MOR), X (FAU) and ZSM-5 (MFI) were ion exchanged with Zn2+ with an exchange efficiency of 60%, 66%, and 28%, respectively.




IRG3 Research Activities Portfolio

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Removal of Contaminants of Emerging Concern (CECs): Hierarchical Nanoporous Carbon-Zeolite Adsorbents UPRM: K. Gonzalez, F. Román, and A. Hernández-Maldonado

Dissemination Products: • González-Ramos, K.M.; Fernández-Reyes, B; Román, F.R.; Hernández-Maldonado, A.J. Microporous Mesoporous Mat. 2014, 200, 225-234. • Ortiz-Martínez, K.; Guerrero-Medina, K.J.; Román, F.R.; Hernández-Maldonado, A.J. Chem. Eng. J. 2015, 264, 152-164

A hierarchical porous carbon - Mn+[FAU] or Mn+-CFAU (Mn+ = Ni2+ or Cu2+; FAU = Y Zeolite) was prepared to develop a platform for the removal of CECs from water. The impetus for this is the possibility of combining the hydrophobic nature of carbons with the unique adsorbent-adsorbate interactions provided by a zeolite.

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Removal of Problematic Compounds During Water Reclamation in Space Missions UPRRP: X. Wei, Z. Chen; UPRM: A. Hernández-Maldonado Computational/theoretical studies are being performed to discover porous materials capable of selectively adsorbing siloxane compounds that persist during water reclamation in the International Space Station (ISS). Compounds include dimethylsilanediol (DMSD), trimethylsilanol (TMS), and dimethylsulfone (DMSO2)

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Potential Adsorbent Frameworks

Adsorbents Isolated from Interactions with Water

Interactions with Solvent Included




Water Treatment: Urea/Ammonia Oxidation UPRRP: C. Cabrera, E. Nicolau NASA: M. Flynn

•  Microgravity Studies of Ammonia Oxidation- Raúl Acevedo ü  Platinum Micropillars Electrodes, experiments performed in microgravity at

NASA JSC “Mitigation of Buoyancy Effects by Employing Pt Micropillared Array Electrodes”

ü  Direct Ammonia Alkaline Fuel Cell, experiments performed in microgravity at NASA JSC “On the performance of a nanocatalyst-based direct ammonia alkaline fuel cell (DAAFC) under microgravity conditions for water reclamation and energy applications”

•  Pt Nanocubes Synthesis- Roberto Martínez Electrochemical study of the effect of adsorbates and precursors in the synthesis

of well-defined platinum nanoparticles with Pt(100) facets using water-in-oil microemulsion and determination of the ammonia oxidation in alkaline media

0.0 0.2 0.4 0.6 0.8

0.0

0.5

1.0

1.5

2.0

2.5

j, m

Acm

-2

E, V vs RHE

•  Enhanced Pt(100) Surfaces at Boron Doped Diamond Electrodes- Yaritza Hernández

Electrochemical deposition of platinum particles by cyclic voltammetry (a) and chronoamperometry (b) techniques on Boron-doped Diamond (BDD) films and the effect on ammonia oxidation in alkaline media.

•  Robust Microbial Ureolysis System- Myreisa Morales Biofuel cell for water reclamation using Proteus vulgaris for the catalysis of urea to ammonia and platinum nanoparticles for the oxidation of ammonia.

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IRG 3 Start-up: In-situ study of direct ammonia alkaline fuel cells (DAAFCs) for water remediation applications PI: H. Rivera, Inter American Univ., Bayamón Long-term goal Is to fabricate high quality membrane electrode assemb l y (MEAs ) t o enhance ammon ia decomposition for water remediation applications.

2014 Specific Aims 1.  Synthesis and characterization Pd-based

catalyst. 2.  Ammonia fuel cell evaluation of Pt/C and Pd-

based catalyst. 3.  Patent evaluation for Catalyst layer applier (2nd

generation).

Accomplishments • Jiang, Z. Z.; Wang, Z. B.; Rivera, H.; Qu, W. L.; Gu, D. M., Effects of Carbonization Temperature and Time during Carbon Riveting Process on the Stability of Pt/C Catalyst. Fuel Cells 2014, 14 (4), 660-666. • Rodríguez-Rodríguez, W. A.; Colón, J.; Guzmán, R.; Rivera, H.; Santiago-Berríos, M. E. B., Synthesis, characterization and electrochemical characterization of lead selenide sub-micron particles capped with a benzoate ligand and prepared at different temperatures. Materials Research Express 2014, 1 (3), 035906. • E. Nicolau, H. Rivera, C.R. Cabrera, PR NASA EPSCoR: Enabling technologies for water reclamation in future long-term space missions: wastewater resource recovery for energy generation, 3 years, October 2014, Approved, $750,000. TEM image and the size distribution of synthetized Pt/C

Cyclic voltammograms of synthetized Pt/C.

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““Occurrence, Fate and Removal of Pharmaceutical and Personal Care Products and Endocrine Disrupting Chemicals”” Symposia – 2011, 2013, 2014 and 2016 American Chemical Society (ACS) National Meetings

IFN Leadership Beyond the Jurisdiction

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IRG3TestbedandCommercializa$on:CO2RemovalHighlights:

• Adsorbents Nanoporous strontium-silicoaluminophosphate and flexible titanium silicates (UPRM-5) adsorbents development started under the IFN and continued with support from NASA and NSF. US Patent Application 12/334,768 and US Patent 8,440,166 (2013). • Best CO2 selectivity and capacity in the ppm and sub-ppm range. Adsorption is completely reversible at room temperature. • Preliminary tests performed @ NASA Ames • NASA SBIR P1 Grant - TDA Research – performance tests to develop a temperature swing desorption unit for CO2 capture and utilization during Mars exploration missions. • New partner: SINTEF Norway - Dr. Carlos A. Grande - tests for natural gas cleanup with UPRM-5 are underway. • Potential for commercialization:

–  Design of next generation aircraft cabin atmospheric control systems

–  Atmospheric control in submersible watercrafts –  Portable applications: suits with life support systems –  Other

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Testbed: Gas Separations and Storage for Portable Applications

Status •  January - May 2015: unit

construction (in house) •  May - July 2015: Systems

integration and validation completed

•  Fall 2015 – Winter 2016: Preliminary data shared with NASA and SINTEF for feedback.

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Feedback from NSF RSV and IFN EAB

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RSV Evaluation Highlights: •  The project’s IRG3 annual report and RSV presentation revealed great strength

in progress towards maturation of efforts. •  IRG seems to be a well-integrated and well managed effort, having made great

progress towards sustainability, with no significant weaknesses noted. EAB Evaluation Highlights: •  The IRG team made great use of computational methods to establish a link

between experiment and theory •  Technology transfer efforts through specific collaborations are stand outs within

the IRG. •  Although IRG3 has shown significant progress within the research areas of CO2

conversion and water remediation, these appear to be broad.




Peer-Reviewed Publications (2014-2015) • Acknowledge the IFN Explicitly : 18 • Related to the IRG: 15 Peer-Reviewed Proceedings (2014-2015) • Acknowledge the IFN Explicitly : 1 • Related to the IRG: 6 Patent Apps (2014-2015): 2 Grants Related to IRG3 Efforts (2014-2015): • A total of 13 research grants • Highlights: 2 NSF Unsolicited Grants;1 NSF CREST P2- $5MM/5 yrs; 2 NASA EPS Grants; 1 NASA SBIR Innovation and Commercialization (up to date) • TDA Research Inc. (Colorado, US) is developing technology based on CO2 selective adsorbents developed as part of the IRG activities. This initiative is a collaboration with UPRM that began under a NASA SBIR grant. A NASA STTR proposal was recently submitted. • The device will be capable of capturing CO2 from Mars atmosphere (Total pressure: 10-2 atm) and deliver it at pressures near the 1 atm mark via temperature swing desorption. • Output will be suitable for conversion to O2 in a Sabatier reactor and/or use in “pneumatic-like” processes.

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Milestones



Milestone Action Status

Postdoctoral fellows and graduate students are hired to strengthen the IRG3 development.

One (1) PDF hired to work on the CO2 testbed components. One (1) PDF hired to work on computational theory for water remediation materials. Five (5) new grad students were hired

Completed

Gaps in expertise within the IRG are identified

Two faculty joined the IRG 3. A junior faculty with expertise in preparation of catalysts via ALD and a faculty with expertise in computational chemistry.

Completed

Integrated experimental and computational approach to develop sorbents for the removal of emerging organic/inorganic contaminants and toxic metals from potable, ground and waste water sources.

One faculty with expertise in computational chemistry has joined IRG 3. One (1) PDF hired to work on computational theory for water remediation materials.

Completed

Seed funds provided for exploratory research to develop interdisciplinary collaborations in the following areas: detection, fate, and remediation of emerging water contaminants.

Yes. Proposals collaborative and individual were submitted. Expanded to include advanced CO2 conversion strategies.

In progress; projects began in Summer 2015




Milestones




External funding is obtained for research related to water remediation

Proposals collaborative and individual have been submitted

In progress. NSF CREST Phase 2 award ($5MM/5 yrs)

External funding is obtained for research related to removal of CO2 and other contaminants in high pressure gas applications

Proposals collaborative and individual have been submitted

In progress. NASA SBIR P1 award was obtained. NSF CREST Phase 2 award ($5MM/5 yrs)

External funding is obtained for research related to the development of CO2 conversion catalysts.

One collaborative proposal was submitted to the NSF PIRE program

In progress

Preliminary performance tests for organics removal are performed at University of Colorado-Boulder (UCB), University of Illinois at Urbana-Champaign (UIUC), and University of California at Santa Barbara (UCSB)

These tests could not be made since some of the PDFs could not be hired. See response to other questions related to the other milestones. Once the PDFs are hired, the IRG3 will give priority to the corresponding research tasks to ensure that this milestone is addressed.

In progress

GCMC tests for prediction of equilibrium adsorption data w. Northwestern University

Yes. Summers 2014 and 2015 Publications were made and new ones are being prepared.




Milestones




IFN increases the number of invention disclosures resulting from the research and testbed activities.

Only disclosures related to research. Testbeds were not operational at the moment

In progress; SINTEF and TDA tested adsorbents. This is a major step in commercialization of the technology

IFN researchers submit SBIR, STTR, and similar proposals to initiate commercialization process

A NASA SBIR Phase 1 award was obtained; a collaboration with TDA Research Inc

In progress. NASA SBIR P1 award was obtained. NSF CREST Phase 2 award ($5MM/5 yrs)

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