Name: solvothermal synthesis of mil-96 and uio-66-nh2 on atomic layer deposited metal oxide coatings on fiber mats
Uploaded: 2018-06-13T14:45:00
Description: Watch this Scientific Journal Video about Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats at JoVE.com

The authors thank their collaborators at RTI International, US Army Natick Soldier RD&#38;E Center, and Edgewood Chemical and Biological Center. They also thank their funding source, the Defense Threat Reduction Agency.

1. Atomic Layer Deposition (ALD) of Al2O3 on Fiber Mats
<ol>
	<li>Place a 2.54 x 2.54 cm2 polypropylene fabric sample in the reactor boat (a thin, rigid, metal mesh holder). A schematic of the reactor is presented in Figure 2.</li>
	<li>Open the pressure gauge. Remove the clasp from the reactor cap. Turn on manual control in the LabView system. Close the carrier nitrogen and gate valve on the ALD reactor. Open the vent nitrogen.</li>
	<li>After removing the...

<ol>
	<li>Furukawa, H., Cordova, K. E., O'Keeffe, M., Yaghi, O. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Chemistry+and+Applications+of+Metal-Organic+Frameworks.">The Chemistry and Applications of Metal-Organic Frameworks.</a> Science (Washington, DC, U. S.). 341 (6149), 974 (2013).</li><li>Farha, O. K., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal-Organic+Framework+Materials+with+Ultrahigh+Surface+Areas:+Is+the+Sky+the+Limit?.">Metal-Organic Framework Materials with Ultrahigh Surface Areas: Is the Sky the Limit?.</a> Journal of the American Chemical Society. 134 (36), 15016-15021 (2012).</li><li>Bobbitt, N. 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Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Effective,+Facile,+and+Selective+Hydrolysis+of+the+Chemical+Warfare+Agent+VX+Using+Zr6-Based+Metal-Organic+Frameworks.">Effective, Facile, and Selective Hydrolysis of the Chemical Warfare Agent VX Using Zr6-Based Metal-Organic Frameworks.</a> Inorganic Chemistry. 54 (22), 10829-10833 (2015).</li><li>Zhou, H., Kitagawa, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal-Organic+Frameworks+(MOFs).">Metal-Organic Frameworks (MOFs).</a> Chemical Society Reviews. 43 (16), 5415-5418 (2014).</li><li>Qiu, M., Chen, C., Li, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rapid+controllable+synthesis+of+Al-MIL-96+and+its+adsorption+of+nitrogenous+VOCs.">Rapid controllable synthesis of Al-MIL-96 and its adsorption of nitrogenous VOCs.</a> Catalysis Today. 258, 132-138 (2015).</li><li>Abid, H. R., Rada, Z. H., Shang, J., Wang, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis,+characterization,+and+CO2+adsorption+of+three+metal-organic+frameworks+(MOFs):+MIL-53,+MIL-96,+and+amino-MIL-53.">Synthesis, characterization, and CO2 adsorption of three metal-organic frameworks (MOFs): MIL-53, MIL-96, and amino-MIL-53.</a> Polyhedron. 120, 103-111 (2016).</li><li>Lee, J. S., Jhung, S. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Vapor-phase+adsorption+of+alkylaromatics+on+aluminum-trimesate+MIL-96:+An+unusual+increase+of+adsorption+capacity+with+temperature.">Vapor-phase adsorption of alkylaromatics on aluminum-trimesate MIL-96: An unusual increase of adsorption capacity with temperature.</a> Microporous Mesoporous Materials. 129 (1-2), 274-277 (2010).</li><li>Gil-San-Millan, R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chemical+Warfare+Agents+Detoxification+Properties+of+Zirconium+Metal-Organic+Frameworks+by+Synergistic+Incorporation+of+Nucleophilic+and+Basic+Sites.">Chemical Warfare Agents Detoxification Properties of Zirconium Metal-Organic Frameworks by Synergistic Incorporation of Nucleophilic and Basic Sites.</a> ACS Appl. Material Interfaces. 9 (28), 23967-23973 (2017).</li><li>Peterson, G. W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Tailoring+the+Pore+Size+and+Functionality+of+UiO-Type+Metal-Organic+Frameworks+for+Optimal+Nerve+Agent+Destruction.">Tailoring the Pore Size and Functionality of UiO-Type Metal-Organic Frameworks for Optimal Nerve Agent Destruction.</a> Inorganic Chemistry. 54 (20), 9684-9686 (2015).</li><li>Katz, M. J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Exploiting+parameter+space+in+MOFs:+a+20-fold+enhancement+of+phosphate-ester+hydrolysis+with+UiO-66-NH2.">Exploiting parameter space in MOFs: a 20-fold enhancement of phosphate-ester hydrolysis with UiO-66-NH2.</a> Chemical Science. 6 (4), 2286-2291 (2015).</li><li>Zhao, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Highly+Adsorptive,+MOF-Functionalized+Nonwoven+Fiber+Mats+for+Hazardous+Gas+Capture+Enabled+by+Atomic+Layer+Deposition.">Highly Adsorptive, MOF-Functionalized Nonwoven Fiber Mats for Hazardous Gas Capture Enabled by Atomic Layer Deposition.</a> Advanced Materials Interface. 1 (4), 1400040 (2014).</li><li>Peterson, G. W., Lu, A. X., Epps, T. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Tuning+the+Morphology+and+Activity+of+Electrospun+Polystyrene/+UiO-66-NH2+Metal-Organic+Framework+Composites+to+Enhance+Chemical+Warfare+Agent+Removal.">Tuning the Morphology and Activity of Electrospun Polystyrene/ UiO-66-NH2 Metal-Organic Framework Composites to Enhance Chemical Warfare Agent Removal.</a> ACS Applied Materials &amp; Interfaces. 9 (37), 32248-32254 (2017).</li><li>Lee, D. T., Zhao, J., Peterson, G. W., Parsons, G. N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Catalytic+'+MOF-Cloth+'+Formed+via+Directed+Supramolecular+Assembly+of+UiO-66-NH+2+Crystals+on+Atomic+Layer+Deposition-+Coated+Textiles+for+Rapid+Degradation+of+Chemical+Warfare+Agent+Simulants.">Catalytic ' MOF-Cloth ' Formed via Directed Supramolecular Assembly of UiO-66-NH 2 Crystals on Atomic Layer Deposition- Coated Textiles for Rapid Degradation of Chemical Warfare Agent Simulants.</a> Chemistry of Materials. 29 (11), 4894-4903 (2017).</li><li>L&#243;pez-maya, E., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Textile+/+Metal+-+Organic-Framework+Composites+as+Self-Detoxifying+Filters+for+Chemical-Warfare+Agents.">Textile / Metal - Organic-Framework Composites as Self-Detoxifying Filters for Chemical-Warfare Agents.</a> Angewandte Chemie International Edition. 54 (23), 6790-6794 (2015).</li><li>Zhao, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Conformal+and+highly+adsorptive+metal-organic+framework+thin+films+via+layer-by-layer+growth+on+ALD-coated+fiber+mats.">Conformal and highly adsorptive metal-organic framework thin films via layer-by-layer growth on ALD-coated fiber mats.</a> Journal of Materials Chemistry. A. 3 (4), 1458-1464 (2015).</li><li>Lemaire, P. C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Copper+Benzenetricarboxylate+Metal-Organic+Framework+Nucleation+Mechanisms+on+Metal+Oxide+Powders+and+Thin+Films+formed+by+Atomic+Layer+Deposition.">Copper Benzenetricarboxylate Metal-Organic Framework Nucleation Mechanisms on Metal Oxide Powders and Thin Films formed by Atomic Layer Deposition.</a> ACS Applied Materials &amp; Interfaces. 8 (14), 9514-9522 (2016).</li><li>Zacher, D., Baunemann, A., Hermes, S., Fischer, R. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Deposition+of+microcrystalline+[Cu3(btc)2]+and+[Zn2(bdc)2(dabco)]+at+alumina+and+silica+surfaces+modified+with+patterned+self+assembled+organic+monolayers:+evidence+of+surface+selective+and+oriented+growth.">Deposition of microcrystalline [Cu3(btc)2] and [Zn2(bdc)2(dabco)] at alumina and silica surfaces modified with patterned self assembled organic monolayers: evidence of surface selective and oriented growth.</a> Journal of Materials Chemistry. 17 (27), 2785-2792 (2007).</li><li>Parsons, G. N., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanisms+and+reactions+during+atomic+layer+deposition+on+polymers.">Mechanisms and reactions during atomic layer deposition on polymers.</a> Coordination Chemisty Reviews. 257 (23-24), 3323-3331 (2013).</li><li>Zhao, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Facile+Conversion+of+Hydroxy+Double+Salts+to+Metal-Organic+Frameworks+Using+Metal+Oxide+Particles+and+Atomic+Layer+Deposition+Thin-Film+Templates.">Facile Conversion of Hydroxy Double Salts to Metal-Organic Frameworks Using Metal Oxide Particles and Atomic Layer Deposition Thin-Film Templates.</a> Journal of the American Chemical Soceity. 137 (43), 13756-13759 (2015).</li><li>Zhao, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ultra-Fast+Degradation+of+Chemical+Warfare+Agents+Using+MOF+-+Nanofiber+Kebabs.">Ultra-Fast Degradation of Chemical Warfare Agents Using MOF - Nanofiber Kebabs.</a> Angewandte Chemie International Edition. 55 (42), 13224-13228 (2016).</li><li>Lee, D., Zhao, J., Oldham, C., Peterson, G., Parsons, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=UiO-66-NH2+Metal–Organic+Framework+(MOF)+Nucleation+on+TiO2,+ZnO,+and+Al2O3+Atomic+Layer+Deposition-Treated+Polymer+Fibers:+Role+of+Metal+Oxide+on+MOF+Growth+and+Catalytic+Hydrolysis+of+Chemical+Warfare+Agent+Simulants.">UiO-66-NH2 Metal–Organic Framework (MOF) Nucleation on TiO2, ZnO, and Al2O3 Atomic Layer Deposition-Treated Polymer Fibers: Role of Metal Oxide on MOF Growth and Catalytic Hydrolysis of Chemical Warfare Agent Simulants.</a> ACS Applied Materials &amp; Interfaces. 9 (51), 44847-44855 (2017).</li><li>Spagnola, J. 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The ALD coating strongly influences the adhesion and loading of the MOF. First, depending on the type of substrate and ALD precursor, the ALD layer can either form a distinct outer shell around the fiber, or diffuse into the fiber to create a gradual transition to the metal oxide coating20. The hard shell has been observed on cotton and nylon substrates, while diffusive layers can be observed in polypropylene under proper conditions. Second, the diffusion into the fiber can also be controlled by v...

Metal-organic frameworks are crystalline structures consisting of reactive metal cluster centers bridged by organic molecule linkers to provide large porosities and surface areas. Their structure, porosity, and functionality can be designed by choosing appropriate clusters and linkers, leading to surface areas as high as&#160;7,000 m2/gMOF1,2. Their high porosity and surface area have made MOFs diversely applicable in adsorption, separation, and heterogeneous catalysis in fields ranging from energy production to environmental concerns to biological processes1,3,4,5,6.
Numerous MOFs have proven successful in selectively adsorbing volatile organic compounds and greenhouse gases or to catalytically degrade chemicals that may prove harmful to human health or the environment. In particular, MIL-96 (Al) has shown to selectively adsorb nitrogenous volatile organic compounds (VOCs) due to the availability of lone pair electrons in the nitrogen groups to coordinate with the weak Lewis acid Al present in the metal clusters7. MIL-96 has also been shown to adsorb gases such as CO2, p-xylene, and m-xylene8,9. MOF adsorption selectivity is dependent on both the Lewis acid of the metal cluster, as well as pore size. The pore size of MIL-96 increases with temperature, resulting in increased adsorption capacity of trimethylbenzene with increased temperature, and presents the opportunity of tuning selectivity with adsorption temperature9.
The second MOF of focus here, UiO-66-NH2 has been shown to catalytically degrade chemical warfare agents (CWAs) and simulants. The amine group on the linker provides a synergistic effect in degrading nerve agents, while preventing agent degradation products from binding irreversibly to the zirconium clusters and poisoning the MOF10. UiO-66-NH2 has catalytically hydrolyzed dimethyl p-nitrophenylphosphate (DMNP) with a half-life as short as 0.7 minutes in buffered conditions, nearly 20 times faster than its base MOF UiO-6611,12.
While these adsorption and catalytic properties are promising, the physical form of the MOFs, primarily bulk powder, can be difficult to incorporate into platforms for gas capture and filtration without adding significant bulk, clogging pores, or reducing MOF flexibility. An alternative is to create MOF functionalized fabrics. MOFs have been incorporated into fabrics in myriad ways, including electrospinning MOF powder/polymer slurries, adhesive mixes, spray coating, solvothermal growth, microwave syntheses, and a layer-by-layer growth method13,14,15,16,17,18. Of these, electrospinning and polymer adhesives can result in blocked functional sites on the MOF as they are encapsulated in the polymer, significantly decreasing adsorption capacity and reactivity. Additionally, many of these techniques fail to create conformal coatings on the fibers due to line of sight difficulties or poor adhesion/nucleation and the reliance on purely electrostatic interactions. An alternative method is to first coat the fabric with a metal oxide to allow for stronger surface interactions with the MOF18,19.
One method of metal oxide deposition is atomic layer deposition (ALD). ALD is a technique for depositing conformal thin films, controllable to the atomic scale. The process utilizes two half reactions that occur only at the surface of the substrate to be coated. The first step is to dose a metal containing precursor, which reacts with hydroxyls on the surface, leaving a metallated surface while excess reactant is purged from the system. The second reactant is an oxygen-containing reactant, typically water, which reacts with the metal sites to form a metal oxide. Again, excess water and any reaction products are purged from the system. These alternating doses and purges can be repeated until the desired film thickness is achieved (Figure 1). Atomic layer deposition is particularly useful because the small-scale vapor phase precursors allow for conformal films on every surface of substrates with complex topology, such as fiber mats. Additionally, for polymers such as polypropylene, the ALD conditions can allow the coating to diffuse into the fiber surface, providing a strong anchor for future MOF growth20.
The metal oxide coating allows for increased nucleation sites on the fibers during traditional solvothermal synthesis by increasing functional groups and roughness18,20. Our group has previously shown the ALD metal oxide base layer is effective for UiO-6X, HKUST-1, and other syntheses through various routes of solvothermal, layer-by-layer, and hydroxy-double salt conversion methods13,17,18,21,22,23. Here we demonstrate two synthesis types. The MIL materials are formed by converting the Al2O3 ALD coating directly to MOF by diffusion of the organic linker. By submerging an Al2O3 ALD coated fiber mat in trimesic acid solution and heating, the organic linker diffuses into the metal oxide coating to form MIL-96. This results in a strongly adhered, conformal MOF coating on every fiber surface. The second synthesis approach calls for typical UiO-66-NH2 hydrothermal synthesis using metal and organic precursors, but adds a metal oxide coated fiber mat on which the MOF nucleates. For both synthesis approaches, the resulting products consist of conformal thin films of MOF crystals strongly adhered to the supporting fabric. In the case of MIL-96, these can be incorporated into filters for adsorption of VOCs or greenhouse gases. For UiO-66-NH2 these fabrics can be easily incorporated into lightweight protective clothing for military personnel, first responders, and civilians for continuous defense against CWA attacks.

<table border="0" cellpadding="0" cellspacing="0" width="625">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">trimethylaluminum</td>
			<td style="width:123px;">Strem Chemicals</td>
			<td style="width:119px;">93-1360</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">home-built ALD reactor</td>
			<td style="width:123px;">N/A</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">nitrogen cylinder</td>
			<td style="width:123px;">Arc3</td>
			<td style="width:119px;">UN1066</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">trimesic acid</td>
			<td style="width:123px;">Sigma-Aldrich</td>
			<td style="width:119px;">482749-500G</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">ethanol</td>
			<td style="width:123px;">Koptec</td>
			<td style="width:119px;">V1001</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">teflon lined autoclave</td>
			<td style="width:123px;">PARR Instrument Company</td>
			<td style="width:119px;">4760-1211</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">isotemp furnace</td>
			<td style="width:123px;">Fisher Scientific</td>
			<td style="width:119px;">F47925</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Zirconium (IV) chloride</td>
			<td style="width:123px;">Alfa Aesar</td>
			<td style="width:119px;">12104</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">2-aminoterephthalic acid</td>
			<td style="width:123px;">Acros Organics</td>
			<td style="width:119px;">278031000</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">N,N-dimethylformamide</td>
			<td style="width:123px;">Fisher Scientific</td>
			<td style="width:119px;">D119-4</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Hydrochloric Acid</td>
			<td style="width:123px;">Fisher Scientific</td>
			<td style="width:119px;">A481-212</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Polypropylene fiber mats</td>
			<td style="width:123px;">N/A</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Polyamide fiber mats</td>
			<td style="width:123px;">N/A</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
	</tbody>
</table>

solvothermal synthesis of mil-96 and uio-66-nh2 on atomic layer deposited metal oxide coatings on fiber mats

Metal-organic frameworks (MOFs), which contain reactive metal clusters and organic ligands allowing for large porosities and surface areas, have proven effective in gas adsorption, separations, and catalysis. MOFs are most commonly synthesized as bulk powder, requiring additional processes to adhere them to functional devices and fabrics that risk decreasing the powder porosity and adsorption capacity. Here, we demonstrate a method of first coating fabrics with metal oxide films using atomic layer deposition (ALD). This process creates conformal films of controllable thickness on each fiber, while providing a more reactive surface for MOF nucleation. By submerging the ALD coated fabric in solution during solvothermal MOF synthesis, the MOFs create a conformal, well-adhered coating on the fibers, resulting in a MOF-functionalized fabric, without additional adhesion materials that may block MOF pores and functional sites. Here we demonstrate two solvothermal synthesis methods. First, we form a MIL-96(Al) layer on polypropylene fibers using synthetic conditions that convert the metal oxide to MOF. Using initial inorganic films of varying thicknesses, diffusion of the organic linker into the inorganic allows us to control the extent of MOF loading on the fabric. Second, we perform a solvothermal synthesis of UiO-66-NH2 in which the MOF nucleates on the conformal metal oxide coating on polyamide-6 (PA-6) fibers, thereby producing a uniform and conformal thin film of MOF on the fabric. The resulting materials can be directly incorporated into filter devices or protective clothing and eliminate the maladroit qualities of loose powder.

To describe the MOF/fabric materials, we delineate two terms related to measured surface area. First, projected surface area, cm2projected, refers to the macroscopic size of the fabric swatch as measured with a ruler, i.e., the area of the sample&#39;s projected shadow. The second surface area of interest is the BET surface area, calculated from a nitrogen isotherm obtained at 77 K. These values are given in units of m2/gFabric, m2...

Watch this Scientific Journal Video about Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats at JoVE.com

Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Metal-organic frameworks are effective in gas storage and heterogeneous catalysis, but typical synthesis methods result in loose powders that are difficult to incorporate into smart materials. We demonstrate a method of first coating fabrics with ALD metal oxides, resulting in conformal films of MOF on the fabrics during solvothermal synthesis.

Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Metal-organic frameworks (MOFs), which contain reactive metal clusters and organic ligands allowing for large porosities and surface areas, have proven ...

This method can help answer key questions in the field of metal organic frameworks such as the nature of surface nucleation and MOF adhesion. The main advantage of this technique is that it produces MOF films on fabric during the MOF synthesis rather than requiring additional processing steps to adhere MOF to the fiber. Demonstrating the procedure will be Dennis Lee, a grad student from my laboratory.First, place a PA-6 fabric sample in a reactor boat. Open the pressure gauge of the ALD reactor and remove the clasp from the reactor cap. Next, turn on manual control in the lab view system.Close the carrier nitrogen and gate valve on the ALD reactor. Then open the vent nitrogen. The reactor will open and the cap will fall off.After removing the reactor cap, load the fabric sample into the ALD reactor. Replace the reactor cap. Then open the gate valve.Following this, open the carrier nitrogen and close the vent. Then turn off manual control. Load the recipe for titanium oxide on fabrics.Set the recipe to run 300 cycles. Next, set the mass flow controller to 20 cubic feet per minute and the furnace temperature to 90 degrees Celsius. Open the manual valve to the titanium tetrachloride and water.Close the pressure gauge and replace the clasp on the reactor cap. Then press start on the interface. Upon completion of the recipe, open the pressure gauge.Remove the clasp from the reactor cap. Then turn on manual control in the system. Following this, close the carrier nitrogen and gate valve on the ALD reactor.Then open the vent nitrogen. The reactor will open and the cap will fall off. Remove the sample boat.Reseal the reactor. Add 0.0878 grams of trimesic acid to an 80 milliliter glass beaker. Add 12 milliliters of water and 12 milliliters of ethanol to the beaker.Then add a magnetic stir bar to the solution and stir until the trimesic acid is fully dissolved. Next, place the solution in a Teflon-lined pressure vessel. Add previously prepared aluminum oxide-coded polypropylene to the solution and prop the fabric on a mesh support so it does not lie flat against the bottom of the vessel.Following this, seal the pressure vessel and place it in the furnace at 110 degrees Celsius for 24 hours. Add 0.08 grams of zirconium chloride to a 20 milliliter glass scintillation vial. Add 20 milliliters of DMF to the zirconium chloride in five milliliter increments.Cap the vial between increments and allow the fumes to dissipate. Next, sonicate the solution for one minute. Add 0.062 grams of 2-aminoterephthalic acid and a magnetic stir to the vial.Stir the solution for five minutes. After stirring, add 25 microliters of deionized water to the vial. Then add 1.33 milliliters of concentrated hydrochloric acid to the vial.Now submerge the titanium dioxide ALD-coded fabric swatch in the solution and cap the vial. Finally, place the sample in the furnace at 85 degrees Celsius for 24 hours. Scanning electron microscopy showed conformal MOF crystal thin films on all fibers resembling a cobblestone pattern.When the aluminum oxide was reduced, the film began to break apart as the MOF formed resulting in a patchy coding. A bare polypropylene sample was exposed to MIL-96 synthesis conditions, but XRD showed no detectable MOF on the fibers. Cross-sectional images revealed the 500 cycle aluminum oxide base layer completely reacted while a fraction of the aluminum oxide base layer remained for the 1, 000 and 2, 000 cycle samples.Cross-sections of the aluminum oxide ALD-coded polypropylene are shown here. Electron dispersion spectroscopy images of the cross-section revealed the carbon-based polypropylene core and predominantly aluminum oxide shell. XRD patterns of the MOF-coded fabric matching the simulated PXRD pattern of MIL-96 are shown here.Following solvothermal MOF synthesis, XRD patterns revealed UIO-66-amine was present on the fibers. SEM images showed flaky MOF codings on the 50 degree Celsius samples, dense MOF codings on the 90 degree Celsius samples, and sparse MOF codings on the 200 degree Celsius samples. An uncoded PA-6 sample was exposed to UIO-66-amine synthesis conditions resulting in a relatively sparse MOF coding.After watching this video, you should have a good understanding of how to produce conformal MOF films on ALD-coded substrates.

Research

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Chemistry

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