Name: microhoneycomb monoliths prepared by the unidirectional freeze-drying of cellulose nanofiber based sols: method and extensions
Uploaded: 2018-05-24T13:30:00
Description: Watch this Scientific Journal Video about Microhoneycomb Monoliths Prepared by the Unidirectional Freeze-drying of Cellulose Nanofiber Based Sols: Method and Extensions at JoVE.com

This work was supported by the National Basic Research Program of China (2014CB932400), National Natural Science Foundation of China (Nos. 51525204 and U1607206) and Shenzhen Basic Research Project (No. JCYJ20150529164918735). Also, we would like to thank Daicel-Allnex Ltd. and JSR Co. for kindly supplying polyurethanes and styrene butadiene rubber, respectively.

1. Preparation of 1 wt% 2,2,6,6-Tetramethylpiperidin-1-oxyl (TEMPO)-mediated Oxidized Cellulose Nanofiber (TOCN) Sol
NOTE: The sol is defined as a colloidal suspension of very small solid particles in a continuous liquid medium.
<ol>
	<li>Suspend 66.7 g of Nadelholz Bleached Kraft Pulp (NBKP, containing 12 g of cellulose) in 700 mL of deionized (DI) water with a mechanical agitator at 300 rpm for 20 min.</li>
	<li>Add 20 mL of aqueous TEMPO solution (containing 0.15 g of TEMPO) and 20 mL of ...

<ol>
	<li>Nishihara, H., Mukai, S. R., Yamashita, D., Tamon, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ordered+macroporous+silica+by+ice+templating.">Ordered macroporous silica by ice templating.</a> Chem. Mater. 17, 683-689 (2005).</li><li>Mukai, S. R., Nishihara, H., Yoshida, T., Taniguchi, K., Tamon, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Morphology+of+resorcinol-formaldehyde+gels+obtained+through+ice-templating.">Morphology of resorcinol-formaldehyde gels obtained through ice-templating.</a> Carbon. 43 (7), 1563-1565 (2005).</li><li>Mukai, S. R., Nishihara, H., Tamon, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Porous+microfibers+and+microhoneycombs+synthesized+by+ice+templating.">Porous microfibers and microhoneycombs synthesized by ice templating.</a> Catal. Surv. Asia. 10 (3-4), 161-171 (2006).</li><li>Nishihara, H., 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=Preparation+of+monolithic+SiO2-Al2O3+cryogels+with+inter-connected+macropores+through+ice+templating.">Preparation of monolithic SiO2-Al2O3 cryogels with inter-connected macropores through ice templating.</a> J. Mater. Chem. 16 (31), 3231-3236 (2006).</li><li>Mukai, S. R., Mitani, K., Murata, S., Nishihara, H., Tamon, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Assembling+of+nanoparticles+using+ice+crystals.">Assembling of nanoparticles using ice crystals.</a> Mater. Chem. Phys. 123 (2), 347-350 (2010).</li><li>Cui, 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=Self-assembled+microhoneycomb+network+of+single-walled+carbon+nanotubes+for+solar+cells.">Self-assembled microhoneycomb network of single-walled carbon nanotubes for solar cells.</a> J. Phy. Chem. Lett. 4 (15), 2571-2576 (2013).</li><li>Xu, T., Wang, C. -. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Effect+of+two-step+sintering+on+micro-honeycomb+BaTiO3+ceramics+prepared+by+freeze-casting+process.">Effect of two-step sintering on micro-honeycomb BaTiO3 ceramics prepared by freeze-casting process.</a> J. Eur. Ceram. Soc. 36 (10), 2647-2652 (2016).</li><li>Yoshida, S., 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=CO2+Separation+in+a+flow+system+by+silica+microhoneycombs+loaded+with+an+ionic+liquid+prepared+by+the+ice-templating+method.">CO2 Separation in a flow system by silica microhoneycombs loaded with an ionic liquid prepared by the ice-templating method.</a> Ind. Eng. Chem. Res. 56 (10), 2834-2839 (2017).</li><li>Mukai, S. R., Nishihara, H., Tamon, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Formation+of+monolithic+silica+gel+microhoneycombs+(SMHs)+using+pseudosteady+state+growth+of+microstructural+ice+crystals.">Formation of monolithic silica gel microhoneycombs (SMHs) using pseudosteady state growth of microstructural ice crystals.</a> Chem. Commun. (7), 874-875 (2004).</li><li>Gutie&#180;rrez, M. 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=Macroporous+3D+Architectures+of+Self-Assembled+MWCNT+Surface+Decorated+with+Pt+Nanoparticles+as+Anodes+for+a+Direct+Methanol+Fuel+Cell.">Macroporous 3D Architectures of Self-Assembled MWCNT Surface Decorated with Pt Nanoparticles as Anodes for a Direct Methanol Fuel Cell.</a> J. Phys. Chem. C. 111, 5557-5560 (2007).</li><li>Mukai, S. R., Nishihara, H., Tamon, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Morphology+maps+of+ice-templated+silica+gels+derived+from+silica+hydrogels+and+hydrosols.">Morphology maps of ice-templated silica gels derived from silica hydrogels and hydrosols.</a> Micropor. Mesopor. Mat. 116 (1-3), 166-170 (2008).</li><li>Okaji, R., Taki, K., Nagamine, S., Ohshima, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+of+porous+honeycomb+monolith+from+UV-curable+monomer/dioxane+solution+via+unidirectional+freezing+and+UV+irradiation.">Preparation of porous honeycomb monolith from UV-curable monomer/dioxane solution via unidirectional freezing and UV irradiation.</a> J. Appl. Polym. Sci. 125 (4), 2874-2881 (2012).</li><li>Pan, Z. -. Z., 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=Cellulose+nanofiber+as+a+distinct+structure-directing+agent+for+xylem-like+microhoneycomb+monoliths+by+unidirectional+freeze-drying.">Cellulose nanofiber as a distinct structure-directing agent for xylem-like microhoneycomb monoliths by unidirectional freeze-drying.</a> ACS Nano. 10 (12), 10689-10697 (2016).</li><li>Saito, T., Nishiyama, Y., Putaux, J. -. L., Vigon, M., Isogai, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Homogeneous+Suspensions+of+Individualized+Microfibrils+from+TEMPO-Catalyzed+Oxidation+of+Native+Cellulose.">Homogeneous Suspensions of Individualized Microfibrils from TEMPO-Catalyzed Oxidation of Native Cellulose.</a> Biomacromolecules. 7 (6), 1687-1691 (2006).</li><li>Saito, T., Kimura, S., Nishiyama, Y., Isogai, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Cellulose+Nanofibers+Prepared+by+TEMPO-Mediated+Oxidation+of+Native+Cellulose.">Cellulose Nanofibers Prepared by TEMPO-Mediated Oxidation of Native Cellulose.</a> Biomacromolecules. 8, 2485-2491 (2007).</li><li>Bekyarova, 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=Multiscale+carbon+nanotube&#8722;+carbon+fiber+reinforcement+for+advanced+epoxy+composites.">Multiscale carbon nanotube&#8722; carbon fiber reinforcement for advanced epoxy composites.</a> Langmuir. 23, 3970-3974 (2007).</li><li>Nishihara, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Study on the simultaneous control of the nanostructure and morphology of the porous materials prepared via the ice-templating method [D]. , (2005).</li><li>Zhang, 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=Three-dimensional+porous+graphene+sponges+assembled+with+the+combination+of+surfactant+and+freeze-drying.">Three-dimensional porous graphene sponges assembled with the combination of surfactant and freeze-drying.</a> Nano Research. 7 (10), 1477-1487 (2014).</li><li>Tao, 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=Towards+ultrahigh+volumetric+capacitance:+graphene+derived+highly+dense+but+porous+carbons+for+supercapacitors.">Towards ultrahigh volumetric capacitance: graphene derived highly dense but porous carbons for supercapacitors.</a> Sci. Rep. 3, 2975 (2013).</li></ol>

The most critical step for achieving the MHMs is the unidirectional freezing step, during which water solidifies to form columnar ice crystals and push the dispersoid aside to form the framework. The unidirectional freezing process basically involves thermal transfer between the precursor sol and the coolant. In our setup, a dipping machine was used to insert a PP tube containing a precursor sol into the coolant (liquid nitrogen) with a constant velocity. Since liquid nitrogen keeps evaporating all the time, a fluctuant ...

As a brand-new material, microhoneycomb monolith (denoted MHM) has recently attracted tremendous attention from multidisciplinary fields1,2,3,4,5,6,7,8. The MHM was first prepared by S. Mukai et al. through a modified unidirectional freeze-drying (UDF) approach as a monolith with an array of straight microchannels with honeycomb-like cross sections9. MHM possesses the general advantages of honeycomb structures, i.e., efficient tessellation, high strength-to-weight ratio, and low pressure drop. Moreover, compared with the honeycomb monolith with a larger channel size, the MHM has a much larger specific surface area. The UDF method involves the unidirectional growth of ice crystals and simultaneous phase separation upon freezing. After the removal of the ice crystals, a solid component molded by the ice crystal is obtained. The morphology formed upon the phase separation depends on the intrinsic nature of the precursor (sol or gel), and in most of cases, lamella10, fiber11, and fishbone12 structures are likely to form rather than the MHMs. As a result, the formation of MHMs has been reported only in limited precursors, and this has significantly hampered the diversity of their chemical property. We have recently found that cellulose nanofibers have a strong structure-directing function toward forming the MHM structure through the UDF process13. Simply by mixing the cellulose nanofibers with other water-dispersible components, it is possible to prepare a variety of MHMs with different chemical properties. Moreover, their exterior shapes and channel sizes are flexibly and easily controlled13. Thus, MHMs are expected to be used as filters, catalyst supports, flow-type electrodes, sensors and scaffolds for biomaterials.
In this paper, we first explain the basic preparation technique of MHMs from the aqueous dispersion of cellulose nanofibers through the UDF process in detail. Moreover, we demonstrate the preparation of several different types of composite MHMs.

<table border="0" cellpadding="0" cellspacing="0" width="572">
	<tbody>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Nadelholz Bleached Kraft Pulp</td>
			<td style="width:100px;">Seioko PMC company</td>
			<td style="width:89px;">CSF=600</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">TEMPO</td>
			<td style="width:100px;">Macklin Inc.</td>
			<td style="width:89px;">T819129</td>
			<td style="width:167px;">98%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">NaBr</td>
			<td style="width:100px;">Macklin Inc.</td>
			<td style="width:89px;">S818075</td>
			<td style="width:167px;">AR, 99%</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">NaClO</td>
			<td style="width:100px;">Aladin Inc.</td>
			<td style="width:89px;">S101636</td>
			<td style="width:167px;">6-14 wt% active chlorine basis</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">SBR colloid</td>
			<td style="width:100px;">JSR corp.</td>
			<td style="width:89px;">TRD102A</td>
			<td style="width:167px;">48.5 wt%</td>
		</tr>
		<tr height="84">
			<td height="84" style="height:84px;width:216px;">TiO2</td>
			<td style="width:100px;">Sinopharm Chemical Reagent Co., Ltd.</td>
			<td style="width:89px;">A63725402</td>
			<td style="width:167px;">crystalline anatase phase</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">carbon fiber</td>
			<td style="width:100px;">Shenzhen Xian&#8217;gu Ltd.</td>
			<td style="width:89px;">XGCP-300</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Nitric acid</td>
			<td style="width:100px;">Huada Reagent Ltd.</td>
			<td style="width:89px;">7697-37-2</td>
			<td style="width:167px;">65-68 wt%</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Mixer</td>
			<td style="width:100px;">Scientific Industries, Inc</td>
			<td style="width:89px;">G-560</td>
			<td style="width:167px;">the mixer&#160;</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;width:216px;">Mechanical blender</td>
			<td style="width:100px;">Waring Lab Ltd.</td>
			<td style="width:89px;">MX1000XTX</td>
			<td style="width:167px;">For disintegrating cellulose bundles into nanofibers.</td>
		</tr>
		<tr height="46">
			<td height="46" style="height:46px;width:216px;">Homogenizer</td>
			<td style="width:100px;">Scientz Ltd.</td>
			<td style="width:89px;">HXF-DY</td>
			<td style="width:167px;">For dispersing TiO2 nanoparticles</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">pH meter&#160;</td>
			<td style="width:100px;">Horiba Ltd.</td>
			<td style="width:89px;">F-74BW</td>
			<td></td>
		</tr>
	</tbody>
</table>

microhoneycomb monoliths prepared by the unidirectional freeze-drying of cellulose nanofiber based sols: method and extensions

Monolithic honeycomb structures have been attractive to multidisciplinary fields due to their high strength-to-weight ratio. Particularly, microhoneycomb monoliths (MHMs) with micrometer-scale channels are expected as efficient platforms for reactions and separations because of their large surface areas. Up to now, MHMs have been prepared by a unidirectional freeze-drying (UDF) method only from very limited precursors. Herein, we report a protocol from which a series of MHMs consisting of different components can be obtained. Recently, we found that cellulose nanofibers function as a distinct structure-directing agent towards the formation of MHMs through the UDF process. By mixing the cellulose nanofibers with water soluble substances which do not yield MHMs, a variety of composite MHMs can be prepared. This significantly enriches the chemical constitution of MHMs towards versatile applications.

The morphologies for different positions of the MHM-TOCN along the direction of unidirectional freezing are investigated and shown in Figure 2. With the position being further away from the bottom part of the MHM-TOCN, a gradual morphology change was revealed (Figure 2, Discussion). By introducing a second component into the TOCN sol to form a homogeneous mixture sol, it is possible to prepare various kinds of co...

Watch this Scientific Journal Video about Microhoneycomb Monoliths Prepared by the Unidirectional Freeze-drying of Cellulose Nanofiber Based Sols: Method and Extensions at JoVE.com

Microhoneycomb Monoliths Prepared by the Unidirectional Freeze-drying of Cellulose Nanofiber Based Sols: Method and Extensions

Here, we present a general protocol to prepare a variety of microhoneycomb monoliths (MHMs) in which fluid can pass through with an extremely low pressure drop. MHMs obtained are expected to be used as filters, catalyst supports, flow-type electrodes, sensors and scaffolds for biomaterials.

Monolithic honeycomb structures have been attractive to multidisciplinary fields due to their high strength-to-weight ratio. Particularly, microhoneycomb ...

Research

JoVE Journal

Bioengineering

Improved Method for the Preparation of a Human Cell-based, Contact Model of the Blood-Brain Barrier

The blood-brain barrier (BBB) comprises impermeable but adaptable brain capillaries which tightly control the brain environment. Failure of the BBB has ...

Manufacturing Of Robust Natural Fiber Preforms Utilizing Bacterial Cellulose as Binder

A novel method of manufacturing rigid and robust natural fiber preforms is presented here. This method is based on a papermaking process, whereby loose ...

Formation of Biomembrane Microarrays with a Squeegee-based Assembly Method

Lipid bilayer membranes form the plasma membranes of cells and define the boundaries of subcellular organelles. In nature, these membranes are ...

Electrospun Nanofiber Scaffolds with Gradations in Fiber Organization

The goal of this protocol is to report a simple method for generating nanofiber scaffolds with gradations in fiber organization and test their possible ...

Biomembrane Fabrication by the Solvent-assisted Lipid Bilayer (SALB) Method

Biomembrane Fabrication by the Solvent-assisted Lipid Bilayer SALB Method

In order to mimic cell membranes, the supported lipid bilayer (SLB) is an attractive platform which enables in vitro investigation of membrane-related ...

Synthesis of Keratin-based Nanofiber for Biomedical Engineering

Electrospinning, due to its versatility and potential for applications in various fields, is being frequently used to fabricate nanofibers. Production of ...

A Net Mold-based Method of Scaffold-free Three-Dimensional Cardiac Tissue Creation

This protocol describes a novel and easy net mold-based method to create three-dimensional (3-D) cardiac tissues without additional scaffold material. ...

Detection of Endotoxin in Nano-formulations Using Limulus Amoebocyte Lysate (LAL) Assays

Detection of Endotoxin in Nano-formulations Using Limulus Amoebocyte Lysate LAL Assays

When present in pharmaceutical products, a Gram-negative bacterial cell wall component endotoxin (often also called lipopolysaccharide) can cause ...

Seeding and Implantation of a Biosynthetic Tissue-engineered Tracheal Graft in a Mouse Model

Treatment options for congenital or secondary long segment tracheal defects have historically been limited due to an inability to replace functional ...

3D Printed Porous Cellulose Nanocomposite Hydrogel Scaffolds

This work demonstrates the use of three-dimensional (3D) printing to produce porous cubic scaffolds using cellulose nanocomposite hydrogel ink, with ...