Patent Publication Number: US-11646403-B2

Title: Porous sheets and method of making same from porous carbon nanotubes and decomposing microorganisms

Description:
BACKGROUND 
     Porous structures benefit diverse systems by facilitating the transport of reactants and increasing the accessibility of reaction sites in extended dimensional scales. In practical applications such as sensors, gas storages, membranes, solar cells and batteries, well established porous structures in a device can directly enhance its performance by improving the liquid or gas flow in a solid frame, thereby maximizing the device efficiency in diverse engineering systems. 
     For example, free-standing porous carbon sheets have a broad range of applications including battery and solar cell electrodes, gas diffusion layers for fuel cells, separation media and the like. By enhancing the supply of reactants to the reaction sites through interconnected porous structures, reaction efficiency may be improved with conducting carbon frames, which require efficient mass transport in addition to fast kinetics. 
     Among various approaches to pore generation in solid materials, the direct templating method provides an easy and controllable route to introduce homogeneous pore structures for pore diameters ranging from mesopores (2-50 nm) to macropores (&gt;50 nm). Two general steps are involved in the direct templating method: interaction of pre-existing templates with materials of interest and removal of templates to create pores. Thus, preformed templates should be chemically inert to matrix materials, easy to remove, and cost efficient for mass production. 
     Since template materials can be expensive and difficult to remove, direct templating methods are often prohibitive for large scale device fabrication. In addition, polymer binders may be generally used to hold the porous structure in a free-standing form, but these polymer binders may increase dead mass in electrodes and cause side reactions during device operations. Further, currently available pore generators, such as silica, polymer beads (e.g., latex), or anodic aluminum oxide, have scale-up limitations for practical applications due to their complicated synthesis process and high material cost. 
     SUMMARY 
     In one aspect, the present disclosure is directed to a method of preparing a porous sheet including mixing a matrix material dispersion including a matrix material dispersed in a first dispersion medium with a microorganism dispersion including microorganisms in a second dispersion medium, to form a mixture. The first and the second dispersion media are removed from the mixture to form a matrix sheet, and the microorganisms are decomposed from the matrix sheet to form the porous sheet. 
     In another aspect, the present disclosure is directed to a method of preparing a porous sheet of carbon nanotubes, including: adding a matrix material dispersion including carbon nanotubes dispersed in a first dispersion medium to a microorganism dispersion including microorganisms dispersed in a second dispersion medium; removing the first and the second dispersion media to generate a sheet of carbon nanotubes, and decomposing the microorganisms from the sheet of carbon nanotubes to form the porous sheet. 
     In yet another aspect, the present disclosure is directed to a porous sheet including a matrix and a plurality pores in the matrix, wherein the pores consist of cylinders with a diameter of about 0.5 micrometers to about 1 micrometer, and a length of about 1 micrometer to about 5 micrometers. 
     The details of one or more examples are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the disclosure will be apparent from the description and drawings, and from the claims. 
    
    
     
       BRIEF DESCRIPTION OF DRAWINGS 
         FIG.  1    is an exemplary schematic representation of  E. coli  mediated pore generation for a multiwalled carbon nanotube (MWCNT) film. 
         FIG.  2    is a flowchart of a method for producing a porous sheet from microorganisms and matrix materials. 
         FIG.  3    is a flowchart of a method for producing a porous carbon nanotube (CNT) sheet from microorganisms and CNTs. 
         FIG.  4    is an exemplary schematic for a MWCNT- E. coli  film fabrication process. 
         FIG.  5 A- 5 F  are exemplary optical microscope images of  E. coli  solutions treated with different chemicals. 
         FIGS.  6 A- 6   ) are exemplary scanning electron microscope images of MWCNT- E. coli  films with various chemical and heat treatments. 
         FIGS.  6 E- 6 F  are exemplary graphs of XPS and Raman analyses of the MWCNT and MWCNT- E. coli  films obtained following the treatments of  FIGS.  6 A- 6 D . 
         FIGS.  7 A- 7   ) are exemplary SEM images of MWCNT films with different pore shapes and porosities. 
         FIGS.  8 A- 8 F  are exemplary SEM images of a MWCNT film and a MWCNT- E. coli  films after battery discharge. 
         FIG.  9 A  is the first Li-oxygen battery galvanostatic cycle profile graph of MWCNT and MWCNT- E. coli  films. 
         FIG.  9 B  is a graph of oxygen recovery ratio of MWCNT-based electrodes with different porosities. 
     
    
    
     DETAILED DESCRIPTION 
     In general, the disclosure describes the use of microorganisms as pore templating materials to generate pores in porous sheets. Microorganisms and matrix materials are dispersed into first and second dispersion media, which may be the same or different. The dispersion medium is removed to form a matrix sheet with spaces or voids occupied by the microorganisms. The microorganisms may be removed from the matrix sheet by thermal or chemical treatments to generate pores inside the matrix at the spaces previously occupied by the microorganisms. The selection and growth of the microorganisms may be controlled to generate matrix sheets with preselected pore sizes, shapes, and concentrations. This technique may be used as a simple, low cost, and binder-free fabrication method for making porous sheets, which may be used in mass production for various applications. 
       FIG.  1    is an exemplary schematic representation of microorganism mediated pore generation for porous sheets using  E. coli  and multiwalled carbon nanotubes.  E. coli  grown or selected for certain pore properties may be present in a multiwalled carbon nanotube film. The  E. coli  act as a pore template for a matrix sheet formed by the multiwalled carbon nanotubes. The  E. coli  may be decomposed to form a porous multiwalled carbon nanotube film. In general, microorganisms may be selected using many of the same selection criteria for which pore templates have been selected in template systems. However, microorganisms may be cheaper to manufacture, easier to remove, more homogeneous, and more environmentally benign. Microorganisms have a relatively low decomposition temperature and are typically cheaper than conventional pore templates. 
       FIG.  2    is a flowchart of a method for producing a porous sheet from microorganisms and matrix materials. A matrix material dispersion may be prepared, as in step  210 . The matrix material dispersion may include one or more matrix materials dispersed in a dispersion medium. The matrix materials may be any material capable of dispersing into the dispersion medium and forming a matrix upon dispersion medium removal. The matrix materials may be stably dispersed in medium when they were mixed with microorganism. A variety of matrix materials may be used that include, but are not limited to: nanostructures such as carbon nanotubes and graphene sheets; ceramics; metals; and polymers. In some examples, more than one matrix material may be used. For example, polymers and carbon nanotubes may be used to fabricate a porous composite. 
     A microorganism dispersion may be prepared. The microorganism dispersion may include microorganisms dispersed into a dispersion medium. The microorganisms may include any microorganism capable of dispersing into the dispersion medium and decomposing in situ from a matrix sheet formed by the matrix materials. In some examples, preparation of the microorganism solution may include dispersing the microorganisms in a growth solution and growing the microorganisms to a desired size and shape. In some embodiments, the microorganisms may be environmentally benign and homogenous in shape. Microorganisms that may be used include, but are not limited to, bacteria such as  E. coli  and  S. epi , prokaryotic or unicellular eukaryotic organisms including diatoms. 
     In some examples, the one or more microorganisms may be grown or selected to produce a particular pore size, shape, or combination thereof. Certain microorganism shapes may result in particular pore shapes, such as cylindrical  E. coli  with cylindrical pores and spherical  S. epi  with spherical pores. In some examples, two or more microorganisms having different shapes may be used. Additionally, for pores with a desired volume greater than individual cells, microorganisms may be selected having group configurations. For example, strepto-bacterium may be used to form long chains, which may correlate upon removal to long pores with high surface area in some embodiments, organisms such as fungi may be used. Shapes and configurations that may be selected include, but are not limited to, spherical, rod-shaped, spiral-shaped, curved, paired, grouped, and chains. 
     In some examples, the one or more microorganisms may be grown or selected to form pores of a particular size. Certain microorganism sizes may correlate with preselected pore sizes, such as  E. coli  for pores with a diameter between 1 and 2 micrometers and a length between 1 and 5 micrometers. As mentioned above, different configurations and groupings of cells may have different sizes, such as clustered  S. epi  for volumes in multiples of their approximately 1 micrometer dimension. In some examples, microorganisms may be in the micron scale and capable of forming macropores having a dimension greater than 50 nm. In some embodiments, the microorganisms have a dimension, such as diameter or length with the scale ranging from 0.1 micrometers to 50 micrometers, or about 5 micrometers to about 25 micrometers, or about 1 micrometer to about 10 micrometers. In some embodiments, which are not intended to be limiting, the pores are cylinders with a diameter of about 0.5 micrometers to about 1 micrometer, and a length of about 1 micrometer to about 5 micrometers. 
     In some examples, the porosity of the resulting porous sheet may be controlled by the number of the microorganisms in the microorganism dispersion. For example, the added microorganism amounts may correlate with the porosity of the resulting porous matrix sheet. 
     In some examples, the microorganisms may be grown or selected for a variety of other properties that include, but are not limited to, uniformity, decomposition temperature, chemical resistance, and growth rate. In some examples, the microorganisms can be incorporated with some materials (metals, oxides or other inorganic materials) that can functionalize the matrix materials. 
     The dispersion medium used in the matrix material dispersion may include any medium capable of dispersing the matrix material. The dispersion medium of the microorganism dispersion may include any medium capable of dispersing the microorganisms. In some examples, the dispersion medium used in the microorganism dispersion may be a growth solution. In other examples, the dispersion medium of the microorganism dispersion may be the same dispersion medium used for the matrix material dispersion medium. In some examples, a dispersion medium may be selected for its removal properties for evaporation or filtration. A variety of dispersion media and combinations thereof may be used including, but not limited to, polar solvents, non-polar solvents, and surfactants. 
     The matrix material dispersion and the microorganism dispersion may be mixed, as in step  230 , to form a mixture having both matrix materials and microorganisms. The mixture may, for example, be mixed to create an evenly dispersed mixture. A matrix sheet may be formed from the mixture, as in step  240 . In some embodiments, the matrix sheet may be formed by any mechanism that removes the dispersion medium from the mixture, as in step  241 . Mechanisms for removal of the dispersion medium may include filtration and evaporation. The matrix sheet may be further treated to form the matrix sheet. For example, the matrix sheet may be freeze dried, cross-linked, or polymerized to further form the matrix sheet. The resulting matrix sheet may include the matrix materials and the microorganisms distributed to a corresponding porosity. In some examples, the microorganisms are evenly dispersed through the matrix sheet. 
     A porous sheet may be formed, as in step  250 , by removal of the microorganisms from the matrix sheet. In some embodiments, the porous sheet may be formed by decomposing the microorganisms present in the matrix sheet, as in step  251 . Decomposition may involve any method that breaks down the microorganisms in the matrix sheet so that the volume of biological material of the microorganisms in the matrix sheet is significantly reduced without collapsing the porous matrix structure. For example, the microorganisms may be decomposed so that they do not provide any significant structural support to the matrix, such as through cellulosic fibers. In some examples, some residual biological material may remain in the matrix without contributing to the structural integrity of the matrix. 
     The microorganisms can be decomposed by any technique that does not decompose the matrix material including, but not limited to, plasma etching, exposure to ozone, chemical treatments, thermal treatments, and combinations thereof. For example, decomposition of the microorganisms may include chemical treatments, as in step  252 , or thermal treatments, as in step  253 . Chemical treatments may include any process designed to kill or break down the microorganism in the matrix sheet. For example, chemical treatments may include adding bleach to the matrix sheet at a concentration to kill the microorganisms. Chemicals that may be used include, but are not limited to, ethanol, bases such as sodium hydroxide and bleach, acids such as sulfuric acid, and drying agents. Thermal treatments may include any process designed to kill, burn, combust, or dry biological material from the microorganisms in the matrix sheet. Thermal treatments may include, but are not limited to, baking, burning, thermal calcination, and application of hot air. 
     The resulting porous sheets may have a matrix with pores, where the matrix material may provide the structure of the matrix sheet and the pores may correspond to the spaces previously filled by microorganisms in the matrix sheet. The porous sheets may be used for a variety of applications, including electronics, filtration, gas separation, and gas storage. The porous sheet may have a variety of configurations, such as thin films, coatings, and membranes. 
       FIG.  3    is a flowchart of a method for producing a porous sheet from microorganisms and multiwalled carbon nanotubes (MWCNT). A carbon nanotube dispersion may be prepared, as in  310 . Preparation of the carbon nanotube dispersion may include addition of a surfactant and sonication of the carbon nanotube dispersion to reduce agglomeration. A microorganism solution may be prepared, as in step  320 . The CNT solution and the microorganism solution may be mixed, as in step  330  to form a mixture. The CNT sheet may be formed from the mixture, as in  340 . The mixture may be filtered, as in step  341 . The dispersion medium from the mixture may be filtered through a filter, resulting in a dry filter cake having the multiwalled carbon nanotubes and the microorganisms. The porous CNT sheet may be formed, as in step  350 , by decomposition of the microorganisms, as in step  251  ( 351 ). This decomposition may be done by chemical treatment, as in step  352 , and/or thermal treatment, as in step  354 . The CNT sheet may be further formed by freeze drying the CNT sheet, as in step  353 . 
     EXAMPLES 
     Example 1: MWCNT- E. coli  Film Fabrication 
       FIG.  4    is an exemplary schematic for a MWCNT- E. coli  film fabrication process, involving preparation of a MWCNT- E. coli  mixture, filtration of the mixture, and decomposition of the  E. coli  to form the MWCNT- E. coli  film. 
     To prepare the MWCNT- E. coli  mixture,  E. coli  (Serotype 06, Biotype 1  E. coli ; available under the tradename ATCC 25922 from ATCC) was grown in tryptic soy broth (TSB) media at 37° C. for 16 hours by ten times dilution of overnight culture to form an E co/i dispersion. The  E. coli  dispersion was dispensed in a dialysis tubing cellulose membrane (available under the tradename D9652-100FT from Sigma Aldrich) and dialyzed overnight in deionized (DI) water to form a dialyzed  E. coli  dispersion. Multi-walled carbon nanotube (MWCNT) powder (12 mg, &gt;95%, OD 15±5 nm, Length 5-20 μm, available from NanoLab Inc.) was dispersed with 0.48 ml (2.5% (w/v)) of sodium dodecylbenzene sulfonate (NaDBS, available from Sigma Aldrich) solution (as the surfactant) and 13.47 ml DI water to form a MWCNT dispersion. The MWCNT dispersion was sonicated by a probe (Model: 102C, available from Branson) in an ice bath for 40 min and the remaining aggregates of MWCNTs were collected by centrifuging at 4000 rpm for 20 minutes. The MWCNT and dialyzed  E. coli  dispersions were then mixed together, at room temperature for 2 hours using a magnetic stirrer at 200 rpm to form a MWCNT- E. coli  mixture. 
     To filter the MWCNT- E. coli  mixture, the MWCNT- E. coli  mixture was vacuum filtered using an anodisc membrane (Dia. 47 mm, Pore Dia. 0.2 μm, available from Whatman) to form a filtered MWCNT- E. coli  mixture. The filtered MWCNT- E. coli  mix, together with the membrane, was first immersed into 10% (v/v) bleach solution for 15 min, and then rinsed overnight in stagnant DI water. 
     The filtered MWCNT- E. coli  mix was separated from the membrane in DI water, and then dried via freeze-drying (Labconco Freeze Dry System, Model: Freezone® 4.5, available from Labconco, Inc.) to preserve the 3D interconnected structure and form a MWCNT- E. coli  film. The obtained MWCNT- E. coli  film was heat treated in a custom-made quartz tube furnace at 400° C. for 3 hours under 300 sccm N 2  flow in order to remove any residual  E. coli.    
     Example 2:  E. coli  Chemical Treatment 
     In some examples, chemicals may be used to decompose microorganisms for removal in forming a porous sheet.  FIGS.  5 A- 5 F  are optical microscope images of  E. coli  solutions treated with different chemicals. The decomposition of an  E. coli  (˜8.44×10 10  cells in 200 μl) solution was investigated by incubating them in diverse chemicals, such as base (NaOH, 1 M, 600 μl; see  FIG.  5 A ), surfactant (NaDBS, 2.5 w/v %, 600 μl; see  FIG.  5 B ), acid (H 2 SO 4  (20 v/v %) or HCl (15 v/v %), 600 μl; see  FIG.  5 C  and  FIG.  5 D , respectively), bleach (10 v/v %, 600 μl; see  FIG.  5 E ) or ethanol (200 Proof, 600 μl, see  FIG.  5 F ) for 2 hours and examining them under an optical microscope. 
     As seen in the optical microscope images in  FIG.  5 A- 5 F , the  E. coli  was most effectively decomposed by bleach solutions ( FIG.  5 E ) compared to other solvents used in these examples. 
       FIGS.  6 A- 6 D  are SEM images of MWCNT- E. coli  films following various chemical and heat treatments. After prescreening several solvents to apply in the  E. coli  removal step, MWCNT- E. coli  films were submerged in 400 ml of each bleach (10 v/v %, 1 h), NaOH (1 M, 1 h), and ethanol (200 Proof, 2 h)/H 2 SO 4  (20 v/v %, 1 h) solvents and then heat-treated at 400° C. for 3 h under N 2 . The decomposition of  E. coli  with chemicals and heat-treatment was evaluated with scanning electron microscope (SEM). With the thermal treatment only, most of the  E. coli  residues remained in MWCNT- E. coli  films as can be seen in  FIG.  6 A . 
     Among the selected removal solvents, MWCNT- E. coli  films incubated with bleach solutions showed better removals of K coil in films after heat treatment ( FIG.  6 D ), while NaOH and ethanol/H 2 SO 4  solvents were less effective in decomposing  E. coli  ( FIGS.  6 B and  6 C , respectively). Since the bleach solution contains the strong oxidizer, sodium hypochlorite (NaClO) that can potentially oxidize MWCNT, the incubation time of MWCNT- E. coli  films were adjusted (15 min of incubation) to lyse the cells, but limited to the extent where the oxidation of MWCNT can be minimized. 
     The surface state of MWCNT- E. coli  films during their fabrication process was investigated with X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy.  FIG.  6 E  is a graph of XPS analyses of MWCNT and MWCNT- E. coli  films for the treatments in  FIGS.  6 A- 6 D . Each spectrum was analyzed by peak deconvolution with a fixed FWHM (full width at half maximum) using CASA XPS software. Carbon bonding was categorized into two groups, the carbon bonding between (1) carbon-carbon (sp 2  C═C at ˜284.4 eV, sp 3  C—C at ˜285.5 eV) and (2) carbon-oxygen (C—OH, C═O, COOH, higher than 286 eV) to determine the oxidation of MWCNT. Although a major peak increase higher than 286 eV was not evident in  FIG.  6 E , the carbon oxidation to generate functional groups increased approximately by 8% from the peak analysis (Table 1). 
       FIG.  6 F  is a graph of Raman analyses of MWCNT and MWCNT- E. coli  films for the treatments in  FIGS.  6 A- 6 D . The partial (8%) disruption of MWCNT during the porous film fabrication process using  E. coli  was further supported by the similar peak intensity ratio between I G  and I D  in Raman spectra. The D band is known to be attributed to the amorphous carbon of CNT while G band intensity originates from in-plane tangential carbon-carbon stretching bonds. The I G /I D  ratio varies from 1.203 to 1.255 but the changes are minor during the porous film fabrication process, matching the 8% of carbon bonds changes from XPS results. 
     Table 1 below is a table of the XPS and Raman analyses of  FIGS.  6 E and  6 F . 
     
       
         
           
               
               
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                   
                 XPS 
                 Raman 
               
            
           
           
               
               
               
               
               
            
               
                   
                 C═C &amp; C—C 
                 G-band 
                 D-band 
                 I G /I D   
               
               
                 Sample 
                 Concentration (%) 
                 (cm −1 ) 
                 (cm −1 ) 
                 ratio 
               
               
                   
               
               
                 MWCNT film 
                 88.07 
                 1586.88 
                 1342.37 
                 1.239 
               
               
                 E-MWCNT film 
                 84.52 
                 1586.46 
                 1350.27 
                 1.255 
               
               
                 E-MWCNT film  
                 83.51 
                 1586.90 
                 1346.79 
                 1.203 
               
               
                 (bleach treated) 
                   
                   
                   
                   
               
               
                 E-MWCNT film  
                 80.4  
                 1581.32 
                 1347.44 
                 1.253 
               
               
                 (bleach + hest treated) 
               
               
                   
               
            
           
         
       
     
     Example 3: Porosity and Pore Shape Control 
     In some examples, porosity and pore shape in porous matrix structures may be controlled through selection and concentration of microorganisms.  FIGS.  7 A- 7 D  are exemplary SEM images of MWCNT films with different pore shapes and porosities.  FIG.  7 A  is a SEM image of a compact MWCNT film.  FIG.  7 B  is a SEM image of an MWCNT- S. epi  film having spherical pores.  FIG.  7 C  is a SEM image of an MWCNT- E. coli  film having cylindrical pores at a first concentration.  FIG.  7 D  is a SEM image of MWCNT- E. coli  film having cylindrical pores at a second concentration. In contrast to the compact MWCNT film of  FIG.  7 A , microscale pores were generated with each cylindrical and spherical shapes as can be seen from  FIGS.  7 C / 7 D and  7 B, respectively, by using cylindrical (named  E. coli  in this work, Serotype O6, Biotype 1  E. Coli ; available under the tradename ATCC 25922 from ATCC) and spherical (named  S. epi  in this work,  Staphylococcus epidermis ; available under the tradename ATCC 358914 from ATCC) shape bacteria as pore templates. In addition, pore volumes (porosity) can be controlled by adjusting the input amount of microorganism used during the fabrication process. The cell amount added was controlled by measuring the optical density (OD) of culture solution at 600 nm with UV spectroscopy. The pore populations in MWCNT film were varied by controlling the  E. coli  amount, such as ˜2.76×10 10  cells for  FIG.  7 C , and ˜8.19×10 10  cells for  FIG.  7 D . 
     Example 4: Application of Porous MWCNT- E. coli  Films for Li—O 2  Battery Cathodes 
     In some examples, porous films with pores formed by microorganisms may be used for electronics applications. FIGS. 8A- 8 F are exemplary SEM images of a MWCNT film and a MWCNT- E. coli  film after battery discharge. MWCNT films ( FIGS.  8 A- 8 C ) and MWCNT- E. coli  films ( FIGS.  8 D- 8 F ) were applied as free-standing binder-free cathodes to utilize their porous 3D structures for Li-oxygen batteries. Since the interconnected porous structure may promote the supply of reactants throughout the cathode thickness, homogeneous distribution of discharge products (Li 2 O 2 ) was observed after Li-oxygen battery discharge. To make an observation of Li 2 O 2  after discharge, toroidal growth of Li 2 O 2  was investigated by using electrolytes with 4000 ppm of HO in 1 M LiTFSI (lithium bis(trifluoromethane sulfonyl) amide)/DME (1,2-Dimethoxyethane) (available from BASF Corp.). While the toroidal Li 2 Oz was only observed on the surface of MWCNT electrode film as seen in  FIGS.  81  and  8 C , E-MWCNT electrodes showed homogeneous distributions of toroidal Li 2 O 2  throughout their thickness after discharge as seen in  FIGS.  8 E and  8 F . 
       FIG.  9 A  is a galvanic cycle profile graph of the MWCNT and MWCNT- E. coli  films of  FIGS.  8 A- 8 F . The better utilization of electrodes also contributed to decrease the overpotential during battery cycling as can be seen from  FIG.  9 A . In a given operation potential window maintaining electrolyte stability (2.2-4.5 V vs. Li/Li +1 ), E-MWCNT electrodes achieved 93.5% of coulombic efficiency while MWCNT electrodes showed only 54.25%. This poor recharging ability of MWCNT electrodes also presented lowered oxygen recovery ratio, 41.83% (ratio between the number of oxygen gas moles created during charging and oxygen gas used during discharge, (O 2 ) OER /n(O 2 ) ORR , %) measured by differential electrochemical mass spectrometry (DEMS).  FIG.  9 B  is a graph of oxygen recovery ratio of the MWCNT- E. coli -based electrodes with different porosities. By adjusting the porosity to achieve maximum oxygen recovery ratio, E-MWCNT electrodes showed 70.56% of recovery efficiency in a Li-oxygen battery, as seen in  FIG.  9 B . 
     Various examples have been described. These and other examples are within the scope of the following claims.