Biotemplates and Their Uses in Nanomaterials …paper.uscip.us/ajbebt/ajbebt.2016.1001.pdfand the...

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Columbia International Publishing American Journal of Bioengineering and Biotechnology (2016) Vol. 2 No. 1 pp. 1-14 doi:10.7726/ajbebt.2016.1001

Review

__________________________________________________________________________________________________________________ *Corresponding e-mail: [email protected] 1 Manav Rachna International University, Faridabad-121004, India

Biotemplates and Their Uses in Nanomaterials Synthesis: A Review

Varsha Singh1 and S.K.Chakarvarti1* Received: 09 September 2015; Published online: 25 June 2016 © The author(s) 2016. Published with open access at www.uscip.us

Abstract: Nature has provided great sophisticated highly ordered nanostructures. Such ordered

hierarchical structures are not easy to fabricate through highly advanced technologies or

methodologies present. So researchers have interest in exploring natural biological materials

which are not only responsible for creating exact replica of their highly ordered morphologies but

also provide nanomaterials with improved properties like controlled size, crysallinity and their

surface chemistry. This review article presents overview on biotemplates whose well defined

architectures and organizations are useful for synthesizing nanomaterials of different dimensions.

This review emphasis on the biotemplates explored to date in terms of their origin and structure

and the methodologies used for the synthesis of nanostructures.

Keywords: Biotemplates; Nanostructures; Architectures

1. Introduction

Recently, low dimensional structures have grabbed special attention due to their excellent physical

and chemical properties which leads to potential applications as compared to bulk materials. For

examples, in the fields like catalysis (MgO), medicine, electronics, ceramics, pigments, sensors and

cosmetics.. Dong Q. et al had shown the use of SnO2 in photovoltaic devices and transparent

conductive electrodes. Black et al. (2002) have done his work on Bismuth nanowires to show

improved optical properties due to increase in optical non linearity by decreasing particle size.

At present there are variety of techniques under the approaches i.e. top down and bottom up which

are used for the synthesis of low dimension structures. Though these techniques are highly advance

Varsha Singh and S.K.Chakarvarti / American Journal of Bioengineering and Biotechnology (2016) Vol. 2 No. 1 pp. 1-14

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but they too suffer in the criteria of controlling size, crystallity of the materials to be synthesized at

low scale. Therefore it is important to develop facile and green technologies in nanomaterials

synthesis. In the past few years, there are many reports on the synthesis of inorganic materials

using biological systems. In this review, first of all, we shall provide a brief overview of some of the

techniques under top down and bottom up approaches and then development taking place in the

field of biotemplating approaches.

1.1 Top-Down Approach

This approach includes mechanical attrition, Lithography based techniques, aerosol based

synthesis and STM based synthesis. This approach generally works on two parameters, first is

creating nanostructures by “sculpting” method. It includes etching (dry or wet), mechanical

attrition, lithography techniques which remove the undesired material to bring in desired shape.

The non equilibrium Mechanical Attrition process helps in creating non crystalline alloys, ceramics,

composites nanostructures by milling tools. Here contamination by mechanical tools (eg Fe) mostly

occurs which can be removed by minimizing the milling time and using the purest, most ductile

metal powder. Another technique Lithograpy is the cost effective and faster technique in which,

with the help of different types of radiation sources like photons, X-rays, electrons, ions, patterns

are transferred on to their respective resists. Ito and Okazaki, 2000 had created nano structures

with size below 70 nm by photo lithography. Spears and Smith (1972) had created 25 nm

nanostructures by X-Ray lithography. Vieu et al. (2000) and Yesin et al. (2001) by using electron

beam as radiation source to fabricate features as small as 3 nm - 5 nm.

However second parameter create nanostructures by adding or rearranging desired material on

substrate which include Aerosol based synthesis, Scanning Tunneling Microscope (STM),

Microprinting, Nanoimprint Lithography. Visca & Matijevic (1978) and Partch et al (1983) had used

these techniques for the preparation of TiO2 and polymer colloids respectively. Here liquid

precursor made of desired constituent elements is used to make a liquid aerosol, which gets solidify

by evaporation solvent through it. It results in the formation of spherical particles and their size is

determined by liquid droplet size and concentration of solid. The non optical microscopy technique

aligns the individual atoms to particular desired patterns through tunneling principle. Nanodots,

nanolines and corrals of gold on Si had been fabricated by Hu et al (1999) through this technique.

Patterned structures are of ultrahigh sub nanometer precision are made. In case of Microcontact

printing technique, in which the desired patterns on PDMS stamps are transferred on substrate

through conformal contact. Whereas Nanoimprint lithography is a low cost, high throughput and

high resolution process which create patterns of imprint resist on the template with the help of

mechanical deformation.

1.2 Bottom-Up

It is a method where simple atomic level components are combined to build the desired patterns.

Here the atoms or molecules get self assembled into nanostructures. This approach generally

includes target-substrate based synthesis which includes template substrates and is chemically or


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topologically patterned. These patterns are effective in directing the process of nucleation and

growth of nanostructures. Such methods are highly precise in sizes, shapes and structures.

Techniques like Chemical Vapors Deposition, Sputtering, Epitaxy, Evaporation-Condensation

Process etc. are the best suited examples of target-substrate based synthesis. Mercury whiskers or

nanowires with diameters of 200 nm SnO2 nanorods were fabricated by Sean (1955) and Liu et al.

(2001) respectively by evaporation and Condensation process.

The bottom-up approach offers a better choice than the top-down approach as the later approach

results in imperfections on the surface structure that in turn would have a significant impact on the

physical properties and the surface chemistry of the nanostructures and the nanomaterials.

Another alternative parallel approach that is emerging for bottom up synthesis of nano structured

materials is the use templates. These templates can be artificial (non-biological) or of biological

origin.

1.3 Templates

Despite of the presence of hi-tech conventional techniques discussed, they are facing certain

drawbacks and problems. Therefore there is a need of alternate approach which is inexpensive,

highly precise, robust ad easily handled and which have high effienciency too. This article will

discuss that alternative approach and its beauty of art and simplicity: Template. A template is a

pattern or mould which fabricate structures same as their morphology and topology. This simple

but innovative technique is used for the production of nanomaterials of different classes like metals,

non metals, semiconductors, glasses, polymers, wires and whiskers of varying dimensions.

Depending on the mode of template based synthesis Ozin et al (1992), it may be classified into three

categories i.e. Negative Template Method, Positive Template Method and Surface Step Edge

Template Method. Among all the three categories mentioned, Negative template Synthesis is highly

popular. Here template pores are filled and deposited with the desired materials through generally

electrochemical techniques and after dissolving or removing the pattern, free standing photocopy

of template like structures in the form of wires, whiskers, cylinders can be obtained. Nanomaterials

produced are the exact replication of topology and morphology of template pores. Materials used

for the making templates can be polymeric foils, mica, glasses etc. In Positive Template Method, the

material of desired dimensions is deposited on the outer surface of wire like template structures

(DNA, CNTs) (Sfullam et al., 2000). It results in wire /tube like structures after removing template.

The surface step-edge templates include selective deposition of the materials on the defect sites of

the subsrate. Zach et al. (2000) and Bera et al. (2004) used this technique for generating conductive

metal oxide (MoOx) at the step edges of HOPG, which after reduction in appropriate environment

yields metallic Mo nanowires.

Apart from various examples of artificial inorganic templates, author is going to describe natural

template which are organic and biological in nature and called as bio templates. These Biotemplates

offer the advantage of having highly ordered morphology and well defined architectures and

organizations and result in much better desired properties of nanomaterials fabricated. There are


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many classes of Biotemplates for example: bacteria, textiles/paper, hair cells insect wings, spider

silk, wool and wood. However among the various structure have been reported, only few have

shown technological interest briefly discussed. Butterfly wings are used to produce nanostructures

having improved optical properties and are used for the applications of photonic sensors as

compared to artificial photonic sensors. Butterfly wings are made of large number of microscopic

scales consist of more than two layers separated by air. Now these layers of thousand of scales are

responsible for multiple reflection of light. The reflectance spectrum covers whole visible range but

reduces at ultraviolet range. Wings with highly précised morphology in the form of aligned lamella

create their exact copy along with the improved optical properties. Wang et al (2014) have used

butterfly wings as a quasi-periodic structures which act as resonance cavities to work like

optoelecronic devices (here they work as a laser with random lasing). Authors impregnate ZnO

nanoparticles of range 200-400nm into the butterfly wings and act as emitting gain media. Similarly

Zhang et al (2008) have used butterfly wing scales for the purpose of dye-sensitized solar cell by

synthesizing Titania photoanodes. Zhang et al (2006) fabricated nanotubules of ZnO structures and

Huang et al (2006) have fabricated Al2O3 coating through butterfly wings, such structures have

found profound applications in photonic devices.

Similarly Diatoms are unicellular photosynthetic micro organisms having silical cell walls. Their cell

walls have unique nanostructured patterns in the form of rod, hexagonal or circle depending on the

species used. These patterned diatoms produce nanoparticles of exact replica in their surface

morphology and shape. Payne et al (2005) have developed Metal coated nanoparticles and have

found potential applications in surface enhanced Raman spectroscopy. On the other hand different

species of bacteria are responsible for creating varying dimensional nanostructures. For example,

Zhou et al (2007) had successfully created ZnS hollow spheres and hollow nanotubes had been

sculpted from bacterial threads of Lactobacillus sprectococcus thermophilus and Lactobacillus

bulgarius respectively. Si particles when mounted on bacterial threads results in the formation of

silica threads, when bacterial flagella are removed, organized array of 0.5um wide channels had

obtained. Similarly Mogul et al (2005) prepared Ni nanoparticles by E.coli and Rhodosprilium

rubrum.The most attractive class of bio templates are various species of virus. For example class of

Tobacco Mosaic Viruses has viral capsids of repeated patterns of charged Amino Acids. They are

used to produce wide varieties of nanoparticles like CdS, PbS, FeO of varying diameters from 4nm

to 22 nm as done by shenton et al 1999.

2. Aim and Scope of Review

This review is written with the aim to provide readers an idea of how naturally occurring templates

are used for the fabrication of highly organized nanostructures in varying dimensions. Use of

resulting nanostructures as important components in various fields of sensors, optoelectronics

devices, catalytic systems etc. this review focuses on those bio templates which are of technical

interest and not yet covered in this review. So far we have overviewed how butterfly wings,

diatoms, bacteria virus act as biotemplates and result in highly hierarchical and ordered

architectural nanostructures , but this review features on how plant products like cotton can act as


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a Biotemplates, wood tissues (hard and soft ) as a biotemplates and various commonly available

vegetable skins(onion) as a Biotemplates.

2.1 Cotton

Cotton provides more uniform morphology in the category of plant fibers. They are natural fiber

arranged in the twisted ribbon morphology. They have cellulose as a main body content of

approximately 88-96 wt%. They are highly cheap and stable biotemplates and easily available. See

fig 1(a) which consist of SEM image depicting morphology of cotton fibers. Many researchers

around the world are working on cotton as a biotemplate. Peng et al (2010) were successfully

synthesized bimorphic LaFeO3 hollow fibers with inner diameters ranging from 4-10 µm with

porous wall. Prepared bimorphic LaFeO3 have improved gas sensing potential because they have

highly porous walls with increased active surface area and gas diffusion through porous wall.

According to the SEM investigation, prepared LaFeO3 fibers are hollow in nature and of high

porosity at walls, the fibers are very long and hollow which retain the cotton fiber morphology.

Yuan Chun et al (2008) produced biomorphic nanocrystal- assembled mesoporous magnesium

oxide by negative template synthesis of cotton fibers and magnesium acetate as MgO precursor

material. Cotton morphology had been replicated in MgO material which results in high surface

area and high selectivity in the catalytic decomposition of alcohols. MgO formed as narrow slit-like

mesoporous structures see fig 1(b). However it was observed that increasing MgO precursor

dosage leads to larger particle size with decreasing adsorption amount.

Fig.1. SEM image of (a) cotton fibers, (b) MgO nanofibers*, (c) biomorphic Al2O3 fibers sintered at

800ºC Ʈ

* Reprinted with permission from Yuan Chun et al (2008)

Ʈ Adapted from Di Zang et al (2005)

When Di Zang et al (2005) replicated morphology of cotton fibers in the form of biomorphic Al2O3

fibers, they observed that crystallinity increased after 800ºC and at 1000ºC γAl2O3 is completely

converted to α Al2O3 as confirmed by SEM images. See fig 1(c).SEM investigated that Al2O3 fibers are

hollow in nature with inner diameter 2um-5um.In both the above mentioned case the fibers

fabricated were in hollow in nature , it may be due to the fact of wetting characteristics of cotton

fibers at the time of impregnation. Therefore solutes are distributed on the outer surface of cotton.

2.2 Sorghum Straw

It is easily available agricultural waste which is abundant and inexpensive and whose structure


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looks like Honeycomb (fig 4(a). Peng Song et al (2014) had worked on this bio template for the

synthesis biomorphic porous LaFeO3. After analysis through scanning electron microscope (SEM),

transmission electron microscope (TEM), see fig: 2(a, b & c) that it is porous and honeycomb like

network framework. Particles have the average size of about nm with plenty of voids between the

nanocrysallites. Gas sensing investigation showed that the sensor based on biomorphic porous

LaFeO3exhibited higher response to acetone gas compared with that of bulk LaFeO3 particles. The

enh0ancement in gas sensing properties was attributed to their porous structure, large surface

areas, numerous surface active sites and more oxygen vacancies.

Fig. 2. (a&b) FESEM images of biomorphic porous LaFeO3. (c)TEM images of biomorphic porous

LaFeO3.

Adapted from Peng Song et al (2014)

2.3 Wood Wood is the excellent candidate of biotemplate if compared from other biotemplate classes available in the nature. It is due to the fact of its diverse species and hierarchically porous structures, large macroscopic scale, large quantity renewability and low cost. Woods as a template can be used to synthesis of porous ceramics and oxides. The hierarchy of wood is composed of mm scale of growth ring and vessel pore, a µm scale of transverse ray parenchyma, longitudinal tracheid and fiber, and nm scale of molecular fiber and cell membrane. Their three-dimensional porous structures with high porosity and network connectivity are known to help ceramics to increase the gas sensitivity and selectivity due to multi-functional combination from hierarchical pores. Di Zhang et al (2008) had successfully synthesized porous ZnO by using Lauan wood (hard wood template having small cells of diameter 5-10µm and large diameter of 15-20µm) and Fir wood (soft wood template with tubular tracheid cells) via hydrothermal method i.e. Zn ions get adsorbed by cell walls from its precursor bulk solution. The adsorption process take place through capillary action and the adsorbed Zn ions get deposited in the homogeneous fashion on the cell walls. ZnO obtained after burning out of wood’s component at higher temperature are exact replica of the porous hierarchical framework and highly ordered morphology of both the wood. ZnO fabricated is porous in nature which has remarkable application as gas sensors. Wood template ZnO had been revealed high in selectivity and sensitivity (5.1 times higher than non-templated ZnO) to H2S gas more than other gases like H2, CO, NH3, Formaldehyde, Methanol, Ethanol, Acetone and Isobutane gases see fig :4. it is justified from the figure that out of all the gases used for test , all three ZnO sensors (Fir- Templated ZnO, Lauan-Templated ZnO and Non-Templated ZnO)exhibit highest reposnse to H2S gas, very little response to Acetone, Ethanol and Methanol and all most no response to H2, CO, NH3, Formaldehyde and Isobutane. It is due to the fact that unsaturated surface atoms of ZnO can easily combine with the H and S atoms to reduce the surface energy while the reaction with the other gases may be not spontaneous or not easily reacted. In comparison of the sensing and selectivity coefficients with respect to H2S, Fir-templated ZnO calcined at 600ºC is proved better.


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Fig. 3. FESEM images of cross sections of carbonized wood pyrolyzed at 600 ◦C for 2 h in vacuum

condition and wood-templated bulk ZnO samples calcined at 600 ◦C in air:(a) carbonized Fir; (b) Fir-templated ZnO; (c) carbonized Lauan; (d) Lauan-templated ZnO.

Reprinted with permission from Di Zhang et al (2008)

Fig. 4. Gas sensing response of ZnO calcined at 600◦C with different templates at the working

temperature of 332 ◦C. Reprinted with permission from Di Zhang et al (2008)


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2.4 Onion

Inner squama layer of onion is very useful for the synthesis of various nanomaterials whether

metallic or semiconducting. It is a simple method of synthesis which is useful for the production of

heavy metals like Ag2S, CdS and PbS with diameter distribution in the range of 10-20 nm for Ag2S,

85-100 nm for CdS and 7-10 nm for PbS see fig: 5 as done by Chen P. et al (2008) and Similarly

SrCrO4 nanostructures in different shapes and sizes were fabricated and assembled through onion

inner layer. Chen P. et al (2009).These materials were explored for their excellent optical

properties. SrCrO4 nanostructures exhibit a broad, strong optical absorption in the region of UV-

visible light and it vary with varying size and shapes by transmission electron microscope, powder

X-ray diffraction, UV-Vis spectroscopy and luminescence spectrophotometer. A possible formation

mechanism was also proposed. In the preparation, the SrCrO4 nanostructures were synthesized at

room temperature without any surfactants. This new bio-template method will have potential

applications in preparation of the nanoscale materials with different morphologies.

Fig. 5. The TEM micrograph of Ag2Snanoparticles (a), CdS hollow nanoparticles (b) and PbS nanoparticles. Reprinted with permission from Chen P. et al (2008)

2.5 Egg Shell Membrane

Nature contains abundance of biominerals in the form of inorganic composites and organic

materials. These biominerals are in a highly organized form with fascinating shapes and structures

by H.A. Lowenstam. Among the biominerals, Egg shell membrane (ESM) is a plentiful industrial

waste biomateral. Structure of ESM is explained in the diagram fig: 6 which were used for the

synthesis of SnO2 nanoparticles by Di Zhang et al (2006) due to special protein structure and

functional groups. Synthesis took place via soaking technique followed by calcinations treatment at

400ºC, 550ºC and 800ºC.XRD patterns see fig:6 revealed that before 400 ºC template hybrid is

mainly amorphous or little crystallization occurs and at 800ºC, peaks of tetragonal SnO2 intensify

sharply whereas at 550ºC diffraction peaks are fairly broad. R.Camaratta et al (2013) had

developed TiO2 crystals which were grown with the help of ESM membrane.TiO2 is an excellent

material for the photocatalyic applications and can be used for energy generation systems. Here

TiO2 powder was used in dye-sensitized solar cells.


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Fig. 6. Typical eggshell structure.

Adapted from T. Maxwell et al 2012

Proper crystallite sizes had an average of about 5.2nm. These prepared nanoparticles were then

assembled into tubular fibers and then into an array for retention of morphology of Egg Shell

membrane and it and been confirmed by SEM images. See fig: 7

Fig. 7. SEM images of (a) SnO2 at 800C* and (b)TiO2 at 800C Ʈ

*Adapted from Di Zhang et al (2006)

Ʈ Reprinted with permission from R.Camaratta et al (2013)

2.6 Grapefruit

Fig. 8. TEM images (a) and high magnification TEM images (b) of the biomorphicSnO2: insets of (a)

showing the corresponding SAED patterns, and insets of (b) displaying the corresponding

magnified section. Reprinted with permission from C.Zhang et al (2015).

C.Zhang et al (2015) have used grapefruit exocarp as a Biotemplate for the synthesis of porous

hierarchical SnO2. Here exocarp of grapefruit was separated and after the ultrasonification and


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calcination treatment, it was used as a Biotemplate. Developed SnO2 were used as semiconductor

metal oxide sensor for formaldehyde gas sensing. Bimorphic SnO2 have average size of about 10nm

which can be verified from TEM images, see fig :8.

3. Summary

Generally different structures obtained by using different types of biotemplates discussed above

are porous in nature. All are exact replicas of their respective biotemplates in the form of their

morphology and structures. We did deep study of XRD patterns (refer table 1) of all the

nanostructures as well as specific surface area on the basis of BET theory (refer table 2):

Table 1 Average crystallite sizes of various nanostructures formed by using above described

biomembranes.

* means µm

S.No. Biotemplate used

Sample prepared XRD based crystallite size in nm

1 Cotton

LaFeO3

20.04 - 36.18 Peng et al (2010)

MgO 12 – 18 Yuan Chun et al (2008)

Al2O3

56 Di Zang et al (2005)

2 Sorghum LaFeO3

20-30 Peng Song et al (2014)

3 Fir wood

ZnO

15.6 - 41.7 Di Zhang et al (2008)

Lauan wood 18.9 Di Zhang et al (2008)

4 Onion Ag2S 10-20 Chen P. et al (2008)

CdS 85-100 Chen P. et al (2008)

PbS 7 – 10 Chen P. et al (2008)

SrCrO4(nanorods) 0⋅70–2* (length),80–180 (width)

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Egg Shell Membrane (ESM)

SnO2 2.8-5.2 Di Zhang et al (2006)

TiO2 15.82-86.02 R.Camaratta et al (2013)

6 Grapefruit SnO2

10 C.Zhang et al (2015)


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Table 2 Various types of BET Isotherms of Various nanostructures formed by using above

described biotemplates.

By studying the different types of BET isotherms we can say that nanomaterials having type IV and

type V have better adsorption capacity. Such materials have mesoporous structure. It results in high

porous volumes. Therefore such materials are excellent for gas sensing purpose. It happens due to

condensation of gases in the tiny capillary pores of adsorbent at pressure below the saturation

pressure of the gas. Whereas in Langmuir type of isotherm, adsorption takes place at low pressure

only thus results in weak adsorption properties. Nanomaterials having Type II isotherm s have high

surface area exhibit high selectivity in the catalytic decomposition, hence can act as a effective

catalysts.

4. Conclusion

Biotemplating when compared with parallel current techniques like Electron Beam Lithography, X-

Ray Lithography is proved to be more time and cost effective. This technique result in

S.No. Biotemplate used

Sample prepared

BET Isotherm type

1 Cotton LaFeO3

Type-IV Peng et al (2010)

MgO type-II Yuan Chun et al (2008)

Al2O3

Langmuir Type Di Zang et al (2005)

2 Sorghum

LaFeO3

Type-IV Peng Song et al (2014)

3 Fir wood

ZnO

Type-IV Di Zhang e al (2008)

Lauan wood

Type-IV Di Zhang et al (2008)

4 Onion Ag2S -

CdS -

PbS -

SrCrO4

(nanorods) -

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Egg Shell Membrane (ESM)

SnO2

Type-IV

Di Zhang et al (2006)

TiO2

Type-V

R.Camaratta et al (2013)

6 Grapefruit SnO2 Type IV C.Zhang et al (2015)


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nanostructures of dimensions <100nm and morphologies is much better than conventional

lithography/ etching techniques. On the basis of above mentioned reports, Biotemplate methods

are superior in selectivity and sensitivity over the existing techniques.

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