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Application of phenolic compounds in plants for green chemical materials

Hisako Okumura

PII: S2452-2236(20)30115-2
DOI: https://doi.org/10.1016/j.cogsc.2020.100418
Reference: COGSC 100418

To appear in: Current Opinion in Green and Sustainable Chemistry

Received Date: 15 April 2020

Revised Date: 12 November 2020
Accepted Date: 13 November 2020

Please cite this article as: H. Okumura, Application of phenolic compounds in plants for green
chemical materials, Current Opinion in Green and Sustainable Chemistry, https://doi.org/10.1016/
j.cogsc.2020.100418.

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Graphical Abstract

Application of phenolic compounds in plants for green chemical materials

Hisako Okumura1

Address

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1
Department of Materials Engineering, National Institute of Technology, Nagaoka College, 888

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Nishikatakai-Machi, Nagaoka 940-8532, Japan

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* Corresponding author: Hisako Okumura (okumura@nagaoka-ac.ac.jp)
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Title Page

Application of phenolic compounds in plants for green chemical materials

Hisako Okumura1

Address
1
Department of Materials Engineering, National Institute of Technology, Nagaoka College,
888 Nishikatakai-Machi, Nagaoka 940-8532, Japan

* Corresponding author: Hisako Okumura (okumura@nagaoka-ct.ac.jp)

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ORCID ID

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Hisako Okumura
ORCID ID: https://orcid.org/0000-0002-6586-0410
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Abstract
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Effective biomass utilization for the generation of functional molecules used for green
materials is paramount for the realization of a sustainable society. In the present review,
phenolic compounds derived from plants represent significant resources for green
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technologies of adsorbents and future tools. Since existing phenolic compounds are
distributed worldwide, namely condensed tannins and hydrolysable tannic acid. In particular,
recent studies on their interactions with metal ions are summarized and analyzed for the
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utilization of adsorbents. In addition, the preparation methods of adsorbents and

recovery/separation agents were outlined for the removal of hazardous, radioactive, precious,
and rare metals along with their performance. Finally, self-assembly technology the emerging
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metal-polyphenol network (MPN) was described as well as the research and development of
new electronic devices were also discussed.

Keywords

phenolic compounds
polyphenol
tannin
tannic acid
metal ion

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Introduction

A great number of phenolic compounds, polyphenols, is present in plants and possesses

molecular weights ranging from approximately hundred to several thousands. Polyphenols are
believed to originate to protect the constituents and exist in a form of bark, branches, stems,
leaves, flowers, seeds, and fruits. This is due to external threats by ultraviolet ray, insects and
animals, and for adaptability to segments of the climate. While living in harmony with plants,
humans have developed methods for a long term and technologies of extracting phenolic
compounds from plants and using them for different purposes. In the past, humans used
tannins for leather production, sedimentation during brewing, rust inhibition, as well as
Chinese herbal medicines. Nowadays, various types of phenolic compounds are used in a
wide range of fields of food [1,2], pharmaceuticals [2–4], biomaterials [5,6], and
environmental purification [7–10].
With regard to their chemical structures, polyphenols share a common functional group

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consisting of two or more phenolic hydroxyl groups. For applications of plant-derived
phenolic compounds as materials, it is crucial to suitably exploit either the chemical

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properties of the original structures or those of modified tannins. Plant phenolic compounds
account for 40% of the organic carbon circulating in the biosphere and have great practical
value in sustainable green chemical processes. For example, when recovering rare metals or
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harmful metals in the environment, it is possible to save fossil resources such as oil and
natural gas, if people can utilize plant raw materials instead of plastic. After adsorption
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operation, the target metal can be easily separated by burning the adsorbent instead of eluting
with organic solvents to be desorbed. Also, the advantage is to reduce unnecessary CO2
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emissions contributing with green technology and the processes. Among them, this review
highlights recent topics in their condensed and hydrolysable tannin derivatives. The
condensed tannins and hydrolysable tannic acid chemically consisting of many densely
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packed phenols comprising aromatic rings and hydroxyl groups are focused on their
interactions with metal ions, adsorption phenomena, and recovery/separation. Also, the
methods converting their structure and shape, and self-assembled network formation [11] are
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described in addition with their recent applications for the field of green chemistry.
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Characteristics of condensed or hydrolysable tannins, and polymerization

There are many kinds of tannins depending on the substituted position and the polymerization
degree as followed. They are roughly classified into condensed tannins and hydrolysable
tannins based on their structures with different chemical bond. Typical structures are shown
in Figure 1. Condensed tannins derived from polyhydroxy-flavan-3-ol oligomers are linked
by C-C bonds between the A rings of the flavanol units and the pyran at the positions of C-
4/C-8 or C-4/C-6. The condensed tannins are present in a wide variety of plants, including
ferns, gymnosperms, and angiosperms. The structure shown in Figure 1 is a persimmon
tannin with approximately 12 to 30 catechin units linked together. Similar condensed tannins
are also extracted from mimosa, quebracho, pine bark, and grape skin and seeds. Most of the
industrially produced tannins are condensed tannins. Hydrolysable tannins are polyesters of
gallic acid or its metabolites with glucose and polyhydric alcohols, and such tannin was found
in angiosperms (choripetalae) extracted from pomegranate skin, alder leaves and walnut. It is
easy to hydrolyze by acids and enzymes for the tannins. Those are classified into gallotannins
to produce only sugar and gallic acid, or ellagitannins to produce ellagic acid.
As common properties, most tannins are water soluble. Thus, insolubilization is required with
some chemical treatments for adsorbent, which are processes of cross-linking by chemical
reagents, oxidative polymerization, and immobilization on carrier matrix (Figure 2, Table 1).
In the chemical structure of tannin, high functionality part capturing metal ions results from a
large number of hydroxyl groups bonded to the aromatic ring. The chemical bonds are formed

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between the non-substituted carbons of the aromatic ring to maintain the functional site.
Through these treatment processes, the polymerized tannin becomes insoluble.

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Figure 1. Chemical Structure of condensed tannin (persimmon tannin) and hydrolysable
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tannic acid (commercially available tannic acid). Photographs inserted are

corresponding to persimmon tannin (left) and tannic acid (right).
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Figure 2. Polymerization and adsorption process of condensed tannin and

hydrolysable tannic acid.

Adsorption recovery and separation for various metals

Among conservation technologies against hazardous metals pollution, using plant biomass
having the abundant of OH groups like tannins or tannic acid mainly operated through the
formation of a metal ion-polyphenol complex. In particular, electrostatic driving force in the

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complex is caused by the electronegative oxygen atoms of adjacent OH (orthodihydroxyl)
groups and positively changed metal ions. In order to selectively capturing for specific metal
ions from multiple metal mixture, the choice of tannin raw material, chemical modification,
and insolubilization method is important. Behaviors for pH, redox potential, and donor
property in the solution differ in each case and depend on the structural characteristics of the
adsorbent prepared. The selective adsorption desorption of metal ions can be achieved under
the appropriate conditions with polymerization and oxidation (Figure 2). The followings are
recent examples of crosslinking adsorbent preparations of tannin adsorbents. There are many
reports on metal elements such as chromium and lead as recovery targets, and much efforts
are currently devoted to the improvement of the recovery rates, process convenience and
economy, reduction of the environmental impact as well as preparation costs and safety. As
shown in Figure 2, Liu et al. achieved over 90% efficiency in the adsorption of Cr(VI) with
adsorbent prepared by cross-linking tannic acid with cheap hexamethylenediamine by simple
treatment [12]. The adsorbent could be prepared by adding hexamethylenediamine to an
aqueous oxidized tannic acid, and kept in the mixture at room temperature for 48 h. The
cross-linking of tannic acid was based on a network formation due to the introduction of C-N

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covalent bonds at the unsubstituted sites of the tannic benzene rings. A similar research was
reported by Zhang et al. using tetraethylenepentamine and acrylamide [13]. Such adsorbent

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was obtained as a composite material with reduced graphene oxide. The maximum adsorption
was approximately 200-300 mg/g per operation. For Cr(VI), the captured ion on the
adsorbents in the form of negative ions was partly reduced to Cr(III) by donating electrons
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from the hydroxyl group of tannic acid with non-toxic form. Although additional chemicals
are required, the simple preparation process at one pot is industrially advantageous.
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On the other hand, the utilization of water-soluble tannins required making them insoluble. A
commonly supported material used was cellulose. Ying et al. chemically synthesized
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cellulose microspheres for the condensed tannins, deriving from the fruits of Areca catechu
and applied for Pb(II) ion recovery [14]. The obtained adsorbent had porous spheres
containing tannins and could be expected to be easily extended to further composite materials.
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Composite materials made of zirconium and tannic acid was applied for the selective Pb(II)
ion recovery from aqueous solutions in multiple heavy metal ions [15]. The selectivity was
due to their very stable interaction with the hydroxyl groups of tannic acid. Tannic acid
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adsorbents possessing magnetic were developed and allowed for an enhanced recovery and
efficiency [16,17]. This exhibited higher adsorption capacities than gelous or resins types of
adsorbents, owing to their porosity and increased surface area, along with a higher selectivity
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and recyclability. Therefore, the use of magnetic nanoparticles of tannin composites may be
considered advantageous [18].
Tannin-based materials were used for treatments of radioactive wastewater from nuclear
power plants and recovery of nuclear fuel resources from oceans. At the recovery of
radionuclides such as 137Cs, 232Th, and 238U, the tannin-based materials have been rapidly
attracting attention in the last ten years. Partly due to the impact of the Fukushima Daiichi
nuclear disaster, such wastewater treatment was required by the ability to simultaneously
adsorb many elements which could be treat with high volumes of wastewater. Tachibana et al.
synthesized an adsorbent by cross-linking sulfonated tannic acid with a commercially
available strongly basic anion exchange resin, are applied for multiple ions in seawater [19].
Bayberry tannin-collagen fibers incorporating Fe/Ni nanoparticles achieved the adsorption
and reduction of U(VI) with a fast recovery process [20]. In order to secure the retrieval of
nuclear fuel resources, it was crucial to develop a technology for the efficient recovery of
uranium from the oceans. Meng et al. achieved a high recovery of U(VI) from a diluted
aqueous solution using high-surface area gelatin/PVA nanofibers incorporating bayberry
tannins [21,22].
Relating with “urban mines” the recovery of precious and rare metals from these stockpiles is
important from a technological standpoint and in a major economic impact. Persimmon tannin
was pinned in viscose fibers and achieved high and selective recovery of Au(III), which was
reduced to Au(0) under acidic conditions [23]. Persimmon tannin was bonded to the fibers, as
earlier converted to aldehyde group by using a periodate oxidizing agent. Similar approach

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was appeared in corn starch, further confirming the adsorption and reduction of Au(III) [24].
Magnetic nanoparticles were also found to be effective for the recovery of the precious metal
Au, when the core-shell Fe3O4 nanoparticles was coated with persimmon tannin. This led
extremely high recovery of 917.43 mg/g for Au(III) without any loss of the magnetic
properties [25]. Kim et al. substantially improved the amount of Au(III) adsorbed by 6 times
as cover light irradiation was present of porous polymer spheres impregnated with tannic acid
[26]. The mechanism was explained as effective reduction of Au(III) under UV light by the
photooxidation of tannic acid and photodecomposition of AuCl4-, due to hot electrons
generated. Furthermore, supporting metal cations such as gold and silver on the surface of
material coated with polyphenols was used for various reduction catalysts [27,28].
On the other hand, securing supplies of rare metals is also a critical issue for countries
worldwide. For the efficient utilization of such limited resources on the earth. Bayberry tannin
was also studied for the recovery of uranium. On chitosan matrix with tannin three trivalent
rare earth metals were tested. In each case, the adsorption equilibrium was quickly reached
within 30 min with different adsorption capacity, performing with continuous adsorption tests
in columns (La3+ < Ce3+ < Nd3+) [29]. In addition, the selectivity of beryllium(II) was

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reported in the presence of graphene modified with tannic acid by using the solid phase
extraction method. The interference of Ag+ was observed due to its high affinity for tannic

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acid [30]. Additional studies were conducted on lanthanoid and erbium by Fe3O4/persimmon
tannin/oxidized graphene [31], as well as metalloids such as antimony and germanium [32,33].
Tannin had a wide range of applications for capturing metals from light to heavy atoms. As a
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study of simultaneous recovery of multiple metals, it was reported that 26 kinds of metals
were recovered using tannic acid-Zr(IV) gel powder from dilute aqueous solution. The results
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showed more than 99% recovery of each metal ions at pH 5 except for Zn(II), Cu(II), and
Ni(II) [34].
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Surface modification and application of polyphenol material

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In order to fully exploit the polyphenol functionality, the shape of the resulting material also
becomes a key factor as seen in membranes, plates, sheets, porous particles, nanoparticles,
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core-shells and capsules. Moreover, the transformation of polyphenols also served the
purpose of immobilization or insolubilization of water-solublely condensed tannins or
hydrolysable tannic acid. The composition and shape of the polyphenolic compound materials
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are summarized in Table 1. The surface coated with polyphenols became hydrophilic due to
the presence of many OH groups. The tannin coated membrane matrix often employed for the
separation of water and oil [35–39]. For practical uses, the coated membrane appeared
antifouling filtration process [35], durability [37], processing capacity and antifouling
properties [35,37–39], chlorine resistance [36], antibacterial properties [38], and simple
preparation methods [38,39]. In contrast, hydrophobic modifications of the material surface
with polyphenols was possible when either reactions to introduce hydrophobic groups or
further chemical reactions was performed [40–42]. In such case, many examples included the
bond formation between an aromatic ring and heteroatom like a Michael addition reaction of
nucleophilic compounds such as thiols and amines, or the formation of an iminoquinone from
a quinone oxo group and amino group by Schiff base reaction (Figure 3).

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 R1

O
N R
Schiff-base
R-NH2 R
R1 : H or OH NH
R1 R1 R1
R-NH2
oxidation Michael addition
OH O OH
o-quinone
OH O OH

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Galloyl group
R-SH Michael addition
or B-ring

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R
S
-p R1
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OH
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OH

Figure 3. Chemical modification of condensed tannin and hydrolysable tannic acid.

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In addition to chemical cross-linking, researchers focused tannin materials in recent years on

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the field of self-assembled metal-polyphenol networks (MPNs) formed physically [11,43–46].

In particular, fabrication of a hollow capsule [45] was formed in a Fe(III)-polyphenol MPN
on the polymer surface when a tea extract or tannic acid was used.
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Table 1. Composition and shape of materials using phenolic compounds discussed in this
report.
Phenolic Connection type with
Support material and reagents Shape Reference
Compounds support material
covalent C–O–C cellulose microspheres [14]

covalent bonds, Collagen / glutaraldehyde / Fe / Ni [20]

fiber
complexation nanoparticles

covalent C-C glutaraldehyde / collagen / PVA nanofiber band [21][22]

Condensed covalent C-C viscose fiber fiber [23]
Tannin
covalent C-C starch powder [24]
core-shell [25]
covalent C-C glutaraldehyde / Fe3O4@SiO2
microsphere
covalent C-C chitosan / glutaraldehyde unknown [29]
π-π interaction Fe3O4 / graphene oxide nanoparticle [31]

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 covalent C-C formaldehyde particles [32]
covalent C-N hexamethylendiamine powder [12]
[13]
tetrathylenepentamine /
covalent C-N, C=N,
polyacrylamide / reduced composite material
intermolecular forces
graphene oxide

self-assembly Zr powder [15]

unknown Ni0.6Fe2.4O4 nanoparticles [16]
azo-bridge, hydrogen [17]
Fe3O4@SiO2 porous polymer
bonds
formaldehyde / strongly basic [19]
covalent bonds porous particle resin
anion exchange resins

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deposition porous polymer porous microspheres [26]
unknown Fe3O4 particles [27]

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π-π interaction reduced graphene oxide composite material [30]

Hydrolysable
self-assembly
coordination
Zr(IV) -p
Ti(Ⅳ) / PVDF
powder
membrane
[34]
[35]
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Tannic acid
Coordination, [36]
Fe(Ⅳ) / polyamide / PVDF membrane
polymerization
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sulfonated N, N- [37]
covalent C-N, C=N membrane
diethylethylenediamine / PVDF
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intermolecular forces PVA / PVDF membrane [38]

covalent C-N, C=N dopamine / PVDF membrane [39]
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[40]
coordination, melamine / SiO2 / Ag+ /
sponge
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fluorination perfluorodecanethiol

covalent C-N, C=N aminopropyltriethoxysilane / [41]

fabric etc.
etc. polyethyleneimine etc.

covalent C-N, C=N cellulose powder [42]

complexation Fe(Ⅳ) film [46]
coordinate bonds, [48]
formaldehyde / Zn2+ mesoporous sphere
covalent bonds
polymerization - coating [49]

Next-generation tools utilized with functionality of polyphenols

In addiction with topics of the polyphenol functionalities in adsorbents having different

fashion of membranes and resins, further advanced applications of tannin, and tannic acid and
their composite materials can be expected for next future tools as green technology. For
example, electronic devices and sensors often require the combination of flexibility so that
organic materials and metals, thereby non-peeling coating is necessary. Fabricated practical
electronic circuits of Cu based plating pressure sensors have been developed using

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poly(ethyleneimine) into a green tea extract to cross-link polyphenols. Thus, strengthening
was introduced on the plating on flexible materials such as PET and melamine sponges [47].
As an application for nucleic acid sensors, microporous material obtained from tannic acid
was coordinated with Zn2+ upon polymerization [48]. The carbonization was followed by
calcination at high temperature to evaporate the Zn2+ at the same time. In general, the
polymerization of polyphenols was accompanied by a color change and physiological decline.
This is an undesirable phenomenon in the food and pharmaceutical industry. Hence,
preventive measures such as blocking oxygen and light are often taken. But, plant phenolic
compounds were used in the polymerization deposition and patterning [49]. In the coating and
patterning applications, film thickness of several nm to several tens of nm was achieved with
the spray method by controlling the molecular association and network growth. The metal
phenolic networking was expected to be widely applied for industrial production [46].
Although the use of polyphenols as industrial materials is meaningful, the effective utilization
of biomass resources aimed at a global environmental protection. Thus, their future
development would further require multiple purposes and motivations. One of such examples
is the easiness of appropriate disposal and processing after use due to biodegradable biomass.

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For example, a dielectric insulator layer in an organic thin-film transistor was reported based
on poly-methacrylated tannic acid, and the degradable properties were examined in saline

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solutions [50]. In addition, polyphenols in dye-sensitized solar cells was one of contribution
to clean energy production, and was expected the improvement of the practical level in the
future [51].
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Conclusion
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In the present review, condensed tannins and hydrolysable tannic acid were selected and
examined among plant-derived polyphenols. In particular, tannin derived materials and the
applications in the context of green chemistry were introduced with an emphasis on
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adsorbents and recovery agents for the removal of hazardous or rare metals. In addition,
studies on MPN and the uses as electronic devices and catalysts were also described. As
biomass source, the chemical structures of tannic acid and tannins are highly useful for the
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preparation of environmental friendly and sustainable materials. Therefore, various

technologies can be expected by using these green chemical materials possessing a
tremendous potential for application in a wide range of fields.
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Conflict of interest statement

Nothing declared.

References

Papers of particular interest, published within the period of review,

have been highlighted as:

* of special interest
** of outstanding interest

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Funding: This research did not receive any specific grant from funding agencies in the public,
commercial, or not-for-profit sectors.
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12
 OH
OH OH
HO OH
HO 8 O B OH
OH
6
C A OH HO
4 OG OH Galloyl (G)
OH O
HO O HO OH O O
OH

f
O OH OH

oo
OH OH
OG OH O OH

pr
OH OH
HO O

e-
OH O O O
OH O O O OH

Pr
OG OH HO O
OH OH O O

al
HO O O O O
OH HO O OH

rn
OG OH O OH
uOH HO
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OH OH
HO O O OH
OH
OH HO OH
OG O
OH OH
HO O HO
OH OH
OH
O
OH OH
O hydrolysable tannic acid
condensed tannin n OH
 metal ions

f
oo
pr
e-
Pr
polymerization adsorption

al
rn
u
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 R1

O
N R
Schiff-base

f
oo
R-NH2 R
R1 : H or OH NH

pr
R1 R1

e-
R1
R-NH2

Pr
oxidation Michael addition

al
OH O OH

rn
o-quinone
OH O
u OH
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Galloyl group
R-SH Michael addition
or B-ring
R
S
R1

OH
OH
Highlights

Research on metal ion adsorbents using tannin or tannic acid were summarized.
Tannin or tannic acid adsorb hazardous, precious, rare and radioactive metals.
Electrostatic interaction and complexation between metal ion and hydroxyl groups.
Tannins are used by insolubilization or immobilization on materials.

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Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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