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9 Green Catalysts in the Synthesis of Biomaterials for Biomedical Applications 235
to imitate in vivo biosynthetic processes make it simple and secure to incorporate
wound healing-boosting molecules and cells during wound dressing hydrogel
(WDH) synthesis. Hydrogels are hydrophilic polymeric networks that keep hold of
large amounts of water while maintaining shape. Their three-dimensional
(3D) structure effectively mimics cell and tissue culture conditions, making them
popular for encapsulating cells in a microenvironment. Hydrogels effec
physiologicall
due to their multilayered structure (Moreira Teixeira et al.
consistent
y active substances like growth factors and organize cells and tissues
2012). This feature is
with the increasing acceptance of in situ synthesis for complicated
tively deliver
sprayable, injectable, and bioprintable wound dressing hydrogels.
Transglutaminases catalyze the coupling of a free lysine amine group from a protein
or peptide to a deamidated glutamine protein or peptide-bound g-carboxamide
group, synthesizing protein/peptide-based WDHs. Oxidative enzymes like
als, m
peroxidases, laccases, and tyrosinases can create reactive radic
for
ideal
Nyanhongo
synthesizing WDHs from natural or synthesized compounds (Guebitz and
2018; Nyanhongo et al. 2012; Moreira
Teixeira et al.
aking them
2012).
Salehi et al. created thermoplastic hydrogels that depend on starch and zeolite
nanoparticles infused with chamomile extract, a herbal medication. Zeoliteembedded wound dressing composites exhibiting appropriate antioxidant and
antibacterial properties showed sustained drug-release behaviour. For example,
chamomile reduces inflamm ation by blocking prostaglandin E2 release triggered
by lipopolysaccharide and reducing EDC [COX-2] activity without compr omising
COX-1, the constitutive form of the enzyme. Zeolite samples have good biocompatibility, particularly for mouse fibroblast, per the MTT assay. Along with angiogenesis, histological examination of treated tissue samples revealed improved collagen
production, epithelialization, and reduced inflammation. Because of the dressing’s
porosity, nanostructure, and controlled fluid absorption rates, burn wounds, ulcers,
and bed sores healed more quickly. Notably, in the clinical pilot research, five
.
refractory ulcers healed without hypersensitive reaction (Salehi et al.
Green synth
esized silver nanoparticles from herbal tea (Stachys lavandulifolia)
2017)
(Zangeneh et al. 2019), leaf extract of Prosopis juliflora (Arya et al. 2019), kiwifruit
juice (Kodasi et al. 2023), Scutellaria barbata (Veeraraghavan et al. 2021) displayed
excellent results in wound healing. Green synthesized copper oxide nanoparticles
from Table Olive also showed better results in burn wound treatment (Wang et al.
2023). Green synthesized zinc oxide nanoparticles from Calendula officinalis flower
extract showed significant antioxidant and wound-healing properties (Aydin Acar
2024).
et al.
Ahmed HE et al. developed a chitosan-based hydrogel incorporating
Cerium oxide nanoparticles that showed antibacterial activity against K. pneumonia
and S. aureus, significantly improving wound-healing progression (Ahmed et al.
2021).
236 M. Krishani et al.
9.3.6 Bioprinting
Over the last few years, there has been a growing interest in using engineered
artificial tissues to mend injured tissues or as in vitro models to assess the human
body’s reaction to drugs. Researchers are using 3D bioprinting, a new fabrication
process, to create artificial tissues that closely resemble authentic tissues.
Bioengineers have expanded the applications of 3D bioprint ing in biomedical fields,
including preoperative surgery simulation, due to its fast and precise controllability
(Li
2019). Enzymes like horse radish peroxidase and glucose peroxidase are
catalyzed for crosslinking in bioprinting (Peng et al. 2021). Freeform bioprinting,
in which cell-suspending ink is ejected into a support bath containing supportive
elements, has become an encouraging method for creating cell-laden soft hydrogel
constructions (Hinton et al. 2015; Bhattacharjee et al. 2015). The supporting
materials provide physical support throughout the 3D printing process, while the
gelation of the embedded ink occurs in the support bath. As a result, freeform
bioprinting allows for the creation of soft constructions with higher shape accuracy
than standard air printing (Shiwarski et al. 2021; Hinton et al. 2015). Sakai et al.
developed a hydrogel using a freeform bioprinting process involving gelat ion
mediated by the enzymatic cascade reaction of horseradish peroxidase (HRP) and
choline oxidase (COD). COD catalyzes the conversion of choline and oxygen into
betaine glycine and hydrogen peroxide. HRP further catalyzes the formation of
covalent bonds between phenolic hydroxyl groups through oxidation in the presence
of H
(Sakai et al. 2021)
2O2
.
9.4 Methods Involved in the Synthesis of Green Catalyst
9.4.1 Green Solvent Synthesis Method of Catalyst
The conventional method used to synthesize catalysts applied at high temperatures
and toxic solvents may cause hazards for both the environment and human usage. To
overcome these problems and to produce a sustainable catalyst, green solvent
synthesis of catalyst was introduced as an alternative method. Water, ionic liquids,
and ethanol are renewable, non-toxic, biodegradable, and sustainable solvents that
can be used as an alternative to conventional solvents. These synthesis processes can
be carried out with low pressure and temperature, which may lead to less energy
consumption (Khalaf et al. 2024; Jiang et al. 2020; Yilmaz and Soylak 2020).
Water cannot be reduced or oxidized promptly. Water’s other advantages for
catalyst use are high polarity and solvation ability. Moreover, water is safe,
non-flammable, non-toxic, cheap and readily available. Sheldon states, “The ideal
solvent is no solvent; if one is required, water is preferred”. Thus, water is a
promising green chemistry solvent (Sheldon 2005).
Low volatility, good dissolving capability in different solutions, high thermal
stability, and non-toxicity make ionic liquids a green solvent in various production
processes. Some ionic liquids immobilize non-metals or metals on polymers or
9 Green Catalysts in the Synthesis of Biomaterials for Biomedical Applications 237
Fig. 9.3 Methods for green catalysts synthesis
minerals, allowing them to be utilized as “immobilized catalysts.” or “biphasic
catalysts” (Sood et a l.
extracts are the best examp
2023). Metal nanoparticles readily synthesized using plant
le of green solvent synthesis. Plant extracts contain
polyphenols and flavonoids, which can reduce metal ions. This process has been
used to create silver nanoparticles from plant extracts, including grapefruit peel,
green tea, and ginger. Another example includes the use of ionic liquids as solvents
in catalytic reactions. Ionic liquids, low-volatile liquid salts at room temperatur
effective solvents for catalytic reactions
such as hydrogenation and oxidation.
e, are
Furthermore, these ionic liquids can be recyclable and used without losing catalytic
activity. An outline of methods involved in synthesising green catalysts is shown in
9.3.
Fig.
9.4.2 Biosynthesis Method of Catalyst
This method synthesizes catalysts from living organisms, including microbes,
plants, and enzymes capable of synthesizing catalytic material or nanoparticles.
Microbes, like bacteria, can also synthesize catalytic materials. Shewanella
oneidensis is a gram-negative bacterial species that can synthesize magnetite
nanoparticles (Chmykhalo et al. 2021). Metal nanoparticle synthesis from
Fe
3O4
microbes and plant extracts are the best examples of biosynthesis methods of
catalysts.
For i
nanoparticles from plant extra ct is explained as follows: First, plant extracts are
collected by boiling plant parts (leaf, stem, root, seed or flower) using appropriate
green solvents. Then, metal ions in precursor material (AgNO
plant extract. Later, the reduction of metal ions (Ag
formation of Ag nanoparticles (Fig. 9.4). The plant extract is a reducing agent and
capping mediator (Zuhrotun et al. 2023).
The green
intracellular and extracellular methods. For extracellular synthesis, after culturing
nce, the basic procedure associated with the biosynthesis of silver
nsta
) are introduced to the
+
) into atoms (Ag0 ) leads to the
3
synthesis of nanoparticles from microbes can be performed using
238 M. Krishani et al.
Fig. 9.4 Synthesis of nanoparticles from plant parts
the microbes in optimum growth conditions, the biomass is harvested using centrifugation, and the recovered supernatant is mixed with aqueous metallic salt solution
to synthesize the nanoparticle. For the Intracellular method, the harvested biomass is
rinsed well with sterile water and incubated with an aqueous metal ion. The change
in the colour indicates the synthesis of nanoparticles. Later, the biomass is physically
disrupted using ultrasonication to releas
e nanoparticles from the cell wall (Soni et al.
2018). The process associated with the biogenic synthesis of nanoparticles from
is
ioned
microbes
ment
in Fig. 9.5.
9.4.3 Electrochemical Synthesis Method of Catalyst
Electrochemical synthesis is a potential green procedure for creating nanocatalysts
due to its ease of use, scalability, and control over nanoparticle size, shape, structure,
efficiency and scalability. Electrochemical synthesis uses an electrochemical cell
with two electrodes submerged in an electrolyte solution. The electrode responsible
for reduction or oxidation is a cathode or anode. When a voltage is applied between
the electrodes, electrons are transported from one to the other via the electrolyte
solution. This technique causes the formation of nanoparticles on one or more
electrodes based on the reaction conditions (Budnikova et al.
green, and inventive approach for producing high-quality graphene oxide
(GO) sheets using water electrolytic oxidation of graphite has been disclosed by
Pei et al. At ambient temperature, the synthesis was conducted after two electrochemical actions. Mercantile pliable graphite samples submerged in H
solutions were first subjected to a high potential to initiate an electrochemical
intercalation process. The chemical was utilized as an anode in diluted H
solutions to initiate an electrochemical reaction. Oxygen radicals from the anodic
electrocatalytic oxygen evolution reaction create low-oxidation GO layers (Pei et al.
2018).
2024). A rapid,
2SO4
2SO4
9 Green Catalysts in the Synthesis of Biomaterials for Biomedical Applications 239
Fig. 9.5 Synthesis of nanoparticles from microbes
9.4.4 Plasma Method
Plasma techniques are a viable way to create green catalysts. Plasma is composed of
charged particles. Creating plasma involves applying an electric field to a gas or
liquid, which causes it to ionize and become conductive. Plasma technologies have
numerous benefits for creating green catalysts. Catalysts are readily synthesized
using inexpensive materials like carbon precursors. Plasma approaches can create
catalysts wi th distinct features that are challenging to generate through regular
synthesis methods. Plasmas are classi fied as high and low-temperature. Thermal
plasma is formed by heating a gas to elevated temperatures.
In contrast, nonthermal plasma is formed by applying an electric field to a gas at
low temperatures. Wang et al. found that both types of plasma can activate and
change catalyst surfaces, enhancing their effectiveness in chemical processes.
Plasma can affect the properties of reactants to make thermodynamically
unfavourable reactions more favourable, even at normal temperatures (Wang et al.
)
2018; Zhao et al. 2017; Zhao et al. 2019). Guo et al. (2013
used cold plasma to
create zirconia with a monoclinic structure at temperatures below 150 °C, usually
accomplished at temperatures above 1000 °C. Plasma generates mostly negatively
charged nanoparticles, avoiding aggregation and resulting in lower dimensions than
thermal techniques. The main benefit of cold plasmas is that they operate at low
temperatures. Cold plasmas may produce structural distortions due to undecomposed precursors and moisture in the surroundings, which can hydrate catalyst
precursors. In many circumstances, thermal therapy must adhere to the plasma
technique (Wang et al. 2018;
Huang et al. 2019).
240 M. Krishani et al.
9.4.5 Ultrasonic-Aided Synthesis
Ultrasonic-aided synthesis is a promising strategy for improving catalyst
characteristics. Ultrasonic-aided synthesis employs high-frequency sound waves to
trigger chemical processes. The procedure follows the fact known as sonic cavitation, which happens as soon as sound waves travel through a liquid medium. It
causes tiny bubbles to form and collapse, resulting in high temperatures and
pressures that encourage chemical reactions (Chatel
Ultrasonic-assisted synthesis provides advantages over typical catalyst preparation methods. Initially, because cavitation bubbles have a larger surface area and
mass transfer, they allow for rapid reaction rates and more remarkable outcomes.
Additionally, it allows for fine control over particle form and size, which can
dramatically impact catalyst activity. Ultrasonic-aided synthesis is an environmentally friendly technology that eliminates the need for complex chemicals or elevated
temperatures, making it ecofriendly benign (Chatel 2019).
Alinavaz et al. used a simple sonochemical approach (ultrasonic radiation) to
create nano-sized nanocomposites with high phase purity (Alinavaz et al. 2023). Yao
et al. synthesized mordenite zeolite under diverse conditions, including salt addition,
hydrothermal process and temperature, and ultr asonic assistance. The ultrasonic
post-treatment of the zeolite sample revealed a unique structure of many mordenite
nanosheets that enhanced catalytic stability and attained an elevated carbonylation
rate (Yao et al. 2020).
2019).
9.4.6 Microwave-Aided Synthesis (MAS)
This technology uses microwave radiation to heat the reaction mixture, producing
more rapid and potent synthesis than traditional heating methods. Rapid heating and
cooling can shorten reaction times (Rao et al. 1999). Compared to convent ional
techniques, microwave-aided alumina and boron carbide sintering can save energy
and time. It can result in increased outcomes and better control over the size and
shape of catalyst particles (Roy et al. 1999). Microwave radiation can heat specific
reaction mixture components based on their dielectric characteristics (Leonelli et al.
2013). It can selectively activate precursors or stimulate particular processes while
limiting adverse effects. MAS can be conducted without or with minimal solvents,
reducing waste, simplifying product purification and being environmentally friendly
(Kokel et al. 2019;Wu etal. 2013).
Microwave
components are not too hot. Microwave research is becoming increasingly popular
due to its potential for time and energy savings and breakthroughs in industrial-scale
technologies—microwave heating results in little conductive and convective heat
losses. A material’s catalytic activity is determined by its surface structure and
capacity to speed up reactions. Microwaves improve catalytic activity by
accelerating the transition of polar reactant molecules, leading to quicker reaction
rates than standard heating methods. Microwave heating can create microplasmas on
ovens can operate safely depending on the technology, as the external
9 Green Catalysts in the Synthesis of Biomaterials for Biomedical Applications 241
metal surfaces, resulting in enhanced selectivity. Changes in grain size, poisoning,
and coking can all impact catalyst stability. In some situations, microwave-assisted
reactions can delay catalyst degradation and extend lifespan (Muley et al.
2021).
This process has been used to create metal nanoparticles on diverse materials,
including zeolites and carbon nanotubes. These catalysts exhibit enhanced activity
and selectivity in numerous methods, including hydrogenation and oxidation
2024)
(Khalaf et al.
He et al. (2019) synthesized MCM-41-NH
.
from fly ash by applying an alkali
2
fusion process with microwave assistance, resulting in a shorter ageing period of
30 minutes compared to the traditional hydrothermal method. Golchinvafa et al. used
a solution combustion synthesis approach to produce FeNi
/NiFe2O4 composites
3
using conventional and microwave heating. Microwave heating produced
composites with higher FeNi
Masoudpanah
2019).
phase and larger sintered particles (Golchinvafa and
3
9.4.7 Alternative Green Methods
An appealing method for producing low-dimensional nanomaterials with an
eco-friendly approach involves sonicating Ni
2+
and Fe
2+
with MoS2 acting as
two-dimensional templates. This technique uses weak van der Waals interactions
at the 2D interfaces to create 2D/2D heterostructures made of NiFe nano-sheets
deposited onto MoS
layers (Wang et al. 2019). Additionally, Zhang et al. proposed
2
an outstanding method to produce high yields of 2D MOFs. Intending to exfoliate
the 3D MOFs and create 2D sheets, they developed a surfactant-mediated technique
in which the surfactant’s interaction with MOF crystal defects produces a
pseudoassembly process. Significant progress has also been made in the environmentally friendly production of MXenes nano-sheets, a relatively new and exciting
2D material (Zhang et al.
2019c). Zhang et al. have progressed in this direction by
creating a straightforward template-free process involving fast liquid freezing in
nitrogen. It opens the door to producing inexpensive 3D microporous structured
MXenes (Zhang et al.
Remarka
bly, z
solvents. ZSM-5 was synthesized using TPABr/SiO
Na
·10H2O/SiO2 mixture to remove the organic template, as reported by
2CO3
2019d).
eolite synthesis has been accomplished without the need for
, rice husk ash, and
2
Zhang et al. The samples were processed in an autoclave at 150 °C for 72 hours
and then calcined at 550 °C for 6 hours. They exhibit similar characteristics when
synthesized by hydrothermal solvent-free approaches (Zhang et al. 2019a). Furthermore, it was observed that hierarchical zeolite Co particles with a large surface area
and remarkable crystallinity were trapped inside ZSM-5.
Compared
to wet impregnation or coprecipitation, the mechanochemical
approach has become a green technology. It enables the nonsolvent manufacture
of the catalyst anchored on mesoporous material, particularly metal oxide
nanoparticles. To demonstrate this, Saberia et al. synthesized Fe
which propionic acid and Fe(NO
O were distributed in a planetary ball mill
3)3·H2
/SBA-15, for
2O3
242 M. Krishani et al.
before being calcined for 30 minutes at 300 °C. The nanomaterial had a high surface
area and could be separated magnetically (Zhou et al.
2019). However, information
on nonmagnetic Fe–SBA-15 modified by sulfonic groups already exists (Ostovar
et al. 2018).
Additionally, Co
was supported on SBA15 by Pineda et al. to improve the
3O4
catalytic qualities, resulting in a bifunctional nanomaterial with redox and acid sites
(Pineda et al.
2018). Gold and silver were similarly supported on SBA-15 by taking
the same approach. Aluminium species were also held up on MOF, MCM41, and
SBA-15. Compared to the impregnation approach, the green synthesis route showed
reduced superficial area and less acidity (Marquez-Medina et al. 2019).
Abundant work has been done to create encapsulated NP materials using solventfree techniques. During the sacrificial phase, the mechanochemical technique
enables the nanoparticles in the MOF matrices through a solid-state reaction.
Consequently, ball milling of Palladium NPs in Zeolitic imidazolate framework8 crystal without stabilizing agents was carried out (Li et al. 2019). The
nanomaterials have a high surface area and an excellent crystalline structure. Furthermore, a quick and easy solvent-free technique was used to create a mesoporous
platinum-iron oxide mechanochemical structure. In a solid-state reaction lasting
0.5 hours, the triblock copolymer and iron salt enable a narrow pore size distribution,
a high surface area, and well-dispersed Platinum (Zhou et al. 2019).
9.5 Conclusion
To summarize, using green synthetic techniques, considerable attempts must be
made to produce green catalysts with exceptional features such as high firmness,
accuracy, and activity. This chapter explains the usage of green catalysts in
synthesising biomaterials for biomedical applications, as well as current
advancements and practical implementations. Green catalysts are essential to sustainable chemistry, providing eco-friendly alternatives to conventional catalysts.
They are prepared using a variety of ways that have a low impact on the environment. Renewable starting materials, including plants, microorganisms, and materials
derived from biomass, are commonly used as precursors. Eco-friendly procedures
such as hydrothermal synthesis, microwave-aided approaches, and enzymatic activation improve the sustainability of catalysts. Techniques such as impregnation,
sol-gel synthesis, and ion exchange use water or toxic-free solvents as the media.
Green c
ataly
sts have numerous applications in synthesising biomaterials for
biomedical applications, including tissue engineering, drug delivery, wound healing,
biosensors in clinical diagnosis, polymer coatings, and inks for bioprinting. Green
catalysts provide excellent selectivity, efficiency, and stability, producing hygienic
manufacturing and less dependence on destructive chemicals. Using green catalysts
can help the industry transition to a more organic future.
Green catalysts
have a bright future in analysis that will help them tackle their
challenges. As our economy becomes more sustainable, there will be a greater need
for eco-friendly and efficient catalysts. Green catalysts have proven helpful in
9 Green Catalysts in the Synthesis of Biomaterials for Biomedical Applications 243
biomedical applications and are expected to improve further. Green catalysts are
predicted to become more cheap, ascendable, and steady as technology advances and
sustainability consciousness grows. Adopting these technologies has significant
promise to create a healthier and more organic future.
Green catalysts confront obstacles in mainstream adoption, but continued analysis opens the way for services to market. Green catalysts are more environmentally
friendly and efficient than conventional catalysts, making them a popular choice.
Green catalysts can help create a more viable and progressive future.
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