Molecular Catalysis 539 (2023) 112893

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Molecular Catalysis
journal homepage: www.journals.elsevier.com/molecular-catalysis

Pretreatment and catalytic conversion of lignocellulosic and algal biomass

into biofuels by metal organic frameworks
Hafiz Adnan Akram a, Muhammad Imran a, *, Ayesha Javaid a, Shoomaila Latif b,
Nayab Batool Rizvi c, Teofil Jesionowski d, Muhammad Bilal d, *
a
Centre for Inorganic Chemistry, School of Chemistry, University of the Punjab, Lahore 54000, Pakistan
b
School of Physical Sciences, University of the Punjab, Lahore 54000, Pakistan
c
Centre for Clinical and Nutritional Chemistry, School of Chemistry, University of the Punjab, Lahore 54000, Pakistan
d
Institute of Chemical Technology and Engineering, Faculty of Chemical Technology, Poznan University of Technology, Berdychowo 4, PL-60965 Poznan, Poland

A R T I C L E I N F O A B S T R A C T

Keywords: Developing countries are facing burning issue of energy crisis and increasing pollution. There is a need of
Biomass exploring alternatives to conventional fuels due to the limited resources of fossil fuels and CO2 emission.
Lignocellulose Hydrogen is considered to be a promising next-generation energy resource because it is sustainable, green, and
Pretreatment methods
carbon free. Various methodologies have been adopted to extract hydrogen from different sources particularly
Metal organic frameworks
Catalytic conversion
from algal and lignocellulosic biomass to cope the hazardous effects of fossil-based fuels. Keeping in view the
importance of algal/lignocellulosic biomass, the first part of the review comparatively analyzes the pretreatment
methods and biohydrogen yields from algal/lignocellulosic biomass are tabulated. The second part of the review
covers the catalytic conversion of pretreated biomass into biofuel and other valuable chemicals using metal
organic frameworks (MOFs). Finally, current challenges and future research directions are also summed up that
will be helpful for the scientists to produce eco-friendly fuels.

1. Introduction their economical and environment friendly qualities. These biofuels

include biohydrogen, biomethane, biomethanol, bioethanol, bio­
Due to rapid urbanization and subsequent industrialization, the need butanol, biodiesel, and fuelwood etc. These are very versatile due to
for energy supplies is tremendously increasing day by day. It is reported their existence in three forms i.e. gas, solid, and liquid [4]. Among these
that 80% of energy demands for industrial revolution are being fulfilled sources, hydrogen is one of the important fuel due to its high potential
by fossil fuels. Transportation (luggage, heavy machinery, or passenger) energy, sustainability, eco-friendliness and high conversion efficiency (1
is a daily activity in modern world which consumes 60% of fossil fuels kg H2 carries about 120 MJ of energy) [5]. It can be used to fuel the
[1]. Fossil- based fuels are a non-renewable resource and have been used vehicles or to generate heat/electricity, as its burning provides me­
as a source of energy since long time. Due to their extensive use, these chanical energy without emitting carbon dioxide. Additionally, it is a
are being depleted and are also cause of environmental pollution due to potential alternate to fossil-based fuels having exceptional energy den­
emissions of carbon-derived gases [2]. These gases have potent effects sity (142 kJ g− 1). In spite of its interesting traits, the applications of
on human health such as asthma, eye problems, and skin cancer etc. biohydrogen (H2) are still limited due to its capture, storage, and
Moreover, the fossil-based fuels pollute water, air, and soil resulting transformation methods on large scale [6].
harmful effects on aquatic organisms, birds, and other living organisms It is well established in the literature that different types of biomass
on earth [3]. including algal and lignocellulosic have been utilized for the production
The aforementioned problems of fossil-based fuels need attention of value-added products and biofuels (biogas, biodiesel, and bio­
and there is an urgent requirement for the exploration of alternative hydrogen etc.) [7]. The annual production of biomass has been esti­
sources of energy that must be cost-effective, eco-friendly, and renew­ mated to be 220 billion tonnes globally which is equivalent to about
able. Biofuels are quite promising fuels alternative to fossil fuels due to 4500 EJ per year of solar energy. This amount of biomass is enough to

* Corresponding authors.
E-mail addresses: imran.hons@pu.edu.pk (M. Imran), muhammad.bilal@put.poznan.pl (M. Bilal).

https://doi.org/10.1016/j.mcat.2022.112893
Received 1 October 2022; Received in revised form 2 December 2022; Accepted 19 December 2022
Available online 1 March 2023
2468-8231/© 2022 Elsevier B.V. All rights reserved.
H.A. Akram et al. Molecular Catalysis 539 (2023) 112893

produce about 270 EJ of bioenergy annually and is sustainable [8,9]. formation of biofuels and also can be cultivated in smaller spaces than
The main sources of biomass are agricultural crops, wood, animal land crops [16].
wastes, microalgae, and aquatic plants, etc. Depending upon the source Fig. 2 illustrates the various processes involved for the production of
of biomass, the biofuels are classified into four generations. Each of the biofuel starting from biomass. A large number of reagents such as acids,
biofuel generation shows different pros and cons. First generation bio­ alkalis, or oxidative delignification, as well as physical pretreatment
fuels are derived from edible feedstock with good efficiency in terms of techniques (milling, grinding, extrusion, microwave, ultrasonic, etc.)
energy production, but their use is questionable due to the shortage of have been reported for the efficient break down of the refractory
food as per requirement of the world’s population. This controversy has bonding in a short interval of time. These procedures, however, are quite
been resolved by shifting towards lignocellulosic biomass to produce expensive, need lot of energy, and also pose a significant threat to the
biofuels [10]. The breakdown of rigid mass is a pre-requisite step in the environment [17]. Contrary to these chemical pretreatments, biological
aforementioned second-generation fuels which was overcome by the pretreatment has attained more attraction due to its low energy needs,
introduction of third generation fuels. It involves algal biomass for the absence of chemicals, reduced environmental impact, and increased
fuel generation which is easy to cultivate but yet not much cost effective. productivity [18]. In biological processes, bacteria and fungi produce
It has led to the genetically modified algae for biofuel production and several lignocellulolytic enzymes which decompose biomass and
this category is classified as fourth generation biofuels [11]. Fig. 1 de­
scribes features of the four generations of biofuel.
It is considered that lignocellulosic biofuel is highly sustainable,
inexpensive and environment friendly. However, enzymatic hydrolysis
of lignocellulosic material is difficult due to their crystalline nature,
hemicellulose encasing, and recalcitrance of their bonding. Therefore,
emphasis is always given for the efficient breakdown of lignin from
lignocellulosic biomass and is generally known as targeted stage of
pretreatment to enhance the digestibility of cellulose and hemicellulose
[12]. Since biomass is a by-product of several procedures used in
forestry and agriculture, lignocellulose waste is quantitatively produced
in large amount with low cost. Lignocellulosic biomass sources are
usually wood, garden residues, wastes from food processing, cellulosic
mass, and agricultural crops etc. It has been estimated that wood waste,
municipal solid waste and agricultural waste approximately produce
64%, 24% and 5% of bioenergy, respectively [13]. The two primary
polysaccharides constituting lignocellulose are cellulose and hemicel­
lulose constituting 40–50% and 25–35% of total mass, respectively. Both
of these are tightly bound to lignin (15–20%), generating intricate
structure of lignocellulose [14]. It has been suggested that poplar and
eucalyptus species grow faster and can be harvested to about 10–13
metric tonnes per hectare annually to produce lignocellulosic biomass in
the majority [15]. Algal biomass is an alternative substitute for ligno­
cellulosic biomass to produce biofuel (methane, bio-hydrogen, and
biodiesel). It keeps the water clean and protected from eutrophication
by collecting algae from waterways to act as biomass for biofuel gen­ Fig. 2. Different steps involved in the production of biofuel from biomass and
eration. Microalgae is one of the promising source of feedstock for the their types.

Fig. 1. Classification of biofuels based on the raw material. Reprinted from [94] with permission from Elsevier. This is an open access article under Creative
Commons Attribution License (CC-BY) (https://creativecommons.org/licenses/by/4.0/).

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H.A. Akram et al. Molecular Catalysis 539 (2023) 112893

produce of 5- and 6-carbon sugars. These sugars are used as a promising 2. Pretreatment methods
feedstock for further synthesis of biofuels and other valuable goods [19].
In spite of several seasonal changes, availability of microalgae and its Pretreatment of the biomass is a crucial step to improve the
carbohydrate-rich biomass have also gained attention as a possible bioavailability of the biomass to be converted into biofuel. It should be
biomass resource for biohydrogen. The green microalgae have simple cost effective in terms of the operational and capital costs which should
carbohydrates such as cellulose, hemicellulose, and storage poly­ not exceed the 40% of the total cost of processing [25]. Pretreatment
saccharides like starch or glycogen. Biohydrogen can be generated methods are of different types and are broadly classified into physical,
through different biological mechanisms like direct and indirect chemical, physico-chemical, and biological methods [26]. Each method
bio-photolysis, photo-fermentation and dark fermentation etc. [20]. involves breaking of the complex cell wall structure and yielding
The pretreatment methods for the biomass have been extensively different products. Pretreatment of lignocellulosic biomass causes the
studied in the recent years and reviewed by many authors [7,9,21-24]. cellulose, hemicellulose, and lignin, to be solubilized or separated [27].
However, the production of biohydrogen is still not much discussed. To The details of commonly used pretreatment methods have been
fill this void, this review provides a general overview of the pretreat­ comprehensively discussed in recently reported reviews [7,9,21-24],
ment methods for the conversion of lignocellulosic/algal biomass with a therefore, only an overview of these methods has been presented here.
special focus on the production of biohydrogen. Moreover, the pre­ Moreover, based on the data extracted from these reviews, the
treated biomass requires appropriate conversion process to obtain bio­ comparative analysis of the advantages and disadvantages of these
fuel/biohydrogen. Metal-organic-frameworks are relatively less methods has been tabulated (Table 1).
explored yet commendable catalysts for such conversions of pretreated
biomass into several valuable fuels and chemicals. We attempted to
compile some of the useful fuel products obtained from the pretreated 2.1. Physical pretreatment methods
biomass using MOFs. The current challenges in the pretreatment of
biomass and their catalytic conversion are also discussed along with the The physical pretreatment methods employ mechanical procedures
future recommendations in this field of research. This review will be and irradiation techniques for changing different characteristics of
beneficial towards academia and industrial researchers to more effi­ biomass such as particle size, degree of polymerization, surface area,
ciently utilize biomass for the production of biofuel using MOFs. and crystallinity index [28]. These methods are advantageous due to the
involvement of simple steps and creation of fewer environmental
problems. However, the high consumption of energy makes them highly
expensive. The choice of the physical pretreatment method is dependent
upon the properties of biomass [9]. A recent study investigated the

Table 1
Main operating conditions, advantages and disadvantages of pretreatment methods.
Pretreatment Type Process Advantages Disadvantages
method

Physical Milling Crushing and grinding of biomass Effectively reduces the size of Requires high energy
biomass and remove lignin
Extrusion Biomass is compressed using extruders Economical, enhances surface area, Costly process
no degradation of biomass
Microwave Microwaves are used to modify the biomass Simple, alternative to thermal Requires microwave-based instrument
effects, less time consuming
Pyrolysis Thermal decomposition of organic matter Economical, energetically feasible Slow production, low energy yield, cause
excessive air pollution
Ultrasonication Mechanoacoustic and sonochemical effects of Short processing time, avoids Requires ultrasound-based instrument and
ultrasound waves cause the delignification of chemical loadings trained personnel
the biomass
Chemical Acid Strong and weak acids can be used Economical Toxic, corrodes the equipment, produces
fermentation inhibitors
Alkali Utilizes bases such as hydroxides of sodium, Does not require sophisticated Prolong reaction time, requires neutralization
calcium, potassium etc. reactors, operates at low of the pretreated biomass
temperature
Oxidative An oxidant is used to degrade the biomass High reactivity Lacks substrate selectivity
Ionic liquid Utilizes ionic liquids to digest biomass Green method, high chemical Sometimes may cause deactivation of enzymes
stability, less dangerous, operates at due to incompatibility, susceptible to side
mild conditions reaction, expensive
Organo-solvent Organic solvents e.g., methanol, acetone and Produces pure and high-quality Flammability and volatility may cause serious
phenol etc. are used lignin risks and it is hazardous to the environment
Physico-chemical Steam explosion Thermal based mechanical-chemical process Eco-friendly, high efficiency, Incomplete removal of lignin, produces few
effectively depolymerizes the toxic chemicals
biomass
Wet oxidation Biomass is treated with water using oxygen as Solubilizes hemicellulose and Produces low yield of sugars, costly due to the
catalyst efficiently removes lignin sophisticated equipment and the expensive
catalyst
Ammonia fiber Anhydrous liquid ammonia is used to treat High efficiency, better enzymatic Uneconomical and difficult to recover at
explosion biomass action upscale level
Hydrothermal Water at high temperature and pressure is Green technique, no harsh chemicals Costly due to high temperature, large water
used are used consumption, produces fermentation
inhibitors
CO2 explosion CO2 permeates through biomass Non-toxic, non-flammable, non- High cost
corrosive
Biological Enzymatic or Involves the microbe’s inherent capacity to Environment friendly Time taking process, requires large space,
microbial breakdown the biomass needs continuous monitoring of microbial
growth

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H.A. Akram et al. Molecular Catalysis 539 (2023) 112893

energy consumed during size reduction of woody biomass pretreatment biomass, making it more receptive to enzymatic digestion. The advan­
and found it highly energy consuming. It has also been observed that tage of this treatment is due to the microbes’ inherent capacity to break
post-chemical pretreatment size reduction could make the process less down the lignin, hence, selection of right microbial community for
energy consuming (20–50 kW h/ton of wood) [29]. Zheng et al. com­ biomass pretreatment is highly crucial. Bacterial and/or fungal con­
bined the extrusion process with the steam explosion pretreatment sortium can manufacture cellulase, hemi-cellulase, and lignases, they
method to investigate the effect on enzymatic hydrolysis of corncobs and are used to pretreat lignocellulosic biomass for biofuels and bioproducts
found an increase in the crystallinity of the biomass thereby resulting generation [39]. In microbial pretreatment for the manufacture of bio­
increased enzymatic conversion [30]. Similarly, Chen et al. studied the fuels, the most important step is the selection of bacterial strains fol­
combined effect of steam explosion and extrusion on corn stover lowed by enzymatic hydrolysis and fermentation [39]. Gonzalo et al.,
biomass. At 150◦ C this combination of pretreatment yielded 89% studied the bacterial enzymes involved in the breakdown of lignin and
enzymatic hydrolysis in only 2 min [31]. Passos et al. reported micro­ found that DyP-type peroxidases and laccases are two main types of
wave pretreatment for the anaerobic digestion of microalgae grown in bacterial lignin-modifying enzymes [40].
wastewater for biogas production and found that microwave made The pretreatment through enzymes employs the application of either
microalgae more easily digestible and disintegrated resulting in an raw, pure, or partially purified enzymes derived from hydrolytic and
increased biogas production [32]. Similarly, Budiman and Wu reported ligninolytic enzymes. It is evident that the quantity of lignin removed
the increase in hydrogen generation (872.4 mL) utilizing ultrasounds for from lignocellulosic biomass by this method may be comparable to that
the pretreatment of combined effluents having biomass whereas without of fungal pretreatment [10]. Enzymes help in the release of fermentable
ultrasound only 467 mL of hydrogen was produced. This improvement sugars from hemicellulose and cellulose. Additionally, they minimize
lies in the fact that ultrasounds enhance the solubility of organic matter the resistance of lignocellulose to increase the production of biofuel
which increases the bacterial activity due to the increased bioavail­ from biomass. Andrea, et al., evaluated the enzymatic processing of
ability of the substrate [33]. microalgae from Trametes versicolor for biogas generation. It was
observed that the methane output in batch tests was increased by both
2.2. Chemical pretreatment methods the microbial broth and commercial laccase pretreatment (100 U L− 1)
over an exposure time of 20 min [41].
Chemical pretreatment methods have also been widely used and
mainly focused to decrease cellulose crystallinity, degree of polymeri­ 3. Biological conversion of biomass into biohydrogen
zation (DP) and to remove lignin and/or hemicellulose to promote cel­
lulose biodegradability. Among various chemical treatment methods, It is well established that the biological methods for hydrogen gen­
most common one are oxidative, ionic liquid, acid, alkali, and ozonolysis eration are more eco-friendly and utilize less energy than other methods
[34]. For instance; Sheng et al. reported the influence of ascorbic acid such as water electrolysis or thermochemical conversion of natural gas.
pretreatment on the agricultural crop to remove lignin which decreased Biohydrogen can be produced by using green microalgae via direct
the amount of surface lignin ultimately increasing the cellulose acces­ photolysis, cyanobacteria for indirect photolysis, photosynthetic bacte­
sibility and enzyme adsorption capacity [35]. Ozonolysis has also been ria for photo-fermentation, and hydrogen-producing microbes for dark
described as an advantageous oxidative pretreatment for lignocellulosic fermentation [42]. Photo-fermentation and dark fermentation are
biomass due to the high delignification (≈80%) of the biomass as ozone recognized as environment friendly, utilize less energy and less renew­
prefers to react with lignin over carbohydrates, thereby releasing sugar able resources. When compared each other, dark fermentation is
(≈75%) by enzymatic hydrolysis [36]. considered more significant due to high yield and less reaction time.
Moreover, it can utilize a broader range of biomass as raw material [43].
2.3. Physico-chemical pretreatment In photo-fermentation, the prominent function of bacteria is to
capture light, then organic acids are converted into hydrogen by
Physico-chemical processes are considered to be more effective than involving nitrogenase (Eq. 1) [42]. Low nitrogenase activity limits the
physical ones and more environmentally friendly than chemical ones. In generation of H2 and also the optimum yield of hydrogen is halted by
these pretreatments, lignin and hemicellulose are removed while cel­ less light conversion, carbon/nitrogen ratio, heavy metals, and their
lulose is decomposed in the absence or presence of a chemical. The ions, and nitrogenase inhibition by oxygen [44].
procedure is relatively difficult and may involve high energy usage.
Steam explosion/autohydrolysis, wet oxidation, ammonia fiber explo­ C6H12O6 + 12H2O (light) →12H2 + 6CO2 (1)
sion, and liquid hot water are the most common physico-chemical pre­ In dark fermentation, there is no use of illumination contrast to photo
treatment methods used for lignocellulosic biomass [37]. Bhatia et al. fermentation. The main factors affecting the yield of H2 in this
reported biofuel from Miscanthus hybrid seed (Mx2779) using steam fermentation are kind of substrate, inoculation, pH, and temperature.
explosion (SE) and ionic liquid (IL) pretreatments separately as well as Generation of byproducts also causes a low yield of H2 on substrates [42,
in combination. The combined treatment of miscanthus with an ionic 44]. Contrast to photofermentation, one benefit of using the dark
liquid (triethylammonium hydrogen sulfate [TEA][HSO4]) and a steam fermentation is its simultaneous production of H2 and also the waste
explosion glucose yield was 40–70% [18]. Lee et al. reported different treatment. Additionally, dark fermentation uses less space and is
ways to improve methane production from palm fruit bunches and approximately 340 times less expensive than photosynthetic route.
revealed its production was increased utilizing the wet oxidation process Therefore, dark H2 fermentation is a straightforward procedure using
involving hydrogen peroxide. In wet oxidation, the superstructure of little energy and can utilize many types of organic waste. Mono­
lignocellulose is disassembled instead of being solubilized which makes saccharides (such as glucose, xylose, and arabinose), polymers like cel­
it simpler for enzymes (cellulases) to reach the lignocellulose compo­ lulose, hemicelluloses, or starch, can be employed as hydrogen feed
nents [38]. stocks [45].

2.4. Biological pretreatment methods

3.1. Biohydrogen from lignocellulosic biomass
When compared with physical and chemical approaches, pretreat­
ment by a biological approach is thought to be an efficient procedure For the fermentation of lignocellulosic biomass, it must be pre-
involving less energy. For lignocellulosic materials, often used biological treated before the fermentation process to enhance the amount of
treatments are enzymatic, microbial, and fungal which alter the monomeric sugars available to the H2 producing microbes [17].

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H.A. Akram et al. Molecular Catalysis 539 (2023) 112893

Biohydrogen yield from lignocellulosic substrates using different or­ Table 2

ganism have been tabulated in Table 2 for better idea. It clearly depicts Biohydrogen production from lignocellulosic substrates.
that various carbon sources are used as a feeding stock for bacteria that Lignocellulosic Organism Biohydrogen References
can produce hydrogen and is quite important with respect to the recy­ substrate
cling biowaste. Sucrose C. saccharolyticus 11.7 mmol/g [95]
dry weight/h
Rice husk Cellulomonas sp. and 0.36 g l− 1 [96]
3.2. Biohydrogen from algal biomass
Cellulosimicrobium reducing sugar
cellulans
The chemical properties of crude algal oil and fossil fuel oil are Clostridium butyricum 17.24 mmol H2
comparable to each other. The transformation of raw algal oil to usable CGS5 g− 1 rice husk
fuels is analogous to the conversion of fossil fuel into useful products by hydrolysate
Xylose T. thermosaccharolyticum 2.39 mol H2/ [97]
petroleum refineries [46]. When the trans-esterification process is car­ W16 mol xylose
ried out in the algal biomass, fatty acid methyl esters (FAMEs) or bio­ Cl. butyricum CGS5 212.5 ml/h/l [98]
diesel are created by first hydrolyzing the ester link between the glycerol and 0.73 mol
and fatty acid chain, and then trans-esterified with methanol. Glycerol H2/mol xylose
E. aerogenes 0.79 mol H2/ [99]
produced during the trans-esterification produces FAME which can be
mol xylose
utilized as a source of carbon moiety in the fermentation process to make Arabinose E. aerogenes 0.81 mol/mol [99]
biohydrogen [47]. arabinose
The two main methods of bio-photolysis to produce biohydrogen Corn stover Thermoanaerobacterium 2.24 mol H2/ [100]
using microalgae are direct bio-photolysis and indirect bio-photolysis. In thermosaccharolyticum mol sugar
W16
the direct bio-photolysis, the microalgae manufacture biohydrogen Cornstalk Thermoanaerobacterium 89.3 ml/g- [101]
directly from water using their photosynthesis mechanism i.e. convert­ thermosaccharolyticum cornstalk
ing solar energy into chemical energy and producing molecular W16
hydrogen (Eq. 2) [48]. Bacillus licheniformis MSU 185 ml/l and [102]
AGM 2 82.5 ml/g
2H2O + light energy → 2H2 + O2 (2) substrate
Clostridium butyricum FS3 92.9 ml g− 1- [103]
The indirect bio-photolysis involves the fixation of CO2 through substrate
Clostridium 3.4 mmol/g [104]
algae and produce starch. Eq. 3 represents the fixation of CO2 using
acetobutylicum X9 steam exploded
indirect bio-photolysis. This starch is then combined with glycogen and corn stalk.
used to ferment the carbs to produce biohydrogen. Grass (4% HCl Clostridium pasteurianum 72.21 mL g− 1 [105]
pretreatment) grass (4% HCl
6H2O + 6CO2 + light → C6H12O6 + 6O2 (3) pretreated)
19.25 mL g− 1
In case of photo fermentation, researchers have paid attention on grass (0.5%
using algal biomass and its residues as a substrate to produce bio­ NaOH
hydrogen through microbial fermentation (Eq. 4) [49]. It has been re­ pretreated)
Switchgrass Caldicellulosiruptor 14.3 mmol H2 [106]
ported that by optimizing the growth conditions and immobilizing
saccharolyticus DSM 8903 L− 1 or 11.2
active cells, the total yield of bio hydrogen can be greatly increased mmol H2 g− 1
using photo fermentation [50]. substrate
Micro-crystalline 23.2 mmol H2
CH3COOH + 2H2O + light → 4H2 + 2CO2 (4) Cellulose L− 1 or 9.4 mmol
H2 g− 1 substrate
In contrast to the aforementioned methods, which rely on solar en­ Wheat straw Caldicellulosiruptor 2.09 mol H2/kg [107]
ergy, microalgae can also create hydrogen anaerobically through the saccharolyticus dry matter
dark metabolism of organic molecules [51,52]. The transformation of Enterobacter aerogenes 19.73 ml/g [108]
straw
organic materials in dark take place through a variety of steps, including
Clostridium sp. IODB-O3 2.54 ± 0.2 mol- [109]
hydrolysis, acidogenesis, and acetogenesis. Due to its benefits of excel­ H2/mol-
lent carbon balancing high energy efficiency, and environmental pro­ reducing sugar
tection, it has gained more attention [51,53]. Table 3 elaborates some of from WSPH
Wheat flour Biohydrogenbacterium R3 0.074 L H2/g [110]
the recent published data for the production of hydrogen using algal
wheat flour or
biomass. 2.34 mol H2/
mol glucose
4. Catalytic conversion of biomass into biofuels Rice husk Clostridium beijerinckii 237.97 mL and [111]
2.63 mmoL H2/g
of cellulose
Apart from the biological process as described above there is another C. termitidis and C. 5.9 mL H2 g− 1 [112]
approach which is becoming popular these days is the catalytic con­ intestinale substrate (when
version of biomass into value added products which can be utilized as particle size <74
fuel. Lignocellulose comprises of cellulose (40%− 50%), hemicellulose μm)
Rice bran E. ludwigii 266 mol H2/mol [113]
(20%− 30%), and lignin (18%− 28%) [54]. The recent studies have
Enterobacter aerogenes 5.4 mmol H2 g− 1 [114]
shown that the cellulose and hemicellulose from lignocellulosic biomass MTCC 2822 of substrate
can be effectively converted into various valuable chemicals. For De-oiled rice Clostridium 132.2 ml H2/g [115]
example, xylan present in hemicellulose can be converted into xylose bran acetobutylicum YM1 total sugars
and arabinose which upon hydrolysis yields furfural which is a valuable Cellulose Clostridium acetobutylicum 3.6 mmol H2/g [116]
cellulose
fuel [55]. Furfural can further be converted into furfuryl alcohol and 8.1 mmol H2/g
methyl furan via hydrogenation having potential applications as fuel cellulose
and solvent. Similarly, various potentially important chemicals can be (continued on next page)
produced from cellulose. The hydrolysis of cellulose yields glucose

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H.A. Akram et al. Molecular Catalysis 539 (2023) 112893

Table 2 (continued ) Table 3

Lignocellulosic Organism Biohydrogen References
Biohydrogen production rates at their maximum from algae.
substrate Algae Condition Biohydrogen References
Ethanoigenens harbinense Anabaena PCC Amylase pretreatment − 1
1600 mL L & 2.68 [128]
and Clostridium 7120 mol/mole of hexose
acetobutylicum coculture Chlorella sp. 0.0532 mmol photons 281 μmol H2 mg− 1 [129]
Delignified wood C. thermocellum 1.60 ± 0.67 mol [117] KLSc59 m− 2 s− 1 (light Chl
fibers H2/mol intensity) & 7.2 (pH)
Cellobiose 1.50 ± 0.67 mol L. japonica 35◦ C temperature, 5% 70 mL L− 1h− 1
[130]
H2/mol substrate
Wood fibers Clostridium thermocellum 1.6 mol H2/mol [118] concentration, 7.5 pH,
ATCC 27405 and ball mill
Bagasse Clostridium pasteurianum 35 ml/L/h and [119] pretreatment
CH4 0.96 mol H2/ Chlorella vulgaris 1% H2SO4, 176.9 mL h− 1 − 1
l [131]
mol glucose FSP-E fermentation using C.
Clostridium butyricum 6.01 mmol H2/g [120] butyricum CGS5
CGS5 reducing sugar Scenedesmus Anaerobic 2.82 ml/h 30.03 ml/ [132]
Sweet sorghum Thermoanaerobacterium 1.42 mol H2/ [121] fermentation using g VS
bagasse thermosaccharolyticum mol sugar Clostridium
KKU19 A. siamensis HupS (uptake 29.7 μmol mg [133]
Sorghum rusk C. beijerinckii 1.6 mol H2/mol [122] TISTR 8012 hydrogenase) chla− 1 h− 1
Sweet sorghum Bacillus subtilis AuChE413 55.2 l H2 kg− 1 [123] inactivation
bagasse Sweet sorghum Arthrospira Grinding and 195.6 mL H2/L/h [134]
bagasse maxima enzymatic
Sugarcane Methanothermobacter and 1.50 mmol/L at [124] pretreatment
basgasse Clostridium (5.84 g/L of NA 49.7–78.7 mL g− 1 [135]
sugarcane dry weight
bagasse and Chlorella vulgaris Batch fermentation, 43.1 mL g− 1 of dry [136]
2.77 g/L of yeast Clostridium sp. cell
extract). Dark fermentation, 31.2 mL H2/g dry [137]
Thermoanaerobacterium 1.86 mol H2/ [125] using response surface cell weight
aotearoense SCUT27 mol total sugar methodology
Bacillus subtilis AuChE413 39.6 l H2 kg− 1 [123] Chlorella Sulfur deprivation 123.60 ml/l [138]
sugarcane
bagasse protothecoides
Clostridium beijerinckii 0.733 mmol H2/ [126] Krueg
KCTC1785 g of sugarcane Chlorella Batch Co-fermentation 94.5–97.0 mL g− 1
[139]
bagasse pyrenoidosa with L. digitata VS
Palm kernel cake Clostridium 1575 ml H2/L [127] TAP medium(2.0 g/L 93.86 mL L− 1 [140]
acetobutylicum YM1 (cumulative sodium acetate) &
hydrogen autotrophic medium
volume) (10 mM NaHCO3)
Marine algal sp., 186 ml H2/l [141]
nitrogen deprivation
which gives 5-hydroxymethylfurfural (HMF) when dehydrated [56]. Nannochloropsis Lipid extracted 60.6 mL/gdry biomass. [142]
Furthermore, 5-hydroxymethylfurfural (HMF) can produce other valu­ sp. microalgal biomass
Clostridium 0.35 mmol H2/L /h [143]
able compounds such as 2, 5-dimethylfuran (DMF), levulinic acid (LA),
acetobutylicum
γ-valerolactone (γ-GVL), and 1,6-hexanediols [57]. S. obliquus alkaline and thermal 45.5 mL H2 g − 1
VS [144]
All such conversions of one compound into other requires suitable pre-treatments
catalyst for the optimized reaction. There are four major categories of
1
Scenedesmus Dark fermentation 56.8 mL g− [145]
catalysts for the conversion of biomass into valuable products which obliquus using Enterobacter
aerogenes
include porous materials [58], metal oxides [59], immobilized metal Chlorella Thermophilic dark 958 dm3 /kg [146]
nanoparticles and sulfonated materials [60]. But there are few key sorokiniana fermentation, HCl- volatile suspended
features of a catalyst that must be fulfilled as they play an important role heat pretreatment solid or 2.68 mol/
in catalysis during bio-fuel generation and these features include high mol of hexose.
Algal biomass that 5.8 mmol/g [147]
surface area, tunable acidity, porous nanostructures and bifunctionality
traps CO2 using CODreduced
such as acid-base. Considering these features, metal organic frameworks Enterobacter cloacae
(MOFs) are the potential candidates for the biomass valorization IIT-BT 08, & HCl-heat
because they have wide tunability, large surface area, brilliant hydro­ pretreatment
thermal stability, large internal cavity and variable pore size [61]. Dunaliella Lipid extracted 183.02 mL/g [148]
tertiolecta biomass, using volatile solid (VS)
Dunaliella Thermococcus 192.35 mL/g VS
primolecta eurythermalis A501,
4.1. Metal organic framework (MOF) based biofuel generation Optimal parameters
include 2.5 g/L algal
Metal organic frameworks are porous coordination polymers having content and a gas/
liquid volume ratio of
crystalline structure and composed of metallic nodes connected with
2:1
organic linkers [62]. The clusters of metal ions coordinate with the C. vulgaris YSL01 Photoautotrophic 0.3 to 0.6 ml l− 1 [149]
organic ligands to form secondary building units (SBUs) which are photoautotrophic
aligned into a porous framework having specific morphology [63]. The H2 (in 3 days)
diversity of metal nodes and organic linkers provide variety of MOFs C. vulgaris YSL16 0.1 ml l− 1 of
photoautotrophic
having unique morphological and textural features [64]. More than 20, H2 (in 4 days)
000 types of MOFs and MOF derived materials have been reported. The [150]
specific surface area, porous nature and tunable structure are some of (continued on next page)
the key features of the MOFs which make them ideal for the catalysis and

6
H.A. Akram et al. Molecular Catalysis 539 (2023) 112893

Table 3 (continued ) Apart from high catalytic activity, MOF based catalysts can easily be
Algae Condition Biohydrogen References separated and are recyclable. Furthermore, the Lewis and Brønsted
acidity associated with the MOF-derived catalyst is another commend­
Scenedesmus Clostridium butyricum 113.1 mL g-1 VS
obliquus DSM 10702 (from 50.0 galga L− 1)
able feature. The open metallic sites of the SBU provide Lewis’s acidity
Enterobacter 57.6 mL g− 1 VS whereas Brønsted acidity (BA) is due to the acid-functionalized ligands.
aerogenes ATCC (from 2.5 galga L− 1) The Lewis acidity and Brønsted acidity provides more selective path­
C. reinhardtii CC- 13048 Co-culture with 122 μmol/ ways for the conversion of sugars, furans and lignin etc. into valuable
503 Thuomonas mg Chl
products and prevents the side reactions [54]. This section along with
intermedia BCRC
17547, Table 4 describes the catalytic conversion of biomass derived products
Photoproduction, into biofuels.
sulfur-deprived
Na2S2O3 [151] 255 μmol mg− 1 Chl 4.1.1. MOF based catalytic production of ethyl levulinate
treatment
Chlamydomonas Co-culture with 255 μmol mg − 1
Chl [152]
Ethyl levulinate (EL) is an important compound derived from
reinhardtii Azotobacter lignocellulosic bio-mass and it can be used as a fuel due to excellent
cc124 chroococcum stability, lower toxicity and high octane number [72]. For instance,
Chlamydomonas Pure 15.11 μmol [153] sulfonic acid functionalized MIL-101(Cr)–SO3H was reported as a cata­
reinhardtii Co-culture with L2 of 60.16 μmol
lyst to convert furfuryl alcohol into ethyl levulinate. The good catalytic
cc849 Stenotrophomonas
genus activity was reported with a yield of 79.2% for ethyl levulinate. The high
Co-culture with L3 of 43.83 μmol catalytic conversion is ascribed to the enlarged surface area, easily
Microbacterium genus accessible –SO3H Brønsted acid sites, good stability, and dispersion of
Co-culture with L4 of 62.66 μmol the MOF. The plausible mechanism for this conversion may involve the
Pseudomonas genus
Chlamydomonas Pure 43.62 μmol/mg chl [154]
two coexisting reactions as shown in Fig. 4 with the formation of
reinhardtii Co-culture with 165.5 ± 10.5 mL 2-ethoxymethyl furfural (2-EMF) as an intermediate compound [73].
Pseudomonas sp. strain L− 1 Guo et al., reported the conversion of levulinic acid into ethyl levulinate
D using MOF supported polyoxometalates [Cu-BTC][HPM] (BTC=1,3,
Co-culture with 255.52 μmol/mg [155]
5-Benzenetricarboxylic acid, HPM= phosphomolybdic acid). Levulinic
Thiomonas intermedia Chl
Co-culture with 226.98 μmol mg− 1
[156] acid was esterified at 120◦ C into ethyl levulinate with an excellent yield
M. sangaii, 3 g/L chl of 92.4% with almost 100% conversion of levulinic acid, achieved in 6 h.
NaNO2 This proposed catalyst was also found to be stable in the recyclability
Chlorella vulgaris Co-culture with 246 ml/L/h [157] test with only slight loss of catalytic activity and provided up to 89.5%
ESP6 Clostridium 240 ml/L/h [158]
yield of ethyl levulinate after three catalytic runs. The stability of the
butyricum CGS5
crystal structure and uniform distribution of HPM in the MOF were the
main contributory factors towards high yield and stability of the catalyst
storage applications [54]. [74].
The recent advancements in the hydrogen storage property of MOFs
has resulted in their potential use for the hydrogenation catalysis [65]. 4.1.2. MOF based catalytic production of γ-valerolactone (GVL)
Such catalytic reactions are very significant for the production of γ-Valerolactone (GVL), derived from cellulose, is one of the main
industrially important chemicals and fuels [66]. The distinctive features high-grade biofuels and also used as fuel additive. Moreover, it can be
of MOFs enable their extensive use for hydrogenation reactions. MOFs converted into other biofuels such 5-nonane and liquid alkenes used as
can be either used as active catalytic supports or the hydrogen storage transportation fuels [75]. Guo et al., reported Ru/MIL-101(Cr) as a
material making them superior to the other catalysts use for hydroge­ catalyst for the hydrogenation of levulinic acid into potential biofuel
nation [67]. The type of hydrogenation reaction decides the required GVL. The reported MOF at optimized reaction conditions provided good
characteristics of the MOF; therefore, variety of metal organic frame­ selectivity for levulinic acid and completely converted (~99%) levulinic
works have been designed so far. For instance, pristine MOFs include acid into GVL. The stability of the Ru/MIL-101(Cr) was reflected from its
UiO-66, MIL-101 and ZIF-8 etc. whereas they can also be functionalized multiple use. Although levulinic acid is highly acidic and it may cause
with acidic/nitro/amino groups [68–70]. They can either be used as damage to the ions of catalyst leading to the reduced reusability but
such or may act as support. The various types of synthetic methods Ru/MIL-101(Cr) was found to be stable (four reuse) due to the mild
adopted for the production of MOFs are illustrated in Fig. 3. Further­ conditions of the reaction which improved the reusability of ruthenium
more, their porous structure and crystalline nature can also be harnessed based catalyst [76]. The research group of Kuwahara et al., reported the
to synthesize MOF derived porous materials [71]. functionalized UiO-66 –SO3H for the catalytic transfer hydrogenation of

Fig. 3. Summary of main routes to obtain catalysts based on MOFs. Reprinted from [71] with permission from MDPI. This is an open access article under the Creative
Commons Attribution License (CC-BY). (https://creativecommons.org/licenses/by/4.0/).

7
 H.A. Akram et al.
Table 4
MOF based catalytic conversion of biomass derived chemicals into biofuels.
MOF/MOF derived MOF synthesis method Substrate Valorized fuel Mechanism involved Catalyst Time Temperature Conversion Yield Reusability (No. of Ref.
product dose (◦ C) (%) cycles)

UiO-66 (Hf)-SO3H Hydrothermal Furfuryl alcohol Alkyl levilunate Catalytic alcoholoysis - 4h 120 100 88 Four [79]
MIL-Cr- SO3H Hydrothermal Furfuryl alcohol Ethyl levilunate Catalytic ethanolysis 100 mg 2h 120 100 79.2 Five [73]
UiO-66-SO3H In-situ mixing Fructose 5-ethoxymethyl furfural - 30 mg 1h 140 99.7 80.4 - [93]
Ru/MIL-101(Cr) Impregnation method Levulinic acid γ-valerolactone Hydrogenation 5.6 mg 5h 70 100 >99 Four [76]
UiO-66-(COOH)2 Aqueous room Levulinic acid Ethyl levulinate catalytic transformation 0.39 mol% 24 h 78 - 97% Five [80]
temperature method of LA
UiO-66 Solvothermal Furfural Furfuryl alcohol Catalytic transfer 75 mg 5h 140 >99 97% Five [82]
hydrogenation
UiO-66-SO3H Solvothermal Levulinic acid γ-valerolactone Catalytic transfer 100 mg 9h 140 - 85 Four [57]
hydrogenation
UiO-66-NH2 - Fructose Hydroxy methyl furfural Catalyzed dehydration 25 mg 1h 100 - 71 Four [86].
Cu-NP@ZIF-8 Room temperature 2,5- dihdroxymethyl 5- hydroxy methyl Hydrogenation - 3h 140 - 99% - [159]
8

precipitation furan furfural

[Cu-BTC][HPM] - Levulinic acid Ethyl levulinate Esterification 40 mg 6h 120 92.4 100 Three [74]
Hf-MOF-808 Hydrothermal Levulinic ester γ-valerolactone Hydrogenation 20 mol % 10 h 120 100% 75% Five [77]
Ni/C NP from Ni-MOF - Levulinic acid γ-valerolactone Hydrogenation 100 mg 5h 200 - 98.2 Eight [78]
ZIF-67 derived Co Reduction of MOF Furfuryl alcohol 2-methyl furan Hydrogenation 10 mg 5h 180 99.4 - Four [160]
nanoparticles
UIO-66-SO3H - Fructose 5-ethoxymethylfurfural Alcoholysis 30 mg 1h 140◦ 99.7 80.4 - [93]
Pd@MIL-125 MOF Solvothermal Vaniline 2-methoxy-4-methyl Hydrodeoxigenation 5 mg 2.5 h Room >99% 96 Five [161]
phenol temperature
UiO-66-NH2-SO3H-2/ Hydrothermal Glucose 5-HMF Dehydration 120 mg 6h 120 92 54.9 Five [88]
C3N4@PDA
MIL-101- SO3H - Fructose 5-HMF Dehydration 30 mg 5 150 ~100 90 Three [89]
min
MOF-808 Hydrothermal Furfural Furfuryl alcohol Catalytic transfer - 2h 100 99.2 93 Five [83]
hydrogenation

Molecular Catalysis 539 (2023) 112893

H.A. Akram et al. Molecular Catalysis 539 (2023) 112893

Fig. 4. Possible conversion pathways of furfuryl alcohol (FA) to ethyl levulinate (EL) using ethyl alcohol over MIL-101(Cr)–SO3H catalyst. Reprinted from [73].
Copyright © 2016 American Chemical Society under the Creative Commons Attribution License (CC-BY-NC-ND) (https://creativecommons.org/licenses/by/4.0/).

levulinic acid and its esters into γ-valerolactone (GVL). The 60 mol% of and carboxylic groups (Brønsted acidic). The as synthesized UiO-66-(­
sulfonic acid was found to be efficient to yield GVL up to 85% at 140◦ C. COOH)2 was also reusable up to at least five runs of catalytic activity
The synthetic pathway involved in the production of γ-Valerolactone which is an indication of the stability of the catalyst [80]. It can be
using lignocellulosic biomass is shown in Fig. 5. This commendable inferred that this synergistic phenomenon can be utilized for the con­
catalytic activity was due to the synergistic role of Lewis acidity of metal version of biomass into biofuel and other valuable chemicals. The above
clusters and Brønsted acidity of sulphonic groups arranged closely with discussed catalysts provide a good reference and could be exploited for
each other [57]. Rojas-Buzo et al., reported Hf-MOF-808 for the catalytic the up-gradation of other lignocellulosic biomass to obtain useful
transfer hydrogenation of levulinic ester to produce γ-valerolactone. The products.
Hf-MOF-808 supported with Brønsted-acidic Al- beta zeolite trans­
formed 75% of furfural to γ-valerolactone in four chemical trans­ 4.1.3. MOF based catalytic production of furfuryl alcohol (FA)
formation steps. The 6-interlinked metal nodes and the Brønsted acidity Among other compounds that are derived from lignocellulose,
of the Al-zeolites facilitated the easy access to the catalytic sites [77]. furfural is also used in many fuel precursors. When hemi-cellulose is
Another study reported the selective hydrogenation of levulinic acid into hydrolyzed it produces xylose which upon dehydration produces
GVL using magnetic Ni/C nanoparticles derived from Ni-MOF precursor. furfural and ultimately dehydrogenation of furfural produce furfuryl
This study found that by simply changing the solvent and keeping the alcohol (FA) [81]. For example, Qiu et al., reported the catalytic transfer
catalyst same different products can be obtained. The use of 1,4-dioxane hydrogenation of furfural to furfuryl alcohol using UiO-66 metal organic
and isopropyl alcohol as solvents provided 98.2% and 86.1% of GVL, framework as a catalyst. The biomass derived furfural was successfully
respectively. In case of methanol as a solvent, methyl levulinate was converted into furfuryl alcohol with a percentage yield of 97%. The
obtained in a good yield of 86.5% whereas ethanol as a solvent produced recyclability of the catalyst ensured its stability over five runs of cata­
45.6% of ethyl levulinate. Furthermore, the magnetic properties of the lytic activity. The structural characteristics and Lewis acidity of the
catalyst provided the easy separation of the catalyst using a simple UiO-66 were the main contributors towards the high catalytic activity.
magnet with good recyclability [78]. Gupta et al., reported acid func­ The authors also reported the catalytic efficiency of UiO-66 against
tionalized hafnium-based MOF, UiO-66(Hf)-SO3H, for the catalytic various aldehydes to yield their respective alcohols [82]. This work
esterification and alcoholysis of furfuryl alcohol into alkyl levulinates. provides insight towards the production of valuable chemicals using
The remarkable Brønsted acidity of the UiO-66(Hf)-SO3H due to the biomass for sustainable environment. Valekar et al., reported various
sulfonic acid groups present in the linker and covalently bonded clusters Zr-MOFs (MOF-88) for the catalytic transfer hydrogenation of furfural
of hafnium, ligated with hydroxyl groups led to the excellent catalytic into furfuryl alcohol. The influence of metal node to the ligand coordi­
activity [79]. Similarly, the outstanding catalytic conversion of levulinic nation was the main aim of the study. It has been found that the lowest
acid into ethyl levulinate has also been reported by functionalizing the coordination number (6) was most satisfactory for the catalytic activity
zirconium-based MOF (UiO-66) with the Brønsted acid (COOH). The among various Zr-MOFs. Moreover, MOF-808 was activated using
functionalized UiO-66-(COOH)2 yielded 97% of ethyl levulinate which methanol (M- MOF-808) and it outperformed than simple MOF-808. The
was ascribed to the synergistic role of zirconium clusters (Lewis acidic) catalytic transfer hydrogenation of furfural was achieved in only 2 h

Fig. 5. The synthetic pathway of γ-Valerolactone using lignocellulosic biomass. Reprinted from [57]. Copyright © 2016 American Chemical Society.

9
H.A. Akram et al. Molecular Catalysis 539 (2023) 112893

with 93% yield of furfuryl alcohol using M- MOF-808. The methanol low flash point (~110◦ C) and larger energy density (30.3 MJ/L)
treatment modified the acid base characteristics of the MOF by devel­ compared to the other fuels like ethanol [90]. Consequently, it is an
oping coordination unsaturated sites and methoxy/hydroxyl groups on excellent choice of fuel for future applications [91]. According to Mascal
the surface of the MOF which facilitated the adsorption of furfural onto and Niktin, an appropriate ratio of EMF as an additive in the fuel led to
the nodal points of the catalyst (Fig. 6) [83]. the smooth run of the engine with the emission of lesser harmful prod­
ucts or sulfides [92]. For instance, UIO-66-SO3H has been reported for
4.1.4. MOF based catalytic production of hydroxyalkyl furfural the catalytic conversion of fructose into high grade liquid fuel 5-ethox­
5-Hydroxymethylfurfural (HMF) is a valuable chemical due to the ymethylfurfural (EMF). The synthesized MOF was viable catalyst for
presence of hydroxyl and carbonyl groups on the furan ring [84]. It can synthesis of bio-fuels from bio-mass as the results showed 97% of fruc­
be further utilized for the conversion of lignocellulose into other useful tose was converted in only 1 hour over temperature of 140◦ C and yield
products such as 2, 5-dihydroxymethylfuran (DHMF) [85]. Fu et al., of EMF was about 80.4% which is an excellent precedent for the syn­
reported NH2/NO2 functionalized UiO-66 for the catalytic dehydration thesis of biofuels using catalyzed mechanism [93].
of fructose into hydroxymethyl furfural. The presence of functionalized The above-described catalytic performance of the MOFs for
group (-NH2) influenced the Brønsted acidity of the catalyst and pro­ upgrading the biomass might be ascribed to the combined role of active
vided a good yield of HMF (71%). It can be inferred that as the fraction sites and the functionalized groups attached with the ligands and itself
of the linker increases, it opens more metallic sites of zirconium that the active metallic centres of the metal organic framework MOF. In
might improve the catalytic activity [86]. A recent study reported the short, MOF and MOF-derived materials are promising catalyst for the
upscale synthesis of UiO-66 functionalized with -SO3H groups for the conversion of biomass derived products involving dehydration of sugars,
better conversion of biomass derived fructose into 5-HMF. The Brønsted catalytic transfer hydrogenation of alcohols and esterification of acids
acidic sites of the UiO-66-SO3H effectively dehydrated the 70% of into platform chemicals.
fructose and yielded 40% of 5-HMF at optimized conditions. The similar
catalytic conversion was also carried out with UiO-66 which showed no 5. Current challenges and future recommendations
conversion of fructose which confirmed the role of -SO3H groups in
catalytic activity [87]. Zhang et al., reported the UiO-66-NH2-­ The easy accessibility of lignocellulosic and algal biomass has
SO3H-2/C3N4@PDA acid-base bi-functional catalyst supported on the motivated scientists for their effective use as a low-cost feedstock for
polydopamine g-C3N4 (C3N4@PDA). The combined influence of biofuels. In this regard, it is very important to discover pretreatment
acid-base bi-functionalities, micro-porosity and thermal stability of the methods that do not require the use of costly chemicals for the pro­
reported MOF has resulted in the 54.9% yield of 5-HMF under mild duction of biofuel. Each pretreatment method has its own pros and cons
conditions. Furthermore, this catalyst also converted other carbohy­ and hence one approach cannot be used on different biomasses. There­
drates into 5-HMF with moderate to good yields [88]. Aljammal et al., fore, it is important to understand the factors, the structure and
reported MIL-101-SO3H for the conversion of fructose into 5-HMF composition of biomass. The future research should focus on the
through dehydration reaction. The observed fructose conversion was improved yields that can be achieved by combining two or more pre­
nearly 99% with 5-HMF yield approaching to 90%. The functionaliza­ treatment procedures. The conversion of pretreated biomass into biofuel
tion of MIL-101-SO3H resulted in the large surface area and more cat­ is an important step towards the practical utilization of the biomass.
alytic sites which contributed to the high yield of 5-HMF [89]. Fig. 7 However, the cost of enzymatic treatment following pretreatment of
shows the conversion route of fructose into 5-HMF which is promoted by lignocellulosic biomass is higher. Metal organic framework based cata­
the Brønsted acidity of the sulphonic acid groups [89]. lytic conversion is a substantial approach to this issue, but it is still at
beginning stage. There are only few types of MOFs that have been
4.1.5. MOF based catalytic production of 5-ethoxymethylfurfural (EMF) studied for the said purpose and direct conversion of biomass into bio­
5-ethoxymethylfurfural (EMF) is another valuable furan derivative hydrogen through MOFs is still lacking in literature. It is therefore
having some advantageous features like higher boiling point (235◦ C), suggested that MOF based catalytic conversions should be more

Fig. 6. Catalytic transfer hydrogenation of furfural (FUR) into furfuryl alcohol (FOL) over metal node modified MOF-808. Reprinted from [83]. Copyright © 2020
American Chemical Society.

10
H.A. Akram et al. Molecular Catalysis 539 (2023) 112893

Fig. 7. The route of fructose conversion into HMF via dehydration.

explored along with the focus on the cost-effectiveness, toxicity, and Norwegian Financial Mechanism 2014-2021 under the Project number
environmental impacts of the MOFs. The study on MOF based valori­ 2020/37/K/ST8/03805.
zation of biomass conducted so far is lab scale only whereas there is a
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