1 s2.0 S0021951722005152 Main

Journal of Catalysis 417 (2023) 286–300
Contents lists available at ScienceDirect
Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat
On the 3D printed catalyst for biomass-bio-oil conversion: Key

technologies and challenges
Vahid Haseltalab, Animesh Dutta, Sheng Yang ⇑
School of Engineering, University of Guelph, Guelph, Ontario N1G 2W1, Canada
a r t i c l e i n f o a b s t r a c t
Article history: The devastative effects of traditional fossil fuel consumption have made biomass (e.g., plants, wood, and
Received 1 October 2022 waste) a widely used renewable source of energy. The variety in biomass properties makes tunable cat-
Revised 29 November 2022 alysts an essential ingredient to promote reactions for desired molecule outputs. Catalysts with optimal
Accepted 12 December 2022
catalytic performance are typically structured with complicated morphology, such as high porosity and
Available online 16 December 2022
sophistic pore network, which makes it challenging for catalyst fabrication. Recent progress in utilizing
3D printing as the fabrication method has demonstrated great potential of handling the complex struc-
Keywords:
ture while improving catalytic performance; however, rare work has focused on biomass-bio-oil conver-
Biomass conversion
Catalyst morphology
sion (BBC). With the aim of developing the optimal structured catalysts for BBC applications, this paper
3D printing particularly reviewed 1) typical catalysts used for biomass conversion applications, 2) 3D printed cata-
Catalyst design lysts, and 3) design and optimization of structured catalysts. It is found that the BBC is often isolated from
Optimization manufacturing and focused more on different catalyst composition with transition metals to provide the
desired catalyst architecture and further to improve upgrading of the BBC product. Current work on 3D-
printed catalysts also show deficiency in several aspects including formation of coke and catalyst deac-
tivation, lack of a comprehensive design for the catalyst structure (e.g., mostly 2D structures), absence of
manufacturing constraints in design operation, and insufficient resolution of 3D printing methods. To
solve these issues, several potential research directions and opportunities are discussed at the end of
the study.
Ó 2022 Elsevier Inc. All rights reserved.
1. Introduction yields and imposes various challenges. For example, catalyst deac-
tivation was observed during the process using ZSM-5 as one of the
As the amount of CO2 in the atmosphere rises, biomass has popular catalysts in this application, since the micro-porous archi-
become a viable non-greenhouse energy source. Biofuel that is cre- tecture of these catalysts are clogged by solid residue (coke). Some
ated from biomass recycles atmospheric carbon, as opposed to fos- studies tried to alleviate the problem by employing dopants into
silised carbon conversion, which only creates carbon dioxide. the catalyst [3,4], however the recent investigations suggest using
However, biomass conversion still has many limitations. For exam- hierarchical catalyst [5]. The inquiries into both approaches require
ple, bio-oil, one product of biomass conversion using fast pyrolysis a general understanding of the catalyst morphology and a proper
(a thermochemical process with controlled environment), is highly design structure.
corrosive and has a low heating value since it comprises a compli- Since the overall objective is to improve the reaction rate and
cated variety of oxygen functional groups [1]. Moreover, bio-oil has product selectivity, adding catalyst to the reaction is essential
high viscosity and is not chemically stable when stored, which is along with the tuning of other parameters, such as concentration
due to a number of processes, such as polymerization, that occur of the reactants, surface area and temperature [6]. A catalyst can
between the various oxygenation functionalities [2]. To improve lower the activation energy for a reaction by i) aligning the react-
bio-oil yield and quality, a catalyst is frequently used in the pro- ing particles to increase the likelihood of a successful collision, and
cess. Some of the instances include zeolite, activated carbon, alu- ii) reacting with the reactants to create an intermediate that
mina, etc., each of which has different impacts on the product requires less energy to complete the reaction [7]. A proper design
of the catalyst architecture can significantly promote the reaction
rate [8]. However, understanding of the catalyst morphology and
⇑ Corresponding author.
the impact of morphological parameters on the reaction rate dur-
E-mail addresses: [email protected] (V. Haseltalab), [email protected] (A.
Dutta), [email protected] (S. Yang). ing the thermochemical processes has rarely been discussed in
https://doi.org/10.1016/j.jcat.2022.12.013
0021-9517/Ó 2022 Elsevier Inc. All rights reserved.
V. Haseltalab, A. Dutta and S. Yang Journal of Catalysis 417 (2023) 286–300
the literature. Furthermore, due to the high geometrical complex- required. In contrast, hydrothermal liquefaction (HTL) requires a
ity of the optimal design, the manufacturing constraints need to be lower temperature (300–400 °C), longer residence durations
considered which is also neglected in previous studies. (0.2–1.0 h), and higher working pressure (5–20 MPa). In addition,
A proper manufacturing technique is critical for securing the the HTL process does not need drying of the feedstock, making it
desired performance of a structured catalyst with complicated particularly ideal for naturally wet biomass. However, a catalyst
structures. The recent advancements in additive manufacturing is frequently used in this process to improve oil yield and quality.
(AM, also known as 3D printing) made this technology a great can- As seen in Table 1, the fast pyrolysis process would have a higher
didate for this application. AM is an advanced fabrication process bio-oil yields while the HTL process can produce bio-oil with
in which precise geometric patterns can be manufactured by depo- higher quality in heating value and moisture content. This section
sition of materials layer by layer. The ability to locally tune catalyst will provide an overview of the typical catalysts that are used for
morphology along both the axial and transversal coordinates and the upgrading of bio-oil quality in both the fast pyrolysis and
control the material compositions has brought unprecedented HTL processes.
design freedoms for optimizing the catalyst patterns. There have
been a variety of studies focused on the 3D fabrication of catalysts
2.1. Hydrothermal liquefaction
for different applications including monolithic catalysts, reactors,
mixers, and ancillaries [9], yet the investigation into the biomass
With a high moisture feedstock and gaseous, aqueous, and solid
application is scarce. The mostly used 3D printing techniques for
phase by-products, hydrothermal liquefaction is a method for con-
catalytic materials in literature are composed of slurry-based
verting biomass to bio-liquids that is performed in water at high
[10], filament-based [11] and powder-based [12] methods. The
pressures (5–20 MPa) and moderate temperatures of 300–400 °C.
process of choosing the right approach while taking into account
In contrast to other methods, its product has a high energy content
the porosity, resolution, and compatible materials may actually
and a distinctive feature of increased heat recovery. To create a
open up opportunities for an infinite number of possible geome-
reaction analogous to pyrolysis, hot compressed water is used in
tries. Despite the recent advancements, there are still many fabri-
liquefaction as the reactant’s catalyst. In liquefaction, other types
cation challenges, such as material limitations, printing quality,
of catalysts are crucial for increasing efficiency and minimising
and resolution of printers for nano-scale porous media.
the development of tar and char. In this regard, heterogenous cat-
With the aim of developing novel structured catalysts for
alysts are popular that can provide high levels of stability, recycla-
biomass-bio-oil conversion with improved catalytic performance,
bility, and hydrogen selectivity. The literature has described the
this paper has reviewed the progress in 3D printing and optimal
use of a variety of heterogeneous catalyst types, including zeolites
design of catalysts. This literature review begins by outlining the
and transition metals, to enhance the quality of bio-oil. Several cat-
catalysts that are most frequently used in biomass conversion pro-
alysts, including Pt/C, Pd/C, Ni/SiO2-Al2O3, Ru/C, and zeolites, were
cesses and then examines various measures that have been taken
evaluated for their impacts on the HTL of microalgae and were
to enhance the quality of the bio-oil. Next, key 3D printing tech-
found to improve oil output by 10–22 wt% when compared to liq-
niques for catalyst fabrication are summarized. Furthermore, the
uefaction without catalysts [15]. Wang et al. [16] examined the
significance of catalyst morphology and how the morphology
impact of transition metals impregnated as nitrate (Fe, Co, Mn,
affects the overall catalytic performance are surveyed. More specif-
Ni, and Mo) on TiO2 as catalysts for microalgal liquefaction. The liq-
ically, the design and optimization of the catalyst structure regard-
uefaction of microalgae was accelerated by Ni/TiO2 catalysts,
ing the design variables and objective functions are presented.
which resulted in bio-liquid with lower viscosity and enhanced
Finally, potential research directions to tackle the identified chal-
hydrocarbon content. To maximise the production of biofuel, Nan
lenges are discussed.
et al. [17] investigated the effects of various heterogeneous cata-
lysts on the HTL of cardboard. Results showed that the reaction
2. Biomass conversion temperature, water ratio, and residence duration all have a signif-
icant impact on the bio-oil output. At 300 °C for 30 min, Ni(NO3)2,
A variety of thermochemical techniques have been used to produced the highest hydrogen yield (=11.46 mL/g), but the high-
make bio-oil. Pyrolysis and hydrothermal liquefaction are the most est bio-oil yield (=47.14 percent) was seen at 275 °C for 30 min. Ni/
common ones [13]. These methods transform biomass feedstock to Al2O3, Pt/Al2O3, and CoMo/Al2O3 were investigated by Biller et al.
bio-oil, biochar, and gas, the compound of which may vary and [18] for their impact on microalgal liquefaction. A lower yield of
depend on the feedstock, pre-treatment, process, operating condi- bio-oil is obtained from liquefaction process of Chlorella vulgaris
tions, and subsequent upgrading. Table 1 [14] compares the char- microalgae without catalysis. Results showed that utilizing Ni/
acteristics and technical practicability of the two thermochemical Al2O3 could boost bio-oil’s heating value and encourage the deoxy-
operations for bio-oil generation. Fast pyrolysis is characterised genation of lipids to produce alkanes. When compared to zeolite
by a short residence time (1 s), atmospheric air pressure, and a and Na2CO3, nano-Ni/SiO2 catalyst delivered the best bio-oil yield
moderate temperature (450–500 °C). However, biomass drying is [19]. Zeolites have also shown promises to increase the bio-oil
Table 1
Comparing thermochemical methods for producing bio-oil [14].
Methods Treatment condition/requirement Process description Technique feasibility

Pros. Cons.
Fast pyrolysis High temperature (500–800 °C); In the gas phase, homogeneous Low initial cost; increased Poor quality of fuel achieved
residence time < 1 s; atmospheric processes turn light tiny molecules oil yield of up to 80 % on
pressure; drying required into greasy compounds. dry feedstocks
HTL Low temperature (300–400 °C); residence Happens in aqueous medium and Bio-oil with higher quality Lower oil yield (20–60 %);
time (0.2–1.0 h); higher pressure (5– contains complicated pathways. (higher HHV and requires high-pressure
20 MPa); no need to dry lower moisture) equipment, more expensive.
287
yield in microalgal biomass. Hierarchical Zeolites (HZSM-5) are pyrolysis process [27]. In the following, the in-situ bio-oil catalytic
mostly used for removing oxygen out of oxygenated compositions. upgrading processes that has been used in recent years is briefly
A higher yield of bio-oil was produced when zeolites and metals described, and for more details, readers are referred to [29]. Bio-
were combined than when zeolites were used alone [20]. The yield mass conversion to fuel using in-situ catalytic rapid pyrolysis with
of oxygenated compounds declined whereas the yield of hydrocar- zeolite catalysts opens up the possibility of generating gasoline-
bons was enhanced when a Co-Zn/HZSM-5 catalyst was used (ke- like aromatics. The acidity of the zeolite, along with its textural
tones, acids, alcohols, and phenols) [21]. The effects of K2CO3 and and topological characteristics, impact the amount of aromatic
HZSM-5 catalysts using various Ni loadings were reported by chemicals generated [28]. In general, noncatalytic pyrolysis pro-
Cheng et al. [22]. Among all catalysts, K2CO3 with Ni loading pro- duces more liquid products than the amount by catalytic pyrolysis
vided the highest yield and the lowest solid by-product. To liquefy where Y zeolite, for instance, is integrated on an active (alumina,
biomass, supercritical ethanol was employed as a solvent and used silica-alumina) or inactive (silica) matrix in a commercialized equi-
to assess the performance of a Zn/HZSM-5 catalyst [23]. Compared librium fluid catalytic cracking (FCC) catalyst. By using a catalyst,
to HZSM-5 alone, Zn/HZSM-5 had a stronger catalytic effect by larger quantities of hydrogen were also observed [29]. Karn-
yielding biofuel with the highest hydrocarbon percentage. To suc- janakom et al. [30] performed in-situ catalytic upgrading of bio-
cessfully scale up the approach, there are various issues with HTL oil to aromatic hydrocarbons. The relative overall hydrocarbon
that should be resolved. Heteroatoms like N, O, and S are some- quantity significantly grew when the catalyst/biomass ratio
times found in microalgae-based HTL bio-oil. To reduce the gener- climbed to 8 wt-%. While the ratio between catalyst and biomass
ation of heteroatoms, temperature and catalyst modification are was more than 8 wt-%, the total relative hydrocarbon content
therefore required. Another instance is catalyst deactivation which decreased slightly, possibly due to the activation of secondary pro-
has been documented and is thought to be caused by phenolic oli- cesses in which hydrocarbons were broken down into gases and
gomers. However, it has been found that simple aromatic chemi- coke during the longer residence time.
cals (such as guaiacol and phenol) and inorganic compounds are Zeolite and biomass pre-treatment and different metal catalysts
not the cause of catalyst deactivation. The optimum reaction for were studied in literature [31]. The vapour from fast pyrolysis of
measuring deactivation is the reformation of glycolic acid in the biomass was directly catalytically cracked (using HZSM-5 catalyst
liquid phase. Additionally, it has been reported that the deactiva- integrated with Fe, Zr, and Co) to enhance bio-oil properties. In
tion is due to the temperature that affects the synthesis of large addition, increasing the temperature of the catalytic reaction pro-
molecular weight compositions [24]. moted the concentration and output of aromatic hydrocarbons sig-
nificantly. The use of 4Fe/HZSM-5 boosted the production of
2.2. Catalytic pyrolysis naphthalene compositions, and 4Zr/HZSM-5 increased the genera-
tion of benzene derivatives when the 4CO/HZSM-5 catalyst was
Fast pyrolysis (FP) is a method for converting biomass into use- used to influence gas generation. Pre-treatment with HCl and
ful biofuels and chemical feedstocks. For bio-oil production, FP NaBH4 also raised the hydrocarbon content; however, pre-
defines as cracking process that takes place without oxygen at treatment with NaOH mostly resulted in the synthesis of phenol.
temperatures ranging from 500 to 800 °C for 0.5–3 s. More biochar The catalytic fast pyrolysis of biomass was studied in a unique
is formed when the residence time is longer, and the temperature study that included methane aromatization [32]. In the presence
is lower. Dried biomass (<10 %), small particles (<3 mm), and quick of HZSM-5 zeolites, this fast pyrolysis technology can be employed
condensation of pyrolyzed vapour are preferred. Pyrolysis yields as a solution to the high price of H2 usage in standard bio-oil
three distinct products: biochar, bio-oil, and gases, such as CO2 upgrading procedures. In comparison to hemicellulose and lignin,
and CO (the most frequent), H2, hydrocarbons like methane and cellulose produced more aromatic compounds. In addition, utiliz-
volatile carboxylic acids [25]. Increasing the moisture translates ing methane (rather than Helium) resulted in a higher HDO of
to high energy expenses as well as worse fuel yield and quality. lignin-derived phenols and a higher aromatic output. Table 2
Due to heat and mass transfer restrictions, larger particle sizes demonstrates the catalysts that are used for bio-oil production
result in incomplete pyrolysis, and quick quenching avoids addi- with associated process conditions. A variety of zeolite catalysts
tional oxidation and cracking. (acidic, basic, and -alumina catalysts with doped metals, as well
Fast pyrolysis has many advantages, including the ability to as their parental counterparts) were examined. The quality of the
operate at atmospheric pressure and at moderate temperatures produced bio-oil was found to be highly dependent on the type
(450 °C), or high yield of bio-oil (more than 70 %). However, as of catalyst; nevertheless, the bio-oils acidity decreased dramati-
mentioned before, the inclusion of water and oxygen molecules cally while deoxygenation increased for all types of catalysts
in crude bio-oils generated from fast pyrolysis results in poor qual- [33]. MgO materials have recently been studied as catalysts (as
ity. Also, other disadvantages, such as high viscosity, storage insta- an alternative to traditional acidic zeolite catalysts) for catalytic
bility, low heating value, and high acidity (corrosiveness) are also rapid pyrolysis of lignocellulosic biomass [34]. The MgO catalysts
identified in the bio-oil produced in this process. Therefore, cat- greatly reduced the oxygen contents of the resulting bio-oil and
alytic upgrading is employed as a solution to improve the bio-oil had equivalent or even higher performance than the industrial
quality for different applications (especially biofuels). Chemical ZSM-5 catalyst. This is because oxygen was eliminated by the
and thermocatalytic operations and physical upgrading methods CO2 production route instead of CO and water synthesis in the case
could be used to improve the physicochemical qualities of bio- of ZSM-5 zeolite. However, formation of coke was marginally
oil. For bio-oil upgrading, several catalytic processes including higher on MgO catalysts than on ZSM-5, although the produced
aldol condensation, ketonization, esterification, and Hydrodeoxy- coke was oxidised at low temperatures [34]. Another study inves-
genation (HDO) can be used [26]. Other upgrading techniques tigated the performance of Fe/ZSM-5 catalyst for quick biomass
include catalytic cracking and deoxygenation over zeolites, as well pyrolysis. The Fe/ZSM-5 catalyst had better activity for oxygenate
as innovative technologies like catalytic plasma reactors. It’s worth conversion and higher generation of aromatic hydrocarbons com-
noting that physical upgrading approaches have received less pared to the ZSM-5 catalyst. Furthermore, the yields of aromatic
attention compared to chemical upgrading methods. Three pri- hydrocarbons increased significantly as the temperature incre-
mary factors are critical in catalytic pyrolysis/upgrading: catalyst mented from 500 to 600 °C, but decreased as the temperature
type, heating rate, and catalyst/feedstock ratio. Catalysts can con- raised from 600 to 800 °C. Further polymerization reactions of aro-
siderably increase the composition of bio-oil during or after the matic hydrocarbons and oxygenates were hampered using the
288
Table 2
Integrated upgrading of fast pyrolysis.
Biomass feedstock Process condition Catalysts Improvements Ref.

Beech – MgO Promoted activity, reduced H2O, higher gas and coke, low oxygen [34]
wood sawdust content
Pine wood Experiments on micropyrolysis and bench- Metal doped catalysts Increased deoxygenation [33]
scale CFP were carried out. reduced the acidity
Loblolly pine Average temperature of 520 °C Non-zeolite, alumina- Maximum average carbon output of 89 [3]
sawdust based catalyst C content of the aqueous phase fraction was quite low. The average
amount of H2 consumed per 1 g of dry biocrude ranged from 0.04
to 0.07 g
Pine sawdust At temperatures ranging from 450 to Metals (Fe-Zr-Co) Aromatic hydrocarbon concentration and production have [31]
650 °C, a continuous two-step fixed bed integrated with HZSM- increased significantly
reactor is used 5 zeolite
Sunflower stalk N2 gas flow (100 cm3/min) as the carrier Doping of Zn, Ce, or Ni There were more aromatic hydrocarbons generated. [30]
gas in a fixed bed reactor. on mesoporous Al2O3
Beech wood xylan, – HZSM-5 Increase deoxygenating of lignin-derived phenols, resulting in a [32]
and kraft lignin 5.47 % carbon yield of polyaromatics
above-mentioned synthesised catalyst [35]. In a downdraft fixed on yield of the product. For instance, Demirbas [39] reported the
bed reactor, a zeolite catalyst modified with copper was employed optimal temperature for the highest yields of liquid in pyrolysis.
to improve bio-oil’s quality in a pyrolysis and upgrading operation. This value is around 700 °C for almost all various biomass feed-
The hydrocarbon selectivity of high silica-zeolite was quite high. stocks. Although using a catalyst reduces the optimal process tem-
Moreover, by altering a small amount of copper, the selectivity perature, the catalyst should have a thermal stability up to 700 °C.
was enhanced considerably [36]. Moreover, there are some morphological aspects of catalyst which
are described in the next section.
2.3. Challenges
3. 3D printing of catalysts
Even though catalytic pyrolysis improves bio-oil production
and quality, some issues remain, including catalyst deactivation, 3D printing or Additive Manufacturing (AM) is a process of
clogging of reactor, formation of coke, and a high H2O content in stacking materials layer by layer to transmute a virtual artifact into
the product. The combination of operations (catalytic pyrolysis a physical part. It is a unique fabrication method that allows the
and catalytic cracking) increases the yield and properties of the manufacturing of very complex geometries with great precision
product. Catalysts and upgrading procedures are used to enhance that would be difficult to achieve using conventional methods like
bio-oil fuel efficiency, which raises the cost of production. Further- casting and machining [40]. Moreover, it effectively gets rid of the
more, bio-oil generation as a fuel replacement is currently not limitations on design and fabrication that come with traditional
thought to be economically viable enough to be a viable replace- production techniques [41]. A wide range of materials, including
ment to petroleum fuels. To obtain maximal yields of the desired ceramic, glass, metals, polymers, and composite materials, can be
mono-phenol and mono-aromatic hydrocarbons, future research fabricated using AM processes [42]. Popular power sources used
will focus on increasing HZSM-5 acidity and preventing coke depo- in AM techniques include lasers and electron beams. There are a
sition. In addition, more research into catalyst preparation and wide range of AM approaches, each of which operates with a cer-
effects is required. Because of the complexity of bio-oil reactions tain type of material and energy source. The most dominant AM
and production, as well as the difficulty of managing several reac- processes that are used in catalyst fabrication are demonstrated
tions occurring at the same time, designing an entire structure of in Fig. 1. Projection light is used in Digital Light Processing (DLP)
bio-oil upgrading and fast pyrolysis is tough. Catalysts can help printers to polymerize materials and create the pre-designed struc-
with this problem, but most of them are very costly and may be tures. As shown in Fig. 1a, light is bounced off a deformable mirror
readily deactivated. The impacts of metal and oxide inclusion over device (DMD) or through a liquid crystal screen to expose the pho-
diffusion, structure, topology, and stability aspects of the zeolites, topolymer. Because a full layer is exposed at once, DLP consumes
as well as the feasibility of optimising aromatics yield (beyond less photopolymer than Stereolithography (SLA) and has the
95 %), are the main issues of in situ catalytic rapid pyrolysis. Bio- potential for quicker manufacturing. This technology has substan-
oil upgrading can also be replaced by cracking bio-oils in the exis- tial advantages over other 3D printing processes in terms of print-
tence of solid acid catalysts using mono- and multifunctional zeo- ing resolution, productivity, and operating conditions. It is used
lite catalysts. Because it works at atmospheric pressure and with mostly in medical [43], jewelry [44] and automotive [45] indus-
the absence of hydrogen, this method is less expensive than ex- tries. Powder bed fusion (PBF) is another technique for sintering
situ operations (like HDO) [37]. The main issue in biomass catalytic or fusing atomized powder particles together using a heat source,
fast pyrolysis is catalyst swamping and deactivation because of usually a laser [46]. This is done one layer at a time as other addi-
alkaline ash in the system (from biomass). In this instance, direct tive procedures. Selective Laser Sintering (SLS) is one of the pro-
interaction of the catalyst and the biomass must be prevented. cesses belonging to this category (Fig. 1b). SLA as displayed in
As a result, before commercialising the technique, this problem Fig. 1c, is a technique that uses photochemical processes by con-
must be discovered and resolved. To address this issue, an ex- centrating an ultraviolet laser on a volume of photopolymer resin
situ procedure for reforming primary pyrolysis vapours has been in the desired pattern, which solidifies the resin due to its photo-
proposed [38]. sensitivity [47]. The final product from SLA has a high level of accu-
The catalyst being used in the thermochemical process needs to racy and a nice surface finish. Fig. 1d shows Fused Deposition
have suitable characteristics to endure the process and leads to Modelling (FDM) approach in which a material is heated and dis-
great catalytic performance. Thermal stability is one of those pensed from a nozzle to construct layers of the final item [48].
essential characteristics for the utilized catalyst. Each thermo- Extrusion causes the material to solidify immediately. The method
chemical process operates with an optimum temperature depends works well with thermoplastics, edible materials, elastomers, and
289
Fig. 1. The schematic of common 3D printing methods, a) DLP, b) SLS, c) SLA, d) FDM, e) DIW [50].
clays. Robocasting (Fig. 1e), also known as direct ink writing (DIW) favorable one for catalytic printing is DIW because of its more rea-
is a meso- and micro-scale additive manufacturing technique based sonable operation cost and simpler material composition. The pro-
on extrusion. In DIW, liquid-phase ‘‘ink” is dispensed through cess starts with material preparation. The catalysts are mostly in
small nozzles at controlled flow rates and deposited along digitally the shape of powder, and they are mixed with dispersant, binder
determined routes layer-by-layer to create 3D structures [49]. and deionized water. The deionized water is usually employed as
Ceramics and metals are the most common materials for DIW. a solvent for ceramics to avoid introducing the impurities. More-
A recent review [51] of 3D-printed structured catalysts summa- over, the binder which is mostly polymers is essential for the print-
rized the progress in the general processes and materials as well as ing process and can be used as the template to control the porosity
its industrial applications (e.g., electrodes and reactors), but it of the catalyst structure. The slurry is provided by mixing these
failed to capture the morphology, design, and quality aspects ingredients via different types of blenders until a homogeneous
which are critical for catalysts in biomass conversion applications. mixture is achieved. Dispersants are necessary to enhance particle
This section will focus on reviewing the recent advances in 3D- detachment and prevent agglomeration or clumping. After the
printed structured catalysts (e.g., zeolites) that potentially could slurry is prepared, it is transferred to the 3D printer to begin the
be used for biomass-bio-oil applications. According to the form fabrication process. The two important parameters must be con-
of the feedstock, these works are classified as slurry-, filament-, sidered while making the slurry are: a) viscosity of mixture which
and powder-based methods. highly affects the quality of the printed part and enables the proper
extrusion, and b) controlling the particle size of the binder to
3.1. Slurry-based 3D printing obtain a catalyst with desired porosity and pore size distribution.
After the part is printed, it is dried to remove the moisture and sin-
Slurry-based 3D printing operates with materials typically in tered or calcinated to remove the binder. In some cases, coagulant
the form of pastes or inks that contain the catalyst (or its precur- is added to regulate the rheological properties by increasing the
sor) particles, dependent upon the solid content and viscosity of viscosity. However, it is rarely used in 3D printing of catalysts.
the system [40]. There are many 3D printing processes in this cat- A wide range of catalysts have been successfully printed by
egory including SLA [52], DLP [53], Two-Photon Polymerization adopting slurry-based techniques including zeolite [10,57–59],
[54], Inkjet Printing [55] and DIW [56]. Among which, the most alumina [60,61], copper [62,63], silica [64], and its compound. 3D
290
printing of structures with zeolite as a catalyst is one of the most integration for the MTO method is a potential 3D-printed ZSM-5
important topics. Lefevere et al. [10] studied the effects of various monolith. 3D-printing of hierarchical zeolites (HZSM-5) as hetero-
binders on zeolite paste, including bentonite, colloidal silica, and geneous catalyst for the n-hexane cracking reaction was studied in
aluminophosphate solution. As a catalyst, zeolite ZSM-5 is made literature [59]. A lab-scale 3D printer (GeetechÒ) was used to build
from an aqueous solution of alumina, silica, and sodium hydroxide monolithic zeolite catalysts. Samples with various types of zeolites
and has a fine pore size and high adsorptive characteristics. The were printed and compared, including HZSM-5, H-Beta, HY and
mechanical properties and number of active sites was investigated pristine zeolites. The results reveal that the HZSM-5 zeolite mono-
and results [10] indicated that using a combination of binders can lith has a stronger selectivity for light olefins and has a more stable
improve these properties. In another study [57], a highly absorbent n-hexane cracking activity than powder zeolites. The other popu-
structure was fabricated using DIW. Zeolites 13X, carboxymethyl- larly investigated material as a catalyst or support is Alumina. Yang
cellulose as a binder, and activated carbon were used to prepare et al. [61] studied the influence of temperature and carrageenan (as
the feedstock material. Adsorption equilibrium isotherms mea- a binder) concentration on the rheology of the paste and optimum
surements were used to assess adsorption capabilities of the slurry suitable for 3D printing process. To control the viscosity of
printed parts. The results showed that the textural properties of the resulting mixture, alumina in the form of powder was used
printed items have improved. Introducing metals in zeolite compo- as the feedstock, together with ammonium citrate (as a dispersion)
sition was another subject investigated by Li et al. [58]. The focus and carrageenan powders as a thermo-curing binder. A barrel
was to incorporate metal doping into ZSM-5 zeolite and test its retains the paste and uses gas pressure to propel it into a chamber.
performance in the methanol-to-olefins (MTO) reaction. Some The paste is then extruded to the printing table through a screw
metals including Cu, Cr, Mg, Zn, etc. were used as dopants. The extruder and solidified by hot airflow and the temperature of the
influence of dopants on the physical and chemical properties of print table. In a different study [60], alumina has been used as cat-
the doped monoliths was investigated using X-ray diffraction alyst support along with Ni as its catalyst. CO2 hydrogenation to
(XRD) analysis, scanning electron microscopy with energy disper- methane was examined using Ni-alumina-based catalysts that
sive X-ray spectroscopy (SEM/EDX) and NH3-TPD (temperature were 3D printed into highly adjustable monolithic and multi-
programmed desorption) analysis. The efficiency of these produced channel systems. In this study, the performance of a 3D-printed
metal–doped zeolite monoliths in MTO reactions was investigated structure of Ni-alumina is compared with OctolystÒ catalyst.
and compared to non-doped counterparts. Metal precursor solu- Fig. 2 b and c show the fabrication of two catalyst using a DIW pro-
tion was mixed into bentonite clay together with the zeolite to cess. The comparative analysis indicated that the 3D-printed parts
form metal-doped ZSM-5 monoliths. Calcination was used after with commercial OctolystÒ has superior performance for conver-
printing to break down and eliminate the methyl cellulose that sion of methane. As alumina proved to be a great catalyst support,
acted as a template. Mg/ZSM showed remarkable coke resistance it was also utilized in a study conducted in literature [62]. Alumina
due to the amount of occupied space in the micropores. The results particles, aqueous copper (II) nitrate hemi(pentahydrate), Cu
of this research reveal that the Mg/ZSM-5 monolith with metal (NO3)2.2.5 H2O, and hydroxypropyl methylcellulose (to modify
Fig. 2. Samples printed using DIW printers. a) optical image of zeolites with various dopants [58], b) 3D-printed Ni/Al2O3, and c) 3Dprinted commercial OctolystÒ [60], d) 3D
structure of Cu after sintering [63].
291
the viscosity) were used to make the final ink. The supported cop- plate for monolithic catalyst preparation. There are two typical
per catalyst plays a critical role in the Ullmann reaction to produce ways to print a product with filament-based technology as can
biaryl. Similarly, copper has been used as a catalyst support for the be seen in Fig. 3. The first method is defined as the pre-
application of CO2 methanation [63]. Through analysing the mor- processing approach where the catalyst is introduced before the
phology of the printed parts (Fig. 2d), the sintering temperature printing process by making a composite of polymer and catalyst
was identified as a critical parameter in which using lower sinter- material. In this method, the catalyst powder is added to melted
ing temperature reduced the inner porosity. To produce heteroge- polymer and mixed until a homogeneous mixture is achieved.
neous multi-catalytic multi-component reactions (MMCRs) After hardening, it is cut into to small granules and extruded to a
catalyst, 3D printing of a silica monolith was performed [64]. The desired diameter using an extruder machine. Producing composite
findings indicated that 3D printing of SiO2 monoliths was a feasible filament is quite challenging, and a few problems might occur dur-
way to make monolithic Pd- and Cu-based MMCRs catalysts that ing this process, including filament diameter instability (pulsa-
are efficient, robust, and reusable. Arriaga et al. [65] conducted tion), air bubbles in the filament’s core, surface defects and
research on 3D printing of TiO2 catalyst which is mostly used in ovalization [67]. The filament produced by this method is
photocatalytic processes. An SEM analysis was carried out to com- employed to print the catalyst structure. Afterwards, the product
pare the performance of the extruded parts with nanopowder TiO2, is sintered inside a furnace to attain a porous structure. The second
and an improvement of the structured catalyst for the photocat- filament-based means is defined as the post-processing approach.
alytic processes was eventuated. In this approach, the structure is printed with the polymer filament
and further coated with the catalyst material. Various coating tech-
3.2. Filament-based 3D printing niques can be applied by using solutions or thermal treatments. 3D
printing of a composite filament was carried out by Mackiewicz
The material used in this category is in the form of filament and et al. [11]. The research focused on developing and using functional
the structures are fabricated via a FDM type of printer. In this pro- 3D printing composite filaments with a catalyst substrate (nickel
cess, the printing material is mostly thermoplastic polymers such powder) integrated in a polymeric binder for 3D printing (PLA,
as acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), or Polyvinyl butyral (PVB) or ABS). The method of filament prepara-
high impact polystyrene (HIPS). Polymers are not known as good tion varied according on the polymer utilised. For instance, a melt-
catalysts, due to their low surface areas and poor thermal stabili- ing approach would be applied for PLA, whereas a solvent
ties. However, they can be combined with an active component (acetone)-assisted process was used for PVB and ABS. Nickel pow-
to create a hybrid organic/inorganic product [66]. These character- der was added in a precise ratio after melting PLA. To get a homo-
istics make the printed polymers acceptable to be used as a tem- geneous consistency, the composite was mixed with a spatula. The
Fig. 3. General fabrication process for filament-based 3D printing of catalyst. a) pre-processing approach, b) post-processing approach [11,68].
292
mixture was then evenly dispersed on a foil substrate and hard- compared to other AM processes, and some of the compositions are
ened completely. The solid composite was chopped into small commercially available. Typically, de-ionized water and disper-
pieces for use in the filament extrusion process. The constructions sants are utilized to make a homogeneous mixture. However, prior
are printed using an UltimakerÒ S5 printer after the filaments were to the printing process, the mixed powder is usually dried to
prepared. To remove organic moieties from the printed composite remove any leftover moisture. The microporosity of the final struc-
item, debinding with heat treatment is performed. Finally, the ture is controlled by the ratio of the powder composition. Those
structure was fully sintered, resulting in a porous part. The impact micropores are produced after the printing process through
of Ni-to-polymer ratio on the final porosity of various structures dealloying.
was discussed. In this section, some instances of SLS and SLM printing of cata-
Another study focused on the mechanical properties of printed lysts are presented. The degradation of methyl orange was exam-
samples using a composite filament of TiO2-ABS [69]. The presence ined using Zr-based Bulk Metallic Glass (BMG) and copper as a
of TiO2 within the polymer nanocomposite was confirmed using catalyst [75]. A great photocatalytic performance was achieved
powder X-ray diffraction analysis. For samples with different ratios using complex geometries such as lattice hollow and cubic struc-
of TiO2, stress analysis was evaluated and discussed. In another tures, which showed to be promising for functional applications.
research [70], a CuFeO2 structure is created from a composite fila- A number of optimised process parameters were used to print
ment that is made up of Cu and Fe components. The transition and the samples directly. Then, free corrosion was employed to dealloy
composition were verified using XRD and Differential Scanning the structure until a copper nanostructure was achieved. The find-
Calorimetry (DSC) /Thermogravimetric Analysis (TGA) analysis. ings indicated that the lattice structure with the highest specific
For the hydrogen evolution and water oxidation reactions, 3D- area has the best catalytic efficacy and cycling stability. A free-
printed graphene/PLA electrodes have been developed [71]. In this standing hierarchical nano-porous copper material was also intro-
study, it was claimed that commercial filament contains metal duced as a highly efficient electrocatalyst for methanol oxidation
impurities, which can act as catalysts for the reactions mentioned [75]. It was created using a SLM 3D printing approach and a deal-
above. However, the solvent and post treatment method have a loying operation. Cu-Mn powder composition with a specific ratio
considerable impact on their reactivity. The presence of Fe and Ti was printed and alloyed during the fusing process. Nanoscale por-
impurities, as well as a low carbon-to-oxygen ratio, were linked ous structure was obtained in the last step of the production pro-
to the optimal performance of the thermally treated 3D-printed cess through chemical dealloying by immersing the 3D Cu/Mn
graphene/PLA electrode for the hydrogen evolution reaction. As a alloy structures in (NH4)2SO4 solution to remove Mn. The findings
result, researchers working in this field should be aware of the showed that a computer-controlled hierarchical structure with
presence of metal impurities in commercial graphene/PLA fila- macro- and nano-scaled pores could be used to promote and direct
ments, as well as their significant impacts on electrocatalysis. mass transport while also improving catalytic capabilities. Essa
The coating routine was investigated in [68] with a goal of creating et al. [74] employed SLM to fabricate catalyst bed samples using
Cu-BTC (benzenetricarboxylate) Metal-organic Frameworks alumina ceramic lattices for the application of High-Test Peroxide
(MOFs) for Methylene Blue removal. The component was first (HTP) monopropellant thruster. The purpose of the study was to
printed with ABS filament and went through a few repeated cycles increase the HTP decomposition. Different wash coatings were
in Cu and BTC solutions (see Fig. 3b); then, Cu-BTC/ABS composites used to increase the surface areas of the specimens, including
were ultimately produced. By synthesising novel frameworks with gamma alumina and a combination of gamma alumina and carbon
MOFs and polymers, 3D printing is a viable technique for produc- nanotubes. Alumina was chosen as the catalyst bed substance
ing materials with application other than adsorption. Similar work because it has excellent mechanical qualities at high temperatures.
was also reported in literature [72]. The 3D-printed part was made Incorporating lattice structures into catalyst samples resulted in a
of high-impact-polystyrene filament and went though a sulfona- great surface area and acceptable pressure drop. The performance
tion process to make the monoliths work as an acid catalyst. of samples with different coating materials were evaluated, and
results indicated a great improvement with additively manufac-
3.3. Powder-based 3D printing tured catalyst beds. SLM was also used in fabricating custom-
made electrodes with a desired shape for electrochemical applica-
Powder-based 3D printing employs powder as the feedstock tions [77]. Stainless steel was chosen as the main feedstock; how-
which can be a combination of ceramic and metal catalyst. The par- ever, steel cannot be used directly as an electrode due to its slow
ticles are merged using either liquid binders or powder fusion with electron transfer and high charge transfer resistance. As a result,
the help of heat energy from a laser beam. The powder fusion a conductive catalyst such as IrO2 was deposited on the steel elec-
approaches mostly investigated for the catalytic technology are trode’s surface. The 3D printed steel-IrO2 electrodes demonstrated
Selective Laser Sintering (SLS) and Selective Laser Melting (SLM). excellent capacitive and catalytic properties in alkaline liquids, as
These methods are very similar with the difference that in SLS well as Nernstian behaviour as a potentiometric pH sensor. In
the laser only sinters the loose powder together rather than melt- the custom-made fabrication of electrochemical devices, the use
ing the entire particles [73]. The SLS approach frequently results in of 3D printing to fabricate sophisticated 3D electrode designs on-
undesirable and uncontrolled porosity inside the material, which site has shown to be a game-changer. The integration of metal cat-
has a negative effect on the overall strength of the produced com- alyst in SLS structures was examined by Wei et al. [12] for the
ponent. The major benefit of selective laser melting or sintering is application of self-catalytic reactor (SCR) for Fischer-Tropsch syn-
the large range of materials that can be used, including Al-based thesis, CO2 hydrogenation, and CO2 reforming of CH4. Metals like
alloys [74], Fe-based alloys [12], copper-based alloys [75], and Fe, Co, and Ni have all been utilised separately as catalysts. Metal
metal composites. Moreover, compared to other 3D printing meth- 3D printing provides the control functions to tailor the catalytic
ods, the strength and mechanical properties of the metal and cera- product distribution, according to the Co-SCR geometrical investi-
mic catalysts are superior in these two processes. Also, 3D printing gations. According to the findings, Fe-SCR and Co-SCR give highly
of catalyst with higher precision is achievable, especially in terms selective liquid fuel synthesis in high-pressure Fischer-Tropsch
of more complicated geometries like porous structures. However, synthesis and CO2 hydrogenation. The Ni-SCR has a high CO2 and
these technologies are more expensive than others with more CH4 conversion rate in high-temperature dry reforming of
material waste. The process usually starts by preparing a compos- methane. Examples of the 3D printed parts are illustrated in
ite powder of metal and ceramic. This operation is less complicated Fig. 4.
293
Fig. 4. Examples of 3D-printed catalyst structures using powder-based methods, a) SLM printing of Cu/Mn composite [75], b) SLM printing of Zr-based BMG before and after
dealloying [78], and c) SLS fabrication of self-catalytic reactors with metal catalysts [12].
3.4. Challenges set of process parameters must be set to reach a desirable dimen-
sional accuracy and better-controlled structure morphology. The
Morphological design and accuracy of the printed catalyst have relation between printing speed and nozzle size, travel duration,
a considerable impact on the catalytic performance. In the slurry- and density of infill has been investigated by Perez et al. [79],
based approaches, the most critical factors of printing accuracy but the understanding between process parameters and desired
are material viscosity and dispersion, nozzle diameter, and printing morphology of 3D printed catalysts remains unknown.
parameters, such as layer thickness, printing speed, infill, and post Most studies on 3D-printed catalyst served as a proof of concept
treatments operations like drying, sintering, etc. The uniform dis- with simple catalyst structure/patterns (2-dimension or 2.5-
persion of catalyst particles in the slurry has a significant impact dimension where there is no variance in Z direction). These struc-
on the quality and morphological accuracy of printing parts. The tures are typically comprised of uniform pores and a single mate-
important conditions for attaining outstanding printability with rial, which do not fully exploit the freedoms of AM to enhance
DIW are the slurry’s pseudoplastic nature, settling upon dispens- catalytic performance. Having a multifunctional reactor can
ing, and uniform dispersion of the particles. While preparing the improve the efficiency of chemical reactions. Some studies attempt
slurry, the particle sizes should be an order of magnitude smaller to fabricate bi-functional catalysts using 3D printing. However,
than the resolution of the final part to make sure that a high- they made the catalyst composite before the fabrication process.
resolution product is achieved. Getting a high-density printed part As demonstrated in Sections 3.1-3.3, the ratio of the catalyst to
without clogging the nozzle is one of the most difficult challenges the base or support material has a great influence on the reaction
in DIW. Only a slurry with proper homogeneous dispersion of the rate and final yield. Yet, the capability of fabricating multiple mate-
particles could make this possible. In order to obtain a desirable rials and spatially controlling the catalyst deposition is missing.
product, the rheology of the slurry, particle size distribution, and
moisture qualities should all be adjusted. Compared to polymer
3D printing, the impact of process parameters on the dimensional 4. Design and optimization of the catalyst structure
accuracy and surface quality are barely discussed in the catalytic
3D printing investigation. In general, a higher printing speed Understanding the interactions between catalysts and biomass
reduces the time it takes to fabricate a layer and makes it easier feedstocks is essential for controlling and optimising the perfor-
to maintain a consistent flow. However, printing with high path mance of thermochemical processes in biomass conversion appli-
accuracy can be problematic for a complicated design with sharp cations. The morphology of the catalyst and the surrounding
corners which are difficult to fabricate. Therefore, it’s critical to chemical environment have a significant impact on reaction [80].
experiment with various printing speed and find the optimal value. As discussed previously, some of the parameters such as the con-
The impact of printing speed was examined for robocast printing of centration of reactants, surface area, temperature, and catalysts,
zirconia before the sintering operation [11]. The range of dimen- affect the rate of a chemical reaction. Due to the fixed process con-
sional accuracy was resulted between 0.14 % and 1.49 % and sur- dition of the thermochemical processes, tuning the environmental
face roughness is between 25 and 43 lm. It was demonstrated conditions is not the focus of this review article, and the main
that the accuracy was highly dependent on the relation between attention goes to the morphological design of catalyst structures.
layer thickness and infill whereas roughness relied more on inter- As discovered in Section 2, zeolites are one of the popular cata-
action between printing speed and infill. Similar deficiency is also lysts used in biomass industry due to their microporous structures
observed in filament-based and powder-based studies. An optimal [81]. However, transport restrictions frequently have a negative
294
impact on their overall performance. A conceptual illustration is a few associated with the environment, including temperature,
presented in Fig. 5a explaining how reactant need to diffuse over pressure, etc. For instance, the effectiveness of a meso-macro por-
a space varying from millimeter to nanometer scale (depends on ous commercial catalyst for the autothermal reforming of methane
catalyst pore type) until arriving to the active site which is located on Ni/Al2O3 is demonstrated to be greatly enhanced by optimising
on the internal surface. After interacting in surface reactions, the the macro-porosity and size of the macropores [83]. The mathe-
product must diffuse out to the outside surface. Wide pores can matical model was initially defined by the relation between effec-
be used as molecular highways to help overcome transportation tive diffusivity, meso-porosity and meso-pore size, and using the
restrictions, manage product dispersion, and counteract the effects effectiveness factor as an objective function. By considering a max-
of catalyst deactivation [82]. Improving the diffusivity requires imum value of effectiveness factor, adjusting the macropore size to
reducing the reactants particle size or enhancing the pore network 1 lm and macroporosity to an optimal value around 0.2–0.3, could
structure. Although having a large internal surface area is impera- increase overall catalytic activity by 40–300 %. In another research,
tive for the higher distribution of active species, increasing nano- Szczygiel [8] constructed a mathematical model to optimize the
pores inside the structure provides more diffusion limitations as radius of the micro- and macropores for the reforming catalysts.
a result of the confinement effect. Therefore, porous channels with The proposed structure was also determined to control the diffu-
wider diameters are needed for greater diffusivity. Thus, a proper sion resistance and the contribution of kinetics to the overall rate.
design of a structural network is essential to maximize efficiency. In order to describe the mass transport in the catalyst grain under
As reported by Coppens et al. [82], the optimised hierarchical cat- the circumstances of reforming, a general equation was derived.
alyst can improve the catalytic activity by 2.8 times while reducing The model makes it possible to calculate pertinent impacts and
catalyst weight by 45 % comparing to a mesoporous benchmark identify the appropriate porous structure to regulate how much
catalyst. Porosity, pore size distribution, and particle size must at kinetics and diffusion resistance contribute to the process’ overall
least be included in the structural parameters for optimization. rate. For the reforming catalyst that had been used to fill the reac-
Pore connectivity and spatial crystal or porosity distribution are tor of an experimental device, efforts were conducted to determine
other significant factors needed to be considered. Therefore, devel- the optimal radius of the pores. The effective diffusion was
opment of a hierarchical catalyst must make it possible to effec- regarded for optimizing the pore size distribution of Alumina as
tively regulate the morphological parameters including, pore size catalyst support [84]. In this regard, tortuosity factor ðsÞ was pre-
distribution, pore volume and pore network. sented to evaluate the porosity ðep Þ, effective diffusion ðDeff Þ and
molecular diffusion ðDm Þ of the alumina (see Equation (1) [84]).
4.1. Optimization of porosity and pore size distribution
Deff ¼ Dm :ep =s ð1Þ
There are several studies attempt to demonstrate the effect of Although all alumina supports had equal total porosities, the
different parameters on catalyst performance. Some of these observed tortuosity values are actually different and significantly
parameters are related to the geometry of the pore network and greater than those anticipated by these theoretical models. The
Fig. 5. a) diffusion and reaction in a porous catalyst particle are shown schematically [82], b) different types of structures including monodisperse (left), bi-disperse (center)
and bimodal (right) [93], c) illustration of various pore network including minimum shielding, fully cruciform, fractal tree, random [92], and d) coke residue in an interspaced
2D network at various levels of burn-off, including (from left to right) after 10% burn-off, after 50%, after 75%; and after 90% [94].
295
assumption of a two-level pore network organization, whose prop- macropores in a large pore network of a hierarchical structured
erties can be entirely calculated from a traditional nitrogen adsorp- hydrodemetalation catalyst. In this study, an optimization model
tion isotherm, has been used to reconcile this disparity. The textural of the broad pore network is proposed for diffusion-limited reac-
features of mesoporous alumina can be evaluated using this tions that are being deactivated in the areas filled with nano-
straightforward methodology, which is helpful for the design and pores of a hierarchical structure catalyst. A scaled yield that repre-
optimization of many catalytic processes. Time as an additional fac- sents the objective function was defined using the reaction yield,
tor affecting the catalytic activity is reported in another research and the broad pore size of bi-disperse and bimodal structure was
[85]. In this regard, a mathematical optimization method is given, optimized and compared considering one year time on stream.
which considers the catalytic performance over time on stream. As a result, compared to the yield achieved from a uniform nano-
The objective function is defined as reaction yield which is described porous catalyst, the integrated reaction rate of the optimum hier-
by macro-porosity, pore size, surface area and reactant concentra- archical catalysts was reported over 8 times greater. The ideal hier-
tion. The optimal values for meso-/macropore diameters, surface archical catalyst uses around 21 % less catalytic material than the
area, meso-/macro-porosity, and grain radius were evaluated. As a pure nano-porous one over the course of a year of operation. They
result, the mesoporous structure indicates superior performance used relation between effectiveness factor and thiele modulus as
in the beginning. However, it starts to fall during the time and show presented in Equation (2).
the worse performance after 10 days. On the contrary, hierarchical
Z 12
structures demonstrates higher rate in the long term. V rðc0 Þ c0
U¼ pffiffiffi Deff rðcÞdc ð2Þ
S 2 cc
4.2. Optimizing the pore network
where, V is the volume of the catalyst particle, S is the external sur-
Pore connectivity is another significant factor highly affecting face area of the catalyst particle, r is reaction rate, Deff defines the
the mass transfer and the amount of active site inside the catalyst effective diffusivity in the porous catalyst, c refers to concentra-
structure. In this regard, Liu et al. [86] provided an optimal pore tion, c0 is the concentration on the external surface of the catalyst
network using the CFD model by considering the effect of concen- and cc is typically assumed to be zero for fast enough reactions.
tration and temperature gradient along with pore size, porosity Prachayawarakorn-Mann [92] simplified the problem by consider-
and pellet shape inside a reactor. The optimal structures at pellet ing a 2D pore network and attempted to optimize the network for
level and reactor level were compared to each other, and the better reactivity. Fig. 5c displays the investigated 2D networks.
results indicated that the catalyst performance must be considered The black region is the nano-porous area, and the small and large
at the reactor level for industrial use. Liu et al. [87] explained the pore channels are presented in yellow. The relation between tortu-
trade-off between reaction rate and diffusion and offered a desired osity and thiele modolus (see Equation (1)) indicates the objective
range of porosity for monodisperse and bi-disperse catalyst pellets function in which less tortuosity results in more reactivity. More-
under various environmental conditions. These types of structures over, the performance was evaluated by effectiveness factor pre-
are demonstrated in Fig. 5b. The black regions present the nano- sented in Equation (3) [92]. The findings showed the minimum
porous material and white regions are the diffusion channels. A shielding in which large channels positioned in its margins had
combination of bi-disperse structures forms the bimodal ones (like the highest reactivity compared to others and the worst case
3 3 bidisperse as indicated in Fig. 5b). In this study, the pore size resulted from the random structures. In fact, the minimum shield-
and porosity were optimized for monodisperse and bi-disperse ing is 8 times more reactive than the random network.
networks. The results present an improved catalytic activity for
tanh U
the bi-disperse structure (50 % – 175 %) as well as lower amount g¼ ð3Þ
of catalyst material (10 % 18 %) in comparison to monodisperse U
structures. The electrode performance for the lithium-ion battery Wang et al. [93] compared the optimal networks in Fig. 5b (bi-
was another case study of Ye et al. [88]. This work created an ana- modal, bi-disperse and monodisperse) in terms of yield. The char-
lytical model based on the relationship between porosity, diffu- acteristics of the nano-porous material, such as its kinetics and
sion, and tortuosity to optimise the hierarchical pore network. texture (more specifically, its pore size), are predetermined and
The objective function was presented as the effective tortuosity are not changed during optimization. The yields from the optimum
which needed to be minimized and the size of the pore channels bimodal and bi-disperse catalysts are approximately the same and
was the optimization variable. The lower porosity and higher elec- can be much higher than those from a monodisperse catalyst.
trode thickness demonstrate superior performance in terms of Therefore, the bi-disperse structures with the optimised channel
energy density of electrodes compared to the benchmark and with- volume fraction and channel diameter ought to be preferred in
out chemical modification of the materials. The reaction yield of a practice because they are simpler to synthesise, have nearly iden-
zeolite catalyst pellet using a composite of meso- and macropores tical catalytic performance to the bimodal ones, and have a signif-
are shown to be almost twice than the pellet that is constructed icantly higher production rate than the monodisperse ones. The
only by macropores with the same macro-porosity [89]. A numer- bimodal structure was also considered in [95] as fractal-like pore
ical optimization method was used to maximize the reaction yield hierarchies and compared with the optimal uniform architectures
in the ethylating of benzene. The mathematical method defines the (bi-disperse). Again, they employed the yield as the objective func-
effectiveness factor by describing the reaction rate, diffusion and tion and attempt to optimize the geometry of the network by max-
the concentration of ethylene and benzene. In another study con- imizing the yield. The performance of the optimal structures was
ducted by Becker et al. [90], it was shown that activity and product compared to that of self-similar, fractal-like pore hierarchies, and
selectivity of Fischer-Tropsch catalysts are significantly impacted it was discovered that the latter could be made to provide the same
by diffusional limitations in the porous network. It has been effectiveness factor as the optimal ones. This finding suggests that
demonstrated that the presence of transport channels permits an fractal-like catalysts operate very close to optimality, even though
extension of the diffusion length while preserving high reaction their structure differs greatly from that of the true optima. To
rates and selectivity. Also, through the improvement of the trans- examine the direct impact of pore assembly on diffusion and reac-
port pore fraction, productivity can be raised up to 47 %. In order tion in FCC catalyst particles, 2D networks were applied in study
to improve the conversion of nickel metalloporphyrin in the crude conducted by Nafaty-Mann [94]. Different pore architectural struc-
oil, Rao and Coppens [91] mathematically tailored nano- and tures, such as random, spiralled positively, spiralled negatively,
296
structured, and interspersed 2D networks, were examined consid- optimization of their functional features. But for multi-size channel
ering the burn-off reaction in coked particles like zeolites. The spi- catalyst architectures, there hasn’t been a precise and comprehen-
ral positively defined by locating the larger pore in the perimeter of sive morphological description. Some studies examined the influ-
the catalyst while the negative one means an interior-pored net- ence of porosity and pore size distribution without considering
work. The interspaced structure presented in Fig. 5d performs bet- pore connectivity [8,83–85], and some attempt to investigate pore
ter than the other structural configurations in terms of reaction network only [87,90,93,95]. A 2D pore network has been studied in
rate and the amount of time needed for full coke combustion in most of the cases, and the same behavior in other directions was
the network. The optimization problem is not only limited to the assumed to lower the computational cost. However, porous struc-
performance of the catalysis as the main objective function but tures have very complicated geometry in which tailoring their
also is investigated in other aspects which are directly affecting physical structures is a big challenge due to manufacturing limita-
the catalytic process. To this end, the ratio of some environmental tions. Therefore, a comprehensive study requires the exploration of
parameters on producing desired specific surface area for the syn- the impact of 3D network along with other parameters like pore
thesis application is determined by means of Artificial Neural Net- size distribution, porosity and surface area. Ye et al. [97] attempted
work (ANN) [96]. This study used incomplete carbonised glucose to consider these facts and make more extensive research. How-
(ICG) as the template and polyethylene glycol as a surfactant to ever, their study can be improved by considering other types of
hydrothermally manufacture mesoporous NiO-ICG catalysts. Five networks. Since it was proved by Prachayawarakorn-Mann [92]
widely used learning systems including quick propagation, batch that random network has much lower efficiency than others.
back propagation, incremental back propagation, Levenberg- Moreover, only a limited number of types of networks are pre-
Marquardt, and genetic algorithm were used to apply a multilayer sented and investigated for various applications rather than devel-
feed-forward neural network. Modeling was carried out to deter- oping a mathematical model to tailor the pore connectivity in an
mine how various hydrothermal reactions, including metal ratio, optimal way. The other significant gap is that the manufacturing
surfactant and template concentrations, and calcination tempera- constraints including catalyst particle size, resolution of the manu-
ture, would affect the predicted surface areas of the produced cat- facturing method, etc. were not considered.
alyst. The most influential factor on the surface area (among the
chosen effective parameters) was the calcination temperature,
5. Future research directions
which had a relative effectiveness of 29.97 % whereas the concen-
tration of the incomplete carbonized glucose was the least effective
There are both new and ongoing challenges, some of which
one. The specific surface area measured had an error of 9.45 %,
were mentioned in prior sections and require considerable amount
which was noticeably close to the amount predicted by the model.
of research and development. Structured catalyst 3D printing has
In the presence of coking-induced deactivation, a 3D network of
been increasingly popular in recent years and is still evolving in
porous structure was suggested by Ye et al. [97] and used to opti-
other fields. Although some progress has been achieved, the fol-
mise the catalyst’s porosity, pore size distribution and pore con-
lowing areas still require further study for biomass conversion
nectivity. The goal was to produce catalyst particles that are very
applications.
resistant to deactivation caused by coking for the propane dehy-
drogenation. The mathematical model used for optimization was
broke down into three components: the pore network, the reaction 5.1. Development of a comprehensive design framework for structured
and diffusion modelling equations, and the coking and deactivation catalysts
equation models. Two types of networks including random uni-
form distribution and bimodal were provided to present the pore As already indicated in Section 2, most of the studies focused on
connectivity model. The pore channels were designed in cylindrical various compositions of catalysts to provide the desirable catalyst
shape in which radius and length of these channels along with sur- architecture. Through understanding of the process, the impact of
face area were utilized to describe the reaction and diffusion catalyst morphology on its performance becomes apparent. For
model. The mathematical presentation of the coke accumulation instance, a hierarchical structure of catalyst meaning a micro/
over time in a cylindrical pore was also provided. The objective macro-porous composition have been proposed in numerous
function, which takes into account a catalyst particle’s activity chemical pathways of biomass conversion [5]. However, the dis-
and stability, is the time-averaged propene production rate per connection between BBC and proper catalyst fabrication method
unit catalyst volume. As a result, it was proven that the unimodal will make the research even more obscure. As discussed, tuning
network with larger pore size in outer zones and with an average the macro channels which is one of the most challenging design
pore diameter of 500 nm was up to 14-folds more active than criteria to improve the diffusivity and proper arrange of pore con-
the benchmark. A correct optimization approach requires sufficient nectivity, can be controlled via 3D printers during the fabrication
understanding of synthesis, mass transport properties and mor- process. Since the investigation of using structured catalyst for
phology. In this context, Stoeckel et al. [98] introduced a method thermochemical process of biomass conversion has been rare,
to describe the morphology of the meso- and macro-porous silica there is a lot of room for research in this area through working
monoliths. They managed to reconstruct the 3D model via analyz- on structured catalyst with optimal 3D network. The vast majority
ing the 2D images obtained from the tomography scan. The find- of studies focused on optimizing 2D networks without considering
ings indicate that the macropore and mesopore spaces have a other significant parameters like surface area and porosity. There-
very similar topology but have different geometrical characteris- fore, a comprehensive design approach needs to be developed for
tics. It has also been revealed that the 3D structures can be deemed biomass thermochemical reactors. It is also expected that the opti-
significant while optimizing the hierarchical porous structure [99]. mal network can alleviate the coke formation of zeolites.
The presented paper investigates the random 3D networks and
their influence on reaction rate and diffusivity. 5.2. Integration of manufacturing constraints into catalyst design
4.3. Challenges As discussed, a suitable design strategy must include the man-
ufacturing limitation for a practical engineering design. The 3D
Understanding the relationship between their synthesis, mor- printers can mitigate the manufacturing restrictions, but they are
phology, and mass transport qualities is necessary for the targeted also limited to a certain amount of resolution. Depending on the
297
reactant’s particle size, utilizing lower macro-pores can enhance Declaration of Competing Interest
the catalytic performance by increasing the surface area and num-
ber of active sites. Therefore, upgrading the printers for fabrication The authors declare that they have no known competing finan-
of catalyst structures with higher resolution is always desirable cial interests or personal relationships that could have appeared
and is expected in the near future for this application. One of the to influence the work reported in this paper.
options is to introduce ceramic particles in high resolution AM
methods like DLP process [100]. Also, the reactant’s particle size
Acknowledgement
can be tuned based on the catalyst pore size. However, a proper
relation between catalyst morphology and reactant’s particle size
The study was supported by the funding from the Natural
is imperative. Another AM challenge which needs consideration
Science and Engineering Research Council of Canada (NSERC) Dis-
is the accuracy of the fabricated part which must be comparable
covery Grant (RGPIN-2022-03448). The authors would like to
to the design artifact. The printing parameters and material prop-
thank the reviewers and editors for their constructive comments.
erties are the significant factors affecting accuracy of the printing
sample [101]. According to the literature, the impact of these
parameters on the accuracy (in the catalytic 3D printing area) is References
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Journal of Catalysis 417 (2023) 286–300

Contents lists available at ScienceDirect

On the 3D printed catalyst for biomass-bio-oil conversion: Key

Methods Treatment condition/requirement Process description Technique feasibility

Biomass feedstock Process condition Catalysts Improvements Ref.

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