FEATURE ARTICLE
Catalyst Manufacturing
Three-dimensional Printing for Catalytic Applications:
Current Status and Perspectives
Xintong Zhou and Chang-jun Liu*
Three-dimensional (3D) printing, also known as additive manufacturing,
is a fabrication method that has recently received worldwide attention.
It provides a convenient and economical way to prepare 3D structures in
designable ways. As the technology has developed and the operational costs
have decreased, the applications of 3D printing have greatly expanded.
Catalyst fabrication is a promising area for 3D printing. Printing processes
result in better control of catalyst structures and catalyst distribution. In
this perspective, a general overview of the commonly available 3D printing
methods that are feasible for the preparation of heterogeneous catalysts is
given. Additionally, recent works on printing strategies and new materials for
catalysts are discussed. Future development is also addressed.
1. Introduction
With ever-increasing environmental consciousness and the
development of sustainable syntheses, the development of new
catalyst systems has become a more important topic. Recently,
the relationships between catalyst structures and catalytic per-
formances have received a great deal of attention.[1] Many dif-
ferent materials with delicate meso/macro structures have
been reported. For most of these materials, their catalytic
performances are closely related to their unique structures.
However, most of these functional structures were prepared
using complex methods such as self-assembly,[2] chemical vapor
deposition (CVD),[3] and templating approaches.[4] There is no
doubt that the high costs of these methods hinder the poten-
tial industrial applications of these materials. Simpler and more
flexible methods are needed for the preparation of specialized
3D functional structures.
Three-dimensional (3D) printing, also known as additive
manufacturing, is a fabrication method that creates structures
from digital models.[5] Unlike conventional fabrication methods,
3D printing processes are bottom-up fabrication methods
which are based on the incremental addition of layers of mate-
rials. Compared with traditional manufacturing technologies,
Dr. X. T. Zhou, Prof. C.-J. Liu
Collaborative Innovation Center of Chemical Science and Engineering
School of Chemical Engineering and Technology
Tianjin University
Tianjin 300072, P. R. China
E-mail: coroncj@tju.edu.cn, ughg_cjl@yahoo.com
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.201701134.
DOI: 10.1002/adfm.201701134
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www.afm-journal.de
3D printing is a more convenient and
efficient way to prepare complex 3D struc-
tures. In addition, 3D printing requires
fewer steps and resources.
Three-dimensional printing is currently
being explored for many different applica-
tions, including electrochemical devices,[6]
biomaterials,[7] and microfluidic devices.[8]
In addition, graphene,[9] metal-organic
frameworks,[10] and many other materials
have been prepared by the printing pro-
cess. Recently, 3D printing has also been
shown to be advantageous to catalytic
applications since a printing approach can
achieve better control of the fine structure
of the target material.[11] As 3D printing
techniques have developed, setup and operational costs have
decreased rapidly. The control and precision of the properties of
the printed materials have improved. Therefore, it is reasonable
to expect that using additive manufacturing to prepare catalytic
materials will continue to develop in the coming years.
In this perspective, a general overview of commonly avail-
able 3D printing methods that are feasible for the prepara-
tion of catalytic materials is given. In addition, recent works
concerning printing strategies and new materials for catalytic
use are summarized. Potential catalyst applications are also
included. Finally, future expected developments in this very
promising field are addressed.
2. 3D Printing Technology
2.1. 3D Printing Overview
Three-dimensional printing is a fabrication method that creates
structures from digital models. In a typical 3D printing process,
the structure of the target material is first designed through
computer-aided design (CAD). The structure is then converted
to a G-code file via a slicing process, and the target material
is then prepared by the printer using this file.[5] During the
printing process, the position of the printing device must
be controlled for every target point in the G-code file, which
can be easily accomplished with step motors, laser beams, and
other mechanical devices. However, building a solid material at
these position target points is not a simple task. In fact, this is a
big challenge in the printing of some materials, and many new
technologies have been designed to solve this problem.
Several 3D printing processes have been invented since the
late 1970s.[12] The printing techniques that are most suitable for
catalyst preparation include fused deposition modeling (FDM),
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direct ink writing (DIW), stereolithography (SLA), laminated

object manufacturing (LOM), and selective laser sintering Xintong Zhou received his
(SLS). B.S. degree (2011) and
M.S. degree (2014) from
School of Chemical
2.2. Fused Deposition Modeling (FDM) Engineering and Technology,
Tianjin University, China. He
Fused deposition modeling was developed by Scott Crump in is currently a Ph.D. candidate
the late 1980s and was commercialized in 1990 by Stratasys.[13] in Tianjin University. His
To date, it is the most commonly used 3D printing strategy. The major research area is the
open-source development community, RepRap, as well as many preparation, characterization,
other DIY programs, all use FDM. Over the last several years, and evaluation of the 3D
the costs associated with this process have greatly decreased, printed catalytic materials.
which has made 3D printing more feasible for industrial
applications.
Dr. Chang-jun Liu is a Chang
FDM uses a wire feed system whereby during the printing
Jiang Distinguished Professor
process, a supply filament is pushed into a heating chamber
and a Fellow of the Royal
where the target material is melted (Figure 1a). The molten
Society of Chemistry. He
material forms layers and then immediately hardens after
received his Ph.D. degree for
extrusion from a nozzle. This method can be used to manufac-
research on the modeling of
ture models with different 3D structures. The most commonly
crystal growth from Tianjin
used materials are thermoplastic polymers like acrylonitrile
University in 1993. After
butadiene styrene (ABS), polylactic acid (PLA), and high impact
postdoctoral positions at
polystyrene (HIPS). Other materials, such as eutectic metals
the University of Oklahoma
and cermet, can also be used in FDM. For most commercial
(2.5 years) and Prairie View
3D printers, layer thickness can be controlled to ≈100 µm
A&M University (1 year),
and accuracies in the x and y axes are within a few hundred
he joined ABB Cooperate Research, Switzerland, as an
micrometers.
engineer. He became a full professor at Tianjin University
Unfortunately, these thermoplastic materials have low glass
in 1999. His current research interests include CO2 utiliza-
state temperatures and low surface areas so they do not make
tion, natural gas conversion, plasma nanoscience, nano
good catalytic materials. Thus, other components have been
energy materials, catalyst preparation by cold plasmas, and
added to the process to form materials with high activities.
3D printing.
One strategy is to incorporate inorganic nanoparticles into the
polymer filaments, which is feasible if the incorporated com-
ponent can be integrated into the polymeric matrix. Research
has demonstrated the feasibility of this strategy on many the catalytic industry. One possible solution to the problem is to
composite materials,[14] including metal oxides[11b,15] and gra- coat active components on the surface of the printed structures.
phene oxide.[9a,16] However, during the incorporation process, Similar to the FDM process, the stability and the uniformity of
a considerable amount of the incorporated materials can be the coating is a concern. The advantage of SLA is that the high
enwrapped by the polymer which prevents the full utilization resolution of the printed structures gives more delicate material
of these materials. One approach of dealing with this problem structures which are important for special uses.
is to load the active components onto the printed structures, so
that these components are exposed.[10] This method requires
a strong interaction between the active component and the 2.4. Direct Ink Writing (DIW)
poly­mer structure.
DIW (also known as robocasting) is another extrusion-based
printing process. Unlike in the FDM process, during the DIW
2.3. Stereolithography (SLA) process the material is extruded directly without melting or
solidification (Figure 1c). The printing ink needs to have a low
Stereolithography was patented in 1986 by Hull[17] and was one viscosity to maintain its fluidity while being extruded out of the
of the first and most widely used 3D printing technologies. SLA nozzle but after the extrusion, a high viscosity is necessary for
is performed by focusing an ultraviolet (UV) laser onto a vat of the material to maintain its shape on the printing bed. Conse-
photopolymer resin (Figure 1b).[18] The photopolymer resin is quently, most materials used for this process are pseudoplastic
photosensitive to UV light, so the resin immediately solidifies fluids,[19] such as ceramic slurries, polymers, and sol–gel inks.
upon exposure. Structures are formed layer by layer to produce DIW was first designed to prepare ceramic materials,[20]
the desired 3D object by pre-programming the scanning path of but carbon materials, aerogels, and biomaterials have all been
the UV laser over the resin surface. printed using this method as well. The DIW process has advan-
SLA printing can only produce materials from photosensi- tages of easy operations and relatively low fixed costs. The DIW
tive materials which is a huge challenge for its applications to process can use a wide range of materials, which is favorable

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Figure 1.  Some 3D printing processes that are useful for catalyst preparation: a) Fused deposition modeling; b) Stereolithography; c) Direct ink writing;
and d) Selective laser sintering.
for catalytic materials. The disadvantage to DIW is that a sol-
vent is usually used in the printing ink, so post treatment steps
such as drying and sintering are usually needed.
2.5. Other 3D Printing Technologies
Several other 3D printing technologies also have potential for
use in the preparation of catalyst. Powder-bed-based processes,
such as selective laser sintering (SLS) (Figure 1d), selective
laser melting (SLM), and inkjet head 3D printing can make
structures using metal and ceramic powders.[21] Laser sintering
and laminated object manufacturing (LOM) have also shown
some promise for catalytic applications.
3. 3D Printing of Catalytic Materials
3.1. Polymers
Polymers are the most commonly used material for 3D
printing. They can be used in extrusion, light polymerization,
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powder bed, and almost all other mainstream printing tech-
nologies.[22] Their plasticity and durability make them suitable
for preparing models and mechanical parts. However, their low
surface areas, poor thermal stabilities, and poor surface proper-
ties hinder the use of polymers in catalytic applications.
One possible solution to this problem is to incorporate an
active ingredient into the polymer filaments to form organic/
inorganic hybrid materials. The preparation of these hybrid
materials is a relatively mature research area. For example,
metal oxide–polymer hybrid composites are a promising
hybrid material.[14a] These materials have been prepared by
blending,[23] sol–gel process,[24] and in situ synthesis.[25] Selected
metal oxide particles, such as zinc oxide (ZnO),[24,26] titanium
oxide (TiO2),[27] and magnetite (Fe3O4),[28] as well as their com-
posites, have all been used in the preparation of organic/inor-
ganic hybrid materials.
When dealing with the printing of these hybrid materials,
the simplest way of incorporating an active ingredient into
printable materials is to disperse the inorganic particles in the
printing filament. This is usually done by dissolving the inor-
ganic particles and the polymer in an organic solvent such as
acetone and chloroform. The solvent is then removed and the
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printing filaments are produced by a special extruder. These
filaments are compatible with most commercial thermoplastic
3D printers. Castles et al.[14d] developed a BaTiO3/ABS filament
which can be used on the commercial desktop 3D printers.
(Figure 2a) The BaTiO3 loading can be up to 70 wt%. Com-
plex structures can be made even at a high BaTiO3 loading.
(Figure 2b) Perez et al. printed with 5% TiO2-ABS materials
and studied the mechanic properties of a series of ABS based
materials.[15a] The tensile test shows that the TiO2-ABS struc-
ture has a higher ultimate tensile strength. Skorski et al.[11b]
expanded the process and developed a 3D printing method for
TiO2-ABS composites with different TiO2 contents. The printed
composite structures also showed good activity for the photo-
degradation of rhodamine 6G in solution.
TiO2 is not the only material that can be added using this
process. Several of other hybrid materials have been devel-
oped, such as Fe-ABS[29] and Fe3O4/polycaprolactone.[15b] Many
delicate structures have been achieved using devices which are
easy to obtain. Wei et al.[9a] prepared a 3D printable graphene-
ABS composite (Figure 3). Graphene loadings of up to 5.6 wt%
were obtained and the material could be made into 1.75 mm
diameter filaments, which are suitable for use in commercial
3D printers. Zhang et al.[16] reported a 3D printable reduced
graphene oxide (r-GO)/PLA composite with a r-GO content of
Figure 2. Extruded filaments and the 3D printed structures. a) Left:
unloaded ABS filament. Right: BaTiO3/ABS composite filament con-
taining 50 wt% BaTiO3. Scale bar, 10 cm. b) Structures printed in ABS
polymer (left) and 50 wt% BaTiO3/ABS polymer composite (right). Scale:
each cubic structure has overall side length of 32 mm. Reproduced with
permission.[14d] Copyright 2015, Nature Publishing Group.
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6 wt %. Recently, some of the composite printing materials
have already been commercialized, which provide a lot of con-
venience for the investigation. For example, Foster et al.[9e]
reported a 3D printed graphene/PLA structure, which can be
used as energy storage devices. The commercial graphene/PLA
filament was used in their study.
The strategy of incorporating active ingredients into the poly-
mers can also be adapted to the light polymerized processes.
Fantino et al.[30] reported the fabrication of conductive 3D
hybrid structures consisting of metal nanoparticles and organic
polymers shaped in complex multilayered architectures.
(Figure  4) The process combines the photoreduction of metal
precursor with the digital light processing (DLP) technique.
The proposed method allows obtaining 3D complex and light
pieces with promising electrical properties.
The disadvantage of the above strategy is that the amount of
additive needs to be carefully controlled so that the rheological
characteristics of the material remain within the appropriate
ranges for 3D printing processes. In addition, some of the addi-
tives may become enwrapped in the polymer structure, which
has a negative effect on catalytic performance.
Another method for incorporating active components is to
load them onto the surface of the printed structure. The addi-
tives are fully exposed and do not have any negative effects on
the printing process. The challenge is obtaining a stable and
uniform coating. Recently, there have been some researches
that have focused on coating materials onto the surfaces of 3D
printed parts.[31] Wang et al.[10] reported a step-by-step growth
process which introduced Cu-BTC metal-organic frameworks
(MOFs) onto 3D printed ABS materials (Figure 5). The printed
Cu-BTC/ABS frameworks were used for the removal of meth-
ylene blue (MB) from aqueous solutions and gave MB removal
efficiencies of 98.3% and 93.3% within 10 min for solutions
with concentrations of 5 and 10 mg L−1, respectively. The flex-
ibility of the Cu-BTC material was enhanced by the printed
ABS structures. Besides, the Cu-BTC particles can be easily
removed by washing with aqueous hydrochloric acid. There-
fore, the printed structures can be conveniently reused. In their
recent work, Au nanoparticles were also introduced into the
Cu-BTC/ABS materials (Figure 5d). The Au loaded Cu-BTC/
ABS material is purple compared to white for ABS, gold for the
Au/ABS and blue for Cu-BTC/ABS. These different colors show
uniform distributions of the Au nanoparticles on Cu-BTC/ABS
material. These results indicate that the MOF coating plays an
important role in the formation and dispersion of metal nano-
particles. This process is also applicable to other noble metal
nanoparticles like silver, palladium and platinum. This method-
ology is promising for preparing novel catalyst composites for
low temperature reactions.
Pure polymers are usually not good catalysts for their low
surface areas, poor thermal stabilities, and poor surface prop-
erties. However, these properties make the printed polymers
suitable for being used as a template to prepare monolithic cat-
alysts. With the help of 3D printing and computer-aided design,
unique monolithic structures that are unable to be made by
conventional methods can be easily prepared. Michorczyk
et al.[32] developed a DLP process to prepare polymer models
which were applied as templates in order to control channel
architectures in monolithic catalysts. (Figure 6) The channel
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coupling of methane, with a high selectivity

of 67–70% towards C2–C3 hydrocarbons.

3.2. Carbon Materials

Carbon materials have been intensively

studied because of their inherent advan-
tages such as high surface areas, interesting
structures, good electrical conductivities,
and chemical stabilities. They are also widely
used as catalytic materials.[33] Many different
carbon structures from nanoscale to macro­
scale have been used to improve catalytic
performances. With the help of 3D printing
techniques, the preparation of carbon macro­
structures is becoming easier and cheaper.
A common method for the preparation
of carbon structures is the carbonization
of thermosetting resins.[34] These mate-
Figure 3. Preparation and 3D printing of graphene-ABS composite. a) Graphite flakes. rials have a high degree of crosslinking,
b,c) Dispersions of graphene oxide (GO) and ABS in N-methyl pyrolidone (NMP) solvent which can prevent deformation during the
respectively. d,e) A homogeneous mixture of GO-ABS in NMP before and after chemical carbonization process. For 3D printing
reduction respectively. f) Graphene-ABS coagulations obtained after isolation of (e) with water. processes, the printing ink needs to be a
g) Graphene-ABS composite powder after washing and drying. h) Schematic illustration of non-Newtonian fluid with high viscosity
fused deposition modelling 3D printing process. i) A typical 3D printed model using 3.8 wt%
[9a]
graphene-ABS composite filament, scale bar: 1 cm. Reproduced with permission. Copyright
so that its flow through the fine nozzle is
2015, Nature Publishing Group. reliable and the self-supported shape main-
tains its integrity after deposition. Pre-
poly­mer solutions are often used as printing
structures prepared by the templates were specially designed by inks. For example, a resorcinol-formaldehyde (R-F) solution
computer modelling, which can influence the catalytic perfor- has good rheological behavior and the chain growth reac-
mance. The resulting Mn- and Na2WO4-containing monoliths tion can be controlled at a relatively low rate in an alkaline
exhibited a stable 23–25% methane conversion in the oxidative system, so that the ink is stable during the extrusion process.

Figure 4.  a) Different types of Ag-polymer composite 3D printed structures. b) Comparison of the scanned component and the CAD model. c) UV-vis
spectra of a sample containing 5 phr of AgNO3 after different irradiation times under UV light. d) Example of a 3D object and its color change related
to the silver nanoparticles formation: orange (just printed), brown (low irradiation time), and silver (longer irradiation time). Reproduced with permis-
sion.[30] Copyright 2016, Wiley-VCH.

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Figure 5. 3D printed Cu-BTC/ABS structures and Au/Cu-BTC/ABS structures. a) Fabrication of Cu-BTC/ABS composites. b) SEM images of the
Cu-BTC/ABS composite. c) Photographs of the synthesized Cu-BTC/ABS composites; the number represents the number of cycles. d) 3D printed ABS,
Cu-BTC/ABS, Au/ABS, and Au/Cu-BTC/ABS. Reproduced with permission.[10] Copyright 2014, Nature Publishing Group.

In addition, R-F materials maintain their structures after car-
bonized at 900 °C, and the prepared carbon material exhibits
a good porous structure.
In our recent work, a carbon-based monolithic catalytic
system was achieved with this method (Figure 7). Palladium
was loaded on 3D printed carbon macro structures with
microporous structures and large surface areas (962.6 m2 g−1).
The Pd/C monolithic structures were then used for the catalytic
combustion of methane. The printed Pd/C possesses enhanced
catalytic performance compared to catalysts prepared via con-
ventional method, and the bed pressure during the combus-
tion reduces significantly. These results show that printed Pd/C
structures can serve as efficient monolithic catalytic materials
for industrial applications.
Printing processes have also been expanded to obtain
carbon materials with other special structures. For example,
carbon aerogels have been prepared using a sol–gel printing
process. Carbon aerogels have been studied as catalytic mate-
rials because of their low densities, special porous structures
and many other characteristics.[35] When preparing carbon
aerogels via 3D printing, special precautions need to be taken
to prevent damage to the sample during extrusion. Preventing
the material from drying is one of the most important aspects.
The evaporation of the solvent at atmospheric conditions can
cause drastic changes in the surface tension of the solvent at
the vapor-liquid interface.[36] This can result in shrinkage which
is most pronounced for pore sizes > 1 nm. As a result, aero-
gels prepared via normal subcritical drying usually have poor
mesoporous structures, since these structures are destroyed
during drying, especially for monolithic structures with large
thickness.
A suitable solution to this problem is to extrude the ink into
a bath of liquid which is immiscible with the solvent. The sol-
vent is then removed through supercritical drying or freeze
drying after printing. Solvent exchange is usually necessary
when freeze-drying an aqueous solution.[37] This strategy was
reported by Zhu et al.[9c] to prepare graphene aerogels with
macroscopic architectures (Figure 8). An R-F solution and silica
filler provided a suitable rheology for the GO ink. Isooctane
was used to prevent solvent evaporation during the printing.
Supercritical CO2 was then used to dry the prepared GO gel.
The printed GO aerogel possesses a porous structure with good
mechanical and electronic properties.[38] This type of material
might be a promising catalytic material.
It is worth mentioning that 3D printing is also feasible for
printing pure graphene-based structures. Graphene-based
material can be dispersed in water or organic solvents to make
printing inks for DIW. The ink viscosity must be strictly con-
trolled and solidification can be achieved by either solvent
evaporation[9b,39] or freezing.[40]

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Figure 6. Scheme showing the monolithic catalyst preparation using
printed model as a template. a) 3D digital model projection; b) printing
the STL file and finishing the template; c) filling the template with α-Al2O3
paste, burning off the template and coating the monolith with active com-
pounds; d) template vs monolith main dimensions. Reproduced with per-
mission.[32] Copyright 2016, Royal Society of Chemistry.
Other approaches have also been used to print carbon
structures. Starch, for example, is a good carbon source for
carbonization processes. 3D printing using starch based mate-
rials has been studied.[41] In the presence of water and heat, the
intermolecular bonds of starch molecules break down due to
gelatinization, allowing the hydrogen bonding sites to engage
more water. The gelatinization process makes starch dissolve
in water, which is favorable for the extrusion process. In our
recent work, a starch-based material was shown to be a prom-
ising 3D printing ink (Figure 9). The carbonization has no neg-
ative effects on the printed macrostructure. The mesostructure
of the carbon material is preserved. These structures may be
very useful for developing improved industrial carbon-based
catalysts.
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3.3. Metals and Metal Oxides
Metals and metal oxides are typical 3D printing materials which
can be applied in powder bed systems, powder feed systems,
and wire feed systems (FDM, DIW, etc.).[42] The printing pro-
cesses for these materials are relatively low cost, which brings
plenty of applications. For the preparation of catalytic materials,
a suitable way is to print pure metal cellular structures and then
disperse the catalyst on the surface. SLM and SLS are usually
used for the printing process. The metal 3D printers are usually
expensive, but the operation cost is relatively low. Another way
is to prepare printing ink consisting of a suspension of various
metal and metal oxide particles. Additives are needed to main-
tain a suitable viscosity. Metal or metal oxide structures can
be prepared through extrusion based printing processes. The
printing equipment needed in this method is relatively simple,
but post processing is usually needed. For example, drying and
sintering are usually needed for the removal of binder and for
the decomposition of the precursors. Reduction of metal ion is
also sometimes needed if metal precursor is applied with metal
as the target material.
Metals can be directly printed through many processes such
as DIW, SLS, and electron-beam melting (EBM).[42a,44] Catalytic
active components can be deposited on the surface of the 3D
printed structures to form various catalytic materials. Ambrosi
et al.[45] designed a 3D printed metal electrode functionalized
by the electrochemical deposition of IrO2 films. The electrode
shows good catalytic properties for the oxygen evolution reac-
tion. Avril et al. reported a novel catalytic static mixers produced
through metal 3D printing.[43] The catalyst was deposited using
either cold spraying or electroplating to form a novel contin-
uous flowing catalytic reactor system. The catalytic reactor was
evaluated for a series of flowing hydrogenations of alkenes and
carbonyls. (Figure 10) The result shows that the printed metal
structures can serve as good catalytic systems, while the man-
ufacturing cost is significantly reduced comparing with other
manufacturing processes. Meanwhile, the printed system also
has the advantage of simple tubular reactor geometry and ease
of manufacturing, which is helpful for the system to be applied
for other reactions.
On the other hand, the dispersion of active components on
the surface of the printed metal structures is still not a simple
case. Some challenges like low surface area still exist. With the
development of printing processes, the printed metal/metal
oxide structures can be directly applied for the catalytic system.
For example, metal and metal oxide structures can be printed
through extrusion. Recently, the extrusion of Al2O3,[47] ZnO,[48]
and zeolites[49] have been reported. Shannon et al.[46] reported
a versatile and simple process for the additive manufacturing
of cellular metallic architectures. The extrusion process was
used with a liquid ink consisting of a suspension of metal or
metal oxide particles. Fe and Ni powders and their oxides are
used as the structural material and a mixture of polylactic-co-
glycolic acid copolymer, dichloromethane, ethylene glycol butyl
ether, and dibutyl phthalate is used to maintain a suitable rhe-
ology. The structure is printed and then subjected to sintering,
with an intermediate thermochemical reduction step if oxide
feedstocks are used. Figure 11 shows the mass changes and
the linear dimension changes of the printed structures. The
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Figure 7.  3D printed Pd/C monolithic catalyst. a) Schematic illustration of the printing process. b–d) Photos of the printed Pd/C catalysts. e–g) TEM
images of the printed Pd/C catalysts.

result shows that the cellular architectures exhibit low stiffness,
high strength and high ductility, leading to excellent elastic and
plastic energy absorption.
Another example was reported by Tubio et al.[11a] A Cu/Al2O3
catalyst (Figure 12) was prepared using an extrusion-based
process. The printing ink was made by dispersing Al2O3 powder
into a Cu(NO3)2 solution. The rheology of the ink was adjusted
using hydroxypropyl methyl cellulose as a viscosity modifier.
After extrusion, a sintering process at 1400 °C was used to
remove the organic components and to decompose the copper

Figure 8.  Fabrication and rheological properties of GO ink. a) Schematic diagram of the fabrication process. b) Optical image of a 3D printed graphene
aerogel microlattice. SEM images of c) a 3D printed graphene aerogel microlattice, d) graphene aerogel without R-F after etching, and e) graphene
aerogel with 4 wt% R-F after etching. Optical image of f) 3D printed graphene aerogel microlattices with varying thicknesses and g) 3D printed gra-
phene aerogel honeycomb. Scale bars: (b) 5 mm, (c) 200 mm, (d,e) 100 nm, and (g) 1 cm. Reproduced with permission.[9c] Copyright 2015, Nature
Publishing Group.

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Figure 9.  3D printed carbon structures using starch as the carbon source. a) Photo of the printed carbon structures. b) N2 adsorption-desorption
isotherm and pore size distribution of the printed carbon material.

nitrate. A delicate structure was achieved through this strategy.
The diameters of the rods in the structure can be controlled
to 410 µm with a large porosity (57%). The Ullmann reaction
was selected as a model reaction to evaluate the catalytic per-
formance of the printed structure. The printed catalyst, even
those with a relatively low Cu loading give much shorter reac-
tion times to achieve complete conversions compared to other
heterogeneous catalytic systems. In addition, the printed catalyst
can be reused at least 10 times without a dramatic loss in yield.
The ease of preparation, reactivity, recyclability, and negligible
metal contamination all make this 3D printing technique a
good alternative to fabricate metal/oxide heterogeneous catalytic
systems.
3.4. Zeolites
Zeolites are also promising materials for the 3D printing of cat-
alysts. Extrusion-based printing strategy has been used for the
printing of zeolites. A suitable method was reported by Harshul
et al.[49a] Zeolite powders were mixed with binders (consisting
of bentonite clay as a binder, methyl cellulose as a plasticizing
organic binder, and poly(vinyl) alcohol (PVA) as a co-binder)
and extruded using a robocasting 3D printer. The material was
then dried and calcined to remove the binders. The printed
structures were used for CO2 removal. Couck et al.[49b] reported
a three dimensional fiber deposition (3DFD) technique for
the preparation of ZSM-5 structures. Self-standing monolithic
zeolite-containing structures were prepared using colloidal
silica with milled bentonite as a watery binder. The structures
show an excellent potential for CO2/N2 and CO2/CH4 separa-
tion. Lefevere et al.[49c] produced catalyst supports with different
structures using 3DFD. Zeolites were then coated on the sup-
ports for the conversion of methanol to dimethyl ether (DME)
and to olefins. They studied the influence of the structure on
the catalytic performances. The result shows that a high selec-
tivity towards DME can be achieved at low temperature using a
structured catalyst with straight channels, while the structures
with tortuous channels exhibit the highest yield of light olefins
at high methanol feed rate. The main reason for the high yield
is attributed to the better mass and heat transfer properties of
the printed structure.

Figure 10.  Simplified process flow diagram of the tubular flow reactor set-up for continuous flow hydrogenations. Bottom left: series of catalytic static
mixers after 3D printing. Reproduced with permission.[43] Copyright 2017, Royal Society of Chemistry.

Adv. Funct. Mater. 2017, 1701134 1701134  (9 of 13) © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.afm-journal.de

channels through which a reacting fluid flows.

The catalyst is usually deposited in the form of
a thin coating on the monolith channel wall.
Compared with traditional packed-bed reactor,
monolithic catalysts have many advantages
such as high transport rates of heat and mass
per unit pressure drop, small transverse tem-
perature gradients and ease of scale-up.[50] In
recent years, monolithic catalysts have become
a vital catalytic material for automotive and
stationary emission control[51] and for enzyme
reactors.[52] The disadvantages of the present
monolithic catalysts are their poor surface
areas, complex preparation processes, and
the stability of the pores under conditions of
rapidly changing temperature. With the 3D
printing preparation, the monolithic catalysts
can be significantly improved. The manufac-
ture can be simplified. With the use of specific
Figure 11.  a) Graph of mass changes and linear dimensional changes for oxide- and metal-
derived structures made of iron and nickel. Due to the loss of oxygen after oxide reduction,
pore-forming agent, the surface area of the
oxide-derived samples have greater changes in mass and dimensions than their metal-derived printed monolithic catalysts can be increased.
counterparts. b,f): Samples derived from Fe2O3 particle-based inks; c,g): Samples derived Three-dimensional printed catalysts have
from Fe particle-based inks; d,h): Samples derived from NiO particle-based inks; e,i): Samples plenty of advantages compared to classical
derived from Ni-particle-based inks. Note the difference in scale bars, all representing 2 mm. catalytic materials (such as powders, pellets,
Reproduced with permission.[46] Copyright 2016, Wiley-VCH. and extrudates) and also to the monolithic
catalysts above mentioned. Firstly, the heat
4. Conclusions and Future Perspectives and mass transfer properties can be significantly enhanced
by the printed structure. The bed pressure drop can be
The 3D printing process is a promising manufacturing method reduced at the same time. The investigation has shown that
that is highly efficient, easily adaptable, and easy to use. It can the printed materials with different structures can affect the
be applied to many different catalytic materials. Diverse struc- yield of the target product.[43,49c] Better heat and mass transfer
tures can be designed and accurately controlled. In many ways, properties are the main reasons for this. Since the printing
3D printing has a great potential for future development of var- model is usually designed by CAD, the structure of the
ious catalysts. printed material can be optimized according to the require-
One area of potential use is for monolithic catalysts. Mono- ment of the target product. With the optimized structure
lithic materials consist of a large number of long and narrow design, the catalytic performance can be further improved.

Figure 12.  3D printed Cu/Al2O3 catalyst. a,b) Optical images of the Cu/Al2O3 structure without sintering. c,d) Optical images of the sintered Cu/Al2O3.
e) Schematic illustration and image of the experimental setup used for the catalytic tests. f–h) SEM images of sintered woodpile structure fabricated
from a concentrated Cu/Al2O3 ink deposited through a 410 µm nozzle. Reproduced with permission.[11a] Copyright 2016, Elsevier.

Adv. Funct. Mater. 2017, 1701134 1701134  (10 of 13) © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Secondly, the 3D printing process can extend the range of
monolithic and other catalytic materials. Various new ingredi-
ents, such as carbon aerogels, graphene, polymers and MOFs,
can be introduced into monolithic catalytic systems. In theory,
3D printing process can be introduced to most of the mate-
rials, as long as these materials can be extruded or sintered.
The active component distribution can also be highly custom-
ized using 3D printing. Different catalysts can be distributed
in different regions of the catalyst structures to complete
complex reactions. This greatly enriched the traditional cata-
lytic materials. For example, during some exothermic reac-
tions (like CO2 hydrogenation to methanol), heat accumula-
tion may happen in certain region of the catalyst bed, which
will reduce the yield of the objective product (like methanol)
in these reaction sites. An optimized catalyst distribution by
3D printing can solve this problem. Thirdly, the 3D printing
process achieves the preparation of fine structures with a rela-
tively low cost. The structures can be customized and strictly
controlled, and the complex manufacturing processes needed
for conventional preparation methods are avoided. The prices
of 3D printers and printing feedstocks are dropping rapidly
in recent years. The cost of printed catalyst has the potential
of being reduced to a reasonable range, which is crucial for
its industrial applications. At the same time, target structures
can be carefully designed to fit the reaction system, and an
accurate rendering of the design can then be easily achieved.
This makes the 3D printing process suitable for industrial
use. In addition, 3D printing, as a flexible approach, is also
suitable for catalyst development. The printing process is
applicable to small batch production and laboratory opera-
tions, which provides a great research tool, allowing to inves-
tigate and to optimize all kind of structures with a variety of
porous materials.
Another potential use for 3D printing is in the preparation
of microreactors. With 3D printing, the boundary between a
catalyst and a reactor is no longer very clear. The printed struc-
ture not only provides the catalyst component, but also controls
the flow of the reactants. This may bring a significant enhance-
ment to catalytic systems. Recently, 3D printed reactionwares
are increasingly being studied. The control of the microfluidic
properties of the reactants helps to achieve good reaction per-
formance with low cost.[53] Other 3D printed reactors have also
been reported. Accurate control of the structure and distribu-
tion of catalyst components is expected to bring a big improve-
ment to the catalytic industry.
The future development of 3D printed catalysts will depend
on the continued development of 3D printing and improve-
ments in the structural designs of catalysts. Thus, progress in
the following areas is critical for continued development:
(1) Better control of the micro/meso structures of printed
catalytic materials is needed. One way to achieve this goal
is to improve the accuracy of 3D printers. The concept
of nanoscale 3D printing is being developed using tech-
niques like electrohydrodynamic printing and focused
ion beam.[54] Great gains are being made, but the output
of these processes cannot yet meet the needs of industrial
applications. A way to improve accuracy is to produce 3D
printable nanoscale ink.[55] Synthetic methods of the ink
Adv. Funct. Mater. 2017, 1701134 1701134  (11 of 13)
www.afm-journal.de
are important for better control of nanoscale structures and
improvements in production capacity are crucial for indus-
trial use.
(2) The feedstock materials for 3D printing need to be further
improved. Recently, a wide range of materials have been
used in 3D printing, but there are still problems to be solved.
Firstly, the material directly determines the cost of the print-
ing process, which is crucial for its applications. Some
materials need to be printed by special equipment, which
leads to a high fixed cost. Meanwhile, the materials made
into filaments, powders and gels that can be compatible
with the commercial 3D printer will be more convenient for
researchers and manufacturers. Secondly, some materials
require complex post-treatment processes. The preservation
of the structures of the 3D printed materials is a challenge.
Both the printed macroporous structure and the inherent
micro/meso structure of the materials may be affected by
the post-treatment processes. Solvent removal is needed for
some extrusion based printing processes, which can cause
shrinkage and pore structure damage. Calcination can cause
negative effects on the pore structure, especially for pow-
der based printing. Improvements are needed to overcome
the effects of the post-treatment processes. In addition, the
mechanical properties and chemical stabilities of the 3D
printed materials have to be considered when being used as
catalysts. The differences in the mechanical properties and
chemical stability between various 3D printed materials and
materials prepared through conventional methods have not
been fully studied. More efforts are needed.
(3) Optimized catalyst design is further needed. With 3D print-
ing techniques, it is feasible to control pore size, pore struc-
tures, and even the distribution of the active ingredients in
catalytic materials. As a result, the structural optimization of
catalysts is becoming more important in order to maximize
catalytic performance.
In summary, in recent years, 3D printing devices have
become cheaper and simpler to use, which has led to the
rapid development of applications of this technology. As a
new rapid fabrication method, 3D printing brings many new
possibilities to the field of catalysis. Structural design, control
of catalyst distribution, and the fabrication of monolithic reac-
tors are becoming easier. However, novel printing materials
and optimized catalyst designs are still needed to achieve even
better catalytic performances. With the depletion of fossil fuel
resources and increasing environmental concerns, advanced
catalysts are playing more important roles in many areas. The
market for catalysts with novel structures will continue to
grow in the future. As a bottom-up method, 3D printing fab-
rication provides new solutions for preparing catalysts with
new structures in a more economical and energy-efficient
way.
Acknowledgements
Support from the National Key Research and Development Program of
China (contract number 2016YFB0600900) and the National Natural
Science Foundation of China (contract number 21536008 and 91334206)
is appreciated.
© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Conflict of Interest
The authors declare no conflict of interest.
Keywords
additive manufacturing, catalysis, monolithic catalysts, three-
dimensional printing
Received: March 1, 2017
Revised: March 31, 2017
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