Renewable Wood Pulp Paper Reactor with Hierarchical Micro/Nanopores for Continuous-Flow Nanocatalysis

Article abstract of DOI:10.1002/cssc.201700576

Continuous-flow nanocatalysis based on metal nanoparticle catalyst-anchored flow reactors has recently provided an excellent platform for effective chemical manufacturing. However, there has been limited progress in porous structure design and recycling systems for metal nanoparticle-anchored flow reactors to create more efficient and sustainable catalytic processes. In this study, traditional paper is used for a highly efficient, recyclable, and even renewable flow reactor by tailoring the ultrastructures of wood pulp. The “paper reactor” offers hierarchically interconnected micro- and nanoscale pores, which can act as convective-flow and rapid-diffusion channels, respectively, for efficient access of reactants to metal nanoparticle catalysts. In continuous-flow, aqueous, room-temperature catalytic reduction of 4-nitrophenol to 4-aminophenol, a gold nanoparticle (AuNP)-anchored paper reactor with hierarchical micro/nanopores provided higher reaction efficiency than state-of-the-art AuNP-anchored flow reactors. Inspired by traditional paper materials, successful recycling and renewal of AuNP-anchored paper reactors were also demonstrated while high reaction efficiency was maintained.

Full text of DOI:10.1002/cssc.201700576

Accepted Article
Title: Renewable Wood Pulp Paper Reactor with Hierarchical Micro/
Nanopores for Efficient Continuous-Flow Nanocatalysis
Authors: Hirotaka Koga, Naoko Namba, Tsukasa Takahashi, Masaya
Nogi, and Yuta Nishina
This manuscript has been accepted after peer review and appears as an
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using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
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the VoR from the journal website shown below when it is published
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To be cited as: ChemSusChem 10.1002/cssc.201700576
Link to VoR: http://dx.doi.org/10.1002/cssc.201700576
A Journal of
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ChemSusChem
10.1002/cssc.201700576
COMMUNICATION
Renewable Wood Pulp Paper Reactor with Hierarchical
Micro/Nanopores for Efficient Continuous-Flow Nanocatalysis
Hirotaka Koga*, Naoko Namba, Tsukasa Takahashi, Masaya Nogi, and Yuta Nishina
Abstract: Continuous-flow nanocatalysis based on metal
nanoparticle catalyst-anchored flow reactors has recently provided
an excellent platform for effective chemical manufacturing. However,
there has been limited progress in porous structure design and
recycling systems for metal nanoparticle-anchored flow reactors to
create more efficient and sustainable catalytic processes. Here, we
renovated traditional paper as a highly efficient, recyclable, and even
renewable flow reactor by tailoring the ultra-structures of wood pulp.
The ‘paper reactor’ offers hierarchically interconnected micro- and
nanoscale pores, which can act as convective-flow and rapid-
diffusion channels, respectively, for efficient access of reactants to
metal nanoparticle catalysts. In continuous-flow, aqueous, room-
temperature catalytic reduction of 4-nitrophenol to 4-aminophenol, a
gold nanoparticle (AuNP)-anchored paper reactor with the
hierarchical micro/nanopores provided higher reaction efficiency
than state-of-the-art AuNP-anchored flow reactors. Inspired by
traditional paper materials, successful recycling and renewing of
AuNP-anchored paper reactors were also demonstrated, while
maintaining its high reaction efficiency. Our strategy offers potential
for highly efficient and truly sustainable chemical manufacturing.
reaction efficiency in practice. In this regard, the development of
flow reactors with tailored porous channels has become the
major center of attraction; a variety of flow reactors with
microscale or nanoscale pores, based on anodic alumina
membranes,[4] ceramic membranes,[15] silica nanosprings,
silica monoliths,[17] glass fibers,[18] and synthetic polymers,[19]
have been investigated. However, the design of nanoscale and
microscale porous structures inside flow reactors remains
challenging for optimizing access of reactants to catalysts for
further improvement of reaction efficiency. From the viewpoints
of eco-friendliness and sustainability, a system for effective
recycling of metal nanoparticle catalyst-anchored flow reactors is
also essential, particularly because metal nanoparticle catalysts
are expensive and a limited resource.[20,21]
As mentioned above, there is a growing need for highly
efficient continuous-flow nanocatalysis with an excellent
recycling system for truly green sustainable chemistry. To
achieve this challenge, paper, which has been used traditionally
on a daily basis, is expected to offer great potential for use as an
efficient and recyclable flow reactor, because it has highly
porous structures, a high absorption capacity for liquids, high
[16]
stability in most solvents, is both hydrophilic and lipophilic nature,
Nanocatalysis, the process of using catalytic metal nanoparticles,
has become key technology for effective conversion of a variety
of chemicals, because metal nanoparticles can dramatically
improve catalytic efficiency through their large surface-area-to-
volume ratios and unique electronic properties.[1−3] Recently,
nanocatalysis under continuous flow, called continuous-flow
nanocatalysis, has been recognized as an ideal system for
[22−36]
and is recyclable.
Paper is composed of wood pulp fibers
with widths ~several 10 μm, derived from wood cells. Wood pulp
has hierarchical micro/nanostructures (Figure S1a); it is a hollow
fiber with a microscale inner pore (lumen), and its wall consists
of bundles of cellulose nanofibrils (nanocellulose) with widths
from 3 to several 10s of nm.[37,38] Although traditional paper
contains microscale pores derived from both the hollow and
network structures of wood pulp, denoted pulp networks, further
tailoring of the nanostructures derived from the nanocellulose
networks in the wall of wood pulp can provide opportunities to
broaden the potential of paper as a new class of flow reactors
with recyclability.
efficient
chemical
manufacturing.[4−7]
Continuous-flow
nanocatalysis has clear advantages over conventional batch
systems, such as high reaction efficiency, safety, and
reproducibility.[8−11] These advantages are consistent with the
regulations recently introduced for green sustainable
chemistry.[12]
Here, we report a highly efficient, recyclable, and even
renewable paper reactor for continuous-flow nanocatalysis. The
paper reactor was constructed by assembly of wood pulp with
tailored nanoscale pores in its wall. Then, hierarchically
interconnected micro- and nanoscale pores were derived from
the pulp and nanocellulose networks, respectively (Figure S1b).
The wood-derived and well-designed porous structures inside
the paper reactor can provide effective access of reactants to
embedded metal nanoparticle catalysts. As a proof-of-concept
demonstration, a gold nanoparticle (AuNP)-anchored paper
reactor achieved efficient continuous-flow nanocatalysis for the
aqueous-phase, room-temperature reduction of 4-nitrophenol to
Metal nanoparticle catalysts anchored within flow reactors can
serve as an excellent platform for continuous-flow nanocatalysis,
because there is no contamination by catalysts in the
products.[5,6,13,14] One of the current challenges in creating more
efficient chemical manufacturing processes is in designing the
porous structure of flow reactors. Porous structures inside flow
reactors can act as flow channels and control the access of
reactants to catalysts anchored within the reactors, determining
[*]
Dr. H. Koga, N. Namba, T. Takahashi, Dr. M. Nogi
The Institute of Scientific and Industrial Research
Osaka University
4-aminophenol. The turnover frequency (TOF) value was up to
8-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan
−1
4
40 h , which is higher than values obtained in state-of-the-art
E-mail: hkoga@eco.sanken.osaka-u.ac.jp
Dr. Y. Nishina
Research Core for Interdisciplinary Science
Okayama University
AuNP-anchored flow reactors. An excellent recycling and
renewing system for AuNP-anchored paper reactors was also
demonstrated, opening new doors for the development of highly
efficient, green, and sustainable chemistry.
3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan
Supporting information for this article is given via a link at the end of
the document.
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10.1002/cssc.201700576
COMMUNICATION
Figure 2. AuNP-anchored paper reactors with tailored porous structures. (a, d,
g) Optical and (b, c, e, f, h, i) FE-SEM images of AuNP-anchored paper
reactors with different porous structures. (a–c) AuNP-anchored paper reactor
with micro/nanoscale pores fabricated from the AuNP-anchored pulp with
nanoscale pores (with t-BuOH treatment). (d–f) AuNP-anchored paper reactor
containing only microscale pores fabricated from the AuNP-anchored pulp
without nanoscale pores (without t-BuOH treatment). (g–i) AuNP-anchored
paper reactor containing only nanoscale pores fabricated from the AuNP-
anchored nanocellulose with t-BuOH treatment, instead of AuNP-anchored
pulp.
Figure 1. AuNP-anchored wood pulp with tailored nanostructures. Field-
emission scanning electron microscope (FE-SEM) images of the AuNP-
anchored pulp prepared (a–c) without and (d–f) with solvent exchange
treatment using t-BuOH. (a, d) Top-view, (b, e) cross-section, and (c, f) wall
surface of the AuNP-anchored pulp. (g) X-ray diffraction (XRD) patterns of the
pulp (blue) and the AuNP-anchored pulp (red), (h) nitrogen adsorption-
desorption isotherms of the AuNP-anchored pulp prepared without (blue) and
with (red) t-BuOH treatment.
Prior to fabrication of the paper reactor, anchoring of AuNP
catalysts in wood pulp was conducted, followed by tailoring of
nanoscale pores in the walls of the wood pulp. First, AuNPs
were synthesized in situ within wood pulp using
polyethylenimine (PEI) as both an adsorbent and reductant for
dispersed and anchored. The specific surface area of the
AuNPs-anchored pulp was thereby increased from about 0.5 to
2
−1
20 m g by solvent exchange with t-BuOH, also indicating the
formation of nanoscale pores (Figure 1h). Thus, AuNP-anchored
pulp having both microscale inner pores and nanoscale
porestailored in its wall was successfully prepared by a simple t-
BuOH treatment.
Subsequently, the AuNP-anchored pulp with nanoscale pores
was fabricated into a paper material, i.e., a paper reactor, using
a facile papermaking process. Although traditional pulp paper is
white, the as-prepared paper reactor was uniformly pink
because of the surface plasmon resonance of AuNPs (Figure
2a),[43] indicating that AuNP catalysts were well dispersed in the
paper reactor. The AuNP-anchored paper reactor had
microscale pores with sizes of 0.1~100 μm, derived from both
Au precursor ions ([AuCl
4
]−), as follows. An aqueous suspension
of never-dried wood pulp with weakly negative charges[39] was
mixed with an aqueous solution of PEI containing high-density
positive charges to prepare positively charged pulp.
Subsequently, negatively charged Au precursor ions were
attached to the positively charged pulp through electrostatic
interaction, followed by dewatering and thermal treatment at
110°C for 30 min. As shown in Figure 1a and b, the as-prepared
pulp had a hollow structure with microscale inner pores. The
formation of crystalline AuNPs with a crystallite size of 2.4 nm on
the surface of the pulp wall was then confirmed (Figure 1c and g, the hollow (Figure 1e) and network structures of the pulp (Figure
see also Figure S2). AuNPs were successfully formed through
PEI-mediated reduction of the Au precursor ions.[40] In this case,
however, dense nanostructures derived from nanocellulose
2b), i.e., pulp networks, in addition to nanoscale pores with sizes
of 4~100 nm, derived from the nanocellulose networks in the
wall of the pulp (Figure 2c, see also Figure S3). Thus, an AuNP-
fibers were observed on the wall surfaces of the pulp (Figure 1c), anchored paper reactor with hierarchically interconnected
suggesting that the nanocellulose fibers became unavoidably micro/nanoscale pores was successfully fabricated. The
agglomerated during the drying process in the presence of water, grammage of the AuNP-anchored paper reactor with
−
1
−2
because of the high surface tension of water (72.14 mN m at
5°C),[41] as in the Campbell effect.[42] In this study, therefore,
micro/nanoscale pores was about 69 g m ; the contents of pulp,
2
PEI, and AuNP were 98.5 wt%, 1.3 wt%, and 0.2 wt%,
respectively. As a control sample, an AuNP-anchored paper
reactor containing only microscale pores was fabricated from
AuNP-anchored pulp without nanoscale pores (Figure 2d–f, see
also Figure S3), through preparation without t-BuOH treatment.
An AuNP-anchored paper reactor containing only nanoscale
pores was also fabricated using AuNP-anchored nanocellulose
solvent exchange from water to tert-buthyl alcohol (t-BuOH),
which has a low surface tension (19.96 mN m−1 at 25°C),[41] was
conducted before the drying process to suppress the
nanocellulose packing. As shown in Figure 1d–f, the resulting
pulp successfully formed nanoscale pores derived from the
nanocellulose networks in its wall, within which AuNPs were
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ChemSusChem
10.1002/cssc.201700576
COMMUNICATION
nitrophenol at 400 nm, assigned to the 4-nitrophenolate ion,[44]
disappeared, while a new peak at 300 nm, ascribed to 4-
aminophenol,[44] appeared. The absorbance at 300 nm was then
approximately equal to that of 50 μM 4-aminophenol solution,
suggesting that the AuNP-anchored paper reactor with
micro/nanoscale pores achieved almost 100% conversion of 4-
nitrophenol to 4-aminophenol. When the AuNP-free paper
reactor was used with NaBH
paper reactor was used without NaBH
proceed at all, indicating that AuNPs and NaBH
4
and when the AuNP-anchored
, the reaction did not
played an
4
4
essential role as a catalyst and a reducing agent, respectively,
and that PEI and wood pulp paper had no catalytic activity
during 4-nitrophenol reduction (Figure S4). In addition, there was
almost no adsorption of both 4-nitrophenol and 4-aminophenol
on the paper reactor, indicating that wood pulp paper did not
inhibit the 4-nitrophenol reduction reaction in an aqueous system
(
Figure S4). As shown in Figure 3d, however, the actual reaction
efficiencies clearly depended on the porous structures within the
paper. It should be noted that the AuNP-anchored paper reactor
with micro/nanoscale pores (Figure 2a–c) demonstrated much
higher reaction efficiency at all feeding-rate conditions than
those containing only microscale (Figure 2d–f) or nanoscale
pores (Figure 2g–i), while reducing the AuNP catalyst usage to
two thirds. The TOF value (the amount of product obtained per
time per unit amount of catalyst) of the AuNPs-anchored paper
reactor with micro/nanoscale pores reached 440 h−1 (Figure S5),
which is superior to the TOF values of state-of-the-art flow
reactors that are based on inorganic and organic materials
(
Figure 3e, see also Table S1). In other words, the catalytic
Figure 3. Continuous-flow nanocatalysis by the AuNP-anchored paper
reactors. Typical reactor setup using (a) a syringe packed containing the
AuNP-anchored paper reactor and (b) a syringe pump for aqueous room-
temperature reduction of 4-nitrophenol to 4-aminophenol, (c) UV-vis
performance of the AuNP-anchored paper reactor with
micro/nanoscale pores was higher than those of various flow
reactors based on Au nanowire-anchored glass fibers
absorption spectra of a 50 μM 4-nitrophenol solution with 50 mM NaBH
4
(
AuNWs@glass),[18] AuNP-anchored polyethersulfone hollow
before (solid line) and after (dotted line) feeding into the AuNP-anchored paper
fiber membranes (AuNPs@PES),[ AuNP-anchored polysulfone
19]
reactor with micro/nanoscale pores at 0.05 mL min−1
,
(d) 4-nitrophenol
conversion versus feed rate for AuNP-anchored paper reactors containing
different porous structures, (e) TOF value versus feed rate for state-of-the-art
flow reactors in the 4-nitrophenol reduction, (f) relative TOF versus reuse
number for the AuNP-anchored paper reactor with micro/nanoscale pores. Au
hollow fiber membranes (AuNPs@PS),[19] AuNP-anchored
[45]
polycarbonate membranes (AuNPs@PC),
and palladium
nanoparticle-anchored cotton fibers (PdNPs@cotton).[ Paper
is easy to handle and can be reusable after the catalytic
reaction; Zheng et al. have recently reported good reusability of
the Pd-loaded cellulose filter paper for cross-coupling reactions
in batch system.[47] In this study, Au leaching from the AuNP-
anchored paper reactor after the flow reaction was not detected
by atomic absorption analysis, and the AuNP-anchored paper
reactor with micro/nanoscale pores could be reused for at least
10 successive runs without a loss in catalytic efficiency (Figure
3f). These results suggest that the wood pulp paper reactor with
tailored flow-through pores, as represented in Figure S1b, is a
promising candidate for the continuous production of useful
chemicals through the use of highly efficient flow nanocatalysis.
To explain the mechanism behind the high reaction efficiency
of the AuNP-anchored paper reactor with micro/nanoscale pores,
the respective roles of microscale and nanoscale pores as flow
channels are discussed below. Nanoscale pores can act as fast-
diffusion channels for rapid access of reactants to catalysts,
because the typical diffusion time scale τ in nanoscale pores is
46]
3
catalyst content in the paper reactor: 0.45 μmol per 110 mm (microscale
pores, nanoscale pores) and 0.30 μmol per 110 mm3 (micro/nanoscale pores).
treated with t-BuOH, instead of the AuNP-anchored pulp (Figure
2g–i, see also Figure S3).
The as-prepared AuNP-anchored paper reactors were
subjected to continuous-flow nanocatalysis for aqueous room-
temperature reduction of 4-nitrophenol, which is a common
4
environmental pollutant, with sodium borohydride (NaBH ) to 4-
aminophenol, which is an important intermediate for the
manufacture of pharmaceuticals. For continuous-flow
nanocatalysis, the AuNP-anchored paper reactor was cut into
circular discs with a diameter of about 9.0 mm, then vertically
stacked and tightly packed into a syringe equipped with a silicon
tube. In all cases, the length and volume of the paper layer were
3
set at about 1.75 mm and 110 mm , respectively. The reaction
solution was then fed into the syringe (Figure 3a and b). Figure
6
3
c shows the UV-vis spectra of a 50 μM 4-nitrophenol solution
with 50 mM NaBH before and after feeding into the AuNP
anchored paper reactor containing micro/nanoscale pores at
considered to be 10 times smaller than that in microscale pores
2
−1
4
(τ = l 2D , where l is the diffusion length and D is the diffusion
coefficient).[17] In practice, nanoscale pores were more efficient
than microscale pores at feeding rates below 0.05 mL min−1
−
1
0.05 mL min . After feeding, the characteristic peak for 4-
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ChemSusChem
10.1002/cssc.201700576
COMMUNICATION
(
Figure 3d). However, nanoscale pores showed
a
drastic
recycled pulp. The solution of the eluted Au ions was then
neutralized using an aqueous solution of sodium hydroxide.
Thus, the AuNP-anchored paper reactor was separated into the
recycled Au ions and pulp. Finally, the recycled Au ions and pulp
were fabricated into the AuNP-anchored paper reactor using the
papermaking process with t-BuOH treatment. The renewed
AuNP-anchored paper reactor maintained its specific
micro/nanoscale pores, the crystalline structure of native
cellulose (Figure S7), and high reaction efficiency (Figure 4b),
indicating the feasibility of truly sustainable continuous-flow
nanocatalysis.
decrease in reaction efficiency with increasing feeding rate,
resulting in lower efficiencies than that of microscale pores
under higher feeding-rate conditions (Figure 3d). To elucidate
this phenomenon, in this study, effect of porous structures within
the paper reactor on flow uniformity of the reactants was
investigated at a feed rate of 0.05 or 10 mL min−1 (Figure S6). In
each feed-rate condition, there was no difference of the
residence time of reactants in the paper layer among the paper
reactors, regardless of their porous structures, indicating good
permeability. However, the flow uniformity in the paper reactors
varied with their porous structures; while small nanoscale pores
caused a non-uniform flow distribution in the paper reactor
possibly due to local flow (i.e., channeling phenomenon),
Scheme 1. Cross-coupling of 4-iodotoluene and n-BuLi.
relatively large microscale pores allowed
a uniform flow
distribution (Figure S6d). From these results, it was speculated
that nanoscale pores allow fast diffusion of reactants but cause
inefficient access of reactants to the AuNP catalyst due to a non-
uniform flow distribution, resulting in relatively low reaction
efficiency, especially at high feeding rates. Meanwhile,
micro/nanoscale pores would offer both uniform flow and fast
diffusion of reactants. Thus, it was suggested that the tailored
micro/nanoscale pores can provide both effective convective-
flow channels and fast-diffusion channels for efficient access of
reactants to the AuNP catalyst, leading to an enhanced reaction
efficiency.
To demonstrate the broad application of our paper reactor, we
investigated to anchor other metal NPs for fine chemical
production. Pd is one of the most popular catalysts to produce
various
useful
chemicals
such
as
pharmaceuticals,
agrochemicals, and cosmetics through cross-coupling reactions.
A PdNP-anchored paper reactor with micro/nanoscale pores
was prepared using similar processes of AuNP-anchored one
(Figure S8), and used for cross-coupling reaction of aryl iodide
with alkyllithium reagent (Scheme 1); it achieved almost 100%
conversion of 4-iodotoluene at room temperature and at a
Although continuous-flow nanocatalysis may be an ideal
system for effective chemical manufacturing, recycling and
renewing of the conventional metal nanoparticle catalyst-
anchored flow reactors remain a challenge for realizing green
sustainable chemistry. The AuNP-anchored paper reactor had
enough mechanical stability to be recovered after use in
-1
feeding rate of 0.2 mL min . While a similar type of reaction in
batch system has been recently reported using a Pd(0) complex
with phosphine ligand,[ the PdNP-anchored paper reactor is
48]
−
1
continuous flow nanocatalysis at a feeding rate of 10 mL min ,
and was also able to overcome this challenge by taking
advantage of paper-specific recyclability. As shown in Figure 4a,
the AuNP-anchored paper reactor with micro/nanoscale pores
was renewable beyond the point of mere recyclability. First, the
AuNPs-anchored paper reactor was thoroughly washed with
distilled water after use in the continuous-flow nanocatalysis and
then immersed in aqua regia at room temperature for several
seconds to elute Au ions from the paper reactor. The resulting
paper was thoroughly washed with distilled water, followed by
sonication treatment to prepare an aqueous suspension of the
expected to realize a continuous-flow and heterogeneous
system of such a cross-coupling reaction without any phosphine
ligand.
In summary, we demonstrated highly efficient continuous-flow
nanocatalysis with an excellent recycling system, based on an
AuNP-anchored paper reactor. The paper reactor contained
hierarchical micro/nanoscale flow-through pores tailored from
wood pulp, boosting reaction efficiency while reducing the use of
AuNPs. Furthermore, successful reuse, recycling, and renewing
of the AuNP-anchored paper reactor were demonstrated. Thus,
the AuNPs-anchored paper reactor provides good opportunities
to support green processing by reducing catalyst wastage, reuse,
recycling, and renewing, while also achieving effective
production of useful chemicals. The paper reactor can be
prepared from ubiquitous and abundant wood resources through
large-area mass production such as the well-established
papermaking process. This novel strategy can be extended to
various other metal nanoparticle catalysts and corresponding
chemical reactions, and enables facile, highly efficient, and truly
sustainable chemical manufacturing using paper, which is a very
familiar material.
Figure 4. Recyclability and renewability performances of the AuNP-anchored
paper reactor. (a) Schematic of a typical recycling and renewing system for the
AuNP-anchored paper reactor with micro/nanoscale pores, (b) reaction
efficiency of the renewed AuNP-anchored paper reactor with micro/nanoscale
pores at a feed rate of 10 mL min−1
.
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ChemSusChem
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COMMUNICATION
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This article is protected by copyright. All rights reserved.

ChemSusChem
10.1002/cssc.201700576
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Highly
efficient
continuous-flow
H. Koga*, N. Namba, T. Takahashi,
nanocatalysis with a recycling and
renewing system is successfully
demonstrated by a metal nanoparticle
catalysts-anchored wood pulp paper
reactor with tailored hierarchically
porous structures. Our strategy opens
new doors for truly green sustainable
chemical manufacturing.
M. Nogi, Y. Nishina
Page No. – Page No.
Renewable Wood Pulp Paper Reactor
with Hierarchical Micro/Nanopores for
Efficient Continuous-Flow
Nanocatalysis
This article is protected by copyright. All rights reserved.