Bio-directed morphology engineering towards hierarchical 1D to 3D macro/meso/nanoscopic morph-tunable carbon nitride assemblies for enhanced artificial photosynthesis

Article abstract of DOI:10.1039/c6ta08691h

The design of artificial photosynthetic systems (APSs) with hierarchical porosity by taking into account liquid flow and gas transport effects is of high significance. Herein we demonstrate a general and facile strategy to prepare hierarchical 1D to 3D ma

Full text of DOI:10.1039/c6ta08691h

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ISSN 2050-7488
PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS nanocages as a lithium ion battery anode material
2
rsc.li/materials-a

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DOI: 10.1039/C6TA08691H
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ARTICLE
Bio-directed Morphology Engineering Towards Hierarchical 1D to
D Macro/meso/nanoscopic Morph-tunable Carbon Nitride
Assemblies for Enhanced Artificial Photosynthesis
3
Received 00th January 20xx,
Accepted 00th January 20xx
Jun Xu,ab Han Zhou,* Kaiyu Shi, Runyu Yan, Yiwen Tang, Jian Liu, Jinhua Ye, Di Zhang and
ab
a
a
a
e
cd
a
DOI: 10.1039/x0xx00000x
Tongxiang Fan*a
www.rsc.org/
The design of artificial photosynthetic systems (APS) with hierarchical porosity by taking into account of liquid flow and gas
transport effects is of high significance. Herein we demonstrate a general and facile strategy to prepare hierarchical 1D to
3
D macro/meso/nanoscopic morph-tunable g-C
3
N
4
assemblies via bio-directed morphology engineering for enhanced
reduction. Escherichia coli (1D), Papilio nephelus wings (2D, planar)
artificial photosynthesis of CO and methane via CO
2
and cole pollen (3D) are adopted for 1D to 3D multiscale assemblies with high surface areas via a two-step transformation
process. Moreover, liquid flow and gas diffusion behaviors are investigated using COMSOL computational simulation to
reveal the relationship between structural effects and output efficiency theoretically. Such methodology can be extended
to realize versatile fabrication of various morph-tunable carbon nitride assemblies. Importantly, this research illustrates
the power of combining theoretical calculations and experimental techniques to achieve the controlled design of high
efficiency APS, may provide further avenues to APS optimization.
porosity is of high significance. Further investigating of liquid
flow and gas transport from the theoretical aspects will
deepen understandings between the performance and
hierarchical morphology.
3 4
Graphitic carbon nitride (g-C N ) is a promising material
with wide applications in photocatalytic solar energy
Introduction
Solar energy conversion by artificial photosynthetic systems
(APS) that is inspired by natural leaves is thought to be a
1
-3
potential and promising approach for solving energy crisis.
The photochemical transformation of CO
fuels (such as CO, CH , HCOOH, and so on) has emerged as a
research hotspot.4-7 However, CO
conversion efficiency in
artificial photosynthesis is still very low comparing with
photocatalytic hydrogen evolution. For the gas involved CO
reduction reactions, gas transport in the gas channels and
within the porous materials is one limiting factor and tends to
affect the activities at some extent. However, there are very
few studies on such exploration. Hierarchical assemblies
featuring the combination of macroscopic and microscopic
structures could in principle allow for enhanced liquid flow and
gas transport in liquid-phase reaction systems.
designing of artificial photosynthetic systems with hierarchical
2
into hydrocarbon
1
2,13
14
15
conversion,
actuators,
NADH regeneration, CO
2
activation, ion
4
1
6
17
18
chemical sensors,
1
biological imaging,
2
9
and so forth.20-22 To date, various
piezoelectricity
nanoarchitectural g-C
3
N
4
,
including 1D nanorods and
2
nanowires, 2D nanosheets, and 3D architectures, have been
3-25
developed
via
hard/soft
template
synthesis,2
6
solvothermal/molten-salt
technology,2
supermolecular
chemistry.28
morphology, electronic structure, optical properties and
functions of g-C can be efficiently regulated through
nanostructure engineering.
exfoliation
The
1
8,27
methods
and
8
,9
3 4
N
2
9-32
However, the current
1
0,11
Thus
approaches are limited to exotemplating (for 0D and 1D
materials) and exfoliation (for 2D materials) strategies.2
Assembling low-dimensional building blocks into bioinspired
hierarchical architectures with superior performance is a
promising but challenging task. Jun and Stucky et al. developed
7,33-35
a.
State Key Lab of Metal Matrix Composites, Shanghai Jiaotong University,
Shanghai 200240, China.
*
E-mail: hanzhou_81@sjtu.edu.cn; txfan@sjtu.edu.cn.
a
molecular cooperative assembly strategy for the
Fax: +86-21-34202749; Tel: +86-21-54747779.
3
6
b.
c.
construction of 3D macroscopic assemblies of carbon nitride.
Advanced Energy Material and Technology Center; Shanghai Jiaotong University,
Shanghai 200240, China.
International Center for Materials Nanoarchitectonics (MANA), National Institute
for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan.
TU-NIMS Joint Research Center, School of Materials Science and Engineering,
Tianjin University, 92 Weijin Road, Nankai District, Tianjin 300072, China.
Department of Chemistry, Northwestern University, Evanston, 60208, USA.
Nevertheless, a more general and effective transformation
strategy for multiscale morph-tunable assemblies will be more
appealing.
d.
Nature has a variety of hierarchical morphologies ranging
See from 1D to 3D structures that generate sophisticated
e.
†
Electronic
Supplementary
Information
(ESI)
available:
DOI: 10.1039/x0xx00000x
37-39
40-42
functions, such as light manipulation,
transportation,
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gas diffusion.43 Bio-directed morphology engineering would Bio-directed g-C
allow facile tailoring of morphology and physical transformation method. Firstly, three bio-templates were
N
was synthesized via
a
two-step
View Article Online
3
4
DOI: 10.1039/C6TA08691H
4
4,45
properties.
However, there are few reports on constructing pretreated by different methods. Escherichia coli was fixed by
multiscale carbon nitride architectures by this bio-directed 2.5% glutaraldehyde solution and dehydrated by ethanol with
4
6
strategy. Herein we demonstrate a general and facile graded concentrations before slightly drying at 30 °C to obtain
synthetic strategy to prepare hierarchical 1D to 3D a solid sample. Butterfly wings of Papilio nephelus were soaked
macro/meso/nanoscopic morph-tunable carbon nitride in ethanol for 10 min, followed by immersing in 4 wt% NaOH
assemblies via bio-directed morphology engineering for solution for 2 h, and then they were thoroughly rinsed with
enhanced artificial photosynthesis of CO and methane via CO
2
deionized water, followed by drying at 60 °C to be used. The
reduction. Three typical kinds of biological systems, Escherichia wall-broken cole pollen was washed with ethanol under
coli (1D), Papilio nephelus butterfly wings (2D, planar) and cole magnetic stirring for three times, once 20 min and then dried
pollen (3D) are employed in the current study. Two-step at 60 °C. Bio-directed SiO
transformation process is applied for the construction of 1D to sol-gel process with hexadecyltrimethylammonium bromide
D macro/meso/nanoscopic carbon nitride assemblies with (CTAB, ≥ 99.0%) as the surfactant. In a typical procedure, CTAB
2
was synthesized through a surface
3
high surface areas (Scheme 1). Moreover, liquid flow and gas (6.0 g) was dissolved in pure water (30 mL) with magnetic
diffusion behaviors are investigated using COMSOL stirring at 60 °C for 15 min. Secondly, 1.4 M HCl solution (30
multiphysics computational simulation to reveal the mL) was added to ethyl silicate (TEOS, SiO
relationship between structural effects and output efficiency dissolved in ethanol (180 mL). The high volume ratio of ethanol
theoretically. To our knowledge, this is the first report of a -to-H O prevented silica from precipitating. Afterwards, the
2
≥ 28.4%, 16 g)
2
comprehensive theoretical modelling and understanding for two solutions were mixed together and stirred for another 10
liquid flow and gas diffusion within hierarchical porous min to obtain a sol. The pretreated Escherichia coli, butterfly
materials in artificial photosynthesis. More importantly, this wings and cole pollen were immersed into the sol for 12 h at
research combining theoretical calculations and experimental room temperature and subsequently pulled out to rinse and
techniques in the controlled design of APS, may provide dry at 60 °C, followed by calcination under continuous air
further avenues to APS optimization.
flowing at 600 °C for 12 h with a heating rate of 1 °C/min to
remove the organic constituents, and the residues were bio-
directed SiO
2
samples.
In the second step, SiO
2
samples were activated with 1 M
HCl solution for 10 min, followed by centrifuging and washing
until pH constant at 7. After vacuum drying at 60 °C, the
pretreated SiO
2
samples were immersed in cyanamide solution
(
SiO /Cyanamide=1/1, w/w). Afterwards, the suspension was
2
brought into vacuum impregnation at 60 °C for 12 h, and then
centrifuged, washed and dried at 60 °C. After that, the
obtained white mixture was sintered under continuous Ar
flowing at 550 °C for 4 h with a heating rate of 2.3 °C/min to
obtain SiO
powder was treated with 4M NH
2
/g-C
3
N
4
hybrids. Finally, the resultant yellow
HF solution at room
4
2
temperature for 48 hours to eliminate the silica template, and
the precipitate was then centrifuged and thoroughly washed
three times with deionized water and ethanol before drying at
Scheme 1. Schematic illustration for the fabrication of
macro/meso/nanoscopic morph-tunable g-C N with butterfly
3 4
wing template as an example via a two-step transformation
process.
8
0 °C in a vacuum oven overnight. The ultimate products were
bio-directed g-C with different architectures.
Bulk g-C was obtained by sintering cyanamide under
continuous Ar flowing at 550 °C for 4 h with a heating rate of
.3 °C/min.
3 4
N
N
3 4
2
Experimental
Materials
Loading of co-catalysts
The loading of 1 wt% Au on g-C
3
N
4
photocatalyst was
as the Au
(1.95 g) was immersed in 10 mM
solution (10 mL) under vigorous stirring at 70 °C for 4 h,
Escherichia coli samples were provided by Beijing Beina
Chuanglian Biotechnology Institute. Papilio nephelus butterfly
wings were provided by Shanghai Qiuyu Biological Technology
Co., Ltd. Wall-broken cole pollen was provided by Shengzhou
Siming Mountain apiculture Co., Ltd. All the commercially
available solvents and reagents were used without further
purification.
conducted by a precipitation method using HAuCl
4
47
source. Typically, g-C
3 4
N
HAuCl
4
with pH value of 9 adjusted by 0.2 M NaOH solution. The
photocatalyst was then recovered, filtered, washed with
deionized water, and dried at 100 °C overnight before heat
preservation at 200 °C for 4 h in air with a heating rate of 5
°
C/min.
3 4
Synthesis of g-C N
2
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The loading of 1 wt% RuO
an established method reported previously.
2
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was performed according to Liquid flow and gas diffusion behaviors were investigated by
8
DOI: 10.1039/C6TA08691H
Firstly, finite element method (FEM) utilizing the COMSOL
photocatalyst powder (986.8 mg, after loading of 1 wt% Au co- multiphysics coupling function (software: COMSOL 5.0).
catalysts) was impregnated with the solution of triruthenium Batteries & Fuel Cells module, CAD Import module, CFD
dodecacarbonyl (Ru
3
(CO)12, ≥ 99%, 21.1 mg) in tetrahydrofuran (Computational Fluid Dynamics) module and Chemical
(THF, 20 mL). The mixed samples were continually stirred at 60 Reaction Engineering module were used here to carry out the
°
C for 4 h, then dried at 60 °C, and the powder obtained was steady state solution. A quasi-2D butterfly wing structural
calcined at 350 °C in air for 2 h to convert ruthenium complex model was developed analytically and the dimension
species to ruthenium oxide.
parameters of the simulation system were derived from SEM
images. The inverse V-type ridges, disordered columnar pillars
and basal substrate were ignored using periodic boundary
conditions to simplify the calculation. The non-structural
model was established by squeezing the corresponding
structural model into a rectangle slab with equal volume. In
Characterization
The morphologies were characterized with a field emission
scanning electron microscopy (SEM, Hitachi S-4800) and
transmission electron microscopy (TEM, JEM-2100F). Raw
Escherichia coli samples were characterized by a biological
TEM (Tecnai G2 spirit Biotwin, FEI). The samples were
examined by the X-ray diffractometer (XRD, Rigaku, D-
max/2550) with Cu Kα radiation (λ=0.154 nm). Fourier
transform infrared spectroscopy (FTIR, Thermo Fisher
Scientific, Nicolet 6700) was used to analyze the composition
and functional groups of the samples. UV–visible (UV–vis)
absorption spectroscopy was recorded using a UV-Vis-NIR
Spectrophotometer (PerkinElmer, Lambda 950). X-ray
photoelectron spectroscopy (XPS, Kratos, AXIS ULTRA DLD)
was utilized to analyze the intramolecular electron valence
state and the chemical adsorption analyzer (ASAP 2010 M+C)
was adopted to evaluate the surface areas and porosity of the
samples. Elemental analysis (EA, Elementar, Vario-EL Cube)
was conducted to measure the content of C, N and H in the
samples.
order
to
reveal
the
effects
of
bio-directed
macro/meso/nanoscopic architectures, models for Laminar
Flow and Transport of Diluted Species were used to simulate
the process of liquid flow, chemical reaction as well as gas
diffusion within a periodic repeating unit. Detailed data used in
the simulation and calculation could be found in the
supporting information.
Results and discussion
Escherichia coli (Figure 1a2), Papilio nephelus butterfly wings
(Figure 1b2) and wall-broken cole pollen (Figure 1c2) are
selected as 1D, 2D and 3D architectures models respectively
because of their large variety and species-specific (Figure S1).
Here butterfly wing serves as 2D planar prototype because of
its film feature though its elaborated structures are more
complex than traditional 2D concept. Typically, the biomass
Photocatalytic CO
2
reduction
Reduction of CO
2
was carried out in a photocatalytic activity was first converted into SiO
evaluation system (Beijing Aulight technology co., LTD) high specific surface area and the bio-directed SiO
composed of a CEL-PE300E-3A Xe lamp (PerkinElmer, 300 W) subsequently templated into g-C N
3 4
2
with CTAB as surfactant to obtain
was
with cyanamide as the
and a 300 mL sealed quartz reactor at ambient temperature. A precursor followed with the removal of SiO (Scheme 1). SEM
CEL-NP2000 optical power meter (Beijing Aulight technology images demonstrate the replication of the original
2
2
co., LTD) was used to test the light intensity on the sample. morphologies of the biomass into the resulting SiO
The average irradiance of the full spectrum is about 690 mW
2 3 4
and g-C N
-2
cm . For the reaction under visible light, an optical cut-off
filter (Beijing perfect light technology co., LTD) was applied to
restrict the wavelength of incident light to ˃ 400 nm,
-2
decreasing light intensity to 330 mW cm . To measure the
photocatalytic performance, the gaseous reaction products
(CO and CH
4
) were detected using a gas chromatography (GC-
7920, Beijing Aulight technology co., LTD) with a flame
ionization detector (FID) and argon as the carrier gas. In a
typical experiment process, catalyst powder (100 mg) was
dispersed in a solution (50 mL) consisting of water (40 mL) as
the solvent and triethanolamine (TEOA, ≥ 78.0%, 10 mL) as the
sacrificial agent under continuous magnetic stirring. Prior to
irradiation, the reaction system was evacuated and purged
with pure CO
residuary air by CO
measured using a gas chromatography sampling each hour.
2
for three or more cycles to substitute all the
. The evolution of CO and CH was
Figure 1. Schematic models, SEM and TEM images of the
3 4
original biological templates, the bio-directed SiO and g-C N
samples, respectively. The 1D, 2D and 3D architectures refer to
Escherichia coli (a1, a2, a3, a4), Papilio nephelus butterfly
wings (b1, b2, b3, b4) and wall-broken cole pollen (c1, c2, c3,
c4), respectively.
2
4
2
Liquid flow and Gas diffusion simulation
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(
Figure 1). Distinctions mainly lie in the shrinkage of the which is also verified by FTIR spectrum.51,52 TVhierweeArtidcliesOtinnlincet
dimensions caused by the heat treatment process. Hierarchical peaks in C 1s spectra at 284.8, 287.5 DanOdI: 1208.1803.39/Ce6VTAc0a8n69b1He
macro/meso/nanoscopic morph-tunable carbon nitride has a identified by XPS spectrum (Figure S2b), corresponding to the
2
number of macropores particularly for 2D and 3D assemblies graphite carbon species, C−NH
Figure 1b4 and 1c4). N adsorption−desorption isotherms hybridizedcarbon (N−C=N) from the g-C
further demonstrate their hierarchical porosity. The Figure 2c shows two peaks presented in N 1s spectra. The
2
species and sp -
N
3 4
, respectively.53
(
2
adsorption−desorption isotherms for bio-directed SiO
2
(Figure dominative N 1s peak centered at 398.8 eV is defined as
2
2a) demonstrate the existence of mesopores with wide size graphite-like sp -hybridized nitrogen (C=N−C) in g-C
3
N
4
.
2
distribution. The BET surface area of bio-directed SiO has Besides, the other peak at 401.1 eV is regarded as amino
2
-1
13
been remarkably improved (up to 734.63 m g ) after CTAB functions (C−N−H). From the UV/vis absorption spectra
was added as a surfactant (Table S1), which is largely derived (Figure 2d), the red-shift of absorption edge of butterfly wing-
from the self-assembly of CTAB into micellar structure and directed g-C
3
N
4
was observed. Typical semiconductor
incorporating into silica network to create nanopore channels absorption with a bandgap of 2.74 eV is observed for butterfly
4
8
after calcination. By contrast, the surface area of SiO
2
replica wing-directed g-C
has higher for bulk g-C
3 4
surface area of 71 m g (cole pollen-directed g-C N ) and pore
3 4
N while the value of 2.77 eV is determined
2
-1
without CTAB is only 45 m g . The resulting g-C
3
N
4
3 4
N .
2
-1
3
-1
volume of 0.16 cm g (Table S1).
3 4
Both bulk g-C and bio-directed g-C N samples possess
3
N
4
almost the same X-ray diffraction (XRD) patterns (Figure S2a)
with slight diminishment of diffraction peaks of the bio-
directed samples. The FTIR spectra of the bio-directed g-C
3 4
N
(
Figure 2b) exhibit characteristic stretching vibration of
-1
-1
aromatic CN heterocycles between 1200 cm and 1650 cm
and breathing vibration of triazine or heptazine units at around
8
-1
08 cm , analogous to those of bulk g-C
3 4
N . The product with
C/N atomic ratio close to 0.65 (Table S2) could be identified as
4
9,50
nitrogen-rich g-C
3
N
4
.
Additionally, a trace of hydrogen (∼2
wt%) derived from the uncondensed amino functions and
adsorbed water was detected through the elemental analysis,
Figure 3. (a) TEM image of the Au and RuO
directed g-C samples. (b) And (c) HRTEM micrograph of the
Au and RuO loaded bio-directed g-C samples. (d) XPS
2
loaded bio-
3 4
N
2
3 4
N
survey spectra, (e) high-resolution XPS spectra of Au 4f, (f)
high-resolution XPS spectra of C 1s and Ru 3d for the Au and
RuO loaded bio-directed g-C N samples, respectively.
2 3 4
Figure 2. (a) Nitrogen adsorption−desorption isotherms of the
SiO
wing-directed SiO
butterfly wing-directed g-C
respectively. (b) FTIR spectra of the bulk g-C
2 3 4
and g-C N samples. A, B, C, D and E refer to butterfly
Nanometer-sized Au and RuO
from 4 to 10 nm were directly deposited on the bare surface of
g-C , as was observed in extensive TEM studies (Figure 3a).
The clear lattice fringe of 0.230 nm can be attributed to the
2
with a grain size ranging
2
, cole pollen-directed SiO
2
, bulk g-C
3
N
N
4
,
,
3 4
N
and cole pollen-directed g-C
3
4
3 4
N
3 4
N and bio-
directed g-C
3
N
4
. (c) XPS spectra of N 1s for the butterfly wing-
5
4,55
(111) facets of Au.
Besides, the interplanar spacing of some
directed g-C
3 4
N . (d) UV-vis absorption spectra and (inset) plots
2
other crystalline grains was calculated to be 0.252 nm,
of (αhν) vs (hν) for the g-C
3 4
N samples. The dotted lines are
the tangents to the curves. The cross value of the X axis is the corresponding to the orientation of atomic plane (101) in the
band gap.
5
6
rutile RuO
2
(Figure 3b). However, extremely trace of Ru
4
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metal (d101=0.199 nm) can also be observed (Figure 3c), which which is 4.1 times as much as that of Au bulk CN (Figure S3). In
View Article Online
5
7
DOI: 10.1039/C6TA08691H
could be the by-product of ruthenium oxide reduction. XPS addition, the photocatalytic activity could be further improved
was carried out to examine the presence of Au and RuO . C 1s, after deposition of 1 wt% RuO co-catalyst (Figure 4b and 4c).
N 1s, O 1s, Au 4f and Ru 3d peak can be detected obviously Ruthenium and its complexes could assist to photocatalyze or
Figure 3d). Au 4f7/2 and 4f5/2 binding energies of 84.1 and 87.8 electrocatalyze CO reduction to form CO or HCOOH with high
eV respectively, were observed in the XPS spectrum (Figure 3e), selectivity and quantum yields.
2
2
(
2
6
4,65
It is worth noting that an
obvious promotion nearly 3.6 folds for CO evolution can be
5
8
which confirms the presence of Au with zero-valent state.
Moreover, the Ru 3d peak is very close to C 1s peaks (Figure observed when compared Au/RuO
f). The Ru 3d spectrum was fitted with two primary spinorbit Au/RuO
components at 282.6 and 285.4 eV for Ru 3d5/2 and Ru 3d3/2 Au/RuO
respectively, which corresponds to the binding energy of Ru
2
bio-directed CN with
−1
3
2
2
2
bulk CN. The CH
4
yield reached 4.34 µmol g−1
h
for
bio-directed CN, 11.6 times higher than that of
bulk CN (Figure 4a and 4c).
4
+
Au/RuO
9
and suggests the presence of RuO
Artificial photosynthesis is operated on g-C
2
in the composites.5
Oxygen was not detected in the current study. The
based oxygen produced by the water splitting is possibly partially
3
N
4
systems in a liquid-phase reaction using triethanolamine consumed by the oxygen vacancies on photocatalyst surface
TEOA) as the sacrificial agent under visible light irradiation (λ and partially employed for oxidizing the evolved products.6
6,67
(
>
400 nm). Bare g-C
products. Other possible products including formic acid, either of TEOA, photocatalyst or light, almost no CO and CH
formaldehyde or methanol were not detected, presumably could be detected. When using Ar gas instead of CO , only
due to the strong oxidizing ability of photoexcited holes (or OH traces of products were detected because of the
radicals), which are able to react with the intermediates and photoreduction of residual CO adsorbed on the photocatalyst
The net hydrocarbon production was negligible. surfaces. Since there is about 2 ppm of CO and 1 ppm of CH in
As expected, butterfly wing-directed g-C (termed bio- the atmosphere, CO and CH in the above control experiments
3 4 4
N evolved CO and CH as the main Control experiments were cautiously performed. Without
4
2
2
6
0-62
products.
4
3
N
4
4
directed CN) without cocatalysts exhibited about 60% are partly regarded as contaminations from the natural air
8
improvements in activities comparing with the bulk g-C
termed bulk CN) (Figure 4a).
3
N
4
during sampling. These results strongly suggest that g-C
3
N
4
(
undergoes photoexcitation with visible light irradiation,
separating the photon-generated electrons and holes.
Subsequently, electrons in the conduction band are consumed
by CO
2
reduction and holes in the valence band are captured
by TEOA. We compared our results with other CO
2
photoreduction systems and the data is listed in Table 1.
However, because the experimental conditions (light intensity,
wavelength range, irradiation distance, reaction temperature,
reaction medium and others) are different, the photocatalytic
performances vary considerably.
We attribute the activity improvements in APS to the
synergy of high liquid flow and gas diffusion efficiency due to
the multiscale macro/meso/nanoscopic architectures, and
more reactive sites originating from high specific surface areas
(
Figure 4d). The surface area factor is a well-known one and
6
8-72
widely investigated already.
Whereas the CO
2
photoreduction was conducted in a liquid-phase system
involving processes of liquid flow and gas diffusion which are
important factors for the catalytic reactions, so here we focus
on liquid flow and gas diffusion behaviors using COMSOL
computational simulation method to reveal the relationship
between structural effects and output efficiency theoretically.
Finite element method (FEM) based on two major physical
models (Laminar Flow and Transport of Diluted Species)7
Figure 4. (a) Photocatalytic activity comparisons between bulk
g-C and bio-directed g-C . (b) And (c) typical time course
of photocatalytic CO and CH evolution in liquid-phase system
with 20 vol% TEOA as the sacrificial agent under visible light
irradiation (λ˃400 nm), respectively. (d) Scheme of the artificial was
photosynthesis processes over butterfly wing-directed g-C
3
N
4
3 4
N
4
3,74
conducted
for
the
simulation
within
a
3
N
4
.
macro/meso/nanoscopic periodic repeating unit based on a
quasi-2D butterfly wing-directed model (Figure 5a1). After
2 3 4
loading with Au and RuO co-catalysts respectively, the g-C N
assemblies still retain the original hierarchical morphologies as
revealed by SEM and EDS mapping (Figure S4). Thus the
simulation based on such bio-directed structures is reasonable
and convincing. The inverse V-type ridges, disordered
columnar pillars and basal substrate were all simplified using
Co-catalysts were loaded to promote the activity. Au
functions as an effective cocatalyst to accelerate CO
reduction. After loading with 1 wt% Au, Au bio-directed CN
evolved approximately 4.09 µmol of CO after 24 h irradiation,
2
6
3
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Journal Name
Table 1. Comparison with other CO
2
photoreduction systems to form CO and hydrocarbons.
View Article Online
DOI: 10.1039/C6TA08691H
Main product
Ref.
Light source
Catalyst
Co-catalyst
Reaction medium
-
1
-1
(
μmol g h )
Nonfocus 300 W Xe lamp,
Bipyridine (15 mg), H2O (1 mL), acetonitrile
(3 mL), triethanolamine (1 mL)
Helical nanorod-like g-C3N4
g-C3N4
0.43 wt% CoCl2
6 wt% ZnO
—
CO (296.7)
CO (29.5)
CH4 (78.0)
82
83
84
visible light (λ> 420 nm)
5
00 W Xe lamp, visible light
Deionized water (4 mL) vapor
(λ> 420 nm)
Mesoporous phosphorylated
g-C3N4
3
00 W high pressure Xe lamp
4 M H2SO4 (5 mL), NaHCO3 (1.0 g)
3
3
00 W Xe arc lamp
00 W Xe arc lamp
Amine-functionalized g-C3N4
g-C3N4
—
2 M H2SO4 (0.3 mL), NaHCO3 (0.084 g)
4 M HCl (0.25 mL), NaHCO3 (0.12 g)
CH4 (0.34)
CH4 (0.3)
85
86
1 wt% Pt
1
1
wt% Au,
3
00 W Xe arc lamp
g-C3N4 nanosheets
g-C3N4/BiOBr
Deionized water (2 mL) vapor
4 M H2SO4 (5 mL), NaHCO3 (1.3 g)
Distilled water (2 mL) vapor
Water (4 mL) vapor
CO (0.5)
87
54
8
wt% ZIF-9
3
3
3
00 W high pressure Xe lamp,
80 nm monochromatic ligh
00 W Xe arc lamp, visible
Au
CO (6.67)
Leaf-architectured SrTiO3
TiO2
1 wt% Au
0.5 wt% Au
CO (0.35)
light (λ> 420 nm)
00 W Xe lamp, UV-vis
λ=320-780 nm)
1
CH4 (3.1)
88
55
89
90
(
Newport Instruments AM 1.5
solar simulator
0.25 μmol Au per
wafer
TiO2 nanotube arrays
Mesoporous g-C3N4
g-C3N4
Water droplets (5 μL, 1 mm diameter)
CH4 (58.47)
HCOOH (46.35)
HCOOH (1100)
CH4 (4.34)
4
00 W high pressure Hg lamp,
visible light (λ> 400 nm)
00 W high pressure Hg lamp,
visible light (λ> 400 nm)
00 W Xe lamp, visible light
λ> 420 nm)
Ru complex
3.9 μmol g-1
Ru complex
7.8 μmol g-1
1 wt% Au,
Acetonitrile and triethanolamine
(4 mL ,4 : 1 v/v)
4
N,N-dimethylacetamide and triethanolamine
(4 mL, 4:1 v/v)
3
Bio-directed hierarchical
porous g-C3N4
This
Water and triethanolamine (4:1 v/v)
(
1 wt% RuO2
work
periodic boundary conditions (Figure 5a1) with dimension
The catalytic reaction occurred in the APS was assumed to
parameters shown in Figure S5a. The non-structural model for be a surface reaction (Figure S5b and S5c). The mass balances
comparison was established by squeezing the corresponding were set up with the Transport of Diluted Species interface
structural model into a rectangle slab with equal volume and solves the diffusion-convection equations at steady
7
4
(
Figure 5a2).
The liquid flow in the structures is modeled with the understanding of structural effects on catalytic efficiency.
Laminar Flow interface that solves the Navier-Stokes equations Differences of gas diffusion mechanism in micro-nano-scale
state. Gas diffusion behavior is discussed to have a better
7
3
77
at steady state (Basic data for the simulation listed in Table distinguish the two models. Gas diffusion in the bio-directed
S3). The numerical modules with long entrance established by model with hierarchical pores on a scale ranging from
software (Figure 5b1 and 5b2) designate the flow direction of nanometer to submicrometre is determined by synergistic
external liquid with periodic boundary condition. The aqueous effect of molecular diffusion, Knudsen diffusion and adsorption
7
4,78
solution
can
circulate
in
the
hierarchical layer surface diffusion (Figure 5d1).
Knudsen diffusion is
macro/meso/nanoscopic holes and reacts on the surfaces of predominant in mesopores while molecular diffusion occupies
7
8,79
the whole substrate (Figure 5c1). Contrastively, only the a leading position in macropores.
While for the non-
external surface is exposed to be contacted in the non- structural model, the molecular diffusion can be ignored and
structural model (Figure 5c2). The substance concentration surface diffusion is foremost leaving internal parts not
and velocity field within the internal structures would change contacting (Figure 5d2) since there is only traces of mesopores
7
8
2
accordingly as time goes on, until the realization of steady existed. The diffusivity of CO and CO (taking as examples) in
state. Figure 5e1 and 5e2 demonstrate that the flow velocity hierarchical macro/meso/nanoscopic gas channels has been
of the liquid in the bio-directed model with hierarchical calculated (Supporting information for details). Obviously, the
architectures gains more than 60% improvements as molecular diffusivity in macropores is about 2~4 folds larger
compared to the non-structural model. Additionally, vortexes than the Knudsen diffusivity in mesopores, both of which are 4
are formed around the hole wall of the porous structure orders of magnitude higher than the surface diffusivity (Table
(Figure 5f1 and 5f2), which partly facilitate the sufficient S5). Thus the diffusion efficiency in bio-directed model with
contact and mass transport of the reacting species, thus hierarchical architectures is definitely superior to the non-
7
5,76
speeding up the reaction kinetically.
structural model.
6
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ARTICLE
View Article Online
DOI: 10.1039/C6TA08691H
Figure 5. Schematic diagram of the simplified butterfly wing-directed model (a1) and non-structural model (a2) using in the
finite element simulation. Numerical modules of the bio-directed model (b1) and non-structural model (b2) with periodic
boundary condition. The blue arrow represents the direction of fluid flow. Sketch of fluid flow and the major gas diffusion
mechanism for the bio-directed model (c1, d1) and non-structural model (c2, d2), respectively. The simulation results of flow
velocity distribution, velocity field distribution and residual CO concentration on the bio-directed model (e1, f1, g1) and non-
structural model (e2, f2, g2) surface, respectively.
Based on the higher gas diffusion efficiency, the reactants
(
CO
2
) can diffuse much faster within the bio-directed
Conclusions
hierarchical framework. Meanwhile, the higher surface areas
and more mesopores increase the local CO
which can prolong the hold-up time of CO
Thus we can infer that the reaction rate is faster because of
2
concentration
In summary, we have proposed a general approach for the
fabrication of hierarchical 1D to 3D macro/meso/nanoscopic
morph-tunable carbon nitride assemblies via bio-directed
morphology engineering. We believe that such approach can
be extended to a large variety of biomass with hierarchical
architectures for realizing versatile fabrication of morph-
tunable functional assemblies (not limited to carbon nitride).
in gas channels.1
1,80
2
8
1
the aggregation of CO
During the reaction, the main products CO and CH
released into the medium. The diffusion of released gases
taking CO as an example) was simulated based on the
2
in the hierarchical porous framework.
4
are
(
Equation S4 and S5 in the supporting information.
Astonishingly, the average CO concentration (integral from
Figure 5g1 and 5g2) residual in the bio-directed model (0.45
2
The CO photoreduction activity improvements are attributed
to the synergy of high liquid flow and gas diffusion efficiency
arising from the multiscale macro/meso/nanoscopic
architectures, and more reactive sites derived from high
specific surface areas. We anticipate that suitable structure
modulations might be applied on other APS to meet the
optimal mass transport requirements. Moreover, this strategy
provides the insight for designing a new family of APS by
tuning morphology and functionality, and may also shed light
on fundamental mechanisms of artificial photosynthesis
processes.
-3
mol m ) is about a quarter of that in the non-structural model
-3
(
1.9 mol m ) (Supporting information for details) in spite of a
faster reaction rate, which means more CO has been released.
So it is reasonable to conclude that the diffusion of reaction
products has been greatly facilitated in the bio-directed
structures.
Above all, the macroscopic output efficiency has been
significantly improved, closely relevant to the structure effects.
First, the multiscale macro/meso/nanoscopic architectures
facilitate the liquid flow. Second, gas transport is promoted by
the mutual effect of hierarchical macro/mesoporous, including Acknowledgements
CO
external liquid medium effectively. Last but not the least, high
porosity and surface areas contribute to increase the local CO
concentration. The simulation results support the experiments
well and give a deep understanding of the processes.
2
entrance to the reactive sites and products release to
We are grateful for financial support by the Foundation for
National Natural Science Foundation of China (51425203), the
Author of National Excellent Doctoral Dissertation of PR China
2
(201434), Innovation Program of Shanghai Municipal
Education Commission (15ZZ008), Program of Shanghai
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Subject Chief Scientist (15XD1501900), Shanghai Rising-Star
Journal Name
Zhang, ACS Nano, 2016, 10, 9036-9043.
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DOI: 10.1039/C6TA08691H
Program (15QA1402700) and International Science
Technology Cooperation Program of China (2015DFE52870).
&
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Hierarchical 1D to 3D multiscale morph-tunable g-C
via two-step transformation strategy for enhanced CO
3
N
4
assemblies were synthesized
2
photoreduction.