The function-led design of Z-scheme photocatalytic systems based on hollow carbon nitride semiconductors

Article abstract of DOI:10.1039/c5cc07867a

A ternary photocatalyst has been successfully constructed through the integration of Au, CdS and hollow carbon nitride nanospheres (HCNS), where Au nanoparticles were designed to shuttle interparticle transfer of charge carriers between CdS and HCNS photo

Full text of DOI:10.1039/c5cc07867a

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COMMUNICATION
Function-Led Design of Z-Scheme Photocatalytic Systems Based on
Hollow Carbon Nitride Semicondutors
Dandan Zheng, Chenyang Pang, and Xinchen Wang*
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
A ternary photocatalyst has been successfully constructed by
integrating Au, CdS and hollow carbon nitride nanospheres
charge separation chain, the probabilities of charge recombination
would be decreased significantly, and thus resulting in more
(HCNS), where Au nanoparticles were designed to shuttle 50 electrons available to participate in the reduction step of the
interpartical transfer of charge carrier between CdS and
reaction.6 Although nature Zꢀtype system is efficient in mediating
the electron and energy transfers in a mobile fashion in bionic
conditions,7 artificial photosynthetic systems typically consisting
of isolated photosensitizers and redox mediators (Ox/Red) are
10 HCNS photosensitizers to extablish two-photon (Z-scheme)
photocatalytic tandem systems for solar fuel production. The
solid-state CdS-Au-HCNS Z-scheme nanocomposites were
efficient for H2 evolution (with quantum yield of 8.7% at 420 55 usually difficult to establish efficient photocatalytic cascades
nm) and CO2 reduction catalysis with visible light. This work
15 further proves the feasibility of employing hollow conjugated
polymer photocatalysts for function-led design of artificial Z-
type photosynthetic machinery on soft materials interface.
because the Ox and Red mobile components in solution compete
with the target redox reactions, respectively.8 Therefore, it calls
for the development of solidꢀstate electron mediators to cooperate
with photocatalysts to achieve a dynamic equilibrium between the
60 electronꢀaccepting and ꢀdonating abilities of the mediator.
Recently, Tada et al. proposed the concept of allꢀsolidꢀstate Zꢀ
scheme photocatalysts in a sandwichꢀstructured CdS/Au/TiO2,
where Au nanoparticles (NPs) acted as an electron transfer
mediator.9 This ternary structure has facilitated the separation and
65 migration of photoexcited electrons and holes, and thus to
enhance their photocatalytic activity. Relative to the solution
Lightꢀinduced water splitting to produce H2 and O2 using
semiconductors has recently been a cuttingꢀedge research area
20 due to the growing expectation for the production of H2 fuel from
water by utilizing abundant sunlight.1 Since visible light accounts
for nearly 50% of solar light energy that reaches the Earth’s
surface, efficient utilization of visible light is undoubtedly
necessary to realize H2 production on a large scale. The
25 development of efficient photocatalysts that can harvest a wide
range of visible light has therefore been actively investigated and
it remains a great challenge.2 In principle, semiconductor
photocatalysts must possess strong redox potentials to
simultaneously provide both photoꢀoxidation and reduction
30 powers to drive the target reactions. But, in particle, it is still
difficult for the singleꢀcomponent photocatalyst to satisfy those
mutually exclusive conditions. For example, some photocatalysts
(e.g., WO3, Fe2O3, BiVO4) are demonstrated to be efficient for
water oxidation, but its reduction potential is too positive to
35 reduce protons, and vice versa.3
systems using IO3 /Iꢀ and Fe3+/Fe2+ redox couples,10 the tight
ꢀ
solidꢀsolid junctions of photocatalysts and mediator has low
electric resistance, which ensured a continuous flow of electrons
70 between the source and target photocatalysts for water splitting,
solar cells, and CO2 conversion.11
The use of two semiconductors with suitable band structures
have been adopted to create photocatalytic cascades with flexible
functionꢀled selection of oxidation and reduction potentials for
efficient utilization of solar irradiation to run chemical reactions,
40 which however relies on the design of surface junctions for
efficient charge separation between the two semiconductors.4
In nature, photosynthesis that converts H2O and CO2 into
carbohydrate and O2 in green plants, resembles the soꢀcalled Zꢀ
scheme photochemical process, which involves a twoꢀstep
45 photoexcitation of two photosensitizers followed by efficient
separation of charge via charge mediators in a cascade manner.5
By taking advantage of the unique photoexcitation process and
Scheme 1. Schematic diagram of Zꢀscheme electron transfer in CdSꢀAuꢀ
HCNS system.
75
The previous studies overwhelmingly focus on the construction
of photoactive solidꢀstate Zꢀscheme based on inorganic
semiconductors.12 To make the system more efficient, hollow
nanospheres mimicking thylakoids and cells have expected to act
as a host scaffold that coꢀassemble with suitable semiconductor
80 and electron mediator to construct a hollow allꢀsolidꢀstate Zꢀ
scheme system. It is particularly interesting for the shell to be
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constructed from conjugated semiconductors. However, most
construction of the tenary CdSꢀAuꢀHCNS hybrids.
hollow polymer nanospheres are soft materials that typically
subjected to deformation during processing.13 Thus far, the
creation of allꢀsolidꢀstate Zꢀscheme systems based on conjugated
semiconductors featuring hollow nanoarchitecture with enlarged
internal and external surface area is still rare.
5
Here, we describe the use of HCNS as a conjugated host
scaffold that coꢀassembles with a secondary semiconductor of
CdS and an electron mediator of Au nanoparticles (NPs) to
10 establish
a solidꢀstate Zꢀscheme system. The photoexcited
electrons in conduction band (CB) of CdS transferred to Au and
then to the valence band (VB) of HCNS, and subsequently
recombined with photogenerated holes in HCNS. Simultaneously,
photogenerated electrons in the CB of HCNS and holes in the VB
15 of CdS exhibited strong reduction power and oxidation power,
respectively. The resulting hollow nanoarchitectural framework
of CdSꢀAuꢀHCNS photocatalyst features a large surface areas
that increase the amount of light absorbed and promote surface
dependent reactions by efficiently shuttling both the electronic
20 and chemical species.14 This realization of a biomimetic Zꢀ
scheme charge transfer mechanism permits higher amounts of
hydrogen fuel to be generated than can be achieved by a typical
sensitizing technique under irradiation by visible light.
HCNS was synthesized using silica templates according to our
25 earlier paper.15 Au NPs are deposited on the HCNS surface by the
in-situ reduction method. CdS NPs are then selectively loaded via
a photodeposition method to form CdS@Au heterostructures. The
samples were named as xCdSꢀAuꢀHCNS, where x (1ꢀ3) is
corresponded to weight percentages of CdS for 5, 15, and 25wt.%,
30 respectively, with respect to the HCNS weight. Other noble
metals such as Pd, Ag and Pt were also adopted to construct the
CdSꢀM (M=Pd, Ag, Pt)ꢀHCNS (Fig. S10) for comparisons. The
morphology, structure and optical/electric properties of the
samples were characterized with various physicochemical
35 techniques, while the performance of these samples was accessed
in a H2 production assay and CO2 reduction reaction.
The morphology and microstructure of the CdSꢀAuꢀHCNS
photocatalysts were examined with scanning electron microscopy
(SEM) and transmission electron microscopy (TEM). As shown
40 in Fig. 1a, the morphology is perfectly preserved as highly
uniform hollow spheres with the diameter of ~320 nm after the
processing, indicating the robust nature of the hollow polymer. In
Fig. 1b, Au NPs of 3 nm in size is evenly deposited on the HCNS
surface, and no particulate aggregation of Au NPs occurs due to
45 the intense stabilization effect created by the nitrogenꢀrich soft
matrix. CdS NPs with a size of 5 nm can be further deposited on
the Au NPs polar surfaces by photodeposition as shown in Fig. 1c.
The more details of the CdSꢀAuꢀHCNS nanocomposits were
further identified by HRTEM. As shows in Fig. 1d, a wellꢀ
50 dispersed hemispherical coreꢀshellꢀtype Au@CdS NPs is
deposited on the HCNS surface. The lattice spacing of the core
and shell, determined to be 0.23 and 0.32 nm, respectively, are in
agreement with the values for the Au (111) plane (No. 04ꢀ0784)
and the hexagonal CdS (101) plane (No. 41ꢀ1049).16 Fig. 1f
55 exhibits the elemental mapping of the CdSꢀAuꢀHCNS sample in
dark field, further illustrating the homogeneous distribution of C,
N, S, Cd and Au in the spheres. This result together with the
microꢀarea EDX (Fig. S1d) analysis revealed the successful
60
Fig. 1 Surface morphology characterization. (a) SEM of 2CdSꢀAuꢀHCNS;
(b) TEM of AuꢀHCNS; (c) TEM, (d) HRTEM images and (e) elemental
mapping of 2CdSꢀAuꢀHCNS photocatalysts.
Fig. 2a shows the XRD pattern of the CdSꢀAuꢀHCNS samples.
65 The peak centering at 13.1° corresponds to (100) crystal plane of
triꢀsꢀtriazine units, whereas the peak at 27.4°, indexed as (002)
crystal plane of gꢀC3N4, is attributed to interlayer stacking of
aromatic segments. 17 The two characteristic peaks of typical gꢀ
C3N4 polymer, suggests that the chemical skeleton of HCNS is
70 mostly unaltered. This result is also confirmed by the Fourier
transformed infrared (FTꢀIR) spectra (Fig. S3), where not any
obvious change is detected for the CdSꢀAuꢀHCNS samples
compared with pure HCNS.18 The XRD peaks at 46.8° and 55.5°
are termed as faceꢀcentered cubic structure of typical CdS phase
75 (Fig. S4).16 The particle size of CdS calculated by the Scherrer
equation is ~5 nm, in good coincidence with that observed in the
TEM images. When increasing the loading contents of CdS,
except for gradually increased peak intensities at 46.8° and 55.5°,
a careful inspection of the XRD peaks reveals a slight shift of the
80 peak (002), whereas the peak (100) remains unchanged at 13.1°,
indicating a slightly loosened packing of the conjugated HCNS
system. In addition, due to the low concentration (3wt.%) of Au
NPs, no diffraction peak of crystallized Au NPs was observed in
XRD spectra of CdSꢀAuꢀHCNS sample, but the deposited
85 metallic Au NPs was also verified by XPS analysis.
XPS measurements were performed to identify the CdSꢀAuꢀ
HCNS sample, which indicates the sample primarily consists of C,
N, S, Cd and Au elements (Fig. 2b). Highꢀresolution XPS spectra
of the Au 4f7/2 and Au 4f5/2 peaks are identified at 83.8 and 87.9
2
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eV, respectively, suggesting the presence of Au NPs (Fig. S5a). 19
Moreover, the peak of S2p and Cd3d could be easily observed in
the survey spectra, confirming that there are both Au and CdS
holes. For the CdSꢀAuꢀHCNS samples, the otherwise strong
photoluminescence quenches quickly, indicating that the energyꢀ
wasteful charge recombination happening in the CdSꢀAuꢀHCNS
species in the CdSꢀAuꢀHCNS samples (Fig. S5b). However, no 35 samples is greatly suppressed. This should be attributed to the
5
evident difference in the binding energy (BE) of CdSꢀAuꢀHCNS
samples can be viewed in comparison with HCNS (Fig. S5c, d).
Solid state 13CꢀNMR spectrum in Fig. S6 certifies that HCNS has
a trazineꢀbased heterocycle. 20
sandwich Au NPs at the interface mediated the effective vectorial
Zꢀscheme chargeꢀcarrier transfer process, which greatly improves
the separation rate of photoꢀinduced charges. As expected, the
electron paramagnetic resonance (EPR) intensity of the CdSꢀAuꢀ
40 HCNS samples is strengthened (Fig. 3c), further confirming the
Zꢀscheme mechanism favoring for separation and migration of
photoꢀinduced charge carriers. The photoelectrochemical
performances of pure HCNS, CdSꢀHCNS and CdSꢀAuꢀHCNS
were presented in Fig. 3d. An enhanced photocurrent for CdSꢀ
45 AuꢀHCNS is generated, which is nearly 3 times higher than that
of the pure HCNS, strongly illustrating that the mobility of the
photoꢀexcited charge carriers is promoted.
a
)
b)
N 1s
3CdSꢀAuꢀHCNS
Cd 3d
O 1s
C 1s
I
I
S 2p
200
Au 4f
100
HCNS
b)
a
)
800
600
400
200
0
1200
800
400
0
CO
H2
300
400
500
20
40
60
8
Ο
BE / eV
2
θ
CdS-Au-HCNS
10 Fig. 2 (a) XRD patterns (b) XPS analysis of 2CdSꢀAuꢀHCNS samples.
6
4
2
0
CdS+Au/HCNS
Fig. 3a is diffuse reflectance UV/Vis spectroscopy of the CdSꢀ
AuꢀHCNS sample that shows distinctly enhanced absorption
capability in the optical region from 420 to 750 nm. While the
optical absorption edge of pure HCNS sample is only located at
15 420 nm, a noticeable absorption capability in the optical region
reached to 600 nm for the CdS/HCNS composite.16 However,
with Au NPs adopted, another absorption band of the CdSꢀAuꢀ
HCNS sample at around 650 nm appears, which can be mainly
ascribed to the surface plasmon resonance (SPR) of Au NPs.21
20 Compared to the characteristic absorption band of Au NPs at
around 590 nm, the new absorption band of the CdSꢀAuꢀHCNS
samples is redꢀshifted by approximately 60 nm. These results also
suggest a fierce interaction amount Au, CdS and HCNS on the
hollow soft interface.
4
8
12
16
CdS-HCNS
t
/ h
HCNS
400
500
600
700
λ
/ nm
Fig. 4 (a) Wavelengthꢀdependent H2 evolution rates and insert the
50 stability test of 2CdSꢀAuꢀHCNS under visible light irradiation at λ > 455
nm. (b) Produced gas from CO2 reduction by CdSꢀAuꢀHCNS
photocatalysts under visible light irradiation (λ > 420 nm).
The photocatalytic activity of the CdSꢀAuꢀHCNS samples
were examined in the hydrogen evolution reaction from aqueous
55 solution using 3 wt% Pt as a coꢀcatalyst and 10 vol%
triethanolamine as an electron donor under visible light
irradiation (λ>455 nm). As shown in Fig. S9, the optimum HER
of 277 ꢁmol hꢀ1 is achieved for 2CdSꢀAuꢀHCNS sample, which is
much higher than the HCNS (81ꢁmol hꢀ1), CdS (23 ꢁmol hꢀ1),
60 Au/HCNS (98 ꢁmol hꢀ1) and CdS/HCNS (129 ꢁmol hꢀ1) (Fig. S8).
This result confirmed that the high photocatalytic performance
only occurred when the Zꢀscheme mechanism is generated. To
further confirm that the high photocatalytic activity was promoted
by the generation of the Zꢀscheme mechanism, CdS and Au NPs
65 were just physically mixed and loaded on the outer surface of
HCNS for photocatalytic H2 evolution test under the same
reaction conditions. As expected, there is no significant
enhancement in the activity (148 ꢁmol hꢀ1). Moreover, the
photocatalytic activities of the CdSꢀM (M=Pd, Ag, Pt)ꢀHCNS
70 samples have been also examined as shown in Fig. S11, which
more or less presents enhanced photocatalytic activity after
a)
b)
HCNS
CdS-HCNS
2CdS-Au-HCNS
I
600
800
λ700
/
nm
2CdSꢀAuꢀHCNS
CdS-HCNS
HCNS
400
500
600
700
800
450
500
550
600
650
λ
/
nm
λ
/
nm
25
d
)
c
)
2CdSꢀAuꢀHCNS
CdSꢀHCNS
HCNS
2CdS-Au-HCNS
CdS-HCNS
HCNS
0.9
0.6
0.3
0.0
10 S
on off
I
forming
the
sandwichꢀstructured
CdSꢀMꢀHCNS.
The
I
photocatalysis process in CdSꢀAuꢀHCNS can be proposed in
Scheme 1. Since both HCNS and CdS can be excited by visible
75 light, CBꢀelectrons (CdS) easily flow into metal Au through the
Schottky barrier because the CB (or the Fermi level) of CdS is
higher than that of the loaded metal Au. This electron transfer
process is faster than the electronꢀhole recombination between the
VB and CB of CdS. Thus, plenty of CBꢀelectrons (CdS) can be
80 stored in Au component, as was true with the previous study. On
the other hand, since the energy level of Au is above the VB of
3480
3500
3520
3540
3560
t
/ s
X / G
Fig. 3 (a) UVꢀVis diffuse reflectance spectra, (b) photoluminescence
spectra, (c) electron paramagnetic resonance spectra and (d) photocurrent
generation performance of 2CdSꢀAuꢀHCNS photocatalysts.
30
The PL spectra of Fig. 3b show a strong emission peak of
HCNS, which is assigned to the recombination of the electronꢀ
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State Key Laboratory of Photocatalysis on Energy and Environment
College of Chemistry and Chemical Engineering
Fuzhou University, Fuzhou 350002, People’s Republic of China
60 Eꢀmail: xcwang@fzu.edu.cn.
† Electronic Supplementary Information (ESI) available. See
DOI: 10.1039/c000000x/
HCNS, VBꢀholes (HCNS) also easily flow into metal Au, which
is faster than the electronꢀhole recombination between the VB
and CB of HCNS.22 As a result, the lifetime of photogenerated
CBꢀelectrons at HCNS becomes longer due to the lower
probability of their recombination, which have a sufficiently high
reducing power. The excited electrons will accumulate on the Pt
NPs and then participate in H2 evolution.
5
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65
70
75
Wavelengthꢀdependent H2 production experiments show that
the H2 evolution matches well with the optical absorption of the
10 photocatalyst (Fig. 4a). Meanwhile, an overall enhanced H2
evolution is observed on CdSꢀAuꢀHCNS across its whole
absorption spectrum, which is actually extended to 600 nm. The
durability of CdSꢀAuꢀHCNS for H2 evolution was examined by
four consecutive operations under similar conditions. As shown
15 in Fig. 4a insert, the H2 produced increases steadily with
irradiation time, without noticeable deactivation. The recycled
catalysts were further certified by TEM, XRD and FTꢀIR analysis,
which revealed that the physicochemical properties in both
structures and morphologies are almost unchanged. (Fig. S12, 13).
20 These observations all support the robust nature and high
operation stability of the ternary CdSꢀAuꢀHCNS materials for
photocatalyzing hydrogen evolution.
The CO2 reduction reaction was also phgotocatalyzed by the
CdSꢀAuꢀHCNS samples using Co(bpy)3Cl2 as a redox mediator,
25 and triethanolamine as an electron donor in acetonitrile under
atmospheric CO2 and visible light (λ > 420 nm). As shown in Fig.
4b, upon visible light irradiation for 1 h, the system with CdSꢀ
AuꢀHCNS photocatalysts exhibit remarkably enhanced catalytic
activity for the photosplitting of CO2 to CO, generating 6.8 ꢁmol
30 CO and 1.2 ꢁmol H2 gases. The catalytic turnover number
relative to the amount of cobalt ions and the selectivity for CO
production were calculated to be 8.0 and 85.0% (Table S2),
respectively, which is higher than that of pure HCNS, CdSꢀ
HCNS, and the physicallyꢀmixed (CdS+Au)/HCNS. This result
35 again reflects the beneficial catalysis effect created by the ternary
CdSꢀAuꢀHCNS Zꢀtype system for solar to chemical conversion.
In summary, a ternary artificial photosynthetic CdSꢀAuꢀHCNS
system was successfully constructed by integrating Au NPs into
the binary CdS/HCNS composite as the electron mediator. The
40 resulting allꢀsolidꢀstate CdSꢀAuꢀHCNS photosynthetic system
shows a high photoactivity for hydrogen evolution and CO2
photosplitting reaction under the irradiation of visible light by
working with the twoꢀstep photoexcitation mechanism. The
present study has paved a new way of using the stable hollow
45 conjugated polymers in the design of new and efficient artificial
Zꢀtype systems for solar energy conversion via water splitting
and CO2 reduction by photoredox cascade catalysis, and could be
generally expected to expand to selective organic synthesis and
environmental purification.
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This work was supported by the National Basic Research Program of
China (2013CB632405), the NSF of China (21425309 and 21173043), the
State Key Laboratory of NBC Protection for Civilian (SKLNBC2013ꢀ04
K), and the Specialized Research Fund for the Doctoral Program of
55 Higher Education (20133514110003).
Notes and references
4
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COMMUNICATION
TOC Figure
5
Hollow conjugated polymer nanospheres mimicking thylakoids act as a host scaffold that coassemble
with CdS and Au as an electron mediator to constructe an artificial Zꢀscheme photosynthesis system,
which shows a highly efficient performance in photocatalytic waterꢀsplitting and CO2 reduction
reaction
under
the
irradiation
of
visible
light.
10
This journal is © The Royal Society of Chemistry [year]
[journal], [year], [vol], 00–00 | 5