Selective organic transformation over a self-assembled all-solid-state Z-scheme core-shell photoredox system

Article abstract of DOI:10.1039/d0ta07235d

Z-Scheme artificial photosystems, resembling the natural photosynthesis procedure, circumvent the disadvantage of a single-ingredient photosystem and hold fascinating prospects for solar energy conversion. Despite the advancements, bottom-up elaborate design of composite heterostructured Z-scheme photosystems by flexible interface engineering for photoredox organic transformation has been poorly investigated. We herein report the construction of a metal-based Z-scheme photoredox systemviaa progressive self-assembly strategy integrated with a facile photo-deposition. Tailor-made hierarchically branched ligand-capped Pd nanocrystals (NCs) sandwiched in-between a WO₃nanorod (NR) core and CdS shell are harnessed as the charge transport modulator to regulate the interfacial oxidation-reduction kinetics for boosted Z-scheme photocatalysis. The intermediate Pd NCs as Schottky-type electron flow mediators considerably accelerate the unidirectional Z-scheme charge motion rate, endowing multilayered WO₃?Pd?CdS core-shell heterostructures with significantly boosted net efficiency of photoactivities toward anaerobic selective nitroaromatic reduction to amino derivatives and aromatic alcohol oxidation to aldehydes under visible light illumination. The predominant active species produced in the versatile photocatalytic selective organic transformation were explored and photocatalytic mechanisms were thus ascertained. Our endeavor could offer a promising route for smartly crafting diverse heterostructured Z-scheme photoredox systems for solar energy conversion.

Full text of DOI:10.1039/d0ta07235d

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Number 12
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Pages 4883-5230
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DOI: 10.1039/D0TA07235D
Journal Name
ARTICLE
Selective Organic Transformation Over Self-Assembled All-Solid-
State Z-scheme Core-Shell Photoredox System
Xin Lin, Shuai Xu, Zhi-Quan Wei, Shuo Hou, Qiao-Ling Mo, Xiao-Yan Fu, Fang-Xing Xiao*
Received 00th January 20xx,
Accepted 00th January 20xx
Z-scheme artificial photosystems, resembling the natural photosynthesis procedure, circumvents the disadvantage of single-
ingredient photosystem and holds fascinating prospect for solar energy conversion. Despite the advancements, bottom-up
elaborate design of composite heterostructured Z-scheme photosystems by flexible interface engineering for photoredox
organic transformation has been poorly investigated. We herein report the construction of metal-based Z-scheme photoredox
system via a progressive self-assembly strategy integrated with a facile photo-deposition. Tailor-made hierarchically branched
DOI: 10.1039/x0xx00000x
www.rsc.org/
3
ligand-capped Pd nanocrystals (NCs) sandwiched in-between WO nanorods (NRs) core and CdS shell are harnessed as the
charge transport modulator to regulate the interfacial oxidation-reduction kinetics for boosted Z-scheme photocatalysis. The
intermediate Pd NCs as Schottky-type electron flow mediators considerably accelerates the unidirectional Z-scheme charge
3
motion rate, endowing multilayered WO @Pd@CdS core-shell heterostructures with significantly boosted net efficiency of
photoactivities toward anaerobic selective nitroaromatics reduction to amino derivatives and aromatic alcohols oxidation to
aldehydes under visible light illumination. Predominant active species produced in the versatile photocatalytic selective
organic transformation were explored and photocatalytic mechanisms were thus ascertained. Our endeavor could offer a
promising route for smartly crafting diverse heterostructured Z-scheme photoredox systems for solar energy conversion.
photocatalysis including hydrogen and oxygen evolution,18, 19
carbon dioxide (CO ) reduction,20 bacteria disinfection and
1
. Introduction
2
selective organic transformation.21-23
Semiconductor-based artificial photocatalysis holds
a
Considering the favorable bandgap and energy band
structures, CdS and WO have been frequently integrated to craft
composite heterostructured Z-scheme photosystems.3,24
Noteworthily, WO is featured by high VB potential, chemical
sustainable and promising prospect for solar energy
conversion.1-10 Solar conversion efficiency of photocatalysts is
predominantly dominated by the following two factors: (1)
bandgap (E ) of photocatalyst should be smaller than the incident
g
photon energy; (2) photoredox potentials of reactants should be
3
3
and thermal stability, but low CB level retards its access to
photoreduction catalysis.5 Contrarily, CdS demonstrates the
favorable CB position which endows it with good
photoreduction capability.25,26 Complementary energy level
positioned in-between the valence band (VB) and conduction
band (CB) of photocatalyst. It means that narrow E
3
g
fosters light
harvesting and conversion, and more negative CB or positive VB
potential is thermodynamically beneficial for the photo-induced
reduction and oxidation kinetics, respectively.11 Single-
component photosystem is featured by ultra-fast charge
recombination rate and scarcity of active sites, which inevitably
results in confined light absorption and insufficient redox
potential.12 In terms of conventional type-II photocatalytic (PC)
system, photo-induced charge carriers are isolated in spatial
separated two reverse direction, which effectively retards the
charge recombination, but redox capabilities of electrons and
holes are substantially reduced after separation.13, 14 Z-scheme
photosystems have been evidenced as a widely accepted tactic to
increase the spatial charge separation and retain the redox
potentials of charge carriers.15-17 Thus, explosive Z-scheme
photosystems have been developed for multifarious
3
alignment thus renders WO and CdS suitable building blocks
for constructing elegant Z-scheme photoredox systems.27-30
Although all-semiconductor-based Z-scheme photosystems can
accelerate the interfacial charge separation to some extent, fine
tuning of charge recombination kinetics between the holes of
3
CdS and electrons WO by metal nanocrystals (NCs) enabled
Schottky-type electron flow provides an alternative strategy to
further boost the Z-scheme charge transport efficiency. Inspired
by our recent work,31 which manifests ligand-initiated self-
3
assembly of Pd NCs on the WO markedly benefits boosted
photoactivities toward versatile visible-light-driven photo-
oxidation reactions owing to the directional Schottky-junction-
driven electron transfer caused by Pd NCs. Hence, we speculate
3
judicious integration of Pd NCs in-between WO and CdS via
elaborate interface engineering could benefit the construction of
elegant Z-scheme PC system by synergistically and
simultaneously harnessing the high-efficiency electron-
College of Materials Science and Engineering, Fuzhou University, New Campus,
Minhou, Fujian Province 350108, China. E-mail: fxxiao@fzu.edu.cn
3
withdrawing capability of Pd NCs, high VB level of WO and
Electronic Supplementary Information (ESI) available. See DOI: 10.1039/x0xx00000x CB level of CdS. On the other hand, it should be particularly
This journal is © The Royal Society of Chemistry 20xx
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ARTICLE
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emphasized that semiconductor-based Z-scheme photoredox spectrophotometer. X-ray photoelectron spectrosVcieowpAyrticl(eXOPnliSne)
catalysis toward selective organic transformation has so far not spectra were recorded on a photoeDleOcI:tr1o0.n1039sp/De0cTtrAo0m72e3t5eDr
yet been reported.
(ESCALAB 250). UV-vis diffuse reflectance spectra (DRS)
Herein, we have constructed all-solid-state metal-based Z- (Varian Cary 500 UV-vis spectrophotometer, America) were
scheme core-shell heterostructure by an efficient self-assembly probed by utilizing BaSO4 as the background. The morphologies
strategy integrated with a photo-deposition method based on were probed by field-emission scanning electron microscopy
elaborate interface engineering. Tailor-made oppositely charged (FESEM, Carl Zeiss). Specific surface areas were determined on
Pd NCs and WO
finely tuning the surface charges, followed by seamless CdS spectra were collected on a Varian Cary Eclipse spectrometer.
encapsulation via photodeposition, which constitutes the Hydrogen peroxide (H ) was determined by a photometric
spatially hierarchical core-shell heterostructures. The resultant method in which N, N-diethyl-p-phenylenediamine (DPD) was
WO
NRs@Pd@CdS heterostructures demonstrate significantly oxidized by a peroxidase (POD)-catalyzed reaction.35 The
3
NRs building blocks are self-assembled by an automated gas sorption analyzer. Photoluminescence (PL)
2
O
2
3
improved net efficiency of photoactivities toward selective detailed information was provided in SI.
aromatic alcohols oxidation to aldehydes and aromatic nitro
2
.3. Photoredox performances
compounds reduction to amino derivatives under the
illumination of visible light. The intermediate Pd NCs between (a) Photocatalytic reduction performances
WO core and CdS shell considerably accelerate the In a typical reaction, a 300 W Xe lamp (PLS-SXE300D,
unidirectional interfacial charge recombination kinetic for Beijing Perfect Light co. LTD, China) equipped with a 420 nm
electrons in the CB of WO and holes in the VB of CdS, thereby cut-off filter (λ>420 nm) was used as the irradiation source. 10
boosting the Z-scheme charge transport efficiency. The mg of catalyst and 40 mg of ammonium formate (HCOONH
3
3
4
)
.
-1
substantial reduction-oxidation potentials of electrons for CdS were added into 40 mL of 4-NA aqueous solution (5 mg L ) in a
and holes for WO take part in the selective photoreduction and glass reactor (80 mL). Prior to irradiation, the suspension was
3
photo-oxidation reactions, respectively. In addition, primary magnetically stirred in the dark for 0.5 h to establish the
active species in-situ formed in the photoredox catalysis were adsorption-desorption equilibrium between reactant and catalyst.
probed and photocatalytic mechanisms of WO NRs@Pd@CdS After the regular time interval of 5 min, 3 mL of the solution was
3
heterostructures were thus presented. This work would provide a withdrawn, centrifuged to separate the catalyst, and then
feasible avenue to construct a host of all-solid-state Z-scheme analyzed on a UV-Vis spectrophotometer (Thermal Fisher,
photosystems for extensive photocatalytic utilizations.
GENESYS, 10S). The whole experiments were conducted under
N bubbling with a flow rate of 80 mL min Photoactivity of the
2 .
.
-1
sample was defined by the following formula.
2
. Experimental section
C —C
0
Conversion （%）=
× 100%
(1)
（
）
2
.1. Preparation
C
0
3
2
(I) Fabrication of WO NRs. WO NRs were prepared by a one-
3 3
where C
0
represents the initial concentration of nitroaromatics
step hydrothermal treatment. Detailed information was provided
in SI. (II) Preparation of Pd@DMAP NCs.33 Detailed
and C is the concentration after a certain time of visible light
irradiation.
information was provided in SI. (III) Self-assembly of WO
NRs@Pd heterostructures.31 WO
NRs@Pd heterostructures
with different percentage of Pd were fabricated by an
electrostatic self-assembly method and detailed information was
3
(
b) Selective photocatalytic oxidation of aromatic alcohols
mg of catalyst, 0.1 mmol alcohol, and 1.5 mL of
benzotrifluoride (BTF) saturated with O were added into a
3
8
2
Pyrex glass bottle with a capacity of 10 mL. The reason for
provided in SI. (IV) Preparation of WO
core−shell heterostructures.34 Specifically, 40 mg of
CdCl ·2.5H O and 10 mg of S were dispersed in 50 mL of
ethanol to form a stable suspension and bubbled with N for 30
min in the dark. WO NRs@Pd nanocomposite was distributed
in the above suspension and irradiated for different time under
simulated solar light (300 W Xe arc lamp, PLS-SXE300D,
Beijing Perfectlight Co. Ltd, China). The samples were rinsed
3
NRs@Pd@CdS
choosing BTF as solvent is because of its inertness to oxidation
and high solubility for molecular oxygen.21 After stirring for 20
2
2
8
min in the dark, the glass bottle was then irradiated by a 300 W
Xe arc lamp (PLS-SXE300D, Beijing Perfectlight Co. Ltd,
China) with a UV-CUT filter (λ>420 nm). After reaction, the
suspension was centrifuged at 12000 rpm and the supernatant
was analyzed by a gas chromatograph (SHIMADZU GC-2014C).
2
3
Conversion and yield were determined by the following
formulas.21
with ethanol/DI H
2
O and dried in a vacuum oven at 333 K.
0
C —Calcohol
2
.2. Characterization
Conversion （%）=
× 100%
(2)
（
）
C
0
Zeta potentials (ξ) were probed by dynamic light scattering
analysis (ZetasizerNano ZS-90). Crystal structure was
determined by X-ray diffraction (XRD, Philips, Holland).
Transmission electron microscopy (TEM) were collected on a
FEI transmission electron microscope. Fourier transform
infrared (FTIR) spectra were recorded on a TJ270-30A infrared
C
aldehyde
Yield （%）=
× 100%
(3)
(4)
C
0
C
aldehyde
Selectivity （%）=
× 100%
C
0
—Calcohol
2
| J. Name., 2012, 00, 1-3
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J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
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where C
is the initial concentration of alcohols, Calcohol and 2834.52 cm−1 in the FTIR spectra of WO
ARTICLE
0
3
NRs@Pd (Fig. 1bIII)
View Article Online
DOI: 10.1039/D0TA07235D
C
aldehyde are the concentrations of alcohols and aldehydes after correspond to the stretching vibration fashion of –CH
irradiation under visible light, respectively.
from DMAP ligands.22 Peak intensity of -NH deformation
vibration at 1612.84 cm−1 in the FTIR spectra of WO
NRs@Pd
and WO NRs@Pd@CdS [Fig. 1b(I & III)] is much stronger
PEC results were probed on an electrochemical workstation than those of WO NRs@CdS and WO NRs [Fig. 1b(II & IV)],
CHI660E, CHI Shanghai, Inc.) utilizing Na SO (100 mL, 0.5 which reflects attachment of DMAP ligand on the WO
NRs.40
M, pH=6.69) as the electrolyte and Pt & Ag/AgCl as the counter The peak at 824.51 cm−1 corresponds to the W–O group from
and reference electrodes, respectively. The working electrodes WO
NRs substrate.23 Hence, FTIR results indicate Pd@DMAP
1 X 1 cm ) were directly irradiated by a 300 W Xe arc lamp NCs have been grafted on the WO NRs. Furthermore, blue-
PLS-SXE300D, Beijing Perfectlight Co. Ltd., China) equipped shifts of the peaks are visualized for WO NRs@Pd relative to
NRs, implying electronic interaction between metal (Pd
NCs) and semiconductor (WO NRs). No typical CdS peak is
2
group
3
2
.4. Photoelectrochemical (PEC) performances
3
3
3
(
2
4
3
3
2
(
(
3
3
with a cut-off filter (λ>420 nm). Potentials were calibrated WO
according to the formula below:36, 37
3
3
ERHE = EAg/AgCl + 0.059pH + 0.1976V
(5) seen in the FTIR spectra of WO NRs@Pd@CdS and WO3
3
NRs@CdS, which is due to the low deposition amount of CdS
layer.
Fig. 1c manifests that WO
substantial absorption from 200 to 465 nm, which corresponds
to the intrinsic bandgap photoexcitation of WO . WO NRs@Pd
exhibits a minute red-shift of the band edge accompanied by
increased intensity in the visible region (465~800 nm) relative to
3 3
NRs and WO NRs@Pd exhibit
3
. Results and discussion
Scheme 1 displays the flowchart for fabricating WO
3
3
3
NRs@Pd@CdS composite core-shell photocatalysts which were
elaborately prepared by depositing Pd NCs on the WO NRs
substrate and then a thin CdS layer was coated on the WO
NRs@Pd by a photo-deposition method. Note that tailor-made
Pd NCs are capped by hierarchical linker (Fig. S1) which
endows Pd@DMAP NCs with positively charged surface (Fig.
S2b) owing to the partial protonation of the exocyclic nitrogen
atom.38 Contrarily, WO
Hence, Pd@DMAP NCs can be uniformly electrostatically self-
assembled on the WO
encapsulation on the WO
photo-deposition, which ultimately results in WO
NRs@Pd@CdS core-shell nano-architecture.
3
3
WO
Moreover, DRS spectra of WO
NRs@Pd@CdS indicate light absorption of WO
3
NRs, which is due to the background absorption of Pd NCs.
NRs@CdS and WO
NRs was
3
3
3
enhanced within the visible region when an ultra-thin CdS layer
was deposited on the outermost layer with absorption band edge
3
NRs is negatively charged (Fig. S2a).
red-shifted to longer wavelength. Apparently, WO
and WO NRs@Pd@CdS demonstrate more improved
absorption in visible domain with respect to WO because of the
photosensitization effect of CdS, which agrees with the sample
color (Fig. S3). As shown in Fig. 1d, bandgaps of WO NRs,
WO NRs@Pd, WO NRs@CdS and WO NRs@Pd@CdS are
determined to be 2.64, 2.54, 2.11 and 2.02 eV, respectively.41
The result implies that depositing Pd NCs on the WO NRs does
not affect the light absorption band edge of WO NRs but rather
enhance the intensity. Obviously, bandgap of WO
NRs@Pd@CdS is reduced with Pd NCs and CdS decoration,
3
NRs@CdS
3
3
NRs. Subsequently, uniform CdS
NRs@Pd was realized by a facile
3
3
3
3
3
3
3
As displayed in Fig. 1a, the peaks at 13.99, 22.84, 24.35, 26.82,
o
2
8.57, 36.55, 49.82 and 55.34 are accurately indexed to the
3
crystallographic facets of WO
pattern of WO NRs@Pd@CdS heterostructure is similar to
WO NRs and no CdS peaks and Pd NCs are observed, which is
attributed to the low deposition amount of CdS and Pd NCs
relative to WO NRs substrate. As displayed in Fig. 1b and
3
(JCPDS: 75-2187).39 XRD
3
3
3
3
3
Table S1, the peaks positioned at 3447.50 and 1619.24 cm−1 are
attributed to the stretching and deformation vibration modes of
surface hydroxyl (–OH) group.37 The peaks at 2924.31 and
Fig. 1. (a) XRD and (b) FTIR results of (IV) WO
NRs@CdS and (I) WO NRs@Pd@CdS; (c) DRS spectra with (d) transformed plots
calculated by the Kubelka-Munk function vs. the energy of light.
3 3 3
NRs, (III) WO NRs@Pd, (II) WO
Scheme 1 Schematic demonstration for fabricating the WO
heterostructures.
3
@Pd@CdS core-shell
3
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which is attributed to the photosensitization of CdS for boosting
3
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As visualized in Fig. S6a, WO NRs substrate is featured by
light harvesting. Fig. S4 suggests that specific surface areas and one-dimensional (1D) morphology with smDOooI:t1h0.s1u0r3f9a/cDe0.TFA0ig72. 3(35Da
pore volumes of WO
3
NRs@Pd, WO
3
NRs@CdS and WO
3
3
& S6b) show that morphology of WO NRs@Pd is almost the
NRs@Pd@CdS were not substantially changed relative to WO
3
same to WO NRs and this is due to the ultra-small size of Pd
3
NRs (Table S2), implying analogous adsorption capability of the NCs (2.43 nm, Fig. S1c), making direct differentiation of Pd NCs
samples to the reactants.42
As exhibited in Fig. S5, survey spectrum of WO
difficult. As displayed in Fig. (3b & S6c) and Fig. (3c & S6d),
both WO NRs@CdS and WO NRs@Pd@CdS demonstrate
3
3
3
NRs@Pd@CdS reveals the appearance of W 4f, O 1s, Cd 3d, rough surface which are capped with a thin CdS layer. As
and S 2p signals, which verifies integration of CdS with WO
NRs. As displayed in the high-resolution W 4f spectrum of WO
3
reflected by the TEM images of WO
3
NRs@Pd in Fig. 3(d & e),
3
WO NRs possesses a size of ca. 60 nm, on which Pd NCs were
3
NRs@Pd@CdS (Fig. 2aII), the peaks at 35.55 and 37.65 eV attached on the surface without agglomeration. HRTEM image
6
+
corresponds to W , consistent with the case of WO
2
3
NRs (Fig. of WO
3
NRs@Pd (Fig. 3f) reveals the close integration of Pd
NRs and the lattice fringes of 0.225 and 0.389 nm
aI).31, 43 The peak in the high-resolution O 1s spectrum of WO
NCs and WO
3
3
3
NRs@Pd@CdS (Fig. 2bI) is deconvoluted to two peaks with are assigned to the (111) and (001) crystal facets of Pd and WO ,
binding energy (B.E.) of 530.5 and 532.05 eV which correspond respectively.52
to lattice oxygen and hydroxyl groups, respectively.44 Similarly,
B.E. of lattice oxygen for WO
slightly shifted relative to WO
the electronic interaction caused by Pd and CdS attachment. As heterostructure. As exhibited in the HRTEM image (Fig. 3i) of
reflected by the high-resolution Cd 3d spectrum of WO WO NRs@Pd@CdS, Pd NCs were intimately integrated in-
NRs@Pd@CdS (Fig. 2c), the peaks at 405.2 and 411.95 eV between CdS layer and WO and the lattice fringes of ca. 0.225,
signify the oxidation state of Cd , which confirms the success 0.338, and 0.388 nm accurately correspond to the (111), (111),
of CdS deposition.18, 26 As well, as reflected by Fig. 2d, high- and (001) crystal facets of Pd, CdS, and WO , respectively.17, 52
resolution S 2p spectrum of WO NRs@Pd@CdS demonstrates Elemental mapping [Fig. 3 (j-o)] and EDS result (Fig. S7)
typical peaks at 162.7 and 161.45 eV which are ascribed to S .
TEM images of WO
NRs@Pd@CdS (Fig. 2bII) is manifest close encapsulation of WO
NRs (Fig. 2bI), which implies layer (ca. 10-20 nm) forming the well-defined core-shell
NRs@Pd@CdS in Fig. 3(g & h)
3
3
3
NRs@Pd with a thin CdS
3
3
3
3
2
+
3
3
2- 45,
corroborate the uniform distribution of W, O, Cd, S and Pd
elements in the WO NRs@Pd@CdS heterostructure. Moreover,
NRs@Pd@CdS, wherein the peaks at 336.5 and 341.9 eV are increased size of the nanorods measured from element mapping
ascribed to metallic Pd0.47-50 No N signal stemming from DMAP results confirms deposition of Pd NCs in-between WO
and CdS,
ligand of Pd NCs was detected in the high-resolution N 1s forming core-shell nanostructure. Consistently, as reflected by
spectrum of WO NRs@Pd@CdS (Fig. 2f & Table S3), which Fig. S8, C and N signals are from the DMAP ligand and the result
4
6
Fig. 2e displays the high-resolution Pd 3d spectrum of WO
3
3
3
3
is attributed to integrating Pd NCs in-between WO
CdS layer, shielding the peak.51
3
NRs and corroborates the monodispersed deposition of Pd NCs in-
between WO NRs and CdS layer.
Photoactivities of WO NRs@Pd@CdS heterostructures are
3
3
probed by reduction of 4-nitroaniline (4-NA) to 4-
phenylenediamine (4-PDA) under the illumination of visible
light (λ>420 nm).45 Blank experiments without adding catalyst
or without light illumination (Fig. S9) indicate it is a
photocatalytic process. As reflected in Fig. S10, conversion
process of 4-NA to 4-PDA can be monitored by UV-vis
absorption spectrum, for which the peak positioned at 380 nm
corresponding to 4-NA was detected before reaction and a new
peak positioned at ca. 240 nm attributable to 4-PDA gradually
arises with reaction progressing, indicating photoreduction of 4-
NA to 4-PDA.46 According to our recent work,31 optimal Pd
deposition percentage of WO
Therefore, WO NRs@11Pd is utilized for fabricating WO
NRs@Pd@CdS heterostructures. Photoactivities of the samples
are displayed in Fig. 4a, wherein WO NRs and WO
NRs@11Pd exhibite negligible photoactivities, which stems
from low CB potential of WO , making reduction of 4-NA
inaccessible. Photoactivities of WO NRs@Pd is remarkably
improved by photo-deposition of CdS, highlighting CdS
encapsulation benefits the photoactivities of WO
NRs@Pd@CdS, which is understandable considering the high
reduction potential of CdS. Photoactivities of WO
NRs@Pd@CdS are substantially influenced by the photo-
deposition time. To be specific, photoactivity of WO
3
NRs@Pd was determined as 11%.
3
3
3
3
3
3
3
3
Fig. 2 High-resolution (a) W 4f, (b) O 1s spectra of (I) WO
NRs@Pd@CdS, and high-resolution (c) Cd 3d, (d) S 2p, (e) Pd 3d and (f) N 1s
spectra of WO NRs@Pd@CdS.
3 3
NRs and (II) WO
3
3
4
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DOI: 10.1039/D0TA07235D
Fig. 3. FESEM images of (a) WO
3
NRs@Pd, (b) WO
3
NRs@CdS and (c) WO
3
NRs@Pd@CdS; TEM images of (d & e) WO
3
NRs@Pd with (f) HRTEM image, (g & h) TEM, (i) HRTEM and (j)
STEM images of WO NRs@Pd@CdS with (k-o) elemental mapping results.
3
−
1
NRs@Pd@CdS increases with prolonging the time to 2h and kinetic rate constants (0.28715 min ) of WO
then it deteriorates when the time approaches to 5h, by which NRs@7Pd@2CdS is ca. 144 and 66 times larger than those of
3
−
1
−1
WO
Over CdS encapsulation blocks the photoexcitation of WO
leading to decreased photoactivity. Alternatively, over-deposited enhanced photoactivity of WO
CdS layer can also cause unfavorable agglomeration which acts WO NRs@2CdS evidences the importance of Pd NCs in
3
NRs@11Pd@2CdS was determined as the optimal catalyst. WO
3
NRs (0.002 min ) and WO
NRs@2CdS (0.07228 min ). The
NRs@7Pd@2CdS relative to
3
NRs@11Pd (0.00433 min )
−
1
3
,
and 4 times larger than WO
3
3
3
as the charge recombination center.
improving the photoactivity.
Fig. 4b shows the photoactivities of WO
3
NRs@βPd@2CdS
To unleash the impact of electrons in photoreduction reactions,
(
β=3, 5, 7, 9, 11%) heterostructures with different loading control experiment by utilizing K
percentages of Pd NCs. The results indicate photoactivity of was carried out.25 Fig. 4e shows that photoactivity of WO
WO NRs@βPd@2CdS increases with Pd NCs amount elevating NRs@7Pd@2CdS with addition of K is conspicuously
from 3 to 7% and then it decreases with additionally increasing reduced. Besides, photoactivity of WO NRs@7Pd@2CdS with
the percentage, among which WO NRs@7Pd@2CdS purge was considerably inferior to that under N purge. The
demonstrate the optimal photoactivity. Fig. 4c shows that WO results concurrently highlight the importance of electrons in
NRs@7Pd@2CdS exhibits good photostability after five cyclic driving the reaction. As displayed in Fig. 4f, an obvious peak at
reactions. Consistently, XRD patterns (Fig. S11) of WO 450 nm is visualized in the action spectrum of WO
2 2 8
S O as electron scavenger
3
3
2 2 8
S O
3
3
O
2
2
3
3
3
NRs@7Pd@2CdS after cyclic reactions manifest its crystal NRs@7Pd@2CdS, strongly implying the pivotal role of
structure was retained, confirming it is a robust and stable photosensitization effect from CdS.
photocatalyst. Photoreduction of 4-NA complies with the first-
To unlock the general photoreduction activities of WO
3
order reaction kinetic, by which kinetic rate constants of the NRs@7Pd@2CdS heterostructure, apart from 4-NA (Fig. 5a), a
samples can thus be obtained (Table S4). As unveiled in Fig. 4d, series of nitroaromatics including 3-nitroaniline (3-NA), 2-
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due to the ultra-short charge lifetime. PhotoactiVvieitwyAroticfleWOnOline
3
DOI: 10.1039/D0TA07235D
NRs@7Pd is higher than WO NRs to some extent, implying Pd
3
NCs deposition can improve the photo-oxidation performance,
which is because Pd NCs can serve as electron reservoirs to boost
the charge separation. Moreover, considerably enhanced WO
NRs@2CdS relative to WO NRs is observed and this
3
3
corroborates the importance of CdS layer in promoting the
photocatalytic activities.
As displayed in Fig 6i, a peak between 365 and 500 nm is
observed in the action spectrum of WO NRs@7Pd@2CdS
3
toward photocatalytic selective oxidation of BA to BAD, which
confirms the photosensitization effect of CdS layer on improving
the photoactivities of WO
main active species participating in the selective oxidation of
alcohols over WO NRs@7Pd@2CdS, control experiments were
performed by adding K , Na SO , TBA, and BQ into the
reaction system to quench electron (e ), hole (h ), hydroxyl
radical (•OH), and superoxide radical (•O –), respectively.53 As
displayed in Fig. 6j, reduced photoactivity of WO
NRs@7Pd@2CdS was observed when Na SO , TBA, and BQ
were added in the reaction system, implying h , •OH and •O
radicals all contribute to the photoactivity enhancement. Besides,
photoactivity of WO NRs@7Pd@2CdS was also remarkably
reduced when the reaction was accessed in N -saturated BTF
3
NRs@7Pd@2CdS. To determine the
3
2
S
2
O
8
2
3
–
+
2
3
2
3
+
–
2
3
Fig. 4. (a) Photocatalytic activities of WO NRs@11 wt% Pd@αh-CdS (α=1, 2, 3, 4, 5) with
3
different photo-deposition time toward 4-NA reduction under the illumination of visible
light (λ>420 nm); (b) photoactivities of WO NRs@β wt% Pd@2h-CdS (β = 3, 5, 7, 9, 11)
with different Pd NCs percentages under the same conditions; (c) cyclic reaction of WO
NRs@7Pd@2CdS and (d) apparent kinetic constants of the samples; (e) control
experiments with adding K in the reaction system and photoreaction performed
under O purge in the presence of WO NRs@7Pd@2CdS; (f) photocatalytic reduction of
-NA over WO NRs@7Pd@2CdS under different monochromatic light irradiation. (WO
NRs@β wt% Pd@αh-CdS was abbreviated as WO NRs@βPd@αCdS).
2
3
solvent, uncovering oxygen is able to reinforce the photoactivity.
Notably, oxygen is indispensable to produce diverse oxygen-
3
containing active species such as •O −
hydrogen peroxide (H ). Similar result was observed when
was added into the reaction system, suggesting electron
also play a crucial role in reinforcing the significantly enhanced
photoactivities of WO NRs@7Pd@2CdS. This is owing to the
fact that electrons quenching refrains the formation of •O −
and
, H
radicals, •OH radicals and
2
2 2 8
S O
2 2
O
2
3
4
3
3
2 2 8
K S O
3
3
nitroaniline (2-NA), 4-nitrophenol (4-NP), 3-nitrophenol (3-NP),
-nitrophenol (2-NP), 4-nitrotoluene (4-NT), 4-nitroanisole,
nitrobenzene, o-nitroacetophenone, 1-chloro-4-nitrobenzene and
-bromo-4-nitrobenzene were also utilized as the substrates for
selective photoreduction catalysis. As displayed by Fig. 5(b-l),
2
2
•
OH radicals. The relationship of electrons with the •O −
2
2 2
O
and •OH formation is demonstrated by the formulas 6−8.21 In
1
+
general, influence of active species follows the order of h >
e−>•OH > •O −
. The variation of •OH radicals and H O
2 2 2
analogous boosted photoactivities are visualized over WO
NRs@7Pd@2CdS relative to single (WO ) and binary (WO
3
produced over different samples is verified by Fig. (S14 & S15),
which is in line with the photoactivities.
3
3
NRs@7Pd, WO
conditions,
NRs@2CdS>WO
3
NRs@2CdS) counterparts under the same
i.e., WO NRs@7Pd@2CdS>WO
NRs@7Pd >WO NRs, signifying its
versatile photoactivities.
-
O
2
+ e → •O2
-
(6)
(7)
(8)
3
3
-
2 2 2 2
+ •O O + O
+ 2H + → H
-
•O
2
3
3
-
→ •OH + OH - + O
2
H
2
O
2
+ •O
2
Beside the selective photoreduction catalysis, photocatalytic
aromatic alcohols oxidation to aromatic aldehydes was also
probed to elucidate the role of Pd NCs in promoting the
interfacial charge transport. Blank experiments without catalyst
or light irradiation indicate negligible conversion of alcohol (Fig.
S12), confirming the reaction is a photocatalytic process.
Detailed variation of the GC spectrum for photocatalytic
selective benzyl alcohol (BA) oxidation to benzyl aldehyde
Besides the photoredox catalysis in selective organic
transformation, WO NRs@7Pd@2CdS also demonstrates
3
significantly improved photoactivity toward mineralization of
organic pollutant (Fig. S16) under the illumination of visible
light, implying its versatile photocatalytic performances.
Photoelectrochemical (PEC) investigations were carried out to
unveil the separation efficiency of electron-hole pairs.37, 54 Fig.
7
a shows that photocurrent of WO
3
NRs@7Pd@2CdS is much
NRs@2CdS and
(
BAD) is displayed in Fig. S13.21 As reflected by Fig. 6(a-h),
larger than WO NRs, WO NRs@7Pd and WO
3
3
3
WO NRs@7Pd@2CdS exhibits the optimal photoactivities
3
the results agree with the photoactivities. The result indicates
CdS encapsulation and Pd NCs deposition favors the charge
toward selective oxidation of a collection of aromatic alcohols to
aldehydes with high conversion and selectivity under the
3
separation of WO and simultaneous Pd NCs & CdS decoration
illumination of visible light, superior to the single (WO
3
NRs)
synergistically retards the charge recombination. As displayed in
and binary (WO
In contrast, WO
3
NRs@7Pd and WO
NRs shows very poor photoactivities, which is
3
NRs@2CdS) counterparts.
Fig. 7b, arc radius of WO
smaller than those of WO
3
NRs@7Pd@2CdS is successively
NRs@2CdS, WO NRs@7Pd and
3
3
3
6
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Journal Name
ARTICLE
View Article Online
DOI: 10.1039/D0TA07235D
Fig. 5. (a) Photoactivities of WO
d) 4-NP, (e) 3-NP, (f) 2-NP, (g) 4-nitrotoluene, (h) 4-nitroanisole, (i) nitrobenzene, (j) o-nitroacetophenone, (k) 1-chloro-4-nitrobenzene, and (l) 4-bromo-1-nitrobenzene under the
illumination of visible light (λ>420 nm) with adding ammonium formate for quenching holes and N bubbling along with (m) reaction model.
3 3 3 3
NRs, WO NRs@7Pd, WO NRs@2CdS and WO NRs@7Pd@2CdS toward reduction of various nitroaromatics including (a) 4-NA, (b) 3-NA, (c) 2-NA,
(
2
―
1
1
퐶2
WO
3
NRs, which agrees with the photocurrents results (Fig. 7a).
NRs@7Pd@2CdS demonstrates the
푑
(
)
Among which, WO
smallest arc radius in comparison with other counterparts,
manifesting its smallest interfacial charge transfer resistance,50
3
2
푁
=
[
]
(9)
퐷
(
)
푒εε0 푑푉
−12
−1
followed by WO
3
NRs@2CdS, WO
3
NRs@7Pd and WO
3
NRs, where e=1.6 × 10−19 C, ε =8.86 × 10 F m , ε is the dielectric
0
respectively. The simulated EIS results are summarized in Table constant and ε=300 for WO3,44 C is the capacitance. As
S5, wherein WO NRs@7Pd@2CdS (6529 ohm) exhibits much manifested in Fig. 7d, N values of WO NRs, WO NRs@7Pd,
lower charge resistance (Rct) under visible light illumination WO NRs@2CdS and WO NRs@7Pd@2CdS are calculated as
3
D
3
3
3
3
1
8
−3
relative to the single (WO
counterparts (WO NRs@7Pd :9872 ohm; WO
857 ohm). Mott–Schottky (M–S) results are displayed in Fig. and 1.4 times larger than those of WO NRs, WO NRs@7Pd,
3
NRs: 17140 ohm) and binary 8.83×10 , 1.18×1019, 1.35×1019 and 1.91×1019 cm ,
3
3
NRs@2CdS: respectively. N of WO NRs@7Pd@2CdS is almost 2.2, 1.6,
D
3
7
3
3
7
c, by which charge densities (N
D
) of the samples are estimated WO3 NRs@2CdS, consistent with other PEC results,
corroborating the cooperativity of Pd NCs and CdS.
by the formula below:54, 55
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DOI: 10.1039/D0TA07235D
3 3 3 3
Fig. 6. Photocatalytic activities of (I) WO NRs, (II) WO NRs@7Pd, (III) WO NRs@2CdS and (IV) WO NRs@7Pd@2CdS toward selective aromatic alcohols oxidation including (a)
benzyl alcohol, (b) p-methylbenzyl alcohol, (c) p-methoxybenzyl alcohol, (d) p-fluorobenzyl alcohol, (e) p-chlorobenzyl alcohol, (f) p-nitrobenzyl alcohol, (g) cinnamyl alcohol, and (h)
3
-methyl-2-buten-1-ol to aldehydes under the illumination of visible light (λ>420 nm) for 4 h; (i) action spectra of WO
3
NRs@7Pd@2CdS; (j) photocatalytic selective oxidation of BA
–
+
–), and photoactivity
over WO
3
NRs@7Pd@2CdS with adding K
2
S
2
O
8
, Na
2
SO
3
, TBA, and BQ for quenching electron (e ), hole (h ), hydroxyl radical (•OH), and superoxide radical (•O
2
2
with N bubbling, along with (k) reaction model.
Photoluminescence (PL) has been deemed as an effective to be -0.24 and 1.86 V vs. NHE, respectively. The possible
technique to evaluate the interfacial charge separation efficiency charge transport pathways were depicted in Fig. S20. There are
of semiconductor.17, 56 As displayed in Fig. 7(e & f), WO
NRs@7Pd demonstrates lower PL intensity than WO
which suggests electrons in the CB of WO can be captured by photocatalytic mechanisms. Concerning the type-II charge
Pd NCs, resulting in decreased charge recombination. PL transfer pathway (Fig. S20a), electrons in the CB of CdS migrate
intensity of WO NRs@CdS is lower than WO NRs, which is to the CB of WO accelerated by Pd NCs and holes in the VB of
owing to the generation of type II energy band structure for WO move to the VB of CdS, resulting in effective charge
enhancing charge separation. The lowest PL intensity was separation. However, redox potentials of electrons and holes
observed over WO NRs@7Pd@2CdS, implying charge would be considerably reduced in such charge transfer pathway,
separation was additionally enhanced with simultaneous Pd NCs thereby rendering photoreduction of nitroaromatics inaccessible,
and CdS deposition. Note that WO NRs@7Pd@2CdS shows which is inconsistent with our results. Furthermore, if such a
lower PL intensity than WO NRs@2CdS, once again type-II charge transport mechanism occurs, electrons in the CB
confirming the crucial role of Pd in increasing interfacial charge of WO (-0.24 V vs. NHE) fail to achieve reduction of O
to •O2−
radicals due to the larger potential of O
NRs@7Pd@2CdS V vs. NHE]. Analogously, holes in the VB of CdS (+1.86 V vs.
O to •OH radicals due to the
O/−OH [E°(•OH/H O)=+2.38 V vs.
two charge transport channels for WO
NRs, heterostructures including conventional type-II and Z-scheme
3
3
NRs@Pd@CdS
3
3
3
3
3
3
3
3
3
3
2
separation.
2
/•O2− [E(O /•O2−)=−0.284
2
3 3
Energy levels of WO and CdS in the WO
were probed by M-S results and VB XPS results. Fig. S17 shows NHE) do not enable oxidation of H
the VB spectrum of WO is determined larger oxidation potential of H
,57 by which VB of WO
2
3
3
2
2
to be 2.62 V vs. NHE. Fig. S18 exhibits the M-S plot of CdS,58 NHE]. However, generation of •O2− and •OH radicals in our
by which flat band potential of CdS is determined as -0.49V vs. current reaction system has been undoubtedly confirmed by
g 3
NHE. Considering the E of WO (2.86 eV) and CdS (2.35 eV) control experiments, eliminating the occurrence of type-II charge
(
Fig. S19), CB level of WO
3
and VB level of CdS are deduced transfer mechanism. Hence, we believe Z-scheme charge
8
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ARTICLE
the Z-scheme charge transport, ultimately leaving VeileewcAtrrtoicnlesOanlninde
DOI: 10.1039/D0TA07235D
holes with substantial redox capacity in the CB of CdS and VB
of WO , respectively. In this way, Pd NCs serve as efficient
3
Schottky-type electron flow mediators for promoted charge
migration. Hence, subsequently, electrons in the CB of CdS are
involved in photoreduction of nitroaromatics, wherein holes in
the VB of WO
under continuous N
active specie in photoreduction reaction. It should be emphasized
that holes left in the VB of WO NRs are beneficial for the
generation of oxygen-containing active species (e.g., •O2− and
OH) to initiate the selective photocatalytic oxidation of BA to
3
are completely quenched by ammonium formate
2
-bubbling and it ensures electrons the only
3
•
BAD. Redox potentials of BA and BAD are determined by CV
analysis. As exhibited in Fig. S21a, CV curves indicate BA
redox potential is not influenced by concentration and the first
peak is assigned to the BA oxidation to BAD (+1.84 V vs. NHE)
and the second peak suggests the BAD oxidation to acids, (+2.49
V vs. NHE). To evidence the speculation, CV results of BAD
(
Fig. S21b) is additionally explored and the result is consistent
with the second BA oxidation peak. As a result, it is reasonably
speculated that holes left in the VB of WO are able to directly
3
oxidize aromatic alcohols to aldehydes owing to the favorable
energy level position. Regarding the selective aromatic alcohols
oxidation to aldehydes (Fig. S22) under visible light illumination,
Fig. 7. (a) Photocurrent, (b) EIS Nyquist plots and (c) M–S results & (d) charge density
) of WO NRs, WO NRs@7Pd, WO NRs@2CdS and WO NRs@7Pd@2CdS under the
illumination of visible light (λ>420 nm) (Na SO : 0.5 M, pH=6.69); (e) PL spectra of
(N
D
3
3
3
3
2
4
3
alcohols are adsorbed on the WO surface by deprotonation to
different samples (λExc=380 nm) and (f) peak intensity comparison.
generate structural-II and the adsorbed alcohols first react with
holes and then deprotonate to form carbon radicals (structure-III).
Considering the appropriate energy level positions, electrons in
transfer constitutes the photocatalytic mechanism of WO
3
3
NRs@Pd@CdS, for which electrons in the CB of WO and holes
the CB of CdS can react with dissolved O
2
to generate
in the VB of CdS rapidly recombine at the interface by way of
Pd NCs, leaving electrons and holes with high redox capability
to trigger the photoredox catalysis (Fig. S20b).
2−
superoxide (•O ) radicals, while holes in the VB of WO
3
2−
2
oxidizes H O/−OH to •OH radicals. The •O /•OH radicals are
involved in selective aromatic alcohols oxidation to aldehydes
and form intermediates IV with carbon radicals. The interaction
between C-O and O-O bonds of alcohols synergistically produce
hydrogen peroxide through the oxygen bridge structure,
fulfilling the photocatalytic selective oxidation process.26, 59
As demonstrated in Scheme 2, once WO
heterostructure is illuminated by visible light, WO
shell are simultaneously photoexcited to yield the electron-hole
pairs. Immediately, electrons in the CB of WO flow to the Pd
NCs which are integrated at the interface of WO and CdS and
then rapidly recombine with holes in the VB of CdS to trigger
3
NRs@Pd@CdS
3
core and CdS
3
3
3
Scheme 2. Schematic diagram illustrating the photoredox mechanism of WO NRs@Pd@CdS heterostructures.
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ARTICLE
Journal Name
1
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DOI: 10.1039/D0TA07235D
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. Conclusions
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There are no conflicts to declare.
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Acknowledgements
The support by the award Program for Minjiang scholar
professorship is greatly acknowledged. This work was
financially supported by the National Natural Science
Foundation of China (Nos. 21703038).
2
2
2
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4
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Journal of Materials Chemistry A
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DOI: 10.1039/D0TA07235D
Table of Contents Graphic
An all-solid-state Z-scheme photoredox system was elaborately designed over core-
shell multilayered heterostructures for multifarious photoredox organic transformation
under visible light.