Anchoring of black phosphorus quantum dots onto WO3nanowires to boost photocatalytic CO2conversion into solar fuels

Article abstract of DOI:10.1039/d0cc00805b

A 0D-1D direct Z-scheme heterojunction consisting of black phosphorus quantum dots (BPQDs) anchored onto WO3 nanowires was well designed. Kelvin probe force microscopy studies provide direct evidence for charge transfer and separation between BPQDs and WO3 in a single nanowire, confirming the Z-scheme model. The BPQD-WO3 heterojunction displays excellent performance of photocatalytic reduction of CO2, exhibiting not only highly efficient carbon monoxide solar fuel conversion, but also a significant amount of ethylene (C2H4), a highly value-added hydrocarbon species, rarely reported in previous photocatalysis processes. Both experimental and theoretical calculations demonstrate that BPQD plays a critical role in photocatalytic formation of C2H4 from CO2.

Full text of DOI:10.1039/d0cc00805b

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Conformational control of nonplanar free base porphyrins:
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DOI: 10.1039/D0CC00805B
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Anchoring of Black Phosphorus Quantum Dots onto WO3
Nanowires to Boost Photocatalytic CO2 Conversion into Solar
Fuels
Received 00th January 20xx,
Wa Gao,a,† Xiaowan Bai,c,† Yuying Gao,e,f,† Jinqiu Liu,a Huichao He,b Yong Yang,d Qiutong Han,a
Xiaoyong Wang,a Xinglong Wu,a Jinlan Wang, c ,* Fengtao Fan,e,* Yong Zhou, a,* Can Li,e Zhigang Zoua
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
A 0D–1D direct Z-scheme heterojunction consisting of black
Black phosphorus (BP), a monoelemental 2D layered material
phosphorus quantum dots (BPQDs) anchoring onto WO3 and holding several attractive properties, is regarded as a rising star
nanowires was well designed. Kelvin probe force microscopy in the post-graphene era with great promise in electronics,
studies provide direct evidence for charge transfer and separation optoelectronics, biomedicine, catalysis, energy storage and so on.3, 4
between BPQDs and WO3 in single nanowire, confirming the Z- A layer-dependent direct-bandgap of BP from 0.3 to 2.0 eV, while
scheme model. The BPQDs-WO3 heterojunction displays excellent retaining its direct gap properties, provides a new degree of
performance of photocatalytic reduction of CO2, exhibiting not freedom in bandgap engineering.5 The transport velocity of holes on
only highly efficient carbon monoxide solar fuel conversion, but BP reaches as high as ~103 cm2 V−1s−1 at room temperature, which is
also significant amount of ethylene (C2H4), a highly value-added a desirable advantage for photoelectric devices. Few-layer BP
hydrocarbon species, rarely reported in precedent photocatalysis nanoflakes demonstrate active as visible and near-infrared
5-7
processes. Both experiment and theoretical calculation photocatalysts for water splitting into H2 and N2 photofixation,8
demonstrate that BPQD plays the critical role of photocatalytic and electroctalysis CO2 reduction.9, 10 BP quantum dots (BPQDs)
formation of C2H4 from CO2.
exhibit additional favorable characteristics: prominent edge, high
Photocatalytic conversion of CO2 to valuable hydrocarbons absorption coefficient, quantum confinement effects, and can be
using solar energy has attracted a great deal of attention, which is hybridized with dissimilar materials.11
one of the best solutions to both the global warming and the energy
In this Communication, anchoring of BPQDs onto WO3
shortage problems.1 It couples the reductive half-reaction of CO2 nanowires was constructed to successfully form a 0D–1D direct Z-
fixation with a matched oxidative half-reaction such as water scheme heterojunction, which was confirmed with Kelvin probe
oxidation to achieve a carbon neutral cycle. The strategy can force microscopy studies, providing direct evidence for charge
generate short-chain hydrocarbon fuels such as CH4, CH3OH, C2H6 transfer and separation between BPQDs and WO3 in single
and so on directly from CO2.
A so-called Z-scheme system nanowire. The BPQDs-WO3 heterojunction in the presence of water
originating from Natural photosynthesis involves two photon vapor displays excellent performance of photocatalytic reduction of
processes connected in series with one electron transfer chain to CO2, exhibiting not only highly efficient carbon monoxide (CO)
drive chemical reactions involved in water oxidation and reduction conversion, but also fortuitously significant amount of ethylene
of coenzyme NADP on two photosystems individually.2 These two (C2H4), a highly value-added hydrocarbon species. The quantum
processes take place simultaneously in time but separately in space, efficiency was detected 0.79% with optimal loading amount of
resulting in the merit of separating electron/hole with strong BPQDs. While precedent WO3-based Z-scheme photocatalyst
reduction/oxidation abilities on different reactive sites.
systems never reported the formation of C2H4 from CO2, BPQD was
demonstrated to play the critical role of the present photocatalytic
transformation of C2H4. Both the armchair and zigzag edges of the
BPQD proves favorable for the automatic coupling of two adsorbed
*CO molecules into *CO-CO configuration, the major mechanism of
the formation of C2H4. The onset potential of subsequent
hydrogenation of *CO dimers for the formation of *CO-COH species
on the BPQD is also calculated much lower than all the other
catalysts that have been reported, and the onset potential of *CO-
COH into *CO-CHOH is estimated even 30% lower than that on the
Cu(100) surface which was recognized as the most effective catalyst
for CO2 reduction into C2H4. Although the productivity of C2H4 is still
low in the presence case, which can be improved through surface
modification of applied BPQDs in our later work, this study proves
the inspiring viability of BP-based heterostructures for production of
highly value-added chemicals and advanced energy conversion and
storage.
a
National Laboratory of Solid State Microstructures, Collaborative Innovation
Center of Advanced Microstructures, Jiangsu Key Laboratory for Nano Technology,
School of Physics, Nanjing University, Nanjing 210093, P. R. China. E-mail:
zhouyong1999@nju.edu.cn.
b
State Key Laboratory of Environmental Friendly Energy Materials, School of
Materials Science and Engineering, Southwest University of Science and
Technology, Mianyang, Sichuan 621010, P. R. China.
c
School of Physics, Southeast University, Nanjing 211189, P. R. China. Email:
jlwang@seu.edu.cn.
d
Key Laboratory of Soft Chemistry and Functional Materials (MOE), Nanjing
University of Science and Technology, Nanjing 210094, P. R. China.
e
State Key Laboratory of Catalysis, iChEM, Dalian Institute of Chemical Physics,
CAS, Dalian National Laboratory for Clean Energy, Dalian 116023, P. R. China. E-
mail: ftfan@dicp.ac.cn.
f University of Chinese Academy of Sciences, 19A Yuquan Road, Beijing 100049, P.
R. China.
† W. Gao, X. Bai, and Y. Gao contributed to this work equally.
Electronic Supplementary Information (ESI) available: Experimental details and
theoretical calculations and so on. See DOI: 10.1039/x0xx00000x
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DOI: 10.1039/D0CC00805B
Figure 2. Photocatalytic (a) CO and (b) C2H4 evolution amounts as
function of light irradiation times, (c) comparison of
photocatalytic activity of the first hour.
Figure 1. (a, b) TEM and (c) HRTEM images of BW-3.
a
Immobilization of BPQDs onto the WO3 nanowire was realized
through a facile hydrothermal treatment of a mixed solution of the
BPQDs and WO3 nanowire, being described in details in Supporting
Information (SI and Figure S2). The samples with different mass
ratio of about 1%, 3%, 7%, and 10% of the BPQDs to WO3 were
investigated, named as BW-1, BW-2, BW-3, and BW-4, respectively.
The TEM image shows that the WO3 nanowire is of the diameter of
∼30 nm and the length of ~ 1−3 μm as well as smooth surface
(Figure S3a). The (001) facets can be observed with the lattice space
of 0.391 nm (JCPDS 33−1387) (Figure S3b), indicating the growth
direction of the nanowire along [001].12 The TEM image also reveals
that the BPQD exhibits uniform size distribution of ~3-4 nm (Figure
S4a). The lattice fringe of BPQDs characterized with HRTEM was
estimated 0.33 and 0.21 nm (Figure S4b), in good agreement with
the (021) and (002) plane of BP crystal, respectively.10 The TEM
image of the BPQD-WO3 reveals that the surface of the WO3
nanowire became obviously rough with loading of the BPQD (Figure
S5). The BPQD was uniformly anchored on the WO3 nanowire
without aggregation (Figure 1a and 1b). The HRTEM image shows
the compact contact between BPQD and WO3 (Figure 1c). The EDX
elemental mapping proves the existence of W, O, and P elements
(Figure S6). The BPQD-WO3 was further characterized with the XRD
(Figure S7), Raman spectra (Figure S8), and XPS spectra (Figure S9).
The average crystallite size based on (001) diffraction peak was
estimated 27.4 nm by applying Scherrer’s formula,14,15 which is well
agreement with the diameter of the nanowire.
The photocatalytic activity of BPQDs-WO3 nanocomposite was
evaluated for CO2 conversion in the presence of water vapor under
simulated solar irradiation. As the CB edge potential (ECB) and VB
edge potential (EVB) of WO3 was determined ∼-0.11 V and ∼+2.86
V (vs NHE), respectively,12,13 WO3 usually shows high oxidation
ability in the photocatalytic process while more positive CB level
than the CO2 redox potential indicates incapable of photocatalytic
reduction of CO2, consistent with previous reports.16,17 The derived
band gap of the BPQD was approximately 2.52 eV based on the UV-
vis absorption spectrum (Figures S10),18 larger than BPQD analogue
reported,19 possibly due to the strong quantum confinement
effects. Combining with the valence XPS spectra, the ECB and EVB
were thus estimated –1.02 V and 1.50 V (details in Figures S12 and
S14). 20,21 Although the band structure of the BPQDs is suitable for
reduction of CO2, only trace amount of CO and C2H4 was detected in
the present case, possibly due to fast recombination of
photogenerated charge on the surface of the BPQD containing large
number of potential defects. In contrast, the BPQDs-WO3
heterostructures display distinct photocatalytic activities with
continuous light irradiation (Figure 2a). Considering the yield during
the first hour for various BW samples (Figure 2b), the BW-1
exhibited the CO conversion and value-added C2H4 generation of
7.89 μmol g−1 and 1.72 μmol g−1, respectively. The production of CO
and C2H4 increases by 9.2 and 1.4 times over BW-2, respectively,
reaching 72.47 μmol g−1 and 2.40 μmol g−1. Inspiringly, the yield of
C2H4 continuously increases to 5.92 μmol g-1 over BW-3 while the
amount of CO decreases to 36.99 μmol g-1. It indicates that with
increased loading of the BPQDs, more CO molecules are apt to
couple together, followed by successive hydrogenation processes
into C2H4. Indeed, the BPQDs enable the C-C dimerization process to
occur easily, which was proved with the density functional theory
(DFT) calculations below. It greatly minimizes possibility of
deliberation of forming CO molecules from the catalyst surface into
gaseous CO. However, the subsequent hydrogenation processes,
the rate-limiting steps (also see DFT calculations below), restricts
the tremendous transformation of CO into C2H4, which can be
improved through surface modification of BPQDs in our later work.
The excessive deposition of the BPQD for BW-4 contrarily lowers
the yield of both CO and C2H4, possibly due to decrease of number
of the oxidation sites on the WO3, negatively on photocatalytic
activity. The quantum efficiency of CO2 photoconversion was
determined maximum 0.79% at 385 nm using monochromatic light
and monitoring the generation of CO and C2H4 for BW-2 (details in
SI). The O2 production has also been detected with 39. 64 μmol g−1
h−1 for BW-2, roughly close to stoichiometric molar ratio of O2 to
CO/C2H4 (CO2 → CO + 1/2O2, CO2 + H2O → 1/2 C2H4 + 3/2 O2). The
identical CO2 reduction experiments operated in the absence of
light or photocatalysts display no appearance of product,
demonstrating that the CO2 reduction reaction occurs under light
over the photocatalysts. Control experiments under UV-vis light
irradiation were also performed over the photocatalysts in Ar
atmosphere. In absence of CO2, neither CO and C2H4 nor other
carbon compounds were detected, proving that the carbon source
was completely derived from the input CO2.
C2H4 is an important basic building block for production of a
wide range of cosmetics, plastics, solvents and so on. Its worldwide
2 | J. Name., 2012, 00, 1-3
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demand makes it almost the most important organic compounds.
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In-situ FTIR spectra were used to monitor the kinetic process of
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Previous studies show that other WO3-base Z-scheme CO2 reduction into CO and C H . BPQDs-WO hybrids show more
DOI: 10.1039/D0CC00805B
2
4
3
photocatalysts generally convert CO2 into CO with Cu2O12, and CH4 intensity peaks of C=O and -COOH than pristine WO3 nanowire
2
with In2S3 under the similar photocatalysis system, and no C2H4 under exposure to the light with time (Figure S19).29-31 It indicates
was detected. Nevertheless, C2H4 product was also found in the that the presence of the BPQD definitely facilitates the absorption
case of the BPQDs-BiVO4 heterostructure as photocatalysts (Figures and activation of CO2 molecules. The peak at ~ 1486 cm-1 assigned
S17 and S18). It indicates the general applicability and critical role of to *CO dimer intermediate (OC-CO) was also clearly observed.32 The
BPQD for photocatalytic transformation of C2H4 from CO2. To COOH* complex may undergoes dehydration to form CO*
understand the potential mechanism for the production of C2H4 on complex,33 which subsequently liberate from the catalyst surface to
the BP, density functional theory (DFT) calculations (see the form gas CO. Additional part of *CO further transform into C2H4
calculation details in SI) were performed on two edge models, species by coupling resident protons and electrons. The reaction
namely, armchair (AC) and zigzag (ZZ) edges (Figure 3a). Previous process for the reduction of CO2 into CO and C2H4 over BPQDs-WO3
studies found that CO dimerization may be the major mechanism of under light illumination is thus proposed in Figure S20.
the formation of C2 products.22-24 Thus, we first examined the
thermodynamic feasibility for forming an adsorbed *CO dimer
(*CO-CO), as shown in Figure 3b. The calculated results suggested
that two adsorbed *CO molecules as initial structure can be
automatically coupled to *CO-CO configuration after full structure
optimization on both the AC and ZZ edges, corresponding to free
energy barrier of -0.20 eV and -0.70 eV, respectively. For the
subsequent hydrogenation reaction steps, the generation of *CO-
COH (*CO-CO + H+ + e− = *CO-COH) and second H2O molecule (*OH
+ H+ + e− = * + H2O) are endothermic, and the rest of the
hydrogenation steps are exothermic. Moreover, the free energy
uphill for first proton−electron pair (H+ + e−) transfer (0.30 eV) is
higher than that of the last one (0.14 eV). Therefore, the generation
Figure 4. KPFM measurements of WO3 and BPQD-WO3. (a, b) AFM
images of WO3 and BPQD-WO3. (c, d) SPV images of WO3 and
BPQD- WO3 under 420 nm excitation. (e, f) SPV line profiles of WO3
and BPQD-WO3 along white lines, as indicated in c, d
of *CO-COH species on the AC edge is the potential-limiting step
and the corresponding onset potential is only 0.30 V (Figure 3c),
much lower than the other catalysts that have been reported.25-27
The hydrogenation of *CO-COH into *CO-CHOH on the ZZ edge has
an even higher free energy barrier, resulting in a higher onset
potential (0.70 V) than that on the AC edge (Figure 4d). However,
this value is still 30% lower than that on the Cu (100) surface (1.00
V) which was recognized as the most effective catalyst for CO2
reduction C2H4.25,28 Therefore, the results indicate that the AC and
ZZ edges of BP can effectively facilitate CO molecules coupling and
further reduce to C2H4 at room temperature, as observed
experimentally.
To confirm the photogenerated charge transfer process in this
Z-scheme heterojunction, photo-irradiation Kelvin probe force
microscopy (KPFM) was employed to directly probe charge spatial
distribution at single nanowire. Figures 4a and 4b show the surface
topography of WO3 and BPQD-WO3 nanowires on silicon substrate.
The presence of BPQDs causes the surface fluctuations in BPQD-
WO3 nanowire. However, the surface potential of WO3 is close to
that of BPQD-WO3 nanowire (Figure S21), indicating that the WO3
exposed at the surface of BPQD-WO3 nanowires due to the sparse
decoration of BPQD. The photo-induced surface potential change,
defined as surface photovoltage (SPV) can reflect the
photogenerated charge separation and local charge accumulation
density.34-36 The SPV image of single nanowire was obtained by
subtracting the surface potential image under light illumination
from that in the dark, as shown in Figures 4c and 4d. Under 420 nm
excitation, the WO3 nanowire shows a distinct positive SPV signal
(Figures 4c and 4e), indicating that photogenerated holes transfer
and accumulate at surface due to the upwards band bending of n-
type semiconductor at equilibrium.31 Under same illumination
condition, the BPQD-WO3 also exhibited a positive SPV signal
(Figures 4d and 4f), but the SPV signal in BPQD-WO3 is significantly
enhanced compared to the individual WO3 nanowire. Control
experiment demonstrated that no obvious surface potential change
was detected on BPQD-WO3 nanowire when excited by 620 nm
(Figure S22), suggesting the negligible photothermal effect in this
measurement. These results clearly demonstrate that the high
density of photogenerated hole at WO3 surface in the BPQD-WO3 is
attributed to the efficient spatial charge separation occurring in
BPQD-WO3 nanowire, under 420 nm excitation. Because the CB
energy level of WO3 is positive than that of BPQD, the enhanced
SPV signal in the BPQD-WO3 is a strong indication for the successful
configuration of Z-scheme charge transfer. The Z-scheme
Figure 3. (a) Plane schematics of the BPQD lattice structure.
Armchair edge (red) and zigzag edge (blue) symmetry directions
are indicated by the colored arrows. (b) The most favorable
reaction path for 2CO reduction to C2H4 on the AC edge.
Hydrogenation steps for C2H4 formation involve electron and
proton transfer. Free energy diagram of 2CO reduction to C2H4
production on the AC edge (c) and ZZ edge (d). The inserts are the
corresponding structures of reaction intermediates. Purple, gray,
red and white spheres represent the P, C, O and H atoms,
respectively.
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photocatalytic mechanism of the BPQDs/WO3 hybrids towards CO2 219.
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the average carrier lifetimes of the WO3 nanowire and BW-3 were
detected 0.908 ns and 0.421 ns, respectively (Figure S24b). As the
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carrier lifetime of BW-3 may dominantly contribute from the photo-
excitation of WO3. The shortened emission lifetime of the WO3
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nanowire after coupling BPQD indicates the existence of
a
nonradiative pathway of the fast charge transfer across the
interface from CB of the WO3 to the VB of the BPQD through the Z-
scheme model, in contrast to the prolonged emission lifetime for
typical BPQD-based type II models such as BPQD-C3N4.37
In summary, a 0D–1D direct Z-scheme heterojunction consisting
of anchoring of BPQDs onto WO3 nanowires was well constructed.
The Z-scheme charge transfer mode detected with KPFM obviously
enhances the oxidizing and reducing capacities of the BPQD-WO3
heterostructure. The BPQDs-WO3 exhibits inspiring performance on
photocatalytic CO2 conversion, generating not only CO major
product, but also meaningful amount of highly value-added C2H4.
The AC and ZZ edges of selected BPQD effectively facilitate the
coupling of CO molecules and further reduction into C2H4. This
study may provide a new strategy for tailoring and exploiting BP-
based nanomaterials for energy applications.
The authors wish to acknowledge the support of National Key
R &D Program of China (SQ2018YFE0208500), 973 Programs (No
2017YFA0204800), NSF of China (No.21972065, 21773114,
21902081, and 21473183), NSF of Jiangsu Province (No.
BK20171246), and the Fundamental Research Funds for the Central
University (020414380135).
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Conflicts of interest
There are no conflicts to declare.
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DOI: 10.1039/D0CC00805B