Delicate Control on the Shell Structure of Hollow Spheres Enables Tunable Mass Transport in Water Splitting

Article abstract of DOI:10.1002/anie.202016285

In the study of structure–property relationships for rational materials design, hollow multishell structures (HoMSs) have attracted tremendous attention owing to the optimal balance between mass transfer and surface exposure. Considering the shell structure can significantly affect the properties of HoMSs, in this paper, we provide a novel one-step strategy to continually regulate the shell structures of HoMSs. Through a simple phosphorization process, we can effectively modify the shell from solid to bubble-like and even duplicate the shells with a narrow spacing. Benefitting from the structure merits, the fabricated CoP HoMSs with close duplicated shells can promote gas release owing to the unbalanced Laplace pressure, while accelerating liquid transfer for enhanced capillary force. It can provide effective channels for water and gas and thus exhibits a superior electrocatalytic performance in the hydrogen and oxygen evolution reaction.

Full text of DOI:10.1002/anie.202016285

Angewandte
Communications
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How to cite: Angew. Chem. Int. Ed. 2021, 60, 6926–6931
International Edition:
German Edition:
doi.org/10.1002/anie.202016285
doi.org/10.1002/ange.202016285
Hollow Nanostructures Very Important Paper
Delicate Control on the Shell Structure of Hollow Spheres Enables
Tunable Mass Transport in Water Splitting
+
+
+
Ping Hou , Dan Li , Nailiang Yang , Jiawei Wan, Chunhui Zhang, Xiqi Zhang, Hongyu Jiang,
Qinghua Zhang, Lin Gu, and Dan Wang*
Abstract: In the study of structure–property relationships for
rational materials design, hollow multishell structures
due to the lack of efficient strategies for precise structure
control. In this work, we provide a facile one-step approach to
continuedly regulate the shell structure of HoMS. In detail,
we introduced the phosphorization reaction into Co O
(
HoMSs) have attracted tremendous attention owing to the
optimal balance between mass transfer and surface exposure.
Considering the shell structure can significantly affect the
properties of HoMSs, in this paper, we provide a novel one-step
strategy to continually regulate the shell structures of HoMSs.
Through a simple phosphorization process, we can effectively
modify the shell from solid to bubble-like and even duplicate
the shells with a narrow spacing. Benefitting from the structure
merits, the fabricated CoP HoMSs with close duplicated shells
can promote gas release owing to the unbalanced Laplace
pressure, while accelerating liquid transfer for enhanced
capillary force. It can provide effective channels for water
and gas and thus exhibits a superior electrocatalytic perfor-
mance in the hydrogen and oxygen evolution reaction.
3
4
HoMSs, and discovered the geometrical shells structure of
HoMSs evolved from solid to bubble-like, subsequently these
“bubbles” fused together forming close duplicated shells, and
it returned to a solid one in the end (Scheme 1). This structure
evolution is experimentally realized for the first time, and
then these materials were conducted for a typical multi-phase
[
6]
reaction of water splitting. Benefitting from the structure
advantages, the CoP HoMSs with close duplicated shells
facilitate the escape of gas bubbles because of unbalanced
[7]
Laplace pressure, and enhance the driving force for liquid
[
8]
diffusion due to capillary action, thus achieving excellent
catalytic performance in both hydrogen evolution reaction
(HER) and oxygen evolution reaction (OER).
R
egulating material structure according to the targeted
Co O -HoMSs were prepared by sequential templating
3
4
[
9]
applications has demonstrated to be an effective strategy for
achieving superior performance. Besides tuning the structure
of building blocks, the rational design on the architecture of
the assemblies can also deliver great contribution for
approach (STA) (Figure 1a, Figure S1). In the subsequent
[
10]
phosphorization process, because the Co atoms in Co O
3
4
11]
[
spread out rapidly while P atoms diffused slowly inward,
a cavity was formed inside the nanoparticles and these hollow
ones crosslinked together forming bubble-like structure in the
shell (B-CoP-HoMSs) (Figure 1b). With the phosphorization
period prolonged, these bubbles fused together and devel-
oped into CoP HoMSs with close duplicated shells (D-CoP-
HoMSs) (Figure 1c), doubling the former number of shells.
[
1,2]
performance enhancement.
HoMSs, the micro-nano archi-
tecture with interior cavities as well as multiple shells spatially
ordered from outside to inside, have been proved to be able to
realize the optimization in mass transfer and effective surface
[
3–5]
area exposure, beneficial for many applications.
As a key
parameter of HoMSs, the micro-nano structure of shell is
significantly important for mass transport, but rarely studied
Moreover, D-CoS -HoMSs can be also prepared with the
2
similar approach by replacing the NaH PO ·H O with sulfur
2
2
2
powder (Figure S2,S3). The high-magnification TEM image
of D-CoP-HoMSs shows the interspacing of ꢀ 30 nm (inset in
Figure 1c). Further phosphorization promoted the fusion of
close duplicated shells into a solid layer (CoP-HoMSs)
[
+]
[+]
[+]
[
*] Dr. P. Hou, Dr. D. Li, Prof. N. Yang, Prof. J. Wan, Prof. D. Wang
State Key Laboratory of Biochemical Engineering, Institute of Process
Engineering, Chinese Academy of Sciences
1
(
(Figure 1d), resulting the same number of shells as half of
North 2nd Street, Zhongguancun, Haidian District, Beijing 100190
P. R. China)
E-mail: danwang@ipe.ac.cn
D-CoP-HoMSs. The transition process can also be revealed
by the respective grinding samples and HoMS at different
phosphorization stages (Figure S4–S8). Additionally, benefit-
ing from the controllability of STA, hollow sphere and
double-shelled Co O -HoMSs, and the corresponding B-CoP-
[
+]
[+]
Dr. P. Hou, Prof. N. Yang, Prof. D. Wang
University of Chinese Academy of Sciences
1
9A Yuquan Road, Beijing 10049 (P. R. China)
3
4
Dr. C. Zhang, Prof. X. Zhang
HoMSs, D-CoP-HoMSs and CoP-HoMSs (Figure S9–S12)
were also successfully fabricated.
Laboratory of Bio-Inspired Materials and Interface Sciences, Techni-
cal Institute of Physics and Chemistry, Chinese Academy of Sciences
Beijing 100190 (P. R. China)
From the spherical-aberration-corrected high-angle annu-
lar dark-field scanning TEM (HAADF-C -TEM) of B-CoP-
S
Dr. H. Jiang, Prof. Q. Zhang, Prof. L. Gu
Institute of Physics, Chinese Academy of Sciences
Beijing 100190 (P. R. China)
HoMSs (Figure 1e), the bubble-like structure can be more
clearly observed. The typical boundary between CoP and
+
[
CoO (Figure 1 f) observed from C -TEM reflects the inter-
] These authors contributed equally to this work.
S
mediate stage during the composition conversion process.
These heterogeneous compositions are further converted to
pure CoP after the further phosphorization (Figure S13). The
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.202016285.
6
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Scheme 1. Illustration of the formation process of CoP HoMSs with different micro-nano structure of shells. The shells transformed from solid to
bubble-like, and then the walls of these bubbles fused together forming close duplicated shells, and to the solid one at the end. The narrow cavity
between the shells of D-CoP-HoMSs can accelerate liquid transfer through enhanced capillary force according to the equation of the liquid height
induced by capillary force, h=2scosq/(1gr), where the height (h) is inversely proportional to the capillary radius (r). Bubbles are generated by
catalysis on the surfaces of HoMSs. Because of the strong confinement effect, the confined space between shells of D-CoP-HoMSs will resist the
overgrowth of bubbles within shells while the bubbles outside would grow to the larger ones. According to Young-Laplace equation, P =2g/R,
s
P=P +P , there is a pressure difference between the small bubbles on the inner surface and the connected large bubbles on the outer surface,
0
s
leading to the diffusion of gas molecules from the small bubbles to the larger ones, and then the large bubbles on the outside will be quickly
released due to the aerophobic surface, which can accelerate the gas releasing.
Figure 1. a–d) Low- and high-magnification (inset) TEM images of Co O -HoMSs and samples after phosphorization reaction for 2 h (B-CoP-
3
4
HoMSs), 4 h (D-CoP-HoMSs), and 8 h (CoP-HoMSs) under 3008C in Ar atmosphere. The scale bar of inset images is 50 nm. e–h) HAADF-CS-
TEM images of B-CoP-HoMSs and D-CoP-HoMSs. i) XRD patterns, j) FT-EXAFS at the Co K edge and k) XPS curves of different samples.
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lattice spacing of D-CoP-HoMSs is ꢀ 0.166 nm (Figure 1g,h),
corresponding to the distance between (020) planes of
orthorhombic CoP. As further proved by XRD (Figure 1i,
Figure S14), both CoO and CoP can be observed after
phosphorization reaction for 2 hours. Further phosphoriza-
tion can thoroughly complete the composition conversion
from CoO to CoP and no additional peaks of impurities can
be observed from the XRD patterns of D-CoP-HoMSs and
CoP-HoMSs. The particle sizes of various samples also reflect
the evolution of the micro-nano structure of HoMSs. Based
on the Scherrer equation, the sizes of nanoparticles are
calculated to be 9.8 nm, 11.4 nm, 16.1 nm for B-CoP-HoMSs,
D-CoP-HoMSs and CoP-HoMSs, respectively, indicting the
longer phosphorization period can induce nanoparticles to
attach with each other and fuse to larger ones. The extended
X-ray absorption fine structure (EXAFS) spectroscopy was
further performed to investigate coordination environment of
the Co species. As shown in Figure 1j, the Fourier-trans-
has a greater drop of current density (69–83%) than those of
CoP-HoMSs with solid shells (17–63%) within the selected
voltage range (Figure 2c and f). Additionally, the LSV curves
and Tafel plots demonstrate that electrocatalytic properties
enhance with the increase of shell number (Figure S18).
Meanwhile, the D-CoP-HoMSs exhibit excellent catalytic and
structural stability in both HER and OER (Figure S19–S20).
Encouraged by the excellent electrocatalytic performance, we
further used triple-shelled D-CoP-HoMSs as both anode and
cathode to assemble a two-electrode electrolyzer for overall
water splitting (Figure 2g,h). As shown in Figure 2i, the
À2
current density of 10 mAcm can be achieved at a cell
voltage as low as 1.57 V, and it shows good performance in the
large current density region with excellent stability (Fig-
ure S21).
This excellent catalytic performance of the duplicated
HoMSs can be understood from both the charge and mass
transport. On the one hand, the electrochemical impedance
spectroscopy (EIS) shows the D-CoP-HoMSs possess the
formed (FT) curve of Co O4 appears a peak at 1.4 ꢀ,
3
[20]
corresponding to the Co-O coordination. As the phosphori-
zation proceeded, the dominated peak at 1.7 ꢀ in B-CoP-
HoMSs, D-CoP-HoMSs and CoP-HoMSs can be corre-
lowest electron-transfer resistance (Figure 3a, Figure S22).
On the other hand, benefitting from the advantages of the
structure, B/D-CoP-HoMSs possess higher hydrophilicity and
aerophobicity compared with the CoP-HoMSs. Especially, the
CoP HoMSs with close duplicated shells are better to be
wetted than CoP HoMSs with porous bubble-like shells and
that with non-duplicated solid shells (Figure 3b–d). The
greater hydrophilicity can be understood from the equation
of the liquid height induced by capillary force, h = 2scosq/
(1gr), which means the height (h) is inversely proportional to
[
12]
sponded to the Co-P coordination. In the Co K-edge X-
ray absorption near-edge structure (XANES) spectrum (Fig-
ure S15), the absorption edge of the prepared CoP HoMSs is
located in the left of CoO, implying the valence state of Co
0
2+ [13]
atom is between Co and Co . Similarly, the peaks at 779.6
and 781.1 eV in high-resolution X-ray photoelectron spec-
troscopy (XPS) spectrum of Co 2p (Figure 1k) can be
3
+
2+
[8]
assigned to Co and Co in Co O -HoMSs, respectively.
the capillary radius (r). Therefore, the small space between
3
4
With the phosphorization proceeding, the peak at 779.6 eV
gradually shifted to a lower energy, which can be attributed to
shells of D-CoP-HoMSs can provide a stronger capillary force
to drive liquid diffusion. Particularly after the release of
produced gas, the liquid can rapidly replenish the space where
the bubble disappears to ensure the fast reaction kinetics.
Moreover, the larger gas contact angle of D-CoP-HoMSs
is in favor of the desorption of the produced gas (Figure 3e–
g). The similar phenomenon of gas releasing can also be
observed from the in situ electrocatalytic reaction. We took
the high-speed digital camara to record the bubble releasing
within the electrode during potentiostatic scan and galvano-
static scan (Supporting Movies). Taking HER tested at
À0.48 V vs. RHE as an example, hydrogen bubbles escaped
easily from the surface of D-CoP-HoMSs with a size of
ꢀ 43 mm, close to the size of B-CoP-HoMSs ( ꢀ 47 mm), while
the bubbles on CoP-HoMSs grew to larger size of ꢀ 165 mm
(Figure 3k–m). The same tendency was observed for the
oxygen bubble releasing under both the potentiostatic scan
(38 mm, 39 mm, 140 mm for D-CoP-HoMSs, B-CoP-HoMSs
and CoP-HoMSs at 1.92 V vs. RHE, respectively) (Figure 3k–
m) and the galvanostatic scan (Figure S23). This phenomenon
is closely related to the nucleation, growth and escape of
gases. The size of bubbles can be seriously affected by the
distance of the space in which they are located. Meanwhile,
according to Young-Laplace equation, P = 2g/R, P = P + P ,
[14]
the decreasing of valence value of Co elements. In addition,
the newly appeared peak at 793.2 eV can be attributed to the
formation of CoÀP bond. With the prolonged phosphoriza-
tion period, the ratio of the peak area of Co-P to Co-O
increased (Table S1), which is consistent with the XRD,
elemental mapping images and corresponding line profile
analysis (Figure S16), indicating the composition transition
[
15]
process.
from the surface oxidization caused by the air contact.
The oxidized species in CoP samples originate
[
16]
Moreover, the binding energy of Co-P shows a positive
deviation from the Co metal, while the P 2p has a negative
shift from the base P (Figure S17). These results indicate that
electrons transferred from Co to P, making Co electron
deficient and P electron rich, thus facilitating the charge
[
17]
transfer in electrocatalysis.
As a typical multi-phase catalytic reaction, electrochem-
ical water splitting including HER and OER was investigated
[
18]
on different HoMSs with different shell structures. The D-
CoP-HoMSs show the highest catalytic activity with smallest
overpotentials of 93 and 294 mV at the current density of
À2
1
0 mAcm for HER and OER, respectively, and followed by
B-CoP-HoMSs (Figure 2a and d, Table S2). The D-CoP-
s
0
s
À1
HoMSs present the smallest Tafel slope of 50 and 67 mVdec
where Ps is the additional pressure and R is radius of
curvature, the pressure of a bubble is inversely proportional
to its radius. For D-CoP-HoMSs, the confined space between
shells will resist the overgrowth of bubbles within shells. The
larger bubbles with lower pressure can only be generated on
for HER and OER respectively among various HoMS
samples (Figure 2b and e, Table S3), indicating the favorable
[19]
electrocatalytic kinetics of this structure.
Notably, the
results reflect after grinding, the duplicated HoMS sample
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À1
Figure 2. a) HER LSV and b) Tafel plots of HoMS samples before and after grinding, and Pt/C with a scan rate of 5 mVs in 1 M KOH electrolyte.
c) The current density at À0.10 V, À0.15 V, À0.20 V vs. RHE catalyzed by different samples before and after grinding during the HER. d) OER LSV
À1
and e) Tafel plots of HoMS samples before and after grinding, and RuO with a scan rate of 5 mVs in 1 M KOH electrolyte. f) The current
2
density at 1.53 V, 1.58 V, 1.63 V vs. RHE catalyzed by various samples before and after grinding during the OER. g) Schematic illustration and
h) optical photograph of two-electrode cell using D-CoP-HoMSs as both anode and cathode for overall water splitting. i) Polarization curves of D-
À1
CoP-HoMSs and Pt/C/RuO for overall water splitting with 5 mVs in 1 M KOH electrolyte.
2
the outer surface of HoMSs. Due to the pressure difference
between the inner small and outer large bubbles, the gas
molecules in the small bubbles diffuse into the large bubbles,
and the large bubbles on the outside will be quickly released
owing to the aerophobic surface (Scheme 1). Contrastively,
because the confinement effect of CoP-HoMSs is not as
strong as that of D-CoP-HoMSs, the bubbles produced on
their inner and outer surface possess similar process and grow
cally investigated the transition process during the phospho-
rization, and found the solid subunits of HoMSs, i.e., Co O
3
4
nanoparticles, transformed to hollow ones and crosslinked
together, forming bubble-like structure composed of CoO
and CoP, and then converted to CoP duplicated shells with
a close interspace, finally the duplicated shells fused into one
solid layer. We found the HoMSs with bubble-like and close
duplicated shells can induce a faster reaction kinetics than the
non-duplicated ones, owing to the better gas-liquid and
electron transport. When applied as a bifunctional multi-
phase catalyst for water splitting, it manifests superior
electrocatalytic activity. The geometry control in HoMS
demonstrates the importance of rational design on the
structure of micro-nano materials and provides an easy way
for structure adjustment.
[
21]
to larger size, which brings stronger adhesion, thus making
them more difficult to remove. Because the ion transfer
coefficient k is positive correlation to the rate of gas escape,
the rapid discharge of gas for D-CoP-HoMSs is conducive to
[22]
accelerating catalytic reaction.
In summary, by surveying the importance of micro-nano
structure of the shell of HoMSs, we developed a novel one-
step strategy to regulate the structure of shell. We systemi-
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