Turning bulk materials into 0D, 1D and 2D metallic nanomaterials by selective aqueous corrosion

Article abstract of DOI:10.1039/c9cc04807c

The realization of the facile and green synthesis of low-dimensional nanomaterials is critical not only for energy storage but also for catalysis. A selective aqueous corrosion strategy is presented here for obtaining low-dimensional metals, including nanoparticles, nanofibers and nanosheets, based on the dealloying of aqueous-favoring metal from its bulk alloy.

Full text of DOI:10.1039/c9cc04807c

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Turn Bulks into 0D, 1D and 2D Metallic Nanomaterials by Selective
Aqueous Corrosion†
Received 00th January 20xx,
Accepted 00th January 20xx
Liang Fang,‡a JingJing Feng,‡a Xiaobin Shi,a Tingzhi Si,*a Yun Song,*b Hong Jia,c Yongtao Li,*a,d Hai-
Wen Lid and Qingan Zhanga
DOI: 10.1039/x0xx00000x
www.rsc.org/
Realization of facile and green synthesis of low-dimensional Following this observation, Chen et al.25 further report a two-
nanomaterials is critical not only for energy storage but also step dealloying approach to fabricate a hierarchical nanoporous
for catalysis. A selective aqueous corrosion strategy is Ni alloy from the NiCu precursor. Indeed, these dealloying (i.e.,
presented here for the obtaining of low-dimensional metals selectively leaching) methods were demonstrated to be a facile
including nanoparticles, nanofibers and nanosheets, based on route to synthesize nanoporous metallic materials. However,
dealloying of the aqueous-favoring metal from its bulk alloy.
there are few attempts to synthesize the other low-dimensional
nanomaterials by dealloying strategy. Excitingly, a recent work
showed that the non-metallic Si nanosheets can be obtained by
chemical leaching lithium atoms from the Li13Si4 alloys, which
were believed to be ascribed to the delithiation-induced
mismatch of Si layers.26 Unfortunately, a rival determination of
how to form Si nanosheets by chemical leaching is also lacking
and further the underlying mechanism is not well understood.
In addition, it has never been reported up to now whether the
etching method can be used for obtaining the metallic
nanosheets or not.
Motivated by these factors, in this communication, we for the
first time demonstrate a selective aqueous corrosion (SAC)
strategy for the efficient realization of low-dimensional metallic
nanomaterials, based on the dealloying of aqueous-favoring
metal from its bulk alloys. This SAC strategy not only exhibits
a facile and recyclable route, but also can be used for diverse
metallic nanomaterials preparation including 0D particles, 1D
fibers and 2D sheets. The possible formation mechanisms of
these nanometals are also discussed.
Nanostructured materials, particularly non-noble nanometals,
have attracted more attentions because of their high surface
area, low-coordination and distortion of atoms, and distinct
intrinsic properties etc,1,2 which usually play exceptional size
effects on the high density energy storage and efficient catalysis.
However, realizing the facile, green, low-cost preparation of
nanomaterial is still too hard for the scale applications.3,4 Even
though substantial effort has been devoted, several methods
were already proposed for nanofabrication including ball
milling,5
hydrothermal,6‒8
self-assembly,9‒11
vapor
deposition,12,13 arc-discharge,14,15 atomic layer deposition and
so on.16‒18 But there exists many problems during synthesis
process, such as uncontrollable particle size, inhomogeneous size
distributions, fastidious hydrothermal process or by-products
pollution, etc.19‒22 So exploring new facile and green methods
for synthesis of nanomaterials is urgent but challenging.
One effective approach in the nanomaterials synthesis is
dealloying, i.e., selectively leaching of the chemical instability
elements in a multicomponent precursor.23,24 Erlebacher et al.24
developed a dealloying/plating/re-dealloying strategy to obtain
nanoporous Au with a bicontinuous pore size distribution.
By using SAC strategy, the metallic bismuth (Bi) nanosheets
were first synthesized and their detailed experiments can be
found in the Electronic Supplementary Information (ESI†). Fig.
1a shows the phase evolution for the Li-Bi system at different
preparation stages. It can be seen that the starting materials of
LiH and Bi with a certain molar ratio would combine to form
LixBi (x = 1, 3) alloys when it was heated at 400 °C. Then the
sintered alloys further reacted with the water at room
a. School of Materials Science and Engineering, Anhui University of Technology,
Maanshan 243002, China. E-mail: toni-li@163.com; tzsiahut@163.com
b. Department of Materials Science, Fudan University, Shanghai 200433, P. R. China.
E-mail: songyun@fudan.edu.cn
c. College of Physics and Electronic Information
& Key Laboratory of
Electromagnetic Transformation and Detection of Henan province, Luoyang temperature with the aid of ultrasonically stirring for sufficient
Normal University, Luoyang 471934, China.
aqueous corrosion. Further eliminating the solution by
d. International Research Center for Hydrogen Energy and WPI International
Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University,
Fukuoka 819-0395, Japan.
† Electronic Supplementary Information (ESI) available: Electrochemical cyclability,
SEM and TEM images, XRD pattern, XPS and EDX spectra for MgAg and TiNiV
alloys. See DOI: 10.1039/x0xx00000x
centrifugation, the final products were pure Bi nanosheets
(denoted as Bi NSs). The XPS results also indicate the zero
valences state for the as-prepared Bi NSs (Fig. S1, ESI†), being
in agreement with the XRD result of pure metallic Bi in Fig. 1a.
‡ These authors contributed equally to this work.
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Fig. 1 (a) Phase evolution for the Li-Bi system at different SAC
stages and (b, c) typical crystal structures for the LixBi alloys
and the residual Bi atoms layers (i.e., Bi NSs) after removal of
Li atoms by SAC treatment.
Fig. 2 SEM images for the LixBi alloys (a) before and (b) after
SAC treatments and its EDX spectrum (c), as well as (d, e)
TEM images, (f) STEM image and (g) its corresponding Bi
To reveal the formation mechanism of Bi nanosheets, their
crystal structures relationships during synthesis procedures elemental mapping for the as-prepared Bi nanosheets.
were examined carefully. Interestingly, both LiBi and Li3Bi
alloys are layered structure where the Li and Bi atoms arrange elemental map (Figs. 2(f, g)) again indicates the formation of Bi
exceptionally in a layer by layer fashion, as shown in Fig. 1b. nanosheets. The typical thicknesses of Bi nanosheets are about
Upon SAC treatment, the Li atomic layers would be removed 3.0 ± 0.4 nm, as detected by AFM analysis (see Fig. S2,
and dissolved into aqueous solution due to its ultra-high activity. ESI†).These obtained Bi nanosheets, as electrodes for hydride solid-
The residual Bi layers as shown in Fig. 1c would lessen stale batteries, can deliver a stable capacity of ~190 mAh g-1 at a rate
intrinsic van der Waals interactions and spontaneously split into of 0.5 A˖g-1 at 120 °C, five times higher than that in LiPF6 liquid
nanosheets under the action of external fields. This explains organic batteries at the room temperature (see Fig. S3, ESI†),
why the Bi nanosheets can be obtained by SAC.
suggesting its high-temperature electrochemical stability
.
The as-prepared Bi nanosheets were further determined by
Based on the fact that the 2D nanomaterials were prepared
electron microscopy techniques. Being distinct from the clean- successfully by SAC strategy, we probe the overall preparation
cut bulk morphology of the LixBi alloys (Fig. 2a), these alloys procedures again. It can be found that the preparation processes
after SAC treatment became more fine and slippy (Fig. 2b). of SAC are recyclable, green and almost do not affect the
Further enlarging it, the obvious layered structures can be seen environment except for some O2 emission. As shown in
in the insertion of Fig. 2b. Combining with the EDX spectrum Scheme 1, the starting AHx or A is alloyed with B to form AyBx,
in Fig. 2c, these above results strongly demonstrate that the Bi and then the resulting alloy reacts with H2O to release H2 by
nanosheets indeed can be synthesized by SAC. Excitingly, the hydrolysis. The elemental A is etched to obtain A(OH)x, while
combined Bi nanoplatelets would split into smaller hexagonal the elemental B is kept by different nanostructures. The by-
thin sheets when it was exposed under the electron beam, as products of A(OH)x and B were separated by centrifugalization.
shown in Figs. 2(d, e). The STEM image and its corresponding
The conversion A(OH)x to metallic A can go through the
2 | Chem. Commun., 2019, 00, 1-3
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(ESI†) where the black Ag nanoparticles were embedded in the
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grey matrix of Mg(OH)2 and alloys. AfteDrOelI:im10i.1n0a3t9in/Cg9MCCg0(4O80H7)C2
by acid washing, only Ag phase was obtained in Fig. S5 (ESI†),
which is in agreement with the XPS results of metallic state
with two distinct peaks of Ag 3d3/2 and Ag 3d5/2 for Ag NPs
(Fig. S6, ESI†). Figs. 3(a‒c) and Fig. S7 (ESI†) present the
spherical morphologies of Ag NPs. The statistic average
diameter is 22 ± 4 nm based on TEM analysis of more than 200
nanoparticles from more than four different syntheses as shown in
Fig. 3d. Similarly, the 1D nanofiber can also be obtained by SAC.
Firstly, the TiNiV alloys were obtained by sintering or melting of Ti,
Ni, V or VHx. The eutectic tissues were then obtained where the
line-shaped TiNi and V overlap each other, as shown in Figs.
S(8‒10) (ESI†). After selective aqueous corrosion, the aqueous-
favoring V was etched with the aid of electric field, and left the
TiNi nanostructure that its fiber morphologies are shown in the
Figs. 3(e‒g) and Figs. S(11, 12) (ESI†). The XPS results of the
TiNi nanofibers in Fig. S13 (ESI†) further indicate that the Ti
2p bands correspond to Ti4+, Ti3+, Ti2+ along with weak
metallic state, suggesting the complex bonds for Ti including
metallic and/or covalent states that are possibly due to some
oxidation of surface layer Ti atoms.28 While the co-existed Ni
clearly exists in a metallic state, as supported by the two typical
Scheme 1 Schematical illustration of the products evolutions
for selective aqueous corrosion (SAC) process. Using SAC, the
0D, 1D and 2D nano-metals can be synthesized successfully. It
should be noted that the by-products can be further recyclable
utilized by multi-steps of pyrolysis, electrolysis, hydrogenation,
alloying and hydrolysis, where the former generated H2 can be
used for latter hydrogenation of metals.
intermediate of A2Ox or AClx back to metallic A by pyrolysis,
electrolysis and molten salt methods.27 Based on the energy
saving, the route involved AClx is favourable. Furthermore, the
new-born metal A can be hydrogenated back to starting AHx by
using the released H2 in hydrolysis process. Thus a recyclable
and green process is realized here to prepare the Bi nanosheets.
A common question is raised whether the recyclable and
green route can be used for synthesizing other low-dimensional
nanomaterials or not, and a positive answer is obtained in this
work. Fig. 3 presents the morphologies of Ag nanoparticles (0D)
and TiNi nanofibers (1D) synthesized by the SAC method. The Ag
nanoparticles were prepared by the selective aqueous corrosion of
MgxAg alloys. The aqueous corrosive products are shown in Fig. S4
peaks of Ni 2p3/2 and Ni 2p1/2
.
Based on our observations, it is noted that the composition
and structural arrangements are the two key factors in the
formation of low-dimensional nanomaterials by SAC. For the
binary and ternary alloys, one element is prone to hydrolysis
relative to the other constitutes, the favourable Li, Mg or V was
thus selected based on following considerations: (i) these
selected metals usually possess highly active reacting with
water; (ii) these selected metals elements deliver more negative
corrosion potential as compared to other retained constitutes,
Fig. 3 SEM and TEM images of the as-prepared Ag nanoparticles and TiNi nanofibers by SAC: (a) SEM, (b, c) TEM and HRTEM
images of Ag nanoparticles and (d) the corresponding histogram for the particle size distribution where the average particle diameter is 22
± 4 nm; (e) SEM image of TiNi nanofibers, (f) TEM image of a single TiNi nanofiber and (g) atomic lattice image of the square
regions marked in (f) obtained by inverse fast Fourier transform (IFFT) where the dashed line in (g) indicates the side surface of
the nanofiber.
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DOI: 10.1039/C9CC04807C
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X. Zhao, Q. Yang and Z. Quan, Chem. Commun., 2019, doi:
10.1039/C9CC02811K.
and are prone to be preferential etched under external effects.
The specific structures such as layered arrangements are also
important for obtaining the nanomaterials. This because that the
structural precursor would be kept after SAC. Moreover, for the
selective aqueous corrosion, the pH of aqueous solution and the
ultrasonic or electric field effects also have facilitated the
dealloying process for the growth of the metallic nanomaterials.
In this regard, further more investigations into the chemical
composition, structures and field effects are currently underway
to define the intrinsic mechanism during SAC process.
In summary, the Ag nanoparticles, TiNi nanofibers and Bi
nanosheets were successfully prepared by selective aqueous
corrosion (SAC) from their bulk alloys at room temperature. A
possible formation mechanism that the nanomaterials are
obtained by the hydrolysis of aqueous-favoring metal from their
bulk alloys is proposed based on our experimental results. The
composition and structural arrangements are the two key factors
in the formation of low-dimensional nanomaterials. The pH of
aqueous solution and the ultrasonic or electric field effects also
have facilitated the dealloying process for the growth of the
metallic nanomaterials. Currently, further investigation of the
preparation and electrochemical storage properties of metallic
nanomaterials are underway in our laboratories. These metallic
nanomaterials obtained using the SAC strategy exhibit not only
promising properties as electrode materials for secondary batteries,
but also provide potential applications for efficient and stable agents
in catalysis.
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This work was financially supported by the National Natural
Science Foundation of China (Nos. 51671001, 51701004,
51871002, 51871059 and 51971001), International Science and
Technology Cooperation Project of Anhui Provincial Key
Research and Development Program (No. 201904b11020028),
Natural Science Foundation of Anhui Province (No.
1708085ME99) and Overseas Visiting Project of the Excellent
Youth Elite in University of Anhui Province (No.gxfx2017016).
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View Article Online
DOI: 10.1039/C9CC04807C
Selective aqueous corrosion strategy was proposed for
synthesizing low-dimensional nanometals by the dealloying of
aqueous-favoring metals from their bulk alloys.
This journal is © The Royal Society of Chemistry 2019
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