Journal of Alloys and Compounds 942 (2023) 169119

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

One-step solvothermal synthesis of CsxWO3: Crystal growth regulation

by halogen acids with generating oxygen vacancies and W5+ for ]]
]]]]]]
]]

improving transparent thermal insulation performance

⁎
Dayi Yang, Jingxiao Liu , Fei Shi, Yi Li, Jiaxiang Wan, Xinyu Yuan, Ziwei Tian, Meiyu Wang,
Chuangchuang Ma
School of Textile and Materials Engineering, Dalian Polytechnic University, Dalian116034, PR China

a r t i cl e i nfo a bstr ac t

Article history: Synthesis of cesium tungsten bronze (CsxWO3) nanorods with excellent near-infrared shielding perfor­
Received 19 October 2022 mance by a one-step solvothermal method from cheap tungsten source is still challenging. In this work,
Received in revised form 28 January 2023 small-sized CsxWO3 nanorods with excellent transparent thermal insulation performance were synthesized
Accepted 30 January 2023
by a one-step solvothermal method. It was found that halogen acids played an important role in regulating
Available online 2 February 2023
the growth and microstructure of CsxWO3 nanorods. Moreover, different halogen acid can regulate the
content of W5+=O and oxygen vacancies (VO) in CsxWO3 nanorods, which is helpful to further improve the
Keywords:
CsxWO3 near-infrared shielding performance of CsxWO3 particles. Compared with HF and HBr, the CsxWO3 nano­
One-step solvent method particles synthesized under the regulation of HCl contain more VOs and W5+=O content, showing more
Structural regulation excellent near-infrared shielding performance, and the as-prepared CsxWO3-PVA composite film exhibits
Near-infrared shielding low haze and high transparency, with the near-infrared light shielding rate at 1500 nm attaining to 97.7%
Energy-saving window when the visible light transmittance is 71.8%. The thermal insulation test results show that the CsxWO3-PVA
composite film synthesized under the regulation of HCl can effectively reduce the indoor temperature by
6.9 °C under the irradiation of sunlight. After 100 cycles of thermal insulation tests, the near-infrared
shielding and thermal insulation performance have not declined, showing excellent photothermal stability.
This work is of great significance for promoting the industrial production of high-performance CsxWO3
nanoparticles and its application in energy-saving windows.
© 2023 Elsevier B.V. All rights reserved.

1. Introduction Generally, the NIR shielding properties can be realized by using NIR
absorption or reflection materials. In recent years, Low-E glass [4,5] and
At present, energy conservation and emission reduction have inorganic nanoparticles such as lanthanum hexaboride (LaB6) [6,7], tin-
received increasing attention from various countries. Building doped indium oxide (ITO) [8], antimony-doped tin oxide (ATO) [9],
thermal insulation and energy saving are especially important, be­ copper sulfide (CuS) [10,11], vanadium dioxide (VO2) [12,13] and
cause building energy consumption accounts for about 40%− 50% of tungsten bronze (MxWO3, M = Li, Na, K, Rb, Cs, NH4) [14,15], etc. have
global energy consumption [1–3], and more than half of it comes attracted significant attention for their potential application in energy-
from cooling and heating. Particularly, in summer, sunlight con­ saving windows. Recent studies demonstrated that metal atom cluster
taining a large amount of near-infrared (NIR) light will shine into the nanocomposites such as [(Ta6Br12)Br2(H2O)4]− 3 H2O and
room, which will lead to a significant increase in energy consump­ K4[ < Nb5TaXi12 > Xa6] (X = Cl, Br) are very promising UV and NIR blocking
tion due to building cooling. Thus, developing energy-saving pigments, which can be coated on the surface of ITO glass to improve
window material with high NIR shielding ability that can shield its near-infrared shielding performance [16,17]. It was reported that
40–50% of solar radiation energy is of great significance for energy metaglasses incorporating plasmonic nanocrystals, such as nanoshell-
saving and emission reduction. shaped Au, Ag, Cu, nanocup-shaped TiN and nanorod-shaped Al, can be
designed, which have the advantages of low cost and are good candi­
dates for passive energy-saving windows [18]. By comprehensive
comparison, cesium tungsten bronze (CsxWO3) nanoparticles with
⁎
Corresponding author. hexagonal structure exhibit excellent NIR absorption/shielding
E-mail address: [email protected] (J. Liu).

https://doi.org/10.1016/j.jallcom.2023.169119
0925-8388/© 2023 Elsevier B.V. All rights reserved.
D. Yang, J. Liu, F. Shi et al. Journal of Alloys and Compounds 942 (2023) 169119

performance and higher thermal stability, because they can shield NIR Co. LTD. Cesium sulfate (Cs2SO4, AR) and polyvinyl alcohol (PVA,
rays with a wider wavelength (780–2500 nm) depending on small [-CH2CHOH-]n, 1788) were purchased from the Aladdin Reagent Co.
polaron conversion and localized surface plasmon resonance (LSPR) LTD. Ethanol (C2H5OH, AR) and hydrofluoric acid (HF, AR) were
effects. At present, the CsxWO3 particles can be synthesized mainly by purchased from the Kermel Chemical Reagents Co. LTD. All materials
solvothermal and high-temperature solid-state reaction method. Stu­ were used without further purification.
dies have shown that the LSPR effect of nanoparticles is greatly influ­
enced by the crystal size and its morphology [19,20], and it is easier to 2.2. Synthesis of CsxWO3 nanoparticles
control the morphology of CsxWO3 nanoparticles by hydrothermal or
solvothermal method [21,22]. For example, 0D, 1D and 2D CsxWO3 At first, tungstic acid gel/ethanol dispersion was prepared ac­
nanoparticles can be synthesized by hydrothermal reaction under the cording to our previous preparation process [24]. A certain amount
regulation of oleic acid and oleylamine, and the obtained 2D Cs0.3WO3 of Na2WO4·2 H2O was added to the deionized water to prepare a
nanosheets show relatively good NIR shielding performance [21]. In 0.25 mol/L sodium tungstate solution, and 3 mol/L hydrochloric acid
addition, CsxWO3 nanocrystals with different morphologies and crys­ was quickly poured into the sodium tungstate solution under stir­
talline phases could be synthesized by tailoring H+ and H2O con­ ring to obtain a yellow flocculent tungstic acid gel suspension. Then,
centrations in the different ligand circumstance of SO42-, Cl-, Ac- and the suspension was filtered, washed with deionized water and
OH- using ammonium metatungstate (AMT) as raw material, and the ethanol for three times, and then dispersed in ethanol solvent to
rod-shaped hexagonal CsxWO3 nanocrystals prepared with SO42- ligand obtain a tungstic acid gel/ethanol dispersion.
environment exhibited better NIR shielding performance [22]. It was The precursor solution was prepared by adding appropriate
reported that hexagonal prisms, truncated cubes, and pseudospheres amount of DL-tartaric acid, Cs2SO4 and halogen acid (HX, X = F, Cl,
CsxWO3 nanocrystals could be prepared by controlling the ratio of oleic Br) into the tungstic acid gel/ethanol dispersion in sequence under
acid to oleylamine using WCl6 as W source, and the obtained CsxWO3 stirring, in which the tartaric acid concentration is 1 mol/L, and Cs/W
nanocrystals with hexagonal prisms exhibited higher NIR shielding and HX/W molar ratio is 0.35 and 1.12, respectively. Then the sol­
ability [23]. Overall, the above mentioned solvothermal methods are vothermal reaction was conducted at 230 °C for 48 h. Finally, the
successful for synthesizing CsxWO3 nanoparticles with controllable obtained CsxWO3 powders was centrifuged and washed with deio­
morphology, however, the raw materials used in the preparation pro­ nized water and ethanol for 3 times. In this work, the CsxWO3 na­
cess are not cheap and friendly to environment, which is not conducive noparticles synthesized without halogen acid and with adding HF,
to their industrial production. HCl and HBr in the reaction solution were named as 0-CsxWO3, HF-
In recent years, synthesis of CsxWO3, Pt-CsxWO3 and (Tm, Yb)- CsxWO3, HCl-CsxWO3 and HBr-CsxWO3, respectively. In addition, in
CsxWO3 nanoparticles using cheaper sodium tungstate as W source order to study the effect of concentration of HCl and pH value of the
via solvothermal method have been studied by our research group precursor solution on the products, CsxWO3 nanoparticles synthe­
[24–27]. It is found that the properties of CsxWO3 particles prepared sized by adding different HCl with HCl/W molar ratio being 0.28,
by one-step solvothermal method using sodium tungstate as W 0.56, 1.12 and 1.68 are named as 0.28HCl-CsxWO3, 0.56HCl-CsxWO3,
source are usually not ideal, and subsequent heat-treatment in N2 1.12HCl-CsxWO3 and 1.68HCl-CsxWO3, respectively.
atmosphere is usually necessary to further improve its crystallinity
and NIR shielding performance. However, heat-treatment will lead
to the secondary growth of crystals to some extent, which will affect 2.3. Preparation of CsxWO3-PVA composite film
the visible light transmittance and haze of the film, and will cause
the increase of the production cost too. Recently, KmCsnWO3 and In this work, CsxWO3-PVA composite film was prepared from a
LimCsnWO3 particles with excellent performance have been syn­ dispersion of CsxWO3 nanoparticles. The CsxWO3 powder was uni­
thesized by solid-state reaction method in H2 atmosphere in our formly dispersed in a 10% polyvinyl alcohol (PVA) solution to obtain
group [28,29], but the particles synthesized at higher temperature a dispersion with CsxWO3 concentration 0.005 mol/L. Then CsxWO3-
are large in size and require subsequent ball milling treatment, PVA film with suitable visible light transmittance can be obtained by
which is not favorable for decreasing the production cost and haze of roller coating method on the glass substrate.
the film. Thus, in order to realize the wide application of CsxWO3, it
is still necessary to further improve the transparent and thermal 2.4. Characterization
insulation performance of CsxWO3 synthesized by one-step sol­
vothermal method with low-cost and environment-friendly process. The crystalline phase of CsxWO3 nanoparticles was analyzed by
Therefore, in this work, hexagonal CsxWO3 nanorods with small X-ray diffraction (XRD, Shimadzu XRD-7000S, Japan) with a scan
grain size and excellent performance were synthesized by using rate of 5° min−1 and a scan range of 10°∼70°. The microscopic
sodium tungstate as W source via one-step solvothermal method morphology and lattice structure of the samples were observed by
without subsequent heat-treatment. The regulation behavior and transmission electron microscopy (TEM, Talos F2000X, Japan). The
mechanism of halogen acids on the crystal growth and NIR shielding particle size of the samples was measured by dynamic light scat­
of CsxWO3 nanorods were investigated. This study provides a cheap tering (DLS, Zetasizer Nano ZS, UK). X-ray photoelectron spectro­
and effective way of one-step synthesizing CsxWO3 with high scopy (XPS, Thermo Scientific K-Alpha, USA) analysis was conducted
transparent thermal insulation performance by controlling the O using the C-1 s level at 284.6 eV as an internal standard to calibrate
defects and W5+ amount in the grains, which will be of great sig­ the change in binding energy caused by surface state charges. The
nificance for promoting the large-scale production of CsxWO3 and its chemical bonds in the samples were characterized by laser Raman
wide application in energy-saving windows. spectroscopy (RS, PI Trivista CRS, USA). The UV-Vis-NIR transmission
spectra of glass coated with CsxWO3-PVA films were measured by
2. Experimental procedure UV-Vis-NIR spectrophotometer (PerkinElmer Lambda 950, USA).
Electrochemical workstation (CHI 660 C, China) was used to test the
2.1. Materials photogenerated current of CsxWO3-PVA films. The haze test of the
CsxWO3-PVA films was carried out with a photoelectric haze meter
Hydrated sodium tungstate (Na2WO4·2 H2O, AR), hydrochloric (INESA WGW, China). The thermal insulation performance of the
acid (HCl, AR), hydrobromic acid (HBr, AR) and DL-tartaric acid samples were tested using a self-made thermal insulation box in the
(C4H6O6, AR) were purchased from the Sinopharm Chemical Reagent laboratory.

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D. Yang, J. Liu, F. Shi et al. Journal of Alloys and Compounds 942 (2023) 169119

(0.154056 nm), B is the FWHM of the diffraction peak of the crystal

plane, and θ is the Bragg diffraction angle. The researches show that
because the Scherrer constant is affected by the shape of the crys­
tallite, it is necessary to recalculate the Scherrer constant for dif­
ferent crystal systems. For the crystal plane (h k l) of hexagonal
system, the Scherrer constant can be calculated by the following
formula [32–35]:

1 h+k+l
Kw = w
2 2 1
3(h2 + k2 + l 2) 2 (2)

where Kw is the corrected Scherrer constant, ψw is the value of wave

function ψ at half maximum intensity, γ is the X-ray wavelength.
Thus, the Scherrer constant Kw of the crystal plane (200) can be
calculated to be 0.6932.
Fig. 1. (a) XRD spectra of CsxWO3 nanoparticles synthesized under different halogen According to the crystal structure of hexagonal CsxWO3 na­
acids; (b) Local amplification of the (002) crystal plane diffraction peak; (c) Local norods, the crystal planes (200) and (002) represent the side and
amplification of the (112) and (202) crystal planes.
bottom of the nanorods, respectively. The average grain sizes of the
ab plane and c-axis of CsxWO3 nanorods synthesized with adding
3. Results and discussion different halogen acids in the reaction solution can be calculated
through the FWHM of the XRD diffraction peak of (200) and (002).
Fig. 1 shows the XRD spectra of CsxWO3 nanoparticles synthe­ The calculation results and corrected diameter (Dw) are shown in
sized under different halogen acids. According to our previous work Table 1.
[30], the larger the diffraction peak intensity ratio of I(112)/I(202) is, Fig. 2 shows the TEM and HRTEM images of CsxWO3 nano­
the higher the incorporation rate of Cs+ in the hexagonal tunnel of particles synthesized with adding different halogen acids in the
CsxWO3 nanorods is, and the stronger the NIR shielding performance precursor solution. It can be found that HBr-CsxWO3 nanoparticles
is. It can be found from Fig. 1 and Table 1 that the main crystalline synthesized under regulation of HBr are mainly irregular Cs0.20WO3
phase of 0-CsxWO3 synthesized in the absence of halogen acid is grains, while the particles HF-CsxWO3 and HCl-CsxWO3 synthesized
Cs0.30WO3 (ICDD97–007–2618). The main crystalline phases of HF- under regulation of HF and HCl are rod-like and more regular. When
CsxWO3, HCl-CsxWO3 and HBr-CsxWO3 synthesized with adding HF, the molar ratio of halogen to W is constant (HX/W=1.12), the water
HCl and HBr into the reaction solution are Cs0.32WO3 content introduced into the reaction solution is different due to the
(ICDD97–010–0193), Cs0.30WO3 (ICDD97–007–2618) and Cs0.20WO3 different concentrations of the halogen acid solutions used, and it
(ICDD97–010–0192) respectively, among which HCl-CsxWO3 exhibits can be calculated that 0.0409, 0.0833 and 0.1619 mol of water were
the sharpest diffraction peak and the highest crystallinity. The above introduced to the reaction solution by HF, HCl and HBr, respectively.
phenomenon indicates that the incorporation rate of Cs+ in the The amount of water in the reaction solution has an important in­
hexagonal tunnel and crystal growth of CsxWO3 nanorods can be fluence on the growth of CsxWO3 nanorods. Introducing an appro­
regulated by different halogen acids. In addition, it can be found that priate amount of water by HCl can moderately accelerate the growth
the diffraction peak on the crystal plane (002) of HF-CsxWO3 has a of CsxWO3 crystals, while the introduction of excess water by HBr
shift toward lower angle, which is ascribed to the formation of the will lead to the too rapid stacking of [WO6] and formation of irre­
crystalline phase pyrochlore-type cesium tungstate Cs0.287W0.95O3 gular grains.
(ICDD97–007–2619). The formation of impurity Cs0.287W0.95O3 is The length (LT) and diameter (DT) of CsxWO3 nanoparticles were
due to the fact that high corrosive HF will cause W-defects in the estimated by TEM, as shown in Fig. 3a and b. It can be found that the
crystal structure and forming an incomplete hexagonal WO3-type length (LT) and diameter (DT) of CsxWO3 nanorods are
framework, similar phenomenon was also found in our previous 10.78–13.49 nm and 6.35–7.46 nm, respectively, and the LT/DT esti­
research [31]. mated by TEM are closer to the L/Dw calculated by the Scherrer
Fig. 1a also shows that the FWHM of (200) and (002) diffraction formula using the corrected Scherrer constant Kw. The ratio (DScherrer
peaks change with the introduction of different halogen acids into - DT)/ DT characterizes the deviation between the average grain size
the precursor solution, indicating that different halogen acids have a determined by the Scherrer formula and the crystallite size esti­
certain influence on the grain size of CsxWO3. The grain size can be mated by TEM. Before the correction of Scherrer constant, the
calculated according to the Scherrer formula: maximum error reached 46.46%, and after the correction, the value
K decreased to 13.39%. The results show that average crystallite size
D= can be calculated more accurately by the corrected Scherrer formula.
B cos (1)
In addition, it is obvious that the particle size measured by DLS is
where D is the average thickness of the grain perpendicular to the much larger than that measured by TEM and XRD, which is due to
grain plane, K is the Scherrer constant, γ is the X-ray wavelength the fact that the small-sized nanoparticles will agglomerate due to

Table 1
Main crystalline phase and average grain size of CsxWO3 particles synthesized by adding different halogen acids into the reaction solution.

Main crystalline phase L & STD (nm) D & STD (nm) Dw & STD (nm) L/D & STD L/Dw & STD

0-CsxWO3 Cs0.30WO3 11.4 0.0234 8.4 0.0099 6.5 0.0077 1.36 0.0012 1.74 0.0016
HF-CsxWO3 Cs0.32WO3 12.0 0.0225 8.3 0.0079 6.5 0.0061 1.45 0.0014 1.86 0.0017
HCl-CsxWO3 Cs0.30WO3 12.8 0.0220 10.1 0.0088 7.9 0.0068 1.27 0.0015 1.63 0.0019
HBr-CsxWO3 Cs0.20WO3 10.6 0.0322 9.3 0.0137 7.2 0.0106 1.13 0.0018 1.46 0.0023

Note: "L" and "D" are the length and diameter of hexagonal rod-like grains calculated by Scherrer's formula, "L/D" is the aspect ratio of hexagonal rod-like grains, "Dw" and "L/Dw"
are calculated using the corrected Scherrer constant Kw, and STD is the standard deviation.

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D. Yang, J. Liu, F. Shi et al. Journal of Alloys and Compounds 942 (2023) 169119

Fig. 2. TEM and HRTEM images of CsxWO3 nanoparticles synthesized under different halogen acids.

the surface energy. The result obtained by DLS is the agglomerated halogen acids in the reaction solution can regulate the W5+ content
particle size, but the particle size can be reduced by ball milling in the product CsxWO3 crystal, which will have important influence
treatment. As is shown in Fig. 3c, the maximum particle size before on the NIR shielding performance of CsxWO3. In addition, the O-1 s
ball milling and after ball milling is 373.1 nm and 106.4 nm, re­ XPS spectra in Fig. 4e-h can be fitted to two curves near 530.3 eV/
spectively. Films prepared from the dispersion of small-sized parti­ 531.5 eV, of which the peak at 531.5 eV is attributed to the -OH group
cles will have better optical properties. adsorbed on the crystal surface. Table 2 shows that the oxygen va­
Fig. 4 shows the XPS spectra of CsxWO3 nanoparticles synthe­ cancies (VO) content in the CsxWO3 nanoparticles can be sig­
sized with adding different halogen acids into the reaction solution. nificantly increased by adding halogen acids into the reaction
The W-4 f curve of CsxWO3 is fitted into two spin orbits of W-4 f7/2/ solution, and the VO content in the HCl-CsxWO3 nanoparticles syn­
W-4 f5/2. The peak of W6+ with high binding energy is located near thesized under HCl regulation is significantly higher than that in the
35.9 eV/38.1 eV, and the peak of W5+ with low binding energy is HF-CsxWO3 and HBr-CsxWO3 nanoparticles. This result indicates that
located near 34.6 eV/36.8 eV. According to the XPS analysis results adding appropriate halogen acid into the reaction solution is helpful
shown in Table 2, the introduction of HF and HCl into the reaction to increase the reducibility and promote the formation of VOs in
solution can increase the W5+/W6+ ratio in the CsxWO3 crystal. The CsxWO3 nanoparticles. It can be seen from Fig. 4i that the F-1 s peak
sample HCl-CsxWO3 synthesized under the control of HCl has the of HF-CsxWO3 is located near 684.4 eV, while the Cl-2p peak of HCl-
highest W5+/W6+ ratio (0.36, standard deviation STD = 0.0062), while CsxWO3 and the Br-3d peak of HBr-CsxWO3 can not be observed,
the W5+/W6+ ratio of sample HBr-CsxWO3 is the lowest (0.19, STD = indicating that the element F is more easily doped into CsxWO3
0.0082). This result indicates that the introduction of different particles.

Fig. 3. Particle size distribution curves of CsxWO3 nanoparticles synthesized under different halogen acids: (a-b) the length (LT) and diameter (DT) of CsxWO3 nanorods estimated
by TEM, (c) the particle size of HCl-CsxWO3 nanoparticles before and after ball milling treatment measured by DLS.

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D. Yang, J. Liu, F. Shi et al. Journal of Alloys and Compounds 942 (2023) 169119

Fig. 4. XPS spectra of CsxWO3 nanoparticles synthesized under different halogen acids.

Fig. 5 shows the schematic diagram of synthesis mechanism of entering the hexagonal tunnel enclosed by octahedrons [WO6] and
CsxWO3 nanoparticles under the regulation of halogen acid. As [WO5F] is small, so the F-doping with a small radius is more con­
shown in Fig. 5a, tartaric acid undergoes a decarboxylation reaction, ducive to improving the doping content of Cs+ in the hexagonal
producing reductive hydrogen ions (H+) and more reductive free tunnel.
hydrogen atoms ([H]). The reaction is as follows [25]： In addition, the amount of water introduced by halogen acid into
the reaction solution has an important effect on the growth of
C4H6O6 → C2H2O2 + 2[H] + 2 H+ + 2CO2↑ (3) CsxWO3 crystal. The water in the reaction solution comes from three
sources: ⅰ) the water introduced by halogen acid; ⅱ) the water pro­
Under the reduction reaction of [H] and halogen acid, the [WO6] duced by the reduction reaction of [WO6] octahedron with [H]; ⅲ)
octahedron gradually bridges and grows, and the introduction of the water generated by the esterification reaction of tartaric acid
halogen acid further enhances the reducibility, resulting in the for­ with ethanol. The esterification reaction is as follows:
mation of VOs in the product CsxWO3 crystal. When HF was added to
the reaction solution, F- substituting O2- could easily occur with
C4H6O6 + 2 C2H5OH → C8H14O6 + 2 H2O (4)
forming [WO5F] octahedrons due to the strong electronegativity of
F-. Furthermore, since the F- radius doped in CsxWO3 crystal is As mentioned above, the amount of water introduced into the
smaller than O2-, the influence of steric hindrance effect on Cs+ reaction solution by HF, HCl and HBr were 0.0409, 0.0833 and

Table 2
XPS analysis results of CsxWO3 nanoparticles synthesized under different halogen acids.

atomic % atomic ratio VO/W & STD W5+/W6+ & STD

Cs W O X Cs/W O/W X/W

0-CsxWO3 7.35 24.09 68.56 - 0.305 2.845 - 0.003 0.0022 0.23 0.0082
HF-CsxWO3 7.64 24.25 65.64 2.47 0.315 2.707 0.102 0.034 0.0016 0.29 0.0047
HCl-CsxWO3 7.75 26.02 65.99 0.24 0.298 2.536 0.009 0.306 0.0026 0.36 0.0062
HBr-CsxWO3 5.87 24.84 69.02 0.27 0.236 2.778 0.011 0.093 0.0028 0.19 0.0082

Note: X = F,Cl,Br

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D. Yang, J. Liu, F. Shi et al. Journal of Alloys and Compounds 942 (2023) 169119

Fig. 5. Schematic diagram of synthesis mechanism of CsxWO3 nanoparticles under the regulation of halogen acids: (a) growth process of hexagonal CsxWO3 nanoparticles under
the regulation of halogen acid; (b) effects of halogen acids on the morphology and microstructure of CsxWO3 nanorods.

0.1619 mol, respectively. In addition, the concentration of H+ in the Cs0.32WO3 in the product HBr-CsxWO3. Similar phenomenon of ex­
reaction solution is different when different halogen acids are added cess water inhibiting the growth of Cs0.32WO3 crystals was also
due to the different electronegativity of halogen ions, so the water found in the work of Guo et al. [36].
amount in the system can be regulated by adding different halogen As for the same halogen acid, the concentration and pH value of
acids. The possible reaction for synthesizing CsxWO3 with generating halogen acid will affect the size and morphology of the synthetic
water is as follows: particles. As is shown in Fig. 6a-b, the CsxWO3 particles synthesized
by adding concentrated HCl into the reaction solution exhibit
x m+n
WO3 + CS2SO4 + m[H] + nHX CSx WO2.845 + H2 smaller size and uniform morphology. By contrast, when adding the
2 2
x n diluted HCl that contains more water and may have a bigger pH
O+ SO2 + X2 value into the reaction solution, abnormal growth of particles occurs
2 2 (5)
and particle agglomeration is very serious. In addition, as shown in
According to the reaction Eq. (5), HF generates less water and HBr Fig. 6c-f, with the increase of HCl amount in the solution, the pH
generates more water into the reaction solution due to the fact that value of the solution decreases and the size of the product particles
the element F has bigger electronegativity than the element Br. In increases gradually. When the pH of the solution is − 0.22, the syn­
addition, introducing appropriate amount of water into the reaction thesized CsxWO3 crystals are rod-like particles with uniform size
solution is helpful for the dissolution and uniform distribution of distribution. Whereas, when the pH is − 0.28, the size distribution
Cs2SO4 in the reaction system, which is more conducive to the becomes uneven, and most of CsxWO3 crystals are irregular particles,
growth of CsxWO3 nanorods, and can be called "water accelerated which is due to the introduction of too much water into the pre­
growth effect". However, on the other hand, excess water will make cursor solution. Therefore, it can be concluded that the micro­
the stacking of [WO6] too fast, as a result, Cs+ can not enter the structure and morphology of CsxWO3 nanoparticles are mainly
hexagonal tunnel of CsxWO3 in time. Thus, excess water will result in affected by the water amount and reducibility in the solvothermal
less Cs+ doping rate, which is not conducive to the growth of reaction, and the regulation of halogen acids on the growth of
Cs0.32WO3 nanorods. In this study, when HBr was added to the re­ CsxWO3 nanoparticles in the reaction solution includes two factors
action solution, the introduction of excess water resulted in the of halogen ions and water. Overall, halogen acids play an important
formation of crystalline phase Cs0.20WO3 instead of Cs0.30WO3 or role in promoting the crystal growth of CsxWO3. In particular, the

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D. Yang, J. Liu, F. Shi et al. Journal of Alloys and Compounds 942 (2023) 169119

Fig. 6. TEM and HRTEM images of CsxWO3 nanoparticles synthesized with (a) concentrated HCl, (b) diluted HCl with HCl/water volume ratio 1:3, and different HCl amount with
HCl/W molar ratio being 0.28, 0.56, 1.12 and 1.68, respectively.

introduction of HCl with HCl/W molar ratio of 1.12 in the reaction and R=I960/I700) in the product HCl-CsxWO3 is the biggest, which
solution could endow the solution with an appropriate amount of indicates that the product HCl-CsxWO3 synthesized under the reg­
water and strong reducibility, which resulted in the formation of ulation of HCl has more W5+=O bonds. As is mentioned above, the
uniform rod-like Cs0.30WO3 nanoparticles. introduction of HCl into the reaction solution could result in largest
Furthermore, the content of VOs and W5+ in CsxWO3 crystals can Vos content in the product, while the pseudo Jahn-Teller effect
also be regulated by adding halogen acids in the reaction solution. caused by VOs could further promote the formation of W5+=O bond
On the one hand, halogen acid with stronger reducibility can pro­ [38,40,41].
duce more VOs and reduce more W6+. On the other hand, the elec­ In order to ensure that the comparison of different film samples
trons donated from Cs+ will usually be in the W-5d orbital is fair, all the film samples with the same thickness were prepared by
hybridized with O-2p to affect the W-O bond in the whole crystal. roller coating method using the same liquid, in which the con­
And when VO is generated, electrons are donated to the adjacent W6+ centration of the CsxWO3 particles was 0.005 mol/L. As shown in
to generate a group of W5+, which can only affect the nearby W-O
bond [22,37,38]. When W6+ is reduced, Cs+ will be attracted into the
hexagonal tunnel according to the law of electrons conservation. As
is shown in Fig. 5b, when HCl was added to the reaction solution, the
synthesized HCl-CsxWO3 exhibited the highest VOs content and W5+/
W6+ ratio (0.36, STD = 0.0062) due to the stronger reducibility of HCl.
Moreover, HCl could introduce the most appropriate amount of
water into the reaction solution, which is conducive to the uniform
distribution of Cs+ in the solution and thereby promoting the growth
of Cs0.30WO3 crystals.
The Raman spectra of the CsxWO3 nanoparticles synthesized
under the regulation of different halogen acids are shown in Fig. 7.
The peaks at 150–360 cm−1 and 500–850 cm−1 are attributed to the
bending mode and stretching mode of O-W-O, respectively, and the
peak at 850–980 cm−1 corresponds to the W]O stretching mode
[38]. It can be noticed that the intensity of total Raman spectra
shows a decreasing trend with the introduction of HF and HCl, which
is due to the increase of light absorption at 800–2500 nm caused by Fig. 7. (a) Raman spectra of CsxWO3 nanoparticles synthesized under different ha­
electrons provided by VOs and Cs+ [38,39]. Furthermore, it can be logen acids, the illustration is the intensity ratios of 960 cm−1 peaks to 700 and
observed that the peak intensity ratio of W]O to O-W-O (R=I960/I760 760 cm−1 peaks.

7
D. Yang, J. Liu, F. Shi et al. Journal of Alloys and Compounds 942 (2023) 169119

Fig. 8. (a)-(d) The SEM section images of CsxWO3-PVA films; I Spectral transmittance curves of CsxWO3-PVA synthesized under different halogen acids; (f) Schematic diagram of
the small polaron effect; (g) Schematic diagram of LSPR effect; (h) Orbital hybridization of [WO6] and electronic transition of small polaron; (i) The influence mechanism of the
W5+=O on the small polaron effect.

Fig. 8a-d, the thickness of CsxWO3-PVA films is in the range of The electrons trapped by VOs and donated by Cs+ undergo an electronic
76.85–82.17 µm. The thickness of the films is uniform and within the transition of the small polaron between the 5d orbitals of W6+ and W5+.
normal range. Fig. 8e shows the spectral transmittance of CsxWO3- Finally, as shown in Fig. 8i, because of the existence of VOs in the
PVA composite films prepared from the dispersion of particles which product HCl-CsxWO3, a large number of unsaturated bonds of W5+=O
was synthesized under the regulation of different halogen acids. It are formed. In this way, when the electrons on the W-5d orbitals are
can be seen that the HCl-CsxWO3-PVA film has the best NIR shielding stimulated, they need to absorb more energy to escape from the po­
performance, and when the visible light transmittance at 560 nm is tential well generated by the double bonds in the hybrid orbitals, and
71.8%, the NIR shielding rate at 1500 nm can attain to as high as the energy consumption of the electronic transition of the small po­
98.2%. Studies have shown that the small polaron and LSPR effect are laron increases, which eventually leads to the enhancement of the
the main reasons for the excellent NIR shielding ability of CsxWO3. near-infrared absorption performance of HCl-CsxWO3.
Fig. 8 f and g show the schematic diagram of NIR shielding me­ Fig. 9a shows the photocurrent test results of CsxWO3-PVA films
chanism of CsxWO3 particles. The small polaron hopping can absorb synthesized under the regulation of different halogen acids. Under
the NIR light at 730–1100 nm through the electrons donated by Cs+ the irradiation of a xenon lamp, HCl-CsxWO3 generates the largest
in the CsxWO3 lattice, and converts the photon energy into phonon photocurrent after being excited by light, which indicates that more
energy, while the LSPR effect can affect the NIR absorption in the electrons in the crystal are excited to the conduction band, gen­
range of 1100–2500 nm [28,42]. erating more electron-hole pairs and higher carrier concentration. In
Fig. 8h shows a schematic diagram of orbital hybridization of [WO6] addition, the existence of a large number of VOs can introduce a new
and electronic transition of small polaron. In the process of forming defect energy level into the band gap, and make the nearby electrons
[WO6] octahedron, d2sp3 hybridization occurs after the outer electron delocalize [43], which can accelerate the separation of carriers in the
orbitals of the central atom W are stimulated, forming six hybrid or­ crystal and promote the NIR absorption due to the LSPR effect.
bitals, these hybrid orbitals overlap with O-2p orbitals to produce six Therefore, HCl-CsxWO3 exhibits the most excellent NIR absorption
electron pairs. But then, under the influence of the pseudo Jahn-Teller and shielding performance in the range of 1100–2500 nm.
effect induced by VOs [38], W deviates from the center of [WO6] oc­ The transparent and thermal Insulation performance of CsxWO3-
tahedron, forming a short W5+=O bond that shares two electron pairs. PVA films can be evaluated from the UV-Vis-NIR spectral

8
D. Yang, J. Liu, F. Shi et al. Journal of Alloys and Compounds 942 (2023) 169119

Fig. 9. (a) Photocurrent test results of CsxWO3-PVA synthesized under different halogen acids; (b) Haze and transparent thermal insulation index (THI) of CsxWO3-PVA films; (c)
Comparison of NIR shielding performance of HCl-Cs0.30WO3-PVA film in this work with the reported data in recent years: ①work of Wu et al. [14], ②work of Zhang et al. [44],
③work of Asakura et al. [45], ④work of Lu et al. [46], ⑤⑥⑦our previous work [27,28,47], ⑧work of Xie et al. [48], ⑨data of CsxWO3 purchased from the market; (d) Comparative
photos of HCl-CsxWO3-PVA and HBr-CsxWO3-PVA composite film samples coated on glass slides.

transmittance curves in Fig. 8e, and the transparent heat insulation refractive index R at the interface between CsxWO3 and PVA can be
(THI) index can be calculated according to the formula (6). The larger calculated based on the Fresnel reflection coefficient [50]:
the THI index is, the better the transparent and thermal insulation
performance of the film is. (nc np)2
R=
(nc + np)2 (10)
THI = TVis/TSol (6)
Where nc and np are the refractive indexes of CsxWO3 and PVA, re­
Where THI represents the transparent heat insulation index, Tsol spectively, np = 1.52, and nc is affected by crystal size and mor­
is the integrated spectral transmittance of a window weighted with phology. The introduction of HCl into the reaction solution leads to
the normalized solar energy distribution spectrum (380–2500 nm). the formation of uniform CsxWO3 nanorods thereby exhibiting
TVis and TNIR are the transmittance in the visible region higher visible light transmittance and the smallest haze of the film
(380–780 nm) and NIR region (780–2500 nm) calculated in a similar with only 0.3%. Fig. 9c shows the visible light transmittance (TVis)
way. Different figure-of-merit (FOM) values can be calculated ac­ and NIR transmittance (TNIR) of the HCl-CsxWO3-PVA composite film,
cording to the following equations [17,18,49]: in which the red dots correspond to the spectral transmittance of the
2500 films with different thicknesses, and the black curve is a fitting curve
380
T( )S( )d
TSol (%) = representing for the Tvis-TNIR relationship and used for evaluating the
2500
380
S( )d (7) NIR shielding performance of the HCl-CsxWO3-PVA film. For con­
venient comparison, the statistics for visible light transmittance
780
380
T( )S( )V( )d (TVis) and near-infrared transmittance (TNIR) were collected at wa­
TVis (%) = 780 velengths of 550 nm and 1100 nm, respectively. As shown in Fig. 9c,
S( )V( )d (8)
380 the (TVis, TNIR) coordinate points of the HCl-CsxWO3-PVA film syn­
2500
thesized under the regulation of HCl in this work are lower than the
780
T( )S( )d previously reported research results, indicating that the prepared
TNIR (%) = 2500
S( )d HCl-CsxWO3-PVA composite film has excellent NIR shielding per­
780 (9)
formance and visible light transmittance. In other word, the as-
where S(λ) is the weighting function of the solar spectrum for direct synthesized HCl-CsxWO3 particles exhibit more excellent trans­
radiation after passing through 1.5 times the perpendicular atmo­ parent and thermal insulation performance.
spheric thickness (AM 1.5 solar spectrum), and V(λ) is the weighting The thermal stability and thermal insulation performance of
function of the human eye spectral response. CsxWO3-PVA composite films prepared under the regulation of dif­
Fig. 9b shows the test results of haze and the transparent heat ferent halogen acids were tested. As shown in Fig. 10a, the experi­
insulation index of CsxWO3-PVA film with particles synthesized mental device for the cyclic thermal insulation test was a self-made
under regulation of different halogen acids. It can be noticed that the thermal insulation box (0.30 m × 0.30 m×0.45 m), which was con­
HCl-CsxWO3-PVA composite film exhibits the largest THI and the tinuously irradiated with an infrared lamp for 1 h at a distance of
smallest haze value. The haze of the film is affected by the grain size 0.30 m from the thermal insulation box. The light intensity at the
and morphology. When the grain size is smaller than the wavelength film was measured by an optical power meter of 0.5082 W. To si­
of visible light, the transmittance of visible light is better. And the mulate the actual application scene, the transmittance of each film

9
D. Yang, J. Liu, F. Shi et al. Journal of Alloys and Compounds 942 (2023) 169119

Fig. 10. (a) Schematic diagram of infrared lamp irradiation test using self-made thermal insulation box (0.30 m × 0.30 m×0.45 m); (b)-(e) Temperature-rising and cooling curves of
the CsxWO3-PVA film surface and the inside of the thermal insulation box under the irradiation of an infrared lamp, the illustrations are the infrared thermal imaging images of
the films after being irradiated with the infrared lamp for 60 min; (f) The peaking temperature of the HCl-CsxWO3-PVA film surface and the inside of the box under 100 cycles of
infrared lamp irradiation; (g) The temperature-rising curves of the HCl-CsxWO3-PVA film surface and the inside of the box under 100 cycles of infrared lamp irradiation; (h)
Comparison of spectral transmittance of HCl-CsxWO3-PVA composite film before and after 100 cycles of infrared lamp irradiation.

sample at 580 nm was controlled to be 70–80%. Fig. 10b-e show the CsxWO3-PVA composite film before and after 100 cycles of infrared
temperature curves of the film surface and the inside of the thermal lamp irradiation. The fact that the transmittance remains unchanged
insulation box under the irradiation of an infrared lamp. It can be after 100 cycles of infrared lamp irradiation shows that the NIR
seen that all the CsxWO3 particles synthesized under the regulation shielding and transparent heat insulation performance of the
of different halogen acid exhibit better thermal insulation perfor­ CsxWO3-PVA film will not decline under the irradiation of infrared
mance than that of without regulation by halogen acid. Especially, lamp. These results indicate that the composite film has excellent
the sample HCl-CsxWO3 synthesized under the regulation of HCl thermal stability and cycle irradiation stability. Combining with the
exhibits the best photothermal conversion and thermal insulation results of XPS and Raman spectra, it can be concluded that the high
performance. After being irradiated by the infrared lamp for 60 min, VOs and W5+=O contents in HCl-CsxWO3 nanoparticles synthesized
the surface temperature of the HCl-CsxWO3-PVA composite film is under the regulation of HCl are the key factors to optimize its NIR
the highest, reaching 74.3 °C (STD = 0.3555), while the internal air shielding, photothermal conversion and transparent thermal in­
temperature of the box is the lowest, and the temperature difference sulation performance. Due to the low VOs content of HF-CsxWO3 and
between the film surface and the inside of the box is the largest (ΔT the corrosivity of HF, the NIR shielding and transparent thermal
= 28.3 °C, STD = 0.5444). insulation performance of HF-CsxWO3 are lower than those of HCl-
Fig. 10f and g show the peaking temperature and the tempera­ CsxWO3.
ture-rising curves of the HCl-CsxWO3-PVA film surface and the in­ In order to further verify the stability of CsxWO3 nanoparticles,
side of the thermal insulation box under 100 cycles of infrared lamp the antioxidant test of the samples was carried out. The CsxWO3-
irradiation. The test results show that the peaking temperature Heat nanoparticles were prepared by heat-treatment under air at­
variation range of the film surface is 73.8–74.9 °C (STD = 0.3555), and mosphere at 400 °C for 30 min. As shown in Fig. 11a, HF-CsxWO3 and
the internal air peaking temperature range is 45.9–46.9 °C (STD = HCl-CsxWO3 particles after heat-treatment were still blue, while 0-
0.3194). Fig. 10h shows the spectral transmittance of the HCl- CsxWO3 and HBr-CsxWO3 are blue-gray and yellow respectively.

10
D. Yang, J. Liu, F. Shi et al. Journal of Alloys and Compounds 942 (2023) 169119

Fig. 11. (a) The photo of CsxWO3 nanoparticles before and after heat-treatment; (b) Spectral transmittance curves of CsxWO3-Heat-PVA; (c) XRD spectra of CsxWO3 nanoparticles
after heat-treatment.

Fig. 11c shows that the main crystalline phases of all samples after In order to further simulate the actual application scene, the
heat-treatment were transformed into Cs0.20WO3 thermal insulation performance of the HCl-CsxWO3-PVA composite
(ICDD97–010–0192), and the impurity crystalline phase of film (spectral transmittance at 580 nm being 80%) was tested by
Cs0.287W0.95O3 (ICDD97–007–2619) appeared. The near-infrared using a larger thermal insulation box (0.55 m × 0.55 m×0.65 m)
shielding performance of HCl-CsxWO3-Heat was slightly lower than under natural sunlight irradiation for a longer time. The internal air
that before heat-treatment, while the near-infrared shielding per­ temperature varying curves of the box with time was recorded. In
formance of other samples was greatly reduced or even disappeared order to simulate the actual indoor environment in summer, the
(Fig. 11b). The results show that the CsxWO3 nanoparticles synthe­ tests were conducted at 121.53°E and 38.97°N, on sunny and rainy
sized under the regulation of HCl have excellent chemical stability. days, and with and without ventilation, respectively. Fig. 12a-b show

Fig. 12. The actual test results of the thermal insulation of the HCl-CsxWO3-PVA composite film under solar irradiation: the internal air temperature curves of the thermal
insulation box equipped with HCl-CsxWO3-PVA composite film and blank glass windows under different weather conditions from 4:00 am to 8:00 pm (a-b) and in a week (c), the
illustration in (a) is the self-made thermal insulation box (0.55 m × 0.55 m×0.65 m).

11
D. Yang, J. Liu, F. Shi et al. Journal of Alloys and Compounds 942 (2023) 169119

the test results of 16 h from sunrise to sunset. Compared with the Declaration of Competing Interest
blank glass, the temperature in the box of glass windows coated with
HCl-CsxWO3-PVA composite film decreased by 4.1–4.7 °C without The authors declare that they have no known competing fi­
ventilation. Under the condition of ventilation, the temperature nancial interests or personal relationships that could have appeared
difference in the box with the composite film glass window from to influence the work reported in this paper.
that of the blank glass window decreased, but the internal air
temperature of the box with the composite film was still sig­ Acknowledgment
nificantly lower than that of the box with the blank glass window.
Fig. 12c shows the test results of the air temperature variation in the This work was financially supported by Basic Scientific Research
box when it was recorded continuously for 7 days. The maximum Project of Education Department of Liaoning Province
temperature difference between the HCl-CsxWO3-PVA composite (LJKMZ20220887), the National Natural Science Foundation of China
film and the blank glass can reach 6.9 °C, indicating that the com­ (51778098) and Dalian Science & Technology Innovation Fund
posite film can effectively regulate the indoor temperature under (2018J12SN066).
different weather conditions. The hotter the weather is, the more
prominent the thermal insulation performance of the composite film References
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