Activated metal Bi and La modified SAPO-34

molecular sieve and its photocatalytic degradation

of formaldehyde in aqueous solution
Wan-ping Chen
Lanzhou University of Technology
Run-quan Wang
Lanzhou University of Technology
Yue-rong Zhang
Lanzhou University of Technology
Kai Song
Lanzhou University of Technology
Xin Li
Lanzhou University of Technology
Yu-bing Liu
Lanzhou University of Technology
Yuan Wei
Lanzhou University of Technology
Rong-hui Liu
Lanzhou University of Technology
Guang-hong Zhao
Lanzhou University of Technology
Gao-feng shi (  gaofengshi_lzh@163.com )
Lanzhou University of Technology

Research Article

Keywords: Molecular Sieve, SAPO-34, Photocatalyst, Formaldehyde

Posted Date: June 7th, 2023

DOI: https://doi.org/10.21203/rs.3.rs-3021872/v1

License:   This work is licensed under a Creative Commons Attribution 4.0 International License.
Read Full License

Page 1/15
Abstract
As a new type of photocatalyst, molecular sieve photocatalysts have shown great promise in the
degradation of organic matter in water bodies. In this paper, a new type of molecular sieve photocatalyst
was successfully prepared by introducing Bi and La elements into the hydrothermal synthesis of SAPO-
34 molecular sieve for the purpose of regulating the molecular sieve backbone. The introduction of active
metals into the skeleton of molecular sieve can enrich the L acid sites on its surface, and at the same
time, the introduction of active metals can accelerate the transfer rate of photogenerated carriers, which
can also suppress the compounding rate of electron holes. It showed excellent performance in the
photocatalytic degradation of formaldehyde, and the degradation rate constant k could reach 0.3222
min− 1 within 6 h. This study provides a new method for the preparation of molecular sieve
photocatalysts and a new idea for the construction of bifunctional photocatalysts.

1. Introduction
Zeolites have good prospects for development as carriers, catalysts and traps due to their special
chemical properties, unique pore structure and good stability. The SAPO-34 molecular sieve has a large
specific surface area [1, 2], well-developed pores, and abundant active sites [3], and has been widely used
in catalytic oxidation [4–6].In recent years, in order to overcome the problem that SAPO-34 molecular
sieve is easy to accumulate carbon in the catalytic process due to the complex pore structure [7–10], its
pore structure can be changed by introducing other elements. For example, the precious metal Bi is
introduced into the skeleton structure of SAPO-34 [11–13], so that it participates in the composition of the
pore structure of SAPO-34 molecular sieve [14–16]. Meanwhile, Bi element itself has diverse valence
states and surface plasmon resonance (SPR) effect, and this doping method makes the prepared
molecular sieve possess certain photoresponse and accelerate the charge mobility in photocatalytic
reaction, thus improving the efficiency of photocatalyst [17–19]. Therefore, the idea of introducing other
elements into the skeleton structure of molecular sieves to change their original morphology and catalytic
properties and apply them to the emerging field of photocatalysis is feasible.

Volatile organic compounds (VOCs) are a class of atmospheric pollutants that are difficult to remove and
have a wide range of sources that can easily cause damage to the environment and humans [20–22].
Among them, formaldehyde (HCHO) is a major source causing urban as well as indoor air pollution, and
researchers have found that formaldehyde in the air can be effectively treated by low-temperature plasma
biological treatment, adsorption, catalytic oxidation, and recycling technologies [23–25]. With the
continuous development of photocatalytic oxidation technology [26–30], it has been found that
formaldehyde can be removed by photocatalytic oxidation process [31–34], which has mild reaction
conditions, is efficient and economical and non-toxic without bringing secondary environmental pollution
[35–37]. However, the active site, adsorption amount, service life and other limitations of the catalyst in
the photocatalytic reaction also affect the catalytic effect, so it is valuable to find a new catalyst to be
applied for formaldehyde removal.

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2. Experimental part
2.1 Chemicals
The reagents used in the experiment are: Bismuth nitrate pentahydrate(65%-68%,wt), nitric acid,
phosphoric acid, aluminum oxide, silicone sol, triethylamine, lanthanum nitrate, formaldehyde aqueous
solution(36%-38%,wt), potassium bromate, p-benzoquinone (chemically pure, ≥ 99.9%), ammonium
oxalate, diphenylamine, acetylacetone, glacial acetic acid, ammonium acetate, all the above drugs are
analytically pure.

2.2 Photocatalyst synthesis

2.2.1 Preparation of SAPO-34 molecular sieve
SAPO-34 molecular sieve was prepared by using silica sol as the silica source and Al2O3 as the aluminum
source: an appropriate amount of deionized water was accurately measured and placed in a beaker, to
which a quantitative amount of H3PO4 was added, stirred to make a uniform mixture, and then an
appropriate amount of Al2O3 was added, and continued to stir for 90 min, and a quantitative amount of
silica sol and triethylamine (TEA) was added and stirred for 48h. Put the above crystallization solution in
the hydrothermal synthesis kettle at 200℃ hydrothermal synthesis for 48h, to get SAPO-34 molecular
sieve raw powder, using deionized water and anhydrous ethanol centrifugal detergent three times, collect
the solid after detergent, placed in the oven at 100℃ dry 10 h, after grinding and placed in the muffle
furnace at high temperature calcination for a certain period of time to remove the template agent, SAPO-
34 molecular sieve crystals can be obtained.

2.2.2 Preparation of Bi@SAPO-34 molecular sieve

Liquid A: accurately measure an appropriate amount of deionized water in a beaker, add a quantitative
amount of H3PO4 to it, stir to make it evenly mixed, add an appropriate amount of Al2O3, and continue to
stir for 90 min; Liquid B: add a quantitative amount of Bi(NO3)3•H2O to an appropriate amount of
deionized water, stir for 30 min to make it evenly dispersed [38]; slowly add Liquid B to Liquid A, stir for 30
min to make it evenly mixed, add a quantitative amount of silica sol and triethylamine (TEA), and stir for
48 h. Put in the hydrothermal synthesis kettle at 200℃ hydrothermal synthesis for 48 h, to get Bi@SAPO-
34 molecular sieve powder, using deionized water and anhydrous ethanol centrifugal detergent three
times, collect the solid after detergent, put in the oven at 100℃ drying 10 h, after grinding and put in the
muffle furnace at high temperature calcination for a certain period of time to remove the template agent,
Bi@SAPO-34 molecular sieve crystals can be obtained.
2.2.3 Preparation of Bi/La@SAPO-34 molecular sieves
Liquid A: accurately measure an appropriate amount of deionized water in a beaker, add a quantitative
amount of H3PO4 to it, stir to make it evenly mixed, add an appropriate amount of Al2O3, and continue to
stir for 90 min; Liquid B: add a quantitative amount of Bi(NO3)3•H2O and LaNO3•12H2O to an appropriate
Page 3/15
amount of deionized water in a molar ratio of 2:1, and stir for 30 min to make it evenly dispersed; Add
liquid B slowly to liquid A, stir for 30 min to make it mixed well, add quantitative silica sol and
triethylamine (TEA), and stir for 48 h. Put the above crystallization solution in the hydrothermal synthesis
kettle at 200℃ hydrothermal synthesis for 48 h, to get Bi/La@SAPO-34 molecular sieve raw powder,
using deionized water and anhydrous ethanol centrifugal detergent three times, collect the solid after
detergent, placed in the oven at 100℃ dry 10 h, after grinding and placed in the muffle furnace at high
temperature calcination for a certain period of time to remove the template agent, Bi/La@SAPO-34
molecular sieve crystals can be obtained.

2.3 Material characterization

The crystal phase structure of the catalyst was tested by X-ray diffraction (XRD, UltimaIV, Japan, Cu Kα
radiation (Kα = 0.15406 nm), 2θ was measured in the range of 5◦-90◦,a while the scanning speed was 20
◦/min);The atomic valence of the catalyst was analyzed by x-ray photoelectron spectroscopy (XPS,
Thermo Scientific K-Alpha, China) Al Kα rays ((Kα = 1486.6 eV) with a flux energy of 150 eV and a step
size of 1 eV; The micromorphology was characterized by scanning electron microscopy (SEM,: TESCAN
MIRA LMS, Czech Republic) and transmission electron microscopy (TEM, Taols F200X, Czech Republic);
Absorption spectra were measured using an ultraviolet-visible spectrophotometer (UV-visDRS, UV-3600i
Plus, Japan); The absorption-desorption isotherm curves of N2 were determined using a surface area and
pore analyzer (BET, Mc2460, USA); A UV spectrophotometer (UV-Vis, GENESYS 10S, USA) was used for
the quantitative analysis of photocatalytic degradation products.

2.4 Electrochemical testing

The EIS of Bi-based catalysts was determined using a three-electrode system with a Pt sheet as the
counter electrode, a saturated glycury electrode as the reference electrode, a catalyst/FTO as the working
electrode, and an aqueous Na2SO4 solution as the electrolyte under visible light and 0.7 V vs. Ag/AgCl
conditions.

2.5 Catalytic activity evaluation.

The catalyst activity was studied using photocatalytic formaldehyde aqueous solution as a probe
reaction. The photocatalytic degradation experiments were performed under a mercury lamp, and an
aqueous formaldehyde solution of 0.5 mg/mL was prepared as the reaction solution with a catalyst
dosage of 5.00 g/L. During the degradation process, 0.50 mL of the reaction solution sample was
removed at predetermined time intervals. It was centrifuged and transferred to a liquid sampling bottle,
and the formaldehyde in the reaction solution was quantified using the acetylacetone UV
spectrophotometer method. The specific operation was as follows: 0.24 mL of the filtered reaction
solution was accurately pipetted, 1.00 ml of acetylacetone buffer (0.25%, wt) was added to it, the volume
was fixed to 10.00 ml with deionized water, heated in a water bath at 91℃ for 6 min and then removed,
and the UV absorbance of the reaction solution was measured after it cooled down to room temperature,
and the content of formaldehyde in the reaction solution was determined based on its UV absorption
peak at 413 nm [39].
Page 4/15
3. Results and discussion
3.1 Material characterization
Figure 1 shows the XRD spectra of SAPO-34, Bi0.9SAPO-34 and Bi0.6La0.3SAPO-34 molecular sieve
catalysts, and comparing the obtained spectra with the standard card information, it was found that the
prepared SAPO-34 molecular sieve showed its characteristic diffraction peaks, and its peak shape was
sharp and obvious. SAPO-34 molecular sieve appears as (101), (003), (211), (214), and (410) facets at 2θ
of 9.51°, 17.87°, 20.54°, 31.14°, and 34.47°. After the introduction of Bi and La metals into the skeleton of
molecular sieve, the XRD patterns show that the diffraction peaks at 20.54°, 31.14° and 34.47° are sharp
and obvious, and the appearance of the above-mentioned crystalline planes indicates that the
introduction of Bi and La elements does not have a large impact on the skeleton structure of SAPO-34
molecular sieve, in which the (211) plane at 2θ of 20.54° decreases in intensity with the introduction of In
the XRD pattern of the modified molecular sieve, new diffraction peaks can be found, and the appearance
of new crystalline surfaces indicates that the crystalline surfaces of SAPO-34 molecular sieve are
enriched with Bi and La elements, which enhance the B acid active sites on the surface of the molecular
sieve and provide more active sites for the catalytic reaction.

Figure 2 SEM of SAPO-34 molecular sieve and its modification. the microscopic morphology of SAPO-34
molecular sieve is shown in Figure 2a and 2b. the prepared samples are cubic crystals with a particle size
of about 1.5 µm, the surface of which is smooth and flat, and some micropores and mesopores can be
found distributed on the surface of SAPO-34 crystals, which provide abundant specific surface area. the
above SEM results show that The above SEM results show that SAPO-34 molecular sieve has a relatively
regular single crystal structure. As shown in 2c and 2d, the SEM images of SAPO-34 molecular sieve after
Bi modification, it can be found that the introduction of Bi element has a greater impact on the
morphology of SAPO-34 molecular sieve, which changes the structure from cubic to trigonal, and clusters
appear on its surface, that is, it indicates that the introduction of Bi element increases the active sites on
the surface of SAPO-34 molecular sieve. The enrichment of Bi and La elements on the surface of SAPO-
34 molecular sieve significantly changed the microscopic morphology of SAPO-34 molecular sieve and
enriched its active sites, which improved its photochemical performance.

Figure 3 shows the XPS spectra of the three catalysts. It can be seen that the energy spectrum peaks of
Bi, La, and the constituent elements of SAPO-34 molecular sieve appear in the modified composite
molecular sieve catalysts. Figures 3a-h show the fine spectra of Al2p, Bi4f, La3d, C1s, O1s, P2p with
Si3n& La4d, respectively. Figure 3a shows the fine spectra of 2p orbitals of Al elements. After the
introduction of Bi and La elements in SAPO-34 molecular sieve, the intensity of the energy spectrum
peaks of 3p orbitals of Al elements showed a significant decrease, indicating that some Al elements in
the molecular sieve backbone were successfully replaced by the introduced Bi and La elements, which
further enhanced the L acid sites in the molecular sieve. Figure 3b shows the fine spectrum of the 4f
orbital of Bi element, in which the energy spectrum peaks of 4f7/2 and 4f5/2 orbitals of Bi element appear.

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After the introduction of La element, it can be found that the energy spectrum peaks of Bi element have
been shifted to a certain extent, indicating that the addition of La element has a certain influence on the
structure of the molecular sieve. The characteristic energy spectral peaks of La-O and La-P bonds are
found at 838.8 eV and 858.9 eV, respectively; Fig. 3f shows the fine spectra of the 3n orbital of Si element
and the 4d orbital of La element, and the energy spectral peak of the 4d5/2 orbital of La element appears
at 105.7 eV. Figure 3d shows the fine spectra of O1s in the molecular sieve modified with Bi and La
elements, and it can be found that the characteristic energy spectrum peaks of Bi-O and La-O bonds
appear at 530.8 eV and 531.1 eV, respectively. The appearance of Bi-O and La-O bonds indicates that Bi
and La elements successfully enter into the skeleton of the molecular sieve and are successfully
connected with O elements, respectively. The above results indicate that Bi and La elements have
successfully entered the skeleton of SAPO-34 molecular sieve by hydrothermal crystallization.

Figure 4a and 4b show the N2 adsorption-resolution curves and pore size distribution of SAPO-34
molecular sieve and Bi and La modified SAPO-34 molecular sieve catalysts, respectively. It is clear that all
three samples are standard type I isothermal curves. SAPO-34 has a large specific surface area of 946.47
cm2g and is rich in mesopores (2–8 nm); after the modification of Bi and La elements, the specific
surface area of the molecular sieve shows a significant decrease, where the specific surface area of the
molecular sieve modified with Bi elements is 17.11 cm2g and the specific surface area of the molecular
sieve modified with Bi The reduction of specific surface area is related to the clustering of metal particles
on the surface of molecular sieve, and the specific surface area of molecular sieve modified by Bi element
and La element can be seen that La element can play a role in improving the specific surface area of
molecular sieve. The figure shows the pore size distribution of the three molecular sieve catalysts, from
the figure, it can be seen that SAPO-34 molecular sieve contains abundant mesopores, and after
modification with Bi element, it can be found that its pore size has increased, but its pore content is
obviously reduced, and the modification of Bi element and La element also makes the pore size of SAPO-
34 molecular sieve increase, but its pore capacity is obviously higher than that of the molecular sieve
modified with Bi element, that is The introduction of La element improves the specific surface area of
molecular sieve and makes the pore structure of molecular sieve more reasonable at the same time.

Figures 5a and 5b show the degradation of formaldehyde aqueous solution by the three molecular sieve
catalysts under mercury lamp atmosphere. From Fig. 5a, it can be seen that the molecular sieves had
poor adsorption performance on formaldehyde under dark conditions. the photocatalytic activity of
SAPO-34 molecular sieve itself was low, and the concentration of formaldehyde did not change
significantly during 6 h of light exposure. the catalysts modified with Bi element produced a certain
degradation effect on aqueous formaldehyde solution under mercury lamp conditions, and the activities
of the molecular sieve catalysts were all enhanced to a certain extent for After the introduction of Bi and
La elements, it was found that the resulting catalysts significantly accelerated the degradation rate of
formaldehyde, reaching 77.61% at 6h. Compared with the single Bi element modification, the introduction
of Bi and La elements in the molecular sieve skeleton can substantially increase the electron-hole transfer
rate, and the O element in the skeleton can play a role as a bridge in the electron transfer process, which

Page 6/15
can substantially increase the electron transfer rate and also inhibit the electron-hole complex. The
degradation of formaldehyde solution by the composite molecular sieve catalysts was found to be in
accordance with the first-order kinetic model, and as expected, the molecular sieve modified with Bi and
La elements possessed the fastest degradation rate with a k value of 0.3222 min− 1, which was more than
three times more efficient than that of 0.0972 min− 1 modified with Bi elements.

The reflectance and absorption properties of the catalysts were tested by ultraviolet-visible diffuse
reflectance spectroscopy (UV Vis DRS), through Figs. 6a and 6b, SAPO-34 molecular sieve basically does
not have a photoresponse range, and after the introduction of Bi metal in its backbone, the resulting
catalyst exhibits a long absorption edge in the UV range. With the introduction of Bi and La metals, it can
be found that the photoabsorption edge of the resulting catalyst is significantly broadened, i.e., the active
metal modification can make the SAPO-34 molecular sieve have a strong photoabsorption ability in the
UV light

Figure 6c shows the fluorescence spectral region of the five catalysts. at the excitation wavelength of 240
nm, it can be found that different catalysts show strong fluorescence absorption peaks at 405 nm. the
higher fluorescence intensity of SAPO-34, that is, its special octet ring structure accelerates the rate of
electron-hole complexation, which makes it have poor photocatalytic performance; after the modification
of SAPO-34 molecular sieve is modified, it can be found that the introduction of metal reduces the
fluorescence intensity substantially and the photochemical performance is enhanced significantly.
Figure 6d shows the impedance spectra of SAPO-34 molecular sieve catalysts modified with Bi and La
metals, and the charge transfer resistance was investigated by measuring the electrochemical impedance
spectra of the catalysts, and the radius of the arc reflects the charge transfer resistance between the
semiconductor and electrolyte interfaces, and it can be seen that the catalysts obtained after the
modification of Bi and La metals possess the smallest arc radius, namely, they have the smallest charge
transfer resistance in the process of photocatalytic oxidation. The results show that the catalysts
modified with Bi and La metals have the smallest arc radius, that is, they have the smallest charge
transfer resistance during photocatalytic oxidation. These results indicate that the new heterojunction
formed during the modification process plays an important role in the extension of the catalyst
photogenerated carrier lifetime and the acceleration of the electron transfer rate.

HCHO +·OH→·CHO + H2O

·CHO+·OH→HCOOH

HCOOH + H+→ HCOO

HCOO− +h+→ H++·CO2−

·CO2−h CO2 + H2O

+
[∙OH] [O]
2 2
−−−−−−−−−−→

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After the contact between the formaldehyde molecule and the catalyst, then under the irradiation of the
light source [40], the modified molecular sieve surface undergoes electron leap, generating electron-hole
pairs [41], and some of the electrons and holes act directly on the formaldehyde molecule to oxidatively
reduce H2O as well as O2 to •OH and •O2− [42]; the HCHO molecule is oxidized to HCOOH under the action
of active radicals. the HCOOH molecule produced after losing H+ generates HCOO− generates H+ and
•CO2− in the presence of h+, and H+ and •CO2− generate our end products H2O and CO2 in the presence of
OH- and •O2− [43, 44].As shown in Fig. 7, the HOMO and LUMO energy levels of SAPO-34 molecular sieve
are extremely close to each other, and after the introduction of Bi metal, its band gap value shows a
substantial increase from 0.36 eV to 4.255 eV, the increase of band gap value makes the compounding
rate of electron-hole decrease dramatically, but the wider band gap value makes the electron leap more
difficult, then, after the introduction of Bi and La metals, it can be found that there is a significant
decrease of band gap value to 4.236 eV, the decrease of band gap value makes the compounding rate of
electron-hole be suppressed. The photogenerated electrons generated by the molecular sieve catalyst
under the light condition enter the HOMO energy level through O-Bi-O and O-La-O, and the presence of O-
Bi-O and O-La-O effectively reduces the compounding rate of electron-hole pairs, meanwhile, the
introduction of metals changes the distribution of B- acids and L-acids of molecular sieve, which makes
B- and L-acids contribute to the degradation process and accelerate the The degradation rate of
formaldehyde was accelerated.

4. Conclusion
In summary, a new Bi0.9La0.6SAPO-34 composite molecular sieve photocatalyst was prepared by in situ
modification of SAPO-34 molecular sieve, and the photochemical properties of the prepared catalyst were
systematically investigated by photodegradation of formaldehyde. Under the light conditions, the
Bi0.9La0.6SAPO-34 catalyst enhanced the degradation rate of formaldehyde with a k-value of 0.3222 min−
1
during the 6h degradation process, which was more than 3 times more efficient than the 0.0972 min− 1
modified by Bi elements. The mechanism of the composite molecular sieve photocatalyst for the
degradation of formaldehyde was investigated based on the HOMO and LUMO energy levels of SAPO-34.
The formation of O-Bi-O and O-La-O can transfer electrons to the LUMO energy level of SAPO-34
molecular sieve, which makes the rate of electron-hole complexation suppressed, while the introduction
of Bi and La metals makes the migration rate of electrons accelerated. The change of active sites of B
and L acids in the molecular sieve led to the further degradation of formic acid, an intermediate product
produced during the degradation of formaldehyde, to generate the final products H2O and CO2. this work
is an important guideline for the modification of molecular sieves and provides a new idea for the
development of new bifunctional photocatalysts.

Declarations
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Data availability
All data generated or analyzed during this study are included in this manuscript.

Competing interests
The authors declare that they have no known competing financial interests or personal relationships that
could have appeared to influence the work reported in this paper.

Authors' contributions
Wan-ping Chen contributed to Conceptualization, Data Curation, Formal Analysis, Methodology,
Visualization, Writing-Original Draft, and Writing-Review & Editing. Run-quan Wang contributed to Formal
analysis and Data Curation. Yue-rong Zhang contributed to Visualization and Formal analysis. Kai
Song contributed to Methodology and Formal analysis. Xin Li contributed to the Investigation. Yu-bing Liu
contributed to the Investigation. Yuan Wei contributed to Supervision.Rong-hui Liu Writing-Original Draft.
Guang-hong Zhao Writing-Original Draft. Gao-feng Shi contributed to Conceptualization, Methodology,
Project administration, Funding acquisition, and Writing-Review & Editing.

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Figures

Figure 1

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XRD spectra of the three catalysts

Figure 2

SEM of SAPO-34 (a, b), Bi0.9SAPO-34 (c, d) and Bi0.6La0.3SAPO-34 (e, f)

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Figure 3

XPS spectra of composite molecular sieve catalysts , Al2p(a), Bi4f (b), La3d(b), C1s(c), O1s(d), P2p(e)
with Si3n& La4d(f) fine spectra

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Figure 4

N2 adsorption and desorption profiles(a), pore size distribution(b) of three composite molecular sieve
catalysts

Figure 5

Degradation of aqueous formaldehyde solution by three molecular sieve catalysts under mercury lamp
atmosphere

Figure 6

UV-Vis spectra of three composite molecular sieve catalysts (a, b); PL spectra (c); EIS spectra (d)
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Figure 7

Schematic diagram of the mechanism of photocatalytic degradation of formaldehyde in aqueous

solution by Bi0.6La0.3SAPO-34 molecular sieve catalyst

Supplementary Files
This is a list of supplementary files associated with this preprint. Click to download.

GA.png

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