Accepted Manuscript

A porous gradient geopolymer-based tube membrane with high PM removal rate for
air pollution

Jie-ting Wang, Yuan-yuan Ge, Yan He, Meng-xue Xu, Xue-min Cui

PII: S0959-6526(19)30293-8
DOI: https://doi.org/10.1016/j.jclepro.2019.01.268
Reference: JCLP 15655

To appear in: Journal of Cleaner Production

Received Date: 28 September 2018

Revised Date: 22 January 2019
Accepted Date: 23 January 2019

Please cite this article as: Wang J-t, Ge Y-y, He Y, Xu M-x, Cui X-m, A porous gradient geopolymer-
based tube membrane with high PM removal rate for air pollution, Journal of Cleaner Production (2019),
doi: https://doi.org/10.1016/j.jclepro.2019.01.268.

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A porous gradient geopolymer-based tube membrane with high PM

removal rate for air pollution

Jie-ting Wang, Yuan-yuan Ge, Yan He, Meng-xue Xu, Xue-min Cui*

Guangxi Key Lab of Petrochemical Resource Process and Process Intensification Technology, School

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of Chemistry and Chemical Engineering, Guangxi University, Nanning, 530004, China

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*Corresponding author: cui-xm@tsinghua.edu.cn

Abstract: Existing technology does not meet the urgent need for a cheap and efficient

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particulate matter (PM) removal filter. In this work, a porous gradient

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geopolymer-based tube membrane was successfully prepared using one-step molding.
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The microstructure, mechanical properties and permeability of the tube membrane

were characterized using scanning electron microscopy (SEM), X-ray diffraction

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(XRD), mercury injection, compressive strength tests, and pressure gauge

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measurements. The PM removal capacity of the membrane was studied using a

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particle counter and TG-DSC analysis. The process and mechanism of PM removal

were studied using SEM and EDS. The results show that the porous gradient structure
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of the membrane can be controlled by adding different contents of foaming agent and
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adjusting the interface properties between a geopolymer paste and a mold surface. In
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this work, the tube membrane with an optimal content of 0.9 wt% H2O2 showed better

mechanical properties and a lower pressure drop than the other samples. Moreover,

the PM filtration experiments demonstrated that the tube membrane can achieve a

high PM2.5 removal efficiency from 96.5% to 98.7%, a PM10 removal efficiency

from 98.0% to 99.5% and good recycling performance. Therefore, the porous gradient

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geopolymer-based tube membrane may have positive potential applications for PM

removal from air pollution.

Key words: Geopolymer; Particulate matter (PM); Porous gradient structure;

Membrane

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1. Introduction

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Particulate matter (PM) pollution has received extensive attention all over the

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world, since it seriously affects people’s quality of life and even poses an intensive

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threat to people’s health (Yin and Xu, 2018) in addition to its adverse effects on
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ecosystems, climate and visibility (Sanap and Pandithurai, 2015; Yu et al, 2016) .

Particulate matter (PM) is a complex mixture of microscale particles and liquid

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droplets, which can be categorized as PM2.5 and PM10, referring to particle sizes
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below 2.5 and 10 µm, respectively (Ji et al., 2017). PM pollution can be very harmful
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since it binds toxic compounds and can be inhaled by people owing to its small size

(Feng et al., 2016). Thus far, many diseases and conditions have been reported to be
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associated with PM pollution, including lung cancer (Wang et al., 2018), asthma
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(Delamater et al., 2012), morbidity and mortality (Li et al., 2017; Achilleos et al.,
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2017). Recently, people in developing countries such as China have suffered from

serious PM pollution problems due to rapid urbanization and industrialization (Ji et al.,

2018; Wu et al., 2018).

Several methods have been undertaken to solve the PM pollution problem. In the

outdoors, people mainly use mask filters for individual protection (Patel et al., 2016),

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which can reduce the harm of PM to people but cannot reduce the original PM

pollution. In factories, electrostatic precipitators (Jaworek et al., 2017), bag house

filters (Simon et al., 2014) and high-gravity technology (Pan et al., 2017) are widely

used for the reduction of dust emissions. In ecological regions, adding wetland areas

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and trees (Lu et al., 2018; Liu et al., 2018) is an effective and sustainable way to

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confront PM pollution, but this solution cannot be easily realized. Therefore, PM

removal filters are imperative in PM source control. To solve this problem, numerous

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excellent publications focused on air filtration have been reported the reduction of the

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emission of particulate matters, such as MOF-based fibrous membranes (Dai et al.,
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2018), surface-modified polymer nanofiber membranes (Kim et al., 2018),

electrospun nanofiber films (Liu et al., 2015), glass wool (Hao et al., 2015) and
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activated carbon (Lv et al., 2018). Organic polymer based filters for air purification
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have been widely studied, showing a good potential in low temperature condition. For
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inorganic products, they can be used for higher temperature conditions to fill in gap in

usage in special circumstance.

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Geopolymers, introduced by Davidovits (Davidovits, 1991), constitute a class of

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amorphous structural materials based on dissolved aluminum and silicon entities,

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which are also considered “green materials” because they possess various

environmental-friendly advantages, such as low manufacturing cost and energy

consumption, low waste gas emission and recyclability (Wang et al., 2017; Han et al.,

2018). Recent innovations in geopolymer technology have led to the development of

various types of geopolymer products, especially porous geopolymers (Bai et al.,

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2017). Recently, porous geopolymers have shown excellent properties and have been

explored for use in various applications such as membranes(Ge et al., 2015),

thermally resistant materials (Zhang et al., 2015), catalyst supports (Sharma et al.,

2015), and applications in adsorption and filtration (Tang et al., 2018; Novais et al.,

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2018) due to their porous structure and large surface area . Using these thermally

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resistant inorganic materials can conquer the insufficiencies of organic PM filters. For

the air pollution treatment, economic efficiency is the first thing to be accounted for.

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The raw material for geopolymer synthesis is clay mineral or industrial waste, which

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are cheap. Meanwhile, the synthesis process of geopolymer is below 100 ºC, which is
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cost-effective for the energy consumption is much lower than the commercial

ceramics-based products (Hosseini et al., 2019). In addition, the porous geopolymers

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can possess a high permeability and a large number of pores, which can offer
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substantial potential in PM filtration. However, the study of PM filtration using

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porous geopolymers has not been reported so far.

In this study, an innovative porous gradient tube membrane for PM removal that
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was fabricated by metakaolin based geopolymers. The synthesis process of gradient

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porous structure was controlled, and its formation mechanism was also studied. The
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PM removal performance was tested using a simulated process of PM filtration.

2. Experimental

2.1 Materials

The metakaolin used in this study was produced by Chaopai Metakaolin

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Corporation (Neimenggu province, China). The chemical composition of metakaolin

is shown in Table 1. The sodium silicate solution (with a ratio of SiO2/Na2O = 1.30),

which serves as alkaline activator, was prepared as follows: 19.13 g of NaOH was

added to 100.00 g of industrial water glass (modulus = 3.35), and then the mixed

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solution was ultrasonicated for 10 min and left for 24 h.
Table 1 Composition of metakaolin.

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Chemical composition SiO2 Al2O3 CaO Fe2O3 K2O Na2O

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Metakaolin/wt% 51.02 44.99 0.21 0.6 0.53 0.17

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2.2 Preparation of porous gradient geopolymer-based tube membrane

The porous gradient geopolymer-based tube membrane (PGTM) was prepared

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with water glass and metakaolin with a liquid-solid ratio = 0.85. Deionized water was
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added at a mass content of 6.5 wt% to make the slurry workable. As shown in Fig. 1,
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porous geopolymer slurry was prepared by stirring the metakaolin powder, modified
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sodium silicate solution, and deionized water in an electric mixer (SW Corp, China)

for 2 min at a speed of 2000 r/min. Subsequently, hydrogen peroxide was added at
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concentrations of 0.7, 0.8, 0.9 and 1.0 wt% of the geopolymer slurry; meanwhile,
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surfactant K12 was also added to create the stable foams and was stirred for an

additional 1 min. Immediately after the mixed slurry was poured into custom-built

polypropylene resin molds, the molds were sealed and placed in an oven to cure for

24 h at 60 °C, and then the porous geopolymers were obtained after demolding

[Rickard, W.D.A., 2013]. The PGTMs were obtained after a tube was drilled by a

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CNC Router and then sealed using rubber plugs and ethoxyline resin. The detailed

parameters of the membranes are shown in Table 2.

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Fig. 1 Fabrication process chart of micro porous geopolymer-based membrane
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Table 2 List of main parameters of membranes
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Membrane Foaming agent Thickness/mm Length/mm Diameter/mm

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#1 0.7 wt% 15 140 50

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#2 0.8 wt% 15 140 50

#3 0.9 wt% 15 140 50

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#4 1.0 wt% 15 140 50

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2.3 Characterization
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The processing conditions and micro structure of the samples were characterized by

X-ray diffraction (MiniFles600, Rigaku Corp., Japan). The pore size distribution was

measured using a mercury injection apparatus (Quantachrome Instruments PM-33-18,

USA). The morphology was characterized by a scanning electron microscope (S-3400,

Hitachi Limited Corp., Japan) and a field emission scanning electron microscope

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(Hitachi Limited Corp., Japan). The compressive strength was measured using a

universal testing machine (DNS100, Changchun Machinery Research Institute Co.,

Ltd., China). The TG-DSC analysis was performed using a Thermal Gravimetric

Analyzer (STA 449 F3 Jupiter, Netzsch Corp.,,Germany). The samples were heated

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from 25 to 600 °C with a heating rate of 10 °C/min under nitrogen flow.

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2.4 Study on PM removal

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An atmosphere full of smoke fog (with extremely high concentrations of PM2.5

above 1000 µg/m3 and PM10 above 2000 µg/m3) was simulated by a smoke generator

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(YWQ-180, Qingdao Lingding Co., Ltd., China). PM2.5 and PM10 concentrations

were tested using a particle counter (HT-9600, Hongtai Instrument Co., Ltd.,
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Hongkong, China). The air flux was measured by a flow meter (LZB-10, Chengfeng
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Instrument Co., Ltd., China). As shown in Fig. 2, the filtration process of PM2.5 or
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PM10 was conducted to simulate the realistic filtration process. To study the ability of

the membrane to remove PM, samples with different contents of H2O2 were employed
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in the filtration of PM. The removal efficiency was calculated by the following
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equation (1):
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Removal efficiency = (1-C/C0) ×100% (1)

Where C0 and C are the PM concentrations before and after passing through the

membrane, respectively. As is vividly shown in Fig. 2, the high PM atmosphere is

filtered and becomes clean and clear with the passage of time.

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Fig. 2 The simulated process of PM filtration.
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3. Results and discussion
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3.1 The formation mechanism of the porous gradient structure

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A small concentration of hydrogen peroxide was added to the geopolymer paste

to create a foamed porous structure; because the hydrogen peroxide decomposes

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rapidly to give off oxygen under strong alkali conditions. The reason why strong base
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promotes the decomposition of hydrogen peroxide is that hydrogen peroxide is more

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acidic than water, and it interacts with strong alkali to form HOO- ion, which has poor

stability and is decomposed faster than H2O2. It was found that the stable microporous

structure can be formed due to the high speed of pore reaction and collapse (Masi, G.,

2014). It must also be mentioned that the surface of the PGTM is smooth and compact

with small pores, whose formation mechanism can be explained by the Young

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equation (Fernandez-Toledano, J.C., 2017) as follows:

ys = ys1 + y1cosθ (2)

Where ys: is the surface tension produced by the gas-solid interface; ys1 is the

surface tension produced by the liquid-solid interface; y1 is the surface tension

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produced by the gas-liquid interface; θ is the contact angle.

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Due to the wetting of the geopolymer paste and mold surface, water and bubbles

inside the geopolymer paste can diffuse out and rise along the mold surface. If the

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geopolymer paste and mold are not wetted, the water and bubbles inside the

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geopolymer can only diffuse from the inside up, not to the surface of the mold, and
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the nonwetted mold cannot form this porous structure. If the geopolymer paste is

wetted too well with the surface of the mold, then the mold will be stuck by the paste
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and there will be no compact layer with small pores. In this work, a type of
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commercial polypropylene plastic was used as the mold of the membrane for easy
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demolding. As shown in Fig. 3a, the geopolymer paste achieves a contact angle of

68.5º on the surface of the mold. In this situation, the surface of the membrane is full
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of large open cells owing to the fact that the geopolymer paste cannot sufficiently wet
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the surface of the mold. When the contact angle of the geopolymer paste can reach
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27.5º through the addition of surfactant, the geopolymer paste can maintain complete

contact with the surface of the mold. As seen in Fig. 3b, a compact surface with

micron-sized pores was fabricated. Therefore, a porous gradient structure with a cross

section of microporous structure and a compact surface was naturally fabricated.

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Fig. 3 a: Surface of the membrane without surfactant, b: Surface of the membrane with surfactant

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3.2 Morphology of porous geopolymer-based tube membrane

SEM was used to study the morphology of the PGTM. Figs. 4a, b, c and d show

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SEM images of cross sections of porous geopolymer with 0.7, 0.8, 0.9, and 1.0 wt%

hydrogen peroxide after 7 days, respectively.

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As seen from Fig. 4a-d, the near millimeter-sized porous geopolymer-based

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membrane bodies show highly amorphous structures consisting of a large number of

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cells created by hydrogen peroxide. It must also be mentioned that the cells observed

in the geopolymer were mainly open. Hence, the porous geopolymer possesses the
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high permeability and poor pollutant removal efficiency for flow media owing to
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these open pores randomly distributed inside the geopolymer. As shown in Fig. 4a-d,
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the size of the pores increased as the content of H2O2 increased, which makes the

geopolymer membrane body much looser. In this work, a porous body and a compact

surface membrane were obtained. The cross-sectional drawing indicates that the

porous body successfully combined with the compact surface, as seen in Fig. 4e. The

FESEM image shows the surface of the compact surface, as shown in Fig. 4f, which

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illustrates that the compact surface with numerous nanopores is structured by the

geopolymer gel. The compact surface mainly ensures the removal efficiency of PM,

as will be discussed in future studies.

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Fig. 4 a, b, c, d: SEM images of cross of membranes with 0.7, 0.8, 0.9, 1.0 wt% H2O2;

e, f: SEM/ FESEM images of surface of the membrane with 0.9 wt% H2O2

3.3 The XRD analysis of metakaolin and geopolymer

X-ray diffraction patterns of metakaolin and geopolymer are shown in Fig. 5.

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The patterns for metakaolin and geopolymer both show a broad dispersion peak

appearing at 2θ between 10° and 40° and no peaks indicative of crystalline phases,

indicating that they are consistent with an amorphous structure.

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Fig. 5 XRD analysis patterns of metakaolin and geopolymer.

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3.4 Pore size distribution of porous geopolymer

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To analyze a wider pore size range, the pore size distribution of the surface

section and cross section were examined using a mercury injection apparatus. As seen
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in Fig. 6, the peak appearing at 0.12 µm results from water evaporation [32], which
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indicates that the compact surface possesses pores of approximately 0.12 µm for air

permeation. Additionally, the pore size of the porous membrane body was distributed

in the range of 10 µm to 100 µm, mainly at 75 µm, which indicates that the pores in

the cross section were mainly 75 µm in size. The pore size distribution suggests the

porous gradient structure. Furthermore, the nanoporous structure of the surface

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ensured the interception of particles, and the near millimeter-sized porous structure of

the membrane body ensured high permeability.

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Fig. 6 Pore size distribution of the membrane.
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3.5 Permeability and mechanical properties of the membrane

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The pressure drop and compressive strength of samples with different contents of

hydrogen peroxide were studied. The small pressure drop reduced the energy
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consumption of the membrane in practical application. As shown in Fig. 7(a), the

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pressure drop decreases with an increase in added foaming agent as well as

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compressive strength, which results from the higher content of hydrogen peroxide

create a looser structure as it can be seen in SEM images. Compared with samples

with 0.7 and 0.8 wt% H2O2 , the membrane with 0.9 wt% H2O2 needed a much lower

pressure drop about 0.01 MPa. Compared with sample with 1.0 wt% H2O2, the sample

with 0.9 wt% H2O2 showed relatively high compressive strength about 3.9 MPa.

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Considering the SEM, permeability and mechanical properties, the optimal ratio of

foaming agent should be 0.9 wt% with a low pressure drop and a sufficient

compressive strength of the geopolymer membrane.

An air flux test was conducted to investigate the permeability of the membrane.

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To understand the effect of pressure drop on the air flux of the membrane, the air flux

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was measured at different pressures from 0.004 to 0.012 MPa. From the permeability

behavior illustrated in Fig. 7(b), it was found that the air flux of all samples with

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different foaming agent contents improved as the pressure increased. The results

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indicate that the permeability of the membrane in the present study can be controlled
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by adding a suitable content of foaming agent. As the SEM results showed, it can be

readily observed that the content of open pores directly affects the air flux of the
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membranes. In addition, a much higher content of foaming agent in geopolymers

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creates a looser structure, which also leads to a high permeability but low rejection
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efficiency. Moreover, the optimal content of foaming agent in the 0.9 wt% sample

surely results from a homogeneous dispersion of open pores inside the geopolymeric
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phase with an appreciable ratio between the air and geopolymer phases.
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Fig. 7. (a) Pressure drop and compressive strength of samples with 0.7-1.0 wt% H2O2, (b) The

effect of pressure drop on air flux of samples with 0.7-1.0 wt% H2O2.

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3.6 Study on PM removal

As seen in Fig. 8(a), 0.7, 0.8, 0.9 and 1.0 wt% samples achieve PM10 and PM2.5

removal efficiencies of 99.8%, 99.5%, 99.2%, and 96.4% and 99.5%, 98.7%, 97.5%,

and 92.8% respectively. A low air resistance is also important to the filtration process.

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As seen in Fig. 8(a), 0.7, 0.8, 0.9 and 1.0 wt% samples demand a pressure drop of

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0.06, 0.025, 0.011, 0.0075 MPa, respectively. In addition, it was found that the sample

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with 0.7 wt% H2O2 showed the highest removal efficiency but required a high

pressure drop of approximately 0.06 MPa. Moreover, the sample with 1.0 wt% H2O2

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shows the lowest removal efficiency of both PM2.5 and PM10. In considering a
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relatively low pressure drop and relatively high removal efficiency, the sample with
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0.9 wt% H2O2 was chosen to be the best candidate for the filtration of PM.

The TG-DSC analysis was performed to evaluate the adsorption capacity of the
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membrane. The TG and DSC curves were generated by the samples before and after
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90 min filtration. As Fig. 8(b) illustrated, the TG curves changed markedly after PM
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filtration. Combining the TG curve and DSC curve before PM filtration, the mass loss

before 150 ºC must result from the surface adsorbing water of the membrane. The
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greater mass loss of the membrane after 90 min PM filtration before 150 ºC must be
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the adsorbed PM and water. The value of PM removal can be calculated by comparing

the mass loss of membrane before and after filtration: a result of approximately 9 wt%

can be seen in Fig. 8(b). Moreover, the TG-DSC analysis illustrates the thermal

resistance of the membrane.

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Fig. 8 (a) PM removal efficiency of membranes with different contents of H2O2, (b) TG-DSC

analysis of the membrane before and after 90 min filtration

The PM removal efficiencies of 0.9 wt% H2O2 samples at different filtration

times are shown in Fig. 9(a). In the 90 min filtration process with an extremely high

PM2.5/10 of above 2000 µg/m3, the membrane achieved PM2.5 and PM10 removal

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efficiencies of 98.5% and 99.3%, respectively. In this situation, the membrane

possesses an increased pressure drop from 0.011-0.018 MPa as time increased, as

shown in Fig. 9(a). There are three stages of the change in removal efficiency over

time. In the first stage, the removal efficiency increased with time as a result of the

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formation of a filtering cake layer. In the second stage, the removal efficiency became

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stable with time, resulting from the fact that the surface filtration and adsorption of

the cross section both were working on. During the last stage, the removal efficiency

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decreased with time because the filtration of surface had been finished and the

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adsorption of cross section had reached adsorption saturation.
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In addition, the recycling performance of the membrane was evaluated. After 90

min of filtration of PM, the membrane was washed in 70% ethanol with
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ultrasonication. Then, the washed membrane was dried in the open air under the
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temperature of 25 ºC. The washed and dried membrane was again used for the
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filtration process, and the removal efficiency was tested by the PM detector. As shown

in Fig. 9(b), the removal efficiency of PM2.5/10 decreased slightly after recycling but
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still remained higher than 90% / 85%. The decrease in removal efficiency is mainly
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due to PM residue adsorbed on the surface and inside. The demanded pressure drop
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decreases with the recycling times, from 0.0115 MPa to 0.0075 MPa, which results

from some part of the microporous structure of the membrane being destroyed by

ultrasonic agitation in the drying and watering cycle.

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Fig. 9 (a) PM removal efficiency of the membrane with 0.9 wt% H2O2 at different timepoints. (b)
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PM removal efficiency of the membrane with 0.9 wt% H2O2 after different recycling times

3.7 The mechanism of the PM removal process

To understand the PM interception process, the morphology of the membrane

before and after filtration was examined by SEM. As shown in Fig. 10, after 60 min of

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filtration of PM, many deposits are observed lying on the compact surface and filling

a portion of the pores on the surface. The results indicate that most of the large PM

was rejected on the surface and that the surface compact layer intercepted most of the

extremely small particulate matter. In addition, after a 60 min filtration process, the

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2-10 µm PM are distributed on the cross section of the membrane, which suggests that

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the PM2.5 can be removed by these pores inside the geopolymer. Meanwhile, EDS

analyses were used to explore the filtration mechanism of the membrane, as shown in

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Fig. 10. Together, the results showed that the carbon element content of the filtered

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surface is higher than that of the surface before filtration as well as the cross section.
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The carbon mainly originated from particulate matter produced by the smoke fog

generator. Thus, EDS analysis also supports the SEM results. The filtration of the
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surface and the adsorption and interception by porous structures inside the
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geopolymer ensure the removal efficiency of particulate matter. Even at extremely

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high PM concentration, the membrane still exhibits good PM removal efficiency.

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Fig. 10 SEM images and EDS analysis of membrane before and after filtration

In the PM filtration experiment, photos of the membrane were taken at different

timepoints, as shown in Fig. 11. The photos show that the color of the membrane

becomes deeper as time passes. Actually, the deeper color illustrates that more PM

was rejected on the surface of the membrane. In addition, the PM filtered area is also

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associated with the adsorption ability of the membrane. After approximately 90 min

of the filtration process, the membrane essentially completed the filtration.

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Fig. 11 Photos of membrane at different filtration timepoints
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The proposed PM filtration mechanism of the PGTM is shown in Fig. 12. The majority of

PM, which cannot pass through the near-nanoporous surface of the membrane, can be filtered
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easily by the membrane. Although nano-sized PM can pass directly through the compact
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nanoporous surface of the membrane, they will be absorbed and removed by the large surface area
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of the membrane body. Hence, the major portion of particulate matter can be removed after

filtration of the porous gradient geopolymer-based membrane.

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Fig. 12 Proposed filtration mechanism of the membrane for PM
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4. Conclusions
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The porous gradient geopolymer-based tube membrane with a high PM removal

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ability was successfully prepared and characterized. Addition of a foaming agent and
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mold surface significantly affected the microstructure of the membrane. Under

optimal conditions, when the content of the foaming agent is 0.9 wt%, the porous
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gradient structure with a 70 µm porous membrane body and 100 nm nanoporous

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surface can be obtained by curing the smooth mold surface. Moreover, the porous
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gradient geopolymer-based tube membrane with 0.9 wt% hydrogen peroxide showed

a compressive strength of 3.9 MPa and a corresponding pressure drop of 0.01 MPa.

The PM filtration experiments suggest that the removal efficiency of PM2.5 or PM10

reached 98.5% and 99.3%, respectively, showing great potential in PM removal

filtration. Although the porous gradient geopolymer-based tube membrane has the

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characteristics of low cost and high temperature resistance, because the pore structure

and thickness of the dense layer is not easy to control, it increases the difficulty of

preparation. However, the new geopolymer membrane can be a good candidate for

ameliorating PM pollution problem, and the synthesis technology also provides a new

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method to fabricate inorganic membranes.

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Acknowledgments

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This work was supported by the Chinese Natural Science Fund (grants: 21566006 and

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51772055) and the Guangxi Natural Science Fund (grant: 2016GXNSFGA380003).
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Highlights

A porous gradient geopolymer-based tube membrane was prepared by

one-step casting.

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The tube membrane showed PM2.5/10 removal efficiency above 98.0%.

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The process and mechanism of PM filtration were studied.

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