Journal Pre-proof

Innovative utilization of molecular imprinting technology for selective adsorption and

(photo)catalytic eradication of organic pollutants

Guijian Guan, Jia Hong Pan, Zibiao Li

PII: S0045-6535(20)33274-4
DOI: https://doi.org/10.1016/j.chemosphere.2020.129077
Reference: CHEM 129077

To appear in: ECSN

Received Date: 8 September 2020

Revised Date: 28 October 2020
Accepted Date: 19 November 2020

Please cite this article as: Guan, G., Pan, J.H., Li, Z., Innovative utilization of molecular imprinting
technology for selective adsorption and (photo)catalytic eradication of organic pollutants, Chemosphere,
https://doi.org/10.1016/j.chemosphere.2020.129077.

This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition
of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of
record. This version will undergo additional copyediting, typesetting and review before it is published
in its final form, but we are providing this version to give early visibility of the article. Please note that,
during the production process, errors may be discovered which could affect the content, and all legal
disclaimers that apply to the journal pertain.

© 2020 Elsevier Ltd. All rights reserved.

 Credit Author Statement

Guan Guijian: Manuscript writing and discussion

Pan Jiahong: Manuscript concept design and discussion

Zibiao Li: Technical advisor and revision

of
ro
-p
re
lP
na
ur
Jo
 1 Innovative utilization of molecular imprinting technology for selective adsorption and
2 (photo)catalytic eradication of organic pollutants

3 Guijian Guana, Jia Hong Panb,*, Zibiao Lic,*

4
a
5 Institute of Molecular Plus, Tianjin University, Tianjin, 300072, P.R. China
6
b
7 MOE Key Laboratory of Resources and Environmental Systems Optimization, College of
8 Environmental Science and Engineering, North China Electric Power University, Beijing
9 102206, China
10
c
11 Institute of Materials Research and Engineering, A*STAR, 2 Fusionopolis Way, Singapore,

of
12 138634, Singapore
13

ro
14
15 *Correspondence to pan@ncepu.edu.cn (J. H. Pan); lizb@imre.a-star.edu.sg (Z. Li)
16
-p
re
17
lP

18

19
na

20

21
ur

22
Jo

23

24

25

26

27

28

29

30

31

32

33

1
 1 Abstract: The rapid development of industrialization and urbanization results in a numerous

2 production of various organic chemicals to meet the increasing demand in high-quality life.

3 During the synthesis and utilization of these chemical products, their residues unavoidably

4 emerged in environments to severely threaten human’s health. It is thus urgent to exploit

5 effective technology for readily removing the organic pollutants with high selectivity and

6 good reusability. Using a chemically synthesized route, molecular imprinting technology

7 (MIT) constructs artificial recognition sites in highly-crosslinked matrix with excellent

of
ro
8 stability and specific binding affinity towards target species, and thus has been attracting

9 -p
more and more interest for environmental remediation, such as the selective
re
10 adsorption/separation and improved catalytic degradation of pollutants. In this review, MIT is
lP

11 first introduced briefly to understand the formation and recognition mechanism of imprinted

12 cavities, and common imprinted systems. Then, the specific affinities of imprinted sites are
na

13 demonstrated for selectively adsorbing and removing target molecules with a large binding
ur

14 capacity. Furthermore, the innovative utilization of MIT in catalytic eradication of pollutants

Jo

15 is comprehensively overviewed to emphasize their enhanced efficiency and improved

16 performances, which is classified by the used catalytically-active nanocrystals and imprinted

17 systems. After summarizing recent advances in these fields, some limitations are discussed

18 and possible suggestions are given to guide the future exploitation on MIT for better

19 environmental applications.

20

21

22

2
 1 1. Introduction
2 In modern world, industrialization and urbanization are rapidly developed to cause an

3 exponential growth in population, which necessarily consumes more and more industrial

4 chemicals for remaining/improving human’s life, such as pharmaceuticals, pesticides, dyes,

5 organic compounds, etc (Huang et al., 2015; Shen et al., 2012). In the synthesized and used

6 processes of the chemical products, large amounts of organic contaminants are unavoidably

7 disposed into and emerged in natural environment to cause a toxicity to living organisms, and

of
ro
8 it is difficult or impossible to eliminate the toxicity via natural degradation (Xie et al., 2016).

9 -p
Due to their persistence in environment and high toxicity to human health, the excessive
re
10 organic chemicals have recently become a major issue around the world (Wu et al., 2018). It
lP

11 is thus urgent to properly control and treat the persistent organic pollutants (POPs) for

12 remediating environment to protect human beings against the pollutants’ toxicity (Bhatnagar
na

13 and Anastopoulos, 2017; Rodriguez-Narvaez et al., 2017). In this field, various

ur

14 graphene-involved materials with unique physicochemical properties have exhibited superb

Jo

15 performance in photocatalytic degradation of POPs through their efficient utilization of solar

16 energy, including gel (Zhang et. al., 2019), aerogels (Lu et al., 2018), and composite

17 photocatalysts with organics, semiconductor, metal (Zhang et al., 2015a). In addition of the

18 photocatalytic degradation, other kinds of treatment techniques have been demonstrated for

19 effectively eliminating organic pollutants from wastewater, such as precipitation, coagulation,

20 adsorption, biodegradation, and so on (Huang et al., 2015; Rodriguez-Narvaez et al., 2017;

21 Ndunda and Mizaikoff, 2016). As indicated, these techniques are applicable for

22 simultaneously removing various pollutants with high concentrations, however they are not

3
 1 efficient for specific pollutants at a low concentration in the complicated system due to their

2 lack of selectivity and high affinity towards target molecules (Shen et al., 2012; Ndunda and

3 Mizaikoff, 2016). With the emergence of more and more highly toxic pollutants in

4 environment, the regular treatments are indeed difficult to address the current requirements

5 for eliminating the highly toxic micropollutants. To this end, new functional materials with

6 high selectivity need to be further exploited for significantly improving the performance of

7 the existing treatment strategies (Huang et al., 2015).

of
ro
8 Aiming at the urgent requirements on molecular selectivity, scientists have started to

9
-p
employ molecular imprinting technology (MIT) for chemically synthesizing molecular
re
10 recognition components, which can specifically generate molecular cavity with high binding
lP

11 affinity and prominent selectivity towards target molecules (Wackerlig and Schirhagl, 2016).
na

12 Moreover, the resultant molecular cavities are surrounded with highly-crosslinked materials
ur

13 to ensure their physical/chemical stability in harsh conditions and good reusability with
Jo

14 cost-effectiveness. As shown in Fig. 1, the imprinted site is generated through cross-linking a

15 complex of target molecule with functional monomers and subsequently removing the target

16 molecule (i.e. molecular template) (Zimmerman and Lemcoff, 2004). Owing to the

17 complementary shape, size and functional groups, the resultant site can specifically and

18 strongly bind the used template molecules and its structural analogue, similar with natural

19 recognition entity (e.g. antibody) (Chen et al., 2016). Based on the process of molecular

20 imprinting, various material’s systems have been developed to provide a wealth of precursors

21 for effectively imprinting diversified molecules of interest in synthetic polymers,

22 macromolecules or inorganic xerogel (BelBruno, 2019). Benefiting from easy preparation

4
 1 and facile hybridization, molecularly imprinted materials with salient advantages have been

2 widely employed as recognition components in various fields, including solid phase

3 extraction, sensor and environmental remediation (Huang et al., 2015; Speltini et al., 2017;

4 Yang et al., 2018).

of
ro
-p
re
5

6 Fig. 1. Schematic illustration for molecular imprinting technology to yield recognition cavity
lP

7 in diversified systems or hybrid materials, which exhibit various advantages in environmental

na

8 remediation via adsorption/separation and catalytic degradation. Reprinted with permission

9 from The Royal Society of Chemistry from Ref. (Zimmerman and Lemcoff, 2004).
ur
Jo

10 Very significantly, molecularly imprinted materials have exhibited outstanding

11 performances in selective adsorption/separation and enhanced catalytic degradation of

12 organic pollutants, which will be more promising for environmental remediation after further

13 combined with colloidal particles or other functional nanostructures as composite materials

14 (Lofgreen and Ozin, 2014; Muratsugu et al., 2020; Shen et al., 2012). Typically, molecular

15 imprinting on TiO2 readily achieves the selective photocatalytic degradation of highly toxic

16 organic pollutants with low concentrations to less toxic chemicals even to CO2 and H2O,

17 which is a green and environmentally friendly solution for eliminating pollutants (Lai et al.,

18 2018; Sajini et al., 2019; Sun et al., 2018; Suyana et al., 2017). In this review, MIT is

5
 1 specially focused on innovative utilization for selectively and rapidly adsorbing/removing

2 target pollutants and photocatalytically degrading organic chemicals with enhanced efficiency

3 and improved performances.

4 2. Foundation of molecular imprinting

5 Imprinted mechanism. Based on the forming mechanism of antibody under the induction

6 of antigen (a supposed process), the concept of molecular imprinting was first raised by

of
7 Pauling in 1940 (Pauling, 1940). After 32 years, Wulff and Sarhan experimentally

ro
8 demonstrated the fabrication of molecularly imprinted polymers (MIPs) by formation and

9
-p
dissociation of covalent bonds of templates with monomers (i.e. reversible chemical bonding),
re
10 in which binding sites are homogenous but it is difficult to completely remove the templates
lP

11 due to the strong interactions (Wulff and Sarhan, 1972). Alternatively, Mosbach’s group used
na

12 noncovalent interaction (e.g. electrostatic forces, hydrogen binding, van der Waals forces) to
ur

13 successfully synthesized MIPs in 1993 (Vlatakis et al., 1993). The noncovalent imprinting
Jo

14 technology is easier to achieve via choosing effective functional groups for imprinting target

15 molecules, and thus becomes the most used one to prepare MIPs although the resultant

16 binding sites is not stable enough at some special conditions. In addition, semicovalent

17 strategy has also been developed to combine the covalent and noncovalent approaches, in

18 which MIPs are synthesized by covalent bonds but the rebinding is achieved via noncovalent

19 interactions (Fuchs et al., 2012).

20 Typical materials’ systems. For synthesizing MIPs, some types of precursors are essential,

21 such as template molecules, functional monomers, cross-linkers, polymerizing initiators and

6
 1 porogen (the first three types are the so-called “three-elements of molecular imprinting”)

2 (Chen et al., 2016). Among them, an feasible template molecule should have an excellent

3 structural/chemical stability and contain special groups for forming complex with functional

4 monomers, but cannot prevent polymerization (Chen et al., 2011). As ideal functional

5 monomers, the species should not only have the functional groups complementary to

6 template molecule, but also be polymerizable with cross-linkers. With carboxyl groups as

7 recognition unit and vinyl double bond as polymerizable unit, methacrylate acid (MAA) has

of
ro
8 been extensively employed as an “universal” imprinting monomer in non-covalent systems

9 -p
via its hydrogen bonding and electrostatic features (Zhang et al., 2010). After forming the
re
10 complex of template and monomers, a cross-linker is further added to highly cross-link the
lP

11 functional monomers around template molecules in a rigid polymer matrix. So far, the

12 commonly used cross-linker in free radical polymerization is ethylene glycol dimethacrylate

na

13 (EGDMA), and azobisisobutyronitrile (AIBN) is the most used initiator with a mild
ur

14 decomposition temperature at 50–70 oC accordingly (Yan and Row, 2006). In polymerization

Jo

15 of molecular imprinting, a porogenic solvent such as acetonitrile is also important to serve as

16 dispersion media, which forms some pores in MIPs for faster diffusion after removal of

17 solvent molecules (Gladis and Rao, 2004). Referring to this imprinting process, the material’s

18 systems have successfully extended from synthetic polymers to cross-linked macromolecules

19 (e.g. gelatin, chitosan) and inorganic xerogel (e.g. SiO2, TiO2) after the continuous

20 exploitation in the past decades (Sajini et al., 2019). Compared with organic polymer systems,

21 molecular imprinting in inorganic xerogel is still a small niche but the related research

22 interest is quickly growing nowadays owing to their better performances in thermal stability

7
 1 and engineering possibility.

of
ro
2
-p
re
3 Fig. 2. Typical imprinted core-shell microspheres reported in our previous works, which are
4 observed by SEM (A,C,D,F) and TEM (B,E) images: (A) SiO2@MIPs, Reprinted with
lP

5 permission from American Chemical Society from Ref. (Gao et al., 2007); (B) SiO2@gelatin,
na

6 Reprinted with permission from The Royal Society of Chemistry from Ref. (Guan et al.,
7 2009); (C) Fe3O4@MIPs, Reprinted with permission from American Chemical Society from
ur

8 Ref. (Liu et al., 2011); (D) PS@MIPs, (E) PS@imprinted SiO2, Reprinted with permission
Jo

9 from Wiley from Ref. (Guan et al., 2012); and (F) hollow imprinted MIP shells obtained from
10 PS@MIPs. Reprinted with permission from Wiley from Ref. (Guan et al., 2007).

11 Representative structures. At early stages for molecular imprinting, MIPs were generally

12 prepared as monoliths by traditional bulky polymerization followed by grinding and sieving

13 for the production of irregularly shaped particles (Pérez-Moral and Mayes, 2004). Bulk

14 polymerization is simple and universal, but it is labor-intensive and is not time-effective, and

15 the yield of useable particles is less than 50%. To this end, several alternative polymerizations

16 have been developed to directly prepare spherical imprinted particles, including

17 suspension/precipitation polymerization, two-step or multiple swelling polymerizations, and

8
 1 core-shell imprinting (Huang et al., 2015). Particularly, the imprinted cavities in core-shell

2 structures are situated at or very near the surface of the polymers, which overcomes the

3 problems in bulky MIPs such as limited mass transfer, incomplete template removal and

4 small binding capacity (Gao et al., 2007). Experimentally, core-shell imprinting is

5 conveniently realized through synthesizing a thin polymer film at the surface of spherical

6 colloids. In this field, our groups reported several interesting research works: (1) silica (SiO2)

7 particles were modified with vinyl functional monomers to direct the selective occurrence of

of
ro
8 imprinting polymerization on SiO2 particles (Fig. 2A) (Gao et al., 2007); (2) a layer-by-layer

9 -p
molecular imprinting strategy was developed for constructing imprinted gelatin on SiO2
re
10 particles by glutaraldehyde-mediated covalent assembly (Fig. 2B) (Guan et al., 2009); (3)
lP

11 Fe3O4 particles were covered with acrylic acid for highly directing the imprinting

12 polymerization to selectively occur at Fe3O4 particles (Fig. 2C) (Liu et al., 2011); (4)
na

13 carboxyl-functionalized polystyrene (PS) microspheres were used as cores to control the

ur

14 surface polymerization of imprinted polymers (Fig. 2D) and imprinted silica (Fig. 2E) via
Jo

15 hydrogen-bonding interactions (Guan et al, 2012). Based on the core-shell imprinting, we

16 further prepared hollow imprinted microspheres with a single hole after removing the core PS

17 particles with tetrahydrofuran (Fig. 2F) (Guan et al., 2007). These core-shell MIPs have

18 well-controlled morphologies and varied imprinting thickness, and can also introduce more

19 functions in MIP systems via choosing special cores (e.g. magnetic, fluorescent, catalytic,

20 etc.), therefore they are highly desirable to satisfy the different application purpose.

21 3. Recent application of MIPs for adsorbing organic chemicals

22 As a selective, easily separated, recyclable, and low-cost adsorbent, MIPs with specific

9
 1 recognition sites toward target pollutants are very promising to analyze and treat organic

2 pollutants with low concentrations in water environments (Lu et al., 2020; Wang et al., 2017).

3 For displaying the advantages of MIPs exhaustively, non-imprinted polymers (NIPs) are also

4 prepared according to the same preparing process in the absence of the template molecules.

5 Then, besides the maximum binding capacity, MIPs are also evaluated by an imprinting

6 factor (IF): i.e. the ratio of binding capacities on MIPs to the one on NIPs. In addition, the

7 selectivity and reusability are very important parameters for MIPs as ideal adsorbents. For

of
ro
8 example, noncovalent interaction-based MIP microspheres having a size range of 1−2 μm

9 exhibited a maximum adsorbing amount of 103 mg g−1 for R-estradiol with a high imprinting
-p
re
10 factor at 35, which was reused without any decrease in binding capacity within at least five
lP

11 repeated cycles (Meng et a., 2005). Utilizing MAA as the functional monomer, MIP

12 microspheres possessing a size of 2−5 μm were produced to show a high binding capacity of
na

13 687 mg g−1 towards polycyclic aromatic hydrocarbons (PAHs) with an imprinting factor of 6,
ur

14 which was higher than the value from powdered activated carbon (386 mg g−1) (Krupadam et
Jo

15 al., 2010). And, the adsorption-desorption process was performed for ten cycles without any

16 decrease in performance. Alternatively, bisphenol A (BPA)-imprinted microspheres

17 synthesized via precipitation polymerization exhibited higher binding selectivity for

18 removing phenolic estrogens from different sources of water than those of activated carbons,

19 which was recycled for at least thirty times without any decrease in removing efficiency (Lin

20 et al., 2008). In this section, we will focus on the recent research works for developing MIP

21 adsorbents through choosing new imprinted systems, synthesizing novel nanostructures or

22 hybridizing into composites with other functional nanomaterials (Table 1).

10
1

2 Table 1
3 Representative research works on MIP adsorbents for binding target pollutants. Bmax and IF
4 are the maximum binding capacity and imprinting factor, respectively.

Classified pollutants Target molecules Imprinting information Bmax (mg g−1) IF Ref.

Industrial chemicals Bisphenol A Hydrophilic MIP microspheres 112 3.6 (Wang et al., 2017)

Thermoresponsive MIPs 5 4.1 (Dong et al., 2014)

Photoresponsive MIPs 6.1 3.2 (Liu et al., 2016a)

Graphene oxide@MIP 85.7 2.1 (Duan et al. 2016)

Temperature and magnetic 8.3 6.1 (Wu et al., 2016a)

of
dual-responsive MIPs
Keratin/Fe3O4/MIPs 600 4.83 (Hassanzadeh et al.,
2018)

ro
2,4-Dichlorophenol SiO2@MIPs 3.07 4.4 (Li et al, 2009)

Attapulgite/Fe3O4@MIPs 145 1.7 (Pan et al., 2011)

Perfluorooctane
sulfonate epichlorohydrin
-p
Chitosan-based MIP with cross-linker 416 2.2 (Yu et al., 2008)
re
SiO2@MIPs 21.1 2.1 (Du et al., 2018)
Polycyclic aromatic MIP microspheres of 2−5 μm 687 6 (Krupadam et al.,
hydrocarbons 2010)
lP

4-Nitrophenol Chitosan-based MIP with cross-linker 101 1.52 (Bello et al., 2017)
glutaraldehyde
2,4,6-Trichlorophenol Amino-modified MIP nanoparticles 898.7 2.03 (Shen et al., 2015)
na

Tetrabromobisphenol A Fe3O4@ZIF-8@MIPs 117.6 1.8 (Li et al., 2018a)

Nonylphenol Fly-ash-cenospheres/Fe3O4@MIPs 434.8 1.4 (Pan et al., 2013)

ur

Pharmaceuticals Carbamazepine 4-Vinylbenzoic acid as monomer 28.4 2.72 (He et al., 2020)

Fe3O4@chitosan@MIPs 90 1.8 (Zhang et al. 2013b)

Jo

Triclosan Fe3O4@SiO2@MIPs 53 2.04 (Lu et al., 2020)

R-estradiol MIP microspheres of 1−2 μm 103 35 (Meng et al., 2005)

Diclofenac Allylthiourea as monomer 160 3.3 (Samah et al., 2018)

Bichlorophen Thermosensitive MIPs 108.4 1.39 (Guo et al., 2019a)

Estrone Semicovalent imprinting strategy 31 4.6 (Gao et al., 2011)

Cyromazine Graphene oxide@MIPs 14.5 3.45 (Chen et al., 2019)

Erythromycin Fe3O4-embeded MIPs 70 3.28 (Kuhn et al., 2020)

Ciprofloxacin Fe3O4-embeded MIPs 32 3.37 (Kuhn et al., 2020)

Tetracycline Fe3O4@MIPs 23 1.98 (Dai et al., 2014)

Aristolochic acid I Fe3O4/CNTs@MIPs 18.54 3.17 (Li et al., 2019)

Pesticides 2,4-D Hollow MIP microspheres 108.1 3.83 (Yang et al., 2019)

Pentachlorophenol Fe3O4/GO@MIPs 789.4 4.36 (Pan et al., 2019)

Dyes Rhodamine B Fe3O4@SiO2@MIPs 29.6 2.5 (Li et al., 2017)

5 3.1. New imprinted systems for adsorbing pollutants

6 Aiming at different target pollutants or special requirements on applications, new

11
 1 imprinted systems have recently been developed, including imprinting methods, functional

2 monomers, etc. For instance, a mixture of acidic pharmaceuticals was used as multi-templates

3 to prepare MIPs for eliminating multi pharmaceuticals from wastewater due to their excellent

4 affinity toward five acidic pharmaceuticals, which was reused for at least fifteen cycles (Dai

5 et al., 2012). For effectively imprinting pharmaceutical carbamazepine (CBZ), 10 different

6 types of functional monomers were simulated to reveal an order for binding affinity with

7 CBZ: 4-vinylbenzoic acid > itaconic acid > MAA > other monomers (He et al., 2020). Using

of
ro
8 4-vinylbenzoic acid as an appropriate monomer, the adsorption capacity was up to 28.40 mg

9 g−1 with an imprinting factor of 2.72. In the synthesis of diclofenac (DCF)-imprinted

-p
re
10 polymers, allylthiourea (AT) was used as the functional monomer to result in an adsorption
lP

11 capacity of 160 mg g−1 (Samah et al., 2018). By using 10 mg of MIPs, the DCF molecules

12 with a concentration of 5 mg L−1 was completely removed within 3 min. In order to imprint
na

13 levofloxacin, Row’s group used choline chloride and MAA to obtain a deeply eutectic solvent,
ur

14 which served as both eco-friendly surfactant and imprinting monomer in polymerization (Li
Jo

15 and Row, 2020). Based on the complex of host−guest, α-cyclodextrin was recently used as

16 functional monomers to imprint dibutyl phthalate (DBP) in a porous polymer and yielded an

17 imprinting factor of 2.6 (Dolai et al., 2020). More cheaply and friendly, chitosan-based MIP

18 membrane was fabricated via employing glutaraldehyde as cross-linker to remove

19 4-nitrophenol (4NP) in aqueous media with a the largest binding capacity of 101 mg g−1

20 (Bello et al., 2017). Alternatively, the molecularly imprinted chitosan was synthesized

21 through cross-linking with epichlorohydrin (ECH) to exhibit an adsorption capacity of 416

22 mg g−1 for perfluorooctane sulfonate (PFOS) with an imprinting factor of 2.2 via the

12
 1 electrostatic interaction of PFOS on imprinted sites (Yu et al., 2008). Meanwhile, the

2 imprinted chitosan could be reused for at least five times and no decrease was observed in

3 adsorption amount.

4 With the facile synthesis of stimuli-responsive materials, the smart molecular recognition

5 has been developed by the introduction of stimuli-responsive molecules into MIPs. Typically,

6 4-vinylpyridine (4-VP) and N-isopropylacrylamide (NIPAM) were employed as dual

of
7 functional monomers to fabricate thermally responsive MIPs on porous carriers for controlled

ro
8 adsorption and desorption of BPA via regulating environmental temperature (Dong et al.,

9
-p
2014). Less than ‘lower critical solution temperature’ (LCST, 33 oC), a slight increment in
re
10 adsorption capacity was observed with the increase of temperature whereas a sharp decrease
lP

11 occurred in adsorption above LCST (i.e. the adsorption capacity reached the largest value of
na

12 ~ 5 mg g−1 at 33 oC with an imprinted factor of 4.1). Through six adsorption–desorption

ur

13 rounds, the resultant MIPs had a relative standard error within 9.8%. Similarly,
Jo

14 thermosensitive MIPs were synthesized in mesoporous silica nanospheres for selectively

15 adsorbing and removing dichlorophen (DCP) in aquatic environments with a binding amount

16 of 108.4 mg g−1 at 25 oC (Guo et al., 2019a). Besides thermosensitive MIPs, photoresponsive

17 MIPs were also developed on mesoporous carriers by utilizing photosensitive molecules with

18 azobenzene group as additive monomer for intelligently separating BPA from a complex

19 environment with a maximal binding amount of 6.1 mg g−1 (Liu et al., 2016a). Under the

20 alternating irradiation, the target molecules can be controlled to bind into the imprinted

21 cavities and detach from imprinted materials into the solution.

22
13
 1

2 3.2. Novel imprinted structures

of
3

ro
4 Fig. 3. Novel synthetic methods of MIP microspheres via Pickering emulsion polymerization.
5 -p
(A) Schematic illustration for preparing procedure. (B) Binding capacities for BPA by MIP
re
6 and NIP microspheres over time. Reprinted with permission from Elsevier from Ref. (Wang
7 et al., 2017).
lP

8 For increasing the binding capacity to BPA, a Pickering oil/water emulsion polymerization
na

9 strategy was developed to synthesize hydrophilic microspheres by using silica particles as the
ur

10 only stabilizer, whose maximum binding capability was as high as 112 mg g−1 with an
Jo

11 imprinting factor of 3.6 (Fig. 3) (Wang et al., 2017). More frequently, surface imprinting or

12 core-shell imprinted microspheres have been conveniently employed as sorbents for

13 removing the target pollutants with excellent performances. For instance, the surface

14 imprinted silica sorbent by 2,4-dichlorophenoxyacetic acid (2,4-D) exhibited a large

15 selectivity coefficient of over 18 for 2,4-D as compared to 2,4-dichlorophenol, in which 73%

16 of binding capacity was performed in the first 5 min and the bound 2,4-D can be easily eluted

17 by the mixed solvent of ethanol and HCl (Han et al., 2010). After five adsorption/desorption

18 cycles, the binding amount still remained 93% of original one. Through reversible

14
 1 addition-fragmentation chain transfer (RAFT) reaction, MIP shell was synthesized on silica

2 gel to show an excellent binding affinity to 2,4-dichlorophenol (3.07 mg g−1) with an

3 imprinting factor of 4.4 (Li et al., 2009). Similarly, the imprinted sites of PFOS were

4 constructed in the mesoporous silica shells by using silica nanoparticles as templates and

5 CTAB as porogen, which exhibited a binding amount of 21.10 mg g−1 after adsorbing for 25

6 min (Du et al., 2018). The porous structures increased the bound amount and the inorganic

7 adsorbents showed super selectivity and excellent recycling ability (five adsorption–

of
ro
8 desorption cycles led to a decreasing rate of <5%). In other exploitations, the silica can be

9 -p
replaced with polymer seeds as a sacrificial template to synthesize single hole hollow MIP
re
10 particles via one-step polymerization for the recognition of BPA (Wang et al., 2019a).
lP

11 Alternatively, zeolite imidazolate framework-8 (ZIF-8) served as a stabilizing agent in

12 Pickering emulsion and spherical templates to synthesize hollow MIP microspheres, which
na

13 produced a maximum binding amount of 108.1 mg g−1 with an imprinting factor of 3.83 to
ur

14 selectively separate 2,4-D in aqueous solutions (Yang et al., 2019).

Jo

15 Except for zero-dimensional particles, one- and two-dimensional MIPs have been reported

16 in the recent years. For example, halloysite nanotubes were used as a sacrificial template to

17 synthesize chloramphenicol (CAP)-imprinted nanorods with uniform and controllable shell

18 thickness via an in situ precipitation polymerization (Shen et al., 2016). In Zhang’s work,

19 carbon nanotubes were first coated by silica films and then surface imprinted with estrone by

20 utilizing the semi-covalent imprinting approach to yield a binding amount of 31 mg g−1 (Gao

21 et al., 2011). Alternatively, graphene oxide was employed as support for synthesizing MIP

22 film to selectively adsorb and separate cyromazine from seawater samples with a binding

15
1 capacity of 14.5 mg g−1, which could keep high adsorption capacity for cyromazine after

2 being reused for six times (Chen et al., 2019). Similarly, water-compatible MIPs were

3 synthesized on porous graphene oxide by using 2-acrylamido-2-methylpropanesulfonic acid

4 as a water-soluble monomer, which exhibited the highest bound capacity of 85.7 mg g−1 for

5 BPA (Fig. 4) (Duan et al., 2016).

of
ro
-p
re
lP
na
ur
Jo

6
7 Fig. 4. (A) Schematic procedure of water-compatible MIP films on porous graphene oxide by
8 using 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and styrene (St) as functional
16
 1 monomers to imprint BPA. (B) Bound amounts for different chemicals by MIPs with various
2 ratios of AMPS to St, as compared with NIPs and porous graphene oxide (PGO). Reprinted
3 with permission from The Royal Society of Chemistry from Ref. (Duan et al., 2016).

4 3.3. Magnetic adsorbents containing MIPs

5 The synergy of selective adsorption and magnetic separation provides a very promising

6 strategy to develop efficient adsorbents for rapidly removing target pollutants. Based on this

7 advantage, magnetic MIPs are continuously attracting the largest research interest for their

of
8 convenient utilization in environmental remediation. As reported, a simple synthesized

ro
9 approach of magnetic MIPs is to embed magnetic nanoparticles (e.g. Fe3O4) into imprinted

10
-p
matrix for forming magnetic MIP networks, which exhibited high adsorbing amounts toward
re
11 the template molecules, e.g. erythromycin and ciprofloxacin with binding capacities of 70
lP

12 and 32 mg g−1, respectively (Kuhn et al., 2020). Alternatively, magnetic MIPs were
na

13 synthesized via Pickering emulsion polymerization by using Fe3O4 nanoparticles-containing

ur

14 chitosan nanoparticles as stabilized agent and magnetic carrier, whose adsorption capacity for
Jo

15 erythromycin (ERY) was up to 38 mg g−1 (Ou et al., 2015). Through three repeated

16 adsorption–desorption rounds, ~5.04% loss in adsorption capacity was observed.

17 Compared to the magnetic networks above, the combination of MIPs and magnetic

18 property was more often carried out through synthesizing MIP shells on Fe3O4 nanoparticles.

19 Typically, Shen’s group combined suspension polymerization and surface imprinting to

20 prepare Fe3O4@MIP nanoparticles modified with ethylenediamine, diethylenetriamine,

21 triethylentetramine and tetraethylenepentamine, respectively (Shen et al., 2015). For template

22 2,4,6-trichlorophenol (2,4,6-TCP), the bound capacities on four amino-modified

17
 1 nanoparticles were 872.8, 880.5, 888.3 and 898.7 mg g−1, and the imprinting factors were

2 2.68, 2.31, 2.22 and 2.03, respectively. Alternatively, surface coating strategy was employed

3 for preparing homogeneous MIP thin film on Fe3O4 nanoparticles by in situ precipitation

4 polymerization to exhibit the maximum binding capacity for tetracycline at 23 mg g−1 within

5 20 min (Dai et al., 2014). More directly, RAFT agent was first modified on Fe3O4

6 nanoparticles and then produced the BPA-imprinted core-shell magnetic nanoparticles, which

7 was easily used in magnetic separation in the assistance of an external magnetic field and

of
ro
8 showed outstanding affinity selectivity and reusability (Li et al., 2010). For inducing the

9 -p
selective generation of MIP shells, Fe3O4 particles were functionalized with polyethylene
re
10 glycol (PEG) to prepare Fe3O4@PEG@MIP particles via the inverse emulsion–suspension
lP

11 polymerization for removing acidic dyes from polluted water (Luo et al., 2011). Similarly,

12 Fe3O4@chitosan@MIP particles were fabricated for rapidly removing CBZ molecules from
na

13 aqueous solution with an equilibrium binding amount of ~90 mg g−1 (Zhang et al., 2013a).
ur
Jo

14 To avoid the leaching of Fe3O4 and achieve better coating of MIPs, SiO2 layers are usually

15 synthesized on Fe3O4 particles before molecular imprinting, which were successfully

16 employed for selective adsorption and convenient collection of triclosan (TCS) with a

17 binding amount of 53 mg g−1 after incubating for 2 min and molecular selectivity of 6.321

18 (Lu et al., 2020). In Li’s work, fluorophore nitrobenzoxadiazole was modified with MAA,

19 which served as both functional monomer for imprinting and the donor for FRET process to

20 imprint Rhodamine B (RhB) on Fe3O4@SiO2 nanoparticles, which exhibited the largest

21 binding amount of 29.6 mg g−1 (Li et al., 2017). More interestingly, temperature and magnetic

22 dual-sensitive MIP shells were fabricated on Fe3O4@SiO2 particles via RAFT precipitation

18
 1 polymerization and further produced water-compatible nanocomposites via modified with

2 hydrophilic brushes to demonstrate superb thermoresponsive ability and rapid magnetic

3 separation for the effective removal of BPA (Fig. 5A,B) (Wu et al., 2016a). As shown in Fig.

4 5C, the maximum adsorption (8.3 mg g−1) and desorbing efficiency for BPA were achieved at

5 35 oC and 45 oC, respectively, and an imprinting factor of ~4.5 was yielded (Fig. 5D). After

6 five adsorption–desorption cycles, the precision less than 5% was observed in recoverability.

7 Through combining selective adsorption, water-compatible feature, magnetic separation and

of
ro
8 temperature manipulation, the intelligent MIPs will be promising to controllably

9 -p
adsorb/detach target pollutants for their high-efficiency enrichment and removal.
re
lP
na
ur
Jo

10
11 Fig. 5. Preparation and characterization of water-compatible temperature and magnetic
12 dual-sensitive MIPs (WC-TMMIPs) (A) Schematic illustrations for preparing WC-TMMIPs
13 and their applications in MSPE and packed SPE. (B) Temperature-regulated adsorption and
14 desorption of BPA molecule on the imprinted sites in WC-TMMIPs. (C) Equilibrium binding
15 curves of BPA by WC-TMMIPs at different temperatures. (D) Equilibrium binding curves of
16 BPA by different samples at 35 oC. Reprinted with permission from Elsevier from Ref. (Wu et
17 al., 2016a).

19
 of
ro
1
2
-p
Fig. 6. (A) Schematic for demonstrating the controlled preparation of MGO@MIP, (B) TEM
re
3 image of MGO@MIP. (C) The bound amount of PCP by imprinted and non-imprinted
lP

4 samples at different pH values. (D) The temporal evolution in adsorption for PCP by
5 MGO@MIP and MGO@NIP. Reprinted with permission from The Royal Society of
na

6 Chemistry from Ref. (Pan et al., 2014).

ur

7 Besides SiO2, other interesting nanostructures were also hybridized with Fe3O4
Jo

8 nanoparticles for further producing magnetic MIP systems. Typically, graphene oxide sheets

9 with magnetic particles were imbedded into MIP microspheres (MGO@MIP) via a

10 reflux-precipitation polymerization to exhibit a maximum binding amount of 789.4 mg g−1

11 and an imprinting factor of 4.36 towards pentachlorophenol (PCP) (Fig. 6) (Pan et al., 2014).

12 In Ma’s work, MIPs were synthesized at the surface of magnetic graphene oxide via a sol-gel

13 approach together with dual-dummy templates imprinting method (Guo et al., 2019b). The

14 usage of dipropyl phthalate (DPRP) and diisononyl phthalate (DINP) resulted in a MIP

15 composite that can simultaneously separate and enrich six typical phthalates esters (PAEs) in

20
 1 aqueous media with equilibrium binding capabilities ranging from 2.3 to 4.8 mg g−1.

2 Alternatively, carbon nanotubes with magnetic particles were hybridized with MIPs to

3 effectively remove aristolochic acid I (AAI) from Chinese medicine, which exhibited a

4 magnetic separation time of 10 s, kinetic time of 15 min for binding equilibrium, the largest

5 binding amount of 18.54 mg g−1 and an imprinting factor of 3.17 (Li et al., 2019). In addition,

6 Fe3O4@ZIF-8@MIPs were fabricated to selectively adsorb tetrabromobisphenol A (TBBPA)

7 from aqueous media with maximum binding capacity of 117.6 mg g−1 within 15 min (Li et al.,

of
ro
8 2018a). Through encapsulating attapulgite/Fe3O4 nanoparticles into MIPs, magnetic MIPs

9 -p
with claviform shape were produced to selectively bind 2,4-dichlorophenol with adsorption
re
10 capacity of 145 mg g−1 (Pan et al., 2011). Similarly, fly-ash-cenospheres/Fe3O4 nanoparticles
lP

11 were first synthesized via a co-precipitation approach and then endowed with surface reactive

12 vinyl groups to further prepare magnetic MIP shells by suspension polymerization, which
na

13 exhibited a monolayer binding capacity of 434.8 mg g−1 toward nonylphenol (Pan et al.,
ur

14 2013). In another work, keratin extracted from chicken feathers was used as an additive agent
Jo

15 to prepare new bio-based magnetic MIP nanoparticles containing MAA and Fe3O4 particles

16 for its interesting utilization in enrichment and separation of BPA from aqueous media (the

17 binding capacity was as high as 600 mg g−1 and the elimination efficiency reached ∼98%

18 within 40 min) (Hassanzadeh et al., 2018).

19 Except for Fe3O4 nanoparticles, γ-Fe2O3 particles with magnetic property were similarly

20 hybridized with MIPs for forming magnetic MIP composites. Typically,

21 norfloxacin-imprinted composites were obtained by the cross-linking reaction of chitosan

22 with γ-Fe2O3 nanoparticles, in which the γ-Fe2O3 particles remained their intrinsic crystalline

21
 1 structures, and interacted with both amino and hydroxyl groups in chitosan (Wu et al., 2016b).

2 In another work, thermal-responsive magnetic nanocomposite of

3 γ-Fe2O3/SiO2/poly(NIPAM-co-acrylamide-co-EGDMA) was synthesized as an effective

4 adsorbing agent for selectively removing sulfamethazine (SMZ) from aqueous media by

5 changing environmental temperatures (Xu et al., 2012a).

6 3.4. MIP-based membrane

of
7 For rapidly adsorbing and separating specific pollutants, membrane-associated MIPs were

ro
8 developed by using a mixed solution of MIPs, polysulfone, and N-methyl-2-pyrrolidone,

9
-p
which demonstrated a well-defined porous arrangement and an enhanced enrichment of
re
10 polychlorinated biphenyls (PCBs) (Mkhize et al., 2017). Via the adhesive process from
lP

11 polydopamine (PDA), the multilevel nanocomposites of Br-Ag-PDA@SiO2 were integrated

na

12 in a porous propranolol-imprinted film by photoinitiated atom transfer radical polymerization

(ATRP), in which enhanced binding capacity (48.5 mg g−1), permselectivity (> 5.5) and
ur

13
Jo

14 permeability (> 9.6) were achieved (Wu et al., 2016c). Similarly, the integration of biomass

15 activated carbon and SiO2 nanoparticles into porous membranes significantly improved the

16 performance of atrazine-imprinted nanocomposite to exhibit a specific adsorption ability of

17 5.857 mg g−1 and permselectivity factor of 2.34 (Xing et al., 2020). Alternatively,

18 phenol-imprinted PS nanospheres were modified on alumina membranes via microemulsion

19 polymerization method, which yielded the recoveries of phenol from real salicylic acid

20 sample between 92.62% and 101.55% (Liu et al., 2016b).

21 4. MIP-enhanced catalytic eradication of organic pollutants

22
 1 With the extensive utilization of MIPs as selective adsorbents, the specific recognition

2 features of molecularly imprinted materials are further used to enhance catalytic eradication

3 of organic pollutants for environmental remediation, which can be achieved via imprinting

4 pollutant (i.e. reactant) and/or degraded product (Sharabi et al., 2010). As known, it is easily

5 understood that the imprinted cavities of reactant can readily catch pollutants into the

6 catalytically active sites from solution, which is definitely favorable for further catalytic

7 degradation of pollutants. For product-imprinted systems, the degraded products or

of
ro
8 intermediate products will be rapidly fallen into the imprinted sites to decrease the

9 -p
concentration of products and thus prompt the catalytic reaction. In addition, MIPs can be
re
10 employed to adjust the selectivity of catalytic reaction for special organic chemicals,
lP

11 providing a highly selective method to remove low concentration of highly toxic organic

12 contaminants rather than high concentration of low toxic organics (Shen et al., 2014). With
na

13 these outstanding advantages in catalytic degradation, MIPs have been attracting a broad
ur

14 research attention to develop novel catalytic systems for environmental applications. In this
Jo

15 section, we will exhaustively summarize the important exploitations with emphasizing on the

16 synergy of MIPs and TiO2 for photocatalytic degradation of organic pollutants.

17 4.1. Greatly enhanced catalytic hydrolysis of pollutants by MIPs

18 In general, the self-hydrolysis of organic pollutants are extremely difficult and slow. Hence,

19 it is very significant to greatly enhance their hydrolysis via developing MIPs with catalytic

20 activity, which is readily performed by introduction of catalytically-active functional

21 monomer in MIPs. Typically, mononuclear zinc (II)-picolinamine-amidoxime (Zn-PAAO)

22 was synthesized and incorporated into porous MIPs as organophosphorus hydrolase (OPH)

23
 1 mimic for rapidly realizing organophosphate (OP) hydrolysis in min level, which exhibited 2

2 ×104-fold in the pseudo first rate constant for hydrolysis of diethyl 4-nitrophenyl phosphate

3 (DENP), greatly higher than that of self-hydrolysis due to the generation of active Lewis

4 acidic zinc(II) ion and a strong free oxime nucleophile in MIPs (Pan et al., 2019).

5 Alternatively, zinc dimethacrylate (MAA-Zn) was employed as the functional monomer and

6 catalytic agent to fabricate reactant–product-dual-template imprinted hollow microspheres

7 after removing vinyl-bearing silica seed, which can simultaneously degrade the reactant and

of
ro
8 eliminate its product (Guo and Guo, 2013). Owing to the existence of the void, the capsule

9 exhibited significantly enhanced catalytic efficiency with an initial reaction rate of 59.6×10-2
-p
re
10 μM min−1, higher than that of corresponding core-shell microspheres by a fold of 1.88 and
lP

11 that of paraoxon self-hydrolysis by a fold of 272. Similarly, imprinted hollow capsule was

12 fabricated by using N-(4-vinylbenzyl)-di(2-picolyl) amine-Zn(II) as additives for effectively

na

13 eliminating organophosphorus pesticide methyl parathion (Fig. 7) (Shi et al., 2015). The
ur

14 initial hydrolysis rate was up to 3.1×10-2 mM h−1, which exhibited a 355-fold higher than
Jo

15 that of the self-hydrolysis of methyl parathion. In addition,

16 (4-vinylbenzyl)-1,4,7-triazacyclononane and

17 1,4-bishydroxyethyl-7-(4-vinylbenzyl)-1,4,7-triazacyclononane were used as novel functional

18 monomers to synthesize MIP hollow nanoparticles for eliminating methyl parathion at an

19 initial rate of 3.51×10-2 mM h−1 (415-fold higher than the self-hydrolysis) (Wang et al.,

20 2019b).

21 Besides functional monomers, some special nanocrystals such as TiO2 can also be utilized

22 as catalytic sites for developing catalytically-active MIPs. In He’s work, a nanocomposite of

24
 1 Fe3O4@SiO2@TiO2@MIPs was synthesized by using methyl orange as dummy template for

2 rapidly degrading Congo red (CR) (Wei et al., 2015). Similarly, the dummy template-based

3 strategy was employed for preparing N-doped P25/Fe3O4-graphene oxide composite with

4 MIPs (Yang et al., 2017). Very recently, an MIL100 material was used as supports for surface

5 molecular imprinting with diethyl phthalate, whose catalytic property was increased by

6 1.5-fold in persulfate catalytic decomposition (Li et al., 2020a).

of
ro
-p
re
lP
na
ur
Jo

8 Fig. 7. MIP-based catalytic hydrolysis for pesticide methyl parathion. (A) Schematic
9 procedure for preparing N-(4-vinylbenzyl)-di(2-picolyl) amine-Zn(II) (VBDA)-MIP
10 nanocapsule and their TEM images (inset image). (B) The hydrolysis curves of methyl
11 parathion in the absence (self-hydrolysis) and presence of VBDA-NIP and VBDA-MIP
12 nanocapsules. (C) The selectivity in catalyzed hydrolysis by the VBDA-MIP and VBDA-NIP
13 nanocapsules. Reprinted with permission from Elsevier from Ref. (Shi et al., 2015).

25
1

4 4.2. Imprinting-enhanced photocatalytic degradation

5 Table 2
6 Typical molecularly imprinted photocatalysts containing TiO2 and/or other photocatalytic

of
7 materials.
Semiconductor Imprinting strategy Template Performance Ref.

ro
TiO2 Incorporation in MIPs 17β-estradiol Completed removal and five cycles of reuse (Tonucci et al., 2020)
Diclofenac A selectivity of of 2.8 and six cycles of reuse (de Escobar et al.,

Incorporation in imprinted pharmaceutical

-p
Enhancing degradation from 5 to 427% as
2018)
(de Escobar et al.,
re
silica compounds compared to that of P25 2016)
RhB Removal efficiency of > 80% after three cycles (de Escobar et al.,
2015)
lP

MIP shells on TiO2 2NP and 4NP 2.46 and 4.61 times higher than neat TiO2 in (Shen et al., 2018)
degradation rate, respectively.
Norfloxacin A degradation efficiency of 77.1% after 1 h. (Wei et al., 2018)
na

RhB A selectivity of 2.99 relative to Rh6G and a (Bao et al., 2014)

degradation rate higher by 216% than that of
NIPs.
ur

Methylene blue/orange A selectivity of 2.83 within five cycles. (Ng et al., 2017)
Imprinted silica shells Oxytetracycline Degrading 80.79% within 120 min. (Guo et al., 2016)
TiO2 shell on MIPs Methyl orange Remaining 60% in catalytic efficiency after ten (Xiao et al., 2015)
Jo

cycles.
Imprinted TiO2 materials DIMP and DEHMP An enhanced mineralization rate by a factor of (Sharabi et al., 2010)
3–4.
Imprinted TiO2 on SiO2 4NP Complete degradation within 30 min (Deng et al., 2014)
particles
S-doped TiO2 MIP shells on TiO2 Salicylic acid 1.7 times higher in degradation rate than the (Wang et al., 2014)
one on S-TiO2 particles.
Co-doped TiO2 MIP shells on TiO2 RhB 337.3% of photodegradation over Co–TiO2. (Liu et al., 2016c)
Cl-doped TiO2 MIP shells on TiO2 Tetracycline A degradation rate of 72.35% after irradiation (Liu et al., 2013)
for 60 min.
N-F codoped Imprinted TiO2 materials 2NP and 4NP 267% and 198% higher than that of (Wu et al., 2016d)
TiO2 non-imprinted ones in degradation rate,
respectively.
Ag/Zn-doped Imprinted TiO2 materials ethyl A selectivity coefficient of 8.55 and a (Zhu et al., 2020)
TiO2 p-hydroxybenzoate photodegadation rate of 99.1% after 2 h.
Ag2S-doped Imprinted TiO2 materials ethyl A selectivity coefficient of 3.57 and a (Liu et al., 2020)
TiO2 p-hydroxybenzoate photocatalytic degradation efficiency of
92.22% within 1.5 h.
NaCl/TiO2 Imprinted TiO2 materials Ciprofloxacin A photodegradation rate of 70.90% after 60 (Liu et al., 2014)
min.
ZnO Directly imprinting in ZnO paracetamol Complete removal within 3 h. (Cantarella et al.,
2018)
ZnO@Zr-MOF MIPs on ZnO@Zr-MOF tetracycline Degrading 61.9% within 30 min. (Du et al., 2020)

26
 CoFe2O4/carbon MIPs on them MBT A coefficient of selectivity of 3.37. (Lu et al., 2015)
nanotube
C3N4 sheets MIPs on C3N4 Guanine Faster for 37 times than that of bare C3N4. (Xing et al., 2013)

1 In order to increase the eliminating speed and decrease the cost for removing contaminants,

2 light energy was exploited to achieve photocatalytic degradation of organic pollutants, i.e.

3 converting light into chemical energy (Guan et al., 2020). Compared to the hydrolysis of

4 pollutants, the photocatalytic decontamination is more efficient and economical, and easier to

5 be realized by using semiconductor photocatalysts. Among various semiconductors, TiO2 has

of
6 been receiving the widest attention owing to its high redox potential, low toxicity, excellent

ro
7 chemical stability and cost-effective feature (Wu et al., 2016d). For overcoming the poor

8
-p
selectivity of TiO2, there are a large number of research works in the past decades to develop
re
9 TiO2 systems with molecularly imprinted sites, which provide molecular recognition ability
lP

10 toward the template pollutants (Table 2). To sum up, the construction of imprinted sites in
na

11 TiO2 systems can be carried out by four different routes (Fig. 8): embedding TiO2 particles
ur

12 into MIPs (de Escobar et al., 2016), coating MIP shells on TiO2 (Shen et al., 2014), coating
Jo

13 TiO2 shells on MIP particles (Xiao et al., 2015), and directly imprinting targets in TiO2 matrix

14 (Fiorenza et al., 2020). Of noted, pure TiO2 is only activated under ultraviolet light because of

15 its band gap at 3.2 eV. To increase the visible light-absorbing efficiency, TiO2 can be doped

16 with special compounds to decrease its band gap and then used as support for surface

17 imprinting (de Escobar et al., 2018).

27
 of
ro
1
2 Fig. 8. Four typical routes for developing photocatalytic systems with imprinted sites and
-p
3 TiO2 nanocrystals: (A) MIPs embedded with TiO2 particles, Reprinted with permission from
re
4 Elsevier from Ref. (de Escobar et al., 2016); (B) TiO2@MIPs, Reprinted with permission
lP

5 from Elsevier from Ref. (Shen et al., 2014); (C) MIP@TiO2 shells, Reprinted with permission
6 from Elsevier from Ref. (Xiao et al., 2015); and (D) imprinted TiO2. Reprinted with
na

7 permission from Elsevier from Ref. (Fiorenza et al., 2020).

ur

8 4.2.1. Combination of MIPs and TiO2

Jo

9 Incorporation. As reported, TiO2 was successfully incorporated in MIPs to prepare

10 mesoporous TiO2-containing MIPs, in which TiO2 decreased the adsorption capacity but

11 resulted in 100% of 17β-estradiol removal via photocatalysis and the removal capacity

12 maintained after at least five cycles of reuse (Tonucci et al., 2020). In another work, low

13 concentration of TiO2 was loaded into diclofenac (DIC)-imprinted MIPs to form a hybrid

14 photocatalyst with an excellent recognition ability for selectively degrading DIC (the average

15 value of selectivity was 2.8) (de Escobar et al., 2018). After six cycles of photodegradation,

16 the MIP-based photocatalysts still exhibited a same efficiency for photocatalytic elimination

28
 1 of DIC. Similar with MIPs, imprinted SiO2 matrix was also used as network to be embedded

2 with TiO2. As shown in Fig. 8A, an imprinted SiO2 photocatalyst loaded with low

3 concentration of TiO2 was synthesized by an acid-catalyzed sol–gel route, which enhanced

4 adsorption and degradation from 48 to 752% and from 5 to 427% compared to that of

5 Degussa P25, respectively (de Escobar et al., 2016). Alternatively, the use of TiCl4 as a TiO2

6 source and TEOS as SiO2 source produced RhB-imprinted photocatalysts to increase

7 selectivity (up to 180%) and competitiveness (up to 290%) as compared to P25 (de Escobar

of
ro
8 et al., 2015). After testing regeneration for three cycles, the removal efficiency remained at

9 more than 80% of the initial value. -p

re
10 Imprinted shell on TiO2. With the development of surface imprinting and nanotechnology,
lP

11 molecular imprinting on TiO2 has gained more and more research interest owing to their
na

12 morphological uniformity, high imprinted ability and photocatalytic efficiency. For instance,
ur

13 2-nitrophenol (2NP) and 4NP were used as templates to synthesize MIP-coated TiO2
Jo

14 microspheres with enhanced photocatalytic selectivity (Shen et al., 2008). In a mixed solution

15 containing 1.8 mg L−1 2NP, 1.8 mg L−1 4NP and 50 mg L−1 BPA, the photodegradation rate

16 constant for two target pollutants over TiO2@MIP was 10.73 × 10-3 and 7.06 × 10-3 min-1,

17 being 2.46 and 4.61 times of that over neat TiO2, respectively. Similarly,

18 norfloxacin-imprinted polymers were fabricated on P25 particles for combining molecular

19 imprinting and photocatalysis, which exhibited a photocatalytically degrading rate of 0.114

20 min−1 in 1 mg L−1 norfloxacin solution with a degradation efficiency of 77.1% after 1 h (Wei

21 et al., 2018). By employing 2,4-dinitrophenol as imprinted molecule and o-phenylenediamine

22 as both imprinting monomer and novel cross-linker, water-compatible MIP shells on

29
 1 thiol-functionalized TiO2 particles were recently synthesized in water for gaining a high

2 removing selectivity and fast photocatalytically degradation (Zhou et al., 2018). In addition,

3 TiO2@RhB-MIP was successfully synthesized to exhibit superb selectivity to RhB with a

4 coefficient of 2.99 relative to rhodamine 6G (Rh6G) (Bao et al., 2014). Moreover, the

5 apparent rate constant for degrading RhB by TiO2@RhB-MIP was 0.0212 min−1, 216%

6 higher than that of TiO2/NIP. In Leo’s work, the dye-imprinted shells were modified on TiO2

7 and then fixed in ultrafiltration membrane of polysulfone for eliminating the leakage of the

of
ro
8 particles (Ng et al., 2017). Under irradiation of UV, a selectivity of 2.00 was obtained for

9 -p
methylene blue/methylene orange within five cycles, which was further enhanced to 2.83
re
10 after the integrated photodegradation-ultrafiltration process. In another work, oxytetracycline
lP

11 (OTC)-imprinted silica shells were synthesized on TiO2 particles by liquid phase deposition

12 method, which achieved photodegradation of OTC wastewater of 80.79% in 120 min reaction
na

13 under a xenon lamp irradiation (Guo et al., 2016).

ur
Jo

14 For utilizing visible light, S-doped TiO2 particles were employed as core seeds for surface

15 imprinting salicylic acid by utilizing p-phenylenediamine as the imprinting monomer, whose

16 absorption edge was increased to across the whole visible region (Wang et al., 2014).

17 Benefiting from the molecular recognition ability, the rate constant for degrading salicylic

18 acid on S-TiO2@MIPs was 1.7 times higher than the one on S-TiO2 particles. Similar use of

19 p-phenylenediamine as monomer, RhB-imprinted shells were synthesized on Co-doped TiO2

20 particles for enhanced photodegradation in the presence of visible light with a k value of

21 0.03606 min−1, which was 215.7% that of RhB on Co–TiO2@NIPs, 337.3% that of RhB over

22 Co–TiO2 and 150.5% that of Rh6G on Co–TiO2@MIPs, respectively (Liu et al., 2016c).

30
 1 Alternatively, Cl-doped TiO2 particles were used as cores to fabricate tetracycline-imprinted

2 photocatalyst, which exhibited a degradation rate of 72.35% after irradiation by visible light

3 for 60 min (Liu et al., 2013). In addition, the coating of methyl orange-imprinted polypyrrole

4 on TiO2 can also narrow the band gap of TiO2 and exhibited enhanced catalytic capability in

5 visible irradiation by two times as compared to polypyrrole/TiO2 owing to the existence of

6 imprinted sites (Deng et al., 2012). Recently, molecularly imprinted SiO2 films were coated

7 on g-C3N4/TiO2 nanocomposite to enhance photodegradation performance for dye methyl

of
ro
8 violet under sunlight (about 99.0% at 160 min) (Rezaei et al., 20018).

9
-p
Aiming at some organic contaminants with high toxicity and low solubility (e.g.
re
10 nitrobenzene), it is usually inappropriate to directly imprint them in cross-linked matrix. To
lP

11 this end, Wang’s group developed a transition state analog (TSA) strategy to synthesize MIP
na

12 modified photocatalysts (i.e. TiO2@TSA-MIP) via utilizing 2NP or 4NP as the TSA template
ur

13 to remove the target nitrobenzene (Fig. 8B) (Shen et al., 2014). As revealed, the resultant
Jo

14 TiO2@TSA-MIP not only exhibited an excellent performance in photodegradation of

15 nitrobenzene, but also avoided the generation of highly toxic intermediates. Under an

16 interference from BPA (225 mol L−1), the photodegradation rate constants towards

17 nitrobenzene (15 mol L−1) on 2NP-P25 and 4NP-P25 were ~4.4 and ~3.6 times higher than

18 the value on pure P25, respectively (for BPA photodegradation, both imprinted samples

19 exhibited a slower efficiency than that on P25). It was thus revealed that the specific affinity

20 toward transition states can greatly decrease the energy for activating catalytic reaction.

21 Alternatively, the imprinting of highly toxic pollutants was also achieved by using structural

22 analogues as pseudo templates, which can avoid the production of more toxic by-products.

31
 1 For instance, 2,4-dinitrophenol was found as the best pseudo template in preparation of

2 TiO2@MIP for the greatly accelerated photodegradation of pentachlorophenol without the

3 generation of toxic intermediates (Shen et al., 2009a).

4 With the facile production of TiO2 nanotubes, surface-imprinted TiO2 nanotubes were

5 reported as photocatalysts for removing estrogenic pollutants from wastewater (Zhang et al.,

6 2013b). As revealed, the imprinted TiO2 nanotubes exhibited higher photodegradation

of
7 selectivity at low concentrations of less than 0.1 mg L−1 as compared with the one at high

ro
8 concentrations of more than 10 mg L−1. Alternatively, the TiO2 nanotube@MIPs were

9
-p
successfully fabricated by precipitation polymerization to selectively photodegrade
re
10 perfluorinated chemicals (e.g. perfluorooctanoic acid (PFOA)) from wastewater under
lP

11 irradiation of 254-nm light (Hu et al., 2016). In another work, Fe-doped TiO2/SiO2
na

12 nanofibrous films were deposited with 4NP-imprinted polymers to exhibit superb molecular
ur

13 selectivity in photocatalytic degradation of 4NP (Li et al., 2018b).

Jo

14 TiO2 shell on MIP particles. In a reverse way, TiO2 shell was coated on MIP particles for

15 photodegradation of imprinted molecules. In Xiao’s work (Xiao et al., 2015),

16 surface-imprinted chitosan particles were first synthesized by using methyl orange as

17 template and epichlorohydrin as cross-linking agent. Then, P25 powder (∼20–30 nm) was

18 covered at the surface of imprinted chitosan particles. As shown in Fig. 8C, TiO2 shells are

19 coated on methyl orange-imprinted chitosan particles to fabricate a novel hybrid material of

20 MIP core@TiO2 shell. No need to perform the process of desorption and regeneration, the

21 photocatalytic composite could be reused directly for ten cycles and remained 60% of its

22 catalytic efficiency in photodegradation.

32
 1 Directly imprinted in TiO2 matrix. As demonstrated above, the synthesis of TiO2-MIP

2 nanocomposites usually requires multistep procedures to cause a great consumption of time

3 and chemicals. And, the covering of polymeric material on the catalytically-active sites

4 causes light scattering to decrease the light conversion and photocatalytic capability (Wei et

5 al., 2018). For addressing these issues, recent researches have started to directly imprint

6 target molecules in TiO2 matrix, which provides a calcination treatment for completely

7 removing templates, like molecular imprinting in SiO2 systems. Typically, a liquid phase

of
ro
8 deposition method was developed for fabricating imprinted TiO2 films on borosilicate glass to

9 -p
exhibit a higher equilibrium adsorption constant by more than 7 times than that of the NIPs
re
10 (Shen et al., 2009b). Similarly, the TiO2 photocatalyst was directly imprinted by 2,4-D to
lP

11 significantly increase the photocatalytic performance of the imprinted TiO2 matrix (Fiorenza

12 et al., 2019). In Paz’s work, the preferential degradation with an enhanced mineralization rate
na

13 by a factor of 3–4 was achieved via the preparation of imprinted TiO2 photocatalyst with two
ur

14 model compounds: diisopropyl methylphosphonate (DIMP) and

Jo

15 diethylhydroxymethylphosphonate (DEHMP) (Sharabi and Paz, 2010). Interestingly, the

16 DEHMP-imprinted photocatalyst was very applicable to be utilized in the photodegradation

17 of the homolog DIMP, suggesting a success to detour the aggregation of target contaminants

18 with low affinity by imprinting the molecules with good affinity. In addition, Fiorenza et al.

19 (2020) fabricated the 2,4-D-imprinted TiO2 photocatalysts by using the standard reactants for

20 TiO2 sol-gel synthesis, as displayed in Fig. 8D. As a result, remarkable enhancements in the

21 photocatalytic performance and selectivity were observed under 368-nm UV lamp.

22 The direct imprinting in TiO2 matrix can also be performed via further doping other

33
 1 elements for utilizing visible light. For instance, N–F codoped TiO2 with imprinted sites was

2 synthesized via ethanol–water solvothermal approach utilizing 2NP and 4NP as the imprinted

3 molecules, respectively (Wu et al., 2016d). Under simulated solar light, the selectivity

4 coefficient on 2NP-imprinted TiO2 was 1.93 while the selectivity coefficient on

5 4NP-imprinted TiO2 was 1.61. And, the apparent rate constants for degrading 2NP and 4NP

6 by the corresponding imprinted TiO2 were 0.05233 min−1 and 0.03734 min−1, 267% and 198%

7 of that on non-imprinted ones, respectively. In another work, Pr-doped imprinted TiO2

of
crystals were prepared via an one-pot solvothermal approach with Pr(NO3)3·6H2O as Pr3+

ro
8

9 -p
precursor and 2-sec-butyl-4,6-dinitrophenol (DNBP) as both imprinted molecule and
re
10 microstructure-directing agent (Qi and Wang, 2020). As expected, Pr-doped imprinted TiO2
lP

11 displayed a higher photocatalytic ability than imprinted TiO2 in visible irradiation owing to

12 the narrower band gap and faster separation of photoproduced electron-hole pairs. In Yu’s
na

13 work, acid orange II-imprinted Fe-doped TiO2 composites were fabricated via a modified
ur

14 sol–gel reaction (Song et al., 2017). Under the interference of high concentrations of sodium
Jo

15 dodecyl benzene sulfonate (100 mg L–1), the imprinted Fe–TiO2 still exhibited a

16 highly-selective Fenton-like photodegradation for low levels of target contaminant (e.g. 20

17 mg L–1).

18 In Wang’s work, molecularly imprinted Ag/Zn-doped TiO2 was prepared through sol-gel

19 approach using ethyl p-hydroxybenzoate as the template (Zhu et al., 2020). At the optimized

20 conditions, the selectivity coefficient was 8.55 and the photodegadation rate reached 99.1%

21 after 2 h. In their another similar work, ethyl p-hydroxybenzoate-imprinted Ag2S-TiO2

22 nanocomposite was synthesized to result in a photocatalytic degradation efficiency of 92.22%

34
 1 within 1.5 h, which was 42% higher compared to neat TiO2 (Liu et al., 2020). The selectivity

2 toward ethyl p-hydroxybenzoate reached 3.57 as compared to phenol, 72% higher than pure

3 TiO2. For improving the visible-induced catalytic ability of TiO2, a molecularly imprinted

4 NaCl/TiO2 hybrid catalyst was prepared for removing ciprofloxacin with a photodegradation

5 rate of 70.90% after visible irradiation for 60 min (Liu et al., 2014). Alternatively,

6 molecularly imprinted TiO2/WO3 composite was recently fabricated by a facile one-step

7 sol-gel reaction, in which the imprinted molecules could be fully detached through

of
ro
8 high-temperature calcination (Fig. 9) (Luo et al., 2013). As demonstrated, the imprinted

9 -p
TiO2/WO3 exhibited higher photocatalytic capability for >2 times than that of non-imprinted
re
10 one under visible irradiation.
lP
na
ur
Jo

11
12 Fig. 9. Molecular imprinting in inorganic TiO2/WO3 matrix. (A) Experimental procedure for
13 forming molecularly imprinted sites in TiO2/WO3 nanocomposites. (B) Binding selectivity on
14 different samples for demonstrating the specific affinity of imprinted sites. Reprinted with
15 permission from American Chemical Society from Ref. (Luo et al., 2013).

16 Similar to the synthesis of MIP shells, imprinted TiO2 layers were coated onto SiO2

17 particles by sol-hydrothermal method to form imprinted SiO2@TiO2 nanocomposite with

18 excellent reusability for completely degrading 4NP in 30 min (the time was 110 min for the

19 non-imprinted one) (Deng et al., 2014). In Luo’s work, anthracene-9-carboxylic

35
 1 acid-imprinted TiO2 layers were fabricated at the surface of TiO2 nanotube arrays to show a

2 greatly increased catalytic ability for photodegrading the target pollutant, which was not

3 destroyed during photocatalysis due to the high physicochemical stability of TiO2 matrix (Liu

4 et al., 2010).

5 4.2.2. MIPs containing TiO2 and other nanomaterials

6 For combining photocatalysis and magnetic separation, TiO2 layers were first coated on

of
7 Fe3O4@SiO2 particles (SiO2 layers can protect Fe3O4 against being oxidized) and then

ro
8 modified with diuron-MIP shells by oxidative polymerization of 3-thiophene acetic acid

9
-p
(Anirudhan et al., 2020). Similar to polypyrrole, the existence of conducting layer not only
re
10 increased the selectivity of the photocatalyst but also adjusted the bandgap of TiO2 from 3.18
lP

11 to 2.87 eV. Under visible light, an enhanced photodegradation of diuron was observed. In
na

12 Wang’s work, estrone-imprinted TiO2 was synthesized on Fe3O4@SiO2 particles through a

ur

13 semicovalent approach for selective photocatalytic degradation of target pollutants (Fig. 10)
Jo

14 (Xu et al., 2014). In the presence of interfering agent (10 times higher than target), the

15 apparent rate constant for degrading estrone was about 6 times higher as compared to net

16 TiO2. Another interesting work was to fabricate 4NP-imprinted TiO2/WO3 layers on magnetic

17 Fe3O4@SiO2 particles, which photodegraded 4NP with a first-order reaction rate of 0.1039 h–

1
18 and exhibited 2.5 times higher than that of the NIP (Wei et al., 2016). Alternatively, a

19 composite of Fe3O4/Al2O3/imprinted TiO2 was also fabricated via a multistep wet chemical

20 reaction to show an enhanced photocatalytic degradation of the target 2NP (Zhang et al.,

21 2015b). In addition, carbon nanotube and polypyrrole were employed as dual conducting

22 elements to fabricate hybrid photocatalysts with imprinted sites of 1-methylimidazole-2-thiol

36
 1 (Luo et al., 2014).

of
ro
-p
re
lP

2
na

3 Fig. 10. The synthesis and characterizations of estrone-imprinted TiO2 layers at the surface of
4 Fe3O4@SiO2 particles. (A) Schematic for preparing Fe3O4@SiO2@TiO2 particles with
ur

5 estrone-imprinted sites in TiO2 shells. (B) Adsorption curves of different samples toward
Jo

6 estrone. (C) Photodegradation of estrone by different photocatalyst. Reprinted with

7 permission from The Royal Society of Chemistry from Ref. (Xu et al., 2014).

9 Fig. 11. (A) Preferential adsorption and photocatalytic degradation of CIP by using carbon
10 nanosheets/TiO2@MIP as photocatalyst. (B) Photocatalytic degradation selectivity in mixed
11 solution of CIP and SMZ for CT-MI4 synthesized under the ratio of CT to MIP as 1:4.
37
 1 Reprinted with permission from Elsevier from Ref. (Li et al., 2020b).

2 For effectively combining specific adsorption and photocatalytic degradation, carbon

3 sheets decorated with TiO2 were fabricated and incorporated in ciprofloxacin (CIP)-imprinted

4 polymers (Fig. 11A) (Li et al., 2020b). Using SMZ as the interfering species, selectivity

5 factors for CIP was 7.2 for adsorption and 3.2 for photodegradation, respectively (Fig. 11B).

6 Besides carbon nanosheets, graphene was hybridized with BPA-imprinted TiO2 by using

7 o-phenylenediamine (OPDA) as imprinted monomer, which increased binding amount

of
ro
8 toward target pollutants and narrowed bandgap of TiO2 (Lai et al., 2016). Similarly, the

9 -p
anatase TiO2 nanocrystals with imprinted sites were modified densely on reduced graphene
re
10 oxide (rGO) sheets via strong interfacial interactions, leading to a greater binding capacity
lP

11 and photocatalytic activity for removing 4NP than neat TiO2/rGO (Li et al., 2015).

12 Alternatively, a composite of TiO2 nanotubes/silylated GO was synthesized as support for

na

13 imprinting 2,4-D by utilizing 2-hydroxyethyl methacrylate (HEMA) and itaconic acid (IA) as
ur

14 dual functional monomers (Anirudhan and Anju, 2019). After this imprinting, its band gap of
Jo

15 composite shifted to 2.42 eV for favoring photodegradation under visible light. In addition,

16 TiO2 and carbon nanodots were hybridized with a pendimethalin (PM)-MIP layer via

17 employing o-phenylenediamine as both the imprinted monomer and the precursor of carbon

18 nanodots (Shahnazi et al., 2020). As a result, the novel nanocomposite exhibited an enhanced

19 photodegradation efficiency (~ 95%) for PM under visible light, resulting from its large

20 binding capacity toward target pollutants and narrowed bandgap by carbon nanodots.

21 As one of the major industrial solidwastes, fly-ash cenospheres (FCs) have high chemical

22 stability, small mass, low cost and hollow shape, so FCs are very promising as carrier to

38
 1 fabricate novel composites. In the synthesis of FC-involved imprinted photocatalysts, Yan’s

2 group contributed several interesting works. Among them, the simplest photocatalyst was

3 synthesized by hybridizing surface imprinted TiO2 and FC, and led to a degradation rate of 76%

4 for oxytetracycline within 60 min and a relative coefficient of 4.51 for selective degradation

5 compared with the ciprofloxacin (Huo et al., 2012a). Further, poly-o-phenylenediamine

6 (POPD) coated TiO2/FC was used carrier for imprinting ciprofloxacin (CIP) via crosslinking

7 agent EGDMA and functional monomer acrylamide (Huo et al., 2012b). The degradation rate

of
ro
8 for CIP was up to 70% after irradiated by visible light for 60 min. Similarly, tetracycline was

9 -p
utilized as the template molecule for obtaining an imprinted photocatalyst containing
re
10 POPD/TiO2/FC, which exhibited a photodegradation rate of 77% for 20 mg L–1 tetracycline
lP

11 solution (Lu et al., 2013a). In addition, enrofloxacin hydrochloride (EH) was used as the

12 template molecule to fabricate TiO2@Fe3O4/FC@MIPs with POPD as monomer, which not

na

13 only exhibited higher photocatalytic activity for degrading EH, but also demonstrated better
ur

14 selection for rapidly adsorbing and photocatalytically degrading EH in single/binary solution

Jo

15 (Lu et al., 2013b).

16 4.2.3. Other photocatalytic systems beyond TiO2

17 Besides TiO2, other semiconductor have also been exploited for developing molecularly

18 imprinted photocatalysts. Unlike TiO2 with good photostability, other semiconductors may

19 tend to decompose under light irradiation (i.e. photocorrosion), which can be significantly

20 inhibited via modifying the crystal structure/morphology of semiconductors, doping with

21 heteroatoms, hybridizing with cocatalysts, and regulating the photocatalytic reaction

22 conditions (Weng et al., 2019). Typically, ZnO matrix was successfully imprinted by drug

39
 1 acetaminophen (i.e. paracetamol) to exhibit a great affinity and catalytically photodegrade all

2 the paracetamol within 3 h (Cantarella et al., 2018). Further, ZnO@Zr-MOF was used as

3 support to develop tetracycline-imprinted catalytic composite with higher photocatalytic

4 degradation efficiency without secondary pollution, which degraded 61.9% of tetracycline

5 within 30 min (Du et al., 2020). In Yan’s work, SiO2/ZnO/ZnS particles were wrapped with

6 thermoresponsive MIPs for photocatalytically degrading sulfadiazine with outstanding

7 capability (Xu et al., 2012b). In their another work, the composite of CoFe2O4/carbon

of
ro
8 nanotube was used as the matrix material for imprinting 2-mercaptobenzothiazole (MBT) via

9 -p
utilizing pyrrole as both the imprinting and conducting monomer (Lu et al., 2015). Due to
re
10 their high photocatalytic efficiency, the novel imprinted photocatalyst exhibited a high
lP

11 capability in photodegradation of MBT, and its coefficient of selectivity was up to 3.37 and

12 3.28 compared to CoFe2O4/carbon nanotubes and NIPs, respectively. Very recently, dual
na

13 inorganic imprinted Ag2O/CuO layers were prepared at the surface of Bi2WO6 nanocubes to
ur

14 form Bi2WO6/CuO/Ag2O hybrid photocatalysts after removing methyl green and auramine O
Jo

15 via calcination (Amiri et al., 2020). In addition, a photocatalyst of

16 Fe3O4/SiO2/simazine-imprinted hydroxyapatite was fabricated via a wet chemical reaction

17 and showed a greatly enhanced photodegradation selectivity to degrade simazine in aqueous

18 suspension (Zhang et al., 2015c).

19

40
 1 Fig. 12. (A) Three typical steps for fabricating MIP-C3N4. (B) Photodegradation of blaNDM‑1
2 by MIP-C3N4, P25, bare C3N4 and NIP-C3N4 in wastewater. Reprinted with permission from
3 American Chemical Society from Ref. (Yuan et al., 2020).

4 Similar to metal oxides, metal sulfides and photocatalytically-active two-dimensional

5 nanomaterials (e.g. C3N4 nanosheets) were also combined with molecularly imprinted

6 systems for photodegradation of organic pollutants. Typically, CdS/halloysite nanotubes were

7 used as support matrix to fabricate a tetracycline-imprinted photocatalyst with

of
8 thermal-responsive properties, which showed a tunable photocatalytic activity via changing

ro
9 the environmental temperature (Xing et al., 2013). In Alvarez’s work, guanine-imprinted

10
-p
C3N4 nanosheets (MIP-C3N4) were synthesized to exhibit an excellent photocatalytic removal
re
11 for plasmid-encoded ARG (blaNDM‑1) in secondary effluent (Fig. 12A), which is faster for 37
lP

12 times than that of bare C3N4 under UV irradiation (Fig. 12B) (Yuan et al., 2020). In another
na

13 work, Z-scheme Ag3VO4/C3N4 structures were hybridized with Ag(0) with surface plasmon
ur

14 resonance to further synthesize molecularly imprinted Ag/Ag3VO4/C3N4 nanocomposites

Jo

15 (Sun et al., 2019). In this photocatalyst, the Z-scheme hybridization and the surface plasmon

16 resonance improved the separation rate of photoproduced charge carriers, while MIP

17 provided the specific recognition capability for selectively binding the target contaminant (i.e.

18 tetracycline).

19 4.3. Electrocatalytic and photoelectrocatalytic degradation of pollutants

20 Besides photocatalytic degradation, there were some researches to report the usage of

21 MIPs in electrocatalytic and photoelectrocatalytic degradation. Typically, a 2,4-D-imprinted

22 SnO2 electrode with mesoporous structure was prepared for reducing concentration of 2,4-D

41
 1 to 54 ppb in the coexisting sewage water through electrocatalytic degradation for 6 h, which

2 indicated the specific electrochemical recognition of template molecules (Tang et al., 2018).

3 Further, 2,4-D-imprinted TiO2@SnO2-Sb anode was similarly developed and used as an

4 electrocatalytic ceramic membrane filtration system for the selective elimination of 2,4-D

5 with an increment of 1.91 times at removal rate (Chen et al., 2020). For achieving

6 photoelectrocatalytic degradation of 2,4-D, single crystalline TiO2 nanoarrays with (001)

7 facets were covered by uniform imprinted layers, which yielded a removal ratio of 100%

of
ro
8 under a potential of 2 V for 3 h (Tang et al., 2020). In Zhao’s work, enhanced and selective

9 -p
photoelectrochemical oxidation of atrazine was realized by using imprinted mesoporous TiO2,
re
10 which revealed that the imprinted sites could serve as surface defects to accelerate the
lP

11 separation of photogenerated holes and electrons for generating more hydroxyl radicals (Shi

12 et al., 2019). Moreover, the high binding affinity for atrazine resulted in the selective
na

13 recognition ability toward atrazine in complex polluted water samples to produce an apparent
ur

14 rate constant of 0.25 h−1, 3 times higher than that of non-imprinted TiO2. In Chai’s work,
Jo

15 spindle-like TiO2 particles compactly grew on the boron-doped diamond substrate and then

16 BPA molecules were successfully imprinted on the TiO2 matrix to form a novel nanoelectrode

17 with n-P heterojunction and molecular recognition (Chai et al., 2012). With outstanding

18 photoelectrocatalytic activity and selectivity, the resulting nanoelectrode removed 97% of

19 BPA after 2 h and yielded a corresponding kinetic constant of 1.76 h−1, which is 4.6 times that

20 of 2NP removal. In the absence of imprinted sites, the removal rate constants of BPA and 2NP

21 were approximately equal, only about 0.5 h−1.

22 5. Summary and outlooks

42
 1 As one type of artificial recognition components, molecularly imprinted materials have

2 readily been synthesized via inducing template molecules into complex with functional

3 monomers and cross-linking the complex in polymers, macromolecules or inorganic xerogel,

4 followed by the removal of templates. Owing to the generation of complementary cavities

5 and functional groups, the resultant imprinted materials exhibited high selectivity and strong

6 affinity toward molecule of interest. Together with other merits such as low costs, high

7 physical/chemical stability and good engineering possibility, molecularly imprinted systems

of
ro
8 have recently been attracting a wide research interest for their promising performances in a

9 -p
variety of applications. Based on the urgent requirement for selectively eliminating organic
re
10 pollutants in environmental remediation, this review specially demonstrates the recent
lP

11 exploitations on the innovative utilization of molecular imprinting technology to selectively

12 adsorb and photocatalytically degrade target chemicals. As revealed, MIT is a very effective
na

13 and important approach for selective adsorption/separation of a highly toxic pollutant or its
ur

14 structurally analogous chemicals through choosing imprinted monomers, fabricating novel

Jo

15 nanostructures or hybridizing into composites with other functional nanomaterials. In

16 particular, the introduction of magnetic nanoparticles provides the interesting synergy of

17 selective adsorption and magnetic separation for rapidly removing target pollutants with

18 excellent reusability. More importantly, the molecular recognition cavities can facilely be

19 constructed on or near photocatalytically-active sites to further photodegrade the highly toxic

20 chemicals into non-toxic products for completely eradicating targeted pollutants via a

21 preferential way. All these works suggest that MIP nanomaterials have exhibited remarkable

22 advantages as molecular recognition elements for environmental remediation.

43
 1 As the investigations on MIP-based adsorbents and photocatalysts are reported more and

2 more frequently, related problems are also found to hinder their further developments towards

3 practical applications. First, the imprinted sites are produced after removal of template

4 molecules via multiple washing with special mixed solvent (for polymers) or

5 high-temperature calcination (for inorganic systems), both of which are not cost-effective and

6 easy-operated methods. Although the photocatalytic removal looks like milder and more

7 perfect, there is not still any reports to involve its great success in this case. Second, most of

of
ro
8 recent MIPs were designed into nanomaterials such as thin shells by nanosynthetic

9 -p
technology for increasing the imprinted efficiency, but the uniformity and yield of imprinted
re
10 products need to be further improved significantly for better repeating performances. Third,
lP

11 how to fabricate high-efficiency water-compatible MIPs is a very important and difficult

12 topics for practical applications in water environment. Although the macromolecules-built

na

13 systems exhibit good water-compatibility, the resultant imprinted sites are not good enough to
ur

14 remain long-term stability and high specific affinity. Forth, it will be an exciting research
Jo

15 direction to on site or in situ produce MIPs in wastewater and remove the contaminants by

16 adsorption and simultaneous extraction or chemical treatment, which can not only simplify

17 the imprinting process but also fully eradicate the target pollutants. Overall, more efforts

18 should be devoted to develop multidisciplinary strategies for addressing the above concerns

19 and facilely realizing the practical applications of MIP nanosystems in environmental

20 remediation.

21

22 Acknowledgements
44
 1 This work was supported by Seed Foundation of Tianjin University (2020XYF-0091).

3 Reference:

4 Amiri, M., Dashtian, K., Ghaedi, M., Mosleh, S., 2020. A dual surface inorganic molecularly
5 imprinted Bi2WO6-CuO/Ag2O heterostructure with enhanced activity-selectivity towards
6 the photocatalytic degradation of target contaminants. Photochem. Photobiol. Sci. 19,
7 943–955.
8 Anirudhan, T.S., Anju, S.M., 2019. Synthesis and evaluation of TiO2 nanotubes/silylated

of
9 graphene oxide-based molecularly imprinted polymer for the selective adsorption and

ro
10 subsequent photocatalytic degradation of 2,4-Dichlorophenoxyacetic acid. J. Environ.
11 Chem. Eng. 7, 103355.
12
-p
Anirudhan, T.S., Shainy, J., Shainy, F., 2020. Magnetic titanium dioxide embedded
re
13 molecularly imprinted polymer nanocomposite for the degradation of diuron under visible
14 light. React. Funct. Polym. 152, 104597.
lP

15 Bao, L., Meng, M., Sun, K., Li, W., Zhao, D., Li, H., He, M., 2014. Selective adsorption and
na

16 degradation of rhodamine B with modified titanium dioxide photocatalyst. J. Appl. Polym.

17 Sci. DOI: 10.1002/APP.40890.
ur

18 BelBruno, J.J., 2019. Molecularly imprinted polymers. Chem. Rev. 119, 94−119.
Jo

19 Bello, M.P.D., Mergola, L., Scorrano, S., Sole, R.D., 2017. Towards a new strategy of a
20 chitosan-based molecularly imprinted membrane for removal of 4-nitrophenol in real
21 water samples. Polym. Int. 66, 1055–1063.
22 Bhatnagar, A., Anastopoulos, I., 2017. Adsorptive removal of bisphenol A (BPA) from
23 aqueous solution: A review. Chemosphere 168, 885–902.
24 Cantarella, M., Mauro, A.D., Gulino, A., Spitaleri, L., Nicotra, G., Privitera, V., Impellizzeri,
25 G., 2018. Selective photodegradation of paracetamol by molecularly imprinted ZnO
26 nanonuts. Appl. Catal. B: Environ. 238, 509–517.
27 Chai, S., Zhao, G., Zhang, Y., Wang, Y., Nong, F., Li, M., LI, D., 2012. Selective
28 photoelectrocatalytic degradation of recalcitrant contaminant driven by an n‑P
29 heterojunction nanoelectrode with molecular recognition ability. Environ. Sci. Technol.
30 46, 10182–10190.
31 Chen, L., Xu, S., Li, J., 2011. Recent advances in molecular imprinting technology: current
32 status, challenges and highlighted applications. Chem. Soc. Rev. 40, 2922–2942.
45
 1 Chen, L., Wang, X., Lu, W., Wu, X., Li, J., 2016. Molecular imprinting: perspectives and
2 applications. Chem. Soc. Rev. 45, 2137−2211.
3 Chen, J., Wang, J., Tan, L., 2019. Highly selective separation and detection of cyromazine
4 from seawater using graphene oxide based molecularly imprinted solid-phase extraction.
5 J. Sep. Sci. 42, 2100–2106.
6 Chen, M., Zheng, J., Dai, R., Wu, Z., Wang, Z., 2020. Preferential removal of
7 2,4-dichlorophenoxyacetic acid from contaminated waters using an electrocatalytic
8 ceramic membrane filtration system: Mechanisms and implications. Chem. Eng. J. 387,
9 124132.
10 Dai, C.M., Zhang, J., Zhang, Y.L., Zhou, X.F., Duan, Y.P., Liu, S.G., 2012. Selective removal

of
11 of acidic pharmaceuticals from contaminated lake water using multi-templates
12 molecularly imprinted polymer. Chem. Eng. J. 211-212, 302−309.

ro
13 Dai, J., Zhou, Z., Zhao, C., Wei, X., Dai, X., Gao, L., Cao, Z., Yan, Y., 2014. Versatile method
14
15
-p
to obtain homogeneous imprinted polymer thin film at surface of superparamagnetic
nanoparticles for tetracycline binding. Ind. Eng. Chem. Res. 53, 7157−7166.
re
16 de Escobar, C.C., Dallegrave, A., Lasarin, M.A., dos Santo, J.H.Z., 2015. The sol–gel route
lP

17 effect on the preparation of molecularly imprinted silica-based materials for selective and
18 competitive photocatalysis. Collod. Surf. A: Physicochem. Eng. Aspects 486, 96−105.
na

19 de Escobar, C.C., Lansarin, M.A., dos Santos, J.H.Z., 2016. Synthesis of molecularly
20 imprinted photocatalysts containing low TiO2 loading: Evaluation for the degradation of
ur

21 pharmaceuticals. J. Hazard. Mater. 306, 359−366.

Jo

22 de Escobar, C. C., Ruiz, Y.P.M., dos Santos, J.H.Z., Ye, L., 2018. Molecularly imprinted TiO2
23 photocatalysts for degradation of diclofenac in water. Colloid. Surf. A 538, 729−738.
24 Deng, F., Li, Y., Luo, X., Yang, L., Tu, X., 2012. Preparation of conductive polypyrrole/TiO2
25 nanocomposite via surface molecular imprinting technique and its photocatalytic activity
26 under simulated solar light irradiation. Collod. Surf. A: Physicochem. Eng. Aspects 395,
27 183–189.
28 Deng, F., Liu, Y., Luo, X., Wu, S., Luo, S., Au, C., Qi, R., 2014. Sol-hydrothermal synthesis
29 of inorganic-framework molecularly imprinted TiO2/SiO2 nanocomposite and its
30 preferential photocatalytic degradation towards target contaminant. J. Hazard. Mater. 278,
31 108−115.
32 Dolai, J., Ali, H., Jana, N.R., 2020. Molecular imprinted poly-cyclodextrin for selective
33 removal of dibutyl phthalate. ACS Appl. Polym. Mater. 2, 691−698.
34 Dong, R., Li, J., Xiong, H., Lu, W., Peng, H., Chen, L., 2014. Thermosensitive molecularly

46
 1 imprinted polymers on porous carriers: Preparation, characterization and properties as
2 novel adsorbents for bisphenol A. Talanta 130, 182–191.
3 Du, L., Cheng, Z., Zhu, P., Chen, Q., Wu, Y., Tan, K., 2018. Preparation of mesoporous silica
4 nanoparticles molecularly imprinted polymer for efficient separation and enrichment of
5 perfluorooctane sulfonate. J. Sep. Sci. 41, 4363–4369.
6 Du, Q., Wu, P., Sun, Y., Zhang, J., He, H., 2020. Selective photodegradation of tetracycline
7 by molecularly imprinted ZnO@NH2-UiO-66 composites. Chem. Eng. J. 390, 124614.
8 Duan, F., Chen, C., Zhao, X., Yang, Y., Liu, X., Qin, Y., 2016. Water-compatible surface
9 molecularly imprinted polymers with synergy of bi-functional monomers for enhanced
10 selective adsorption of bisphenol A from aqueous solution. Environ. Sci.: Nano. 3, 213–

of
11 222.

ro
12 Fiorenza, R., Mauro, A.D., Cantarella, M., Privitera, V., Impellizzeri, G., 2019. Selective
13 photodegradation of 2,4-D pesticide from water by molecularly imprinted TiO2. J.
14 Photochem. Photobio. A: Chem. 380, 111872. -p
re
15 Fiorenza, R., Mauro, A.D., Cantarella, M., Iaria, C., Scalisi, E.M., Brundo, M.V., Gulino, A.,
16 Spitaleri, L., Nicotra, G., Dattilo, S., Carroccio, S.C., Privitera, V., Impellizzeri, G., 2020.
lP

17 Preferential removal of pesticides from water by molecular imprinting on TiO2

18 photocatalysts. Chem. Eng. J. 379, 122309.
na

19 Fuchs, Y., Soppera, O., Haupt, K., 2012. Photopolymerization and photostructuring of
20 molecularly imprinted polymers for sensor applications—A review. Anal. Chim. Acta 717,
ur

21 7–20.
Jo

22 Gao, D., Zhang, Z., Wu, M., Xie, C., Guan, G., Wang, D., 2007. A surface functional
23 monomer-directing strategy for highly dense imprinting of TNT at surface of silica
24 nanoparticles, J. Am. Chem. Soc. 129, 7859–7866.
25 Gao, R., Su, X., He, X., Chen, L., Zhang, Y., 2011. Preparation and characterisation of core–
26 shell CNTs@MIPs nanocomposites and selective removal of estrone from water samples.
27 Talanta 83, 757–764.
28 Gladis, J.M., Rao, T.P., 2004. Effect of progen type on the synthesis of uranium ion imprinted
29 polymer materials for the preconcentration/separation of traces of uranium. Microchim.
30 Acta 146, 251–258.
31 Guan, G., Zhang, Z., Wang, Z., Liu, B., Gao, D., Xie, C., 2007. Single-hole hollow polymer
32 microspheres toward specific high-capacity uptake of target species. Adv. Mater. 19,
33 2370–2374.
34 Guan, G., Liu, R., Wu, M., Li, Z., Liu, B., Wang, Z., Gao, D., Zhang, Z., 2009.

47
 1 Protein-building molecular recognition sites by layer-by-layer molecular imprinting on
2 colloidal particles. Analyst 134, 1880–1886.
3 Guan, G., Liu, R., Mei, Q., Zhang, Z., 2012. Molecularly imprinted shells from polymer and
4 xerogel matrices on polystyrene colloidal spheres. Chem. Eur. J. 18, 4692–4698.
5 Guan, G., Ye, E., You, M., Li, Z., 2020. Hybridized 2D nanomaterials toward highly efficient
6 photocatalysis for degrading pollutants: current status and future perspectives. Small 16,
7 1907087.
8 Guo, Y., Guo, T., 2013. A dual-template imprinted capsule with remarkably enhanced
9 catalytic activity for pesticide degradation and elimination simultaneously. Chem.
10 Commun. 49, 1073−1075.

of
11 Guo, J., Li, S., Duan, L., Guo, P., Li, X., Cui, Q., Wang, H., Jiang, Q., 2016. Preparation of Si

ro
12 doped molecularly imprinted TiO2 photocatalyst and its degradation to antibiotic
13 wastewater. Integr. Ferroelectr. 168, 170–182.
14
-p
Guo, J., Chen, H., Wei, X., 2019. Thermally sensitive molecularly imprinted polymers on
re
15 mesoporous silica nanospheres: preparation, characterization, and properties as novel
16 adsorbents for dichlorophen. J. Chem. Eng. Data 64, 4005−4012.
lP

17 Guo, L., Ma, X., Xie, X., Huang, R., Zhang, M., Li, J., Zeng, G., Fan, Y., 2019. Preparation
18 of dual-dummy-template molecularly imprinted polymers coated magnetic graphene
na

19 oxide for separation and enrichment of phthalate esters in water. Chem. Eng. J. 361, 245–
20 255.
ur

21 Han, D., Jia, W., Liang, H., 2010. Selective removal of 2,4-dichlorophenoxyacetic acid from
Jo

22 water by molecularly-imprinted amino-functionalized silica gel sorbent. J. Environ. Sci.

23 22, 237−241.
24 Hassanzadeh, M., Ghaemy, M., 2018. Preparation of bio-based keratin-derived magnetic
25 molecularly imprinted polymer nanoparticles for the facile and selective separation of
26 bisphenol A from water. J. Sep. Sci. 41, 2296–2304.
27 He, Q., Liang, J.J., Chen, L.X., Chen, S.L., Zheng, H.L., Liu, H.X., Zhang, H.J., 2020.
28 Removal of the environmental pollutant carbamazepine using molecular imprinted
29 adsorbents: Molecular simulation, adsorption properties, and mechanisms. Water Res. 168,
30 115164.
31 Hu, L., Li, Y., Zhang, W., 2016. Characterization and application of surface-molecular-
32 imprinted-polymer modified TiO2 nanotubes for removal of perfluorinated chemicals.
33 Water Sci. Technol. 74, 1417–1425.
34 Huang, D.L., Wang, R.Z., Liu, Y.G., Zeng, G.M., Lai, C., Xu, P., Lu, B.A., Xu, J.J., Wang, C.,

48
 1 Huang, C., 2015. Application of molecularly imprinted polymers in wastewater treatment:
2 a review. Environ. Sci. Pollut. Res. 22, 963–977.
3 Huo, P., Lu, Z., Liu, X., Liu, X., Gao, X., Pan, J., Wu, D., Ying, J., Li, H., Yan, Y., 2012.
4 Preparation molecular/ions imprinted photocatalysts of La3+@POPD/TiO2/fly-ash
5 cenospheres: Preferential photodegradation of TCs antibiotics. Chem. Eng. J. 198-199,
6 73–80.
7 Huo, P., Lu, Z., Liu, X., Wu, D., Liu, X., Pan, J., Gao, X., Guo, W., Li, H., Yan, Y., 2012.
8 Preparation photocatalyst of selected photodegradation antibiotics by molecular
9 imprinting technology onto TiO2/fly-ash cenospheres. Chem. Eng. J. 189-190, 75–83.
10 Krupadam, R.J., Khan, M.S., Wate, S.R., 2010. Removal of probable human carcinogenic

of
11 polycyclic aromatic hydrocarbons from contaminated water using molecularly imprinted
12 polymer. Water Reseach 44, 681−688.

ro
13 Kuhn, J., Aylaz, G., Sari, E., Marco, M., Yiu, H.H.P., Duman, M., 2020. Selective binding of
14
15
-p
antibiotics using magnetic molecular imprint polymer (MMIP) networks prepared from
vinyl-functionalized magnetic nanoparticles. J. Hazard. Mater. 387, 121709.
re
16 Lai, C., Wang, M.M., Zeng, G.M., Liu, Y.G., Huang, D.L., Zhang, C., Wang, R.Z., Xu, P.,
lP

17 Cheng, M., Huang, C., Wu, H.P., Qin, L., 2016. Synthesis of surface molecular imprinted
18 TiO2/graphene photocatalyst and its highly efficient photocatalytic degradation of target
na

19 pollutant under visible light irradiation. Appl. Surf. Sci. 390, 368–376.
20 Lai, C., Zhou, X., Huang, D., Zeng, G., Cheng, M., Qin, L., Yi, H., Zhang, C., Xu, P., Zhou,
ur

21 C., Wang, R.Z., Huang, C., 2018. A review of titanium dioxide and its highlighted
Jo

22 application in molecular imprinting technology in environment. J. Taiwan Ins. Chem.

23 Engineers. 91, 517−531.
24 Li, Y., Li, X., Dong, C., Li, Y., Jin, P., Qi, J., 2009. Selective recognition and removal of
25 chlorophenols from aqueous solution using molecularly imprinted polymer prepared by
26 reversible addition-fragmentation chain transfer polymerization. Biosens. Bioelectron. 25,
27 306−312.
28 Li, Y., Li, X., Chu, J., Dong, C., Qi, J., Yuan, Y., 2010. Synthesis of core-shell magnetic
29 molecular imprinted polymer by the surface RAFT polymerization for the fast and
30 selective removal of endocrine disrupting chemicals from aqueous solutions. Environ.
31 Pollut. 158, 2317−2323.
32 Li, W., Pei, X., Deng, F., Luo, X., Li, F., Xiao, Y., 2015. Bio-inspired artificial functional
33 photocatalyst: biomimetic enzyme-like TiO2/reduced graphene oxide nanocomposite with
34 excellent molecular recognition ability. Nanotechnology 26, 175706.

49
 1 Li, H., Li, N., Jiang, J., Chen, D., Xu, Q., Li, H., He, J., Lu, J., 2017. Molecularly imprinted
2 magnetic microparticles for the simultaneousdetection and extraction of Rhodamine B.
3 Sens. Actuat. B 249, 286−292.
4 Li, M., Sun, P., Wu, Q., Liu, D., Zhou, L., 2018. Core–shell magnetic metal–organic
5 framework molecularly imprinted nanospheres for specific adsorption of
6 tetrabromobisphenol A from water. Environ. Sci.: Nano 5, 2651–2662.
7 Li, X., Wang, J., Li, M., Jin, Y., Gu, Z., Liu, C., Ogino, K., 2018. Fe-doped TiO2/SiO2
8 nanofibrous membranes with surface molecular imprinted modification for selective
9 photodegradation of 4-nitrophenol. Chinese Chem. Lett. 29, 527–530.
10 Li, F., Gao, J., Li, X., Li, Y., He, X., Chen, L., Zhang, Y., 2019. Preparation of magnetic

of
11 molecularly imprinted polymers functionalized carbon nanotubes for highly selective
12 removal of aristolochic acid. J. Chromatogr. A 1602, 168–177.

ro
13 Li, X., Row, K.H., 2020. Preparation of levofloxacin-imprinted nanoparticles using designed
14
15
-p
deep eutectic solvents for the selective removal of levofloxacin pollutants from
environmental waste water. Analyst 145, 2958–2965.
re
16 Li, X., Wan, J., Wang, Y., Chi, H., Yan, Z., Ding, S., 2020. Selective removal and persulfate
lP

17 catalytic decomposition of diethyl phthalate from contaminated water on modified

18 MIL100 through surface molecular imprinting. Chemosphere 240, 124875.
na

19 Li, L., Zheng, X., Chi, Y., Wang, Y., Sun, X., Yue, Q., Gao, B., Xu, S., 2020. Molecularly
20 imprinted carbon nanosheets supported TiO2: Strong selectivity and synergic
ur

21 adsorption-photocatalysis for antibiotics removal. J. Hazard. Mater. 383, 121211.

Jo

22 Lin, Y., Shi, Y., Jiang, M., Jin, Y., Peng, Y., Lu, B., Dai, K., 2008. Removal of phenolic
23 estrogen pollutants from different sources of water using molecularly imprinted
24 polymeric microspheres. Environ. Pollut. 153, 483−491.
25 Liu, Y., Liu, R., Liu, C., Luo, S., Yang, L., Sui, F., Teng, Y., Yang, R., Cai, Q., 2010.
26 Enhanced photocatalysis on TiO2 nanotube arrays modified with molecularly imprinted
27 TiO2 thin film. J. Hazard. Mater. 182, 912−918.
28 Liu, B., Han, M., Guan, G., Wang, S., Liu, R., Zhang, Z., 2011. Highly-controllable
29 molecular imprinting at superparamagnetic iron oxide nanoparticles for ultrafast
30 enrichment and separation. J. Phys. Chem. C 115, 17320–17327.
31 Liu, X., Lv, P., Yao, G., Ma, C., Huo, P., Yan, Y., 2013. Microwave-assisted synthesis of
32 selective degradation photocatalyst by surface molecular imprinting method for the
33 degradation of tetracycline onto Cl-TiO2. Chem. Eng. J. 217, 398–406.
34 Liu, X., Lv, P., Yao, G., Ma, C., Tang, Y., Wu, Y., Huo, P., Pan, J., Shi, W., Yan, Y., 2014.

50
 1 Selective degradation of ciprofloxacin with modified NaCl/TiO2 photocatalyst by surface
2 molecular imprinted technology. Collod. Surf. A: Physicochem. Eng. Aspects 441, 420–
3 426.
4 Liu, Y., Zhong, G., Liu, Z., Meng, M., Liu, F., Ni, L., 2016. Facile synthesis of novel
5 photoresponsive mesoporous molecularly imprinted polymers for photo-regulated
6 selective separation of bisphenol A. Chem. Eng. J. 296, 437−446.
7 Liu, Y., Meng, M., Yao, J., Da, Z., Feng, Y., Yan, Y., Li, C., 2016. Selective separation of
8 phenol from salicylic acid effluent over molecularly imprinted polystyrene nanospheres
9 composite alumina membranes. Chem. Eng. J. 286, 622−631.
10 Liu, Y., Zhu, J., Liu, X., Li, H., 2016. A convenient approach of MIP/Co–TiO2

of
11 nanocomposites with highly enhanced photocatalytic activity and selectivity under visible
12 light irradiation. RSC Adv. 6, 69326–69333.

ro
13 Liu, X., Zhu, L., Wang, X., Meng, X., 2020. Photocatalytic degradation of wastewater by
14 -p
molecularly imprinted Ag2S-TiO2 with high selectively. Sci. Rep. 10, 1192.
re
15 Lofgreen, J.E., Ozin, G.A., 2014. Controlling morphology and porosity to improve
16 performance of molecularly imprinted sol–gel silica. Chem. Soc. Rev. 43, 911−933.
lP

17 Lu, Z., Huo, P., Luo, Y., Liu, X., Wu, D., Gao, X., Li, C., Yan, Y., 2013. Performance of
18 molecularly imprinted photocatalysts based on fly-ash cenospheres for selective
na

19 photodegradation of single and ternary antibiotics solution. J. Molecular Catal. A: Chem.

20 378, 91–98.
ur

21 Lu, Z., Luo, Y., He, M., Huo, P., Chen, T., Shi, W., Yan, Y., Pan, J., Ma, Z., Yang, S., 2013.
Jo

22 Preparation and performance of a novel magnetic conductive imprinted photocatalyst for

23 selective photodegradation of antibiotic solution. RSC Adv. 3, 18373–18382.
24 Lu, Z., He, M., Yang, L., Ma, Z., Yang, L., Wang, D., Yan, Y., Shi, W., Liu, Y., Hua, Z., 2015.
25 Selective photodegradation of 2-mercaptobenzothiazole by a novel imprinted
26 CoFe2O4/MWCNTs photocatalyst. RSC Adv. 5, 47820–47829.
27 Lu, K.Q., Xin, X., Zhang, N., Tang, Z.R., Xu, Y.J., 2018. Photoredox catalysis over graphene
28 aerogel-supported composites. J. Mater. Chem. A 6, 4590.
29 Lu, Y.C., Mao, J.H., Zhang, W., Wang, C., Cao, M., Wang, X. D., Wang, K. Y., Xiong, X. H.,
30 2020. A novel strategy for selective removal and rapid collection of triclosan from aquatic
31 environment using magnetic molecularly imprinted nano-polymers. Chemosphere 238,
32 124640.
33 Luo, X., Zhan, Y., Huang, Y., Yang, L., Tu, X., Luo, S., 2011. Removal of water-soluble acid
34 dyes from water environment using a novel magnetic molecularly imprinted polymer. J.

51
 1 Hazard. Mater. 187, 274−282.
2 Luo, X., Deng, F., Min, L., Luo, S., Guo, B., Zeng, G., Au, C., 2013. Facile one-step
3 synthesis of inorganic-framework molecularly imprinted TiO2/WO3 nanocomposite and
4 its molecular recognitive photocatalytic degradation of target contaminant. Environ. Sci.
5 Technol. 47, 7404−7412.
6 Luo, Y., Lu, Z., Jiang, Y., Wang, D., Yang, L., Huo, P., Da, Z., Bai, X., Xie, X., Yang, P., 2014.
7 Selective photodegradation of 1-methylimidazole-2-thiol by the magnetic and dual
8 conductive imprinted photocatalysts based on TiO2/Fe3O4/MWCNTs. Chem. Eng. J. 240,
9 244–252.
10 Meng, Z., Chen, W., Mulchandani, A., 2005. Removal of estrogenic pollutants from

of
11 contaminated water using molecularly imprinted polymers. Environ. Sci. Technol. 39,
12 8958−8962.

ro
13 Mkhize, D.S., Nyoni, H., Quinn, L.P., Mamba, B.B., Msagati, T.A.M., 2017. Molecularly
14
15
-p
imprinted membranes (MIMs) for selective removal of polychlorinated biphenyls (PCBs)
in environmental waters: fabrication and characterization. Environ. Sci. Pollut. Res. 24,
re
16 11694–11707.
lP

17 Muratsugu, S., Shirai, S., Tada, M., 2020. Recent progress in molecularly imprinted approach
18 for catalysis. Tetrahedron Lett. 61, 151603.
na

19 Ndunda, E.N., Mizaikoff, B., 2016. Molecularly imprinted polymers for the analysis and
20 removal of polychlorinated aromatic compounds in the environment: a review. Analyst
ur

21 141, 3141–3156.
Jo

22 Ng, H.K.M., Leo, C.P., Abdullah, A.Z., 2017. Selective removal of dyes by molecular
23 imprinted TiO2 nanoparticles in polysulfone ultrafiltration membrane. J. Environ. Chem.
24 Eng. 5, 3991–3998.
25 Ou, H., Chen, Q., Pan, J., Zhang, Y., Huang, Y., Qi, X., 2015. Selective removal of
26 erythromycin by magnetic imprinted polymers synthesized from chitosan-stabilized
27 Pickering emulsion. J. Hazard. Mater. 289, 28–37.
28 Pan, J., Xu, L., Dai, J., Li, X., Hang, H., Huo, P., Li, C., Yan, Y., 2011. Magnetic molecularly
29 imprinted polymers based on attapulgite/Fe3O4 particles for the selective recognition of
30 2,4-dichlorophenol. Chem. Eng. J. 174, 68–75.
31 Pan, J., LI, L., Hang, H., Ou, H., Zhang, L., Yan, Y., Shi, W., 2013. Study on the nonylphenol
32 removal from aqueous solution using magnetic molecularly imprinted polymers based on
33 fly-ash-cenospheres. Chem. Eng. J. 223, 824–832.
34 Pan, S.D., Shen, H.Y., Zhou, L.X., Chen, X.H., Zhao, Y.G., Cai, M.Q., Jin, M.C., 2014.

52
 1 Controlled synthesis of pentachlorophenol-imprinted polymers on the surface of magnetic
2 graphene oxide for highly selective adsorption. J. Mater. Chem. A 2, 15345–15356.
3 Pan, J., Liu, S., Jia, H., Yang, J., Qin, M., Zhou, T., Chen, Z., Jia, X., Guo, T., 2019. Rapid
4 hydrolysis of nerve agent simulants by molecularly imprinted porous crosslinked polymer
5 incorporating mononuclear zinc(II)-picolinamine-amidoxime module. J. Catal. 380,
6 83−90.
7 Pauling, L., 1940. A theory of the structure and process of formation of antibodies. J. Am.
8 Chem. Soc. 62, 2643–2657.
9 Pérez-Moral, N., Mayes, A.G., 2004. Comparative study of imprinted polymer particles
10 prepared by different polymerisation methods. Anal. Chim. Acta 504, 15–21.

of
11 Qi, H.P., Wang, H.L., 2020. Facile synthesis of Pr-doped molecularly imprinted TiO2

ro
12 mesocrystals with high preferential photocatalytic degradation performance. Appl. Surf.
13 Sci. 511, 145607.
14
-p
Rezaei, B., Irannejad, N., Ensafi, A. A., 2018. 3D TiO2 self-acting system based on
re
15 dye-sensitized solar cell and g-C3N4/TiO2-MIP to enhanced photodegradation
16 performance. Renew. Energy 123, 281–293.
lP

17 Rodriguez-Narvaez, O.M., Peralta-Hernandez, J.M., Goonetilleke, A., Bandala, E.R., 2017.

18 Treatment technologies for emerging contaminants in water: A review. Chem. Eng. J. 323,
na

19 361–380.
ur

20 Sajini, T., Gigimol, M.G., Mathew, B., 2019. A brief overview of molecularly imprinted
21 polymers supported on titanium dioxide matrices. Mater. Today Chem. 11, 283−295.
Jo

22 Samah, N.A., Sánchez-Martín, M.J., Sebastián, R.M., Valiente, M., López-Mesas, M., 2018.
23 Molecularly imprinted polymer for the removal of diclofenac fromwater: Synthesis and
24 characterization. Sci. Total Environ. 631-632, 1534–1543.
25 Shahnazi, A., Nabid, M.R., Sedghi, R., 2020. Synthesis of surface molecularly imprinted
26 poly-o-phenylenediamine/TiO2/carbon nanodots with a highly enhanced selective
27 photocatalytic degradation of pendimethalin herbicide under visible light. React. Funct.
28 Polym. 151, 104580.
29 Sharabi, D., Paz, Y., 2010. Preferential photodegradation of contaminants by molecular
30 imprinting on titanium dioxide. Appl. Catal. B: Environ. 95, 169−178.
31 Shen, X., Zhu, L., Liu, G., Yu, H., Tang, H., 2008. Enhanced photocatalytic degradation and
32 selective removal of nitrophenols by using surface molecular imprinted titania. Environ.
33 Sci. Technol. 42, 1687−1692.
34 Shen, X., Zhu, L., Liu, G., Tang, H., Liu, S., Li, W., 2009. Photocatalytic removal of
53
 1 pentachlorophenol by means of an enzyme-like molecular imprinted photocatalyst and
2 inhibition of the generation of highly toxic intermediates. New J. Chem. 33, 2278–2285.
3 Shen, X., Zhu, L., Yu, H., Tang, H., Liu, S., Li, W., 2009. Selective photocatalysis on
4 molecular imprinted TiO2 thin films prepared via an improved liquid phase deposition
5 method. New J. Chem. 33, 1673–1679.
6 Shen, X., Zhu, L., Wang, N., Ye, L., Tang, H., 2012. Molecular imprinting for removing
7 highly toxic organic pollutants. Chem. Commun. 48, 788–798.
8 Shen, X., Zhu, L., Wang, N., Zhang, T., Tang, H., 2014. Selective photocatalytic degradation
9 of nitrobenzene facilitated by molecular imprinting with a transition state analog.
10 Catalysis today 225, 164−170.

of
11 Shen, H.Y., Chen, Z.X., Li, Z.H., Hu, M.Q., Dong, X.Y., Xia, Q.H., 2015. Controlled

ro
12 synthesis of 2,4,6-trichlorophenol-imprinted amino-functionalized nano-Fe3O4-polymer
13 magnetic composite for highly selective adsorption. Colloid. Surf. A 481, 439–450.
14
-p
Shi, H., Wang, R., Yang, J., Ren, H., Liu, S., Guo, T., 2015. Novel imprinted nanocapsule
re
15 with highly enhanced hydrolytic activity for organophosphorus pesticide degradation and
16 elimination. Eur. Polym. J. 72, 190−201.
lP

17 Shi, H., Wang, Y., Tang, C., Wang, W., Liu, M., Zhao, G., 2019. Mechanisim investigation on
18 the enhanced and selective photoelectrochemical oxidation of atrazine on molecular
na

19 imprinted mesoporous TiO2. Appl. Catal. B: Environ. 246, 50–60.

ur

20 Song, Y., Rong, C., Shang, J., Wang, Y., Zhang, Y., Yu, K., 2017. Synthesis of an
21 inorganic-framework molecularly imprinted Fe-doped TiO2 composite and its selective
Jo

22 photo-Fenton-like degradation of acid orange II. J. Chem. Technol. Biotechnol. 92, 2038–
23 2049.
24 Speltini, A., Scalabrini, A., Maraschi, F., Sturini, M., Profumo, A., 2017. Newest applications
25 of molecularly imprinted polymers for extraction of contaminants from environmental
26 and food matrices: a review. Anal. Chim. Acta 974, 1−26.
27 Sun, L., Guan, J., Xu, Q., Yang, X., Wang, J., Hu, X., 2018. Synthesis and applications of
28 molecularly imprinted polymers modified TiO2 nanomaterials: a review. Polymers 10,
29 1248.
30 Sun, L., Li, J., Li, X., Liu, C., Wang, H., Huo, P., Yan, Y., 2019. Molecularly imprinted
31 Ag/Ag3VO4/g-C3N4 Z-scheme photocatalysts for enhanced preferential removal of
32 tetracycline. J. Colloid. Interf. Sci. 552, 271–286.
33 Suyana, P., Ganguly, P., Nair, B.N., Mohamed, A.P., Warrier, K.G.K., Hareesh, U.S., 2017.
34 Co3O4–C3N4 p–n nano-heterojunctions for the simultaneous degradation of a mixture of

54
 1 pollutants under solar irradiation. Environ. Sci.: Nano 4, 212–221.
2 Tang, B., Shi, H., Fan, Z., Zhao, G., 2018. Preferential electrocatalytic degradation of
3 2,4-dichlorophenoxyacetic acid on molecular imprinted mesoporous SnO2 surface. Chem.
4 Eng. J. 334, 882–890.
5 Tang, B., Zhang, J., Yang, N., Zhao, G., 2020. Selective photoelectrocatalytic removal of
6 environmental pollutants on molecular imprints decorated TiO2 single crystalline
7 nanoarrays. Chem. Eng. J. 383, 123188.
8 Tonucci, M.C., Xavier, L.P.S., da Siva, A.C., Aquino, S.F., Baeta, B.E.L., 2020. Removal of
9 estradiol from water with a hybrid MIP-TiO2 catalytic adsorbent. Water Air Soil Pollut.
10 231, 215.

of
11 Vlatakis, G., Andersson, L.I., Müller, R., Mosbach, K., 1993. Drug assay using antibody

ro
12 mimics made by molecular imprinting. Nature 361, 645–647.
13 Wackerlig, J., Schirhagl, R., 2016. Applications of molecularly imprinted polymer
14
-p
nanoparticles and their advances toward industrial use: a review. Anal. Chem. 88,
re
15 250−261.
16 Wang, Z., Liu, X., Li, W., Wang, H., Li, H., 2014. Enhancing the photocatalytic degradation
lP

17 of salicylic acid by using molecular imprinted S-doped TiO2 under simulated solar light.
18 Ceram. Int. 40, 8863–8867.
na

19 Wang, Z., Qiu, T., Guo, L., Ye, J., He, L., Li, X., 2017. The synthesis of hydrophilic
ur

20 molecularly imprinted polymer microspheres and their application for selective removal
21 of bisphenol A from water. React. Funct. Polym. 116, 69−76.
Jo

22 Wang, Z., Qiu, T., Guo, L., Ye, J., He, L., Li, X., 2019. The building of molecularly imprinted
23 single hole hollow particles: A miniemulsion polymerization approach. Chem. Eng. J. 357,
24 348–357.
25 Wang, R., Pan, J., Qin, M., Guo, T., 2019. Molecularly imprinted nanocapsule mimicking
26 phosphotriesterase for the catalytic hydrolysis of organophosphorus pesticides. Eur.
27 Polym. J. 110, 1−8.
28 Wei, S., Hu, X., Liu, H., Wang, Q., He, C., 2015. Rapid degradation of Congo red by
29 molecularly imprinted polypyrrole-coated magnetic TiO2 nanoparticles in dark at ambient
30 conditions. J. Hazard. Mater. 294, 168−176.
31 Wei, S., Liu, H., He, C., Liang, Y., 2016. Molecularly imprinted TiO2/WO3-coated magnetic
32 nanocomposite for photocatalytic degradation of 4-nitrophenol under visible light. Aust. J.
33 Chem. 69, 638–644.
34 Wei, D., Li, S., Fang, L., Zhang, Y., 2018. Effect of environmental factors on enhanced
55
 1 adsorption and photocatalytic regeneration of molecular imprinted TiO2 polymers for
2 fluoroquinolones. Environ. Sci. Pollut. Res. 25, 6729–6738.
3 Weng, B., Qi, M.Y., Han, G., Tang, Z.R., Xu, Y.J., 2019. Photocorrosion inhibition of
4 semiconductor-based photocatalysts: Basic principle, current development, and future
5 perspective. ACS Catal. 9, 4642–4687.
6 Wu, X., Wang, X., Lu, W., Wang, X., Li, J., You, H., Xiong, H., Chen, L., 2016.
7 Water-compatible temperature and magnetic dual-responsive molecularly imprinted
8 polymers for recognition and extraction of bisphenol A. J. Chromatogr. A 1435, 30−38.
9 Wu, X., Huang, M., Zhou, T., Mao, J., 2016. Recognizing removal of norfloxacin by novel
10 magnetic molecular imprinted chitosan/γ-Fe2O3 composites: Selective adsorption

of
11 mechanisms, practical application and regeneration. Separat. Purif. Technol. 165, 92–100.

ro
12 Wu, Y., Zhao, J., Wang, C., Lu, J., Meng, M., Dai, X., Yan, Y., Li, C., 2016. A novel approach
13 toward fabrication of porous molecularly imprinted nanocomposites with bioinspired
14
15 Chem. Eng. J. 306, 492–503.
-p
multilevel internal domains: Application to selective adsorption and separation membrane.
re
16 Wu, Y., Dong, Y., Xia, X., Liu, X., Li, H., 2016. Facile synthesis of N–F codoped and
lP

17 molecularly imprinted TiO2 for enhancing photocatalytic degradation of target

18 contaminants. Appl. Surf. Sci. 364, 829−836.
na

19 Wu, M.H., Li, L., Liu, N., Wang, D., Xue, Y., Tang, L., 2018. Molybdenum disulfide (MoS2)
20 as a co-catalyst for photocatalytic degradation of organic contaminants: A review. Process
ur

21 Saf. Environ. Prot. 2018, 118, 40–58.

Jo

22 Wulff, G., Sarhan, A., 1972. The use of polymers with enzyme-analogous structures for
23 resolution of racemates. Angew. Chem. Int. Ed. 11, 341.
24 Xiao, G., Su, H., Tan, T., 2015. Synthesis of core–shell bioaffinity chitosan–TiO2 composite
25 and its environmental applications. J. Hazard. Mater. 283, 888−896.
26 Xie, A., Dai, J., Chen, X., Zou, T., He, J., Chang, Z., Li, C., Yan, Y., 2016. Hollow imprinted
27 polymer nanorods with a tunable shell using halloysite nanotubes as a sacrificial template
28 for selective recognition and separation of chloramphenicol. RSC Adv. 6, 51014–51023.
29 Xing, W., Ni, L., Liu, X., Luo, Y., Lu, Z., Yan, Y., Huo, P., 2013. Synthesis of
30 thermal-responsive photocatalysts by surface molecular imprinting for selective
31 degradation of tetracycline. RSC Adv. 3, 26334–26342.
32 Xing, W., Wu, Y., Li, C., Lu, J., Lin, X., Yu, C., 2020. Biomass activated carbon/SiO2‑based
33 imprinted membranes for selective separation of atrazine: a synergistic integration system.
34 ACS Sustainable Chem. Eng. 8, 5636−5647.

56
 1 Xu, L., Pan, J., Dai, J., Li, X., Hang, H., Cao, Z., Yan, Y., 2012. Preparation of
2 thermal-responsive magnetic molecularly imprinted polymers for selective removal of
3 antibiotics from aqueous solution. J. Hazard. Mater. 233-234, 48–56.
4 Xu, L., Pan, J., Xia, Q., Shi, F., Dai, J., Wei, X., Yan, Y., 2012. Composites of silica and
5 molecularly imprinted polymers for degradation of sulfadiazine. J. Phys. Chem. C 116,
6 25309−25318.
7 Xu, S., Lu, H., Chen, L., Wang, X., 2014. Molecularly imprinted TiO2 hybridized magnetic
8 Fe3O4 nanoparticles for selective photocatalytic degradation and removal of estrone. RSC
9 Adv. 4, 45266–45274.
10 Yan H., Row, K.H., 2006. Characteristic and Synthetic Approach of Molecularly Imprinted

of
11 Polymer. Int. J. Mol. Sci. 7, 155–178.

ro
12 Yang, X., You, X., Zhang, B., Guo, C., Yu, C., 2017. Preparation of magnetic imprinted
13 graphene oxide composite for catalytic degradation of Congo red under dark ambient
14 -p
conditions. Water Sci. Technol. 76, 1676−1686.
re
15 Yang, Q., Li, J., Wang, X., Peng, H., Xiong, H., Chen, L., 2018. Strategies of molecular
16 imprinting-based fluorescence sensors for chemical and biological analysis. Biosens.
lP

17 Bioelectron. 112, 54−71.

18 Yang, X., Chen, J., Liu, H., Li, X., Zhong, S., 2019. Molecularly imprinted polymers based
na

19 on zeolite imidazolate framework-8 for selective removal of 2,4-dichlorophenoxyacetic

20 acid. Colloid. Surf. A 570, 244–250.
ur

21 Yu, Q., Deng, S., Yu, G., 2008. Selective removal of perfluorooctane sulfonate from aqueous
Jo

22 solution using chitosan-based molecularly imprinted polymer adsorbents. Water Res. 42,
23 3089–3097.
24 Yuan, Q., Zhang, D., Yu, P., Sun, R., Javed, H., Wu, G., Alvarez, P.J.J., 2020. Selective
25 adsorption and photocatalytic degradation of extracellular antibiotic resistance genes by
26 molecularly-imprinted graphitic carbon nitride. Environ. Sci. Technol. 54, 4621−4630.
27 Zhang, Y., Song, D., Lanni, L.M., Shimizu, K.D., 2010. Importance of functional monomer
28 dimerization in the molecular imprinting process. Macromolecules 43, 6284–6294.
29 Zhang, Y.L., Zhang, J., Dai, C.M., Zhou, X.F., Liu, S.G., 2013. Sorption of carbamazepine
30 from water by magnetic molecularly imprinted polymers based on chitosan-Fe3O4.
31 Carbodydrate polym. 97, 809−816.
32 Zhang, W., Li, Y., Wang, Q., Wang, C., Wang, P., Mao, K., 2013. Performance evaluation and
33 application of surface-molecular-imprinted polymer-modified TiO2 nanotubes for the
34 removal of estrogenic chemicals from secondary effluents. Environ. Sci. Pollut. Res. 20,

57
 1 1431–1440.
2 Zhang, N., Yang, M.Q., Liu, S., Sun, Y., Xu, Y.J., 2015. Waltzing with the versatile platform
3 of graphene to synthesize composite photocatalysts. 115, 10307–10377.
4 Zhang, C., Chen, H., Ma, M., Yang, Z., 2015. Facile synthesis of magnetically recoverable
5 Fe3O4/Al2O3/molecularly imprinted TiO2 nanocomposites and its molecular recognitive
6 photocatalytic degradation of target contaminant. J. Molecular Catal. A: Chem. 402, 10–
7 16.
8 Zhang, C., Si, S., Yang, Z., 2015. Facile synthesis of Fe3O4/SiO2/molecularly imprinted
9 hydroxyapatite nanocomposite and its enhanced photocatalytic degradation of target
10 contaminant. Separat. Purif. Technol. 143, 88–93.

of
11 Zhang, F., Li, Y.H., Li, J.Y., Tang, Z.R., Xu, Y.J., 2019. 3D graphene-based gel photocatalysts

ro
12 for environmental pollutants degradation. Environ. Pollut. 253, 365–376.
13 Zhou, X., Lai, C., Huang, D., Zeng, G., Chen, L., Qin, L., Xu, P., Cheng, M., Huang, C.,
14
-p
Zhang, C., Zhou, C., 2018. Preparation of water-compatible molecularly imprinted
re
15 thiol-functionalized activated titanium dioxide: Selective adsorption and efficient
16 photodegradation of 2, 4-dinitrophenol in aqueous solution. J. Hazard. Mater. 346, 113–
lP

17 123.
18 Zhu, L., Liu, X., Wang, X., Meng, X., 2020. Evaluation of photocatalytic selectivity of Ag/Zn
na

19 modified molecularly imprinted TiO2 by multiwavelength measurement. Sci. Total

20 Environ. 703, 134732.
ur

21 Zimmerman, S.C., Lemcoff, N. G., 2004. Synthetic hosts via molecular imprinting-are
Jo

22 universal synthetic antibodies realistically possible? Chem. Commun. 5–14.

23

58
Highlights

The preparing process, recognition mechanism and common imprinted systems of

MIT are summarized.

Insights of their specific binding affinities are demonstrated for removing target

molecules

The innovative utilization of MIT in catalytic eradication of pollutants is

overviewed

of
ro
Perspectives in guiding the future exploitation on MIT for environmental

protection is provided -p
re
lP
na
ur
Jo
The authors confirm that there are no known conflicts of interest associated with
this publication and there has been no significant financial support for this work
that could have influenced its outcome.

of
ro
-p
re
lP
na
ur
Jo