Accepted Manuscript

Membrane technology coupled with electrochemical advanced oxidation pro-

cesses for organic wastewater treatment: recent advances and future prospects

Zonglin Pan, Chengwen Song, Lin Li, Hong Wang, Yanqiu Pan, Chunlei Wang,
Jianxin Li, Tonghua Wang, Xianshe Feng

PII: S1385-8947(19)30215-3
DOI: https://doi.org/10.1016/j.cej.2019.01.188
Reference: CEJ 20909

To appear in: Chemical Engineering Journal

Received Date: 31 July 2018

Revised Date: 26 January 2019
Accepted Date: 30 January 2019

Please cite this article as: Z. Pan, C. Song, L. Li, H. Wang, Y. Pan, C. Wang, J. Li, T. Wang, X. Feng, Membrane
technology coupled with electrochemical advanced oxidation processes for organic wastewater treatment: recent
advances and future prospects, Chemical Engineering Journal (2019), doi: https://doi.org/10.1016/j.cej.
2019.01.188

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 Revised manuscript submission no. CEJ-S-18-10810 R2

Membrane technology coupled with electrochemical advanced

oxidation processes for organic wastewater treatment: recent advances
and future prospects
Zonglin Pana, Chengwen Songb,*, Lin Lia, Hong Wangc, Yanqiu Pana, Chunlei Wanga, Jianxin Lic,**,

Tonghua Wanga,***, Xianshe Fengd

a
State key Laboratory of Fine chemicals, Carbon Research Laboratory, School of Chemical

Engineering, Dalian University of Technology, 2 Linggong Road, Dalian, 116024, China

b
College of Environmental Science and Engineering, Dalian Maritime University, 1 Linghai Road,

Dalian 116026, China

c
State Key Laboratory of Hollow Fiber Membrane Materials and Processes, School of Materials

Science and Engineering, Tianjin Polytechnic University, Tianjin 300387, PR China

d
Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario, N2L 3G1,

Canada

* Corresponding author:

Tel: +86-411-84724342;

E-mail: chengwensong@dlmu.edu.cn (C. Song); jxli@tjpu.edu.cn (J. Li); wangth@dlut.edu.cn (T.

Wang)

Author Contributions: Zonglin Pan and Chengwen Song contributed equally.

1
Abstract：Organic contaminants in wastewater have become one of the most serious environmental

problems due to their toxicity, persistence and being bio-refractory. Many efforts have been made to

develop effective technologies for wastewater treatment over the past few decades. In this review,

membrane technologies coupled with electrochemical advanced oxidation processes (EAOPs) for

wastewater treatment are presented, where membrane materials used in such systems are

categorized based on their electrical conductivities. Various EAOPs, including electro-chemical

anodic oxidation, electro-catalysis, photoelectro-catalysis, and electro-Fenton integrated with

membrane technologies for effective wastewater treatment, are discussed. The coupling systems

using the membrane as an electrode are particularly examined. This review also elaborates the

existing challenges with membrane technologies coupled with EAOPs for wastewater treatment,

and their prospects are provided as well.

Keywords: Membrane technology; Electrochemical advanced oxidation processes (EAOPs);

Conductive membranes; Wastewater treatment

2
Contents

1. Introduction ...................................................................................................................................... 6

2. The design of membrane technology coupled with EAOPs ............................................................ 8

3. Membrane materials ....................................................................................................................... 12

3.1 Non-conductive membrane materials ................................................................................... 13

3.2 Conductive membrane materials ........................................................................................... 18

3.2.1 Conductive metal and metal oxide membranes .......................................................... 18

3.2.2 Carbon-based conductive membranes ........................................................................ 23

3.2.3 Conductive polymeric membranes.............................................................................. 31

4. Recent advances in membrane technology coupled with EAOPs ................................................. 34

4.1 Membrane processes coupled with EAO .............................................................................. 34

4.2 Membrane processes coupled with ECO .............................................................................. 38

4.3 Membrane processes coupled with PECO ............................................................................ 55

4.4 Membrane processes coupled with E-Fenton ....................................................................... 57

5. Conclusions and prospects ............................................................................................................. 59

Acknowledgements ............................................................................................................................ 59

References .......................................................................................................................................... 63

3
List of Abbreviations

AOP Advanced oxidation process MWCNTs Multi-walled carbon nanotubes

BDD Boron-doped diamond MWCO Molecular weight cut off

BSA Bovine serum albumin NC Networked cellulose

CB Carbon black NF Nanofiltration

CBCM Coal based carbon membrane NOM Nature organic matters

CBMs Carbon based membrane OEP Oxygen evolution potential

CMSM Carbon molecular sieve membrane PA Polyamide

CN Cellulose nitrate PANI Polyaniline

CNTs Carbon nano tubes PCO Photo-catalytic oxidation

CNS Carbon nanostructures PECO Photoelectro-catalysis oxidation

COD Chemical oxygen demands PE-Fenton photoelectro-Fenton

CPMs Conductive polymer membranes PF Particle filtration

CVD Chemical vapor deposition PPy Polypyrrole

EAO Electrochemical anodic oxidation PSF Polysulfone

Electrochemical advanced oxidation

EAOP PTFE Polytetrafluoroethylene
process

ECCM Electro-catalytic carbon membrane PVA Polyvinyl alcohol

ECMR Electro-catalytic membrane reactor PVB polyvinyl butyral

ECO Electro-catalytic oxidation PVDF Poly(vinylidene fluoride)

E-Fenton Electro-Fenton REM Reactive electrochemical membrane

EMBR Electrochemical membrane bioreactor RO reverse osmosis

4
FO Forward osmosis SE-Fenton Sonoelectro-Fenton

HFMs Hollow-fiber membranes TKN Total Kjeldahl nitrogen

MBR Membrane bioreactor SS Stainless steel

MD Membrane distillation TOC Total Organic Carbon

MF Microfiltration TSS Total suspended solids

MOF Metal organic framework UF Ultrafiltration

5
1. Introduction

Nearly 70.8% of the Earth’s surface is covered by water, accounting for about 361 million square

kilometres. However, only 2.5% of the water on Earth is fresh water; most of the available water

should be purified before it is safe to drink or use for other purposes. Importantly, due to population

growth and industry development, there is ever increasing amounts of uncontrolled wastewater

discharge; this not only reduces the clean water resources, but also causes serious environmental

problems and even threatens the health and safety of human beings and other living organisms. The

wastewater containing various synthetic organic contaminants as associated with petrochemicals,

pharmaceuticals, pesticides, and dyestuffs, has become a concerns globally due to their toxicity,

carcinogenicity and persistence [1-3].

Over the past few decades, various technologies have been explored for the treatment of organic

wastewater. However, such conventional processes as biological treatment, adsorption,

sedimentation, and coagulation are not very effective for complete removal of organic pollutants.

These technologies usually need complicated equipment, with a high energy consumption and high

operating costs, and some of them also require large amounts of chemicals, resulting in byproduct

wastes and sludge [4].

Membrane technology has been considered as one of the most promising methods for water

decontamination owing to its advantages of high separation selectivity, low energy consumption, no

requirements for additional chemicals, easy scale up and continuous operation [5, 6]. In recent years,

membrane-based processes have been developed and applied for different applications, including

particle filtration (PF), microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), reverse

osmosis (RO), forward osmosis (FO), membrane distillation (MD) and membrane bioreactor (MBR)

[7, 8]. However, these membrane processes often suffer from their own “Achilles heel”. During the
6
course of filtration, the retention and accumulation of pollutants on the membrane surface or/and

inside the membrane pores as a results of the membrane rejection will lead to membrane fouling [9],

which inevitably deteriorates the membrane performance [10]. Moreover, membrane separation is a

physical process, while it can concentrates the contaminants, the wastewater is actually not

“decontaminated”. This is especially the case for wastewater with complex compositions where a

complete retention of the contaminants is difficult or impractical.

On the other hand, electrochemical advanced oxidation processes (EAOPs) are a group of

emerging technologies which can decompose the organic compounds to less refractory products,

and even mineralize them to CO2, H2O, and other inorganic species [11]. In recent years, EAOPs

have gained increasing attentions due to their favorable characteristics ( i.e., no chemical reagents

needed, easy process control, stabile performance, and environmental friendliness) [11-14].

However, there are some limitations for each individual EAOP to scale up for large-scale industrial

applications. The efficiencies of conventional EAOP reactors are often limited by the weak mass

transfer of the pollutant molecules in the reactor, and the energy consumption is still at a relative

high level for commercial uses. Moreover, the EAOPs are not particularly feasible to treat

large-volumes of wastewater at low contaminant concentrations [15]. However, it is encouraging

that the combination of membrane technology with EAOPs can effectively mitigate the membrane

fouling problems, thereby improving the overall separation performance [14-17]. As expected, a

synergistic design of such coupling processes can further improve the process performance and

reduce the energy consumption [15].

In the past decade, many studies on the coupling process of membrane technology and EAOPs

(membrane-EAOPs) for wastewater decontamination have been reported. However, there is a

scarcity of reviews that summarize the membrane-EAOPs. For example, Ganiyu et al. [15]
7
presented a general overview on the coupling of membrane filtration and advanced oxidation

process (membrane-AOPs) for removal of pharmaceutical residues. The coupled membrane-AOP

processes were considered to be promising for effective removal of hazardous substances as

compared to the individual process component alone. In their review, the combined techniques of

membrane filtration with such AOPs as ozonation, peroxone, UV/H2O2, photo-Fenton,

photocatalysis and EAOPs for the removal of pharmaceutical residues were summarized. For

membrane-EAOPs, only few studies on pharmaceutical residues treatment were illustrated.

Similarly, Li et al.[18] reviewed the studies on membrane-EAOPs for treatment of dye wastewater,

and the coupled membrane-EAOPs were briefly discussed. The effects of such operating parameters

as the initial dye concentration and pH of the feed solution, the current density and supporting

electrolyte used on the process efficiency for the dye wastewater treatment were evaluated.

In this work, we intend to present a comprehensive review on the recent developments on the

coupled processes integrating membrane filtration with EAOPs. Prior work on membrane-EAOPs

for wastewater treatment was summarized, and appropriate strategies for process design and

specific features of the coupled process were analyzed. The membrane materials suitable for the

coupled processes and the conductive membranes which can be potentially used in the processes

were summarized. In addition, current work on wastewater treatment with membrane-EAOPs based

on membrane-(electrochemical anodic oxidation) (EAO), membrane-(electro-catalytic oxidation)

(ECO), membrane-(photoelectron-catalytic oxidation) (PECO), and membrane-(electro-Fenton)

(E-Fenton) reaction was evaluated. The technical challenges with the coupled technology for

wastewater treatment at present were discussed, and a prospect of the hybrid processes was

provided as well.

2. The design of membrane technology coupled with EAOPs

8
 The combination of membrane filtration with EAOPs can be achieved in two modes: two-stage

coupling process and one-pot coupling process.

In the two-stage coupling process, the membrane technology and EAOP are set as two

stand-alone units. Depending on the location and function of the EAOP unit in the coupled

processes, the following three process integrations are proposed. (a): The EAOP acts as a

pre-treatment stage for the membrane process (Figure 1a). This process mode is usually used for

decontamination of wastewater that imposes serious problems of membrane fouling. Pretreating the

wastewater with an EAOPs will decrease the pollutant concentration and thus reduce or eliminate

membrane fouling. (b): The EAOP acts as a post-treatment of the membrane concentrate (Figure

1b). The membrane process(e.g. NF, RO) will concentrate the organic compounds and salts, and

“clean water” is generated on the permeate side of the membrane. The membrane concentrate is

enriched with pollutants and must be further degraded so as to reduce its impact on the environment.

In view of the electrical conductivity of the membrane concentrate due to increased salinity, the

EAOPs are expected to be promising methods for post-treatment of membrane concentrate stream

[19-21]. (c): The EAOPs are used for further treatment of the membrane permeate (Figure 1c). This

is, however, not particularly advantageous due to the relative low pollutant concentration and thus

the low electric-conductivity in the permeate stream from membrane unit.

9
Figure 1. Coupling of membrane processes with EAOPs (the two-stage processes). (a).

Pre-treatment of feed; (b). Post-treatment of concentrate; (c). Advance treatment of permeate [15].

In the one-pot coupling process, the removal of pollutants by membrane separation and EAOPs is

accomplished simultaneously in a single unit (Figure 2). Compared with the two-stage coupling

processes, the one-pot coupling process provides additional advantages in wastewater treatment: (a)

The membrane process is enhanced under the assistance of electrical field due to such electrokinetic

effects as electroosmosis, electrophoresis, and electrostatic interaction, thereby achieving a high

permeation flux and treatment efficiency [22-25]. (b) The concentration polarization and membrane
10
fouling are reduced by the in-situ electrochemical oxidation of the pollutants and the microflow

disturbance near the electrode surface, which helps maintain the high permeation flux and extend

the life span of the membrane [17, 26, 27]. (c) The membrane and electrodes are set in one single

reactor, yielding a small footprint because of its compact design [15].

Moreover, in the one-pot coupling mode, two types of integration patterns are reported depending

on the conductivity of membrane materials. Different from the system that integrate non-conductive

membranes and electrodes for physical filtration and electrochemical degradation respectively

(Figure 3), the one-pot mode, which adopts a conductive membrane as the electrode, has several

advantages. On the one hand, this makes the coupling system more compact, allowing it to achieve

higher removal efficiency at the same voltage, thus reducing energy consumption (Figure 4) [18,

28]. On the other hand, the flow of the feed solution will drag the organic pollutants toward the

surface of the membrane/electrode, which enhance the mass transfer coefficient in the liquid phase

effectively [29, 30].

Figure 2. The one-pot process coupling membrane with EAOP [15].

11
Figure 3. A schematic of one-pot membrane-EAOP design using non-conductive membranes [28].

Figure 4. A schematic of the one-pot membrane-EAOP design using conductive membranes.(a) flat

membrane; (b) tubular membrane.

3. Membrane materials

Thanks to the development of material science and manufacturing technology, membrane

technology has advanced considerably in recent years. A large number of membrane materials with

different unique properties have been synthesized. Depending on the nature of the membrane

materials, current membranes can be divided into organic membranes, inorganic membranes and

inorganic-organic hybrid membranes (Figure 5) [5]. They can also be categorized as isotropic and

anisotropic membranes [7]. Isotropic membranes are uniform in composition and structure, while

anisotropic membranes include phase-separation membranes and composite membranes that are

often asymmetric in structure. Furthermore, based on membrane geometry, the membranes may also

be classified into flat sheet, tubular, capillary and hollow fiber membranes, which are aimed to suit

for different engineering applications.

12
Figure 5. The classification of membranes according to the nature of membrane materials.

The electrical conductivity of the membrane materials has a significant effect on the structure,

design and manner of coupling of a membrane-EAOP system, and is also relevant for treatment

performance and energy consumption. Here, we briefly summarize the currently available

membrane materials that have been applied in the membrane-EAOPs and the conductive

membranes that have been used in wastewater treatment.

3.1 Non-conductive membrane materials

Non-conductive membranes are extensively used in the large-scale water purification

applications, and thus they are also the primary constituent in the membrane-EAOPs. In the

two-stage membrane-EAOP coupling mode, the membrane process is an stand-alone unit for

physical separation, and ceramic membranes [31] and polymer membranes [32-34] have been used

in such applications. On the other hand, in the one-pot membrane-EAOPs, membrane separation

and EAOP are carried out simultaneously in the same unit, where, non-conductive membranes are

predominately used as the separation media or as a substrate of composite conductive membranes.

13
 Recent studies on non-conductive membranes used in membrane-EAOPs are summarized in

Table 1. Various polymeric membranes (e.g., PA, PVDF, PTFE and PS) and ceramic membranes

(e.g., Al2O3 and TiO2) are commonly used as the separation media in the coupling systems.

Generally, when non-conductive membranes are used as the separation media in the one-pot

coupling systems where they are located between the anode and the cathode, there is an electrical

potential gradient across the membrane. Both good water permeability and pollutant retention by

the membrane are necessary. For example, NF membranes have a high rejection for dye [26, 35-37]

and tetracycline [38] molecules, and MF membranes are more suitable for NOM-water separation

[27, 39]. On the other hand, the good resistance against electrochemical etch is an essential property

of membrane materials to ensure the stability and life span of the membrane. In the case of a

composite conductive membrane formed on a substrate, the overall membrane resistance to

electrochemical etching is also important. Obviously, the substrate should offer minimum resistance

to water permeation. The PTFE membranes used as a substrate for composite membranes typically

have a pore size of 5 μm, which is too big to reject such organic pollutants as phenol methanol,

methylene blue and formaldehyde, however, at the same time, large mass transfer resistance does

not occur [40-44]. In addition, the mechanical strength and thermal stability of the substrate

membranes are also critical when they are subjected to a high transmembrane pressure or thermal

treatment is needed. In these cases, ceramic membranes (e.g., alumina membranes [45-48] and TiO2

membranes [49, 50]) are proper choices.

14
Table 1 Non-conductive membrane materials used in membrane-EAOPs.

Membrane Characteristics Application Process and function Reference

Polyamide (PA) NF membrane Membrane Charge: Treatment of simulated ECO; separation [26, 36,

negative; MWCO dye wastewater media 37]

more than 150Da

Polyamide (PA) NF membrane Membrane Charge: Dye and tetracycline ECO; separation [35, 38]

negative; MWCO: hydrochloride removal media

Polymeric 200Da

membrane PVDF MF membrane Nominal membrane NOM tailwater ECO; separation [39]

pore size: 0.1 μm containing scaling media

metal ions

PVDF MF membrane Nominal membrane Reuse of industrial ECO; separation [27]

pore size: 0.1 μm tailwater media

PTFE membrane Membrane pore size: 5 Treatment of persistent EAO; substrate [40-44,

15
 μm organic pollutant 51-53]

PTFE membrane Membrane pore size: 5 Virus removal and EAO; substrate [54]

μm deactivation

Polysulfone (PSF) membranes Membrane pore size: E. coli removal and EAO; substrate [55]

(P20) 1.65 μm deactivation

PTFE membrane Membrane pore size: 5 Treatment of persistent E-Fenton; substrate [56]

μm organic pollutants

Tubular ceramic MF membrane Membrane pore size: Dye wastewater ECO, separation [57]

1.4μm treatment media

Flat sheet ceramic MF membranes Nominal membrane Tertiary treatment of ECO, separation [58]
Ceramic
pore size: 0.5 μm secondary industrial media
membrane
wastewater effluent

α-Al2O3 MF membrane Membrane pore size: Oily wastewater EAO; substrate [45]

0.2 μm treatment

16
TiO2 UF membrane MWCO: 50 kDa Organic pollutant EAO; substrate [49]

oxidation

Al2O3 membrane Pore size: 150nm Removal of organic EAO; substrate [46]

pollutant

TiO2 ceramic hollow fiber Pore size: 150nm Removal of E. coli and EAO; substrate [50]

membrane humic acid

Ceramic membrane —— Phenol oxidation ECO; substrate [59]

Alumina ceramic membrane Mean pore size: 0.2µm Removal of organic ECO; substrate [47]

pollutants in

wastewater

α-Al2O3 membrane Membrane pore size: Oily wastewater ECO; substrate [48]

600 nm treatment

Al2O3 membrane Mean pore size: 504 Removal of organic PECO; substrate [60, 61]

nm pollutants

17
 3.2 Conductive membrane materials

At present, the most common types of conductive membrane materials applied for wastewater

purification include conductive metal/metal oxide membranes, carbon-based membranes and

conductive polymer membranes (CPMs).

3.2.1 Conductive metal and metal oxide membranes

The commonly used porous metal membranes are mainly fabricated by using press forming and

sintering of metal powder. Among them, stainless steel membranes and porous titanium membranes

are most widely investigated. Owning to their mechanical stability and low costs, stainless steel

membranes are also widely used as porous support of composite membranes [62-71]. However,

stainless steel membranes are not stable when a positive potential is applied during the water

treatment as a result of the electrochemical etching [72]. On the other hand, porous Ti membranes

have attracted attentions because of their good corrosion resistance and the feasibility of loading

electro-catalysts. To today, porous Ti membranes have been applied in electro-catalytic membrane

reactors (ECMR) where the Ti membranes serve as both an anode and filtration medium

simultaneously for wastewater treatment [73-76]. It is shown that the cell conductivity and mass

transfer on the membrane electrode surface are improved and the treatment efficiency is

considerably enhanced. Table 2 presents recent studies of porous metal membranes for water

purification. Besides, the ECMR has also been used for controllable oxidation of such organic

chemicals as n-propanol[77], cyclohexane[78, 79], glucose[80], benzyl alcohol[81], and

2,2,3,3-tetrafluoro-1-propanol[82, 83].

Most metal oxides are non-conductive at room temperature, but the sub-stoichiometric titanium

oxides TinO2n-1 (n≥3) (Magnéli phase) are an exception. These oxides (4≤n≤ 6) possess high

electrical conductivity (~166 Ω-1cm-1) at room temperature [84] and good resistance to corrosion
18
making them suitable for use as electrodes [85]. It has been reported that the Ti4O7-based electrodes

behave as both an active electrode for direct electron transfer reactions and an inactive electrode for

producing •OH via water oxidation [86, 87]. Consequently the Ti4O7 electrode is a promising

candidate for electrochemical wastewater remediation applications [85]. Magnéli phase Ti4O7 is

usually produced by heating titanium oxide at a temperature above 900°C, followed by reduction in

hydrogen [88-93]. The ECMR using Ti4O7 based porous membranes for treatment of organic

wastewater via electrochemical oxidation has attracted significant interest, as shown in Table 2.

Excellent performance has been observed for the removal of such organic compounds as phenols

[84, 94, 95], oily wastewater [45], humic acid [45, 96] as well as bacteria deactivation [97].

19
 Table 2. Recent studies of metal membranes and metal oxide membranes in water purification.

Membrane Characteristics Application & functions Reference

Separating Alamin and calcite particles from the

SS MF membrane Membrane pore size: 0.5 µm and 2.5µm [72]
suspensions under electric filed

Flat porous Ti Separating Blue 2BLN solution;

-- [98]
membrane Conductive membrane substrate

Membrane pore size: about 2.50 µm;

Metal Tubular porous Ti Degradation of pyridine in wastewater;
Diameter: 26mm (inside) and 30 mm [75]
membra membrane Conductive membrane substrate
(outside)
ne
Average pore size: 51µm;
Tubular porous Ti Degradation of methylene orange in wastewater;
Diameters: 20mm (outside) and 10 [74]
membranes Conductive membrane substrate
mm(inside)

Tubular macro-porous Ti Pore size: 0.98 µm; porosity: 27% (Ti-RuO2 Treatment of tricyclazole and anticancer drugs in
[99, 100]
membranes membrane) wastewater;

20
 Conductive membrane substrate

Tubular porous Ti Degradation of the aqueous flutriafol;

Diameter: 60 mm; Average pore size: 5µm [30]
membrane Conductive membrane substrate

Tubular porous Ti Average pore size: 7.0µm; Diameter: 1.0 Phenolic wastewater Treatment;
[101]
membrane cm (inside) and 1.5 cm (outside) Conductive membrane substrate

Tubular porous Ti Electrochemical oxidation of pyrimidine;

Pore size: 5µm [73]
membrane Conductive membrane substrate

Porous Ti4O7 tubular Median pore size: 1.7μm; Porosity: 31%; p-methoxyphenol, p‑Substituted Phenol;
[84, 94]
membrane Diameters: 28 mm (outer) and 20 (inner) REM
Metal
Sub-stoichiometric TiO2 Median pore size: 1.7μm; Porosity: 31%; Bacteria (E. coli) deactivation;
oxide [97]
membrane Diameters: 10 mm (outer) and 7.5 (inner) REM
membra
Tubular asymmetric
ne Mean pore size: about 10.4 nm; Diameters: Electrodialysis water treatment;
TiO2 Magn li Phase [49]
1 mm (outer) and 0.5 mm (inner) REM
ultrafiltration

21
membranes

Porous Magneli phase Median pore diameter: 1.4μm; Porosity: Electro-oxidation of paracetamol and phenol;
[95]
MF membrane 41%; Specific surface area: 0.40m2·g-1 REM

Thickness of Ti4O7 layer: 13.0 μm; Treatment of oily wastewater, humic acid (HA),
Tubular Magnéli
Conductivity: about 200 S·cm-1; and BSA; [45, 96]
Ti4O7/Al2O3 membrane
Average pore diameter: 350 nm REM

22
3.2.2 Carbon-based conductive membranes

Carbon-based membranes (CBMs) are derived from the pyrolysis of carbonaceous materials (e.g.

polymers) or fabricated directly from the carbon materials. Due to abundant resources, a wide range

of species and good conductivity, CBMs have been investigated for various applications, including

gas separation [102-107], vapor separation [108-110], fuel cells [111, 112] and water treatment

[113]. As an important part of conductive membranes, CBMs become promising alternative top

other conductive membranes in the electrochemically-assisted membrane processes for wastewater

treatment [55, 113-121].

Table 3 lists recent studies on CBMs for electrochemical-assisted water purification. In these

studies, CBMs can be categorized into two groups: (1) carbon-based membranes fabricated from

novel nano-carbon materials; (2) carbon-based membranes derived from such conventional granular

carbon materials as graphite and coal. Graphene and CNTs are representative nano-structured

carbon materials, and their unique physicochemical properties (e.g. high surface area, thermal

conductivity, electron mobility and mechanical strength) make them a hot research subject for

environmental applications [122]. Conductive membranes derived from these nano-carbon materials

are shown to perform well in wastewater treatment [6, 123-125]. Generally, composite conductive

membranes with a nano-carbon conductive layer can be fabricated by deposition under pressure [28]

or via vacuum filtration [46, 53]. Free standing nano-carbon based membranes can also be prepared

using the phase inversion process, with appropriate polymers such as PVA, PVDF and PVB being

used as the binders [126-128]. The conventional carbon-based membranes derived from graphite

[29, 129] and coal [130-134] have the advantages of low costs of raw material, good chemical and

thermal stabilities. In addition, the simple preparation procedure makes them especially suitable for

large scale productions. The novel design of membrane reactors that use coal-based carbon
23
membranes (CBCM) as an electrode demonstrated excellent performance in decontamination of

organic wastewater [120, 121, 135].

24
Table 3. Recent studies of carbon-based conductive membranes for water purification applications.

Materials Fabrication method Characteristics Application Reference

Pressurized deposition, Electrical conductivity: 2412±97

CNTs-PVA-PSF Electrofiltration for alginic acid solution [28]
followed by cross-linking S/m; Pore sizes: 10-100 nm;

Electrical conductivity: 2400 S·m−1;

Pressurized deposition,
CNTs-PVA-PSF Average porosity: 60-50%; Pore Electrofiltration for microbial [136]
followed by cross-linking
sizes: 100-150 nm

The effluent from anaerobic sequencing

Pressurized deposition,
CNTs-PVA-PSF Resistivity: 1132±32Ω batch reactors, the membrane act as [137]
followed by cross-linking
cathode

Pressurized deposition, Electrochemical removal of hexavalent

CNTs-PVA-PSF —— [138]
followed by cross-linking chromium

Filtration under pressure and

CNTs-PVA-CN Electrical conductivity: 3.6×103 S/m Biofouling-resistant membranes [139]
cross-linking

25
 Electrical conductivity: 3.20×10-4 Organic pollutant mineralization and
CNTs-PVDF Phase inversion [126, 127]
S/m fouling mitigation

A novel in-situ combination Electrical conductivity: about 105 Removal of foulant in the presence of
CNTs-PVDF [140]
-1
approach S·cm an external electric field

Electrical conductivity: 3.7×10-3 Removal and electro-oxidation of [40-44,

CNTs-PTFE Vacuum filtration
S·m-1 chemicals and microorganisms in water 51-54, 56]

Cathode in an electrochemical system

-1
MWCNTs-PVDF Vacuum filtration Electrical conductivity: 10 S·cm [141]
for in situ membrane cleaning

Pore size: about 450 nm;

Wet-spinning and thermal Electro-assisted separation of
CNTs HFMs Porosity: about 85 %; [128, 142]
calcination nano-particles and NOM
-1
Electrical conductivity:1.2 Sm

Porosity: 93%;
Wet-spinning and interfacial Electro-assisted FO for humic
CNTs HFMs Pore size: 194 nm; [117]
polymerization acid,CaCl2, E. coli, oily water treatment
Electrical conductivity:1500 S/m

26
MWCNTs-graphe
Vacuum filtration Resistivity: 11.7 ± 0.9Ω sq−1 Electric vacuum membrane distillation [143]
ne-PTFE

Electro-conductivity : 8928 ± 307

Electropolymerization of Fouling prevention and
−1
CNTs-PANI S·m ; [144]
aniline on a CNTs substrate electro-oxidation of organic compound
−1
Resistivity: 56 ±2 Ω sq

Water treatment and electrochemical

CNTs-epoxy resin Microtome-cut method —— [145]
recovery of fouling

Vacuum filtration assisted Electrical conductivity: 4.1×10-3 Electrochemical filtration of organic

MWNTs-PSF [55]
-1
layer-by-layer deposition S·m and bacteria in wastewater

Porosity: 81%;
CNTs-ceramic Vacuum filtration-pyrolysis
Pore size: 142 nm; Organic waste water treatment [46]
membrane process
Electrical conductivity: 1615 S/m

CNTs-ceramic Vacuum filtration-pyrolysis Porosity: 82%; Electrofiltration to remove pollutants

[50]
HFMs process Pore size: 129 nm; from water

27
 Electrical conductivity: 1900S/m

Porosity: 92%;

Wet-spinning coupled with Pore size: 129 nm;

CNTs HFMs NOM removal from water treatment [146]
fluorination Electrical conductivity: about 98

S·m-1

Chemical vapor Electrical conductivity: ≥40,000 Bacteria removal under a low voltage
CNTs [115]
deposition(CVD) S/m; electric field

Anaerobic electrochemical membrane

Graphene-HFMs Chemical vapor deposition —— [116]
bioreactors

Ballistic protection, electromagnetic

GO-cellulose Spinning assisted Electrical conductivity: around 5000 interference shielding, biofluid
[147]
nanocrystals layer-by-layer assembly S m-1 separation, and wearable electronic

devices.

CNS-PVDF Vacuum filtration, followed Electrical conductivity: around 50 S Electrochemical filtration of yeast [148]

28
 by heat treatment cm-1 suspensions

Porosity: 5%;
Electrically enhanced fouling control in
CNS- NC Vacuum filtration Electrical conductivity: about 22 [118]
nanofiltration
-1
S·cm

CB-ceramic Electrochemical oxidation of phenol in

Spray deposition —— [59]
membrane water

Porosity: 37%;
Extrusion and thermal Degradation of Acid Orange 7 in an
Graphite Average pore size: 3μm; [129]
treatment electro-Fenton process
-1 -1
Electrical conductivity: 190Ω ·cm

Extrusion and thermal Average pore size of 0.44 μm;

Coal Organic wastewater treatment [17]
-3
treatment Resistivity: 1.0×10 Ω·m

29
 Porosity: 32.6%;
Extrusion and thermal
Coal Average pore size: 0.40μm; Oily wastewater treatment [149]
treatment
Resistivity: 1.1×10-3 Ω·m

[120, 121,
Extrusion and thermal Porosity:49.56%; Organic wastewater treatment and
Coal 135, 150,
treatment Average pore size: 0.38μm Microalgae removal
151]

Cotton
In situ redox polymerization Resistance: 2-10 Ohm sq.-1 Bacteria deactivation [152]
fiber-PANI

Conductive
Template diamond growth on
diamond Pore size: 0.3 μm Wastewater treatment and desalination, [153]
quartz fiber filter
membrane

30
3.2.3 Conductive polymeric membranes

Polymers with conjugated backbones formed by a series of alternating single and double carbon

bonds, tend to exhibit good electrical conductivity. The p-orbitals in the series of π-bonds overlap,

allowing the electrons to be easily delocalized and to move freely between the atoms [154]. The

most common conductive polymers are polypyrrole (PPy), polyaniline (PANI), polythiophene and

polyacetylene [155]. Due to their unique properties, membrane made from these polymers have

attracted considerable attention[156-161].

Table 4 lists the recent studies on conductive polymer membranes used for water treatment. PPy

appears to be the most popular conductive polymer for the preparation of conductive membranes

because of its relatively high conductivity and good environmental stability [155, 162]. Having a

tight and rigid structure with weakly basic anion-exchangeable groups, PPy can be polymerized

easily by chemical or electrochemical oxidation. Moreover, the conducting polymers are not readily

soluble in common solvents, and membranes are difficult to cast with the solution casting technique.

Thus PPy conductive membranes are normally prepared via the chemical/electrochemical

polymerization deposition method on appropriate porous supports. However, in contrast to

carbon-based materials and other inorganic conductive materials (e.g. T4O7), conductive polymers

generally have a low electro-conductivity and weak electrochemical activity. Since these polymers

are vulnerable to corrosion by electrochemical oxidation, conductive polymeric membranes are

always used to serve as a cathode in water treatment, and the enhancement in foulant rejection is

mainly contributed to the electrostatic forces [155, 163-165].

31
Table 4. Recent studies of electrically conductive polymeric membranes in water treatment.

Material Fabrication method Characteristics Application Reference

Diffusive chemical oxidative Electrical conductivities: Insulating

PPy-PSF Removal of NaCl and MgSO4 [166]
polymerization range

Average measured resistance: 10 Removal of bovine serum albumin

PPy-PM30 Chemical polymerization [167, 168]
-1
KΩ·cm (BSA)

Vapor phase chemical oxidative Conductivity resistivity: 42.1 Fouling reductions in a membrane
PPy-terylene [165]
polymerization KΩ·cm bioreactor as a cathode

Resistance: 2.48 ± 0.66 kΩ cm-1 Fouling reduction in EMBR as a

PPy-polyester Chemical oxidative polymerization [164, 169]
cathode

Average electrical conductivity: Removal of azo dyes in an

PPy-PAN Chemical oxidative polymerization [170]
-3
2×10 S/cm electro-separation process

PPy-bacterial Electrical conductivity: 0.32 S/cm Electromagnetic shielding with

In situ chemical synthesis [171]
cellulose self-cleaning functions

32
 Phase inversion induced by Surface electrical resistance: about Filtration of yeast solution under
PPy-PVDF [172]
immersion precipitation 2.0 MΩ/cm DC electric field

Electrical conductivity: 8.8 × 10−3

PANI-PAA Chemical deposition —— [173]
−1
S·cm

33
4. Recent advances in membrane technology coupled with EAOPs

As a promising technology for removal of organic contaminants in wastewater, EAOPs can

decompose the organic pollutants into less refractory compounds or inorganic matters such as H2O

and CO2 by electrochemical oxidation[11, 174]. There are two main types of EAOPs: EAO-based

and Fenton-based EAOPs. The EAO-based EAOPs degrade of refractory organic pollutants on the

anode surface through direct electron transfer and oxidation with ·OH (or other reactive oxygen

species) produced on anode surface. They include electrochemical anodic oxidation (EAO),

electro-catalytic oxidation (ECO) and photoelectro-catalytic oxidation (PECO). In Fenton-based

EAOPs, the degradation reaction is carried out in the bulk solution using the Fenton reagents

generated partially or completely from the electrode reactions (cathode). The electro-Fenton

(E-Fenton) and its variant technologies including photoelectro-Fenton (PE-Fenton) and

sonoelectro-Fenton (SE-Fenton) are primary Fenton-based EAOPs.

4.1 Membrane processes coupled with EAO

Electrochemical anodic oxidation (EAO) is one of the important EAOPs. As shown in Figure 6,

in the EAO process, the direct electrochemical oxidation of pollutants usually occurs at a low

potential (below the potential of the oxygen evolution reaction). In general, the reaction rate of

direct electrochemical oxidation is low. When the operating potential is higher than the potential of

oxygen evolution reaction, indirect electrochemical oxidation will occur, and the reactive oxygen

species (e.g. ·OH) are thus formed on the surface of the anode, which further enhances the

degradation efficiency of the contaminants [175].

34
Figure 6. Direct and indirect electrochemical oxidation of pollutants. (a) Direct electrochemical

oxidation; (b) Indirect electrochemical oxidation.

Currently, coupling membrane filtration with EAO is extensively studied. In the two-stage

coupling process, the membrane fouling and permeation resistance are effectively reduced when the

EAO is used as a pretreatment process for membrane separation, and the particles and pollutant

molecules are effectively rejected by the membrane [31, 32, 176]. Further, the EAO process is

appropriate for post-treatment of NF and RO concentrate streams. Boopathy et al. [177]

investigated the treatment of reverse osmosis concentrate from the leather industry using a

Cu-graphite anodic oxidation system. Results showed that TKN and COD removal was higher than

98% at optimum operating conditions in the presence of chloride ions.

The sub-stoichiometric titanium oxide (mainly Ti4O7) based membranes and carbon-based

membranes are the most popular electro-conductive membranes used in the one-pot

membrane-EAO coupling process. Chaplin and coworkers reported a series of studies on the

membrane-EAO system using porous Ti4O7 tubular membranes as the anode [49, 84, 93, 94, 178].

The membrane-EAO system demonstrated high degradation efficiency for various organic

compounds such as p-substituted phenol [84, 94], phenol [179], oily wastewater [45] and humic

acid [96]. Additionally, mass transfer rates were also increased when the system was operated in

35
filtration-mode relative to the traditional electrochemical oxidation mode [84]. In addition to pure

Ti4O7 membrane, Ti4O7/Al2O3 composite membranes with a Ti4O7 conductive inner layer also

showed excellent antifouling property in the membrane-EAO hybrid system, and the coupling

process exhibited higher humic acid degradation efficiency than a single MF process [45, 96]. All

the results mentioned above indicate that Ti4O7 membrane electrodes have a great potential for use

in wastewater treatment. However, the high preparation costs and rigorously controlled fabrication

conditions (H2 atmosphere) might limit their further development, and alternative synthesis routes

have been explored[95]. For example, Magnéli phase TiOx membranes can be fabricated by using

carbonthermal reduction of TiO2 instead of using H2 as a reduction agent. The obtained membranes

consisted of Ti5O9 and Ti4O7, and they showed good reactivity and permeability for the degradation

of biorefractory pollutants in when used in membrane-EAO coupling process.

Nanocarbon-based membranes integrated with electrochemical oxidation for organic wastewater

treatment and bacteria deactivation are another area of intense research [180]. CNTs membranes, a

representative nanocarbon-based conductive membranes, showed good water permeability and

mechanical strength [181-184]. The electrochemical oxidation reaction and the generation of gas

bubbles on the CNTs membrane during the process help enhance their resistance to bio-fouling and

organic fouling [46, 50, 114, 115, 145]. Vecitis et al [40-44, 51, 52, 54] developed a CNTs

membrane electrode by vacuum-filtration, and the membrane showed excellent efficiency for

removal of dyes[41], phenol[42], tetracycline[53] and virus [54] form water when integrated with

electrochemical oxidation taking place on electrode surface. Simple chemical treatments can change

the surface properties of the CNTs membrane, and the function groups on the membrane surface

produced significantly effect on the electrochemical performance of the CNTs membranes [40, 52,

185, 186]. Compared with CNTs, graphene, a two-dimensional nanocarbon material with special
36
properties, has attracted widespread attention in many fields [187]. Graphene-based membranes

have shown excellent performance for removal of such organic contaminants as tetracycline, phenol,

and oxalate when used as the membrane/anode in the one-pot membrane-EAO process [188].

Carbon membranes derived from coal tend to have good electrical conductivity, and they are

suitable for wastewater treatment by means of electrochemical oxidation. Furthermore, coal-based

carbon membrane (CBCM) have a great potential for uses on large scale because of their low price

and abundant deposit of the raw material, as well as the simple extrusion production method. In

recent years, our group has carried out a series of systematic studies on the controlled preparation of

CBCMs. The pore structure [133, 189], mechanical strength [190] and electrical conductivity [191]

of CBCMs have been further optimized. Subsequently, various CBCMs, including flat, hollow flat,

tubular and honeycomb carbon membranes, have been produced by our laboratory (as shown in

Figure 7) [192]. As expected, these CBCMs demonstrated excellent performance for gas separation

[103-105, 193] (CMSM substrate) and wastewater treatment [130, 132]. Additionally, utilizing the

electrical conductivity of CBCMs, our group designed a coupling system which employs a CBCM

as the anode and a Ti plate surrounding the membrane as the cathode (Figure 8); this system

achieved significant improvement on removal efficiency and antifouling ability under an external

electric field due to the electrochemical oxidation[120]. This system also exhibits excellent removal

efficiency for pollutants with a smaller molecule size than the membrane pore size such as dyes

[121, 135] and phenol [151]. Moreover, microorganisms such as microalgae [150] and Vibrio

cholerae [194] are also effectively removed.

37
 Figure 7. CBCM products with different shapes.

Figure 8. Scheme of the electrochemical CBCM system [120].

4.2 Membrane processes coupled with ECO

The membrane-EAO system has been proved to be effective for organic wastewater treatment.

However, further potential for improvement in the removal efficiency and life span of the coupling

system is often limited by the relatively low electrochemical activity of the electrode materials [174,

195-197]. Therefore, the development of the electrode materials with high electrochemical activity

is key to making a significant breakthrough in this field.

Efforts have thus been made to fabricate the electro-catalytic electrodes by coating

electro-catalysts on the surface of electrodes via chemical vapor deposition (CVD) [198, 199],

sol-gel and dip coating [200, 201], electro-deposition [202, 203], and hydrothermal synthesis [204].

To date, various electro-catalysts such as boron-doped diamond (BDD), TiO2, PbO2, SnO2, IrO2,

RuO2 and composite metal oxide catalysts have been applied in the ECO processes for the

elimination of organic contaminants [12, 174, 205].

Depending on the interactions between hydroxyl radicals (·OH) and electrodes, the
38
electro-catalytic anodes can be group as active and inactive electrodes (Figure 9). For active

electro-catalytic electrodes, the adsorbed ·OH radicals are generated on the electrodes surface via

H2O electrolysis (Eq. 1) at a potential higher than oxygen evolution potential (OEP) [206], and their

strong interactions with the electrode materials lead to the formation of high valence oxides (MO)

(Eq. 2). Then, MO and the adsorbed ·OH react with the organic pollutants to form oxidation

products (Eq. 3 and Eq.4), which are typical reactions for the electrodes with a relatively low OEP

(e.g., IrO2, RuO2). On the other hand, the inactive electro-catalytic anodes (e.g., BDD, SnO2-SbO2

or PbO2) have a high OEP and weak adsorptions of ·OH, and they only act as an inert electron sink

for the removal of electrons from the pollutant compounds, resulting in the reduction of oxygen

evolution reaction that helps with the mineralization of organic compounds (Eq. 4). However, there

exists competition between the oxidation of organic pollutants and the oxygen evolution reaction in

the case of both active and non-active anodes (Eq. 5 and Eq. 6); each reaction occurs at its minimal

energy consumption [174].

H2O +M → M(·OH) + H+ + e- (1)

M(·OH) → MO + H+ + e- (2)

MO +R → M + RO (3)

M(·OH) + R → M + mCO2 +nH2O + H+ + e- (4)

MO → M + 1/2O2 (5)

M(·OH) →M + 1/2O2 + H+ + e- (6)

39
Figure 9. ECO of organic compounds on “active” and “inactive” electrodes [207].

In addition, the overall electro-catalytic degradation efficiency of organic pollutants is greatly

improved by active chlorines (e.g., hypochlorite, chlorine dioxide and chlorine), which are

electro-generated in the bulk (Eq. 7 to 9) in the presence of chloride [14, 19].

2Cl- → Cl2 + 2e- (7)

Cl2 + H2O → HClO + H+ + Cl- (8)

HClO ⇌ H+ + ClO- (9)

The studies on the membrane-ECO coupling system, which have been carried out extensively in

recent years, prove that the membrane-ECO coupling systems are more effective than

membrane-EAO coupling systems for organic wastewater treatment [101, 113, 208]. For instance,

Rafael et al.[209] demonstrated that the electro-catalysis process using BDD electrode as a

pretreatment unit could effectively reduce membrane fouling, and the quality of effluent from the

membrane process was enhanced. When ECO was used as a post-treatment unit of the membrane

process, the membrane separation unit was able to concentrate the feed solution to a high pollutant

concentration level, ensuring high degradation efficiency during the electro-catalytic process [34].

40
Thus, the energy consumption of the electro-catalytic process was further reduced [210]. In

comparison to the combination with nanofiltration unit, the coupled ECO-RO processes have

additional benefits because of the reduced in water volume and the high rejection of the salinity and

chloride which contribute to conductivity and oxidation activity, respectively [210].

Comparatively, the coupling process of a membrane and ECO in the one-pot mode has attracted

more attention than the two-stage mode. Recent studies on the one-pot membrane-ECO processes

for wastewater treatment are summarized in Table 5. For example, Xu et al. [26, 35-38] attempted

to combine a NF membrane with ECO in the one-pot mode. They found that the pollutant

concentration near the membrane surface was sharply reduced due to the degradation of organic

pollutants by ECO. In addition, there was an improvement in permeate flux resulting from

electroosmosis and electrophoresis [211]. Moreover, the fluid turbulence that is enhanced by the

generation of bubbles also reduces the thickness of the fouling cake and the concentration

polarization layer near the membrane surface [26, 36]. In practice, real wastewater contains not only

organic contaminants, but also some inorganic ions and particulate matters. It has been reported that

both the organic matters and particulate matters can be effectively removed by membrane filtration

coupled with ECO, and the membrane fouling can be reduced in the hybrid process [57, 212]. In

addition, novel one-pot membrane-ECO coupling systems, such as ECO-MBR (integration of an

electro-catalysis oxidation apparatus into a conventional MBR with a microfiltration module) [213]

and FO-ECO (forward osmosis combined with electro-catalysis oxidation) [214], have also been

investigated, and the findings have highlighted the promising prospects of these systems. Although

the membrane materials mentioned above and ECO are set in one-pot and are operated

simultaneously in the membrane-ECO process, in order to obtain a high removal efficiency, the

applied potentials used are always higher than 10 V, even up to 100 V [27, 39] due to the
41
non-conductivity of the membrane materials; this inevitably results in high energy consumption

[28]. Hence, the coupling processes using conductive membrane as the separation media and

electro-catalytic anode to serve the dual purpose simultaneously are desirable. Nonconductive

membranes are often coated with a conductive electro-catalytic layer such as pyrolytic carbon

supported Pt catalyst[47], carbon black supported SnO2-Sb[59] and 1D IrO2 nano-rod layer[48] for

uses in membrane-ECO system for organic wastewater treatment. Compared with the composite

membranes with a conductive active layer, the self-conductive membranes including porous metal

membranes and carbon-based membranes have gained more interest in recent years. Moreover, the

high mechanical strength and corrosion resistance of these membranes make them more suitable

membrane substrates for the one-pot membrane-ECO process.

Porous Ti membranes are the most popular metal membrane substrates used in the

membrane-ECO processes. The Ti-BDD electro-catalysis membrane developed by Li et al. [98]

exhibited good electrochemical self-cleaning ability due to its wide potential range (-1.8V to +2.2V)

for water stability and low background current. Several other Ti-based electro-catalytic membranes

such as Ti-SnO2-Sb [75] and Ti-RuO2 [99, 100], have been successfully fabricated. These

electro-catalytic membranes possess a large electrochemical surface area and high mass transfer in

the coupling system, which lead to excellent wastewater treatment performance. Recently, attempts

have been made to further improve the electrochemical properties of membrane electrodes. For

instance, Zhang et al. [215] fabricated a tubular porous Ti-based electro-catalytic membrane by

coating with a composite catalyst RuO2-Sb2O5-SnO2. Liu et al. [30] prepared an electro-catalytic

membrane electrode through template deposition of 3D macroporous PbO2 (3DEM-PbO2) on a

porous Ti substrate, and Li et al. [74] prepared a membrane electrode that display a TiO2

mesoflower interlayer between the porous Ti membrane surface and the SnO2-Sb layer. The
42
electrochemical activity and stability of these membrane electrodes are significantly improved due

to increased number of electroactive sites and the higher OEP.

The carbon-based electro-catalytic membranes are also important for membrane-ECO hybrid

systems. As mentioned in section 4.1, the coal-based carbon membranes (CBCM) coupled with

EAO showed good performance for wastewater treatment. However, the performance of CBCM for

treating high concentration wastewater is still limited due to the low electrochemical activity of

carbon materials [121]. In order to overcome this problem, electro-catalytic carbon membranes

(ECCM) had been fabricated by loading a nano-sized metallic oxide catalyst (TiO2 and SnO2-Sb) on

the membrane surface via the sol-gel method and dip-coating techniques. The ECCM have a higher

electro-chemical activity and longer life span than the original CBCM, while still maintaining good

electrical conductivity [113]. The outstanding performance of ECCM has been demonstrated in the

treatment of oily wastewater [17, 149], phenolic wastewater [216] and pharmaceutical residues[113,

208]. In addition, the adsorption property of carbon-based membranes is also beneficial for the

removal of organic contaminants [29, 113]. Figure 10 is an illustration of the mechanism of the

membrane-ECO process using ECCM. The excellent performance of ECCM for treating organic

pollutants is contributed to the enhanced mass transfer, electrochemical oxidation (direct oxidation

and indirect oxidation) and membrane rejection/adsorption [29, 113]. As expected, both Ti-based

electro-catalytic membrane and ECCM in the membrane-ECO processes perform well in organic

wastewater treatment, while the coal-based ECCM have the advantages of low cost and abundant

sources of raw materials.

43
Figure 10. The mechanism of the water treatment process of ECCM [113].

44
 Table 5. Recent studies of one-pot membrane-ECO processes for water treatment.

Membrane Catalytic Modification Operational Referenc

Wastewater properties Treating performance
materials anode method parameters e

Both the RCOD of NF and coupling process are

D series Coating and
Simulated dye wastewater higher than 90%, Rcolor reaches almost 100%;
commercial Ti/SnO2-Sb2 thermal
containing Reactive Red 118 U=0-20V the membrane fouling of the NF membrane [26]
NF O3 electrode decomposition
(C0=0.1-0.6 g·L−1 ) can be effectively restrained in the coupling
membrane technique
process.

ΔP=0.5 MPa,
Ti/SnO2-Sb- Simulated dye wastewater The permeation flux can be improved by
o
Pechini method; T=30 C,
NF90 Y anodes; containing C.I. Acid Red 73 applying a current density and the Rcolor
−1
Electrodepositio V=0.011 m s , [35]
−1
membranes Ti/SnO2-Sb (0.1-0.3 g·L ) and 0.1 M reached 100% when current density is higher
n J=0-30 mA
anodes Na2SO4. than 15 mA cm−2.
cm-2.

NF-90 Ti/SnO2-Sb Pulsed Aqueous solution containing ΔP=0.4-1.2 In the coupling process, the retention rate is [38]

45
membranes anodes electrodepositio 250 mg·L−1 tetracycline MPa, basically higher than 99.0% and the permeate

n hydrochloride and 0.06M T=25±2 °C, flux of nanofiltration have been promoted.

NaCl. V=20 L·h-1,

J=20-25 mA

cm-2.

Simulated wastewater The retention rate is closed to 99% in the

ΔP=0.8MPa,
-1
DL NF Ti/SnO2-Sb- containing 0.5 g L C.I. Acid coupling process which is higher than single
Pechini method U=10V, [36]
membrane Y anodes; Red 73, and Na2SO4 (0.1 mol NF process (≈97%), the permeate flux has
V=0.0258ms-1;
L-1) been also promoted.

ΔP=1.2 Mpa, The permeation flux and rejection in the

Ti/SnO2-Sb- Pulse Simulated wastewater V=0.0258m·s− coupling process using Ti/SnO2-Sb-CNT are
NF90
CNTs electrodepositio containing 0.5 g·L−1 C.I. Acid 1
, 61.9L·h−1·m−2 and 97.3%, which are superior [37]
membranes
electrode n method Red 73 and0.1 mol L-1 Na2SO4 J=100mA·cm− than that of Ti/SnO2-Sb (54.01 L·h−1·m−2,

2
. 96.9%).

46
 Tubular
Simulated wastewater
ceramic MF
BDD/Ti containing 20 mg/L acid The COD remove rate is 100% after 6h
−2
membrane CVD method J=30 mA·cm [57]
anode yellow 36 dye and 5 mg/L operation time.
(pore size:
kaolin, TV=2L.
1.4 μm)

PVDF Synthetic wastewater

U=0-100V, In permeate, the RHS=97.56% at 100V, and
membranes Ti-RuO2 containing humic substances
-- ΔP=49 kPa, the permeate flux increased with the applied [39]
(pore size: plate anode (3mg/L TOC) and 23.3mg/L
V=0.1 m/s potential.
0.1 μm) calcium sulfate, TV=3L.

Synthetic tailwater (advanced

PVDF
treatment follow ECO and ED U=0-100 V, In the permeate: C pyridine = 0.107 mg/L,
membranes, Ti-RuO2
-- process), the influent of the filtration time UV254 = 0.025 after two times operation [27]
(pore size: plate anode
coupling process containing was 30min (when U=100V),
0.1 μm)
1.33 mg/L pyridine and the

47
 UV254 =0.360, TV=500 ml.

Model feed solutions

containing 200μg·L−1 of each

In the coupling process, when J = 1 mA cm-2,
Asymmetric Provided by antibiotic (sulfamethoxazole,
Ti/IrO2-Ta2 the rejected rate of trace antibiotics from the
cellulose Long Sheng trimethoprim, norfloxacin and J=0.5-1.0
O5-SnO2 wastewater was higher than 98%; 99% of [214]
−1 −2
triacetate FO Electrode Co., roxithromycin), 15mg·L mA·cm
anode the antibiotics from concentrate can be
−1
membrane China alginate, 10mmol·L NaCl,
eliminated after 3 h operation.
1mmol·L−1 NaHCO3, and

0.5mmol·L−1 CaCl2. TV=1L.

Sol-gel and
J=30
Ceramic membranes with thermal Aqueous solution containing
mA·cm−2, The remove rate of phenol ranges between 40
-1
the layer of carbon black decomposition 0.1 g·L phenol and 0.7-5.0 g [59]
-1
F=250 and 60% in 5.0 g·L H2SO4.
-1
supported SnO2-Sb method, and L H2SO4
L·m-2· h-1
then sprayed on

48
 the membrane

surface

Emulsifying peanut oil The COD rejection reach 95.8% at 0.15A and
Successive
α-Al2O3 membrane with 1D solution, C0=200 mg/L, 96.3% at 0.3A, and the time-average permeate
brushing or I=0-0.3A [48]
IrO2 nano-rod layer C(Tween 20) =10mg/L. fluxes of them are 22% and 44% higher than
dip-coating
TV=2L. that at no electricity.

Depositing BDD
Synthetic dye wastewater with U=4V, In the coupling process, it maintains a high
Composite Ti/BDD film on Ti
50 mg/L Blue 2BLN and 10g/L J=1.6 flux (220L· m-2·h-1) after 8h operation, and [98]
membrane membrane by
Na2SO4. mA·cm−2 the remove rate of dye is higher than 85%.
CVD method

Simulated pyridine wastewater: The remove rate of pyridine is 98% under the
J=20-40
-1
Ti/SnO2-Sb tubular porous C0=100-500 mg·L , optimal operation conditions ( C0=100
-2
Pechini method mA·cm , F=8 [75]
-1 -1 -1 -2
membrane C0(Na2SO4)=1-15 g·L , mg·L , C(Na2SO4)=10 g·L , J=30 mA·cm
-1
mL·min ;
pH=3-11. TV=400ml. and pH=3).

49
 TPTM/TMF/ATO TMF interlayer:

membrane (Tubular porous hydrothermal J=0.1-15mA·c

Simulated dye wastewater
titanium membrane/ TiO2 method; m-2, Removal efficiency of methyl orange is
-1
containing 50 mg·L methyl [74]
- -2
mesoflower interlayer / ATO active F=3.5mL·min 71.0% at a current density of 15 mA·cm .
-1
orange and 0.1mol·L Na2SO4.
1
Sb-doped SnO2 active layer: sol-gel ;

layer) method

Sol-gel

technique and Simulated wastewater After 180 min treatment, the remove rate of
−2
Tubular porous Ti-RuO2 J=3mA·cm ,
thermal containing tricyclazole (20-100 tricyclazole is approximate 100% for all four [99]
-1
membrane F=8mL·s
-1 -1
decomposition mg·L ) and 5 g L Na2SO4. concentration.

method

Sol-gel Actual anticancer drugs J=3.0-5.0 After 180min treatment, the remove rate of
Tubular porous Ti-RuO2
technique and wastewater containing mA·cm−2, the drug and COD are 100% and 84.1%, [100]
membrane
thermal 61.2mg/L F=0.08-0.40 respectively. (when J=5.0 mA·cm−2, F=0.31

50
 decomposition 5-Fluoro-2-Methoxypyrimidine L·min-1, pH L·min-1, pH=2.0, no electrolyte)

method , and C0(COD)= 4340 mg·L-1, was adjust to

Conductivity is 3390μs·cm-1 2-9.

3DEM-PbO2 REM
Templated
(REM with Flutriafol solution with 0.05 M J=5mA·cm−2, The remove rate of flutriafol is 73.8% at
electrochemical [30]
-1 −2
three-dimensional ordered Na2SO4, TV=200 ml. F=10mL·s 5mA·cm after 180min operation.
deposition
macroporous PbO2 film)

Ti nano-tubes:

Electrochemical
A: SnO2-Sb tubular porous Simulated wastewater After 6 h operation, the pyrimidine removal
anodization; J=2.5-20mA·c
-1
membrane; containing 100 mg·L efficiency achieves 89.5% for membrane A
−2
SnO2-Sb: sol-gel m , [73]
-1
B: TiO2-NT/SnO2-Sb pyrimidine and 5 g L Na2SO4. and 97.9% for membrane B, respectively
-1
and thermal F=8mL·s ;
tubular porous membrane TV=400mL. (when J=10mA·cm-2).
decomposition

method

51
 Actual pesticide tailwater

Sol-gel method, containing 45.3 mg·L-1

vacuum 1H-1,2,4-triazole (Tz), 10.3 F=50-250

Tubular porous After 90min treatment, RTz=98.9%,
-1 -1
induction and mg·L tricyclazole (TC) and mL·min ,
Ti/RuO2-Sb2O5-SnO2 RTC=99.0%, RPPC=98.4%, RCOD=81.9%. [215]
-1
thermal 3.2mg·L propiconazole J=1-4 mA
membrane (when F=250 mL·min-1, J=4 mA cm-2)
decomposition (PPC); cm-2;

method C0(COD)=243.2 mg·L-1, TV=1

L.

Sol-gel method,

vacuum
Simulated phenolic J=0.3mA·cm−2 In the permeate, the removal efficiency of
MnOX/Ti composite induction and
wastewater: C0=450 mg·L-1, , Residence phenol, COD and TOC are 93.09%, 79.25%, [101]
membrane thermal
C0(Na2SO4)=15g L-1 time=5 min; 68.54%, respectively. ( MnOx/Ti-220oC,)
decomposition

method

52
 RuO2: sol-gel

and thermal
After 3h operation, the remove rate of pyrrole
decomposition;
Graphite-RuO2-MWCNTs Pyrrole solution: C0=100-700 and TOC are 97.7% and 75.7%, respectively.
−2
MWCNTs layer: J=1-7mA·cm [29]
−1 −1 −1 −1
membrane mg L , C0(Na2SO4)=3-9 g·L (When C0=300 mg L , C(Na2SO4)=7 g·L ,
vacuum
J=3 mA·cm−2)
filtration

synthesis

Simulated oily wastewater

Sol-gel and U=2.0 V; In the permeate, removal efficiency of oil and
Tubular TiO2/carbon containing commercial 0#
thermal ΔP=0.01-0.03 COD are 86.2% and 94.4%, respectively. [17, 149]
−1
membrane diesel fuel (200-1000mg L )
decomposition MPa (when C0=200 mg L−1, ΔP=0.01MPa)
and 15 g·L−1 Na2SO4.

Sol-gel and Simulated phenolic F=111.6L·m-2·

Tubular TiO2/carbon The removal efficiency of phenol and COD
-1
thermal wastewater, C0= 2.0 mM, h , [216]
membrane are 99.96% and 86.3% after 2h operation.
decomposition C0(Na2SO4)=15g·L−1, J=0.3mA·cm−2

53
 TV=150ml.

Sol-gel and In the permeate, the remove rate of

Flat Sb-SnO2/carbon Aqueous tetracycline, U=0-4V, F=1
thermal tetracycline is 96.5%, RTOC is approximately [113]
−1 -1
membrane C0=50mg L mL·min
decomposition 60% after 6h treatment.

C0:Initial concentration of feed solution;

J:Current density;

V: Cross-flow velocity;

ΔP: Operating pressure;

F: Permeation flux or flow rate;

R: Rejection rate;

TV: Total volume of the feed

54
 4.3 Membrane processes coupled with PECO

Many electro-catalysts, including TiO2, SnO2 and ZnO, also have good photo-catalytic

characteristics [217]. Under light irradiation, the electrons in the highest energy band (valence band)

of the catalysts leap to the conduction band when hv > Eg (here h and v are the Planck constant and

frequency, respectively). The generated holes and electrons are highly active to get involved in

chemical reactions. As shown in Eq. 9-11 (where PC is the photo catalyst), the generated oxidizing

hydroxyl (·OH and ·O2-) will degrade the pollutants[218, 219].

PC + hv → h+VB + e-CB (9)

H2O + h+VB → ·OH + H+ (10)

O2 + e-CB → ·O2- (11)

Over the last decade, photo-catalytic oxidation (PCO) was shown to be an effective AOP for

wastewater treatment using solar energy [220]. Recent work shows that photo-catalysis can be

combined with membrane filtration, and the resultant membrane-PCO system is promising for

water disposal owning to the enhanced pollutant degradation performance and membrane fouling

reduction [221]. The integrated process is shown to be able to treat of various pollutants including

natural organic matters (NOM) [222, 223], dyes [224, 225], pharmaceuticals [226, 227], phenol

[228], virus [229] and bacteria [230]. However, the performance of PCO itself is rather limited by

the quick recombination of photo-generated electron-holes of photo-catalyst, which compromises

the efficiency of the coupled process of photo-catalysis and membrane filtration in water treatment.

On the other hand, photoelectro-catalytic oxidation (PECO) is a photo-assisted electro-catalytic

process. The photo assistance can enhance the electro-catalytic performance of degradation, and in

the meantime, the potential applied between the anode and cathode can help decrease the internal

recombination of photo-generated electron-hole pairs, thereby increasing the life time of the
55
electron-hole pairs and promoting the photo-catalytic efficiency [231-237]. Figure 11 shows the

mechanism of typical PECO process (TiO2 photocatalyst).

Figure 11. Schematic of the mechanism for PECO process using TiO2 photocatalyst [218].

As an emerging technique, little work is done on the membrane-PECO process. Wang et al [60]

reported a TiO2/carbon/Al2O3 membrane fabricated through sequentially depositing a conductive

graphitic carbon layer and TiO2 nano-particles layer on Al2O3 membrane substrate. When the

membrane is integrated into a membrane-PECO process, the contaminant removal efficiency is

higher than that of membrane-PCO or membrane filtration alone, and the permeation flux and the

NOM removal are increased with an increase in the applied potential. Furthermore, the organic

pollutants smaller than the membrane pores can be well removed by the membrane-PECO process.

Similar results were reported by Wang et al [61] using a g-C3N4/CNTs/Al2O3 membrane fabricated

via sequential coating of conductive CNTs and g-C3N4 layers on Al2O3 membrane substrate. As a

result of photoelectron-catalytic oxidation and membrane filtration, the integrated membrane-PECO

processes perform well for the decontamination of wastewater. However, the complicated

fabrication procedure of the aforementioned composite membrane electrodes appear to a barrier for

their wide spread applications. The self-conductive membranes may be a better to the composite

56
conductive membranes in terms of electric-conductivity and mechanical strength, and therefore

self-conductive membranes coated with appropriate photo-catalysts may be a proper approach for

further studies.

4.4 Membrane processes coupled with E-Fenton

All the EAOPs mentioned above are the EAO-based processes, and the electro-Fenton (E-Fenton)

is another promising EAOP for the decomposition of organic pollutants [238-244]. Its mechanism is

described as follows:

In the system, H2O2 is continuously electro-generated at the cathode surface with the supply of

O2 (Eq. 12), the oxidant ·OH is produced in the bulk solution via the Fenton reaction of

electro-generated H2O2 and the iron catalyst (Eq. 13) [196, 245], as shown in Figure 12. Compared

with traditional chemical Fenton process, this EAOP has several advantages: (1) there is no risk

related to the storage, transport and handling of H2O2 because the electro-generation on site; (2) the

continuous regeneration of Fe2+ at the cathode helps maintain a high degradation rate of organic

pollutants and minimize the iron sludge production (Eq. 14); (3) the operating cost can be further

reduced by optimizing the operating parameters [246].

O2 + 2H+ + 2e¯ → H2O2 (12)

Fe2+ + H2O2 + H+→ Fe3+ + ·OH + H2O (13)

Fe3+ + e¯ → Fe2+ (14)

57
Figure 12. Schematic of the main reactions of E-Fenton process.[247].

It has been reported that the E-Fenton process using a high H2O2 production cathode has good

performance for processing RO concentrate[248, 249] and NF concentrate[250] under a suitable

ferrous ion dosage, voltage and acid conditions.

Furthermore, the E-Fenton process can be combined with the membrane process in one-pot mode

using carbon-based membranes as the cathode. Using the vapor phase polymerization method

(VPM), Zhao et al. [251] developed a conductive Gr/PPy membrane for use as a membrane and a

cathode simultaneously in the coupling process, and a good performance is observed because of the

synergistic effects of membrane separation and E-Fenton reactions. Similar conclusions are made

by Liang et al [252] who used a tubular porous graphite membrane. Gao et al developed an

electrochemical reactor with a 4-layer CNTs-based membrane stack for sequential flow-through

E-Fenton [56]. They found that the refractory trifluoroacetic acid and trichloroacetic acid are

effectively decomposed, and the electro-Fenton oxidation rate in the flow-through mode is 4-fold

higher than the sum of the individual electrochemical and Fenton reactions. It should be mentioned

that, similar to the traditional E-Fenton process, the performance of membrane-(E-Fenton)

processes is also affected by the pH of the solution[251]. In addition, the homogeneous system
58
always suffers from the problem of Fenton catalyst outflow from the reactor and undesirable

generation of iron sludge in the reactor [245]. These two issues have to be taken into consideration

in further studies.

5. Conclusions and prospects

Membrane technology coupled with EAOPs has become one of the most promising technologies

for organic wastewater treatment, which reinforces the advantages of the membrane separation and

EAOPs, and enhances the removal efficiency for the organic contaminants. The coupling processes

are normally designed in two modes: the one-pot process and two-stage process. Compared to the

two-stage process, the one-pot process is technically. Specifically, the one-pot process occupies less

space, and the overall efficiency of this process is significantly improved by the electrokinetic

effects and in-situ reduction of membrane fouling.

The membrane materials used in the coupling process can be categorized as nonconductive

membranes and conductive membranes. The nonconductive membranes based on polymers and

ceramic materials are only used as the separation medium or the substrate of composite conductive

membranes. The conductive membranes mainly consisted of the inorganic membrane materials,

including sub-stoichiometric titanium oxide membranes, porous Ti-based membranes and

carbon-based membranes, are adopted as the electrode and membrane filter simultaneously in the

one-pot membrane-EAOPs. In the future development of the membrane-EAOPs, the conductive

membrane will become more attractive and exhibit potential application prospects due to its more

compact structure, higher efficiency and lower energy consumption.

In the membrane-EAOPs, the coupling processes, including membrane-EAO, membrane-ECO,

membrane-PECO and membrane-(E-Fenton), have been extensively investigated in recent years.

59
The membrane-EAO processes show a good performance in the antifouling of membranes and

removal efficiency of the organic contaminants, however, the treatment ability and life span of the

coupling system still require to be further improved owing to the relatively low electrochemical

activity of the membrane electrodes. The membrane-ECO processes, in which use of the

electro-catalytic membrane to replace the conductive membrane, are more efficient than

membrane-EAO processes due to the higher electrochemical activity of membrane electrodes and

have become the research focus in the membrane-EAOPs. The membrane-PECO processes, in

which the membrane-ECO systems are assisted with the photo-catalysis, might further enhance the

degradation of organic contaminants and antipollution of membrane in the wastewater treatment. It

should be needed to further concern in the future research on the membrane-EAOPs. For the

membrane-(E-Fenton) process, the membrane is set as the cathode and the degradation of pollutants

occurs in the bulk solution via the Fenton reaction of electro-generated H2O2 and the iron catalyst,

exhibiting the high degradation efficiency of organic pollutants. However, the pH value and catalyst

outflow will greatly affect the high degradation efficiency of organic pollutants.

As the review mentioned above, the integration of membrane and EAOPs has shown the

significant improvement in the removal efficiency of organic contaminants from wastewater and

antifouling ability of membranes compared to conventional EAOPs and membrane processes,

which exhibits a great potential in commercialized applications. Nevertheless, it is still at its infancy

and there are still lots of works to be done before their commercialization. The following aspects

would most likely be important in the future researches and developments for the

membrane-EAOPs.

(1) The performance (electrochemical activity, stability, etc.) of conductive membrane materials

should be further ameliorated. In this aspects, the research efforts should be aimed to not only
60
develop the modifying techniques of existed conductive membrane materials to enhance their

electrochemical performance, but also explore the novel membrane materials such as metal organic

frame, MoS2 and Mxene, etc. due to their special electrochemical properties. For the coupling

processes of membrane filtration and Fenton-based EAOPs, the novel heterogeneous catalysts with

wide applicable pH range should be developed to solve the problems on the limitation of pH value

and catalyst outflow.

(2) Considering the variety of EAOPs, the innovative coupling processes between membrane

technology and EAOPs might be developed. In addition, the development of membrane-EAOPs

assisted with other functions such as ultrasound, magnetic field or other AOPs should also be

explored to enhance the treatment capacity.

(3) At present, the most works on membrane-EAOPs are carried out to treat simulated organic

wastewater. Actually, the real wastewater is more complex, and it should be taken into account to

further evaluate the treatment ability of membrane-EAOPs for the real wastewater. Meanwhile, the

following items should also be considered for the long-time operation of the membrane-EAOPs.

The reactor structure needs to be optimally design to minimize the specific energy consumption and

costs. The methods and techniques of membrane cleaning and regeneration should be developed to

enhance the life span of membranes. Moreover, effects of the effluent from membrane-EAOPs on

environment also require to be investigated.

Acknowledgements

We gratefully acknowledge the financial support of the National Natural Science Foundation of

China (No. 21476034, 21676044, 21676200 and 21576208) and the Changjiang Scholars and

Innovative Research Team at the University of Ministry of Education, China (Grant no.
61
IRT-17R80).

62
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1. Recent advances on coupling process of membrane technology with EAOPs were reviewed.

2. Typical membrane-EAOPs including one-pot process and two-stage process were discussed；

3. Nonconductive membranes and conductive membranes related to membrane-EAOPs were

summarized;

4. EAOPs such as EAO, ECO, PECO, E-Fenton were integrated with membrane technology；

5. The future prospects of membrane-EAOPs process were proposed.

93