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Separation and Purification Technology 230 (2020) 115878

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Separation and Purification Technology


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

Photo-catalytic membrane reactors for the remediation of persistent organic T


pollutants – A review
⁎ ⁎
Priyanka Kumaria,b, Nupur Bahadurb, , Ludovic F. Duméea,
a
Deakin University, Geelong, Institute for Frontier Materials, Geelong 3216, Victoria, Australia
b
TERI-Deakin Nano-Biotechnology Center (TDNBC), Gwal Pahadi, Gurugram 122001, India

A R T I C LE I N FO A B S T R A C T

Keywords: A major problem that is worldwide prominent is limited access to clean water. The process of catalysis coupled
Persistent organic pollutants with the separation process carried by catalytically active membranes, takes place in device known as a catalytic
Wastewater remediation membrane reactor (CMR). In this paper, CMRs that are driven by light as external stimuli known as photo-
Photo catalytically active catalytic membrane reactors (PCMRs) are comprehensively described and compared on the basis of their per-
Membrane technology
formance to remediate persistent organic pollutants (POPs) in the wastewater. There is rapid development in the
PCMR technology in the past decade, and this review gives an overview of conventional methods employed in
treatment of selected POPs and progress in the types, configuration, and operational parameters of PCMRs. The
split and integrated types of photocatalytic membrane reactors, their construction techniques and properties of
photo-catalytically active membranes are discussed. The PCMRs are compared on basis of degradation rate of
common POPs in wastewater. Additionally, a discussion on practical application is presented with regard to
major challenges and gaps in the development and up-scalability of PCMR technology.

1. Introduction contaminants within oceanic currents or major rivers leads to adverse


impacts on ecosystems naturally secluded and devoid of industrial and
Excessive usage of chemicals in industries such as food processing, agricultural activities [8,9]. Elevated concentrations of POPs in alpine
paper making, agriculture and aquaculture, leads to production and fishes, wildlife and vegetation are eco-toxicological hazards [9–11] due
release of potentially toxic organic compounds in the environment [1] to bio-assimilation of POPs result in disruptions of thyroid function,
such as polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans immune systems suppression, cancers, endocrine disruptions, and
(PCDDF), polyaromatic hydrocarbons (PAHs), polychlorinated biphe- neurobehavioral and foetal developmental challenges leading to loss of
nyls (PCB), polybrominated flame retardants (BFRs), pharmaceuticals, genetic diversity [12,13].
endosulfans, organochlorine and organophosphate pesticides. Such or- Effective remediation routes to tackle the impact of POPs have
ganic contaminants are termed as Persistent Organic Pollutants (POPs) therefore been developed [14]. The elimination of pharmaceutical
[2]. As per latest Stockholm conventions, POPs are grouped as in- products and endocrine disruptive complexes by activated sludge pro-
dustrial chemicals, pesticides, and by-products of several combustion cess was incompetent as most of these compounds with slightly low
processes [3]. octanol/water partition coefficient (Kow) remained soluble in the ef-
POPs are problematic substance due to their (i) long persistence fluent [15]. Physicochemical treatment process such as coagulation-
with extended half-lives on the scale of years to decades, (ii) bio-ac- flocculation however offers relatively poor efficiency with pesticides or
cumulation in fatty tissues due to their high lipophilicity, (iii) high pharmaceuticals concentration reduction of only 10–40% [16,17] due
toxicity even at low concentration and (iv) long range transportability to competitive sorption with more hydrophobic compounds present in
[4,5]. Amongst the most alarming POPs, PCDD/Fs have half-life of wastewater and overall increase in total suspended solid at the end of
10–100 years, while different PCBs have half-lives ranging from 5 to treatment [18]. Adsorption of recalcitrant organic pollutants has also
20 years [6]. The presence of dioxins, furans or PCBs in the range or been widely trialed for various POP materials [19]. Although efficient
above 1.5–10 pg/g of fat in food products is considered toxic and a risk at removing large amounts of chemicals, the major limitations however
for human health (Commission Regulation (EU) 1259/2011) [7]. The lie in the lack of selectivity of the adsorptive technique for minute
long-range transportability of POPs as airborne or water-borne concentrations [20]. Regeneration of the adsorbents is also costly,


Corresponding authors.
E-mail addresses: nupur.bahadur@teri.res.in (N. Bahadur), ludovic.dumee@deakin.edu.au (L.F. Dumée).

https://doi.org/10.1016/j.seppur.2019.115878
Received 7 May 2019; Received in revised form 26 July 2019; Accepted 26 July 2019
Available online 02 August 2019
1383-5866/ © 2019 Elsevier B.V. All rights reserved.
P. Kumari, et al. Separation and Purification Technology 230 (2020) 115878

requiring large amounts of chemicals for operation and thus limiting 60 million E-waste is produced globally which contains persistent,
their large-scale application [19]. bioaccumulative and toxic brominated flame retardants (BFRs) such as
Advanced Oxidation Processes (AOP) which include several types of several types of bromodiphenyl ethers, tetrabromobisphenol A
reactions such as Fenton, photo-Fenton, ozonation, photocatalysis are (TBBPA), hexabromocyclododecane (HBCD) and several poly-
most efficient alternative that offer high efficiency and fast degradation chlorinated biphenyls (PCB) [36]. The addition of BFRs in the plastics
kinetics ensuring relatively fast and efficient reduction of total organic employed in electronics serves in slowing down or preventing the fire
carbon (TOC) in treated water [21]. A challenge however, lies in the ignition [37]. Existence of persistent pharmaceutical compounds, cos-
elimination of by-products of the POPs which are toxic and in the slow metics and the personal care products in the water bodies also raise
poisoning and inactivation of the catalytic materials over time and global concerns [38]. The major sources are untreated effluents from
operation cycles [22–27]. hospitals, sewage treatment plants [39].
Membrane systems have also been efficiently used for the con- Another major source of POP contaminating ground, surface and
centration of POPs from wastewater systems [28]. Reverse osmosis drinking water is related to agricultural run offs primarily containing
(RO) membranes were found to lead to removal efficiencies over 92% pesticides and chemical fertilizers [40]. The major classes of pesticides
while nanofiltration (NF) membranes restricted 30–82% of POP passage causing water pollution are organochlorine and organophosphate pes-
[29]. Membrane technologies are nonetheless more suitable to the ticides [41,42]. Pesticides are abundantly used in agriculture world-
treatment of effluents in relatively large concentrations, and the com- wide as they play important part is cultivation and preservation of crops
plexity of the source waters generates adverse fouling issues. The main [42]. In 2016, almost 400,000 tons of pesticides were used in Europe
limitation therefore lies in the cost of working at high hydraulic pres- vastly in agriculture, out of which 72% was solely consumed in France,
sures and in the regeneration of the materials upon fouling and cleaning Germany, Spain, UK, Poland and Italy. During 2016–17, developing
[19]. The development of catalytically active porous membrane tech- countries such as India had total pesticide consumption of about 57,000
nologies, called Catalytic Membrane Reactors (CMR) can serve the gaps ton according to the authorized data of the Directorate of Plant Pro-
in such conventional treatment processes [30,31]. CMR technology tection, Quarantine and Storage, Govt. of India. The consumption and
integrates two important aspects of wastewater purification which are pollution of pesticides has only increased over the years even after
molecular sieving and catalysis in a single unit in which the membranes enforcement of several laws such as Hudson's pesticide bylaw (Canada
can be fabricated to be catalytically active [32]. 1991), The Insecticides Act (India 1968), according to which the use of
CMRs may include conductive or chemically active materials which pesticides should be banned [43].
may operate with external stimuli such as light, electrical current, The presence of such POPs is likely to affect humans by disrupting
chemical activation, enzymatic response, or their combination, to allow thyroid function, immunity, endocrine disruption, serving as cancer
for enhanced concentration and degradation of the pollutants. Nano or causing agents [2]. Hyperactivity is also observed with disorders oc-
mesoporous membrane materials are employed that offer high specific curring in learning and memory [13]. POPs adversely affect wildlife
surface area and hence fast degradation kinetics due to forced con- and aquatic species by disturbing their reproductive cycle and sub-
vective delivery of contaminants on the surface or pores of membranes, jecting them to a disease called porphyria, which is a severe condition
along with filtration which is realized based on porosity, selectivity of accumulation of Porphyrin in the body that inhibit red blood cells
and/or electric charge of the membrane [32]. The performance of CMRs production in the body [40]. In plants, POPs interfere with the phyto-
can be tuned by anchoring of metal or metal oxide nanoparticles in the hormones at ambient concentration causing phytotoxic effects [44].
membrane material by doping, coating, immobilization and surface
grafting [33,34]. CMRs offer a cost-effective solution to the recovery of 2.2. Conventional treatment of POPs
valuable resources and limits footprint of separation systems as pollu-
tant degradation and pollutant rejection occur in one step in same The complexity and broad range of POP pollution types and sources
physical device, thus, this method has potential to offer cost effective- require non-selective techniques to deal with their often seasonal and
ness by economizing on permeate cleaning front [35]. non-constant occurrence in nature. The existing remediation techniques
This review aims at presenting the CMR as emerging technologies are presented in this part to divulge the performance of each of these
for remediation of POPs in wastewater. In the present work, a com- methods for removal of selective POPs and to develop better under-
prehensive analysis of PCMR application is provided and materials standing of further improvements These conventional methods include
fabrication processes, properties and performance in terms of re- coagulation-flocculation-sedimentation, adsorption [20,45], membrane
mediation of selected POPs such as pesticides, chemical fertilizers, dyes, filtration [46], ozonation and AOPs [21]. The primary aim of this
pharmaceuticals, will be discussed. section is to introduce benchmarks for the later comparison and ana-
lysis of POP remediation with CMR systems.
2. POP pollution and conventional remediation techniques
2.2.1. Coagulation-flocculation
In this section, the source and complexity of POP pollution and Coagulation-flocculation-sedimentation (CF) is one of the most
conventional remediation techniques will be presented. This aspect is conventional methods that are basically engaged as either a pre-treat-
critical to justify the choice of remediation, CMR technique and choice ment or post-treatment step or both in wastewater treatment plants
of material, to ensure appropriate release of non-toxic by-products and [47]. A chemical coagulant with charges opposite to that of suspended
long term and stable operation. The section will present major sources pollutant is added to wastewater so as to neutralize them [48] After
of POP pollution, risks and complexity, prior to assessment of existing which they start to stick together and forms micro-flocs. Process of
technologies for remediation of selected POPs to provide a performance flocculation is gentle mixing stage that allows micro-flocs to change to
benchmark for comparison with PCMR technology. visible macro-flocs. Once flocs are of optimum size and strength, water
is ready for sedimentation. CF is the process which employ usage of
2.1. Sources of pollution and water complexity coagulants such as FeCl3, Al3(SO4)3 which are promptly dispersed in the
polluted streams which is followed by another step of intense agitation
Industries such as textile & dyeing, pharmaceutical, glassworks, iron [48].
foundries, leather goods, oil refinery, petrochemicals, paper mills, sugar Thus, pollutants which are slightly less hydrophobic do not coagu-
mills or thermal power plants contribute significantly in circulating late easily. Atrazine, with a log Kow value of 2.6, is poorly removed by
POPs in the environment by releasing inadequately treated wastewater CF, of the order of 10 to 20%, while Aldrin, offering a higher log Kow
in rivers and streams. Electronic waste is also a rising concern, as nearly value of 6.75, is slightly better removed on the order of 40 to 45% (N3,

2
P. Kumari, et al. Separation and Purification Technology 230 (2020) 115878

Table 1) [17]. Competitive sorption with natural organic matters also

[47]
[49]

[17]

[50]
Ref.
leads lower efficiency of this method (N2, Table 1) [49]. In case of
doubling the dosage of coagulant for treatment of Bisphenol-A using
FeCl3 lead to only slight increment in removal efficiency up to 15–20%
No facility to improve settlement and biodegradation of PCBs

Slightly better for more hydrophobic pesticide like Aldrin yet


showing even change in coagulant dosages do not significantly influ-
ence removal of POPs (N4, Table 1) [50]. Thus, CF process employed as
individual treatment process removes less than 20–25% POPs from
wastewater (Table 1), proves highly insignificant.
Poor removal of compounds having Kow < 4

2.2.2. Adsorption
Partitioning of BPA in the supernatant

Adsorption on the porous or granular materials are extensively used


in the elimination of organic pollutants as the capacity of adsorption
offered by them is high for contamination range between 80 mg/L and
15 g/L as per the literature [45] As a matter of fact, activated carbons
that are commercially available are very expensive. Thus, several al-
ternatives are explored in order to obtain cost-effective adsorbents. For
removal < 50%

example, inexpensive option of using biomass which is also present in


abundance for bio-sorption has been well explored but the issues of
Problems

non-regenerability of bio-sorbent and pollutant disposal are of concern


[45].
Nowadays, low cost commercially available materials are more
sought after things for the remediation of wastewater. The low cost
materials, such as clay minerals [51], bagasse pith [52], wood [53],
12.0 ± 4.8%, 21.6 ± 19.4%, 31.8 ± 10.2%,

maize cob, fly ash are being exploited as possible alternatives for acti-
vated carbon for wastewater treatment. However, they suffer usual
disadvantage of low adsorption capacities and short term stability and
re-generability. Fast removal of BFRs such as BDE-3, BDE-15 using low
cost adsorbents are realised from model aqueous solution, which may
not be effective in real wastewater samples containing (N4, Table 2).
The requirement of various pre-treatment steps such as acid functio-
nalization, base functionalization, pressure stream washing become
Removal efficiency

mandatory in case of low cost adsorbents for better performance (N4,


6.3 ± 15.9%

Table 2) [19]. The use of alternative adsorbents such as Ambersorb-563


20% in 1 h

or silica rich zeolites with smaller and uniform pore size is restricted for
3–43%
23.2%

adsorptive removal of particular POP, which have matching size, for


instance (N-2,3, Table 2) Carbamazepine which is a bigger molecule
was poorly adsorbed by Ambersorb-563 with pore volume (0.201 cm3/
Fe(OH)3 + anaerobic hydrolysis + aerobic bioprocess

g) half in dimensions than activated carbon (0.437 cm3/g) [54]. Ad-


sorption process using higher dosage of activated carbon (25 mg/L) for
longer contact time of 2 days employed as a post-treatment step to treat
membrane bioreactor treated permeate leads to substantial removal of
contaminants up to 86% (N1, Table 2) [55]. This shows that elimina-
tion of contaminants using activated carbon predominantly depends of
Assessing removal efficiency of selective POPs by Coagulation-flocculation.

FeCl3/Al2(SO4)3 (25–50 ppm)

factors like adsorbent dosage, contact time and wastewater composition


as established by other studies as well [56,57].
Coagulant with dosage

FeCl3 (100, 200 mg/L)


Al2(SO4)3 (300 mg/L)

2.2.3. Membrane technology


Membrane technology is also widely used for the retention of pol-
lutants which is basically attained by following the principle of size
exclusion, repulsion of charges and membrane adsorption [58].
Number of factors determines the filtration mechanism such as mem-
brane process type (MF, UF, NF, RO), characteristics of the membrane
material and the pollutants, the conditions of operation, and the issues
Atrazine, Dieldrin, Aldrin (0.1–100 µg/L)

of membrane fouling [59].


UF process poorly removes pollutants due to bigger pore size of
Ibuprofen, Diclofenac Naproxen,

these membranes in comparison with pollutants [59]. For instance,


removal of Ibuprofen which is a small compound with 1.39 nm length
by UF process using a hydrophobic PES membrane only retained 25% of
Bisphenol-A (95 µg/L)

Ibuprofen (N1, Table 3) [60]. Electrostatic interaction plays an im-


209 types of PCBs

portant role in rejection [61]. Diclofenac and Naproxen are moderately


Carbamazepine

retained (60%) on negatively charged membrane at neutral pH, they


are highly acidic with pKa values 4.2 and 4.15 respectively; while
carbamazinepine is basic (pKa = 13.9) so, could not be removed (N2,
POP

Table 3) [61]. Such an additional step for treating effluent from was-
Table 1

tewater treatment plants (WWTP) by incorporating NF membranes


N

1
2

operating at low 0.3–0.7 bar could not be justified as removal efficiency

3
P. Kumari, et al. Separation and Purification Technology 230 (2020) 115878

of POP is low [61]. Employment of NF membranes such Filmtec NF90

[55]

[54]

[54]

[19]
Ref.
(tight), Filmtec NF200 (loose) at higher pressure of 3.45 bar and
4.83 bar respectively led to significant removal of POP up to 97% (N3,

Smaller pores in comparison with activated carbons lead to more


Low efficiency when employed as individual treatment process

Several pre-treatment steps are required to functionalize low


Table 3) [62]. RO process can remove up to 95–99% contaminants in
Efficiency decreases on saturation of adsorption sites. Cost

effluent from membrane bioreactor (MBR), yet even minute presence in


the range 28–223 ng/L of Ibuprofen and diclofenac in permeate proves
RO not being an absolute barrier to POPs (N4, Table 3) [63]. The
performance of NF in terms of removal of pollutants is very near to that
of RO membranes, which is an advantage when operating costs come
into consideration [62].

2.2.4. Advanced oxidation process (AOP)


Advanced Oxidation process (AOP) is a way out in which hydroxyl
radicals (OH·) are generated to reclaim wastewater offering high de-
gradation rate and non-selectivity [64] Hydroxyl radical is one of the
specific adsorption

most reactive oxidizing agent for wastewater treatment and reacts with
cost adsorbents

organic pollutants to degrade it in less or complete non-toxic products.


inefficient
Problems

It is highly non selective, thus react with numerous species in waste-


water with rate constant (108-1010 m-1s−1). The lifetime of hydroxyl
radicals is very short so they tend to undergo in-situ generation during
aapplications such as reaction of oxidizing agents (H2O2 and O3) [65],
28.7%, 20.9%, 31.2%, 41.3%, 38.9% respectively
23.3%, 25.5%, 46.6%, 53%, 69.9% in 4 h contact

ultraviolet irradiation [66], and in Fenton related reactions [67]. One of


the major cause of concern in full-fledged application of AOPS for water
treatment is the production of by-products of oxidation from pollutants
as complete mineralization is not assured in oxidative processes [65].
97.8%, 98.5% in 4 min respectively

As previously discussed, in many cases the reaction intermediates are


more toxic for biological systems than parent pollutant which is major
88% in 2 days contact time

setback of this process [21]. An organophosphate pesticide-methyl


parathion showed TOC abatement of 95% by UV-C assisted photo-
Fenton oxidation [22] but its photo-product methyl paraoxan is 10
Removal efficiency

time respectively

times more toxic than methyl parathion [23].


Simple irradiation process (photolysis) offers extremely low de-
gradation rate of recalcitrant BDEs (N1, Table 4). Photocatalysts such as
Titania increase the degradation rate of BDE 209 to an extent (N2,
Table 4). However, Pd doped Titania increases the degradation rate
manifolds due to narrowing of band gap of Titania which will lead to
Carboneous resin-Ambersorb 563 (1 mg/L)

Black Tea, green tea, coconut palm leaves

storing of electrons on the surface of Pd and then further getting


Coconut shell based activated carbon

transferred to BDEs for degradation (N3, Table 4). Degradation is sig-


nificantly lower in realistic environmental conditions with pollutant
concentration in µg/L.
Activated carbon (25 mg/L)

2.2.5. Shortcomings of conventional methods for treating POP rich effluents


The conventional methods to treat selected POPs are reviewed and
it is observed that factors such as pH, dosage, concentration and com-
position of wastewater, contact time play important role especially in
Adsorbent

(0.01 g/L)
Assessing removal efficiency of selective POPs by Adsorption method.

(1 mg/L)

processes like coagulation-flocculation and adsorption by activated


carbon [17,65]. Transmembrane pressure, feed qualities are to be
considered for concentration of POPs by membrane technology [28].
Ibuprofen, Diclofenac Naproxen, Atrazine, Carbamazepine

Hydrophobicity and molecular size of the contaminants also affect their


Ibuprofen Diclofenac Naproxen Atrazine Carbamazepine

treatment [16]. Even after abundant optimization of several parameters


associated with coagulation-flocculation method, the ineffective re-
moval of POP and large amount of sludge generation remain its per-
sistent failure [50]. Relatively high cost, lower efficiency in presence of
dissolved organic matters, inorganic salts, need for regeneration and
disposal of used adsorbents are common problems associated with ad-
sorption methods [54]. CF and adsorption are used effectively only as
post or pre-treatment steps in wastewater treatment. Membrane tech-
Diclofenac, Carbamazepine

nology suffers the usual disadvantage of high energy requirement,


BDE-3, BDE-15 (5 mg/L)

disposal of concentrate and issues of membrane fouling [60]. Major


deterrent to AOPs is high toxicity level of the effluent due to highly
(200–900 ng/L)

(200–900 ng/L)

toxic by-products of target pollutant, high energy consumption and


interference of radical scavengers [64].
Thus, there is clear need for a specific technology that can provide
POP

high removal efficiency (> 99%), fast degradation or remediation ki-


Table 2

netics, recyclability and low fabrication cost along with efficient sieving
N

capability offering separation of degraded product from permeate.

4
P. Kumari, et al. Separation and Purification Technology 230 (2020) 115878

Table 3
Assessing concentration of selective POPs by Membrane technology.
N POP Membrane Technology Membrane TMP (bar) Removal Efficiency Ref.

1 Ibuprofen (100 ng/L) UF PES, flat sheet MWCO = 100 kDa 0.01–0.5 7% [60]
2 Diclofenac, Naproxen, Carbamazepine NF Flat Sheet modules 0.3–0.7 60%, 60% Trace removal [61]
3 Atrazine, Carbamazepine (5–18 µg/L) NF Filmtec NF90; MWCO = 90–200 Da 3.45 97%, 91% respectively [62]
4 Ibuprofen, Diclofenac (3.7–53.5 µg/L) RO Filmtec TW30 MWCO = 100 Da 9.5–10.2 95–99% [63]

3. Catalytic membrane reactors advantages over the conventional photocatalytic reactors which are
simultaneous separation and photocatalytic degradation of pollutants.
A catalytic membrane reactor (CMR) is an integrative unit in which There is significant reduction in the loss of photocatalyst in reaction
process of separation by membranes and catalytic reactions are coupled process, and this technology possess the ability to be implemented at
in parallel [72,73]. CMRs selectively allow the passage of specific commercial scale [101–103]. Photo-catalytic membrane reactors for
components from the feed relying of the principle of surface reactivity wastewater treatment can be categorized broadly in two parts based on
which facilitates chains of chemical reactions simultaneously occurring the mode of existence of photocatalyst including (i) slurry PCMR in
on the surface of the catalytically active membranes and the inter- which powdered catalyst is used in the form of suspended particles
connecting pores. The combination of both separation and catalytic [104–106] and (ii) immobilized PCMR in which membranes can be self-
processes in the single unit in CMRs gives a way that can be economical catalytic or photocatalyst embedded within the membrane matrix or
to carry out remediation processes, chemical synthesis or chemicals coated on the porous substrates [107–109]. Further, the selection cri-
regeneration, improving efficiency and stability of both membrane and teria for proper substrate support include high specific surface area,
catalytic systems [72,74]. high abrasion, chemical resistance, high stability against photolysis and
CMR technology for wastewater treatment include Photocatalytic reactivity with ROS [80]. The substrate materials require a physical
membrane reactors which integrates advanced oxidation processes like configuration that supports liquid–solid separation and junctions be-
photocatalysis with membrane technology [75–80]; Electrocatalytic tween the substrate and photocatalyst which must resist strain from
membrane reactors (ECMRs) that integrates electrocatalytic reactions particle to particle and particle–fluid mechanics interactions in order to
and process of membrane separation into one processing stage [81–83] have better adhesion [80]. Ceramics such as alumina, titania, polymeric
and most recent photo-electrocatalytic membrane reactors (PECMRs) materials such as poly(vinylidene fluoride) (PVDF), poly(sulfone) (PSF),
[84,85] in which photo-catalysis is assisted by electro-catalysis together poly(ethersulfone) (PES), poly(acrylonitrile) (PAN), and metallic sub-
to membrane filtration technology. This section of review will cover the stances such as stainless steel are used as substrate materials for pre-
different materials, configurations, types, fabrication processes, and paring catalytically active membranes to be further employed in im-
performance in terms of mineralization of POPs and filtration of de- mobilized PCMR [76,110,111] (see Fig. 1).
graded species of PCMRs.
3.2. Slurry based photocatalytic membrane reactors
3.1. Photo-catalytic membrane reactors (PCMR)
At industrial scale the slurry based photocatalytic membrane re-
actors are more effective as it offers greater contact between pollutants
Photocatalysis is a kind of process that comes in category of ad-
and suspended photocatalyst in the slurry combined with direct usage
vanced oxidation process (AOP) which uses suitable light irradiation to
of commercial membranes for filtration purposes [104]. It can be of two
activate semiconductor metal oxides such as TiO2 [79], ZnO [86], SnO2
types namely (i) split and (ii) integrative type based on the configura-
[87], ZrO2 [88], WO3 [66], Fe2O3 [89], CeO2 [90] for conversion of
tion of reactor [112]. One in which the photocatalytic oxidation and
compounds in wastewater to eventually mineralize into less or non-
membrane separation occurs in different compartments are called Split-
toxic minerals such carbon dioxide, ammonia, and water [91].
type slurry PCMR (Fig. 2) while integrative-type slurry PCMR realizes
The significant properties of the metal oxides system used as pho-
both in same compartment [112]. The latter provides a more compact
tocatalyst are the shorter band gap, desired morphology, size, shape,
system by integrating photocatalysis and membrane module. Thus, such
high specific surface area, high stability and reusability [92]. The
configuration reduces costs by limiting the capital requirements, in-
photocatalytic process starts as soon as the beam of light from a source
cluding pumps, pipelines, and footprint. However, selection of mem-
(sunlight of fluorescent lamps) is irradiated on the surface of the pho-
brane material for integrative-type requires greater scrutiny as mem-
tocatalyst. This lead to expulsion of electrons from the valence band
branes could be damaged under UV irradiation or reactive oxygen
which jumps to the conduction band leading to the production of
species [113].
electron-hole pairs [91]. Further reaction between the electron-holes
pairs with the oxygen and water produces reactive oxygen species
(ROS) such as ·OH, O2–, H2O2, 1O2. These ROS are strong oxidizing 3.2.1. Split-type slurry based PCMR
agents, and possess the ability to degrade different types of POPs along A split type slurry system employed for the treatment of synthetic
with inactivating the metabolic pathways of pathogenic microorgan- wastewater comprising humic acid, tannic acid in the range 0.9–18 mg/
isms [91]. L consist of a continuous photocatalysis apparatus (CP) and bench-top
Amongst the mentioned photocatalysts, anatase TiO2 is most widely membrane filtration set up for retention of photocatalyst [105]. The
in use for its chemical inertness, mechanical strength, non-toxicity as slurry of wastewater and commercial TiO2 P-25 Degussa (1 g/L) having
well as hydrophilicity, photostability and low cost [75,93–95]. How- the surface area of 50 m2/g and particle size of 21 nm was pumped from
ever, titania bandgap of titania which is 3.2 eV limits its visible light feed reservoir to mixed tank following 15 min adsorption in dark and
activation while its high electron-hole recombination rate restricts en- subsequently pumped to three annular photo-reactors (8 W each,
hanced photocatalytic activity and hence the overall reduction in pro- λmax = 253.7 nm) in series for photocatalytic treatment that led to 60%
cess efficiency and the quantum yield [91]. These short-comings are DOC removal in 30 min. The UV treated suspension from photo-reactors
resolved by doping Titania with transition metals ions [96–98] and is returned to mixed tank and stored in effluent reservoir where is it
non-metals ions [99,100]. further treated with an 0.05 g/L dosage of adsorbent (powdered acti-
Membrane technology coupled with photocatalysis suggests many vated carbon) and a small dosage AlCl3 coagulant as well about 12 mg/

5
P. Kumari, et al. Separation and Purification Technology 230 (2020) 115878

L which led to 76% DOC removal in 2 h at the system load of 46 mL/

[68]

[69]

[70]

[71]

[65]

[65]
Ref.
min. The suspension is pumped to membrane unit for retention of
catalyst, coagulant and adsorbents in the system. The entire train

Photocatalysis rate higher for BDE concentration in mg/L which is

Ineffective for contaminants that are not susceptible to oxidation


achieved 92% DOC removal with incorporation of an in line coagula-
Extremely low debromination with rate constant 0.10–2.64 h−1

Formation of toxic by-products such as carcinogenic amine on


Extremely low degradation rate in the realistic environmental
tion and membrane filtration [105]. Similarly, a split type PCMR for
treatment of dye wastewater consisted UV chamber, a system for the
circulation of feed water and membrane module. The UV reactor
comprised a reaction mixture of commercial TiO2 (0.5 mg/L) and dye

ozonation of atrazine, high energy consumption


pollutant (15 mg/L) which is photo-catalytically degraded using 18 W
UV lamps (λ = 254 nm) and circulated to hollow fibre MF membrane
unit. Pressure gauge which is employed to measures the transmembrane
pressure (TMP) is generally placed in permeate line and air bubbling is
far from real condition i.e. in µg/L

ensured to provide oxygen saturation and prevent settling of TiO2


Agglomeration of bare titania

suspension [114]. This system led to 100% color removal, 76% TOC
removal and 60% DOC removal in 90 min. Major problem associated
with split type slurry system is formation of cake layer on membrane
which was monitored through sharp decrease in permeate flux from
100 L/M2 h to 75 L/M2 h [114].
conditions.
Problems

Split type PCMRs have been designed at pilot scale consisting of


photocatalytic reactor and membrane vessel for the degradation of
frequently encountered POPs in wastewater such as Diclofenac (N1, N2,
Table 5) [115,116]. TOC removal of 2 mg/L Diclofenac in ultrapure
8.5%, 5.4%, 49%, 83% in 4 h for BDE 28, 100,

83%, 99%, 99%, 69%, respectively in 25 days

Milli water was ~ 69% in 2.6 h, higher than tap water and ground water
with 39–45% in same time. This specifies that feed water composition
60% after 40 min, 100% after 60 min

also plays an important role on POP mineralization in the mineraliza-


13%, 26% respectively in 25 days

tion of POP as presence of natural organic matters and inorganic salts in


real water retards photocatalytic oxidation (N2, Table 5) [115]. It was
observed in another study that photolysis of Diclofenac under UV ir-
153 and 183 respectively

radiation (253.7 nm at 1.04 W/L) degraded the pollutant leading to


40–50% after 14 days
Removal efficiency

95% removal in 30 min (N1, Table 5). In comparison with photolysis,


the removal of diclofenac in presence of 0.5 mg/L TiO2 was way lesser
30% after 4 h

i.e. 40% in 30 min at 1.04 W/L and 90% in 30 at 2.08 W/L which can be
explained by the significant light scattering phenomenon because of
TiO2 nanoparticles getting deposited on quartz tubes of UV lamps.
However, mineralization of Diclofenac was only 19.5% in 3 h in pho-
tolysis experiment when compared with photocatalysis experiments
Photocatalysis –Pd doped TiO2 (0.2 g/L), 100 W
Photocatalysis-powdered TiO2 (1 mg/mL) & Xe

with 52% in same time analyzed by TOC percentage removal which


1% nano-sized TiO2 ; BDE sol in visible light

explained that oxidation product could not be degraded further in


Ozonation (5 mg/L) + H2O2 (3.5 mg/L)

photolysis alone [116]. Similar type of pilot scale development was


used for the removal of 32 POPs present in the range 0.25–50 ng/L
including pharmaceuticals (diclofenac, ibuprofen, diazepam, na-
proxen), endocrine disrupting (atrazine, bisphenol A, TCEP, TCPP) and
Photolysis-500 W Hg lamp

estrogenic compounds (progesterone, testosterone) as well (N9,


a = Tetra (4-carboxyphenyl) porphyrin; b = tris (2-chloroethyl) phosphate.

Table 5) [117]. In this study, 11 target POPs were easily removed with
Ozonation + H2O2
Hg lamp (360 nm)

0.53 kWh/m3 treatment while other target POPs required higher level
lamp (360 nm)

treatment of 0.8–4.27 kWh/m3 to achieve 70% removal. Low removal


irradiation

efficacies of this study is involved with the fact that very low amount of
TiO2 dose was subjected in the system i.e. 50 mg/L when compared
AOP

with the standard dose of 0.5–1 g/L in bench-top models as well as at


Assessing removal efficiency of selective POPs by AOP.

the pilot-scale. Continuous air circulation and stirring need to be


Brominated diphenyl ethers (BDEs) 28, 100, 153 and

maintained in the photocatalytic chamber for the inclusion of oxygen


Ibuprofen, Diclofenac, Carbamazepine, Atrazine,

that would aid the photocatalytic reaction and to prevent undesirable


settling of photocatalyst and POP in the slurry [118]. It is necessity in
these systems to employ 3 way valves controlled by timer for periodic
backwashing of membrane [115]. The backwashing needs to be done
TCPPa (250 ng/L) TCEPb (35 ng/L)

after every 60 sec to avoid cake layer formation on the membrane


which is a setback as it requires high energy consumption [117]. In an
183 (10 ng/mL in hexane)

investigation to degrade ibuprofen (N4, Table 5), it was observed that


the flux decreased by 86% after 188 h continuous process due to for-
BDE-209, (10 mg/L)
BDE-209 (5.5 µg/L)

BDE-209 (75 µg/L)

mation of cake layer of TiO2, calcite and other impurities like aragonite
crystals confirmed by XRD. The process of cleaning with HCl was em-
ployed which helped in recovering of the flux but it anyway started to
(110 µg/L)

decrease with same rate after 70 h of cleaning [119].


POP

In split type PCMR for degradation of a refractory dye Disperse Red


Table 4

73 (DR73), there were some parameters which played important role


N

such as pH, dosage of TiO2 and concentration of dye (N6, table 5)

6
P. Kumari, et al. Separation and Purification Technology 230 (2020) 115878

Fig. 1. (a) Slurry Photocatalytic membrane reactor; (b) Immobilized Photocatalytic membrane reactor.

[120]. At pH 4, the degradation of dye was observed to be 90% in solution, thus at lower pH positively charged TiO2 attracts it more ef-
180 min while at pH 10, it was 61% in the same duration. This is due to ficiently for photo-degradation [120]. The investigation of different
the fact that for P-25 Titania, the point of zero charge is at 6.5 due to loadings of TiO2 (0.5, 1, 1.5, 2 g/L) for dye degradation showed best
which in acidic medium it maintains the positive charge and in alkaline results for 2 g/L dosage leading to 90% removal in 180 min in com-
conditions it is negatively charged. Since DR73 is negatively charged in parison with 70–75% removal with 0.5 g/L and 1 g/L loadings.

Fig. 2. Split type slurry continuous photocatalysis apparatus with membrane filtration unit consisting UV chamber for photocatalytic oxidation of wastewater, a
system for the circulation of feed water and membrane unit for retention of catalyst, coagulant and adsorbents in the system and pass on clean permeate.

7
P. Kumari, et al. Separation and Purification Technology 230 (2020) 115878

However, the point to be noted is that excess of photocatalyst may lead

[116]
[115]
[126]
[119]
[122]

[120]

[106]

[121]
[117]
[113]
Ref.
to agglomeration causing reduction in surface area that potentially
decrease overall photocatalytic performance of the system and also lead

100% degradation of 18 PhC and 50–88% degradation of other 14

83–100% colour, 43–90% TOC and 55–85% COD removal after


to greater membrane fouling. The experiments carried out at different

97% degradation in 90 min, 90% mineralization in 120 min.


dye concentration from 50 to 100 mg/L showed the best outcome with
82% degradation in 150 min at 50 mg/L initial concentration of dye

70% removal of 29 pollutants with 0.8–4.27 kWh/m3


following the Langmuir-Hinshelwood model [120]. Addition of oxidant
such as H2O2 (3 g/L) in reaction vessel containing slurry of TiO2 and
96% degradation & 69% TOC removal in 2.6 h
56% degradation; 52% removal of TOC in 3 h

60–90% degradation, 70–98% COD removal


insecticide Chlorpyrifos increased the COD removal from 55% to 90%
100% degradation and drug reject in 5 h.

in 5 h as H2O2 generates more radicals for oxidation of intermediate


compounds of Chlorpyrifos (N8, Table 5) [121]. This study supports
that fact that TiO2 alone may not be sufficient for complete miner-
alization of POP and requires doping or other oxidants for enhanced
55% COD removal after 8 h

mineralization [121]. Membrane with 0.45 µm pores is merely used to


98% degraded after 24 h

filter out agglomerates to Titania in suspension. Further, the fouling of


catalyst and their loss in filtration process over few cycles render it
ineffective for efficient photocatalytic degradation for long term re-
Performance

PhCs in 1 h.

cycling. For instance, in this study the COD removal decreased from
90% to 60% in 5th cycle only [121].
4h

3.2.2. Integrative slurry based PCMRs


Integrative

Integrative

Integrative

Integrative PCMRs employ membranes immersed in the photo-


Reactor

catalytic chamber containing suspension of photocatalyst and pollu-


Split
Split
Split
Split

Split

Split
Split

tants and UV lamps could be positioned well outside or inside the re-
action chamber [106,122]. Integrative PCMRs are successfully engaged
PVDF + PP + Ceramic Al2O3 (0.2 µm)

for the removal of dyes, viruses, organic, inorganic pollutants and other
POPs [106,123,124]. However, in configuration with UV lights inside
Poly(sulphone) (0.3 m2, 0.2 µm)

reaction chamber, UV irradiation may damage the membrane, thus a


PTFE (0.0151 m2, 0.22 µm)

light baffle is applied to avoid direct exposure with UV [123].


MF membrane (0.45 µm)
PVDF (100 m2, 0.04 µm)
PP (0.0127 m2, 0.2 µm)

Integrative PCMR was used in the removal of 33 POPs including


pharmaceuticals and endocrine disrupting chemicals (N5, Table 5)
PVDF (0.03 µm)
PVDF (0.04 µm)

PVDF (0.2 µm)

[122]. The slurry of TiO2 photocatalyst in the reactor starts degrading


Ceramic MF
Membrane

pollutants present in the range 350–500 ng/L similar to realistic con-


centration followed by simultaneous filtration to recover photocatalyst
and sieve degradation products of pollutants. The outcome proved
complete degradation of 18 POPs in 1 h. Slow degradation was ob-
Commercial TiO2 (0.5–2 g/

Commercial TiO2 (0.5 g/L)

served up to 50–88% in 60 min of other POPs which have amide groups


0.5–0.75 g/L
0.3–0.75 g/L

such as carbamazepine, diazepam, caffeine, paracetamol [122]. This


P-25 TiO2 50 mg/L

establishes the co-relation of chemical structure of POPs with their


0.5 g/L
0.5 g/L

P-25 TiO2 4.0 g/L

P-25 TiO2 0.5 g/L


1 g/L

photo-degradability under UV irradiation [122] which is supported by


Photo-catalyst

other studies as well [125]. A similar PCMR system was designed for
TiO2
TiO2
TiO2
TiO2
TiO2

the removal of a specific POP bisphenol A (BPA). This set up included a


P-25
P-25
P-25
P-25
P-25

photo-reactor that had borosilicate glass holders having 4 UV lamps


L)

(λ = 315 nm, 8 W each) placed outside the reaction chamber having


slurry of P-25 TiO2 and BPA together with centrally placed hollow fiber
2 Hg UV-C lamps (254 nm)

4 UV (355 nm), 8 W each


(364 nm) 24 W each

membrane (PVDF, 0.2 µm pore size). Photocatalytic degradation of


pollutant and simultaneous filtration led to 97% photo-degradation of
UV (365 nm), 24 W

UV (185–254 nm)

the BPA in 90 min and 93% mineralization in 120 min analysed by TOC
(253.7 nm)

(254 nm)
(365 nm)
(365 nm)

UV (365 nm)
Light Source

removal (N10, Table 5) [113]. Another integrative submerged PCMR


system is employed for degradation of carbamazepine (5 mg/L)[118].
Slurry based PCMR for degradation of selected POPs.

This system consisted of a tubular borosilicate glass photo-reactor


UV
UV
UV
UV
UV

having 1 L feed capacity and 240 visible light LED units (4–15 W/m2)
with submerged hollow fibre MF membrane module (PVDF, pore size
C.I Disperse Red Dye-73 50, 75, 100 mg/L

0.1 µm) [118]. This system ensured good photo-resistance of the


33 Pharmaceutical Compounds (PhC)

membrane from visible LEDs as no variation in the contact angle


measurement was observed and no release of organic species even after
10 days of vis-LED irradiation as per the TOC measurements. C-N-S
Reactive Black 5 125 mg/L

tridoped Titania (1 g/L) used as photocatalyst allowed visible light


Carbamazepine 2 mg/L

Chlorpyrifos 480 mg/L

Bisphenol-A 10 mg/L

activation led to photo-degradation of carbamazepine by 69% in 10 h.


Diclofenac 2 mg/L
Diclofenac 2 mg/L

32 different POPs
Ibuprofen 9 mg/L

The particle size of titania in suspension was found to be in the range


0.9–50 µm after mixing for 10 h which depended on titania dosage, pH,
presence of inorganic ions and humic acid content in the solution [118].
Pollutant

500 ng/L

Slurry based photocatalytic membrane reactors as discussed above


are extensively used for remediation of POPs in wastewater treatment
Table 5

technologies as they offer enhanced mass transfer and increased pho-


10
N

1
2
3
4
5

8
9

tocatalytic performance because of greater contact between

8
P. Kumari, et al. Separation and Purification Technology 230 (2020) 115878

(continued on next page)


photocatalyst and pollutants [112]. In slurry based systems optimiza-
tion of catalyst loading from 0.5 to 2 mg/L could be easily achieved as

[109]

[131]

[129]

[130]

[136]

[110]

[102]

[135]

[137]
Refs.
discussed in few cases [115,116].
The damaging of the membrane by UV irradiation and reactive

Flux recovery of 63% from 42% in 240 min for

98.75% degradation of reactive black 5 dye in


95% degradation of orange II dye in 6 h. 60%

The rate of degradation of methylene blue was

89% cimetidine degradation in 200 min at 10


100% methylene blue degradation in 90 min
oxygen species can be escaped in split type PCMRs and by application of

70% degradation of Rhodamine B in 60 min


0.03% TiO2 deposited membrane from bare

70% dye MB dye degradation in 160 min


light baffle in integrative type PCMRs [115,118]. Slurry based system

UV-sensitive polymer surfaces can be


requires wide range of accessories, additional pumps, and pipelines,
reaction tanks [105]. All this unnecessarily increase the manufacturing

under 0.6 mW/m2 UV irradiation

L/m2 h flux under UV irradiance

protected using this technique


and operating cost. To enhance the permeate quality, a post treatment
process such as centrifugation may be required. Photocatalyst losses
during filtration are consistent problem as membranes employed for

(350–400 nm) of 30 W
TOC removal in 10 h

0.9–1.0 mol S-1 m−2


their recovery have pore size ranging from 0.2 to 0.04 µm which can
only recover agglomerates of TiO2 and not TiO2 crystals (21 nm) [121].

PES membrane
Performance
Serious membrane fouling issues are observed caused by slurry of
pollutants and catalyst as such a system does not employ any membrane
modification step to improve their hydrophilicity and anti-fouling

5h
ability which is generally realized in PCMRs with immobilized photo-

Uniformly distributed TiO2 nanoparticles on the surface

easily reproducible, uniform and defect-free membranes

(29 µm) beyond which limited light penetration restricts


Use of bulky alkoxy group (TTIP) promote homogeneous

TiO2 nanostructures are deposited homogeneously with


catalysts [112]. Furthermore, slurry systems do not have much scope of

Interaction of TiO2 with negatively charged conjugated

Formulated sol and usual deposition procedures enable

Needle like nanostructured titania nanotube may block


carboxylic of the Poly (ethylene) led to stabilized film

Excellent grafting between Silanized titania nanotube


Suspended titania nanoparticles between nanofibers,
R&D to modify morphological properties of photocatalyst as most of

sol formation due to reduced rate of hydrolysis and

Enhanced PC up to certain thickness of titania film

the pores of membranes with pore size < 0.22 µm


of surface but agglomeration in the micron range
them use commercial photocatalysts and membranes. Such a develop-

and surface activated PU enable better PC and


ment in terms of obtaining better nano-texturation, nano-crystallinity

creating a fully 3D structure performance


and higher specific surface areas compared to commercial photo-
catalysts are key aspect to obtain better photocatalytic efficiency
(Table 5).

3.3. Photocatalytic membrane reactor with immobilized photocatalyst

having ~3 µm thickness

thickness up to 21 nm
Catalysts properties
Immobilized Photocatalytic membrane reactors involve multi-
functional applications of membrane i.e. supporting the photocatalyst

condensation

PC efficiency
along with acting as sieving unit for the pollutants [127]. Photo-

reusability.
catalytic membrane reactor not only sieve contaminants but also allow
for degradation of pollutants [127,128]. Immobilized PCMRs can be
further divided into three types on the basis of incorporation of pho-
Commercial Poly(ethylene) with conjugated

Alumina (200 nm pore size, MWCO-50 kDa)


tocatalytic materials across the membrane including, (i) photocatalyst
PAA functionalized & plasma treated PVDF
Synthesised Poly(ethersulfone) (PES) (low

PVDF nanofibres on stainless steel filters


hydrophilicity with contact angle 66.2°)

coated on the membranes [103,108,109,129–132]; (ii) photocatalyst

(pore size = 2 µm, thickness = 1.7 mm)


Membrane structure and characteristics

Electrospun nanofibre nylon-6 (100 nm


blended with the membranes [107,109,111]; (iii) self-photocatalytic

Poly(ethersulfone) (PES) (0.45 µm)


membranes [133,134].
membrane (0.45 µm pore size)

Poly(ethersulfone) (0.8 µm)


3.3.1. Photocatalyst coated across the membrane material
Photocatalytic membranes prepared by depositing photocatalysts

Poly(urethane) (PU)
across commercially available or synthesized membranes may be at-
tained by various techniques such as dip-coating [129], magnetron
Examples of membranes coated with photocatalyst using different techniques.

sputtering, electrospinning [110] and electrospraying [132] and highly


carboxylic

diameter)

advanced physical methods such as atomic layer deposition (ALD)


[135] and chemical vapor deposition (CVD) [103,108]. Such deposi-
tions may be performed either on polymeric, ceramic, hybrid or metal
membrane bases.
P-25 titania suspension in ethanol

TiO2 nanofibre (film thickness10-


PVP-TTIP sol electrospun to form
Titania sol using TTIP precursor

The process of sol–gel deposition by dip-coating is a low cost, widely


ALD grown TiO2 from TDMAT
P-25 TiO2 suspension (5 g/L)
suspension in distilled water

Commercial titania hydrosol

used and robust route to uniformly coat the surface of membrane with
P-25 TiO2 (0.01–0.07 wt%)

titania nanotube (13 nm)

mesoporous titanium dioxide with nano-crystallinity [130]. P-25 Ti-


tania suspension and commercial Titania hydrosol are also used to coat
(3 wt%) for 5 min

titania Nanotube

the membrane. P-25 have humongous aggregates of nanoparticles that


Photo-Catalyst

ever after sonication in water such that the agglomerates of a few mi-
precursor

crons in size persist in the suspension leading to larger clusters ob-


84 µm)

servable across the surface of the membrane (N1, Table 6) [109]. The
contact angle measurement which is a good criterion to measure the
hydrophilicity of membranes revealed that for neat PES membranes it is
Magnetron sputtering and

higher up to 66.2°. While with increasing concentration of titania sus-


Electrospinning & hot

pension for deposition the contact angle measurement reduced to 53.5°


Coating Technique

indicating the fact that low hydrophilicity of poly(ethersulphone)


Surface grafting
Electrospraying

membranes was countered with of film of titania nanoparticles de-


Dip Coating

Dip Coating

Dip Coating

Dip Coating

anodization

posited on the surface of the membrane (N1, Table 6) [109]. The


pressing

contact angle measurement is assessed by evaluating the angle of


ALD

contact between water and the surface of membrane. Hydrophilicity


Table 6

has inverse relation with the contact angle in which a decrease in angle
N

specifies an increase in hydrophilicity. A 50% lower filtration resistance

9
P. Kumari, et al. Separation and Purification Technology 230 (2020) 115878

of such a titania decorated membrane works as good anti-fouling ma-

[103,108]
terial supporting higher permeate flux recovery in comparison with
Refs.

neat membranes (N1, Table 6) [109].


Derivatized Poly(ethylene) membranes ensure no leaching of titania
80% methyl orange (6.3 mg/L) degradation in

during photocatalytic degradation giving satisfactory performance in


terms of dye degradation (N2, Table 6) [131]. Dip-coating membranes
in commercially available titania sol or one prepared from a titania
precursor in optimized conditions lead to more reproducible, homo-
genous and defect free photocatalytic membranes as observed from the
SEM images (N3, Table 6) [129]. Mesoporous substance is developed
with uniform pore size up to 12 nm, porosity 68%, BET specific surface
area 190 m2/g with 30–40 nm packed Titania particles (N3, Table 6).
The role of pH is also very significant in sol–gel process for synthesis of
Performance

titania film [130]. Decreasing the pH of Titania sol from 1.5 to 1 lead to
60% increased density due to higher rate of hydrolysis at higher acidic
10 h

conditions [130]. Photocatalytic membranes prepared from denser Ti-


tania sol showed 45% better photocatalytic efficiency in same time (N4,
Table 6). Surface functionalization of neat PVDF membranes with Poly
possessing high porosity and enhanced hydrophilicity

(acrylic acid) (PAA) led to enhanced hydrophilicity and anti-fouling


Ultra-thin photo-catalytically active TiO2 layers,

abilities with contact angle measurement decreasing from 119.2° to


107.8° (N4, Table 6). Filtration results of 1% BSA solution through
functionalized PVDF membranes indicated 70% higher flux at 50%
lower TMP suggesting enhanced anti-fouling abilities of the modified
membranes (N4, Table 6) [130].
Electrospinning and electrospraying can allow for the construction
of 2D and 3D structured photocatalytic membranes the suspension of
the nanoparticles between nanofibers [110,136]. Operating parameters
Catalysts properties

of the device such as flow rate, voltage, spraying duration, distance


between nozzle and substrate can be easily controlled which in turn
lead to control the important properties of the membrane such as pore
size, roughness and morphology [137]. Electropraying of P-25 titania
suspension for a period of 5 min on electro spun Nylon-6 membranes in
continuous process lead to formation of 3-D networks with 100–105 nm
diameters of nanofibers and 0.65–1.85 µm diameter of suspended ti-
tania particles (N5, Table 6). The deposition of extensively agglomer-
Membrane structure and characteristics

ated nanoparticles in the micron range even after evaporation of sol-


vent from P-25 titania suspension at high temperature on the substrates
tend to reduce the photoactive interfacial area [136]. titania nanofibre
can also be spun from sol comprising titania precursor and a polymer
(N6, Table 6) [110]. The free standing Titania nanofibres were hot
ϒ-alumina (5–10 nm)

pressed with porous stainless steel filters (0.2 µm pore size) with PVDF
as intermediate binder layer to prepare the photocatalytic membrane.
PVDF nanofibres get uniformly distributed in the square shaped pores
of stainless steel filters. The PVDF nanofibres melt during the integra-
tion process and fuses into Titania film leading to complete adherence
(N6, Table 6).
Another common method for thin film deposition or to develop
coatings on the substrates is sputtering technique in which electric field
TiO2 Nanoparticles from TTIP

is applied. As per the force of drive, sputtering operation can be


achieved by either radio frequency (RF) or direct current (DC) excita-
tion [102]. This technique is commonly used to fabricate TiO2 nano-
tubes in which a titanium precursor is sputtered on the membrane and
Photo-Catalyst

then steps of anodization is followed that coverts Titanium to TiO2 and


precursor

further crystallinity is achieved by vapour thermal or hydrothermal


method (N7, Table 6). Optimized thickness of Titanium film was
900 nm for further anodization to TiO2 without blocking the pores of
PES membranes with surface debris such as Ti(OH)4 [102] With in-
creasing the voltage of anodization, diameter of nanotube also in-
creases. At 15 V, nanotube was 13 nm in size and at 40 V, the size of
Coating Technique

Chemical Vapour
deposition (CVD)

nanotube was 42 nm. So, desirable size can be easily achieved by


Table 6 (continued)

varying the anodization voltage and such Titania nanotubes have 5


times higher surface area (N7, Table 6).
Physical deposition methods such as ALD and CVD are also em-
ployed for fabrication of photocatalytic membranes. The thickness of
the film and coatings with high conformality is easily controlled by
10
N

ALD. It is a method that is used to develop in-situ nanostructures in

10
P. Kumari, et al. Separation and Purification Technology 230 (2020) 115878

which very low growth temperature is required (N8, Table 6) [135]. fabricated Titania film and calcination to invoke crystallinity of Titania
The technique of Chemical Vapour Deposition (CVD) is one more useful for photocatalytic degradation of pollutants [133,134]. Hydrothermal
route to fabricate films of highly pure Titania by coating the substrates method is also used for synthesis of self-photocatalytic TiO2 membranes
that can be in different sizes or shapes. The process of CVD is initiated for degradation of pharmaceuticals [140].
by the vaporization of a Titania precursor in a chamber which has the The advantages and short-comings of the photocatalytic membrane
placement of the target substrates that has vacuum. This is followed by systems have been recognized by extensive characterization of physical
the series of homogeneous reactions occurring in the gas phase between properties and their kinetic performance, yet, it is important to note
the precursors. Then, heterogeneous reaction takes place subsequently that such characterization is acquired under conditions representative
leading to growth of titania film on the surface of the target material of photocatalytic application. Clearly, for efficient functionality of
[108] (N10, Table 6). photocatalytic membrane reactors, it is important to have responsive
composite materials (membranes, catalysts, etc.) together with well-
elaborated models of how to integrate a membrane catalyst into a full-
3.3.2. Photocatalyst blended within the membrane
scale reactor for required application [141]. Photocatalyst coated
Photocatalyst blended with the membrane material constitute
membranes have several advantages such as higher hydrophilicity,
second type of photocatalytic membranes used in PCMRs. This ap-
improved anti-fouling properties and help protects UV sensitive mem-
proach is beneficial as it reduces the leaching of photocatalyst while
branes. However, sometimes the coatings can be non-uniform and is-
coupling all the advantages of membrane processes [111,128]. How-
sues of leaching of photocatalyst are persistent with photocatalysts
ever, the stability and reactivity of membrane can be assured only by
coated membranes. Thus, for proper adherence of photocatalyst special
vigorous optimization of the ratio of the photocatalyst and the mem-
functionalization steps are required. Membranes prepared by blending
brane precursor [132]. Such membranes are synthesized by methods
photocatalyst with membrane material offer no leaching of photo-
like non solvent induced phase separation (NIPS) [109,111], electro-
catalyst but suffer the disadvantages of marginal increase in hydro-
spinning [132], sintering [138], wet spinning [139]. A blended pho-
philicity and less reproducibility. Self-photocatalytic membranes gen-
tocatalytic membrane prepared by NIPs process (N1, Table 7) show
erally have higher anatase crystallinity, hydrophilicity and surface area
visible pores with size less than 1 μm nearly corresponding to the UF
which also behave as anti-fouling membranes maintain same TMP for
membranes. It was observed that the surface porosity was almost si-
longer time.
milar even without TiO2. The surface morphology and the typical
structure of the neat PCDF membranes were similar to the composite
membranes that are fabricated by the NIPs wet process. The membrane
3.3.4. Photocatalytic membrane reactor with immobilized photocatalyst for
showed improved hydrophilicity and permeability only at 25 wt% of
treatment of POPs
titania which is comparatively a very high dose (N1, Table 7) [111].
A PCMR with immobilized photocatalyst is a compact system gen-
Another PVDF membrane with LiCl doped TiO2 was prepared by PIP
erally comprising of a tank for the feed and other tank for the catalytic
process (N2, Table 7). In comparison to neat PVDF membranes, LiCl-
reaction as heterogeneous photocatalysis and membrane filtration are
TiO2-PVDF membrane tend to intensify the rate of rejection of humic
achieved in same vessel by photocatalytic membrane (Fig. 3) [111].
acid along with decreasing the decline in the flux leading to 25% flux
The membrane separation process is usually carried out in either dead
recovery in comparison with neat PVDF, this is basically due to
end mode of filtration or cross flow filtration mode [107,128]. Lower
homogeneous membrane pores, along with membrane surface which is
energy consumption is required in a dead end mode in comparison with
hydrophilic and smooth (N2, Table 7). Electrospun membrane prepared
the cross flow, however since the feed solution passes normally to the
by adding 0.07 wt% titania in polyamide 6 solution lead to fabrication
membrane, the formation of cake layer onto the surface of membrane is
of highly uniform nanofibre membrane composing a fibre diameter of
a common concern with them leading to serious issues of fouling. This
160–180 nm (N3, Table 7) and led to the degradation of 84% MB dye
is the reason cross flow mode of filtration is employed at industrial scale
(10 mg/L) in 2 h of UV irradiation (5 mW/cm2) [132].
as in such a system feed flows tangentially to the membrane minimizing
cake layer deposition on the membrane [142].
3.3.3. Self-catalytic membranes One such typical PCMR with Ag-TiO2 coated alumina membrane
Self-catalytic membranes do not require any immobilization step as was employed for the degradation of Rhodamine via photocatalysis
in case of coated or blended membranes [133]. These systems were [128]. Membrane porosimetry result suggested development of meso-
most recently reported ones which are generally produced via electro- porous material from Type-IV adsorption isotherm. With increase in the
chemical anodization tending to provide high anatase crystallinity, amount of pluronic 123, BET surface area also increased [128]. The
hydrophilicity, surface area, nano tubular morphology all tending to degradation rate of Rhodamine (25 µm) was 1007 mg m-2h−1 Similarly,
increase photocatalytic efficiency [133]. The electrochemical anodiza- a PCMR with LiCl doped TiO2 that is blended PVDF membrane to de-
tion method for fabrication of TiO2 membranes is widely prevalent in grade natural organic matters (NOMs) works in cross-flow filtration
which a titanium substrate is electrochemically anodized leading to mode (N2, Table 7) [107]. The volume of feed reservoir is 10 L to hold
formation of Titania nanotube. This followed by separation of the humic acid solution which is pumped to membrane cell. This system

Table 7
Examples of photocatalyst blended membrane matrix by different processes.
N Membrane Photocatalyst Blending Process Refs.

1 PVDF P-25 TiO2 NIPS wet process. [109,111]


nanoparticle Homogenized solution of PVDF + TiO2 + DMAc + additives was cast on Teflon sheet followed by immersion in
non-solvent for solidification.
2 PVDF LiCl doped TiO2 Phase inversion process (PIP). Casting solution of PVDF + TiO2 + LiCl + DMAc was placed on glass plate followed [107]
by immersion of membrane in tap water coagulation bath.
3 Polyamide-6 (PA- Degussa P25 TiO2 Prior to the process of electrospinning, a suspension of TiO2 nanoparticles is added to the solution of PA-6. [132]
6)
4 Porous α-alumina Commercial TiO2 Application of TiO2 suspension in micro channels of porous alumina by pipette and sintering at high temperature. [138]
5 PVDF Degussa P25 TiO2 Spinning of membrane from homogenized sol of PVDF + TiO2 + DMAc using dry-jet wet spinning method that has [139]
the fibre’s take up velocity equal as the falling velocity of fibres in the water containing coagulation bath.

11
P. Kumari, et al. Separation and Purification Technology 230 (2020) 115878

Fig. 3. Schematic diagram of PCMR with photocatalyst coated membrane for degradation of POP operating under dead end filtration mode. This exhibits a compact
system containing only a feed tank for wastewater, circulation system and catalytic membrane module to achieve heterogeneous photocatalysis and filtration
simultaneously.

led to rejection of humic acid by 80–84% in the time span of 100 min involves elaborate study on how each of these components in the
[107]. wastewater affects the performance of PCMR. This will make PCMRs
All of the above-mentioned photocatalytic membranes were em- practically more applicable leading to easy up scaling potential of the
ployed in PCMRs for remediation of POPs such as dyes, pharmaceu- process. Moreover, in the present scenario, the PCMRs that offer high
ticals, phenolic compounds, humic acid [110,118,124,139,143,144], as promising outcomes are restricted at lab scale. It may not be replicated
summarized in Table 8. at industrial scale as in that conditions, the parameters of the operation
The efficiency to remove POPs especially Carbamazepine and will be different as well as the energy consumptions [149]. Therefore,
Ibuprofen is higher in case of slurry based PCMR; observed by com- in order to scale up the system it is important to conduct studies at pilot
paring Table-5 and Table-8 as such a system provide higher contact scale.
time between catalyst and pollutant. However, advanced immobiliza- The competition between adsorption and reactivity on the surface of
tion techniques like CVD allow fabrication of highly thin photocatalytic catalytic membranes is another aspect that requires to be highlighted. It
TiO2 layer, with increased porosity and hydrophilicity that further in- is of importance to have rate of degradation of contaminants higher
crease photocatalytic efficiency leading to 90% removal of methyl or- than their rate of adsorption for effective functioning of the PCMRs and
ange [108]. Deposition of photocatalyst on membrane surface also avoid issues of membrane fouling [146].
elongates membrane life-span by protecting it from UV damage [135]. The stability of the membranes in PCMR system is another cause of
Additional step of catalyst recovery is not required which makes such concern that restricts its practical use. Source of UV light has deterrent
process more cost-efficient compared to the slurry based reactors [105]. effect on the polymeric membranes which are chemically unstable.
Furthermore, in case of slurry based PCMRs, the efficiency of mem-
4. Major gaps and challenges in PCMR technology brane separation is affected by wearing of the surface of membrane
caused by photocatalyst. Thus, there is urgent need to develop novel
As discussed in the review, one of the most promising tactics for the class of membranes that can overcome the problems mentioned above
treatment of wastewater is PCMR technology. The remediation of water by incorporating properties such as high chemical permanence and
contaminated with organics, micro pollutants, pharmaceutical wastes, stability that can withstand chemical and physical impairment.
dyes, effluent from the secondary treatment has been tackled by PCMRs PCMRs have lesser challenges in comparison with bare MF or UF
[28]. A synergistic approach is adopted in PCMR in which the in- membranes when comes to fouling as pollutants are degraded by cat-
tegration of catalysis and molecular sieving by the membranes that alytic mechanisms. However, still there is cake layer formation by ad-
surpassed the technical and functional loop holes of single process sorption of small degraded pollutants and photocatalyst on the mem-
while extracting advantage of the functions of one another. PCMRs brane surface causing severe conditions of fouling and pore blocking.
have potential of mineralizing of POPs into simpler by-products which This leads to declined flux conditions and overall efficiency of the
are non-toxic. However, PCMRs suffer some major challenges that have system. This brings an opportunity to develop more novel ways and
hampered its practical application. techniques to counter the issue of membrane fouling.
The major challenge is that most of research and studies employ use PCMR is still facing competition from conventional wastewater
of simulated feed water as a contamination source instead of real treatment systems as they may be cheaper in terms of operational costs.
wastewater sample. The fact that source of real wastewater contains The use of UV lamps, is the source of ample energy consumption that
natural and dissolved organic matters, inorganic salts, suspended solid occupies majority of share in the total cost of operation. Therefore,
particles cannot be ignored as they tend to have higher degree of effect development of a catalytically active material which is solar light
in both the synergistic process of the PCMR [33]. This gap can be driven with high activity and stability can be an ideal set-up to mitigate
overcome by adopting an approach which is more systematic that this problem.

12
P. Kumari, et al. Separation and Purification Technology 230 (2020) 115878

5. Conclusion

[110]

[145]
[146]

[147]
[148]
[140]
Ref.

PCMRs have been active for the remediation of POPs but majority of

Fairly moderate removal of diclofenac, bisphenol A, atrazine with Kap values 0.0398, 0.227,
and 0.0155 respectively. Poor removal of Carbamazepine, Ibuprofen with Kap value 0.008,
the studies involve simulated wastewater [106]. Membrane fouling is-
sues are another deterrent to long term use of PCMR [150]. Use of UV
lamps for activation of titania for photocatalytic performance is a costly
affair as they require higher energy consumption [121]. Thus, PCMR is
still in contest with existing water treatment technologies. However,
more research in this area needs to be done on pilot level with real time
samples for paving a way to scale up this technology [35]. Advanced
routes are sought after that can comprehensively fabricate catalytically
active materials which incorporate desired properties such as high
crystallinity, high surface area and high nano-scale roughness [151].
These properties are essential to ensure high reactivity of the fabricated
PCMR system. Such routes are looked upon which can lead to devel-
oping of a material that has a better interface between catalytically
73% degradation; 35% mineralization in 4 h

active parts and substrates [148,151,152] leading to formation of ver-


satile and robust membranes to be employed in PCMR technology.

Acknowledgement

Dr. Ludovic DUMEE acknowledges the Australian Research Council


90% degradation in 4 h

94% degradation in 4 h

(ARC) for his DECRA award (DE180100130).


50%, 55%, in 2.5 h
Catalysis rate

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