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Prospects of Synthesized Magnetic TiO2-Based Membranes for Wastewater Treatment: A Review

Global accessibility to clean water has stressed the need to develop advanced technologies for the removal of toxic organic and inorganic pollutants and pathogens from wastewater to meet stringent discharge water quality limits. Conventionally, the high separation efficiencies, relative low costs, small footprint, and ease of operation associated with integrated photocatalytic-membrane (IPM) technologies are gaining an all-inclusive attention. Conversely, photocatalysis and membrane technologies face some degree of setbacks, which limit their worldwide application in wastewater settings for the treatment of emerging contaminants. Therefore, this review elucidated titanium dioxide (TiO2), based on its unique properties (low cost, non-toxicity, biocompatibility, and high chemical stability), to have great potential in engineering photocatalytic-based membranes for reclamation of wastewater for re-use. The environmental pathway of TiO2 nanoparticles, membranes and configuration types, modification process, characteristics, and applications of IPMs in water settings are discussed. Future research and prospects of magnetized TiO2-based membrane technology is highlighted as a viable water purification technology to mitigate fouling in the membrane process and photocatalyst recoverability. In addition, exploring life cycle assessment research would also aid in utilizing the concept and pressing for large-scale application of this technology.


Introduction
In a growing economy, clean and drinkable water, free from toxic chemicals, carcinogenic substances and harmful microorganisms are essential for human health and sustainability [1,2]. However, the fast population growth associated with urbanization, irrigated agriculture and industrialization have driven the environmental concern of wastewater and demand for fresh water globally [3,4]. This opioid epidemic, be it due to insufficient accessibility to clean water, poor water quality or waterborne diseases, has seriously threatened human lives in many underdeveloped and developing countries [4][5][6]. The result has been an upsurge of stringent environmental standards to provide clean water with high quality and sustainable waste management facilities [4][5][6][7]. In addition, conventional technologies (coagulation, flocculation, biological) are limited when it comes to complete decontamination of water containing emerging contaminants (hormones, persistent organic pollutants, antibiotics, pharmaceuticals, heavy metals, nano plastics, etc.) [6,[8][9][10], and to avoid secondary pollution problems an advanced treatment technology is required. It is therefore valuable to explore the development of advanced wastewater treatment technologies to effectively purify water in a more ecofriendly and economical routine.

Advanced Oxidation Process (AOP)
Advanced oxidation processes (AOPs) have attracted a great deal of attention of stakeholders in the water and wastewater treatment sector. Photocatalytic degradation technology, being one of the AOPs, involves the use of a semiconductor photocatalyst and photogeneration of highly oxidative hydroxyl radicals [22,34]. In addition, the chemical reactions in AOPs caused by the absorption or desorption of photocatalysts remains unchanged in both photocatalysis and photoelectrochemical splitting of water using titania [19,22,49]. Furthermore, AOPs differ from conventional chemical and biological wastewater treatment systems as their produced hydroxyl radicals are potent oxidants used to degrade toxic and recalcitrant contaminants into simple and harmless inorganic molecules without creating a secondary excess [46,50,51]. Additionally, AOPs are very robust so as to enhance precipitations and elimination of heavy metals as metal hydroxides, and subsequently, based on the irradiation period, can lead to total mineralization

Advanced Oxidation Process (AOP)
Advanced oxidation processes (AOPs) have attracted a great deal of attention of stakeholders in the water and wastewater treatment sector. Photocatalytic degradation technology, being one of the AOPs, involves the use of a semiconductor photocatalyst and photogeneration of highly oxidative hydroxyl radicals [22,34]. In addition, the chemical reactions in AOPs caused by the absorption or desorption of photocatalysts remains unchanged in both photocatalysis and photoelectrochemical splitting of water using titania [19,22,49]. Furthermore, AOPs differ from conventional chemical and biological wastewater treatment systems as their produced hydroxyl radicals are potent oxidants used to degrade toxic and recalcitrant contaminants into simple and harmless inorganic molecules without creating a secondary excess [46,50,51]. Additionally, AOPs are very robust so as to enhance precipitations and elimination of heavy metals as metal hydroxides, and subsequently, based on the irradiation period, can lead to total mineralization [19,34,52]. AOPs are classified into two categories, namely homogeneous and heterogeneous systems, that can be carried out with or without UV radiation. Table 1 presents some of the reported AOPs commonly used in wastewater treatment settings. The thermal Fenton reaction process is a homogeneous process that involves Fe 2+ reacting with H 2 O 2 . The aforementioned phase (Fe 2+/ Fe 3+, H 2 O 2 , UV-Vis) is commonly termed as a photo-Fenton reaction [19]. Heterogeneous photocatalysis involves a photoinduced reaction accelerated by the presence of TiO 2 photocatalysts [53,54]. This process stands out among the heterogeneous AOPs because UV irradiation of TiO 2 creates hydroxyl radicals. This facilitates the oxidation and more efficient mineralization of organic material present in the effluent when it is photocatalyzed [55]. In contrast with other AOPs and biological treatments, TiO 2 photocatalysis offers significant advantages [19,46]. Thus, the TiO 2 /UV system can handle contaminants in both the gas and solution phases. Furthermore, TiO 2 is inexpensive, practically insoluble in water, and biologically and chemically inert [19,22,46]. Table 1. Types of advanced oxidation processes; adapted from [19,46].

Chemical Process Photochemical Process
Wet air oxidation Photo-Fenton reaction Supercritical water oxidation UV/ultrasound system Ultrasound/H 2 O

TiO 2 Photocatalyst
TiO 2 is the most widely used photocatalyst because of its strong physical and chemical stability, insolubility in water, resistance to acids, inertness to most chemicals and long-term photostability [25,40,47]. TiO 2 exhibits three main crystal structures such as rutile (stable), anatase (metastable), and brookite structures ( Table 2). Table 2. Chemo-physical properties of TiO 2 (adapted from [49,54] The tetragonal structure consists of both rutile and anatase, while brookite has a rhombohedral structure [48][49][50]. In addition to their shape and nanoscale or size, the unique physicochemical properties of TiO 2 crystals are a result of their intrinsic electronic structure and crystal structures [17,25,51]. Anatase has been found to be more active than rutile, but both forms of TiO 2 have been reported to be photoactive. Additionally, a mixture of anatase and rutile for photocatalysis has been found to exhibit synergy due to the photoinduced interfacial electrons of anatase that can be transformed into rutile [27,39].
Rutile and anatase, with 3.0 eV and 3.2 eV band gaps, respectively, are the most common polymorphs of TiO 2 [49,50]. In Figure 2, the large TiO 2 energy band means that higher UV light energy is required to excite electrons to create hydroxyl radicals, which is the key to the photodegradation of contaminants in the presence of oxygen [20,27,52].
The crystalline phase of anatase is desired because of its maximum efficiency under UV irradiation [20]. The photogenerated electrons form superoxide radicals in the rutile conduction band and the holes in the anatase valence band play a significant role in oxidation reactions. In addition, the 3.2 eV anatase band gap ( Figure 2) corresponding to the light wavelength of 388 nm means that only UV light will activate TiO 2 . This limits the use of sunlight and greener energy for the activation of TiO 2 , as only around 5% of sunlight is formed by UV radiation. Thus, during the photo activation step, TiO 2 undergoes a rapid recombination of electrons and holes, which then reduces photoactivity. Hence, by doping the TiO 2 with inert supports, the electron-hole recombination and wide band gap can be addressed while increasing the TiO 2 nanoparticle size [20,25]. The crystalline phase of anatase is desired because of its maximum efficiency unde UV irradiation [20]. The photogenerated electrons form superoxide radicals in the rutile conduction band and the holes in the anatase valence band play a significant role in oxi dation reactions. In addition, the 3.2 eV anatase band gap ( Figure 2) corresponding to the light wavelength of 388 nm means that only UV light will activate TiO2. This limits the use of sunlight and greener energy for the activation of TiO2, as only around 5% of sunlight i formed by UV radiation. Thus, during the photo activation step, TiO2 undergoes a rapid recombination of electrons and holes, which then reduces photoactivity. Hence, by doping the TiO2 with inert supports, the electron-hole recombination and wide band gap can be addressed while increasing the TiO2 nanoparticle size [20,25].
Furthermore, in photocatalytic activities, TiO2 with a valence band (VB) and conduc tion band (CB) levels of +2.9 and −0.33 eV can result in a band gap energy of 3.2 eV. As shown in Figure 2, the TiO2 VB and CB levels are more positive and negative than the distinctive redox potential of O2/H2O (1.23 eV). The presence of Ti 3+ defects beneath the CB surface causes the band gap reduction in F-doped TiO2 (3.02 eV), while in N-doped TiO2 (2.95 eV) the mid-band states are created as the N species fill voids as impurities above the VB. However, there is a doping-induced effect and a transition in the VB tail co-doping N and F into TiO2 results in the greatest band gap reduction, from 3.2 eV to 2.24 eV ( Figure 2).

TiO2 Modification Supports
In wastewater treatment settings, TiO2 photocatalysis in practical applications is very limited due to low quantum efficiency under visible radiations as well as difficulties o being separated in suspensions [18,55,56]. To ensure that TiO2 will work optimally with out any complexity, modification becomes essential [6,54]. Filtration following photocata lytic activities is very costly and, therefore, catalyst supports can be explored. Some of the supporting materials of TiO2 reported include glass beads, fiber, glass, silica and zeolite mater [6,20,25,53,57]. Consequently, there are diverse techniques used to modify TiO2 where doping of pure TiO2 with either anions or cations remain one of the most common methods for enhancing its sensitivity to visible light and lowering the rate of charge carrie recombination [20,39,53,54]. Furthermore, photocatalysts synthesized via chemical dop ing or ion implantation with metals and nonmetals result in a narrowing of the TiO2 band gap as well as the crystal lattice or structure [20,25,39]. Therefore, in selecting these metal and nonmetals, their sensitivity should be considered.

•
Cationic doping of TiO2 To dope TiO2, cations like rare earth metals, noble metals, weak metals and transition metals have been used [26]. In addition, when a metallic ion is doped with TiO2, the ligh Furthermore, in photocatalytic activities, TiO 2 with a valence band (VB) and conduction band (CB) levels of +2.9 and −0.33 eV can result in a band gap energy of 3.2 eV. As shown in Figure 2, the TiO 2 VB and CB levels are more positive and negative than the distinctive redox potential of O 2 /H 2 O (1.23 eV). The presence of Ti 3+ defects beneath the CB surface causes the band gap reduction in F-doped TiO 2 (3.02 eV), while in N-doped TiO 2 (2.95 eV) the mid-band states are created as the N species fill voids as impurities above the VB. However, there is a doping-induced effect and a transition in the VB tail; co-doping N and F into TiO 2 results in the greatest band gap reduction, from 3.2 eV to 2.24 eV (Figure 2).

TiO 2 Modification Supports
In wastewater treatment settings, TiO 2 photocatalysis in practical applications is very limited due to low quantum efficiency under visible radiations as well as difficulties of being separated in suspensions [18,55,56]. To ensure that TiO 2 will work optimally without any complexity, modification becomes essential [6,54]. Filtration following photocatalytic activities is very costly and, therefore, catalyst supports can be explored. Some of the supporting materials of TiO 2 reported include glass beads, fiber, glass, silica and zeolite mater [6,20,25,53,57]. Consequently, there are diverse techniques used to modify TiO 2 , where doping of pure TiO 2 with either anions or cations remain one of the most common methods for enhancing its sensitivity to visible light and lowering the rate of charge carrier recombination [20,39,53,54]. Furthermore, photocatalysts synthesized via chemical doping or ion implantation with metals and nonmetals result in a narrowing of the TiO 2 band gap as well as the crystal lattice or structure [20,25,39]. Therefore, in selecting these metals and nonmetals, their sensitivity should be considered.

•
Cationic doping of TiO 2 To dope TiO 2 , cations like rare earth metals, noble metals, weak metals and transition metals have been used [26]. In addition, when a metallic ion is doped with TiO 2 , the light absorption range expands, whereas the redox potential of the photogenerated radicals increases [58][59][60]. This generally results in the transfer of photoexcited electrons from the TiO 2 conduction band to metal particles deposited on the TiO 2 surface. Cationic doping can also decrease the probability of electron-hole recombination, leading to an effective separation of the charge and thus improved photocatalytic activity [61]. However, the nature and concentration of the dopant inducing the charge surface together with the corrosion mechanism can affect the photocatalytic property of the materials [20,40]. Thus, cationic dopants have a distinctive impact on the catalyst lattice. Some of these metal dopants (Ag, Fe, Mn, Ni, Cu, Pt, Rh, and Pd) act as free electrons, which facilitates the conjugation of the photogenerated carriers [26]. Conversely, metal-doped materials have been reported to be thermodynamically unstable, which can be captured on the TiO 2 band gap at the d-level and can subsequently shift the redox potential [26,30,62,63]. However, by removing the electron hole, TiO 2 doped with metallic cations with lower oxidation states can maintain electron stability [30]. In addition, TiO 2 doped with metallic cations with higher oxidation states, by adding electrons to the already empty conduction band, can also enhance the electron stability [20,40].

•
Anionic doping of TiO 2 Doping TiO 2 with anionic nonmetals, including carbon, sulfur, nitrogen, and iodine, has been found to be more efficient in ensuring higher photocatalytic activity under visible light [26]. Anionic dopants result in p-state substitution in TiO 2 by altering the atomic level in the valance band and subsequent shift of the conduction band. For instance, incorporation of carbon into TiO 2 contributes to the formation of carbonaceous species on the surface, which increases the visible light absorption [18,58,60]. Furthermore, the presence of more reactive sites, which facilitate the adsorption of more target contaminants, is another explanation for the increase in photocatalytic activity of C-doped TiO 2 due to its higher surface area [26]. Nitrogen doping in TiO 2 adjusts the stiffness, elastic modulus, refractive index, electrical conductivity, and photocatalytic behavior of TiO 2 under visible light absorption activity [18].
Subsequently, silica is reported to have higher surface area, which provides the effective adsorption and catalyst support structure for heterogeneous photocatalysis. According to Ghosh and Das [26], silica modified TiO 2 is more effective as a photocatalyst than TiO 2 alone. Thus, doping TiO 2 with silica can enhance and stabilize both the external and internal surfaces of the catalyst within the silica-based matrix, where contaminants are adsorbed. Zeolite is also found to play an important role in charge and electron transfer during the photocatalytic reaction [20,34]. Due to uniform pores and straight paths, zeolites have been found to be good photocatalyst supports. The zeolite acts as a supporting material for the homogeneous dispersion of TiO 2 particles on its surface, which improves TiO 2 -based zeolite composites. Activated carbon (AC), due to its pore structure, also has benefits as a photocatalyst support for promoting the photocatalytic process [25,53,64]. AC is commonly used as a supporting material to extract organic and inorganic pollutants from water and wastewater. Contrariwise, the surface chemistry of AC carbon may obstruct effective coating of TiO 2 photocatalysts [64]. However, the application of AC-TiO 2 photocatalysts in wastewater treatment settings comes with a cost and, therefore, necessitates the use of a reactor to effectively expose the photocatalytic surface to light photons [2,53,64].

•
Other supporting metallic oxides Coupling TiO 2 with other semiconductors to increase its photocatalytic activity is another way to produce photoinduced electron-hole pairs [26]. A good match between the conduction and valence bands of two semiconductors ensures a potential charge carrier movement from one to the other. Several studies have indicated that TiO 2 photocatalytic activity can be enhanced by the presence of metal oxides like CdS, ZnO, ZrO 2 , Cu 2 O, CeO 2, SnO 2 , WO 3 , and Fe 3 O 4 [17,18,26,62,65,66]. Among them, Fe 3 O 4 has been studied extensively due to its ability to facilitate magnetic separation of the nanocomposite from the aqueous medium [39,67]. Ahangar et al. [60] prepared a Fe 3 O 4 -embedded SiO 2 nanocomposite and compared its magnetic properties with pure Fe 3 O 4 . It was found that the Fe 3 O 4 nanoparticles embedded in SiO 2 have a much higher photocatalytic efficiency. Furthermore, the photocatalytic performance of the resulting nanocomposite was nearly identical. As a result, the core-shell framework is an efficient way to incorporate the desirable properties of two or more nanomaterials into a single nanocomposite. However, adding semiconductor dopants can alter the surface properties of TiO 2 catalysts, such as surface area and surface acidity [16,41]. Wang et al. [68] used a hydrothermal method followed by co-precipitation to develop anatase-structured TiO 2 nanoparticles (Fe/TiO 2 ) with elongated morphological characteristics.

Mechanism of TiO 2 Photocatalysis
The heterogeneous photocatalysis mechanism involves the ability of semiconductors to produce charge carriers under light irradiation, preceded by the production of free radicals such as OH − , which contributes to further reactions, eventually forming CO 2 and H 2 O [32]. Excitation, bulk diffusion, light-induced surface transfer, and photon absorption with a potential energy greater than the band gap are all part of the basic photocatalytic activation mechanism [30,47]. As shown in Figure 3, when UV light with an energy greater than the band gap energy of TiO 2 is irradiated, electrons in the valance band are excited to the conductance band, which leaves positive charge holes (h + ) in the valance band. more, the photocatalytic performance of the resulting nanocomposite was nearly identical. As a result, the core-shell framework is an efficient way to incorporate the desirable properties of two or more nanomaterials into a single nanocomposite. However, adding semiconductor dopants can alter the surface properties of TiO2 catalysts, such as surface area and surface acidity [16,41]. Wang et al. [68] used a hydrothermal method followed by co-precipitation to develop anatase-structured TiO2 nanoparticles (Fe/TiO2) with elongated morphological characteristics.

Mechanism of TiO2 Photocatalysis
The heterogeneous photocatalysis mechanism involves the ability of semiconductors to produce charge carriers under light irradiation, preceded by the production of free radicals such as OH -, which contributes to further reactions, eventually forming CO2 and H2O [32]. Excitation, bulk diffusion, light-induced surface transfer, and photon absorption with a potential energy greater than the band gap are all part of the basic photocatalytic activation mechanism [30,47]. As shown in Figure 3, when UV light with an energy greater than the band gap energy of TiO2 is irradiated, electrons in the valance band are excited to the conductance band, which leaves positive charge holes (h + ) in the valance band. The electrons extracted from the VB are passed to the CB, which then react with the absorbed oxygen (O2) on the TiO2 surface. As a result, a positive area (h + ) forms in the VB holes and causes free electrons (e − ) to form in the CB. Simultaneously, the holes (h + ) react with water molecules (H2O) adsorbed on the TiO2 surface to create hydroxyl radicals (OH), as shown in Figure 3 and Equations (1)-(4). Furthermore, the CB electron reduces oxygen to superoxide ions (O2 •− ). This reaction prevents the e − /h + from recombining, which happens when other electron acceptors such as pollutants are absent [30,40]. Organic pollutants (R) in wastewater can be oxidized to carbon dioxide ( and water by oxygen reactive radicals. (1) Figure 3. Schematic presentation of the photocatalysis mechanism; adapted from [26].
The electrons extracted from the VB are passed to the CB, which then react with the absorbed oxygen (O 2 ) on the TiO 2 surface. As a result, a positive area (h + ) forms in the VB holes and causes free electrons (e − ) to form in the CB. Simultaneously, the holes (h + ) react with water molecules (H 2 O) adsorbed on the TiO 2 surface to create hydroxyl radicals (OH), as shown in Figure 3 and Equations (1)-(4). Furthermore, the CB electron reduces oxygen to superoxide ions (O 2 •− ). This reaction prevents the e − /h + from recombining, which happens when other electron acceptors such as pollutants are absent [30,40]. Organic pollutants (R) in wastewater can be oxidized to carbon dioxide (CO 2 ) and water (H 2 O) by oxygen reactive radicals.

Operational Parameters in Photocatalysis
The photocatalytic system's oxidation rates and semiconductor catalyst performance coupled with a photoreactor are all highly dependent on several operational parameters that regulate the kinetics [18,26,69]. Outstanding studies of the different parameters affecting the photocatalysis process, including pH, catalyst loading, amount of oxygen, contaminant loading, light intensity and duration of light irradiation, preparation method of the catalyst, its calcination temperature, and amount and type of dopant, have been carried out and reported in the literature [18,25,26,51,53,70,71]. In comparison to immobilized films, photocatalysts mostly take the form of suspended powder (slurries), giving higher efficiency [25]. However, separating photocatalysts from treated water in this form is difficult, implying that a recovery step for photocatalyst re-use is required [72][73][74]. Pho-tocatalysts based on TiO 2 with a large surface area have a high photocatalytic efficiency, so nano-sized TiO 2 particles have been used in most studies [25,74].
• pH pH affects the surface charge or isoelectric point of the photocatalyst directly as well as the catalyst particles, size of catalyst aggregates, and the positions of conductance and valence bands [75,76]. The point of zero charge (PZC) of TiO 2 is the main parameter used to study the effect of pH in photocatalyst reactions. PZC is a condition where the surface charge of TiO 2 is zero or neutral in the range of 4.5-7.0 [69,75]. The catalyst surface will be negatively charged and repel the anionic compounds in water, which can affect the charge densities [75]. At pH = PZC, the neutral surface charge of the catalyst particles will not be able to produce the interactive rejection necessary for the separation of the solid liquid. When this happens, the catalyst becomes larger, thereby leading to the sedimentation of the catalyst. Since this can induce the aggregation of the catalyst, optimization becomes necessary [76].

•
Catalyst loading One of the key factors affecting photodegradation efficiency and overall cost is the amount of catalyst used. Increasing the TiO 2 load does not only increase the number of active sites for pollutant adsorption, but it also increases the number of e−/h+ pairs, which speeds up the reaction rate [18,19,75]. However, if the amount of TiO 2 is increased above a saturation level, the catalyst may agglomerate, resulting in a light screening deficiency [69,75]. This makes the excess TiO 2 particles reduce the active surface area of the TiO 2 exposed to illumination and consequently reduces the photocatalytic efficiency. Thus, the absence or obstruction of the irradiated light prevents it from penetrating the effluent's interior mass, hence hindering photocatalysis [69]. Therefore, in order to avoid excessive usage and gain optimal photonic efficiency, an optimal value of catalyst dosage must be used [76].

Light intensity
The light intensity ensures that sufficient photons of energy are delivered to the TiO 2 surface-active sites. This should be significant enough to achieve a reasonable photocatalytic reaction rate, particularly in water treatment [51,69]. This is usually limited to photons with wavelengths that are smaller than the absorption edge of nearly 400 nm [51]. However, attenuation of radiation reaching the photocatalyst is one of the reasons for lower efficacy. Attenuation can occur for a variety of reasons, including insufficient light spatial distribution within the reactor, reflection losses, transmission losses, scattering, and so on [18,25]. According to Naldoni et al. [51], the rate of reaction can be associated with the high thermodynamic efficiency of reactor photons distributed within it.

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Catalyst type and temperature The development of visible/solar light-active photocatalysts has been a continued effort in recent years [19,25,77,78]. Some of these photocatalysts have been synthesized and their efficacy in wastewater treatment has been determined. Additionally, most of the early photocatalysts developed were UV-only active and, therefore, research into photocatalysts' physical and chemical properties is required to support their future prospective use. Modification of TiO 2 with promising results has been reported as a solution. Some researchers have worked on incorporating activated carbon, graphite, graphene oxide, nanosheets, and other elements into TiO 2 while others have focused on the incorporation of various metallic and nonmetallic additives [18,19,25,51,77,79,80]. Furthermore, doping metals and nonmetals into conventional photocatalysts enhances photoreactivity, and thus quantum efficiency, by altering the intrinsic and surface properties in a favorable approach [51]. In photocatalytic activity, temperature seems to have no effect. The ideal temperature range initiated by photon adsorption reaction is reported to be 20 to 80 • C [25]. Meanwhile, the activation energy, being relatively stable at these temperatures, makes it possible for a wide range of photon-induced reactions. However, an increase in temperature above 80 • C has been reported to have negative consequences on the overall photocatalytic process [25,51].

• Dissolved oxygen and contaminant concentration
The presence of dissolved oxygen (DO) is critical in TiO 2 photocatalysis. The DO ensures that there are enough electron scavengers present to aid in the trapping of the excited conduction-band electrons during the recombination step [18,51,77]. The presence of DO has no effect on the adsorption onto the TiO 2 catalyst surface since the reduction reaction occurs at several sites separate from where the oxidation occurs. The DO influences the formation of reactive oxygen species, the stabilization of radical intermediates, mineralization, and direct photocatalytic reactions [77]. The total amount of DO produced in a reactor is determined by a few factors such as the environmental condition, the catalyst type and concentration, the contaminant, and so on [80]. The pollutant's initial concentration has a significant impact on its photodegradation. The effectiveness of photodegradation decreases as the initial concentration increases for two reasons: (i) equilibrium adsorption of the pollutant rises with increasing concentration and thus competes with adsorption of OH − on the same site, and (ii) high-concentration pollutants absorb than the photocatalyst itself, which tends to prevent degradation [25].

Integrated Photocatalytic Membrane (IPM) Reactors
Membrane separation has become one of the most improved technologies for water treatment in recent decades due to its small carbon footprint, high separation efficiency, and ease of operation [2,39,71]. Membrane fouling is caused by the formation of a cake layer on the membrane surface and results in pore blocking in conventional membrane processes [81]. As a result, water flux is reduced significantly, and energy consumption and treatment costs are increased. Furthermore, membrane filtration can only concentrate contaminants into a high concentration retentate, which requires additional treatment prior to discharge [39,81,82]. Therefore, advancements in membrane science and technology are useful in developing a cost-effective membrane process. In essence, membrane technology has progressed to the point where there is a plethora of membranes made for specific pollutants as well as membrane configurations and technologies tailored for specific industries (milk production, beer production, desalination, solvent separation) and material regeneration [2,4,18,25,83].
Moreover, membranes are classified according to their pore sizes as microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO), which determine their selectivity [25,82,83]. Nanoporous membranes (0.1-1 nm) are made up of a thin film through which molecules are transported via solution diffusion. The driving forces across such membrane transport include pressure, concentration, or potential gradient [2,25,61]. Reverse osmosis (RO), NF and most recently forward osmosis (FO) are processes that use nonporous membranes. Microfiltration (MF) and ultrafiltration (UF) are two pressuredriven processes that use microporous membranes. MF membranes can separate particles with diameters ranging from 0.1 to 10 µm, while UF membranes can remove particles with diameters ranging from 1 to 100 nm [2,84].
Generally, to meet strict wastewater discharge standards, a conventional activated sludge process is used to biologically treat wastewater for organic/nutrient removal, accompanied by an MF/UF process to produce high-quality permeate water (i.e., removing particles and bacteria/viruses, etc.) Furthermore, membrane filtration can only trap contaminants in a high concentration retentate, which requires additional post-treatment prior to discharge. In contrast, photocatalytic membrane processes may degrade contaminants in feed solutions by producing oxygen-reactive radicals in the presence of UV light, preventing the formation of a cake layer on the membrane surface [3,45]. As a result, pore blocking is reduced, pollutant concentrations in the filtrate are reduced, and permeate quality is improved [3,45]. This section delves into the different types of membranes used as supports as well as related photocatalytic membrane types, preparation, attributes and applications of TiO 2 photocatalytic membranes in removing contaminants in wastewater settings.

Types of IPM Reactors
Simple photocatalytic reactors that use TiO 2 -coated glass beads and a UV lamp to illuminate and activate sites are referred to as slurry/immobilized photocatalytic reactors or fixed-bed photocatalytic reactors [16,48,82]. In recent years, photocatalytic reactors have been upgraded in a variety of ways to increase the irradiated surface area and boost performance. Consistently, the difficulty in separating nano sized TiO 2 particles from treated water has been attributed to its restricted use. To solve the separation problem, some researchers have attempted to salvage nano sized TiO 2 particles from suspensions using membrane filtration [20,39,48,63,82,85].
IPMs are classified into four different configurations: (Figure 4a) a membrane inserted inside a photoreactor with internal walls coated with a photocatalyst such as TiO 2 ; (Figure 4b) a pure TiO 2 porous photocatalytic membrane; (Figure 4c) a slurry photocatalytic reactor followed by a membrane filtration unit; (Figure 4d) an inorganic or polymeric membrane submerged in a slurry photocatalytic reactor.
Among these four configurations, the photocatalytic membrane (Figure 4b) has potential advantages over the other three configurations [26,53]. Here, both the separation membrane and the TiO 2 photocatalytic degradation of the organics occurs in a single unit [26]. In addition, photocatalytic membranes generally outperform conventional membranes in terms of reducing membrane fouling and improving permeate quality [85,86]. Even though the reactor configuration covers a broad range, the reactor design should ensure that the catalyst is irradiated uniformly [25]. This is because the photocatalytic surface available for the possible solutions can decrease and cause a loss in the photocatalytic efficiency.
sludge process is used to biologically treat wastewater for organic/nutrient removal, accompanied by an MF/UF process to produce high-quality permeate water (i.e., removing particles and bacteria/viruses, etc.) Furthermore, membrane filtration can only trap contaminants in a high concentration retentate, which requires additional post-treatment prior to discharge. In contrast, photocatalytic membrane processes may degrade contaminants in feed solutions by producing oxygen-reactive radicals in the presence of UV light, preventing the formation of a cake layer on the membrane surface [3,45]. As a result, pore blocking is reduced, pollutant concentrations in the filtrate are reduced, and permeate quality is improved [3,45]. This section delves into the different types of membranes used as supports as well as related photocatalytic membrane types, preparation, attributes and applications of TiO2 photocatalytic membranes in removing contaminants in wastewater settings.

Types of IPM Reactors
Simple photocatalytic reactors that use TiO2-coated glass beads and a UV lamp to illuminate and activate sites are referred to as slurry/immobilized photocatalytic reactors or fixed-bed photocatalytic reactors [16,48,82]. In recent years, photocatalytic reactors have been upgraded in a variety of ways to increase the irradiated surface area and boost performance. Consistently, the difficulty in separating nano sized TiO2 particles from treated water has been attributed to its restricted use. To solve the separation problem, some researchers have attempted to salvage nano sized TiO2 particles from suspensions using membrane filtration [20,39,48,63,82,85].
IPMs are classified into four different configurations: (Figure 4a) a membrane inserted inside a photoreactor with internal walls coated with a photocatalyst such as TiO2; (Figure 4b) a pure TiO2 porous photocatalytic membrane; (Figure 4c) a slurry photocatalytic reactor followed by a membrane filtration unit; (Figure 4d) an inorganic or polymeric membrane submerged in a slurry photocatalytic reactor.  Among these four configurations, the photocatalytic membrane ( Figure 4b) has potential advantages over the other three configurations [26,53]. Here, both the separation membrane and the TiO2 photocatalytic degradation of the organics occurs in a single unit [26]. In addition, photocatalytic membranes generally outperform conventional membranes in terms of reducing membrane fouling and improving permeate quality [85,86]. Even though the reactor configuration covers a broad range, the reactor design should ensure that the catalyst is irradiated uniformly [25]. This is because the photocatalytic surface available for the possible solutions can decrease and cause a loss in the photocatalytic efficiency.
Notwithstanding, IPMs have proven to be very promising in wastewater treatment settings, however, they are still limited in a large-scale application. In response, several organic, inorganic, metallic, and polymeric materials have been used as support materials in the fabrication of TiO2-based photocatalytic membrane reactors [25,26,53,70,87,88]. In contrast to immobilized TiO2 membranes, TiO2 nanofibers, nanowires, and nanotubes are also used to make pure TiO2 photocatalytic membranes. These are classified into two major categories: (i) freestanding pure TiO2 photocatalytic membrane reactors and (ii) composite TiO2 photocatalytic membrane reactors [87,89,90].

Freestanding Pure TiO2-Based Membrane Reactors
Engineered TiO2 nanoparticles have various properties that allow them to bind specific pollutants or catalyze degradation reactions when deposited or embedded on membrane surfaces [26,88,90]. However, the nanomaterial loading, matrix content, particle dispersion, nanoscale phase size, shape and orientation, as well as interactions between the phases all affect the hybrid material's overall properties [26,90]. This has inspired interest in making TiO2-engineered membranes for a variety of applications, including self-clean- Notwithstanding, IPMs have proven to be very promising in wastewater treatment settings, however, they are still limited in a large-scale application. In response, several organic, inorganic, metallic, and polymeric materials have been used as support materials in the fabrication of TiO 2 -based photocatalytic membrane reactors [25,26,53,70,87,88]. In contrast to immobilized TiO 2 membranes, TiO 2 nanofibers, nanowires, and nanotubes are also used to make pure TiO 2 photocatalytic membranes. These are classified into two major categories: (i) freestanding pure TiO 2 photocatalytic membrane reactors and (ii) composite TiO 2 photocatalytic membrane reactors [87,89,90].

Freestanding Pure TiO 2 -Based Membrane Reactors
Engineered TiO 2 nanoparticles have various properties that allow them to bind specific pollutants or catalyze degradation reactions when deposited or embedded on membrane surfaces [26,88,90]. However, the nanomaterial loading, matrix content, particle dispersion, nanoscale phase size, shape and orientation, as well as interactions between the phases all affect the hybrid material's overall properties [26,90]. This has inspired interest in making TiO 2 -engineered membranes for a variety of applications, including self-cleaning, antimicrobial thin film coatings, photocatalysis, gas sensing and dye-sensitized solar cell nanofibers with well-controlled morphology [25,26,[87][88][89][90]. One-dimensional freestanding TiO 2 membrane reactors with various TiO 2 morphologies, such as nanotubes (NTs), nanofibers (NFs), and nanowires (NWs), have been developed to improve photocatalytic activity and reduce membrane fouling [31,45].

TiO 2 Nanotube-Based Reactors
The photocatalyst surface-to-volume ratio of synthesized TiO 2 NTs make them more advantageous for wastewater treatment. Some reported applications are presented in Table 3. Although TiO 2 NTs are available in both crystalline and amorphous forms to enhance performance, high-temperature annealing is required to convert the amorphous form to crystalline [83,91]. For example (Figure 5), from a two-electrode electrochemical cell with titanium foil as the working electrode, a freestanding TiO 2 NT was synthesized using an anodization method.

TiO2 Nanotube-Based Reactors
The photocatalyst surface-to-volume ratio of synthesized TiO2 NTs make them more advantageous for wastewater treatment. Some reported applications are presented in Table 3. Direct black 168 85 [83] Although TiO2 NTs are available in both crystalline and amorphous forms to enhance performance, high-temperature annealing is required to convert the amorphous form to crystalline [83,91]. For example (Figure 5), from a two-electrode electrochemical cell with titanium foil as the working electrode, a freestanding TiO2 NT was synthesized using an anodization method. In the preparation of TiO2 NTs, Cai et al. [83] stated that voltage pulses were applied for a short time at the end of the anodization process to achieve open nanochannels; this was a quick and successful bottom-opening method that did not involve the use of engraving solutions. Another method for creating a TiO2 nanotube alumina membrane was represented by Wang et al. [89], where the TiO2 NTs were developed by immersing the alumina membrane in a 2.2 pH titanium tetrafluoride (TiF4) aqueous solution. Their reported SEM image results showed that the TiO2 NTs were grafted and lined inside the channels of the alumina membrane. Chong et al. [84] reported that the effect of nanotube packing and grafting was highly dependent on the pH of the solution. Additionally, grafting time can be used to monitor TiO2 NT inner diameter, with a longer grafting time resulting in a smaller internal diameter and therefore, a lower pure water flux [91,92]. In the preparation of TiO 2 NTs, Cai et al. [83] stated that voltage pulses were applied for a short time at the end of the anodization process to achieve open nanochannels; this was a quick and successful bottom-opening method that did not involve the use of engraving solutions. Another method for creating a TiO 2 nanotube alumina membrane was represented by Wang et al. [89], where the TiO 2 NTs were developed by immersing the alumina membrane in a 2.2 pH titanium tetrafluoride (TiF 4 ) aqueous solution. Their reported SEM image results showed that the TiO 2 NTs were grafted and lined inside the channels of the alumina membrane. Chong et al. [84] reported that the effect of nanotube packing and grafting was highly dependent on the pH of the solution. Additionally, grafting time can be used to monitor TiO 2 NT inner diameter, with a longer grafting time resulting in a smaller internal diameter and therefore, a lower pure water flux [91,92].
Electrospinning is a versatile and efficient technique for synthesizing uniform fibers with a broad specific surface region [28,89,93]. In electrospinning, a polymer solution or melt containing a precursor salt of metal oxide in a syringe is subjected to a high static voltage [94,95]. The properties of nanofibers can be tweaked to provide more versatility in the end-product's surface functionalities. Many studies use Ti-alkoxides and Ti-halides as TiO 2 precursors, but these are insoluble in water [65,89,[94][95][96][97][98]. TiO 2 nanofibers made from water-soluble precursors make it possible to combine TiO 2 with other metal oxides via water-soluble precursors [99]. At a voltage of 30 kV, nanofibers are electrodeposited, collected and dried at a temperature of 25 • C. Liu et al. [100] fabricated silver (Ag) nanoparticle-decorated TiO 2 nanofiber (TiO 2 /Ag NF) membranes using the polyol synthesis mechanism. The Ag-decorated membrane (TiO 2 /Ag/CdS/Ag NF) was obtained by immersing TiO 2 /Ag/CdS nanofibers in an algae solution for 72 h [98,100].
Electrospinning is a versatile and efficient technique for synthesizing uniform fibers with a broad specific surface region [28,89,93]. In electrospinning, a polymer solution or melt containing a precursor salt of metal oxide in a syringe is subjected to a high static voltage [94,95]. The properties of nanofibers can be tweaked to provide more versatility in the end-product's surface functionalities. Many studies use Ti-alkoxides and Ti-halides as TiO2 precursors, but these are insoluble in water [65,89,[94][95][96][97][98]. TiO2 nanofibers made from water-soluble precursors make it possible to combine TiO2 with other metal oxides via water-soluble precursors [99]. At a voltage of 30 kV, nanofibers are electrodeposited, collected and dried at a temperature of 25 °C. Liu et al. [100] fabricated silver (Ag) nanoparticle-decorated TiO2 nanofiber (TiO2/Ag NF) membranes using the polyol synthesis mechanism. The Ag-decorated membrane (TiO2/Ag/CdS/Ag NF) was obtained by immersing TiO2/Ag/CdS nanofibers in an algae solution for 72 h [98,100].

TiO2 Nanowires
The successful synthesis of titanium dioxide nanowires (NWs) was achieved using a novel approach based on a hydrothermal process [101,102]. A novel TiO2 nanowire nanostructure (Figure 7) was developed by hydrothermally treating TiO2 nanopowder as a precursor for 6 h with highly concentrated sodium hydroxide [102]. In the thermal evaporation processes reported in the literature, the sputtering of a Ti buffer layer and the evaporation of Ti at high temperatures are considered mandatory [102][103][104]. These processes require a lot of energy and a sophisticated setup for the nanostructures to expand [101]. The thermal oxidation method has been used to produce TiO2 NWs in recent studies [102,103]. The development of TiO2 NWs with a stable rutile phase is possible with this method. Zhang et al. [102] demonstrated that a direct oxidation of a Ti foil in an organic atmosphere was possible to develop a membrane filtration process and photocatalytic degradation of humic acid in wastewater.

TiO 2 Nanowires
The successful synthesis of titanium dioxide nanowires (NWs) was achieved using a novel approach based on a hydrothermal process [101,102]. A novel TiO 2 nanowire nanostructure (Figure 7) was developed by hydrothermally treating TiO 2 nanopowder as a precursor for 6 h with highly concentrated sodium hydroxide [102]. In the thermal evaporation processes reported in the literature, the sputtering of a Ti buffer layer and the evaporation of Ti at high temperatures are considered mandatory [102][103][104]. These processes require a lot of energy and a sophisticated setup for the nanostructures to expand [101]. The thermal oxidation method has been used to produce TiO 2 NWs in recent studies [102,103]. The development of TiO 2 NWs with a stable rutile phase is possible with this method. Zhang et al. [102] demonstrated that a direct oxidation of a Ti foil in an organic atmosphere was possible to develop a membrane filtration process and photocatalytic degradation of humic acid in wastewater.

Composite TiO 2 Photocatalytic Membrane Reactors
TiO 2 composite membrane reactors are classified based on the types of support materials used on the membrane. Among these are TiO 2 polymer composite membranes, TiO 2 ceramic composite membranes and TiO 2 -inorganic/organic materials composite membranes [82,105]. The TiO 2 NPs can either be deposited onto the membrane surface or dispersed in the polymer dope solution prior to membrane casting.

Composite TiO2 Photocatalytic Membrane Reactors
TiO2 composite membrane reactors are classified based on the types of support materials used on the membrane. Among these are TiO2 polymer composite membranes, TiO2 ceramic composite membranes and TiO2-inorganic/organic materials composite membranes [82,105]. The TiO2 NPs can either be deposited onto the membrane surface or dispersed in the polymer dope solution prior to membrane casting.

TiO2 Nanoparticle-Coated Polymer Membranes
In photocatalytic membranes, nanoscale inorganic/organic photocatalysts are embedded in a membrane matrix to improve the properties of the resulting polymer [82,[105][106][107]. Hamed et al. [108] eluded that TiO2 nanoparticles can coordinate with the surface of the polymer membrane and Ti +4 makes ion connections with oxygen atoms of carboxylic groups of polymers or by making H-bonding with carbonyl or hydroxyl groups on the TiO2 surface. Hyeok et al. [109] increased the hydrophilicity of a commercial membrane via plasma immersion in a nitrogen-purged aqueous acrylic acid solution at various concentrations. The plasma treatment irradiated the membrane surface, causing radicals to form and promoting grafting reactions. TiO2 was then successfully deposited onto the functionalized membrane surface [82,105].
Some researchers have investigated the photocatalytic behavior of TiO2 nanoparticles photografted onto commercial polymer membranes, such as polyester membranes [24,82,108,110]. Dong et al. [98] used the activation reaction to coat TiO2 nanotubes on a polyurethane (PU) membrane surface. The TiO2 nanotube suspension was formed by ultrasonically dissolving salinized TiO2 nanotubes in toluene for 10 min. The activated PU membrane was added to the coating process, which was then heated to 60 °C. Furthermore, the TiO2 nanotube-PU hybrid membrane was collected and washed in ethanol before being dried in a vacuum oven. When the membranes were modified with diethanolamine (DEA), Hamed et al. [108] found that a high concentration of TiO2 coated on the polyvinylidene fluoride (PVDF) membrane improved pure water flux. Although embedding nanoparticles onto membranes remove unwanted nanoparticles after treatment, the polymer phase material covering the nanoparticles can reduce the active usable surface area [107]. Owing to the blockage of the membrane pores by TiO2 nanoparticles, the photocatalytic membrane's pure water flux usually decreases as the concentration of TiO2 in the coating phase rises [58,107,109,111].

TiO 2 Nanoparticle-Coated Polymer Membranes
In photocatalytic membranes, nanoscale inorganic/organic photocatalysts are embedded in a membrane matrix to improve the properties of the resulting polymer [82,[105][106][107]. Hamed et al. [108] eluded that TiO 2 nanoparticles can coordinate with the surface of the polymer membrane and Ti +4 makes ion connections with oxygen atoms of carboxylic groups of polymers or by making H-bonding with carbonyl or hydroxyl groups on the TiO 2 surface. Hyeok et al. [109] increased the hydrophilicity of a commercial membrane via plasma immersion in a nitrogen-purged aqueous acrylic acid solution at various concentrations. The plasma treatment irradiated the membrane surface, causing radicals to form and promoting grafting reactions. TiO 2 was then successfully deposited onto the functionalized membrane surface [82,105].
Some researchers have investigated the photocatalytic behavior of TiO 2 nanoparticles photografted onto commercial polymer membranes, such as polyester membranes [24,82,108,110]. Dong et al. [98] used the activation reaction to coat TiO 2 nanotubes on a polyurethane (PU) membrane surface. The TiO 2 nanotube suspension was formed by ultrasonically dissolving salinized TiO 2 nanotubes in toluene for 10 min. The activated PU membrane was added to the coating process, which was then heated to 60 • C. Furthermore, the TiO 2 nanotube-PU hybrid membrane was collected and washed in ethanol before being dried in a vacuum oven. When the membranes were modified with diethanolamine (DEA), Hamed et al. [108] found that a high concentration of TiO 2 coated on the polyvinylidene fluoride (PVDF) membrane improved pure water flux. Although embedding nanoparticles onto membranes remove unwanted nanoparticles after treatment, the polymer phase material covering the nanoparticles can reduce the active usable surface area [107]. Owing to the blockage of the membrane pores by TiO 2 nanoparticles, the photocatalytic membrane's pure water flux usually decreases as the concentration of TiO 2 in the coating phase rises [58,107,109,111].

TiO 2 Ceramic Membranes
Ceramic membranes, especially Al 2 O 3 membranes, have been extensively investigated as supports for photocatalyst immobilization in membrane photocatalytic processes (Table 5).  [115] These are more chemically, thermally and mechanically stable than polymeric membranes. A summary of comparing the ceramic and polymeric membranes is presented in Table 6.
Polymeric membranes are commonly used for the treatment of industrial wastewater due to their availability [115]. On the other hand, ceramic membranes have an advantage over other wastewater treatment options because of their chemical and thermal stability [18,20,115]. Ceramic membranes, for example, can withstand high chlorine doses and work between pH levels of 1 to 14 and temperatures of up to 500 • C. Despite the advantages of ceramic membranes over polymeric membranes, their use has been restricted due to their high initial cost [20].

TiO 2 -Based Membrane Modification Techniques
TiO 2 -based catalysts can be deposited on structured membranes through aqueous or gaseous routes [117]. Membranes with desired morphology and properties are prepared using sol-gel, immersion precipitation, vapor-mediated phase separation and immersion precipitation, electrospinning, dip-coating, sintering, track-etching, stretching, templateleaching, and phase-inversion techniques [71,86,87,90,108,112,113]. Aqueous or gaseous routes can also be used to deposit TiO 2 -based catalysts on standardized membranes. The advantages and drawbacks of various methods for immobilizing TiO 2 catalysts on membranes are summarized in Table 7. Table 7. Advantages and disadvantages of different methods used for immobilizing TiO 2 photocatalysts [116,117].

Chemical vapor deposition
Processing time is short. Suitable for high-deposition-rate uniform films.
High deposition temperature (>600 • C) is required. Due to varying evaporation times, deposition of many sources of precursors is difficult. When a vacuum system is used, the price skyrockets.
Does not involve complex chemical reactions.
Expensive as vacuum systems are used. Deposition of multiple sources of precursors are difficult.

Sol-gel
High purity of materials Hydrolysis rate is difficult to control.
Homogeneity is achievable. Versatile means processing and control of parameters. Large surface area materials are produced.
Longer processing time required. Chemical bonding results in strong adherence of coating to the substrate.
Calcination at higher temperatures is required.
Among them, the sol-gel method is the most used method for making TiO 2 photocatalysts and subsequent incorporation of membrane matrices. This method is notable for producing unique stable structures at low temperatures as well as for its excellent chemical homogeneity [85,108,113]. Controlling the precursor chemistry and processing conditions will tailor the compositional and microstructural properties of nano-sized samples. As precursors, inorganic metal salts such as titanyl sulphate, titanium tetrachloride and others (non-alkoxide), and metal alkoxides such as titanium (IV) butoxide are commonly used [90,118]. The pH of the reaction medium, the water/alkoxide ratio, and reaction temperatures can influence the sol-gel phase. Horovitz et al. [119] prepared a TiO 2 sol by stirring an ethanol solution in an ice bath while adding a specific amount of TiO 2 precursor.
The second solution was gradually added with a 50:1:3 volume ratio of ethanol, water, and acetic acid. The mixed solution was held at 20 • C for 30 min before being ultrasonicated to produce a visible TiO 2 sol. Dip-coating was achieved by immersing a substrate membrane in the sol for a set period and then drying the coated membrane [71,86]. Penboon et al. [85] made a distinction between TiO 2 -coated membranes and TiO 2 -blended polymer membranes. It was deduced that the TiO 2 -blended membranes had a more porous structure, but the coated TiO 2 composite membranes had greater antifouling properties and long-term flux stability. They went on to say that TiO 2 nanoparticles, which were spread on the membrane's surface using the coating process, could minimize pore blockage. Furthermore, TiO 2 -coated membranes are more hydrophilic than TiO 2 -blended membranes.

Characteristics of Photocatalytic Membranes
Characterization of photocatalytic membranes is based on two parameters, membrane morphology and efficiency (permeability, flux, rejection, and separation factors), which are used to describe the membranes (pore size, pore size distribution, thickness of membrane, charge density and pore shape, chemical properties, and physical properties) [3,18,120]. Improving the hydrophilicity of the membrane surface for TiO 2 nanoparticle deposition involves the introduction of functional groups to the membrane matrix (Table 8).
On the other hand, little research has been done on the impact of immersion time on the properties of photocatalytic membranes. According to Zhang et al. [121], longer immersion periods resulted in more TiO 2 nanoparticles coating the membrane surface, which appeared to clog the membrane pores and reduce flux. Nanomaterials and membranes must be characterized in order to understand their structure, chemistry, morphology, surface charge, wet potential, tensile strength and selectivity for a particular application [39,71,82,112]. Notwithstanding, membrane efficiency degrades over time due to a variety of factors such as fouling, chemical contamination, disintegration and cleaning. Therefore, characterization in this case using particular techniques provides useful information about membrane structure and topography in order to gain insight into performance loss or affected membrane structure.
Similarly, modified membranes (modification with nanomaterials) are also characterized in order to better understand the modified surface layer and how it affects membrane performance. Commonly used techniques and methods for characterization include scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photo electron spectroscopy (XPS), thermogravimetric analysis (TGA), energy dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS), contact angle, porosity, and zeta potential (Table 8). Thiruvenkatachari et al. [19] reported that after 30 min of reverse osmosis-pressurized activity, some TiO 2 particles detached from the membranes, but no further loss occurred after 7 days that was evidently noticeable in SEM images. Koseoglu-Imer and Koyuncu [105] eluded that diethanolamine increased the hydroxyl groups on the membrane surface, lowering the steric hindrance for attracting TiO 2 nanoparticles. The content of TiO 2 on the DEA-modified membrane was three times higher than on the membrane without DEA, according to the results of energy disperse X-ray spectroscopy.
Furthermore, membrane fouling is the accumulation of macromolecules (polysaccharides, proteins), colloids, microorganisms (bacteria, viruses) and salts (multivalent/monovalent) on the surface or within the pores of a membrane [45,113]. Fouling has a few significant drawbacks in membrane technology, including a reduction in permeation flux, a change in selectivity, and a reduction in membrane life during filtration. Membrane fouling is categorized into inorganic fouling, colloidal fouling, organic fouling and biofouling [45,113,118,122]. Therefore, developing photocatalytic membranes (fouling resistant membranes) are a safer alternative for fouling mitigation since they reduce foulant coagulation on the membrane surface, which contributes to clogging.

Application of TiO 2 -Based Membranes
Photocatalytic membranes, which combine membrane filtration with photocatalytic degradation of organics and subsequent antibacterial treatment in a single system, have shown great prospects in water and wastewater treatment settings [12,[123][124][125][126][127]. Furthermore, membrane flux is a critical parameter for the photocatalytic membrane system, as it can be enhanced by multilayered deposition of TiO 2 nanoparticles on the membrane surface, but pore blockage can minimize water flux in some cases [20,87]. In order to achieve the best overall performance of the membrane, the optimal balance between photocatalytic activity and membrane flux must be considered.

Wastewater Treatment
Photocatalytic membranes are becoming more prominent to deal with emerging contaminants (antibiotics, pharmaceuticals, nanoplastics, and so on) re-routed to wastewater treatment plants, as well as pre-and post-treatment concerns [128][129][130]. Increased attempts to eliminate toxic contaminants and pathogens from water have come about from the need for high-quality drinking water [12,15]. Photocatalytic membranes have proven to be more effective in removing recalcitrant organic matter than conventional wastewater treatment processes such as coagulation and filtration [131]. Therefore, they have been the subject of comprehensive research over the last few decades for the removal of toxic organic and inorganic compounds from water (Table 9). Zheng [20] reported on photocatalytic membranes for the removal of heavy metals such as mercury, lead, mercury, and cadmium from wastewater settings. Other researchers have reported that multilayered nanocomposite membranes have promising properties for heavy metal ion adsorption, photocatalysis, self-cleaning, enhanced dye rejection performance and reduced fouling [39,61,81,82]. Batch reactors and photocatalytic polycrystalline TiO 2 membrane reactors were used by Shetty et al. [131] to degrade various pharmaceuticals from water at various pH levels. Due to the catalysts' different hydrophilicity/hydrophobicity at different pH levels, the substrates showed different adsorption on catalyst surfaces when the system was in recirculation mode. The treated water had a permeate flux of 31.5-60.0 L/h.m 2 in both the alkaline and acidic mediums, with a rejection percentage of 10-60% for furosemide and 5-30% for ranitidine [131]. Table 9 summarizes the removal of pollutants using different types of photocatalytic membranes.

Other Industrial Applications
The development and production of simple and responsive biosensors have sparked a lot of interest due to their wide range of applications, including disease detection, drug discovery, food protection and environmental monitoring [82,85,106,133,134]. Due to the small active surface area of microelectrodes and the low recognition signal, electrochemical biosensors have a difficult time working [125]. As a result, chemical and thermal stability with good biocompatibility makes TiO 2 appear to be a promising biosensor material [48]. Therefore, combining it with membranes would improve its suitability for environmentally friendly designs and applications. Examples of these materials include TiO 2 nanotubes, nanosheets, solgel matrices, and three-dimensional microporous matrices [48,71,98,125]. Chen and Zhao [39] reported their first study on the production of a Fe 3 O 4 @TiO 2 magnetic NP-based disposable test strip immunosensor that uses a multienzyme labeled amplification strategy to detect organophosphorus (OP) pesticides in human plasma.

Challenges and Future Prospects of Photocatalytic Membranes
Membrane-based technologies are gaining worldwide popularity in wastewater treatment settings due to their high separation efficiencies, low cost, small carbon footprint and ease of operation. This process can also be used to eliminate a wide variety of harmful pollutants, including pesticides and herbicides used in agriculture, as well as dyes and toxic metal ions used in industry. Despite extensive research and thorough studies of photocatalytic semiconductors (TiO 2 ), many aspects of this process remain unsolved. One of the pressing issues as to whether the photocatalytic process should be used as a pretreatment or as a standalone form of water purification is the operating conditions that pose major constraints. Consequentially, the chemical composition and pH of industrial wastewater vary by region. Therefore, efforts should be made to develop photocatalytic membrane materials that can be used under a wide range or optimized operating conditions such as temperature, pH and contaminant concentrations. Furthermore, to achieve continuous irradiation with visible light over a wider range of operating conditions, a significant amount of research should be devoted to the doping and modification of TiO 2 and other semiconductors. However, catalyst immobilization is an obstacle that must be overcome in order to maximize the photocatalysts' irradiated surface area. This is needed to avoid issues such as catalyst recovery and agglomeration, which are very common in slurry-based photoreactors.

Photocatalytic Membranes
Membrane fouling, which is caused by the accumulation of anthropogenic organic contaminants and microorganisms on the membrane pores' surface, results in poor water quality, high operating costs, and a limited membrane life. In order to perform equal photocatalytic operation with minimal water flow consequences, an adequate level of photocatalysts should be incorporated into the membrane. In addition to TiO 2 loading, light intensity and irradiation time influence membrane quality.
In order to execute reasonable photocatalytic activity with minimal water flow repercussions, an appropriate level of the photocatalyst should be incorporated into the membrane. Membrane performance is also influenced by light intensity and irradiation time in addition to TiO 2 loading. Addressing this, photocatalytic membranes have been reported to have better fouling resistance as well as antimicrobial properties. Two-dimensional nanosheets with graphene have been reported to be useful for membrane applications. Additionally, combinations of nanowires with graphene sheets have also gained attention recently. Such types of structures provide antifouling and antimicrobial properties as well as hydrophilicity and aqueous stability.

Magnetized TiO 2 Photocatalytic Membranes
In order to implement heterogeneous photocatalysis into practical water and wastewater treatment applications, the overall cost of the process should be minimized. One of the ways to decrease the cost is to improve the recyclability of the photocatalyst. This can be achieved by introducing magnetic constituents into the photocatalytic nanocomposite to enhance recoverability by the application of an external magnetic field. Magnetic components (Fe 3 O 4 ) can benefit in the recovery of photocatalyst particles by preventing them from clumping together [39,67]. Magnetite (Fe 3 O 4 ) NPs, maghemite (Fe 2 O 3 ) NPs and nanorods, and hexagonal ferrites are examples of ferritic nanomaterials that are simple to recover by magnetic fields and are re-usable due to their long-term stability.
In some studies, Fe 3 O 4 and TiO 2 nanoparticles have also been successfully used as a filler for composite membranes. This opens a broad spectrum of recycling possibilities in the form of magnetized photocatalytic membrane applications (Table 10). Thus, Fe 3 O 4 NPs display exceptional superparamagnetic behavior, which provides an additional benefit of a much easier magnetic separation of the semiconductor and the solution. The coprecipitation method or thermal decomposition method is widely used to make Fe 3 O 4 nanoparticles, with minor variations such as room temperature (25-80 • C). The exemplary adsorption potential for toxic metal ion removal was achieved by the finite-size effect of magnetic nanoparticles with high surface-to-volume ratios [118]. Magnetite has also been used as an additive due to its unique features, such as physicochemical properties and high biocompatibility. Many polymeric-based membranes, such as polysulfide and polyether sulfone, had their membranes magnetized with magnetite to strengthen antifouling properties. However, knowledge of magnetized TiO 2 photocatalytic membranes is still limited and therefore requires more attention.

Life Cycle Assessment (LCA)
A life cycle assessment (LCA) is needed to incorporate TiO 2 photocatalytic-based membrane technology on a large scale [3,84]. LCA is one of the most useful instruments for determining a process's environmental effects as well as its viability and costs. Although there is a large amount of information in the literature about the recyclability and reusability of TiO 2 photocatalysts, there is still limited knowledge about their end of life [3,19]. The photocatalytic process performance, on the other hand, is highly dependent on the feed water's consistency, the operating conditions and type of treatment configuration. Apart from the environmental impacts of high organic wastewater, the amount of energy required has a major impact on the photocatalysis process [3,84]. This is one of the reasons why solar photocatalysis has received so much attention in recent years. Consequently, the toxicological and environmental impacts of a wastewater treatment facility can be detected and minimized using LCA.

Conclusions
This review study presents the photocatalytic membrane process as a game-changing technology to mitigate fouling and other drawbacks of membrane processes in addressing water scarcity and major environmental challenges. Characteristics of TiO 2 -based photocatalytic membranes with insight into their types, fabrication techniques, operational conditions and applications in water settings are discussed. As a result, the advancement of photocatalytic membrane reactors based on a wide range of nanomaterials and TiO 2 photocatalyst phase modification is anticipated to have an unparalleled future in water and wastewater treatment settings. The development of magnetite TiO 2 photocatalytic membranes was found to be an ecofriendly choice to increase photocatalytic and recoverability activities as well as reduce membrane fouling. Additionally, incorporating magnetized TiO 2 photocatalytic membranes as a post-treatment to an existing biological system can reduce eutrophication potential while increasing biomethane potential for energy usage. The prospects of life cycle assessment, research and development of magnetic photoactivebased membranes is foreseen to be economically viable with the possible potential to resolve the current membrane setbacks and bring the application of this technology to industrial scale.