The Role of The Current Waveform in Mitigating Passivation and Enhancing Electrocoagulation Performance: A Critical Review

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The role of the current waveform in mitigating passivation and enhancing

electrocoagulation performance: A critical review
Javad Abdollahi, Mohammad Reza Alavi Moghaddam, Sajjad Habibzadeh
PII: S0045-6535(22)03705-5
DOI: https://doi.org/10.1016/j.chemosphere.2022.137212
Reference: CHEM 137212
To appear in: ECSN
Received Date: 18 August 2022

Revised Date: 7 November 2022
Accepted Date: 8 November 2022
Please cite this article as: Abdollahi, J., Alavi Moghaddam, M.R., Habibzadeh, S., The role of the current
waveform in mitigating passivation and enhancing electrocoagulation performance: A critical review,
Chemosphere (2022), doi: https://doi.org/10.1016/j.chemosphere.2022.137212.
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CRediT authorship contribution statement
Javad Abdollahi: Conceptualization, Investigation, Literature review, Writing- original draft
preparation, Writing- reviewing and editing, Visualization. Mohammad Reza Alavi
Moghaddam: Conceptualization, Writing- reviewing and editing, Supervision. Sajjad
Habibzadeh: Conceptualization, Writing- reviewing and editing, Supervision.
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1 The role of the current waveform in mitigating passivation and
2 enhancing electrocoagulation performance: A critical review
3 Javad Abdollahi a, Mohammad Reza Alavi Moghaddam a,*, Sajjad Habibzadeh b
a
4 Department of Civil & Environmental Engineering, Amirkabir University of Technology
5 (Tehran Polytechnic), Iran.
b
6 Department of Chemical Engineering, Amirkabir University of Technology (Tehran
7 Polytechnic), Iran.
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8 * Corresponding author: alavim@yahoo.com (M. R. Alavi Moghaddam)
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9 Tel: +98-21-64543008; Fax: +98-21-66414213
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10 Abstract
11 Electrocoagulation (EC) can be an efficient alternative to existing water and wastewater
12 treatment methods due to its eco-friendly nature, low footprint, and facile operation. However,
13 the electrodes applied in the EC process suffer from passivation or fouling, an issue resulting
14 from the buildup of poorly conducting materials on the electrode surface. Indeed, such
15 passivation gives rise to various operational problems and restricts the practical implementation
16 of EC on a large scale. Therefore, it has been suggested that using pulsed direct current (PDC),
17 alternating pulse current (APC), and sinusoidal alternating current (AC) waveforms in EC as
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18 alternatives to conventional direct current (DC) can help mitigate passivation and alleviate its
19
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associated detrimental effects. This paper presents a critical review of the impact of the current
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20 waveform on the EC process towards the capabilities of the PDC, APC, and AC waveforms in
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21 de-passivation and performance enhancement while comparing them to the conventional DC.
22 Additionally, current waveform parameters influencing the surface passivation of electrodes

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23 and process efficiency are elaborately discussed. Meanwhile, the performance of the EC
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24 process is evaluated under different current waveforms based on pollutant removal efficiency,
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25 energy consumption, electrode usage, sludge production, and operating cost. The proper
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26 current waveforms for treating various water and wastewater matrices are also explained.
27 Finally, concluding remarks and outlooks for future research are provided.
28 Keywords: Electrocoagulation; Passivation; Current waveform; Pulse current; Polarity
29 reversal; Alternating current
2
30 1. Introduction
31 Electrocoagulation (EC) has been praised recently as a robust and eco-sustainable
32 technology in water and wastewater treatment, capable of eliminating a broad spectrum of
33 pollutants. EC incorporates the merits and capabilities of coagulation, flotation, adsorption, as
34 well as electrochemistry (Chen et al., 2018; Nidheesh et al., 2021). As a result, it offers many
35 advantages over the conventional treatment methods and is characterized by an eco-friendly
36 nature, ease of operation, versatility, a small footprint, and a minimum requirement of
37 chemicals (Sefatjoo et al., 2020; Shokri and Fard, 2022). However, the EC process, which is
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38 often operated with direct current (DC), suffers from high energy and electrode consumption,
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plus electrode passivation (Garcia-Segura et al., 2017; Al-Raad and Hanafiah, 2021; Yasri et
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40 al., 2022). This latter issue discourages the large-scale applicability and commercialization of
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41 EC and can cause various malfunctions over long-term operations, such as decreased coagulant
42 production, excessive energy consumption, and diminished treatment efficiency (Fu et al.,
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43 2021; Oliveira et al., 2021; Yu et al., 2021). Accordingly, electrode passivation should be
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44 controlled or eliminated to overcome these adverse aftereffects and harness the full potential
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45 of the EC process (Ibrahim et al., 2020).

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46 Many approaches have been proposed to deal with passivation, among which changing
47 the current waveform has gained the most attention. In recent years, there has been a growing
48 interest in operating EC with pulsed direct current (PDC-EC), alternating pulse current (APC-
49 EC), and sinusoidal alternating current (AC-EC). Although these current waveforms can
50 potentially prevent electrode passivation, their impact on the overall EC performance is still
51 unclear, and sometimes contradictory findings have been reported. Research in this field has
52 been intensive during the last two decades, and various research papers have been published.
53 However, although a few reviews addressed electrode passivation and discussed
54 passivation mitigation approaches (Ingelsson et al., 2020; Al-Raad and Hanafiah, 2021; Moradi
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55 et al., 2021), to the authors' knowledge, no review article has been published specifically
56 regarding the role of PDC, APC, and AC waveforms in reducing electrode passivation and
57 improving EC performance. Bearing this in mind, this review seeks to fill this gap.
58 Accordingly, this study will summarize the main current waveforms employed in the EC
59 process after outlining the fundamentals of EC and explaining the passivation phenomenon.
60 This will be followed by comparing PDC-EC, APC-EC, and AC-EC with conventional DC-
61 EC and providing an in-depth discussion regarding the impact of the current waveform on
62 passivation and process performance from the viewpoints of pollutant removal efficiency,
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63 energy requirements, electrode consumption, sludge production, and operating costs.
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Meanwhile, the impact of current waveform parameters on PDC-EC and APC-EC will be
discussed. The proper current waveforms for treating various water and wastewater matrices
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66 will also be explained. Finally, several perspectives for future research will be highlighted.
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68 2. Fundamentals of the electrocoagulation process

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69 EC is an electrochemical technology that resembles chemical coagulation, except that

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70 coagulant species are generated in situ by applying electric current to the sacrificial electrodes
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71 (Behbahani et al., 2011a; Taheri et al., 2013; Nazlabadi et al., 2019). EC involves multiple
72 mechanisms operating synergistically to eliminate pollutants. When the electrodes are exposed
73 to electric current, the anode is oxidized into metal ions (Eq. (1)), while concurrently, at the
74 cathode, water is reduced into H2 gas and OH− ions (Eq. (2)). Then, metal ions and OH− transfer
75 into the solution and undergo spontaneous hydrolysis reactions (Eq. (3)), forming monomeric
76 and polymeric species that eventually transform into insoluble metal oxides, hydroxides, or
77 oxyhydroxides (herein collectively referred to as metal (oxy)hydroxide flocs) (Karimifard and
78 Alavi Moghaddam, 2018; Tegladza et al., 2021). These compounds are responsible for the
79 adsorption or entrapment of pollutants due to their large surface area and high adsorption
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80 capacity (Taheri et al., 2012). The agglomerated flocs and pollutants can settle as sludge or
81 attach to hydrogen bubbles and float via electro-flotation (Behbahani et al., 2011b; Karamati
82 Niaragh et al., 2017; Nazlabadi and Alavi Moghaddam, 2017).
n+
83 M(s) → M(aq) + ne− (1)
−
84 2H2 O(l) + 2e− → H2(g) ↑ +2OH(aq) (2)
n+ +
85 M(aq) + nH2 O(l) → M(OH)n(s) + nH(aq) (3)
86 The amount of coagulant generated from metal anode material dissociation can be
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87 estimated by Faraday's law (Eq. (4)) (Mollah et al., 2004). The faradaic efficiency, which is the
88 ratio of the amount of anode material actually dissolved to the theoretical value expected from
89 pr
Faraday's law, is generally used as an appraisal index to evaluate the EC process performance
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90 (Müller et al., 2019).
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𝐼𝑡𝑀𝑤
91 𝑚= (4)
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𝑛𝐹
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92 where m represents the mass of anode dissolved (g), Mw is the specific molecular weight of
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93 anode material (g mol−1), I is the applied current intensity (A), t is the electrolysis time (s), F
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94 is the Faraday's constant (96485 C mol−1), and n is the number of electrons involved in the
95 anodic reaction.
96 The overall performance of EC depends on a multitude of factors. The main factors that
97 influence EC and the vectors through which EC performance could be affected are illustrated
98 in Fig. 1. Given the focus of this review on the current waveform and the passivation
99 phenomenon, Fig. 1 only depicts how these two factors interact with others, which will be
100 discussed in the following sections.
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102 Fig. 1. Factors affecting EC performance.
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103 3. Electrode passivation in the electrocoagulation process
104 Maintaining a steady and high faradaic efficiency during prolonged operation is essential
105 for reliable EC performance (Müller et al., 2019). However, the accumulation of solid materials
106 on the electrode in the form of a surface layer/film, an issue that is referred to by different terms
107 such as electrode passivation or fouling, can impede the mass transfer of metal ions into the
108 bulk solution due to their entrapment in the structure of the surface layer or lead to insufficient
109 metal ions production due to the occurrence of side reactions instead of electrode oxidation
110 (van Genuchten et al., 2016; Müller et al., 2019). Several factors can affect electrode
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111 passivation, such as solution composition, solution pH, current density, current waveform,
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reactor design, pollutant concentration, dissolved oxygen, and electrode material (Ingelsson et
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113 al., 2020; Al-Raad and Hanafiah, 2021; Chow and Pham, 2021; Guo et al., 2022).
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114 Among these factors, solution composition is of great importance (Syam Babu et al.,
115 2021). The passivation rate in various water and wastewater matrices may vary dramatically
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116 owing to the different types and amounts of pollutant species in their composition. Lower
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117 passivation rates are expected in tap water due to the low concentration of interfering ions
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118 (Khandegar and Saroha, 2013), while in groundwater, the presence of Ca and Mg cations and
119 oxyanions, such as nitrate, carbonate, phosphate, and sulfate, can contribute to higher
120 passivation rates (van Genuchten et al., 2017; Chow et al., 2021; AlJaberi et al., 2022).
121 Additionally, natural pollutants in water, such as natural organic matter (NOM), have been
122 reported to intensify passivation (Mohora et al., 2014). However, the passivation rate could be
123 much higher and particularly problematic in various wastewater matrices because of the higher
124 contaminants and COD load (Sadeghi et al., 2022; Yasasve et al., 2022). Due to the diversity
125 of ionic species and contaminants causing passivation (van Genuchten et al., 2017), the
126 passivation rate can differ from one industrial wastewater to another. The passivation
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127 mechanisms, detrimental effects of passivation on EC, and de-passivation approaches are
128 summarized in Fig. SM-1 and discussed in the following paragraphs.
129
130 3.1. Passivation mechanisms
131 Electrode passivation results from electrochemical and physicochemical mechanisms
132 that involve coagulants and aqueous-phase species reacting and precipitating on the electrode
133 surface (Yasri et al., 2022). Water electrolysis forms acidic and alkaline pH environments
134 around the anode and cathode, respectively. Therefore, ionic species in the electrolyte may
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135 deposit on the electrode surface if they exceed their solubility limitations (Ingelsson et al.,
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2020; Yasri et al., 2022). The following are the main reactions and mechanisms that contribute
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137 to the formation of the surface layer and increase passivation: (1) the precipitation of a portion
of metal (oxy)hydroxide flocs on the electrode surface (Timmes et al., 2010; Fu et al., 2021;
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139 Yu et al., 2021; W. Zhang et al., 2021), (2) the bonding of oxyanions to metal ions and thus the
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140 formation of the oxyanion-rich passivating film on the anode surface (Mansouri et al., 2011;
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141 Dubrawski et al., 2015; van Genuchten et al., 2017; Xu et al., 2017), (3) the precipitation of Ca
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142 and Mg minerals on the cathode surface (Haldar and Gupta, 2020; Dutta et al., 2021; AlJaberi
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143 et al., 2022; Dutta and Gupta, 2022), (4) the accumulation of contaminant residues on the
144 electrode surface (Eyvaz et al., 2009; Xu et al., 2015; Yang et al., 2015), and (5) the adsorption
145 of other particles in solution to the anode or cathode surface (Ingelsson et al., 2020). A
146 schematic of the mechanisms occurring during EC is illustrated in Fig. 2.
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148 Fig. 2. The schematic diagram of EC and the mechanisms involved in the process
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150 3.2. Detrimental effects of passivation
151 Once the surface layer is formed on the electrode surface, this layer is expected to thicken
152 over time due to the decreased probability of metal ion migration through the layer to the bulk
153 solution (Cesar Lopes Geraldino et al., 2016). If the surface layer consists of poorly conducting
154 materials, the solid buildup can result in various operational concerns (Bandaru et al., 2020).
155 The passivated electrode is prone to pitting corrosion, resulting in structural failure and periodic
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156 replacement at shorter intervals (Punckt et al., 2004; Dura and Breslin, 2019; Zhang and Ma,
157 2019; Trompette and Lahitte, 2021). Besides, electrode passivation makes the electrode surface
158 quasi-inert and impedes normal electron flow. This phenomenon subsequently increases ohmic
159 resistance and overpotential, resulting in excessive energy consumption and higher operating
160 costs (Madhavan and Antony, 2021; Payami Shabestar et al., 2021; Zhu et al., 2022). In
161 addition, at sufficiently high anodic overpotentials, the formation of passive film favors water
162 oxidation (Eq. (5)) rather than electrode oxidation, which reduces the amount of formed flocs
163 and diminishes pollutant removal efficiency markedly (Yang et al., 2015; Ashraf et al., 2019;
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164 Alkhatib et al., 2020). Moreover, severe passivation can cause the system to shut down (Yasri
165 et al., 2022).

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166 2H2 O(l) → 4H(aq) + O2(g) ↑ +4e− (5)
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168 3.3. Passivation mitigation or prevention approaches

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169 Since the formation and growth of the passivating layer on the electrode surface can
170 negatively affect the EC process, electrode de-passivation is needed to maintain the EC
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171 performance over extended periods. The main strategies employed in EC to de-passivate
172 electrodes, along with their merits and drawbacks, are mentioned below:
173 (1) Mechanical or chemical cleaning of electrodes. Merits: effective de-passivation; no
174 need for additional equipment. Drawbacks: high labor expenses; requires system
175 shutdown (a challenge for automating EC); needs acid waste management (for
176 chemical cleaning) (Amrose et al., 2014; Bandaru et al., 2020).
177 (2) Adding aggressive ions such as Cl− to the electrolyte. Merits: effective in-situ de-
178 passivation; simple; no need for extra equipment. Drawbacks: risk of hazardous
179 byproducts; needs further treatment (Arroyo et al., 2009; Ingelsson et al., 2020).
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180 (3) Increase the turbulent state by modifying the electrode shape, reactor geometry, or
181 flow velocity. Merits: effective in-situ de-passivation; no need for chemicals.
182 Drawbacks: not applicable for a batch system; requires a continuous pump (Timmes
183 et al., 2010; Ibrahim et al., 2020; Al-Raad and Hanafiah, 2021).
184 (4) Applying a super-gravity field. Merits: effective in-situ de-passivation; no need for
185 chemicals. Drawbacks: requires extra infrastructure; complex setup (Yu et al., 2021).
186 (5) Combining the EC process with the ultrasonic (Sono-EC). Merits: effective in-situ
187 de-passivation; no need for chemicals. Drawbacks: requires special infrastructure;
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188 expensive; may cause flocs to break down (He et al., 2016; Moradi et al., 2021).
189
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(6) Using current waveforms other than DC. Merits: in-situ de-passivation; complete
automatability; no complex design modification; no additional treatment phases; no

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191 need for chemicals. Drawbacks: requires additional electrical equipment (Chow and
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192 Pham, 2021; Arabameri et al., 2022; Dong et al., 2022).

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193 Although strategies 1 to 5 could be effective in passivation mitigation, they require either
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194 chemical addition, system termination, or special infrastructure, all of which considerably raise
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195 the cost and complexity of the process. However, EC operation with current waveforms other
196 than DC (strategy 6) has become increasingly appealing in recent years due to the various
197 advantages outlined above. In addition, uniform electrode corrosion, reduced energy and
198 electrode consumption, lower sludge production, and cost-effectiveness make this approach
199 more desirable. Accordingly, this review focuses on this strategy and evaluates its capabilities
200 for electrode de-passivation and performance enhancement of EC.
201
202 4. Current waveforms in the electrocoagulation process
203 According to Fig. 3, the EC process can be classified into four main techniques based on
204 the current waveform adopted: direct current EC (DC-EC), pulsed direct current EC (PDC-
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205 EC), alternating pulse current EC (APC-EC), and sinusoidal alternating current EC (AC-EC).
206 The electric current in DC-EC and PDC-EC is unidirectional, with the latter being
207 discontinuous. In contrast, the electric current in APC-EC and AC-EC is bidirectional; thus,
208 the current direction and polarity of electrodes alter intermittently. Most EC studies have used
209 DC, which has several drawbacks, such as high energy and electrode consumption, insufficient
210 residence time for flocculation, electrode inefficiency, and electrode passivation (Rajaei et al.,
211 2021). The PDC-EC, APC-EC, and AC-EC techniques have been proposed to overcome the
212 disadvantages of DC-EC. These techniques have drawn significant attention since they can
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213 improve performance by manipulating coagulant mass transfer, system resistance, coagulant
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species produced, and bubble gas generation (Karamati-Niaragh et al., 2019; Zhou et al., 2020;
Madhavan and Antony, 2021; Payami Shabestar et al., 2021; Arabameri et al., 2022).
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216 Several studies have operated the EC process with PDC, APC, and AC waveforms in the
217 last two decades. This review focuses on those studies that compared these waveforms to
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218 conventional DC by considering different criteria, namely pollutant removal efficiency, energy
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219 usage, electrode consumption, sludge production, and operation cost, as well as research that
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220 optimized current waveform parameters to fully exploit EC potential.
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221
222 Fig. 3. EC techniques based on the current waveform: (a) DC-EC, (b) PDC-EC, (c) AC-EC, and (d) APC-EC
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223 5. Pulsed direct current electrocoagulation (PDC-EC)
224 Periodic interruptions of direct current in EC have been demonstrated to help manage
225 electrode passivation and improve performance. In this technique, which is referred to by
226 different terms such as pulsed direct current EC (PDC-EC), pulse EC (PEC), or positive single
227 pulse current EC (PSPC-EC), the DC power supply is kept on for a given time and then
228 switched off for a specified time in a pulse period (Fig. 3(b)). Therefore, unlike in DC-EC, the
229 electrode reactions are discontinuous in PDC-EC (Ren et al., 2011). The duration of current
230 on- and off-times in this technique is compared to DC-EC. The duration of current on- and off-
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231 times in this technique can be adjusted by modifying the current waveform parameters, which
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would affect process performance. In the following, the role of current waveform parameters
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233 on PDC-EC is discussed, and the capability of this technique in reducing electrode passivation
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234 and enhancing treatment performance is compared to DC-EC.
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236 5.1. The impact of current waveform parameters on PDC-EC

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237 The waveform of every PDC is unique and can be characterized by (1) pulse frequency
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238 and (2) duty cycle. Table SM-1 presents a summary of studies that explored the impact of these
239 parameters on PDC-EC.
240
241 5.1.1. Pulse frequency
242 The pulse frequency is the reciprocal of the single operating period of the pulse (f= 1/T)
243 and represents the number of pulses per unit of time (Zhou et al., 2020; Dong et al., 2022).
244 According to Table SM-1, the optimal pulse frequencies recommended in the literature range
245 from 2.78 mHz (6 min pulse period) for treating synthetic dye wastewater with Al/Fe electrode
246 pairs (Akhbarati et al., 2017) to 10 kHz (100 μs pulse period) for COD removal from municipal
247 wastewater with Al electrodes (Chen et al., 2011). The broad scope of suggested pulse
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248 frequencies could be attributed to differences in criteria considered in PDC-EC optimization
249 and operating conditions, such as solution chemistry, pollutant type, and electrode material.
250 Generally, a low-frequency PDC can passivate the electrode surface (Yang et al., 2020),
251 while a high pulse frequency can impede concentration polarization and passive layer
252 formation within a short pulse period, resulting in enhanced treatment efficiency (Zhou et al.,
253 2020). The high-frequency PDC has also been claimed to have a stronger penetrability to
254 puncture passivating film to help produce more coagulant agents (Zhou et al., 2020; An et al.,
2022). However, most studies reported that the pulse frequency had a non-linear impact on
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256 treatment efficiency, and increasing this variable did not necessarily enhance pollutant removal
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efficiency (Chen et al., 2011; Ren et al., 2011; Zheng, 2017; Yang et al., 2020; Zhou et al.,
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258 2020; An et al., 2022; Dong et al., 2022). This behavior could be explained by the concept that
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259 the electrical double-layer in EC functions as a capacitor (Hasani et al., 2019), so at very high
260 pulse frequencies, the pulse width and current off-time can become shorter than the charge-
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261 discharge time of the electrode double-layer, causing PDC-EC to fail to eliminate passivation
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262 and leading to lower pollutant removal efficiency (Ren et al., 2011). Thus, the current on-time
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263 in a pulse period should be long enough for the electrical double-layer to be fully charged, and
264 the off-time should be so long that the double-layer has enough time to discharge (Hasani et
265 al., 2019). As a result, depending on the experimental conditions and the scope of investigated
266 frequencies, changes in pulse frequency can result in different scenarios in terms of passivation
267 mitigation and pollutant removal efficiency.
268
269 5.1.2. Duty cycle
270 The duty cycle (γ), which is the ratio of pulse width (ton) to the pulse period (T= ton +
271 toff), distinguishes between the PDC and conventional DC waveforms (Wang and Liu, 2017)
272 and directly affects energy consumption and faradaic efficiency in PDC-EC (Chen et al., 2011).
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273 With a very low duty cycle, only a tiny proportion of the time in a pulse period is spent on
274 electrification, which reduces metal ion production and treatment efficiency (Dong et al.,
275 2022). However, a low duty cycle can decrease concentration polarization and electrode
276 passivation, resulting in higher pollutant removal efficiency (Yang et al., 2020). On the other
277 hand, increasing the duty cycle can increase metal ion generation and floc formation, improving
278 pollutant removal effectiveness. However, due to increased electrode dissolution at higher duty
279 cycles, the metal ions can be difficult to diffuse into the bulk solution, which results in
280 concentration polarization and electrode passivation, diminishing treatment efficiency (Yang
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281 et al., 2020; An et al., 2022; Zhang et al., 2022). Some studies also claimed that the duty cycle
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might affect floc structure and, thus, treatment efficacy (Dong et al., 2022).
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283 Furthermore, according to Eq. (6), the energy consumption in PDC-EC is dependent on
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284 the duty cycle, and lower values of this variable may favor more energy conservation, while at
285 higher duty cycles, PDC tilts toward DC, leading to higher energy usage (Ren et al., 2011;
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286 Wang and Liu, 2017). However, it should be noted that operation time may be prolonged with
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287 a low duty cycle to achieve similar removal efficiency to that of a high duty cycle, increasing
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288 energy consumption (Zhou et al., 2020). Considering all the above, the majority of authors
289 reported that duty cycles in the range of 0.3–0.6 were favorable for optimum PDC-EC
290 performance (see Table SM-1).
291 𝐸 = 𝑈𝐼𝑡𝛾 2 (6)
292 where E is the energy consumption, U is the peak voltage, I is the peak current, t is the reaction
293 time, and γ is the duty cycle.
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294 5.2. Comparison of PDC-EC and DC-EC techniques
295 Table 1 compiles the studies that compared PDC-EC and DC-EC techniques for various
296 pollutants and different electrode materials (e.g., aluminum, iron, and stainless steel) in terms
297 of electrode passivation and treatment performance. In most studies, the PDC-EC technique
298 has proven to be more efficient in abating pollutants than DC-EC (Ren et al., 2011; Akhbarati
299 et al., 2017; Wang and Liu, 2017; Zheng, 2017; H. Nguyen, 2020; Nguyen et al., 2020; Que et
300 al., 2021; Zhang et al., 2022). Higher treatment efficiency in PDC-EC has been attributed to
301 lower concentration polarization and diminished electrode passivation, as metal ions can
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302 diffuse into the solution and their concentration near the electrodes returns to the initial value
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when the current is turned off (Ren et al., 2011; Dong et al., 2022). It has also been reported
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304 that the PDC waveform can provoke mass transport by transient disruption of
attracting/repelling forces caused by electrodes, allowing ions or molecules such as metal

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306 cations and OH− to readily contact each other (Chen et al., 2011). Besides, each pulse period's
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307 current break (current off-time) can contribute to higher efficiency by giving the coagulants
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308 sufficient time to complete coagulation/flocculation reactions (Oliveira et al., 2021). For
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309 instance, it has been revealed that employing the PDC waveform in the electrochemical process
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310 using the Fe anode to eliminate Cr(VI) facilitated the Fe ion formation and led to more Fe ion
311 generation than the DC system (Zhou et al., 2019). As such, the concentration of Fe ions was
312 significantly enhanced by 707%, and the Cr concentration was reduced by 96% in the system
313 driven with the PDC compared to the system with the DC, demonstrating the more exhaustive
314 reactions when the PDC waveform was applied (Zhou et al., 2019).
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315 Table 1. The summary of the reported studies on the comparison of PDC-EC with DC-EC
Process performance
Opt. PDC
Pollutant and
Anode/cathode waveform I, U, or j Removal Sludge Major outcomes References
solution Energy consumption Electrode consumption Operating
parameters efficiency production
(ENC) (ELC) cost (OC)
(RE) (SLP)
Al/Al COD in real f= 10 kHz PDC-EC: PDC-EC: PDC-EC: – – – Prevented ELP and uniform electrode Que et al.
municipal WW γ= 0.01 50 V 80% COD 2.8 kWh m−3 (for 68% corrosion in PDC-EC; 12% higher RE (2021)
DC-EC: DC-EC: COD) and 12.5% reduced ENC in PDC-EC
5V 68% COD DC-EC: than in DC-EC
3.2 kWh m−3
Al/Al COD in real f= 10 kHz PDC-EC: PDC-EC: PDC-EC: – – – PDC-EC: 17% higher RE and 24% less Nguyen et
textile WW γ= 0.01 45 V 77% COD 1.6 kWh m−3 (for 60% ENC than DC-EC al. (2020)
of
DC-EC: DC-EC: COD)
4V 60% COD DC-EC:
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2.1 kWh m−3
Al/Al, Fe/Fe* BH and COD in f= 1 kHz 194 A m−2 PDC-EC: PDC-EC: PDC-EC: – – Avoided ELP and more uniform Ren et al.
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synthetic and real γ= 0.3 90.1% BH 0.73 Wh (kg COD)−1 5.1 kg Fe (kg COD)−1 corrosion in PDC-EC; Higher removal (2011)
re
pharmaceutical 62.6% COD DC-EC: DC-EC: rates, 91% less ENC, and 11% lower
factory WW 8.20 Wh (kg COD)−1 5.7 kg Fe (kg COD)−1 ELC in PDC-EC than in DC-EC; Higher
lP
REs with Fe than with Al in PDC-EC
Al/Al, Fe/Fe* Dibutyl phthalate γ= 0.6 150 A m−2 PDC-EC: PDC-EC: PDC-EC: – – Greater passivation and lower RE with Wang and
in synthetic and 75% DBP 860 J (ppm DBP)−1 0.35 mg (ppm DBP)−1 Al than with Fe in PDC-EC; 41% lower Liu (2017)
na
real plastic DC-EC: DC-EC: ELC, 39% reduced ENC, and higher RE
factory WW 1420 J (ppm DBP)−1 0.59 mg (ppm DBP)−1 in PDC-EC than in DC-EC
Al/Al, Fe/Fe, Antimony in f= 0.4 kHz 15 V PDC-EC:

ur
PDC-EC: – – – PDC-EC: lower ENC than DC-EC for Dong et al.
Jo
Al/Fe, Fe/Al* synthetic WW γ= 0.5 97.4 antimony 54.8% less ENC than almost the same RE (2022)
DC-EC: DC-EC
97.2 antimony
Al/Fe Acid Blue 113 in f= 2.78 mHz 0.68 A PDC-EC: PDC-EC: – – – PDC-EC: 86% less ENC and a slightly Akhbarati et
synthetic WW γ= 0.5 99.66% dye 1.2 kWh m−3 higher RE than DC-EC al. (2017)
DC-EC: DC-EC:
98% dye 8.5 kWh m−3
Fe/Fe Direct Scarlet f= 0.2 kHz 168 A m−2 PDC-EC: PDC-EC: PDC-EC: – – PDC-EC: 51% lower ENC, 5% less ELC, Chen et al.
4BS and COD in γ= 0.1 99.61% color 1.110 J (mg COD)−1 0.187 kg Fe (kg and slightly lower REs than DC-EC (2011)
synthetic WW 91.46% COD DC-EC: COD)−1
DC-EC: 2.273 J (mg COD)−1 DC-EC:
99.72% color 0.197 kg Fe (kg
92.75 COD COD)−1
18
Process performance
Opt. PDC
Pollutant and
Anode/cathode waveform I, U, or j Removal Sludge Major outcomes References
solution Energy consumption Electrode consumption Operating
parameters efficiency production
(ENC) (ELC) cost (OC)
(RE) (SLP)
Fe/Fe COD, oil, f= 3 kHz PDC-EC: PDC-EC: PDC-EC: PDC-EC: PDC-EC: – Lessened ELP in PDC-EC; 76% lower Zheng
turbidity, TSS, γ= 0.3 350 A m−2 98.3% COD 0.19 kWh (kg COD)−1 3.1 kg Fe (kg COD)−1 5.3 kg (kg ENC, 9% less ELC, 4% reduced SLP, (2017)
and PAM in real DC-EC: 99.0% oil DC-EC: DC-EC: COD)−1 and slightly higher REs in PDC-EC than
oilfield produced 100 A m−2 DC-EC: 0.78 kWh (kg COD)−1 3.4 kg Fe (kg COD)−1 DC-EC: in DC-EC
water 94.7% COD 5.5 kg (kg
96.2% oil COD)−1
Fe/Fe Cadmium in f= 2 kHz PDC-EC: PDC-EC: PDC-EC: – – – Reduced ELP and larger surface area of Yang et al.
synthetic WW γ= 0.4 16 A m−2 99.92% Cd 0.400 kWh m−3 flocs in PDC-EC than in DC-EC; 44% (2020)
DC-EC: DC-EC: DC-EC: less ENC in PDC-EC than in DC-EC for
40 A m−2 99.74% Cd 0.714 kWh m−3 similar RE
of
Fe/Fe COD in real f= 10 kHz PDC-EC: PDC-EC: PDC-EC: – – – Uniform Fe corrosion in PDC-EC; H. Nguyen
γ= 0.01 1.7 kWh m−3 (for 72%
ro
municipal WW 50 V 82% COD Enhanced adsorption capacity of PDC- (2020)
DC-EC: DC-EC: COD) EC's flocs than those of DC-EC; 10%
-p
5V 72% COD DC-EC: higher RE and 39% less ENC in PDC-
2.8 kWh m−3 EC than in DC-EC
re
Fe/Fe Hardness and f= 2 kHz 120 A m−2 PDC-EC: PDC-EC: – – PDC-EC: Slightly less TH removal and 8% lower An et al.
turbidity in real γ= 0.6 23.35% TH 0.81 kWh m−3 0.15 $ m−3 ENC in PDC-EC than in DC-EC (2022)
lP
coal gasification 28.57% turbidity DC-EC:
gray water DC-EC: 0.88 kWh m−3
24.46% TH
na
22.86% turbidity
Fe/Fe Tetracycline in γ= 0.6 0.2 A PDC-EC: PDC-EC: PDC-EC: – PDC-EC: Improved adsorption efficiency in PDC- Zhang et al.
ur
synthetic and real 96.69% TC 0.11 kWh m−3 0.2042 kg Fe m−3 0.011 $ m−3 EC compared to DC-EC; Almost similar (2022)
livestock WW DC-EC: RE in both techniques
Jo
96.16% TC
Al/Al*, SS/SS Trimethoprim f= 120 Hz 120 A m−2 PDC-EC: PDC-EC: PDC-EC: – PDC-EC: Passivation effect of AMX and TMP Oliveira et
and amoxicillin γ= 0.7 8.2% TMP 1.65 kWh m−3 0.21 kg Al m−3 0.6 $ m−3 toward Al/Al. Corrosion effect of AMX al. (2021)
in real municipal 21.9% AMX toward SS/SS. 30% lower ENC in PDC-
WW 9.38% TPM + EC than in DC-EC
AMX
Al/SS Pharmaceuticals f= 0.67 mHz 3 A m−2 PDC-EC: ~15% PDC-EC: PDC-EC: – PDC-EC: Limited ELP in PDC-EC; 96% less ENC, Ensano et
in real municipal γ= 0.2 less REs than 0.21 kWh m−3 31.88 g m−3 0.1 € m−3 and 15% lower RE in PDC-EC than in al. (2019)
WW DC-EC DC-EC
Al/SS Sulfate in real f= 1.11 mHz 65 A m−2 PDC-EC: – – – – PDC-EC: 26% lower RE than DC-EC Rodrigues et
mine-impacted γ= 0.33 45.29% sulfate al. (2020)
water DC-EC:
70.95% sulfate
* The best electrode combination
316
I: Current; U: Voltage; j: Current Density; WW: Wastewater; ELP: Electrode passivation; SS: Stainless steel
317
19
318 Furthermore, it was found that the pulse current significantly impacts pollutant removal
319 in EC by affecting the adsorption efficiency (Zhang et al., 2022). Periodic terminating and
320 restarting the current in PDC-EC has been shown to help generate flocs with better adsorption
321 characteristics than those produced in DC-EC (H. Nguyen, 2020; Nguyen et al., 2020; Yang et
322 al., 2020; Zhou et al., 2020). For example, it was found that the flocs produced by PDC-EC
323 had a larger surface area for cadmium (Cd) adsorption and formed larger particles compared
324 to DC-EC (Yang et al., 2020). Due to the longer electrification time in DC-EC, it was also
325 demonstrated that a large amount of oxygen was produced due to water oxidation, leading to
f
oo
326 lepidocrocite (γ–FeOOH) formation. On the contrary, the green rust–Cl was produced in PDC-
EC in the absence of dissolved oxygen and the presence of Cl−, with the latter having a superior
327
pr
Cd removal property to the former (Yang et al., 2020). In contrast to these findings, a few
e-
328
329 studies have reported poorer performance of PDC-EC in removing pollutants than DC-EC
Pr
330 (Chen et al., 2011; Ensano et al., 2019; Rodrigues et al., 2020). For instance, it was shown that
al
331 the removal efficiency of pharmaceuticals was around 15% lower in the PDC-EC (5 min on/20
rn
332 min off) compared to the DC-EC (Ensano et al., 2019). The lower treatment efficiency in PDC-
u
333 EC was explained by the insufficient liberation of Al3+ species, which are responsible for the
Jo
334 charge neutralization of suspended pollutants and the adsorption of dissolved organic matter
335 (Ensano et al., 2019).
336 Regarding energy consumption, all the reviewed studies indicated that the PDC-EC
337 technique was more efficient than DC-EC. This behavior can be attributed to the shorter
338 electrification time in PDC-EC (Ren et al., 2011; Oliveira et al., 2021). Besides, reduced
339 electrode passivation in PDC-EC can lead to lower cell voltage and, thus, decreased energy
340 consumption. Also, due to the discontinuous reactions of converting electrical energy to
341 chemical energy in PDC-EC, the energy conversion in this technique could be more efficient
342 than that of DC-EC, and all the electrical energy can be concentrated on electrode corrosion
20
343 rather than diverted to water electrolysis for oxygen generation. As a result, efficient energy
344 utilization in PDC-EC can contribute to energy conservation (Chen et al., 2011). An inspection
345 of the articles reported in Table 1 reveals that PDC-EC can save up to 96% energy compared
346 to DC-EC for the same treatment efficiency (Ensano et al., 2019).
347 It has also been demonstrated that PDC-EC consumes fewer electrodes (Chen et al.,
348 2011; Ren et al., 2011; Wang and Liu, 2017; Zheng, 2017) and generates less sludge than DC-
349 EC (Zheng, 2017; Zhou et al., 2020). In PDC-EC, the electrode corrosion stops during the
current breaks, leading to reduced electrode utilization and lower sludge production (Ren et al.,
f
350
oo
351 2011). According to the data presented in Table 1, changing the current from DC to PDC can
352
pr
cut off electrode consumption and sludge production by up to 41% (Wang and Liu, 2017) and
e-
353 30% (Zhou et al., 2020), respectively. Unfortunately, among the reviewed publications, no
Pr
354 study has compared the operating costs of the PDC-EC and DC-EC techniques; however, due
355 to the decreased electrode and energy consumption and reduced sludge production in PDC-EC,
al
356 the overall operational cost of this technique is expected to be less than that of DC-EC.
rn
357
u
Jo
358 6. Alternating pulse current electrocoagulation (APC-EC)
359 EC with alternating pulse current, referred to as APC-EC, has drawn the most attention
360 among the EC techniques to restrain passive layer growth and improve process performance.
361 This technique involves intermittently reversing the current direction, which is generally
362 carried out by using an APC power supply (Xu et al., 2018; J. Zhang et al., 2021) or plugging
363 a programmable time relay into a DC power source (Eyvaz et al., 2009; Yang et al., 2015; Yasri
364 et al., 2022), allowing the electrodes to serve either as the anode or cathode for the prescribed
365 time intervals. Most studies in APC-EC just reversed the electrode's polarity, which is often
366 referred to as polarity reversal EC, or PR-EC (Fig. 3(d1)) (Eyvaz et al., 2009; Secula et al.,
367 2013; Donneys-Victoria et al., 2020; Chow et al., 2021). However, some researchers
21
368 interrupted the electric current in between polarity reversals (Fig. 3(d2)) (Jiang et al., 2018;
369 Xin et al., 2018) or employed varying numbers of pulses during the original and reversed
370 polarity (Fig. 3(d3)) (Mao et al., 2008; Xu et al., 2017; J. Zhang et al., 2021). The duration and
371 sequence of current on/off times and polarity reversal can be adjusted by manipulating the
372 current waveform parameters, influencing APC-EC performance. In this context, several
373 studies have been conducted, the noteworthy findings of which are reviewed in the section
374 below:
375
f
oo
376 6.1. The impact of current waveform parameters on APC-EC
377
pr
The following current waveform parameters have been found to affect APC-EC: (1)
e-
378 polarity reversal time, (2) pulse frequency, and (3) duty cycle. The polarity reversal time is
unique to the APC waveform, whereas pulse frequency and duty cycle are the common
Pr
379
380 properties of pulse current waveforms (PDC and APC). Properly controlling the APC
al
381 waveform parameters can help mitigate electrode passivation and assure high process
rn
382 performance.
u
383
Jo
384 6.1.1. Polarity reversal time
385 The polarity reversal time (PR time, Trev), which is the operation time before the
386 electrode's polarity is inverted, is considered a crucial element in APC-EC; as a result, the
387 proper selection of the PR time is critical. Table SM-2 compiles the studies that explored the
388 impact of PR time on the APC-EC technique and highlights the optimal PR times and the
389 authors' findings. In most studies, the duration of the forward and reversed polarities was the
390 same and equal to half of the cycle period (Pi et al., 2014; Yang et al., 2015; Fekete et al., 2016;
391 Betancor-Abreu et al., 2019; Maher et al., 2019; Ashraf et al., 2021; Chow et al., 2021; Yasri
392 et al., 2022). Meanwhile, some researchers operated the process with asynchronous polarity
22
393 reversal for hybrid electrode pairs (e.g., Fe/Al and Al/Fe), where electrodes serve as the anode
394 for different lengths of time (Xu et al., 2017; Fu, 2018; Jiang et al., 2018).
395 According to Table SM-2, the suggested PR times for optimal APC-EC performance
396 were too diverse, and different studies proposed a broad scope of optimal PR times, with the
397 shortest being 4 s for treating oily bilge water (Bian et al., 2019) and the longest being 30 min
398 for arsenic and NOM removal (Mohora et al., 2014). From Table SM-2, it can be inferred that
399 the optimal PR time for high APC-EC performance is dependent on operating conditions. For
example, the ideal PR time has been shown to vary for different electrode materials. Chow and
f
400
oo
401 Pham (Chow and Pham, 2021) found that a 10 min PR time gave the greatest balance of
402
pr
electrode de-passivation, high faradaic efficiency, and low energy consumption when using
e-
403 aluminum electrodes, yet it lowered neither passivation nor energy usage in the case of iron
Pr
404 electrodes. Besides, different PR times were found to have a contradictory impact on the
405 removal efficiency of various pollutants. For instance, it was shown that a 2 min PR time was
al
406 best for eliminating organic matters, but an 8 min PR time was ideal for removing chloride ions
rn
407 (Donneys-Victoria et al., 2020). Moreover, the suggested PR times vary in systems with
u
Jo
408 different electrolyte compositions since, for example, oxyanions such as sulfate and carbonate
409 can contribute to passivation while Cl− ions can de-passivate electrodes by inducing pitting
410 corrosion (Timmes et al., 2010; Dubrawski et al., 2015; van Genuchten et al., 2017; Wellner et
411 al., 2018; W. Zhang et al., 2021). As a result, it is not straightforward to directly compare the
412 results of previous studies due to the varying nature of passivating films and differences in
413 operating conditions such as electrode material, pollutant type, and electrolyte composition.
414 However, the optimal PR time should prevent passivation and ensure adequate coagulant
415 generation since high faradaic efficiency is a prerequisite for high APC-EC performance
416 (Chow et al., 2021).
23
417 From a mechanistic point of view, after each polarity reversal, three main mechanisms
418 have been reported to occur: (1) inversion of local pH around electrodes; (2) occurrence of side
419 reactions; and (3) charging of the electrode double-layer (Chow et al., 2021; Yasri et al., 2022).
420 The inversion of local pH around electrodes could be detrimental or beneficial to process
421 performance. For example, upon the reaction of metal ions generated in the acidic pH at the
422 anode with OH− produced in the basic pH at the cathode (the same electrode that served as the
423 anode before the polarity change), metal (oxy)hydroxides can form (Chow and Pham, 2021).
424 In addition to serving as coagulants, these species could precipitate on both the anode and
f
oo
425 cathode and contribute to passivation (van Genuchten et al., 2017). Thus, before the polarity is
426
pr
reversed, adequate time should be given for these species to transfer into the solution rather
than accumulate on the electrodes. However, the formation of high acidic/alkaline pH near Al
e-
427
428 electrodes after each polarity reversal can promote non-faradaic chemical corrosion of both the
Pr
429 anode and cathode (Fekete et al., 2016; Nidheesh et al., 2022), which aids in detaching the
al
430 precipitates from the electrode surface, removing the passive layer (Chow and Pham, 2021).
rn
431 The electrochemical side reactions can divert the electric current away from the metal
u
Jo
432 corrosion reaction and negatively affect process performance. Side reactions will likely occur
433 after polarity reversal by reactive species at the electrode interface, especially when Fe
434 electrodes are used. The Fe2+ and Fe3+ species generated from the oxidation of the Fe electrode
435 could be reduced and electrodeposited as Fe(0) and, in the subsequent reversal, oxidized again
436 (van Genuchten et al., 2016). Accordingly, fewer Fe species can transfer to the solution over
437 consecutive cycles, which lowers process efficiency. In contrast, Al3+ species have a relatively
438 low reduction potential compared to water hydrolysis, which prevents them from
439 electrodepositing as Al(0); thus, more Al ions can transfer into the solution (Ingelsson et al.,
440 2020). Other possible side reactions that might diminish process efficiency are Cl− and H2O
441 oxidation and the oxidation of H2 gas produced in the prior reversal cycle when the electrode
24
442 served as a cathode (Dubrawski et al., 2015; Ashraf et al., 2019). Charging of the electrode
443 double-layer is another mechanism that could impact treatment efficiency. The time required
444 for charging the double-layer is estimated to be about 2–100 ms for common electrolyte
445 conductivities of 1–20 mS cm−2 in the EC process, where higher conductivity shortens charging
446 time (Ingelsson et al., 2020). Since the main electrochemical reactions may not occur during
447 this time, shorter PR times than the charging time of the double-layer should be avoided.
448 Given all three mechanisms discussed above, under optimal operating conditions, the
application of the APC waveform could effectively mitigate passivation and improve EC
f
449
oo
450 efficacy, especially when Al electrodes were applied. However, the Fe electrode exhibits more
451
pr
complex electrochemical behavior than the Al electrode, which may explain the conflicting
e-
452 findings when Fe electrodes were employed in APC-EC. According to Fig. 4, longer PR times
Pr
453 were typically applied when the Fe electrode was employed compared to the Al electrodes. The
454 suggested PR times in various studies have been mostly longer than 4 min for Fe electrodes,
al
455 while PR times in the 1–5 min range have been recommended for Al electrodes.
u rn
Jo
25
f
oo
pr
e-
Pr
al
u rn
Jo
456
457 Fig. 4. The range of PR times investigated in various research and the optimal PR times
458 recommended for Al and Fe electrodes
26
459 6.1.2. Pulse frequency
460 The pulse frequency (f) is another essential property of the APC waveform that influences
461 electrode passivation and coagulant generation, thus affecting pollutant removal effectiveness
462 (Xu et al., 2021). The pulse frequency can also be adjusted to control APC-EC energy usage,
463 electrode consumption, and sludge generation. A few studies have been conducted to determine
464 the impact of pulse frequency on APC-EC performance, and conflicting results have been
465 reported in the literature (Xu et al., 2017, 2021; J. Zhang et al., 2021). The reviewed studies
466 showed that changes in pulse frequency result in varying effects on performance, so the
f
oo
467 recommended frequencies for optimal APC-EC performance varied greatly from 1 Hz for
468
pr
removing Cu2+ and COD in Fe APC-EC (Xu et al., 2021) to 5 kHz for eliminating Zn2+ and
Mn2+ from smelting wastewater using Fe/Al electrode pairs (Xu et al., 2017). These findings
e-
469
470 indicate that the optimal pulse frequency range for favorable APC-EC performance is still
Pr
471 unclear, and thus, further research is required to find the relationship between the tested
al
472 frequencies, operational conditions, and process performance.

rn
473
u
474 6.1.3. Duty cycle

Jo
475 The duty cycle plays a pivotal role in APC-EC and, similar to PDC-EC, influences the
476 energy usage and the number of dissolved metal cations from the electrodes. A handful of
477 studies investigated the impact of the duty cycle on APC-EC and optimized this variable to
478 achieve high treatment performance (Asaithambi et al., 2016, 2021; Xu et al., 2017; J. Zhang
479 et al., 2021). The reviewed studies reported that duty cycles of around 0.3–0.5 allowed the best
480 balance of electrode de-passivation, enhanced pollutant removal efficiency, and minimized
481 energy usage. In most cases, the duty cycle had a non-linear impact on pollutant removal
482 efficiency, such that by increasing the duty cycle, the pollutant removal efficiency first
483 increased and then decreased (Asaithambi et al., 2016, 2021; J. Zhang et al., 2021).
27
484
485 6.2. Comparison of APC-EC and DC-EC techniques
486 Table 2 summarizes the studies that compared the APC-EC technique to the conventional
487 DC-EC for treating various contaminants under different operating conditions. According to
488 Table 2, in most studies, APC-EC outperformed DC-EC in removing pollutants and
489 maintaining high treatment effectiveness over consecutive cycles (Mao et al., 2008; Eyvaz et
490 al., 2009; Pi et al., 2014; Ozyonar and Karagozoglu, 2015; Eyvaz, 2016; Jiang et al., 2018; Xin
491 et al., 2018; Alimohammadi et al., 2019; Donneys-Victoria et al., 2019; Asaithambi et al., 2021;
f
oo
492 Xu et al., 2021; J. Zhang et al., 2021; Yasri et al., 2022). Although improved efficiency in APC-
493
pr
EC is often claimed to be the direct consequence of reduced passivation, only a few authors
e-
494 (Mao et al., 2008; Chow et al., 2021; Chow and Pham, 2021; Yasri et al., 2022) analyzed the
Pr
495 properties of the electrode surface through material characterization methods.
496 The electrochemical reactions sweep between anode and cathode due to polarity reversal
al
497 in APC-EC, so gas formation and associated bubbling as well as electrode corrosion inverse
rn
498 intermittently, leading to a well-mixed situation in the EC cell, which can decrease the buildup
u
Jo
499 of the electrode passivating layer (Madhavan and Antony, 2021). Following the polarity
500 reversal, H2 gas generation at the cathode (the electrode that functioned as the anode before the
501 polarity change) can detach passivating layers formed on the electrode surface (Bian et al.,
502 2019; Chow et al., 2021). Meanwhile, the passive layers on the anode (the electrode that
503 formerly acted as the cathode) can be removed by the corrosion of the underneath electrode
504 (Bian et al., 2019; Chow et al., 2021). Besides, when the alkaline environment at the cathode
505 turns acidic after polarity reversal, the materials precipitated on the electrode surface may
506 dissolve, decreasing the formation rate of passive layers (Fekete et al., 2016; Chow et al., 2021;
507 Syam Babu et al., 2021; Yasri et al., 2022). Reduced passivation improves the EC's capability
508 to generate coagulants and enhances pollutant removal efficiency.
28
509 Table 2. The summary of the reported studies on the comparison of APC-EC with the DC-EC technique
Process performance
Opt. APC
Pollutant and
Anode/cathode waveform I, U, or j Removal Electrode Major outcomes References
solution Energy consumption Sludge production Operating
parameters efficiency consumption
(ENC) (SLP) cost (OC)
(RE) (ELC)
Al/Al COD in – 2A APC-EC: higher APC-EC: 30% less – – – Prevented ELP and uniform Al Mao et al.
synthetic WW RE removal than ENC than DC-EC corrosion in APC-EC; Higher RE (2008)
DC-EC and lower ENC in APC-EC than in
DC-EC
Al/Al Disperse and Trev= 150 s 105 A m−2 APC-EC: – – – APC-EC: Reduced ELP in APC-EC; Reduced Eyvaz et al.
reactive dyes 57–89% TOC 1.3–2.61 $ REs over time in DC-EC; Higher (2009)
in synthetic 63–99.9% dye (kg TOC)−1 REs in APC-EC than in DC-EC;
WW DC-EC: DC-EC: Lower OC in APC-EC than in DC-
of
49–81% TOC 1.43–3.43 $ EC
59–96% dye (kg TOC)−1
ro
Al/Al Silica in tap Trev= 900 s 48 A m−2 APC-EC: – APC-EC: – – ELP occurred in both techniques; Gelover-
-p
water 64.3% silica 0.0373 kg m−3 Slightly reduced RE and 6% higher Santiago et al.
DC-EC DC-EC: ELC in APC-EC than in DC-EC (2012)
re
66.5% silica 0.0353 kg m−3
1850 A m−2 –
lP
Al/Al Methyl Orange Trev= 15 s APC-EC: APC-EC: APC-EC: APC-EC: Delayed ELP in APC-EC; 15% Pi et al. (2014)
in synthetic 97% color 44 kWh (kg MO)−1 4.1 kg (kg MO)−1 17.2 kg (kg MO)−1 increased RE, 20% reduced ENC,
WW DC-EC: DC-EC: DC-EC: DC-EC: 11% higher ELC, and 6% less SLP
na
82% color 55 kWh (kg MO)−1 3.7 kg (kg MO)−1 18.3 kg (kg MO)−1 in APC-EC than in DC-EC
Al/Al TSS, turbidity, Trev= 300 s 1.2 V APC-EC & DC- APC-EC/biochar: – – – Reduced ELP in APC-EC, 57% less Lobo et al.
ur
and COD in EC: 0.079 kWh m−3 ENC in APC-EC than in DC-EC (2016)
real produced 99% TSS DC-EC/biochar:
Jo
water 99% turbidity 0.183 kWh m−3
5–14% COD
Al/Al CN‾, Ni, Cu, Trev= 60 s 80 A m−2 APC-EC: >20% – APC-EC: – – Improved REs and 6% higher ELC Pertile and
and Zn in higher CN‾, Ni, 36.29 g m−3 in APC-EC than in DC-EC Birriel (2017)
simulated and Cu removal DC-EC:
galvanic than DC-EC; 34.13 g m−3
effluent >98% Zn removal
in APC-EC and
DC-EC
Al/Al NaCl and Trev= 180 s 37.9 V – APC-EC: APC-EC: – – Effective de-passivation in APC- Wellner et al.
NaHCO3, in 2.56 kWh m−3 0.448 gr min−1 EC; 8% and 7% higher ENC and (2018)
synthetic WW DC-EC: DC-EC: ELC in APC-EC than in DC-EC
2.36 kWh m−3 0.419 gr min−1
29
Process performance
Opt. APC
Pollutant and
(RE) (ELC)
Al/Al Oil in Trev= 4 s 36 A m−2 APC-EC & DC- APC-EC: – – – Reduced ELP in APC-EC; Lower Bian et al.
simulated EC: 0.787-0.936 kWh m−3 ENC in APC-EC than in DC-EC (2019)
bilge water >99% oil DC-EC: after 24 h; >158% increase in ENC
0.378-0.977 kWh m−3 after 24 h in DC-EC
Al/Al Silica in real Trev= 20 s 160 A m−2 APC-EC & DC- APC-EC: APC-EC: – APC-EC: Soft powdery surface layer in APC- Yasri et al.
blowdown EC: 0.52 kWh m−3 156 g m−3 0.40 $ m−3 EC; Hard scale on the electrode in (2022)
water >95% SiO2 DC-EC; Lower ENC in APC-EC
than in DC-EC; 40% reduced RE
over time in DC-EC
Fe/Al Cr(VI) in Trev= 240 s 56–222 A APC-EC & DC- APC-EC: – – – Slower anode passivation and lower Keshmirizadeh
of
synthetic WW m−2 EC: 4-58 kWh m−3 ENC in APC-EC than in DC-EC et al. (2011)
98–99.9% Cr(VI)
ro
Al/Al, Fe/Fe*, Rhodamine 6G – 109 A m−2 APC-EC: APC-EC: APC-EC: – – Avoided ELP in APC-EC; Higher Zaleschi et al.
Fe/Al in synthetic 98% dye 6.84 kWh (kg dye)−1 1.73 kg Fe (kg RE and less ENC and ELC in APC- (2014)
-p
WW dye)−1 EC than in DC-EC; Fastest dye
removal with Fe/Fe
re
Al/Al*, Fe/Fe COD, color, Trev= 150 s 150 A m−2 APC-EC: APC-EC: APC-EC: APC-EC: APC-EC: Prevented ELP in APC-EC; 11% Eyvaz (2016)
lP
turbidity, TN, 91% COD 1.24 kWh (kg COD)−1 0.63 kg Al (kg 1.56 kg (kg COD)−1 2.80 $ m−3 higher COD removal and ~12%
and TP in real DC-EC: DC-EC: COD)−1 DC-EC: DC-EC: less ENC, ELC, SLP, and OC in
brewery 80% COD 1.41 kWh (kg COD)−1 DC-EC: 1.78 kg (kg COD)−1 3.18 $ m−3 APC-EC than in DC-EC
na
factory WW 0.72 kg Al (kg
COD)−1
Al/Fe*, Fe/Al Fluoride in
drinking water
Trev= 120 s
γ= 0.25
120 A m−2 APC-EC:
95% F‾ (20%
ur
APC-EC:
0.9 kWh m−3
APC-EC:
1.42 kg m−3
APC-EC:
0.108 kg m−3
– Avoided ELP and super FEs in
APC-EC
Alimohammadi
et al. (2019)
Jo
higher RE than
DC-EC)
Al/Fe, Fe/Al* Total and Trev= 120 s 90 A m−2 APC-EC: APC-EC: APC-EC: APC-EC: – APC-EC: 5% and 7% higher TH Yaghmaeian et
calcium γ= 0.25 98.26% TH 0.90 kWh m−3 1.03 kg m−3 0.098 kg m−3 and CH removal, 64% less ENC, al. (2020)
hardness in 87.69% CH DC-EC: DC-EC: DC-EC: 51% reduced ELC, and 10% lower
drinking water DC-EC: 2.47 kWh m−3 2.12 kg m−3 0.109 kg m−3 SLP than DC-EC
93.48% TH
80.23% CH
Al/Al, Fe/Fe*, Color and f= 50 Hz 40 A m−2 APC-EC: APC-EC: – APC-EC: lower SLP – Less ELP in APC-EC than in DC- Asaithambi et
Al/Fe, Fe/Al COD in real γ= 0.45 100% color 3.2 kWh m−3 than DC-EC EC; 9% higher REs and less ENC al. (2021)
distillery 95% COD DC-EC: in APC-EC than DC-EC; Higher
industrial DC-EC: 3.5 kWh m−3 COD removal and lower ENC with
effluent 90.57% color Fe/Fe
86.54% COD
30
Process performance
Opt. APC
Pollutant and
(RE) (ELC)
Fe/Fe Acid, basic, Trev= 300 s 2.73–27.32 A APC-EC: slightly APC-EC: APC-EC: 4% – – APC-EC: 9% and 4% less ENC and Secula et al.
and reactive m−2 enhanced REs 4.65 kWh (kg dye) −1 lower ELC than ELC than DC-EC (2013)
dyes in than DC-EC DC-EC: DC-EC
synthetic WW 5.12 kWh (kg dye) −1
Fe/Fe COD, TOC, Trev= 300 s 200 A m−2 H2O2/APC-EC: H2O2/APC-EC: H2O2/APC-EC: H2O2/APC-EC: H2O2/APC- Slower ELP in APC-EC than in Ozyonar and
phenol, CN‾, 92% COD 4.41 kWh m−3 1.08 kg m−3 1.89 kg m−3 EC: DC-EC; 35-42% higher REs in Karagozoglu
and SCN‾ in 90% TOC 5.64 € m−3 APC-EC than in DC-EC (2015)
raw coke WW H2O2/DC-EC:
50.2% COD
51% TOC
of
Fe/Fe COD, color, Trev= 3600 1.5 A APC-EC: – APC-EC: – – Reduced ELP in APC-EC; 137% Cesar Lopes
and turbidity s (PR 95% COD 0.2412 kg m−3 increase in ELC in APC-EC than Geraldino et al.
ro
in real dairy between 90% color DC-EC: DC-EC; Decreased REs over time (2016)
industry each exp.) 99% turbidity 0.1017 kg m−3 in DC-EC
-p
effluent
re
Fe/Fe COD and color Trev= 900 s 13 A m−2 APC-EC: APC-EC: – – – Reduced passive layer formation Asaithambi et
in real γ= 0.5 87% COD 1.31 kWh m−3 (lower and 20% higher COD removal in al. (2016)
lP
distillery 95% color ENC than DC-EC) APC-EC than in DC-EC
industrial DC-EC:
effluent 67% COD
na
Fe/Fe Zn2+, Cd2+, and Trev= 10 s 50–200 A APC-EC: higher APC-EC: lower ENC – – – The higher overall efficiency of Xu et al.
Mn2+ in real f= 5 kHz m−2 REs at 50 A m−2 at 50 A m−2 DC-EC than APC-EC. Greater REs (2018)
smelting WW γ= 0.4 DC-EC: higher
REs at 100-200 A ur
DC-EC: lower ENC at
150-200 A m−2
and lower ENC at lower j in APC-
EC
Jo
m−2
Fe/Fe Synthetic GW Trev= 1260, 8 A m−2 – APC-EC: APC-EC: – – Greater mass of the surface layer in Müller et al.
3150 s 0.21–0.22 kWh m−3 FE= 0.6–0.72 APC-EC than in DC-EC; 18-24% (2019)
DC-EC: DC-EC: less ENC and lower FEs in APC-
0.26 kWh m−3 FE= 0.75 EC than in DC-EC
Fe/Fe Cr(VI) in f= 5 kHz APC-EC: APC-EC: APC-EC: – APC-EC: – Reduced ELP in PDC-EC and Zhou et al.
synthetic WW γ= 0.3 +11, -3 A m−2 99.4% total Cr 760 kWh (kg 1.12 kg m−3 APC-EC; 80% less ENC and 90% (2020)
PDC-EC: PDC-EC: Cr(VI))−1 PDC-EC: more ENC in APC-EC than in DC-
25 A m−2 99.5% total Cr PDC-EC: 1.30 kg m−3 EC and PDC-EC, respectively; 40%
DC-EC: DC-EC: 400 kWh (kg DC-EC: and 14% lower SLP in APC-EC
20 A m−2 99.3% total Cr Cr(VI))−1 1.86 kg m−3 than in DC-EC and PDC-EC,
DC-EC: respectively
3800 kWh (kg
Cr(VI))−1
31
Process performance
Opt. APC
Pollutant and
(RE) (ELC)
Fe/Fe Cu2+ and COD f= 1 Hz 2 A m−2 Electro- Electro-Fenton/APC- – Electro- – Avoided ELP in APC-EC; 9% Xu et al.
in simulated Fenton/APC-EC: EC: Fenton/APC-EC: higher COD removal, 25% less (2021)
plating WW 99.59% Cu2+ 0.170 kWh m−3 0.928 kg m−3 ENC, and 9% less SLP in APC-EC
90.21% COD Electro-Fenton/DC- Electro-Fenton/DC- than in DC-EC
Electro- EC: EC:
Fenton/DC-EC: 0.226 kWh m−3 1.019 kg m−3
98.60% Cu2+
81.68% COD
Fe/Fe Polyvinyl f= 0.5 kHz 10 A m−2 APC-EC: APC-EC: APC-EC: APC-EC: – Reduced ELP in APC-EC; Stronger J. Zhang et al.
alcohol in γ= 0.3 99.73% PVA 0.049 kWh m−3 0.105 kg m−3 0.0674 g adsorption of flocs in APC-EC; 7% (2021)
of
synthetic WW DC-EC: DC-EC: DC-EC: DC-EC: higher RE and 90%, 45%, and 44%
92.82% PVA 0.480 kWh m−3 0.190 kg m−3 0.1193 g less ENC, ELC, and SLP in APC-
ro
EC than in DC-EC
-p
Fe, Ti Arsenic in Trev= 9 s 50 mA APC-EC: APC-EC: – – – Eliminated ELP in APC-EC; 40% Xin et al.
synthetic GW 98.4% As(tot) 0.101 kWh m−3 lower ENC in APC-EC than in DC- (2018)
re
DC-EC: DC-EC: EC
94.4% As(tot) 0.167 kWh m−3
lP
Fe/Ti Arsenic in Trev= 9 s: 40 mA APC-EC: APC-EC: – – – APC-EC: 85% higher RE than DC- Jiang et al.
synthetic GW 15 s 92% As(tot) 0.11 kWh m−3 EC (2018)
na
DC-EC:
7% As(tot)
Mg/Mg Indigo carmine

in synthetic
Trev= 450 s 50 A m−2 APC-EC: 43%
higher NPOC
ur
APC-EC:
22.1 kWh (kg COD)−1
– – – Avoided ELP and the formation of
highly branched flocs in APC-EC;
Donneys-
Victoria et al.
Jo
WW removal than DC- DC-EC: 55% higher ENC in APC-EC than (2019)
EC; Equal dye 14.3 kWh (kg COD)−1 in DC-EC; The formation of tightly
removal in APC- packed flocs in DC-EC
EC and DC-EC
Mg/Mg*, Indigo carmine Trev= 120 s 0.34 A APC-EC: – – – – APC-EC: 33% higher NPOC Donneys-
Mg/Al and Cl‾ in 90.4% NPOC removal and 61% less Cl− removal Victoria et al.
synthetic WW 7.8% Cl− than DC-EC (2020)
DC-EC:
57.1% NPOC
69.1% Cl−
32
Process performance
Opt. APC
Pollutant and
(RE) (ELC)
Al/Al*, Fe/Fe, Synthetic GW Trev= 600 s 10–130 A – APC-EC: higher ENC APC-EC: less FE – – APC-EC: ELP occurred for Fe/Fe; Chow and
Al/Ti-IrO2, m−2 than DC-EC for than DC-EC for Reduced ELP for Al/Al, Al/Ti-IrO2, Pham (2021)
Fe/Ti-IrO2 Fe/Fe; less ENC than Fe/Fe; and Fe/Ti-IrO2
DC-EC for Al/Al Comparable FE to
that of DC-EC for
Al/Al
MS/MS COD and oil Trev= 1.9 214 A m−2 APC-EC: APC-EC: APC-EC: APC-EC: increased APC-EC: Reduced ELP in APC-EC; Less Madhavan and
in Synthetic min 90% COD Higher ELC than DC- Lesser ENC than SLP compared to 0.65 $ (kg ENC and higher COD removal, FE, Antony (2021)
produced 88% oil EC DC-EC DC-EC COD)−1 and SLP in APC-EC than in DC-
water EC
of
St/St COD and color Trev= 5 min 144 A m−2 APC-EC: APC-EC: – APC-EC: – Reduced ELP in APC-EC; Reduced Sanei and
ro
in real leachate 35% COD 39.8 kWh (kg COD)−1 12 kg(TSS) (kg COD removal over time in DC-EC; Mokhtarani
50% color COD)−1 18% and 14% higher COD and (2022)
-p
color removal, and 12% and 51%
less ENC and SLP in APC-EC than
re
in DC-EC
510
lP
I: Current; U: Voltage; j: Current Density; FE: Faradaic efficiency; WW: Wastewater; GW: Groundwater; MS: Mild steel; St: Steel
511
na
ur
Jo
33
512 Polarity reversal also allows a uniform distribution of the oxidation reactions between
513 electrodes, improving coagulant mass transfer and providing greater contact between
514 contaminants and coagulant agents in the solution (Pertile and Birriel, 2017; Gobbi et al., 2018;
515 Donneys-Victoria et al., 2019). It has been stated that the greater the distance between
516 electrodes, the longer the route the ions must take from one electrode to the other, and the
517 greater the likelihood that polarity may reverse while the coagulants are still in migration. This
518 increases their permanency and route, enhancing the likelihood of floc formation through
519 interaction with contaminants (Gobbi et al., 2018). Furthermore, flocs generated in APC-EC
f
oo
520 have been shown to have a more robust adsorption capacity than those produced in DC-EC
521
pr
(Zhou et al., 2020; Xu et al., 2021; J. Zhang et al., 2021). For example, Zhou et al. compared
the characteristics of flocs produced by APC-EC, PDC-EC, and DC-EC techniques and found
e-
522
523 that the flocs formed in APC-EC had a larger surface to adsorb Cr(VI) than those in DC-EC;
Pr
524 however, the flocs in PDC-EC have been reported to have a better spread performance than
al
525 those of others (Zhou et al., 2020).

rn
526 Several explanations have been proposed for the possible lower contaminant removal in
u
Jo
527 APC-EC compared to DC-EC, such as unsuccessful electrode de-passivation and inadequate
528 coagulant production, which can arise from improper selection of operating conditions,
529 including electrode material, current density, and waveform characteristics (e.g., PR time)
530 (Gelover-Santiago et al., 2012; Xu et al., 2018). For example, it has been asserted that at very
531 brief PR times, bubble gas generation from both the anode and cathode could be high and
532 instantaneous flotation could occur. As a result, coagulants could rise to the top of the EC cell
533 even before interacting with pollutants. In addition, enhanced bubble generation can impede
534 the transmission of electrons between electrodes, which can be detrimental to electrochemical
535 reactions and result in diminished pollutant removal (Madhavan and Antony, 2021).
34
536 Regarding energy efficiency, most authors demonstrated that reversing the polarity of the
537 electrodes reduced the voltage required compared to when a direct current was used (Lobo et
538 al., 2016; Xin et al., 2018; Yaghmaeian et al., 2020; Zhou et al., 2020; Asaithambi et al., 2021;
539 Madhavan and Antony, 2021; Xu et al., 2021; J. Zhang et al., 2021; Yasri et al., 2022). In the
540 case of the passivated electrode surface, passive overpotential—one of the elements
541 contributing to cell potential—will be greater. Periodic polarity reversal in APC-EC can lower
542 the passive overpotential and lead to diminished cell voltage, which eventually will reduce
543 energy utilization compared to DC-EC (Madhavan and Antony, 2021). Changing the current
f
oo
544 waveform from DC to APC, for example, has been proven to reduce energy consumption by
545
pr
up to 90% (J. Zhang et al., 2021). Of course, in this study, in addition to passivation reduction,
the current breaks during original and reversed polarity also helped to reduce energy
e-
546
547 consumption significantly. On the contrary, the interruption of the circuit caused by the reversal
Pr
548 cycles of the polarity might increase the cell voltage for a few seconds afterward, resulting in
al
549 higher energy consumption (Bian et al., 2019; Donneys-Victoria et al., 2019). Bian et al.
rn
550 reported that the energy usage under APC power was higher than under DC power at the
u
551 beginning of the operation due to the higher voltage at the start of every shift of the electric
Jo
552 field direction (Bian et al., 2019). This research group (Bian et al., 2019) reported that the
553 advantage of APC power became apparent after 24 hours of operation when APC-EC
554 consumed less power than DC-EC, probably owing to reduced passivation.
555 The literature includes contradictory findings regarding electrode consumption. Some
556 authors reported that diminished passivation in APC-EC led to increased current density and
557 higher electrode consumption (and thus higher faradaic efficiency), while in DC-EC, the
558 amount of material lost from the electrodes was smaller due to passivation (Pi et al., 2014;
559 Cesar Lopes Geraldino et al., 2016; Pertile and Birriel, 2017; Wellner et al., 2018). Based on
560 the literature, electrode usage has often been higher in APC-EC than in DC-EC when Al
35
561 electrodes are used. At prolonged PR times, acidic/basic boundary layers around the Al
562 electrode have adequate time to develop after polarity reversal, which contributes to the
563 chemical corrosion of Al electrodes and de-passivation (Fuladpanjeh‐Hojaghan et al., 2019;
564 Yasri et al., 2022). Another explanation for higher electrode consumption in APC-EC could be
565 the lower possibility of side reactions caused by polarity reversal when the Al electrode is used
566 since aluminum is less reactive than iron within water's electrochemical stability range
567 (Roberge, 2008). In contrast, some studies indicated that fewer electrodes were consumed in
568 APC-EC than in DC-EC (Secula et al., 2013; Zaleschi et al., 2014; Eyvaz, 2016; Yaghmaeian
f
oo
569 et al., 2020; J. Zhang et al., 2021). This behavior can be attributed to uniform electrode
570
pr
corrosion in APC-EC caused by cyclical energization between anode and cathode, ensuring
longer electrode life (Eyvaz, 2016; J. Zhang et al., 2021). Also, shorter actual electrification
e-
571
572 times in APC-EC can reduce electrode consumption (Yaghmaeian et al., 2020). Moreover,
Pr
573 unsuccessful electrode de-passivation and the occurrence of electrochemical side reactions in
al
574 APC-EC can result in decreased electrode consumption and coagulant production (Müller et
rn
575 al., 2019; Chow and Pham, 2021).

u
Jo
576 According to almost all the studies reviewed, the amount of sludge generated during
577 APC-EC was less than that produced during DC-EC (Eyvaz, 2016; Yaghmaeian et al., 2020;
578 Zhou et al., 2020; Asaithambi et al., 2021; Xu et al., 2021; J. Zhang et al., 2021; Sanei and
579 Mokhtarani, 2022). For instance, Zhang et al. indicated that sludge production under APC
580 conditions was about 44% less than in DC (J. Zhang et al., 2021). The reason for this could be
581 the shorter electrification time in APC-EC compared to DC-EC, which results in less electrode
582 usage and sludge generation. As another example, it was discovered that APC-EC produced
583 about 40% and 14% less sludge than PDC-EC and DC-EC, respectively, when treating Cr(VI)
584 from synthetic wastewater (Zhou et al., 2020). In contrast, it was reported that reversing the
585 electrode polarity enhanced sludge production owing to a significantly improved electrode
36
586 corrosion and coagulation process (Madhavan and Antony, 2021). Finally, since the overall
587 energy usage, electrode consumption, and sludge generation in most studies were lower in the
588 case of APC-EC, the operating cost for this technique is expected to be less compared to that
589 of DC-EC, as proved in some studies (Eyvaz et al., 2009; Eyvaz, 2016).
590
591 7. Sinusoidal alternating current electrocoagulation (AC-EC)
592 Several studies have operated EC with sinusoidal alternating current (AC-EC) to reduce
593 passivation and improve efficiency. The anode and cathode in AC-EC are switched periodically
f
oo
594 based on the sinusoidal waveform; thus, each electrode is potentially an exchangeable anode
595
pr
or cathode. An overview of studies that evaluated the passivation mitigation capability of AC-
e-
596 EC and compared its performance with DC-EC is presented in Table 3. As indicated in Table
Pr
597 3, AC-EC has been mainly operated at 50 Hz and evaluated with different electrode materials
598 for various applications. Most authors have reported that AC-EC and DC-EC exhibit
al
599 comparable pollutant removal, with AC-EC having a slight advantage (Vasudevan and
rn
600 Lakshmi, 2012; Kamaraj et al., 2013; Karamati-Niaragh et al., 2019; Kong et al., 2020; Xu et
u
601 al., 2020). Higher removal efficiencies in AC-EC could probably be due to the occasional shift
Jo
602 in the anode and cathode operations, which reduces the load on the function of each electrode,
603 postpones passivation, and improves metal (oxy)hydroxide formation (Alkhatib et al., 2020).
604 Moreover, similar to APC-EC, the metallic cations scatter more uniformly throughout the cell
605 in AC-EC due to the corrosion of both the anode and cathode, which improves coagulant mass
606 transfer and facilitates the interactions of coagulants with the pollutant, thereby enhancing
607 efficiency. It was also found that the flocs produced by AC-EC had many pores, a loose
608 structure, and a large specific surface area, which was favorable for the adsorption of heavy
609 metals, while the flocs formed by DC-EC had a compact structure. As such, the Cr(VI) content
610 adsorbed by Fe(OH)3 flocs in AC-EC was more significant than in DC-EC (Xu et al., 2019).
37
611 Table 3. Summary of reported studies on the comparison of AC-EC with DC-EC technique
Process performance
Pollutant and AC
Anode/cathode I, U, or j Sludge Major outcomes Reference
solution frequency Pollutant removal Energy consumption Electrode consumption Operation
production
efficiency (RE) (ENC) (ELC) cost (OC)
(SLP)
Al/Al F‾ in deionized 50 Hz 100 A AC-EC: AC-EC: – – – Avoided ELP and uniform Al corrosion in Vasudevan
water m−2 93.0% F‾ 1.88 kWh m−3 AC-EC; Slightly higher RE and 26% less et al. (2011a)
DC-EC: DC-EC: ENC in AC-EC than in DC-EC
91.5% F‾ 2.54 kWh m−3
Al/Al Cd in synthetic 50 Hz 20 A m−2 AC-EC: AC-EC: – – – Slightly higher RE and 55% less ENC in Vasudevan
WW 97.5% Cd 0.45 kWh m−3 AC-EC than DC-EC et al. (2011b)
DC-EC: DC-EC:
96.2% Cd 1.00 kWh m−3
of
Al/Al Oil, color, and AC-EC: 3A AC-EC: AC-EC: AC-EC: – – Reduced ELP in AC-EC; Similar RE and Cerqueira et
ro
turbidity in 60 Hz 94.3% oil 0.28 kWh m−3 0.12 kg m−3 ENC in AC-EC and APC-EC; 33% less al. (2014)
simulated APC-EC: APC-EC: APC-EC: APC-EC: ELC in AC-EC than in APC-EC
-p
produced water Trev= 5 94.1% oil 0.28 kWh m−3 0.18 kg m−3
min
re
Al/Al NO3‾ in tap water 50 Hz 70–80 A AC-EC: Slightly higher ENC AC-EC: – AC-EC: Minimized ELP and uniform Al corrosion in Karamati-
m−2 76.67% NO3‾ in AC-EC than DC- 4.96 kg Al (kg NO3‾)−1 29 $ (kg AC-EC; 75% reduced ELC and 46% lower Niaragh et
lP
DC-EC: EC. DC-EC: NO3‾)−1 OC in AC-EC than in DC-EC for similar RE al. (2019)
74.67% NO3‾ 19.96 kg Al (kg DC-EC:
na
NO3‾)−1 54 $ (kg
NO3‾)−1
Al/Al COD and total 50 Hz 43 A m−2 AC-EC: – AC-EC: – – Decreased ELP in AC-EC; 23.5% and Alkhatib et
phosphorus in
secondary treated
66.8% COD
68.2% TP
ur 0.15 g
DC-EC:
22.2% higher COD and TP removal, and
93% less ELC in AC-EC than DC-EC
al. (2020)
Jo
WW DC-EC: 2.12 g
43.3% COD
46% TP
Al/Al Nickel in 50 Hz 50–90 A Almost equal AC-EC: AC-EC: – – Uniform Al corrosion in AC-EC; 16% and Arabameri et
synthetic WW m−2 nickel removal in 29.2 kWh (kg Ni)−1 1.20 kg Al (kg Ni)−1 48% lower ENC and ELC in AC-EC than in al. (2022)
AC-EC and DC- DC-EC: DC-EC: DC-EC for similar RE
EC 34.9 kWh (kg Ni)−1 2.3 kg Al (kg Ni)−1
Al/Al*, Fe/Fe COD, color, and 60 Hz 18.5– AC-EC & DC- – Almost double ELC in – – Higher COD removal with Al than with Fe Rodrigues
turbidity in 55.5 A EC: DC-EC than AC-EC. in both techniques; 50% less ELC in AC-EC Pires da
synthetic oil-in- m−2 >92% COD than in DC-EC for similar REs Silva et al.
water emulsion >96% color (2015)
>99.5% turbidity
38
Process performance
Pollutant and AC
production
(SLP)
Al/Al*, Fe/Fe F‾ in distilled – 40 V AC-EC: – – – – Higher REs with Al than with Fe; 5.75% Ghanizadeh
water 81.75% F‾ less RE in AC-EC than in DC-EC et al. (2016)
DC-EC:
87.50% F‾
Al/Al, Fe/Fe* Acid Red 18 in 50 Hz 30–130 AC-EC: Higher ENC in AC- AC-EC: Lower SLP in AC-EC: Reduced ELP and uniform electrode Payami
synthetic WW A m−2 71% dye (Fe) EC for Al; Higher 0.15 g (Fe) AC-EC than 9.4 $ (kg corrosion in AC-EC; 14% less RE (with Fe), Shabestar et
42% dye (Al) ENC in DC-EC for 0.25 g (Al) DC-EC dye)−1 92% and 64% lower Fe and Al usage, and al. (2021)
DC-EC: Fe. DC-EC: DC-EC: 36% lower OC in AC-EC than in DC-EC;
85% dye (Fe) 1.78 g (Fe) 14.6 $ (kg Higher efficiency of AC-EC with Fe
42% dye (Al) 0.70 g (Al) dye)−1
20 A m−2 – – –
of
Fe/Fe Cd in synthetic 50 Hz AC-EC: AC-EC: Uniform Fe corrosion in AC-EC; Slightly Vasudevan
WW 98.1% Cd 0.734 kWh m−3 higher RE and 48% lower ENC in AC-EC and Lakshmi
ro
DC-EC: DC-EC: than in DC-EC (2012)
97.3% Cd 1.413 kWh m−3
-p
Fe/Fe Cr(VI) in AC-EC: 2.7 A m−2 AC-EC, PDC-EC, AC-EC: AC-EC: – – Reduced ELP in AC-EC than in DC-EC and Xu et al.
synthetic WW 50 Hz DC-EC: 0.0267 kW h−1 0.0128 g PDC-EC; Better adsorption of flocs in AC- (2019)
re
PDC-EC: >99% Cr(VI) PDC-EC: DC-EC: EC; 13% and 6% less ENC in AC-EC than
f= 1 kHz, (removal rate: 0.0284 kW h−1 0.0149 g in DC-EC and PDC-EC; 14% less ELC in
lP
γ= 0.2 AC>PDC>DC) DC-EC: AC-EC than in DC-EC; Reduced FE with
0.0307 kW h−1 time in DC-EC
na
Fe/Fe COD in 50 Hz 1000 A Fenton/AC-EC: – – Lower SLP in – Fenton/AC-EC: Reduced ELP, slightly Kong et al.
simulated m−3 91.0% COD Fenton/AC-EC higher RE, a larger specific area of flocs, (2020)
ur
electroplating Fenton/DC-EC: than in and less SLP than Fenton/DC-EC
WW 87.25% COD Fenton/DC-EC
Jo
Fe/Fe Cu2+ in synthetic 50 Hz 0.25 A AC-EC: AC-EC: AC-EC: AC-EC: – Prevented ELP and enhanced adsorption of Xu et al.
and real printed m−2 99.2% Cu2+ 0.99 kWh m−3 12 g m−3 18.9 g m‾3 Cu2+ in AC-EC; Slightly higher RE, 26%, (2020)
circuit WW DC-EC: DC-EC: DC-EC: DC-EC: 45%, and 54% lower ENC, ELC, and SLP
97.5% Cu2+ 1.342 kWh m−3 22 g m−3 41.2 g m‾3 in AC-EC than in DC-EC
Fe-Fe Total phosphorus 50 Hz 21.2 A AC-EC: – – – – Increased specific area and better adsorption Zhou et al.
in synthetic WW m−2 90.9% TP (higher of flocs in AC-EC than in DC-EC (2021)
RE than DC-EC)
Fe/Fe*, SS/SS Pb and Zn in real – 60 A m−2 AC-EC: AC-EC: AC-EC: AC-EC: – Slightly lower REs and 65%, 39%, and 8% Mansoorian
battery industry 96.7% Pb 0.69 kWh m−3 0.69–0.72 kg Fe m−3 0.084 kg m‾3 less ENC, ELC, and SLP in AC-EC than in et al. (2014)
WW 95.2% Zn DC-EC: DC-EC: DC-EC: DC-EC; Higher efficiencies with Fe than
DC-EC: 1.97 kWh m−3 1.13–1.17 kg Fe m−3 0.091 kg m‾3 with SS
97.2% Pb
95.5% Zn
39
Process performance
Pollutant and AC
production
(SLP)
Fe/Fe*, SS/SS Malathion in – 100 A AC-EC: AC-EC: AC-EC: AC-EC: – Similar RE and SLP in both techniques; Khaghani et
synthetic WW m−2 95.6% malathion 0.91 kWh m−3 1.06 kg Fe m−3 0.093 kg m‾3 71% and 42% less ENC and ELC in AC-EC al. (2020)
DC-EC: DC-EC: DC-EC: DC-EC: than in DC-EC
95.8% malathion 3.12 kWh m−3 1.82 kg Fe m−3 0.095 kg m‾3
Zn/Zn Cd in synthetic 50 Hz 20 A m−2 AC-EC: AC-EC: – – – Reduced ELP and uniform Zn corrosion in Vasudevan
WW 97.8% Cd 0.665 kWh m−3 AC-EC; 46% lower ENC in AC-EC than in and Lakshmi
DC-EC: DC-EC: DC-EC for almost equal RE (2011)
96.9% Cd 1.236 kWh m−3
Zn/Zn Fe in water 50 Hz 6 A m−2 AC-EC: AC-EC: – – – Diminished ELP and uniform Zn corrosion Vasudevan
99.6% Fe 0.625 kWh m−3 in AC-EC; 37% less ENC in AC-EC than in (2012)
of
DC-EC: DC-EC: DC-EC for almost equal RE
99.1% Fe 0.991 kWh m−3
ro
Mg/Mg Arsenate in water 50 Hz 20 A m−2 AC-EC: AC-EC: – – – AC-EC: 30% less ENC than DC-EC for Vasudevan
98.3% arsenate 0.724 kWh m−3 almost equal RE. et al. (2012)
-p
DC-EC: DC-EC:
1.035 kWh m−3
re
97.9% arsenate
Mg/Mg Copper in water 50 Hz 2.5 A m−2 AC-EC: AC-EC: – – – ELP in AC-EC in the presence of carbonate; Kamaraj et
lP
97.8% Cu 0.634 kWh m−3 Uniform Mg corrosion in AC-EC; 36% less al. (2013)
DC-EC: DC-EC: ENC in AC-EC than in DC-EC for almost
0.996 kWh m−3
na
97.2% Cu equal RE
Pb/Pb Indigo Carmine – 0.5 A m−2 AC-EC: AC-EC: – – – Ductile and frangible surface layers in AC- Othmani et
ur
and Methylene 100% IC 0.44×10-6 kWh m−3 EC and DC-EC, respectively; Uniform al. (2017)
Blue in synthetic 99% MB (IC) electrode corrosion in AC-EC; Slightly
Jo
WW DC-EC: 4.89×10-6 kWh m−3 higher RE and 36–78% less ENC in AC-EC
98.8% IC (MB) than in DC-EC
96.5% MB DC-EC:
2.03×10-6 kWh m−3
(IC)
7.61×10-6 kWh m−3
(MB)
612
I: Current; U: Voltage; j: Current Density; WW: Wastewater; ELP: Electrode passivation; SS: Stainless steel
613
40
614 However, in some studies, AC-EC was less efficient than DC-EC in removing pollutants
615 (Mansoorian et al., 2014; Ghanizadeh et al., 2016; Payami Shabestar et al., 2021). For example,
616 the findings of our research group (Payami Shabestar et al., 2021) showed that DC-EC was
617 more efficient than AC-EC in removing Acid Red 18 when using Fe electrodes, but the removal
618 efficiencies for Al electrodes were nearly equal in both techniques. This is because the higher
619 final pH of DC-EC was more conducive to the formation of Fe-(oxy)hydroxides, resulting in a
620 higher pollutant removal efficiency (Payami Shabestar et al., 2021). Besides, the rate and
621 mechanism of electrode passivation depend on the electrode material, so various electrode
f
oo
622 materials passivate differently (Chow and Pham, 2021; Payami Shabestar et al., 2021). As a
623
pr
result, employing an AC waveform to prevent electrode passivation could have different results
based on the electrode material. Furthermore, based on the literature, the improvements in
e-
624
625 pollutant removal efficiency in AC-EC compared to DC-EC are less significant than the
Pr
626 differences between APC-EC and DC-EC (see Tables 2 and 3). The PR time in AC-EC (often
al
627 20 ms PR time, i.e., 50 Hz PR frequency) might be shorter than the time required for charging
rn
628 the electrode double-layer, making this technique inefficient in some experimental conditions,
u
629 especially when treating solutions with poor conductivity (Ingelsson et al., 2020). Lower
Jo
630 faradaic efficiencies could also contribute to decreased contaminant removal in AC-EC than in
631 DC-EC (Mansoorian et al., 2014).
632 From the viewpoint of energy usage, most research indicates that AC-EC is more
633 efficient than DC-EC. Based on the data reported in Table 3, AC-EC consumed approximately
634 13–80% less energy than DC-EC (Vasudevan et al., 2011a; Vasudevan and Lakshmi, 2012;
635 Kamaraj et al., 2013; Mansoorian et al., 2014; Othmani et al., 2017; Xu et al., 2019, 2020;
636 Khaghani et al., 2020; Arabameri et al., 2022). The passivating layer in DC-EC prevents
637 electrode corrosion, which increases passivation overpotential and energy consumption.
638 However, alternating the polarity between the anode and cathode in AC-EC reduces the
41
639 passivating film growth (Xu et al., 2020). In contrast, a few studies have reported that the
640 energy consumption in AC-EC tended to be greater than that of DC-EC, but the differences
641 were not significant (Karamati-Niaragh et al., 2019; Payami Shabestar et al., 2021). For
642 instance, in the study accomplished by our team (Karamati-Niaragh et al., 2019) to eliminate
643 nitrate from water, DC-EC was slightly more energy-efficient than AC-EC at current intensities
644 between 2 and 4 A. The higher energy consumption in AC-EC may be related to the types of
645 contaminants and their complexes of removal mechanisms.
All the reviewed studies reported that using the AC waveform instead of the DC
f
646
oo
647 waveform lowers electrode consumption. It was shown that electrode utilization in AC-EC can
648
pr
be reduced by about 14–93% compared to DC-EC, regardless of the electrode material used
e-
649 (Mansoorian et al., 2014; Rodrigues Pires da Silva et al., 2015; Karamati-Niaragh et al., 2019;
Pr
650 Xu et al., 2019, 2020; Alkhatib et al., 2020; Khaghani et al., 2020; Payami Shabestar et al.,
651 2021; Arabameri et al., 2022). Through scanning electron microscopy (SEM) imaging, it was
al
652 shown that electrode oxidation in DC-EC occurs at the same preferential spots of the electrode
rn
653 surface due to the unidirectional current. Therefore, the electrode corrodes irregularly and non-
u
Jo
654 uniformly (Karamati-Niaragh et al., 2019). Conversely, the returning current in AC-EC forms
655 new oxidation spots, which decreases the locally attacked portion of the anode/cathode surface
656 and extends the uniformly attacked area (Payami Shabestar et al., 2021). Thus, electrodes in
657 DC-EC are more susceptible to localized corrosion and precipitation of minerals than those in
658 AC-EC. As a result, the corrosion type changes from pitting corrosion in DC-EC to uniform
659 corrosion in AC-EC, decreasing the electrode mass loss.
660 Furthermore, frequent changes in electrode polarity in AC-EC increase the likelihood of
661 side reactions, which divert the current away from electrode corrosion. For example, it has been
662 reported that the Pb2+ and Zn2+ ions in battery industry wastewater could be reduced at the
663 cathode and Pb2+ oxidized to Pb4+ at the anode repeatedly following each polarity reversal,
42
664 diverting the current away from electrode corrosion and lowering coagulant generation
665 (Mansoorian et al., 2014; Nidheesh et al., 2022). In the reviewed studies, the AC-EC has
666 utilized fewer Al electrodes, in contrast to the APC-EC, which often has been demonstrated to
667 have more Al electrode mass loss than the DC-EC. With the frequent polarity reversal in AC-
668 EC, the pH boundary layers change repeatedly and have less time to reconstitute. As a result,
669 low acidic/basic pH regions develop at the electrode interfaces, which lessens the likelihood of
670 Al electrodes' chemical corrosion (Yasri et al., 2022). For example, Cerqueira et al. showed
671 that AC-EC (60 Hz) consumed about 50% less aluminum mass than APC-EC (a 5 min PR
f
oo
672 time) for the same oil and grease removal (Cerqueira et al., 2014). Xu et al. compared the AC-
EC (50 Hz), PDC-EC (1 kHz and γ= 0.2), and DC-EC using Fe electrodes and found that the
673
pr
AC-EC was the best and most energy-efficient technique in Cr(VI) removal; however, it had a
e-
674
675 lower faradaic efficiency than the DC-EC (Xu et al., 2019). The lower faradaic efficiency in
Pr
676 AC-EC was attributed to Fe2+ species reduction to Fe(0) because Fe electrodes instantly turned
al
677 into a cathode after corroding as an anode (Xu et al., 2019).

rn
678 EC studies have shown a decrease in sludge production when using the AC waveform
u
Jo
679 instead of the DC waveform due to the uniform dissolution of anode and cathode and decreased
680 electrode consumption (Mansoorian et al., 2014; Kong et al., 2020; Xu et al., 2020; Payami
681 Shabestar et al., 2021). For example, it has been reported that sludge production can be
682 decreased by up to 54% by altering the current waveform from DC to AC (Xu et al., 2020).
683 Therefore, since EC's operating costs mainly include the cost of energy, electrode usage, and
684 sludge disposal, AC-EC is more cost-effective than DC-EC. The previous work of our research
685 group (Karamati-Niaragh et al., 2019) indicated that using an AC waveform instead of DC in
686 the EC process could even drop the operating cost by about half.
687
43
688 8. The suitable current waveforms for treating various solution matrices
689 Solution chemistry is a critical factor that should be considered while selecting the proper
690 current waveform in the EC process. Based on Fig. SM-2, various water and wastewater
691 matrices have been treated in EC under PDC, APC, and AC waveforms that can be categorized
692 as follows: water, groundwater, synthetic industrial wastewater, real industrial wastewater, and
693 municipal wastewater. For water treatment, the AC has been the most widely used waveform
694 that has exhibited comparable pollutant removal (e.g., fluoride, iron, arsenate, and copper) to
695 the DC while requiring significantly less energy (Vasudevan et al., 2011a, 2012; Vasudevan,
f
oo
696 2012; Kamaraj et al., 2013). In addition, the APC waveform has shown remarkable
697
pr
performance in removing fluoride (Alimohammadi et al., 2019) and hardness (Yaghmaeian et
e-
698 al., 2020) from drinking water. However, only the APC waveform has been used for treating
Pr
699 groundwater, and conflicting results have been reported. It was found that 21 and 52.5 min PR
700 times were insufficient to successfully de-passivate Fe electrodes (Müller et al., 2019), while a
al
701 30 min PR time was enough to prevent Al passivation when treating groundwater (Mohora et
rn
702 al., 2014). These conflicting results can be attributed to the different operational conditions,
u
703 such as the type and concentration of ionic species in groundwater and the electrode material.
Jo
704 For instance, it was found that Al electrodes were not covered by Ca and Mg minerals to the
705 same extent as the Fe electrode when treating groundwater by PR-EC due to the chemical
706 corrosion of aluminum, which contributes to de-passivation (Chow and Pham, 2021).
707 Synthetic industrial wastewaters containing pollutants, such as oil, COD, dyes, and heavy
708 metals (Pi et al., 2014; Bian et al., 2019; Zhou et al., 2021; Arabameri et al., 2022), have been
709 the most common matrices treated in EC under various current waveforms. According to the
710 literature, the APC and PDC have provided a better balance of pollutant removal, energy
711 consumption, electrode usage, and sludge production (Eyvaz et al., 2009; Ren et al., 2011;
712 Zhou et al., 2020; J. Zhang et al., 2021). In most cases, the combination of the APC waveform
44
713 and Al electrodes resulted in superior de-passivation capability when treating synthetic
714 industrial wastewaters (Pi et al., 2014; Wellner et al., 2018). Meanwhile, the AC has shown
715 almost similar contaminant removal compared to the DC (Karamati-Niaragh et al., 2019; Xu
716 et al., 2019; Arabameri et al., 2022). Based on Fig. SM-2, researchers have been more inclined
717 to operate EC with the APC and PDC waveforms when treating real industrial wastewater. The
718 majority of research has shown that applying the APC waveform in EC results in improved
719 treatment efficiency and diminished energy and electrode usage (Eyvaz, 2016; Asaithambi et
720 al., 2021; Sanei and Mokhtarani, 2022). However, due to the complex chemistry of real
f
oo
721 industrial wastewaters and the presence of a high concentration of interfering ions, their
722
pr
treatment could be more challenging compared to other water and wastewater matrices
(Mansoorian et al., 2014; Xu et al., 2018; Rodrigues et al., 2020). Besides, the PDC waveform
e-
723
724 has received the most attention for treating municipal wastewater and has been proven to
Pr
725 outperform the DC in removing COD from municipal wastewater while being more energy-
al
726 efficient (H. Nguyen, 2020; Que et al., 2021). However, low pharmaceutical and antibiotic
rn
727 removal from municipal wastewater has been reported using the PDC waveform (Ensano et
u
728 al., 2019; Oliveira et al., 2021).

Jo
729 Accordingly, various water and wastewater matrices can be efficiently treated in EC
730 under the PDC, APC, and AC waveforms. However, when selecting the proper current
731 waveform, it is crucial to carefully weigh the trade-offs between de-passivation, pollutant
732 removal efficiency, energy and electrode use, sludge formation, and operating cost. Based on
733 the literature, a few studies have compared the efficacy of PDC-EC, APC-EC, and AC-EC in
734 treating different water and wastewater matrices. Thus, there is still a need for more research
735 on choosing the current waveform and waveform characteristics for various combinations of
736 electrode material and water and wastewater matrices. It is also suggested to compare the
737 efficacy of various current waveforms in treating synthetic and real wastewater.
45
738
739 9. Conclusions
740 Despite various advantages, the EC process is subjected to high energy and electrode
741 consumption and electrode passivation, which prevent it from being fully commercialized and
742 practically used. To overcome these shortcomings, the role of the current waveform in the EC
743 process has received much consideration, and it has been the topic of intensive research over
744 the past two decades. This review paper outlines the PDC, APC, and AC waveforms employed
745 in the EC process as alternatives to DC. The role of these waveforms in de-passivation was
f
oo
746 thoroughly explored, and their influence on the overall EC performance was compared to DC.
747
pr
Besides, the impact of current waveform parameters on PDC-EC and APC-EC was evaluated.
e-
748 Moreover, the suitable current waveforms for treating various water and wastewater matrices
Pr
749 were discussed. Based on this review, the PDC-EC, APC-EC, and AC-EC techniques have
750 often exhibited similar or greater pollutant removal than DC-EC while mitigating passivation,
al
751 consuming less energy and electrode, producing lower sludge, and decreasing operational
rn
752 costs. They could also provide other benefits, such as uniform corrosion of electrodes,
u
753 enhanced coagulant mass transport, and better adsorption properties of flocs.
Jo
754
755 10. Future outlooks
756 Based on this review, the following are the main aspects of future research on mitigating
757 electrode passivation and enhancing EC efficiency using PDC, APC, and AC waveforms:
758 (1) EC operation under PDC, APC, and AC waveforms has been demonstrated in most
759 studies to offer a better balance of pollutant removal, energy requirements, electrode
760 usage, sludge production, and operating expenses compared with conventional DC.
761 This improvement is often attributed to reduced passivation. However, few
762 researchers have analyzed the electrode surface to support this hypothesis. More
46
763 research on this subject will help clarify the impact of various current waveforms on
764 the properties of the electrode surface layer.
765 (2) Some authors have reported that the application of PDC, APC, and AC waveforms
766 in the EC process, in addition to de-passivating electrodes, could contribute to
767 uniform corrosion of electrodes, enhance coagulant mass transfer, and improve the
768 adsorption properties of flocs. These mechanisms deserve further attention, and more
769 research in this area is encouraged.
770 (3) There have been conflicting findings on how current waveform parameters affect the
f
oo
771 EC process and the optimal amounts of these parameters to select. The optimal pulse
772
pr
frequency in PDC-EC and the suggested PR time and pulse frequency values in APC-
EC differed widely. Besides, no studies have explored the impact of current

e-
773
774 frequency on AC-EC. Thus, more research is needed regarding optimizing waveform
Pr
775 parameters in all the above-mentioned techniques.

al
776 (4) Based on the solution chemistry, there would probably be an optimal current
rn
777 waveform and electrode material. Hence, more research on selecting the current
u
778 waveform (DC, PDC, APC, and AC), waveform characteristics (e.g., PR time, pulse
Jo
779 frequency, and duty cycle), and electrode material for various water and wastewater
780 matrices is required.
781 (5) Most studies evaluated the impact of current waveforms on the EC in small-scale
782 batch reactors, while most commercial applications require continuous flow mode.
783 Thus, future research should also consider the long-term continuous flow modes of
784 PDC-EC, APC-EC, and AC-EC techniques in pilot-scale systems to simulate
785 industrial implementation.
786
47
787 CRediT authorship contribution statement
788 Javad Abdollahi: Conceptualization, Investigation, Literature review, Writing- original draft
789 preparation, Writing- reviewing and editing, Visualization. Mohammad Reza Alavi
790 Moghaddam: Conceptualization, Writing- reviewing and editing, Supervision. Sajjad
791 Habibzadeh: Conceptualization, Writing- reviewing and editing, Supervision.
792
793 Declaration of Competing Interest
794 The authors declare that they have no known competing financial interests or personal
f
oo
795 relationships that could have appeared to influence the work reported in this paper.
796
pr
e-
797 Acknowledgments
Pr
798 The authors gratefully acknowledge the financial support of the Amirkabir University of
799 Technology (Tehran Polytechnic).

al
800
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Highlights
▪ Electrode passivation as a detrimental phenomenon to the EC process is outlined
▪ Mechanisms involved in improved EC under various current waveforms are discussed
▪ The PDC, APC, and AC waveforms as alternatives to conventional DC are summarized
▪ The role of these waveforms in de-passivation and enhancing performance is explored
▪ How current waveform parameters affect PDC-EC and APC-EC performance is
discussed
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Declaration of interests
☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.
☐ The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:
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The Role of The Current Waveform in Mitigating Passivation and Enhancing Electrocoagulation Performance: A Critical Review

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The role of the current waveform in mitigating passivation and enhancing

Javad Abdollahi, Mohammad Reza Alavi Moghaddam, Sajjad Habibzadeh

To appear in: ECSN

Received Date: 18 August 2022

© 2022 Published by Elsevier Ltd.

Javad Abdollahi: Conceptualization, Investigation, Literature review, Writing- original draft

preparation, Writing- reviewing and editing, Visualization. Mohammad Reza Alavi

Moghaddam: Conceptualization, Writing- reviewing and editing, Supervision. Sajjad

Habibzadeh: Conceptualization, Writing- reviewing and editing, Supervision.

3 Javad Abdollahi a, Mohammad Reza Alavi Moghaddam a,*, Sajjad Habibzadeh b

11 Electrocoagulation (EC) can be an efficient alternative to existing water and wastewater

22 Additionally, current waveform parameters influencing the surface passivation of electrodes

28 Keywords: Electrocoagulation; Passivation; Current waveform; Pulse current; Polarity

29 reversal; Alternating current

31 Electrocoagulation (EC) has been praised recently as a robust and eco-sustainable

32 technology in water and wastewater treatment, capable of eliminating a broad spectrum of

33 pollutants. EC incorporates the merits and capabilities of coagulation, flotation, adsorption, as

35 advantages over the conventional treatment methods and is characterized by an eco-friendly

36 nature, ease of operation, versatility, a small footprint, and a minimum requirement of

45 of the EC process (Ibrahim et al., 2020).

53 However, although a few reviews addressed electrode passivation and discussed

68 2. Fundamentals of the electrocoagulation process

69 EC is an electrochemical technology that resembles chemical coagulation, except that

77 oxyhydroxides (herein collectively referred to as metal (oxy)hydroxide flocs) (Karimifard and

82 Niaragh et al., 2017; Nazlabadi and Alavi Moghaddam, 2017).

100 discussed in the following sections.

102 Fig. 1. Factors affecting EC performance.

128 summarized in Fig. SM-1 and discussed in the following paragraphs.

130 3.1. Passivation mechanisms

131 Electrode passivation results from electrochemical and physicochemical mechanisms

146 schematic of the mechanisms occurring during EC is illustrated in Fig. 2.

150 3.2. Detrimental effects of passivation

165 et al., 2022).

168 3.3. Passivation mitigation or prevention approaches

173 (1) Mechanical or chemical cleaning of electrodes. Merits: effective de-passivation; no

176 chemical cleaning) (Amrose et al., 2014; Bandaru et al., 2020).

187 de-passivation; no need for chemicals. Drawbacks: requires special infrastructure;

automatability; no complex design modification; no additional treatment phases; no

192 Pham, 2021; Arabameri et al., 2022; Dong et al., 2022).

200 for electrode de-passivation and performance enhancement of EC.

202 4. Current waveforms in the electrocoagulation process

220 optimized current waveform parameters to fully exploit EC potential.

234 and enhancing treatment performance is compared to DC-EC.

236 5.1. The impact of current waveform parameters on PDC-EC

239 parameters on PDC-EC.

241 5.1.1. Pulse frequency

267 mitigation and pollutant removal efficiency.

269 5.1.2. Duty cycle

290 performance (see Table SM-1).

291 𝐸 = 𝑈𝐼𝑡𝛾 2 (6)

293 time, and γ is the duty cycle.

attracting/repelling forces caused by electrodes, allowing ions or molecules such as metal

Al/Al, Fe/Fe, Antimony in f= 0.4 kHz 15 V PDC-EC:

335 (Ensano et al., 2019).

358 6. Alternating pulse current electrocoagulation (APC-EC)

384 6.1.1. Polarity reversal time

416 (Chow et al., 2021).

458 recommended for Al and Fe electrodes

472 frequencies, operational conditions, and process performance.

474 6.1.3. Duty cycle

485 6.2. Comparison of APC-EC and DC-EC techniques

495 properties of the electrode surface through material characterization methods.