Chemical Engineering Journal 457 (2023) 141009

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Chemical Engineering Journal

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Electro-activation of peroxymonosulfate by β-PbO2 partial filling/covering

TiO2 nanotube arrays anode for alkaloid berberine degradation:
Performance, mechanism and practicability
Guoquan Zhang a, *, Shaowei Hu b, Xiaoyu Zhu a, Xiaoxin Hu a, Fenglin Yang a
a
Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian
116024, China
b
Technology Center of Angang Steel Co. Ltd., Anshan 114009, China

A R T I C L E I N F O A B S T R A C T

Keywords: An interlocking “T-shape” structure was built by uniform filling β-PbO2 crystalline inside the trace Ti3+ self-
Berberine doping TiO2 nanotube arrays (TNAs) channels and depositing the cauliflower-like β-PbO2 clusters on its upper
β-PbO2 surface through a facile current pulse deposition method. We elaborated the interfacial engineering strategy for
PMS electro-activation
generating compact oxide layers at TNAs bottoms and growing β-PbO2 crystalline from the selectively conductive
SR-AOPs
TiO2 nanotube arrays
TNAs bottoms. Different characterization techniques and electrochemical analyses were conducted to charac­
terize the morphology, structure, and electrochemical property of the β-PbO2 partial filling/covering TNAs
(β-PbO2/TNAs/Ti) materials. We also systematically investigated and elucidated the performance and mecha­
nism of β-PbO2/TNAs/Ti anode activated peroxymonosulfate (PMS) system via berberine removal/mineraliza­
tion, reactive oxygen species (ROS) identification/contribution, intermediates analysis, energy consumption and
practical applicability estimation. Results illustrated that filling β-PbO2 inside TNAs can efficiently improve the
directional electron-transfer efficiency, oxygen evolution over-potential, tolerance to the varied water matrices
1
and service lifetime of β-PbO2/TNAs/Ti anode activated PMS system. The ROS including •OH, SO•− 4 and O2 that
generated from PMS electro-activation are responsible for efficient berberine degradation through two pathways.
This study will provide a general approach to construct the versatile tube-filled TNAs-based materials for wide
applications in water/wastewater treatment.

1. Introduction developed lately, which is an efficient method enabling to realize the

anode/cathode’s synergetic effect for forming both radicals and non-
Sulfate radical (SO•− 4 )-based advanced oxidation processes (SR- radicals reactive oxygen species (ROS) [7–13]. Organic contaminants
AOPs) have been considered as an attractive method for degrading (R) can be efficiently degraded through the following three combined
organic contaminants, because of its higher redox potential (2.5–3.1 V effects: (i) direct electron transfer on anode surface (M) (Eq. (1)), (ii)
1
vs RHE) than that of hydroxyl radicals (•OH, 1.8–2.7 V vs RHE), longer ROS, such as •OH,SO•− 4 ,SO5 ,HO2 ,O2 , O2, etc., generated from the
•− • •−

half-life (30 ~ 40 μs vs 20 ns of •OH), more moderate pH conditions and non-active anode (Eq. (2)) and PMS electro-activation (Eqs. (3)-(5)), and
higher selectivity [1]. Peroxymonosulfate (PMS, HSO−5 ) peroxydisulfate (iii) the transitional state of persulfate (PMS*/PDS*, Eq. (6)) [9–11].
(PDS, S2 O2−8 ) is generally deemed as the basic sources ofSO4 . Aiming to
•−
2- R − ne− →Products (1)
split the [O O] bond, PMS/PDS activation is usually categorized in (i)
–
physical activation using heat (>35 0C), UV irradiation (<400 nm), and (• )
M + H2 O→M OH + H + + e− (2)
ultrasonic waves; and (ii) chemical activation using transition metal
ions, alkaline (pH > 10.5), strong oxidizers, carbonaceous materials and M + PMS/PDS + H2 O→ROS (3)
electric field [2–6].
Electrochemical activation of PMS/PDS has been prosperously HSO−5 + e− →OH − + SO•−4 or •
OH + SO2−4 (4)

* Corresponding author.
E-mail address: guoquanz@126.com (G. Zhang).

https://doi.org/10.1016/j.cej.2022.141009
Received 5 October 2022; Received in revised form 28 November 2022; Accepted 15 December 2022
Available online 24 December 2022
1385-8947/© 2022 Elsevier B.V. All rights reserved.
G. Zhang et al.
S2 O2−8 + e− →SO•−4 + SO2−4 (5)
M + PMS/PDS → M (PMS* /PDS* ) (6)
In this context, the anode materials are critical for PMS/PDS electro-
activation. As one of the optimum non-active anode materials, β-PbO2
has good corrosion resistance and long service lifetime. What’s more,
the special chain structure endows β-PbO2 excellent metal-like con­
ductivity, and the hydrated lead oxide layer, i.e., colloidal PbO(OH)2,
will form during the electrochemical oxidation, which further undergoes
Pb-OH bond breakage, producing •OH above the upper limit of polari­
zation potential [14–17]. However, the “layer-by-layer” structural
β-PbO2 coating can easily be stripped from substrate and deactivation,
due to the strong inner stress between β-PbO2 coating and underlying
material [18]. To improve the corrosion resistance and electro-oxidation
ability of the β-PbO2-based anodes, great efforts have been devoted to
introduce the dense and uniform intermediate layer [16,17,19] between
substrate and β-PbO2 layer, doping metal or non-metallic ions into the
β-PbO2 layer [19,20].
The vertically oriented blue-black TiO2 nanotube arrays (TNAs) have
also been widely employed as the host catalyst or the intermediate layer
in (photo-)electrochemical AOPs for organic pollutant removal [21–28],
because of the tubular structure-induced high aspect ratio, large specific
surface areas and more active sites. The anodized anatase TNAs is a
suitable substrate for β-PbO2 crystal growth on its surface through the
direct galvanostatic/potentiostatic electrodeposition [29–31]. Never­
theless, the anatase TNAs generally display the N-type semiconductive
nature, and its surface-confined nanoparticles are randomly interacted
and bring the grain boundary effects, which are critical limitations in
charge transport [32]. To solve this problem, the uniform filling of
nanoparticles inside TNAs channels is an effective approach [33–36],
which can evidently improve the directional electron-transfer efficiency
and the available surface. Unlike BDD anode, nearly no attention has
been focused on PMS electro-activation by β-PbO2 filled/covered TNAs
anodes as far as we know. Thus, it is necessary to deeply understand the
filling strategy and gain insights into the PMS electro-activation mech­
anism, ROS generation avenue and the practicability of the β-PbO2
modified TNAs anodes.
Alkaloid berberine has been extensively used to treat diseases or
served as prophylactics and growth stimulants in livestock and aqua­
culture in China, which causes the residual concentration up to 1000
mg/L in some berberine-containing aquaculture wastewater, incurring
the potential risk of resistance gene to the ecosystem and human-being
[37]. The conventional physicochemical and biological treatments are
inadequate to degrade berberine meeting the emission standard because
of its complex structure, long half-life, and persistent biotoxicity
[38,39], leading to a considerable number of the residual berberine (up
to 100 mg/L) in effluent. Thus, more efficient advanced treatment
technologies are urgently needed to be developed to reduce the risk of
the residual berberine.
This study developed a novel PMS activation approach by using
β-PbO2 partial filling/covering TNAs (β-PbO2/TNAs/Ti) anode for the
efficient degradation of alkaloid berberine. The main objectives are: (i)
establishing an interfacial engineering strategy for β-PbO2 uniform
filling in TNAs’ channels, (ii) evaluating the effects of supporting elec­
trolyte, operating parameters, inorganic ions, organic matter and water
matrices on PMS electro-activation performance and efficiency, (iii)
clarifying the PMS electro-activation mechanism through discerning the
generated ROS, (iv) evaluating the practicability of β-PbO2/TNAs/Ti
anode through the long-term operation and service lifetime testing.
2. Material and methods
2.1. Reagents
All chemical reagents purchased from Aladdin and Sinopharm
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Chemical Engineering Journal 457 (2023) 141009
Chemical Reagent Co., ltd. are analytical grade and used as received
without further purification. Ultrapure deionized water (18.2 MΩ cm− 1
from Milli-Q system) was used in all experiments.
2.2. Preparation of TNAs and β-PbO2 filled/covered TNAs
Ti sheet (25 mm × 20 mm × 0.3 mm, 99.6 % purity, Sigma-Aldrich)
was first degreased, followed by mechanical polishing, washing and
chemical etching, then the β-PbO2 partial filling/covering trace Ti3+
self-doping TNAs (β-PbO2/TNAs/Ti) was prepared via a two-step
anodization/pulse electro-deposition method (Scheme 1), and the
detailed synthesis process was described in Test S1.
2.3. Physicochemical characterization
The information for the physicochemical and electrochemical char­
acterizations of anatase TNAs/Ti, trace Ti3+ self-doping TNAs (Tsd-
TNAs/Ti), and β-PbO2/TNAs/Ti anodes, including scanning electron
microscopy (SEM-EDS), X-ray diffraction (XRD), X-ray photoelectron
spectroscopy (XPS), linear sweep voltammetry (LSV), cyclic voltam­
metry (CV), electrochemical impedance spectroscopy (EIS) and accel­
erated lifetime tests were described in the Supporting Information Test
S2.
2.4. Electrochemical degradation experiments
The details of experimental setup (Fig. S1) and electrochemical
degradation procedures were described in Supporting Information Test
S3.
2.5. Analytical methods
The detailed information of the analysis methods and processes were
provided in the Supporting Information Test S4.
3. Results and discussion
3.1. Characterization of the prepared samples
The trace Ti3+ self-doping can be affirmed by cyclic voltammetry
(CV) behavior in Fig. 1. Clearly, the onset potentials for Ti4+ reduction to
Ti3+ is about − 1.0 V, thus the Tsd-TNAs/Ti can still remain in the
electro-reduction atmosphere for at least 5 s during cathodic polariza­
tion at 200 mV/s. According to previous report [36], the hydrogen
evolution reaction (HER) will occur once the bottoms of TNAs were
electrochemically reduced into high conductivity state. Further, when
the Ti3+ was fully self-doped in anatase TNAs, the onset potential of HER
will move to more positive value accompanying a significantly enhanced
HER current [23,28]. However, in present study, the beginning potential
of HER is observed at ca. − 1.75 V, and nearly no drastic HER current is
found in the potential range from − 1.75 to − 2.0 V, suggesting that the
short-time cathodic polarization at − 1.35 V (corresponding to the half-
wave potential of Ti4+ reduction to Ti3+) in neutral medium cannot
achieve the sufficient proton intercalation but only trace Ti3+ self-
doping in the entire anatase TNAs.
The SEM images shown in Fig. 2a-c exhibit the highly ordered and
vertically distributed anatase TNAs with high aspect ratio on Ti sub­
strate after two-step anodization and calcination process. The TNAs
display hexagonal open-mouth top pattern with 60 nm of diameter, 4.4
μm of length and a closed cap at tubes bottom. Moreover, a compact
oxide layers with ca. 193 nm thickness was observed between TNAs and
Ti substrate, due to applying the additional anodization in the fluoride-
free electrolyte [40]. This well-aligned high-density nanotube structures
are benefited from a rough surface after the fine mechanical polishing
and chemical etching, which is favorable to uniformly distribute electric
field over Ti substrate forming regular TNAs.
G. Zhang et al.
Scheme 1. Schematic illustration of the preparation process of β-PbO2 partial filling/covering trace Ti3+ self-doping TNAs anode through a two-step anodization/
pulse electro-deposition method.
Fig. 1. CV of Tsd-TNAs/Ti obtained from the cathodic polarization of anatase
TNAs/Ti at − 1.35 V vs Ag/AgCl in 1.0 M (NH4)2SO4 solution for 20 s. Scanning
rate: 200 mV/s.
The cross-section SEM image of anatase TNAs (Fig. S2a) shows a
homogenous β-PbO2 filling in TNAs’ hollow channels after 10 min pulse
deposition, implying that the anatase TNAs provide uniform and smooth
diffusion paths for Pb(NO3)2 infusion. After 35- and 60-min pulsing
deposition, the SEM images of cross-section and top views (Fig. 2d and e)
present the partial filling of the crystalline β-PbO2 in TNAs’ channels,
and the partial covering of the accumulated cauliflower-like β-PbO2
clusters over TNAs surface, forming the interlocking “T-shape” struc­
ture. As for the direct electro-deposition of β-PbO2 over Ti substrate, its
top-view SEM image and elemental mappings (Fig. 2f) exhibit that Ti
surface is completely covered by larger size, less uniform and tight
tetragonal pyramid-shape β-PbO2 crystals. Comparison between Fig. 2e
and 2f indicates that the anatase TNAs can provide a larger surface area
and more nucleation sites for β-PbO2 deposition, which not only increase
nucleation rate but also reduce grain size and achieve a sufficient β-PbO2
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Chemical Engineering Journal 457 (2023) 141009
filling in TNAs’ channels, causing a good adhesion between β-PbO2 and
the inner walls of TNAs.
XRD patterns of Ti substrate, Tsd-TNAs/Ti, β-PbO2/Ti and β-PbO2/
TNAs/Ti are illustrated in Fig. 3a. The XRD spectrum of Tsd-TNAs/Ti
exhibits the predominant crystalline planes peaks of the anatase phase
TiO2 (JCPDS #21–1271) [41]. A sharp peak related to Ti substrate
(JCPDS #44–1294) [30] also appears at 2θ = 70.8◦ . The main crystalline
phases of β-PbO2/Ti and β-PbO2/TNAs/Ti can be indexed as the platt­
nerite phase with a tetragonal structure according to the typical
diffraction peaks for (1 1 0), (1 0 1), (2 0 0), (2 1 1), (2 2 0), (3 1 0), (3 0 1),
and (3 2 1) planes of β-PbO2 (PDF #41–1492) [18,35]. Two weak
diffraction peaks at 2θ = 66.8 and 76.6 , corresponding to the ortho­
◦ ◦
rhombic α-PbO2 (JCPDS # 72–2400) [19], are also found. Notably, the
diffraction peak intensity and the FWHM of main crystal planes at
(1 1 0), (2 0 0), (2 1 1) and (3 0 1) of β-PbO2/TNAs/Ti are higher and
larger than those of β-PbO2/Ti, implying that the TNAs interlayer is
beneficial for forming PbO2 crystals with smaller grain size. Besides, the
(0 0 4) and (2 2 0) diffraction peaks of β-PbO2/TNAs/Ti do not disappear
completely, also indicating the incomplete coverage of β-PbO2 over
TNAs surface, as revealed in SEM images.
The survey XPS spectra (Fig. S2b) present O 1 s, C 1 s, Pb 4f and Ti 2p
signals in β-PbO2/TNAs/Ti spectrum, while an additional Pb 4f peak and
a weak Ti 2p signal were detected in β-PbO2/TNAs/Ti spectrum due to
the partial coverage of β-PbO2 over TNAs upper surface. The Ti 2p high-
resolution spectra of Tsd-TNAs/Ti and β-PbO2/TNAs/Ti (Fig. 3b) exhibit
two characteristic Ti 2p3/2 and Ti 2p1/2 doublet structure, in which the
main fitting peaks at 458.5 and 464.3 eV are assigned to Ti4+
[22,24,27]. No Ti3+ shoulder peaks were fitted out in both Tsd-TNAs/Ti
and β-PbO2/TNAs/Ti samples due to: (i) XPS technique just analyzes the
chemical properties of material surfaces within 1–10 nm depth, thus
Ti3+ present at the bottom of Tsd-TNAs/Ti cannot be detected, (ii)
partial Ti3+ will be oxidized into Ti4+ again during the anodic pulse
deposition of PbO2. The core-level O 1 s spectra of both Tsd-TNAs/Ti and
β-PbO2/TNAs/Ti (Fig. 3c) display an intensified main peak at 528.3 eV
and a shoulder peaks centered at 529.9 eV, which belong to the lattice
oxygen and the chemisorbed OH– (Oads,OH) [35], respectively. The
contents of two kinds of O can be evaluated using the integral area of
fitted peaks, from which the content ratio of Oads,OH in Tsd-TNAs/Ti and
G. Zhang et al.
Fig. 2. SEM images of (a) and (b) top views at low and high magnifications, (c) the cross-section views of anatase TNAs (insets show partial enlarged cross-section
and bottom views), (d) the cross-section and (e) top views of β-PbO2/TNAs/Ti after 35 and 60 min pulse deposition, respectively, the insets in (d) and (e) show the
partial enlarged top views, (f) the top view of β-PbO2/Ti and the corresponding Pb and O elemental mappings.
β-PbO2/TNAs/Ti is ca. 50.5 % and 63.3 %, respectively. The higher
content ratio of Oads,OH is beneficial to generate more •OH [7,13]. The
high-resolution Pb 4f spectrum of β-PbO2/TNAs/Ti shown in Fig. 3d can
be split into two characteristic peaks at 137.0 (4f 7/2) and 141.9 eV (4f
5/2) with the binding energy difference of ca. 4.9 eV, which was iden­
tified as the particular spectral values of β-PbO2 (Pb4+) [34].
The oxygen evolution reaction (OER) performances of β-PbO2/Ti,
Tsd-TNAs/Ti and β-PbO2/TNAs/Ti anodes were examined by linear
sweep voltammetry (LSV) in 0.1 M H2SO4 at a scan rate of 20 mV/s. As
presented in Fig. 3e, almost no anodic response was observed in LSV of
Tsd-TNAs/Ti, because the short-time cathodic polarization cannot
realize sufficient Ti3+ self-doping and improve the conductivity and
electrocatalytic activity of Tsd-TNAs/Ti remarkably. While the β-PbO2/
TNAs/Ti anode exhibits an OER potential at ca. 2.18 V, which is higher
than that of β-PbO2/Ti (1.86 V). The increased OER potential may be
derived from the fact that the TNAs intermediate layers facilitate the
preferential crystalline orientation and (2 0 0) crystal planes exposure of
β-PbO2 (Fig. 3a), leading to the enhanced OER barrier [35]. The higher
OER potential is beneficial for β-PbO2/TNAs/Ti anode to generate more
•
OH, which will effectively promote PMS activation and organic
pollutant degradation.
The Nyquist plots of β-PbO2/Ti and β-PbO2/TNAs/Ti anodes (Fig. 3f)
are characterized by two semicircle arcs. From the fitted EIS results of
Table S1, the Tsd-TNAs/Ti exhibits much larger diameter of semicircle
arc when compared with other two samples, hinting a larger charge-
transfer resistance owing to the low conductivity of TNAs’ tube walls
after the short-time cathodic polarization. The β-PbO2/TNAs/Ti displays
the smallest semicircle arc in middle and high frequency regions with
the solid/electrolyte interface charge-transport resistance of Rct1 =
23.43 Ω and Rct2 = 52.16 Ω, respectively. This result may be due to the
efficient filling of β-PbO2 in TNAs’ channels, in which the good adhesion
of PbO2 to TNAs’ inner walls improves the electrical conductivity of
β-PbO2/TNAs/Ti.
3.2. Berberine degradation by PMS electro-activation
3.2.1. Effects of supporting electrolyte and anode
The effects of different supporting electrolyte on berberine degra­
dation were first investigated in β-PbO2/TNAs/Ti + PMS electro-
oxidation system. As shown in Fig. 4a and b, berberinbe degradation
rate and its electro-oxidation kinetics in Na2SO4 and NaNO3 were not
significantly changed in comparison to NaClO4 under the same
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Chemical Engineering Journal 457 (2023) 141009
condition, which suggest that the three types of electrolytes exhibit little
effect on berberine degradation during 180 min electrolysis when
β-PbO2/TNAs/Ti was used as anode. In fact, the inhibition effect of NO–3
ions on radical-based electro-oxidation processes is remarkably affected
by its concentration, the applied current density/potential and anode
materials used. Here, 50 mM NaNO3 electrolyte can be considered as
inert in front of β-PbO2/TNAs/Ti anode at current density of 17.5 mA/
cm2. Therefore, we selected 50 mM NaNO3 as supporting electrolyte for
the subsequent berberine electro-oxidation process.
In order to compare the electro-oxidative performances of Tsd-
TNAs/Ti, β-PbO2/Ti and β-PbO2/TNAs/Ti anodes, berberine removal
was investigated in the absence and presence of PMS under the open-
circuit condition. As shown in Fig. S3a, berberine removal through
anodic adsorption in the absence of PMS is negligible for all the studied
anodes after 60 min treatment, while about 8.7 % of degradation rate
achieved by adding 10 mM PMS, indicating that β-PbO2/TNAs/Ti + PMS
(open-circuit) has limited effect on berberine removal, which is attrib­
uted to the low oxidation potential of PMS (HSO−5 /SO2− 4 , E0 = 1.82 V)
[1,5]. This result also indicates the negligible catalytic activity of
β-PbO2/TNAs/Ti for PMS activation under open-circuit condition.
PMS electro-activation by different anodes (power on) for berberine
degradation was further compared under the same conditions. The
complete decolorization of berberine was achieved within 60 min
(Fig. S3b) by β-PbO2/TNAs/Ti + PMS electro-oxidation system. As
illustrated in Fig. 4c, about 64.4 % berberine was destructed by β-PbO2/
Ti and β-PbO2/TNAs/Ti anodes, while ca. 81.7 % and 100 % of degra­
dation rates achieved after 180 min electrolysis in β-PbO2/Ti and
β-PbO2/TNAs/Ti activated PMS systems, respectively, which is signifi­
cantly higher than that of Tsd-TNAs/Ti + PMS electro-oxidation system
(27.7 %), implying the enhanced oxidation ability of β-PbO2/TNAs/Ti
activated PMS process and the sluggish electron-transfer of Tsd-TNAs/Ti
anode. It should be pointed out that compared to the result of Tsd-TNAs/
Ti + PMS system under open-circuit condition, the enhanced oxidation
ability of Tsd-TNAs/Ti + PMS system under the condition of power on
was primarily ascribed to PMS activation by the anatase TNAs/Ti
cathode (Eqs. (4)). Additionally, all berberine decay follow the pseudo-
first-order kinetics (Fig. 4d), and the apparent degradation rate constant
of β-PbO2/TNAs/Ti + PMS electro-oxidation system (k = 0.02685
min− 1) is 2.7 and 12.6 folds to that of β-PbO2/Ti and Tsd-TNAs/Ti
activated PMS systems, respectively. Above results demonstrate the
crucial role of the β-PbO2 filled TNAs intermediate layers, which endows
G. Zhang et al.
Fig. 3. (a) XRD patterns of Ti substrate, Tsd-TNAs/Ti, β-PbO2/Ti and β-PbO2/TNAs/Ti samples, the high-resolution core-level XPS spectra of Tsd-TNAs/Ti and
β-PbO2/TNAs/Ti anodes: (b) Ti 2p, (c) O 1 s and (d) Pb 4f. (e) LSV curves recorded in 0.1 M H2SO4 at a scan rate of 20 mV/s, (f) EIS plots recorded in 50 mM NaNO3
at 1.6 V vs Ag/AgCl.
β-PbO2/TNAs/Ti anode a higher OER potential and allows yielding more
ROS such as •OH and SO•−
4 [21,28,42] during PMS electro-activation.
3.2.2. Effects of operating parameters
The effect of current density shown in Fig. 5a illustrates that 100 %
berberine was degraded at 17.5, 25 and 50 mA/cm2 after 180 min
electrolysis in the batch experiments, while the removal rate declines to
85.7 % at 10 mA/cm2. The apparent rate constant increases from
0.01058 to 0.02685 min− 1 and then decreases to 0.02506 and 0.02294
min− 1 when the current density further increases to 25 and 50 mA/cm2,
respectively. Above result can be attributed to two aspects: (i) the
relative low degradation rate at low current density is due to the inferior
electron transfer rate and the limited amounts of generated ROS, and (ii)
the generation of SO•−4 and OH will be promoted by increasing current
•
density, while oxygen evolution side reaction that happened at higher
current density will hinder ROS generation [28,31].
5
Chemical Engineering Journal 457 (2023) 141009
The effect of initial PMS concentration on berberine degradation are
shown in Fig. 5b. As PMS dosage increases from 5.0 to 7.5 and 10.0 mM,
the berberine removal rate is rapidly enhanced with the k values of
0.00919, 0.02416 and 0.02685 min− 1, respectively. In β-PbO2/TNAs/Ti
+ PMS electro-oxidation system, multiple processes including the mass
transfer between bulk solution and electrode/solution interface, the
adsorption of PMS and berberine on electrode surface, and the electro­
chemical reaction were involved in berberine degradation. The increase
in PMS concentration not only accelerates PMS mass transfer but also
leads to an increase in electrical conductivity of the aqueous electrolyte,
which is beneficial to PMS electro-activation, producing more ROS.
However, further addition of PMS dosage to 12.5, 20 and 50 mM results
in a gradually decreased degradation rate, corresponding the k value of
0.01969, 0.01971 and 0.01498 min− 1. Above results can be interpreted
by the facts: (i) the excess PMS quenching SO•− 4 and OH to produce
•
SO5 and HO2 (Eq. (7)-(10)) with low oxidation ability [43,44], and (ii)
•− •
G. Zhang et al. Chemical Engineering Journal 457 (2023) 141009

Fig. 4. Berberine degradation by (a) β-PbO2/TNAs/Ti + PMS electro-oxidation system in 50 mM different electrolytes, (c) different anodes + PMS electro-oxidation
systems in 50 mM NaNO3. (b) and (d) the corresponding degradation kinetics profiles. Conditions: C0 = 0.1 M, j = 17.5 mA/cm2, [PMS] = 10 mM, [NaNO3] = 50
mM, pH = 6.9.

the self-scavenging reaction of SO•−

4 (Eq. (11)). superior to that of under alkaline conditions, whereas the strong acidic
medium is not beneficial to berberine removal. The change profile of
HSO−5 + SO•−4 →SO2−4 + SO•−5 +H +
(7) initial pH with electrolysis time (Fig. S4b) further verified the pH-
dependent acid-base catalyzed β-PbO2/TNAs/Ti + PMS electro-
HSO−5 + SO•−4 + H2 O→2SO2−4 + HO•2 + 2H + (8)
oxidation system. The overall degradation and pH variation behaviour
can be ascribed to the following aspects: (i) PMS (pKa1 = 0.4 and pKa2 =
HSO−5 + • OH→SO•−5 + H2 O (9)
9.3) [2,6] exists in mono-anion form (HSO−5 ) under acidic and neutral
conditions, but dissociates into dianion form (SO2−5 ) as pH increases to
HSO−5 + • OH→HO•2 + SO2−4 + H + (10)
10.1 and 12.8, which will further transform into HO−2 via alkaline
SO•−4 + SO•−4 →S2 O2−8 (11) activation (Eq. (12)) [5], suppressing the yield ofSO•−4 ; (ii) OER over-
potential increases at the low pH, which is favorable for accelerating
The efficient decomposition and conversion of PMS during its more ROS generation, but H+ ions tend to capture •OH and SO•− 4 under
electro-activation is of importance for organics degradation [42]. It is strong acidic condition [45], leading to an increase in pH; (iii) partial
obvious from Fig. 5b and Fig. S4a that at a given PMS concentration, a SO•−
4 will undergo hydrolysis in alkaline condition forming OH (Eq.
•

rapider PMS decomposition than berberine degradation was found for
β-PbO2/TNAs/Ti + PMS electro-oxidation system, implying the quick
production of •OH and SO•−4 from β-PbO2/TNAs/Ti activated PMS pro­
cess for efficient berberine degradation.
The electrolyte pH plays an important role in both ROS generation
and pollution removal, because of protons participating in radicals chain
reactions [16,28]. As seen from Fig. 5c, berberine degradation rate in­
creases from 79.1 % to 100 % as the initial pH increases from 1.3 to 6.9,
and then decreases to 93.4 % and 90.3 % as pH further increases to 10.1
and 12.8, respectively. Accordingly, the k value increases from 0.00883
to 0.03438 min− 1 and then declines to 0.01328 min− 1, achieving an
optimal value at pH 4.2. Above results demonstrate that the removal
efficiencies of berberine under acidic and neutral conditions were
(13)) with the lower oxidation potential than that in acidic media
[1–3,27], and meanwhile, causing a decreases pH value by OH– con­
sumption and H+ generation via Eqs. (7), (8) and (10);
SO2−5 + OH − →SO2−4 + HO−2 (12)
SO•−4 + OH − →SO2−4 + • OH (13)
(iv) berberine is mainly in cation form at pH < pKa (pKa = 2.47),
which is not susceptible to the electrophilic ROS, because the positively-
charged berberine structure inhibits the delocalization of lone-pair
electrons from N atom to aromatic ring [46].
The degradation and mineralization of berberine were also investi­
gated under the optimal experimental conditions (C0 = 0.1 M, j = 17.5

6
G. Zhang et al. Chemical Engineering Journal 457 (2023) 141009

Fig. 5. Effects of (a) current density, (b) PMS concentration and (c) pH on berberine degradation by β-PbO2/TNAs/Ti + PMS electro-oxidation system. Unless
otherwise specified, other conditions were C0 = 0.1 M, j = 17.5 mA/cm2, [PMS] = 10 mM, pH = 6.9. (d) berberine degradation and (e) TOC removal by different
anodes activated PMS systems under the optimal operation conditions, (f) the corresponding mineralization current efficiency (MCE) and energy consumption (ECTOC
and EE/O), respectively.

mA/cm2, [PMS] = 10 mM, pH = 4.2). As seem from Fig. 5d and e, the
berberine degradation rate and its TOC removal efficiency are only 53.5
% and 20.9 % for Tsd-TNAs/Ti + PMS electro-oxidation system,
respectively, while a higher degradation and mineralization rate of
about 88.5 %, 63 % and 100 %, 76.8 % were achieved for β-PbO2/Ti and
β-PbO2/TNAs/Ti anodes activated PMS systems, respectively. It is clear
from Table S2 that the β-PbO2/TNAs/Ti + PMS electro-oxidation system
shows a comparable performance with the previous reported (photo)
electrochemical oxidation systems using non-active anode materials for
berberine removal. The corresponding MCE value (Fig. S4c) gives the
analogous tendency as TOC removal rate, while an obvious declined
MCE is observed in β-PbO2/Ti + PMS and β-PbO2/TNAs/Ti + PMS
electro-oxidation systems after 1 h electrolysis, which indicates the
gradual accumulation of more recalcitrant intermediates. From Fig. 5f,
the energy consumption during berberine degradation (the electrical
energy required to degrade 90 % berberine, EE/O) and mineralization
(the energy consumption per unit TOC mass, ECTOC) displays an oppo­
site trend to MCE (3.7 kWh m− 3 order–1 and 0.3 kWh (gTOC)–1 for
β-PbO2/TNAs/Ti). This different MCE and energy consumption can be
associated with the different oxidation ability of the applied anodes
[25]. Apparently, more electrolysis time was required for Tsd-TNAs/Ti
and β-PbO2/Ti anodes to generate adequate ROS for berberine degra­
dation and mineralization due to their relative low ability for PMS
activation as compared to β-PbO2/TNAs/Ti anode, which further
affirmed that uniform filling β-PbO2 into TNAs’ channels can efficiently
improve the directional electron-transfer efficiency and the available
active sites, thus producing more ROS during PMS electro-activation.
3.3. ROS identification and PMS electro-activation mechanism
3.3.1. ROS identification
The radicals quenching experiments were first performed to detect
the generated ROS in β-PbO2/TNAs/Ti + PMS electro-oxidation system.
1
Generally, •OH, SO•−4 and O2 are considered to be the main ROS during
PMS electro-activation [2,46]. In this study, tert-butanol (TBA, k • OH =
6.0 × 108 M− 1 s− 1, kSO•−4 = 4.0 × 105 M− 1 s− 1) was used as scavenger of

7
G. Zhang et al.
•
OH, and methanol (MeOH, k • OH = 9.7 × 108 M− 1 s− 1, kSO•−4 = 3.2 × 106
M− 1 s− 1) [23,27] was selected to scavenge both •OH andSO•− 4 , while
furfuryl alcohol (FFA, k1O2 = 1.8 × 108 M− 1 s− 1) [42,47] was applied to
inhibit both •OH, SO•− 4 and 1O2. As depicted in Fig. 6a, berberine
degradation rate decreases from 100 % to 80.5 % and 61.3 % by adding
400 mM TBA and MeOH, respectively. The inhibition difference be­
tween TBA and MeOH scavengers is attributed to the contribution of
SO•−
4 [48], suggesting that SO4 together with OH plays a major role on
•− •
berberine degradation. When 400 mM FFA was added, a higher inhib­
itory effect towards berberine degradation (only 25.3 % removal rate)
was achieved than that by MeOH, which indicates that 1O2 also play an
important role of in β-PbO2/TNAs/Ti + PMS electro-oxidation system.
The berberine degradation kinetics (Fig. 6b) in the presence of different
scavengers exhibits an opposite result to their inhibitory effects. The
1
relative contribution rate of •OH, SO•−
4 and O2 can be calculated by the
method described in Text S3, from which the inhibition of TBA refers to
•
OH contribution, while the inhibition differences between MeOH and
TBA, between FFA and MeOH represent the contribution rates of SO•− 4 circuit) system, while a typical quadruple signals of DMPO-•OH
and 1O2, respectively. The calculated contribution proportions of •OH,
1
4 and O2 for berberine removal are 38.1 %, 33.3 %, and 23.9 %,
SO•−
demonstrating the joint-attack mechanism of radicals and non-radicals
in β-PbO2/TNAs/Ti anode activatd PMS system. Of note, the total
1
contribution of •OH, SO•− 4 and O2 is<100 %. Thus, some other un­
identified reactive species maybe produced during PMS electro-
activation process. Song et al. [9–11] verified that the electrochemi­
cally activated PDS/PMS molecules, i.e., PDS*/PMS*, a special transi­
tion state structure with high reaction activity, were also responsible for
Fig. 6. (a) Quenching effects of 0.4 M TBA, MeOH, FFA and 50 mM BQ on berberine removal by the β-PbO2/TNAs/Ti + PMS electro-oxidation system, (b) the
corresponding degradation kinetics and ROS contribution rate, (c) and (d) EPR spectra of β-PbO2/TNAs/Ti anode under different conditions. (C0 = 0.1 M, j = 17.5
mA/cm2, [PMS] = 10 mM, [NaNO3] = 50 mM, pH = 4.2).
8
Chemical Engineering Journal 457 (2023) 141009
non-radical oxidation. Furthermore, as a dominating sources of 1O2,
HO•2 /O•−
2 can be generated from Eqs. (8), (10) and (14).
SO2−5 + H2 O→O•−2 + SO2−4 + 2H + (14)
Considering the low redox potential, it is difficult for HO•2 /O•−2
to
effectively degrade berberine in theory. However, a non-ignored inhi­
bition effect on berberine removal efficiency was obtained by the
addition of 50 mM p-benzoquinone (BQ, an effective scavenger for HO•2 /
O•−2 with the second-order rate constant of (0.9–1.0) × 109 M− 1 s− 1)
[47], which indicates that the HO•2 /O•−2 is an indispensable intermediate
species for 1O2 generation in the β-PbO2/TNAs/Ti anode activatd PMS
system.
Using DMPO as spin-trapping reagents, the EPR tests were carried
out under different conditions to further discern the generated ROS in
the PMS electro-activation process. As shown in Fig. 6c, no measurable
characteristic signals of DMPO-•OH, DMPO-SO•− 4 or DMPO-O2 adducts
•−
were detected in the EPR profiles of β-PbO2/TNAs/Ti + PMS (open
(1:2:2:1), both DMPO-•OH and DMPO-SO•− 4 (1:1:1:1:1:1) with the
different intensities were observed in β-PbO2/TNAs/Ti and β-PbO2/
TNAs/Ti anodes activated PMS systems, respectively. The weak signals
of DMPO-SO•− 4 adducts was reported ascribing to the rapid nucleophilic
substitution of DMPO-SO•− 4 by H2O/OH− , conversing to DMPO-•OH
[27,33]. In addition, TEMP was also used as a spin trapping agent to
confirm whether the non-radical 1O2 species were indeed produced. As
illustrated in Fig. 6d, the characteristic triplet signal of TEMP-1O2
(1:1:1) adduct is observed in β-PbO2/TNAs/Ti + PMS (power on)
G. Zhang et al. Chemical Engineering Journal 457 (2023) 141009

system, while there is no TEMP-1O2 signals in β-PbO2/TNAs/Ti (power

PMS* + H2 O→ • OH + SO2−4 + H + (22)
on), β-PbO2/TNAs/Ti + PMS (open circuit) and β-PbO2/TNAs/Ti + PMS
+ MeOH (power on) systems, indicating that 1O2 was generated pri­ Based on the above findings and discussions, we proposed the
marily from the PMS electro-activation process rather than its self- mechanism of ROS generation in β-PbO2/TNAs/Ti//anatase TNAs/Ti
decomposition via Eq. (15). activated PMS system, as depicted in Scheme 2.
(i) water dissociation by β-PbO2/TNAs/Ti anode generating •OH (Eq.
HSO−5 + SO−5 →HSO−4 + SO2−4 + 1 O2 (15)
(2)), which then activates PMS forming SO•−
4 through Eqs. (9) and (23)-
However, the DMPO-O•−2 spin adducts with six characteristic peaks (25). At the same time, •OH and SO•− 4 can also be generated by PMS
was not detected. This phenomenon may be caused by the facts: (i) the activation on the anatase TNAs/Ti cathode via Eq. (4).
low yield ofO•−2 , (ii) the facile disproportionation of O•−2 in water (Eq.
2SO•−5 →2SO•−4 + O2 (23)
(16)), and its rapid reaction with •OH or SO•−4 forming 1O2 through Eqs.
(17)-(19), and (iii) the faster reaction rate of DMPO with •OH impedes 2SO•−5 →S2 O2−8 + O2 (24)
the slow reaction between O•−2 and DMPO [33].

2O•−2 + 2H2 O→H2 O2 + 2OH − + 1 O2 (16) S2 O2−8 + HO•2 →SO•−4 + SO2−4 + O•−2 + 2H + (25)

(ii) HO•2 /O•−2 generated from Eqs. (8), (10) and (14) will self-
O•−2 + • OH→OH − + 1 O2 (17) combining (Eq. (16)) or react with •OH and SO•−4 forming 1O2 (Eqs.
(17) - (19)). What’s more, PMS might accumulate on the anode surface
HO•2 + • OH→H2 O + 1 O2 (18)
via electrostatic attraction, thus accelerating 1O2 production through
PMS self-decomposition (Eq. (15)) [46].
HO•2 + SO•−4 →HSO−4 + 1 O2 (19)
(iii) the adsorbed PMS* on β-PbO2/TNAs/Ti anode surface promotes
water dissociation generating •OH (Eq. (22)), and PMS* self-decomposes
3.3.2. PMS electro-activation mechanism
Based on above quenching and EPR spin-trapping results, berberine
degradation in β-PbO2/TNAs/Ti + PMS electro-oxidation system was
mainly dominated by active radicals (•OH and SO•− 4 ) and non-radical
(1O2) oxidation. As seem from Fig. 7a, no obvious current change was
observed at E < 2.1 V on the potential-forward scanning CV branch of
β-PbO2/TNAs/Ti when compared to the cases of adding and without
adding berberine, implying that in the potential region below OER po­
tential, the direct electron-transfer between berberine and β-PbO2/
TNAs/Ti does not occur. However, the anodic current is significantly
decreased and the OER potential is synchronous right-shift after adding
10 mM PMS (Fig. 7b), indicating that PMS effectively inhibits OER and
inversely promotes •OH production [9–11]. It has been well documented
that as the intermediate reactive species, the anodically activated PMS, i.
e., PMS*, is also responsible for organic pollutant removal, which exerts
its oxidative function mainly through the following three ways
[2,10,46]: (i) direct oxidation via Eq. (20), (ii) decomposition to form
SO•−4 via Eq. (21), (iii) boosting OH generation via enhancing OER
•

over-potential (Eq. (22)).

PMS* + Berberine→Intermediates + SO2−4 (20)

Scheme 2. Possible mechanism of ROS generation in the β-PbO2/TNAs/Ti//
PMS* →SO•−4 (21)
anatase TNAs/Ti + PMS electro-oxidation system.

Fig. 7. (a) CV curves of β-PbO2/TNAs/Ti electrode recorded in 50 mM NaNO3 (pH = 4.2) in the absence and presence of 0.1 M berberine or 10 mM PMS at 20 mV/s,
(b) the enlarged figure of specific area in (a).

9
G. Zhang et al. Chemical Engineering Journal 457 (2023) 141009

into SO•−
4 (Eq. (21)), while the direct contribution of PMS* towards
berberine degradation via Eq. (20) is minor (4.7 %, inset of Fig. 6b).

3.3.3. Effect of water matrices on berberine degradation

Previous studies [1–5] affirmed that the ubiquitous inorganic anions
and natural organic matters (NOM) in natural and waste water impose
the pronounced impacts on the radical-based AOPs. To evaluate the
practical applicability of the β-PbO2/TNAs/Ti + PMS electro-oxidation
system, berberine degradation in presence of Cl–,H2 PO−4 , HCO−3 and
humic acid (HA) were investigated. As shown in Fig. 8a and b, adding
20 mM Cl– evidently improve berberine removal efficiency (k = Scheme 3. The generation mechanism of active chlorine species via the
0.03552 min− 1), while introducing 20 mMH2 PO−4 , HCO−3 or HA leads to interaction of Cl– with PMS, •OH andSO•−
4 .

different inhibitory effects with the degradation rate constant order of

kH2 PO−4 > kHCO−3 >kHA . HClO + • OH→ClO• + H2 O (28)
The Cl- ions will be oxidized at anode surface or react withSO•− 4 , OH
•

and PMS to form reactive chlorine species (Scheme 3), such as chlorine Cl− + SO•−4 →SO2−4 + Cl• (29)
radicals (Cl•, E0(Cl•/Cl–) = 2.47 V), dichlorine radicals (Cl•− 2 , E
0

(Cl2 /Cl ) = 2.09 V), chlorine oxide radicals (ClO ) and Cl2/HClO (E0
•− – •
Cl− + Cl• →Cl•−2 (30)
(Cl2/Cl–) = 1.4 V) through Eqs. (26)-(31). The generated active chlorine
species can catalyze propagation reactions, thereby producing more 2Cl− + SO•−4 →Cl•−2 + SO2−4 (31)
-
SO•−
4 [48]. The positive effect of Cl on berberine degradation by adding
- As for theHCO−3 and H2 PO−4
ions, on one hand they would occupy the
20 mM Cl ions is mainly due to the fact that the superimposed oxidation
active site of β-PbO2/TNAs/Ti anode, and on the other hand could react
effect of these active chlorine species is far greater than Cl--induced •OH
rapidly with •OH (kHCO−3 =8.5 × 106 M− 1 s− 1, kH2 PO−4 = 2.0 × 104 M− 1 s− 1)
and SO•− 4 quenching effect.
and SO•−4 (kHCO−3 =1.6 × 106 M− 1
s− 1, kH2 PO−4 < 7.2 × 104 M− 1
s− 1) to
(26) generate HCO•3 and H2 PO•4 (Eqs. (32)–(35)) [49].
− − H2 O
2Cl − 2e →Cl2 ̅̅→ HClO
HCO−3 +• OH→OH − + HCO•3 (32)
HSO−5 + Cl− →SO2−4 + HClO (27)

Fig. 8. Effects of (a) common water matrices constituents (20 mM) and (c) different actual water matrices on berberine removal by the β-PbO2/TNAs/Ti + PMS
electro-oxidation system. (b) and (d) the corresponding degradation kinetic rate. Conditions: C0 = 0.1 M, j = 17.5 mA/cm2, [PMS] = 10 mM, [NaNO3] = 50 mM.

10
G. Zhang et al.
HCO−3 + SO•−4 →SO2−4 + HCO•3 (33)
H2 PO−4 + • OH→OH − + H2 PO•4 (34)
H2 PO−4 + SO•−4 →SO2−4 + H2 PO•4 (35)
However, the contributions of these lower active HCO•3 and H2 PO•4
species to berberine degradation are not enough to offset their inhibitory
effects on: i) PMS electro-activation, due to the competitive adsorption
of HCO−3 and H2 PO−4 with PMS on anode surface, and ii) the oxidation
efficiency of •OH andSO•−4 , due to the radicals quenching effect. For HA,
the following three aspects deteriorate berberine degradation: i) the
competitive adsorption between HA and PMS on β-PbO2/TNAs/Ti sur­
face inhibiting PMS electro-activation [9,10], ii) HA serving as •OH and
SO•−4 radicals’ scavenger, and iii) the competitive oxidation between HA
and berberine.
To explore the practical applicability of β-PbO2/TNAs/Ti activated
PMS system, berberine degradation was carried out in different actual
water matrices including tap water, seawater and reservoir water
(Table S3) with ultrapure water as control, in which 50 mM NaNO3 was
added as supporting electrolyte. As seen from Fig. 8c and d, berberine
degradation are not significantly depressed in reservoir water (k =
0.02021 min− 1) and tap water (k = 0.02087 min− 1), implying that the
low-level common water matrices constituents impose a negligible
impact on the β-PbO2/TNAs/Ti activated PMS process. However,
obvious depression is observed using seawater as supporting electrolyte.
The main halide ions in seawater, i.e., Cl– (~540 mM) and Br– (~0.8
mM) are known as the important scavengers of •OH and SO•− 4 in the
activated peroxygens systems [48]. Considering the formation of reac­
tive chlorine species in AOPs is concentration-dependent [47,50], the
excess Cl- ions in seawater results in the low reactive Cl•- 2 and ClO
•
-
dominating the oxidation process. On the other hand, the excess Cl ions
in seawater not only results in the decreasedSO•− 4 , but also causes much
lower •OH content than SO•− 4 because of the competition of Cl- with the
adsorbed water and PMS molecules on β-PbO2/TNAs/Ti anode surface.
Furthermore, it is reported that the co-existence of Cl– and Br– tends to
generate the mixed-halogen radicals (such as ClBr•–) during peroxygens
activation processes, which also plays the critical roles in pollutants
degradation efficiency [51,52]. Therefore, the low berberine removal
efficiency and its slow degradation kinetics in seawater should attribute
to the comprehensive effect of oxidation (reactive chlorine species) and
ROS quenching (the halide ions and CO2− 3 /HCO3 in seawater).
−
3.4. Berberine degradation pathway
To affirm the degradation pathway of berberine, the intermediate
products generated in different electrolysis time were analyzed by Q-
TOF LC/MS. The total ion chromatograms, MS m/z values and possible
Fig. 9. Possible pathways of berberine degradation by the β-PbO2/TNAs/Ti + PMS electro-oxidation system.
11
Chemical Engineering Journal 457 (2023) 141009
molecular structures of the identified intermediates are listed in Fig. S5,
S6 and Table S4. According to these intermediates and the previous
reports [27,53], two possible degradation pathways were proposed
(Fig. 9). First, the most susceptible sites in berberine molecule, such as
pyridine ring, lateral -O-CH2-O- and dangling methyl groups were des­
tructed to generate the intermediates, C1/C1′ isomers (m/z = 338) and
C2 (m/z = 323). In pathway 1: C1 and C1′ were attacked to further
undergo pyridine ring-opening, loss methoxyl groups and ring-
refactoring reactions leading to the formation of intermediate C3 (m/
z = 283), followed by the losses of hydroxyl, ethyl/methoxyl groups and
ring-opening reaction generating C4 (m/z = 200), C5 (m/z = 166) and
C6 (m/z = 133). In pathway 2: C2 was further degraded to the in­
termediates C7 (m/z = 191) and C8 (m/z = 183) via the pyridine ring-
opening, -O-CH2-O- cleavage, demethylation and hydroxylation re­
actions. Then, C9 (m/z = 151) was produced after the loss of hydroxyl,
methyl and -O-CH2-O- groups of C7 and C8. As the electrolysis proceeds,
the smaller molecular structures of C10 (m/z = 120) and C11 (m/z =
122) were produced from the intermediates C4-C6 and C9, and subse­
quently decayed to C12 (m/z = 112) via the combined attacks of •OH,
1
SO•−
4 and O2.
3.5. The stability of β-PbO2/TNAs/Ti anode
The recyclability and stability of β-PbO2/TNAs/Ti anode were
investigated by the continuous circulating flow and five consecutive
batch experiments at 17.5 mA/cm2. As depicted in Fig. 10a and b,
decreasing the influent flow rate from 20 mL/min to 16 and 8 mL/min
increased the berberine degradation efficiency from 62.6 % to 74.1 %
and 77.2 % accordingly, while the corresponding TOC removal ratio was
49.6 %, 56.8 % and 58.9 % after 16 h electrolysis, indicating that the
β-PbO2/TNAs/Ti + PMS electro-oxidation system can achieve an effec­
tive and stable berberine degradation in a relatively wide range of
influent flow rate. Five consecutive batch experiments display a stable
TOC abatement with the mineralization rate in the last test being still
79.5 % of that in the first test (Fig. 10c). The sectional and surface
morphology as well as the crystalline structure of β-PbO2/TNAs/Ti
anode after five-circle operation are shown in Fig. S7, which still exhibit
the partial inside filling and the local surface covering of β-PbO2.
Meanwhile, the XRD spectrum of the five-time used anode shows no
obvious change compared to the fresh one. In addition, very low lead
ions leakage (ca. 9.84 μg/L) was detected by ICP-MS for the β-PbO2/
TNAs/Ti anode after continuous circulating flow operation, and only
27.2 μg/L of total lead ions leaching concentration was detected after
five consecutive batch experiments, both which are far below the
limiting value of surface water III quality standards (Pb < 50 μg/L) in
China (GB3838-2002). Above results demonstrate the superior cycling
capability and structural stability of the β-PbO2/TNAs/Ti anode.
Generally, a high-performance non-active anode that is qualified for
the practical application in EAOPs is expected possessing a longer
G. Zhang et al.
Fig. 10. (a) Effect of influent flow rate on berberine degradation in β-PbO2/TNAs/Ti + PMS electro-oxidation system operating at continuous circulating flow mode,
(b) the corresponding TOC removal, (c) berberine mineralization during five consecutive batch experiments. Conditions: C0 = 0.1 M, [NaNO3] = 50 mM, j = 17.5
mA/cm2, [PMS] = 10 mM, pH = 4.2, (d) accelerated lifetime test of β-PbO2/TNAs/Ti anode in 0.5 M H2SO4 at current density of 0.5 and 1.0 A/cm2.
service lifetime in the strong acidic media under a high current density
[54]. Considering the substrate corrosion, the deactivation is usually
characterized by a sharp increased cell voltage (Ecell) that reaches or
exceeds 10 V. As seen from Fig. 10d, the lifetime of β-PbO2/TNAs/Ti
anode tested in 0.5 M H2SO4 solution is ca. 128 and 325 h at j = 1.0 and
0.5 A/cm2, respectively. Accordingly, the adjustable parameter, n, of Eq.
S8 was calculated as 1.35. Hence, the actual service lifetime of β-PbO2/
TNAs/Ti anode can be estimated as ca. 3.5 years at 17.5 mA/cm2. This
long service lifetime can be ascribed to: i) employing the additional
anodization in a fluoride-free electrolyte enhances the adhesion of TNAs
to Ti substrate through the formed compact oxide layer, ii) the short-
time cathodic polarization of TNAs promotes β-PbO2 preferential
filling inside TNAs channels, and the formed interlocking “T-shape”
structure was beneficial to increase the adhesion between TNAs and
β-PbO2, inhibiting its peel-off, iii) the β-PbO2 filling and covering can
effectively prevent the infiltration of electrolyte and ROS, leading to a
good corrosion resistance of Ti substrate. In summary, the high oxygen
evolution potential, orderly electrons transfer and good electrical con­
ductivity, long service lifetime and low energy consumption endow the
β-PbO2/TNAs/Ti anode a comparable electrocatalytic and electro-
oxidation performance to the previous reported other non-active
anode materials (Table S5).
4. Conclusions
In summary, employing an additional anodization in a fluoride-free
electrolyte achieved the successful introduction of compact oxide layers
at the bottom of highly ordered anatase TNAs. After selectively convert
12
Chemical Engineering Journal 457 (2023) 141009
the TNAs bottom to a relatively high conductivity state by the short-time
cathodic polarization, β-PbO2 partial filling/covering TNAs anode with
the interlocking “T-shape” structure was facilely fabricated by the cur­
rent pulse electro-deposition approach. The filling of β-PbO2 crystalline
in TNAs’ channels endows β-PbO2/TNAs/Ti anode with excellent
directional electron-transfer efficiency, high OER over-potential and
more available active sites, as a result boosting its electrocatalytic ability
for PMS activation and enabling the electro-generated •OH, SO•− 4 and
1
O2 to efficiently degrade berberine through two pathways. The effects
of common inorganic anions, HA and water matrices together with
continuous circulating flow operation, multi-cycle batch experiments
and service lifetime tests approved that the β-PbO2/TNAs/Ti activated
PMS electro-oxidation system possesses excellent practicability. We
believe that getting good understandings of the interfacial engineering
strategy for β-PbO2 filling inside TNAs, and deep insights into the gen­
eration mechanism of ROS from PMS electro-activation will promote the
extensive application of the tube-filled TNAs-based materials in water/
wastewater treatment.
CRediT authorship contribution statement
Guoquan Zhang: Conceptualization, Methodology, Writing – orig­
inal draft, Writing – review & editing, Supervision. Shaowei Hu:
Investigation, Data curation, Validation, Writing – original draft.
Xiaoyu Zhu: Investigation, Data curation, Validation. Xiaoxin Hu:
Investigation, Data curation, Validation, Writing – review & editing.
Fenglin Yang: Project administration.
G. Zhang et al.
Declaration of Competing Interest
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.
Data availability
The data that has been used is confidential.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (No. 21437001) and the Programme of Introducing
Talents of Discipline to Universities (No. B13012).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2022.141009.
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