catalysts

Article
Do Gas Nanobubbles Enhance Aqueous Photocatalysis?
Experiment and Analysis of Mechanism
Weijia Yu 1,† , Jiaying Chen 1,† , Mohamed Ateia 2,3, * , Ezra L. Cates 3 and Matthew S. Johnson 1, *

1 Department of Chemistry, Faculty of Science, Universitetsparken 5, University of Copenhagen,

DK-2100 Copenhagen, Denmark; weijia@chem.ku.dk (W.Y.); qkn963@alumni.ku.dk (J.C.)
2 Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, USA
3 Department of Environmental Engineering and Earth Sciences, Clemson University, Clemson, SC 29634, USA;
ecates@clemson.edu
* Correspondence: ateia@northwestern.edu (M.A.); msj@chem.ku.dk (M.S.J.); Tel.: +45-35320300 (M.S.J.)
† These authors contribute equally to this work.

Abstract: The performance of photocatalytic advanced oxidation must be improved in order for the
technology to make the jump from academic research to widespread use. Research is needed on
the factors that cause photocatalysis to become self-limiting. In this study, we introduced, for the
first time, nanobubbles continuously into a running photocatalytic reactor. Synthetic air, O2 , and
N2 bubbles in the size range of 40 to 700 nm were added to a reaction system comprising P25 TiO2
photocatalyst in stirred aqueous solution excited by UV-A lamps, with methyl orange as a target
contaminant. The removal of methyl orange was tested under conditions of changing pH and with
the addition of different radical scavengers. Results indicated that the oxygen and air nanobubbles





 improved the photocatalytic degradation of methyl orange—the removal efficiency of methyl orange
increased from 58.2 ± 3.5% (N2 aeration) to 71.9 ± 0.6% (O2 aeration). Dissolved oxygen (DO) of
Citation: Yu, W.; Chen, J.; Ateia, M.;
14.93 ± 0.13 mg/L was achieved using O2 nanobubbles in comparison to 8.43 ± 0.34 mg/L without
Cates, E.L.; Johnson, M.S. Do Gas
Nanobubbles Enhance Aqueous
aeration. The photodegradation of methyl orange decreased from 70.8 ± 0.4% to 53.9 ± 0.5% as
Photocatalysis? Experiment and pH increased from 2 to 10. Experiments using the scavengers showed that O2 − was the main
Analysis of Mechanism. Catalysts reactive species in photocatalytic degradation under highly dissolved oxygen conditions, which also
2021, 11, 511. https://doi.org/ accounted for the observation that the removal efficiency for methyl orange decreased at higher pH.
10.3390/catal11040511 However, without photocatalyst, nanobubbles alone did not improve the removal of methyl orange,
and nanobubbles also did not increase the degradation of methyl orange by only photolysis. These
Academic Editors: Gassan Hodaifa experiments show that oxygen and air nanobubbles can act as environmentally friendly catalysts for
and Ewa Kowalska boosting the performance of photocatalytic water treatment systems.

Received: 19 March 2021

Keywords: nanobubbles; photocatalysis; TiO2 ; methyl orange; dissolved oxygen; scavenger
Accepted: 17 April 2021
Published: 19 April 2021

Publisher’s Note: MDPI stays neutral

1. Introduction
with regard to jurisdictional claims in
published maps and institutional affil- Despite decades of research, photocatalysis has not made the jump from academic
iations. research to widespread use in water treatment and consumer products. Further progress
requires analysis of the factors limiting the performance with the goal of enabling the
technology transfer. In use, photocatalytic pollution control relies on the irradiation of a
photocatalyst resulting in the production of an electron–hole pair. These primary products
Copyright: © 2021 by the authors.
react to produce a cascade of secondary reactive species. Many of the details concerning
Licensee MDPI, Basel, Switzerland.
these species, such as their rate of production, concentration, lifetime, and mutual interac-
This article is an open access article
tions, are only known in broad outline. Going into detail, in the idealized oxidative view,
distributed under the terms and conduction band electrons (e− cb ) react with O2 to form O2 •− , and valence band holes (h+ )
conditions of the Creative Commons react with H2 O to form •OH [1]. Then, O2 •− and •OH react with organic compounds.
Attribution (CC BY) license (https:// While h+ and e− cb could react directly with pollutants, dissolved oxygen and especially
creativecommons.org/licenses/by/ water are likely to be at much higher concentrations than other components and will react
4.0/). first. Reductive photocatalysis can occur in anoxic solution, wherein reactions of e− cb are

Catalysts 2021, 11, 511. https://doi.org/10.3390/catal11040511 https://www.mdpi.com/journal/catalysts

Catalysts 2021, 11, x FOR PEER REVIEW 2 of 14
Catalysts 2021, 11, 511 2 of 14

first. Reductive photocatalysis can occur in anoxic solution, wherein reactions of e−cb are
the
the main
main drivers
drivers of
of contaminant
contaminant degradation
degradation [2].
[2]. The
The loss
loss of
of reactive
reactive radicals
radicals to
to side
side and
and
− +
self-reactions
self-reactions (Figure
(Figure 1),
1), including
including the recombinationofofe e−cb
therecombination and h , is the largest factor
cb and h+, is the largest factor
limiting
limiting the
the performance
performance andand efficiency
efficiency of
of photocatalysts
photocatalysts[3,4].
[3,4].

Figure 1.
Figure 1. Direct
Direct and
and indirect
indirect photocatalytic
photocatalytic degradation
degradation mechanisms
mechanismsof
ofpollutants
pollutantsin
inwater.
water.

− and h+
Researchers
Researchers have tried triedmany
manymethods
methodstotoprevent preventthe the recombination
recombination e−cbeand
of of cb h with
+

with
somesome
success;success; for example,
for example, composite
composite materials
materials havehavebeenbeen developed
developed that that
join join
widewide and
and narrow
narrow band bandgapgap photocatalysts
photocatalysts [5–9]
[5–9] with
with thethedifferent
differentregions
regionsacting
acting asas sources and and
reservoirs of e−−cbcb
reservoirs . Inaddition,
. In addition, defects
defects onon thethe surface
surface of of photocatalysts
photocatalysts cancan
traptrap − and
e−cbeandcb pre-
+ [10,11]. One strategy to prevent the recombi-
prevent
vent them them from from diffusing
diffusing to to stationary
stationary h+ h[10,11]. One strategy to prevent the recombina-
− and +
nation e−cbe and
tion of of cb h+ ishtoistrap to trap the excitation
the excitation in another
in another form. form. The requirements
The requirements werewere to
to gen-
generate species
erate species with
with sufficiently
sufficiently longlifetime
long lifetimeand andreactivity
reactivitywith with target
target compounds.
compounds. The The
− + by converting them into other
strategy
strategy would
would be betotoprevent recombinationofofe e−cbcb and
preventrecombination and hh+ by converting them into other
species, for example, O trapping e − as superoxide, O •− .
species, for example, O22 trapping e as superoxide, O22‧ .
− –

In
In addition
additiontoto chemical
chemical species,
species,physical
physicalstructures including
structures phase boundaries
including phase boundaries should
be included in the discussion. Neppolian et al. [12] showed that
should be included in the discussion. Neppolian et al. [12] showed that reactions on the reactions on the surfaces
of bubbles,
surfaces of bubbles, •OH reactions,
includingincluding accelerate
‧OH reactions, the photocatalytic
accelerate the photocatalyticdegradation of dode-
degradation of
cylbenzensulfonate.
dodecylbenzensulfonate. It had It also beenbeen
had also suggested
suggested that that
the higher
the higherthe the
O2 concentration
O2 concentration in
the solution,
in the solution, thethe
higher
higher thethepollutant
pollutantdegradation
degradationefficiency.
efficiency.Fotiou
Fotiouetetal.al.[13]
[13]reported
reported
that
that when O2 was saturated in the solution, the performance of photocatalysts improved.
when O 2 was saturated in the solution, the performance of photocatalysts improved.
Wöhrle
Wöhrle et et alal [14]
[14] showed
showed that that DODO waswas thethe main
main oxygen
oxygen source
source in in the
the photocatalytic
photocatalytic oxi- ox-
idation of benzene to phenol. Zhang et al. [15]
dation of benzene to phenol. Zhang et al. [15] showed that O2 plays showed that O 2 plays an important
an important role in role
in
the photocatalytic oxidation of alcohols. Overall, on the basis of these studies,
the photocatalytic oxidation of alcohols. Overall, on the basis of these studies, there
there isis
good evidence that dissolved oxygen is a key component of photocatalytic activity [16].
good evidence that dissolved oxygen is a key component of photocatalytic activity [16].
However, the DO level in water is limited not just by its equilibrium with the atmosphere,
However, the DO level in water is limited not just by its equilibrium with the atmosphere,
but also transport into the bulk solution. As a result, most previous studies have been
but also transport into the bulk solution. As a result, most previous studies have been
performed within a narrow range of DO values, and no studies have tested the effect of
performed within a narrow range of DO values, and no studies have tested the effect of
DO on the photocatalytic oxidation under supersaturation conditions.
DO on the photocatalytic oxidation under supersaturation conditions.
Nanobubbles introduce a unique chemical environment that can be used to test
Nanobubbles introduce a unique chemical environment that can be used to test the-
theories regarding the mechanisms and bottlenecks of photocatalysis. Nanobubbles provide
ories regarding the mechanisms and bottlenecks of photocatalysis. Nanobubbles provide
abundant surface interface for a small amount of material, and in addition change the
abundant surface interface for a small amount of material, and in addition change the
chemical composition of the bulk solution [17]. The Kelvin equation describes the vapor
chemical composition of the bulk solution [17]. The Kelvin equation describes the vapor
pressure of a curved surface such as a bubble of gas in a liquid [18]. Moreover, because
Catalysts 2021, 11, 511 3 of 14

of surface tension, the pressure inside a bubble increases with curvature and increases as
the inverse of bubble radius. Very high pressures can be achieved. For example, according
to the Young–Laplace equation, the pressure inside a 100 nm bubble in water is 1.54 MPa
or over 15 bar [19]. Nanobubbles have minimal buoyancy due to their small volume and
can remain suspended in solution indefinitely, allowing their dispersion throughout the
bulk solution.
The rate of oxygen transfer into water depends on the mass transfer coefficient and
the area of the gas–water interface [17]. Nanobubbles have a higher interfacial area per
volume of gas than micrometer or larger bubbles, which results in higher rate of transfer
into water. Research has shown that by using nanobubbles, the mass transfer rate into
water for low solubility gases such as O2 and ozone can double [20,21]. Unique chemistry
occurs on a bubble surface, and high gas pressure can counteract local depletion in DO [17];
equilibrium between the gas and the solution is rapid, occurring in under a second.
The goal of this paper was to test the limits and mechanism of photocatalytic efficiency
by using nanobubbles to impact the recombination of e− cb and holes, due to increased
trapping of e− cb as O2 •− as a consequence of enhanced DO, or because of the trapping of
e− cb or other reactive species on bubble surfaces. The experiments used nano-particulate
titanium dioxide dispersed in water solution containing an organic indicator dye (methyl
orange). Conditions such as pH, addition of scavengers, and presence and composition of
nanobubbles were varied. Photochemistry was initiated using UV-A lamps, and the con-
centration of methyl orange was measured at regular intervals to establish photocatalytic
activity.

2. Results and Discussion

2.1. Bubble Size Distribution and DO Level
Several methods are available for making nanobubbles including hydrodynamic cavi-
tation, particle cavitation, acoustic sonication, electrochemical cavitation, and mechanical
agitation. In this study, hydrodynamic cavitation resulted as a consequence of high flow
velocity caused by the release of a high-pressure gas through a small orifice. As described
by Bernoulli’s equation, the total pressure is conserved and if the dynamic pressure is
increased the static pressure decreases accordingly. If it is lower than the vapor pressure of
the liquid, cavitation results.
ρV 2
PS + = P0 (1)
2
where Ps is the static pressure, ρ the density, V the flow velocity, ρV 2 /2 the dynamic
pressure, and P0 the total pressure to remain constant [22].
Bubbles generated by the ceramic diffuser were mainly from 40 to 700 nm. Oxygen
gas was seen to form smaller nanobubbles (40–700 nm) than air (200–700 nm). The size
distributions are shown in Figure 2. The bubbles generated in this work had size distri-
butions comparable with the bubbles generated in other studies using water circulation
techniques in bubble generators (Table 1). It should be noted that most previous studies
have prepared nanobubble solutions via generators that require circulation of the solution
within the system, which can run only in batch-mode. In this study, however, the use of
the ceramic diffuser is less complex and allows the continuous addition of nanobubbles to
a running reaction.
Catalysts 2021,
Catalysts 11, x511
2021, 11, FOR PEER REVIEW 4 4ofof14
14

18
Air aeration
16 O2 aeration
14

12
Volume / %

10

-2
100 1000
Size / nm
Figure
Figure2.2.Size
Sizedistribution
distributionofofoxygen
oxygenbubbles
bubblesandandair
airnano-bubbles
nano-bubblesgenerated
generatedby bythe
theceramic
ceramicplate
plate
diffuser.
diffuser. The
Theresults
results shown
shown are
are the
the average
average of
of 33 measurements
measurements using
using aa Zetasizer.
Zetasizer.

Table
Table 1.
1. Size
Size ranges
ranges and
and DO
DO concentration
concentration of
of bubbles
bubbles generated
generated using
using different
different gases.
gases.
Gas
Gas
dbubble/nm
dbubble /nm
DO/mg/L DO/mg/L
Reference
Reference
Air
Air 140–350
140–350 10.7 10.7
[23] [23]
OO2 2 137–380
137–380 39.6 39.6
Air
Air 20–20420–204 - -
O2 67–159 - [24]
O2 67–159 - [24]
N2 38–166 -
NO2
2
38–166
100–500 - 30.0 [25]
OAir
2 100–500
400–6990 30.0 9.3 [25] [26]
Air
Air 200–700
400–6990 9.3 8.7 [26]
This study
O2
Air 200–70040–700 8.7 14.9
This study
O2 40–700 14.9
Using different gases, the solutions showed different DO levels. The highest DO was
in the O2 aerated
Using solution,
different gases, which was 14.93
the solutions showedmg/L, while the
different DO least saturated
levels. DO was
The highest DOgener-
was
ated by N bubbling
in the O2 aerated
2 (6.53 mg/L) (the air equilibrated
solution, which was 14.93 mg/L, while the O concentration was 8.18
2 least saturated DO was gen- mg/L).
Compared
erated by Nto nanobubbles
2 bubbling (6.53generated
mg/L) (the byair
generators withO
equilibrated hydrodynamic
2 concentration cavitation
was 8.18method,
mg/L).
the ceramic diffusor that is used in this study could
Compared to nanobubbles generated by generators with hydrodynamicnot result in as high of a pressure as
cavitation
the pump
method, theprovides
ceramic(0.6 MPa),that
diffusor andisthus
usedit did not study
in this reach as highnot
could of aresult
DO concentration
in as high of asa
with the as
pressure nanobubble
the pumpgenerator;
provides (0.6however,
MPa), itandprovides
thus it adid
lowernot cost
reach(Price: ≈166
as high of aUSD, 0 W)
DO con-
compare toasnanobubble
centration with the nanobubble (Price: ≈2000
generatorsgenerator; USD, ≥
however, it3provides
kW) and acontinuous
lower costbubbling.
(Price: ≈
166 USD, 0 W) compare to nanobubble generators (Price: ≈ 2000 USD, ≥3 kW) and contin-
2.2. Effect of Applied Gasses on the Degradation
uous bubbling.
Figure 3 shows the results of methyl orange photodegradation catalyzed by TiO2
with
2.2. different
Effect gas types
of Applied Gassesbubbling continuously and at neutral pH conditions. Control
on the Degradation
tests were performed using only TiO2 or with air, O2 , or N2 bubbles without TiO2 . The
Figure 3 shows the results of methyl orange photodegradation catalyzed by TiO2 with
pseudo-first-order rate was calculated using the following equation:
different gas types bubbling continuously and at neutral pH conditions. Control tests
were performed using only TiO2 or with air, O2, or N2 bubbles without TiO2. The pseudo-
first-order rate was calculated using the following equation:
Catalysts
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11,x 511
FOR PEER REVIEW 5 of 1414
5 of

k0c KO2 [O2 ]

k1 =
= 1 + KO [O2 ] (2)
(2)
1+ 2
wherek1k1isisthe
where thepseudo-first-order
pseudo-first-order raterate constant (min−−11 ) of
constant(min of methyl
methylorange
orangephotodegradation
photodegrada-
(apparent firstfirst
order reaction raterate
constant), 0
k c iskcthe −1 ) [27]
tion (apparent order reaction constant), ' is intrinsic rate rate
the intrinsic constant (min(min
constant −1)

forfor
[27] methyl
methyl orange
orangephotodegradation,
photodegradation, KO2 is Langmuir
andand is Langmuir adsorption
adsorptionconstant of oxygen
constant of ox-
overover
TiO2TiOsurface (L mg −1 ).−1
ygen 2 surface (L mg ).

110
100
(C0-C1) / C0 × 100% / %

90
A
80
70
60
No aeration
50 Air aeration
Oxygen aeration
40 Nitrogen aeration
MO
30 No photocatalyst
20

16

14
B
12
DO / mg/L

10

0 20 40 60 80 100 120
Time / min
Figure
Figure 3. 3.
(A) Photocatalytic
(A) Photocatalyticdegradation
degradationofofmethyl
methylorange
orangewith
withnanobubbling
nanobubblingat atneutral
neutral pH.pH. (B)
(B) The
The disappearance of dissolved oxygen during the experiment in the presence of different
disappearance of dissolved oxygen during the experiment in the presence of different gas-aerated gas-
aerated nanobubbles
nanobubbles at neutral
at neutral pH. Air:pH.
airAir: air aeration,
aeration, 20 mg L20−1 mg ̇L−1 methyl
methyl orange,orange, g ̇L−1; oxygen:
2 g L−12TiO TiO2; oxy-
oxygen
2
gen: oxygen aeration, − 1 20 mg ̇L−1 methyl orange,
− 1 2 g ̇L−1 TiO2; nitrogen: N2 aeration, 20 − 1 mg ̇L−1 me-
aeration, 20 mg −1L methyl orange, 2 g L −1TiO2 ; nitrogen: N2 aeration, 20 mg L methyl orange,
thyl orange, 2 g ̇L TiO2; no aeration: 20−1mg ̇L methyl orange, 2−g1 ̇L−1 TiO2; MO: without aeration
2 g L−1 TiO2 ; no aeration: 20 mg −1 L methyl orange, 2 g L TiO ; MO: without aeration and
and TiO2. No photocatalytst: 20 mg−̇L1 methyl orange, oxygen aeration.2 All experiments include
UVA radiation. The results shown aremethyl
TiO 2 . No photocatalytst: 20 mg L orange,
the average of 3oxygen aeration. and
measurements, All experiments
the error barsinclude
are UVA
radiation. The results shown are the
standard deviation of triplicated experiments. average of 3 measurements, and the error bars are standard
deviation of triplicated experiments.
The methyl orange removal efficiencies with O2, air, and N2 bubbling after 2 h of
The methyl orange removal efficiencies with O2 , air, and N2 bubbling after 2 h of
irradiation were 71.9 ± 0.6%, 64.7 ± 0.3%, and 58.2 ± 3.5%, corresponding to the pseudo-
irradiation were 71.9 ± 0.6%, 64.7 ± 0.3%, and 58.2 ± 3.5%, corresponding to the pseudo-
first order reaction rate constants (k1) of 10.3 ± 0.1 × 10−3, 8.5
−3 ,±8.5
0.3 × 10−3, and−7.3 ± 0.7 × 10−3
3 , and
first order reaction rate constants (k 1 ) of 10.3 ± 0.1 × 10 ± 0.3 × 10 7.3 ± 0.7
min−1, −respectively. Without gas aeration the removal efficiency was 60.3 ± 3.4% with a
× 10 3 min−1 , respectively. Without gas aeration the removal efficiency was 60.3 ± 3.4%
pseudo-first-order reaction rate constant of 7.5 ± 0.6 × 10 min . −
−3 −1 The experiment showed
with a pseudo-first-order reaction rate constant of 7.5 ± 0.6 × 10 3 min−1 . The experiment
Catalysts 2021, 11, 511 6 of 14

showed negligible removal of methyl orange in dark environment or under light irradiation,
which aligned with other studies [28].
With the assistance of O2 nano-bubbles, the photocatalytic performance of TiO2 in-
creased 11.6% compared to no bubbling, and with N2 aeration, the removal of methyl
orange was slightly decreased (−1.9%). The observed results could be due to the follow-
ing factors: (a) dissolved oxygen helps increase photocatalytic oxidation; (b) nanobubble
collapse increases photocatalytic oxidation; (c) the nanobubble surfaces modify the con-
centrations of reactive species acting both as a reservoir and a catalyst. On the basis of the
evidence, we can strike option ‘b’ from the list, while research has shown that during the
process of nanobubble collapse, reactive radicals such as •OH are generated [29]. However,
in our study, O2 nanobubbles alone did not degrade methyl orange. Thus, there was
no evidence that nanobubbles themselves have oxidation potential, but they can act as
co-catalysts.
Reactive oxygen species (ROS) include short-lived radical species such as hydroxyl
(•OH), superoxide (O2 •− ), and singlet oxygen (1 O2 ). Of these, only •OH has been reported
to coexist with nanobubbles [30]; the existence of other ROS species has not been reported
(H2 O2 , 1 O2 , O2 •− ). Liu et al reported 1014 •OH molecule per milliliter were generated from
nanobubbles [31]; however, this was questioned by Yasui et al. as their numerical simulation
suggested that only a few •OH may be created per 107 dissolving O2 nanobubbles without
dynamic stimuli [32]. In our study, without photocatalysts, there was no removal of
methyl orange by using only nanobubbles and light irradiation observed; however, with
the presence of air and O2 nanobubbles, the photocatalytic degradation of methyl orange
increased (with TiO2 and light irradiation).
DO concentrations decreased during the experiments due to the consumption of
dissolved oxygen by the reaction (Figure 3B). The initial DO for air aeration and no aeration
were similar; however, with air nanobubble aeration, the removal efficiency of methyl
orange, 64.7 ± 0.3%, was higher than for no aeration, 60.3 ± 3.4%. This result showed
that introducing nanobubbles into the system enhanced the photocatalytic efficiency of
degrading methyl orange. The depletion rate of dissolved oxygen was calculated by linear
fitting. The absolute value of the depletion rate of dissolved oxygen was 6.16 × 10−2 ,
2.60 × 10−2 , 4.30 × 10−2 mg/(L min) in O2 -, N2 -, and air-saturated solution, respectively.
Without aeration, the rate was 3.86 × 10−2 mg/(L min). With neither TiO2 nor aeration, or
without TiO2 but with O2 aeration, the depletion rate was close to 0. This result indicates
there was no consumption of DO. The O2 -saturated solution showed fastest DO depletion
rate along with the largest k1 . The consumption rate of dissolved oxygen and removal
efficiency of methyl orange were correlated (Pearson’s correlation coefficient 0.9977). This
indicates that dissolved oxygen plays an important role in methyl orange removal.

2.3. The Role of Reactive Species in the Degradation Mechanisms

According to the established mechanisms of photocatalysis, the key reactive species
are the photogenerated h+ and e− cb , and reactive radical species such as O2 •− and •OH [33].
The contributions of the separate reactive species for pollutant removal can be identified
using specific scavengers. All experiments were performed at neutral pH. The charac-
terization of the reactive species was performed by introducing radical scavengers into
the system.
Potassium iodide (KI) [34,35] was used as the h+ and •OH radical scavenger. Sodium
nitrate NaNO3 was used as the e− cb scavenger [36], tert-butyl alcohol (TBA) [37,38] was
the •OH scavenger, and p-benzoquinone (pBQ) [39,40] was the O2 •− scavenger. During
the tests, a 5.5 mM aliquot of a single scavenger was added into solution with 20 mg L−1
methyl orange and 2 g L−1 TiO2 to monitor the change of methyl orange removal efficiency
compared with the results from tests without scavengers.
As shown in Figure 4, the inhibition effects of KI, TBA, NaNO3 , and pBQ without
aeration were 28.2%, 47.0%, 26.5%, and 24%, respectively.
Catalysts
Catalysts 2021,
2021, 11,
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FOR PEER REVIEW 7 7ofof14
14

100 A
80 Without Scavenger
NaNO3
60 TBA
KI
40 pBQ

C/C0 / %
100
0 20 40 60 80 100 120
B
80
60
40
0 20 40 60 80 100 120
100
C
80
60
40

0 20 40 60 80 100 120
Time / min
Figure4.4.The
Figure Theeffects
effects ofof scavengers
scavengers onon
thethe photodegradation
photodegradation of methyl
of methyl orange
orange without
without aeration
aeration
(conditions: 2020 mg − 1
mg LL methylmethylorange, − 1
orange,22ggLL TiO TiO , UVAirradiation,
irradiation,neutral
neutralpH).
pH).(A):
(A):Air
Airbub-
bubbling;
(conditions: −1 −1 2, 2
UVA
(B): N(B):
bling; 2 bubbling; (C): no
N2 bubbling; aeration.
(C): Potassium
no aeration. Potassiumiodide iodide h+ and
(KI):(KI): •OH
h+ and ‧OH
scavengers, sodium
scavengers, sodiumnitrate
nitrate
(NaNO(NaNO − 3):scavenger,
3 ): e cb e−cb scavenger, tert-butyl
tert-butyl alcohol
alcohol (TBA):
(TBA): •OH‧OH scavenger,
scavenger, andp-benzoquinone
and p-benzoquinone(pBQ):
O2 •− scavenger.
(pBQ): O2·− scavenger.

As
As shown
shown inin Table
Table 2, 2, the pseudo-first-order
pseudo-first-order reaction
reaction rate
rate constant
constant k11 decreased
decreased to to
min−1−when
0.0017min
0.0017 1 when pBQ was added, thus indicating the O·− •− played a predominant role
pBQ was added, thus indicating the O2 2played a predominant role in
in the
the air air nanobubble
nanobubble photocatalytic
photocatalytic degradation
degradation ofofmethyl
methylorange.
orange.With
Withthe
theaddition
addition of of
NaNO33, ,kk11decreased
NaNO decreased to 0.0026 min−
to 0.0026 −1,1 ,which
whichwe
weinterpret demonstrating ee−−ebebisisanother
interpret as demonstrating another
majoractive
major active species of air
air nanobubble
nanobubblephotocatalytic
photocatalyticdegradation
degradationofofmethyl
methylorange.
orange. With
Withh+
−1−1while with only •OH, k
hand •OH
+ and ‧OHtogether,
together,k1kdecreased
1 decreased toto0.0042
0.0042 min
min while with only ‧OH, k11 was 0.0066 min min−−11. .
+ •OH
With N
With aeration,hh and
N22aeration, + and ‧OH play
play a dominant
a dominant rolerole
duedue to the
to the lowlow dissolved
dissolved oxygenoxygen in
in the
the solution.
solution.
Table 2. Comparison of different gas aeration methods and decrease in the apparent first-order reaction rate constant k1
Table 2. Comparison of different gas aeration methods and decrease in the apparent first-order reaction rate constant k1
(/min)for
(/min) fordifferent
differentscavengers
scavengers(20 mgLL−1−methyl
(20mg 1 methyl orange, 2 g L−1 TiO , UVA).
orange, 2 g L−1 TiO2, UVA).
2

Target Reactive
Target Reactive k1 for No No
k1 for kk11 for
for Air
Air k1 for
k1 for N2N2
Species Aeration/min−1 Aeration/min−−11 Aeration/min −1
Species Aeration/min −1 Aeration/min Aeration/min −1

7.5 × −3 −3 −3
Without
Withoutscavengers
scavengers 7.510× 10−3 8.5×× 10
8.5 10−3 ××
7.37.3 1010
−3
KI h+ and •OH 2.8 × 10−3 −3 4.2 × 10−−33 2.9 × 10 −3
KI h+ and ‧OH 2.8 × 10 4.2 × 10 2.9 × 10−3 −3
TBA •OH 5.1 × 10−3 −3 6.6 × 10−−33 4.4 × 10
TBA e− cb‧OH 5.1 × 10 6.6 × 10 4.46.3
××1010
−3
NaNO 3 3.5 × 10−3 2.6 × 10−3 −3
NaNO
pBQ 3 O2 −e cb
−
3.6 × 10×−10
3.5 3 −3 2.6×× 10
1.7 10−−33 6.36.4
××1010
−3 −3

pBQ O2 − 3.6 × 10−3 1.7 × 10−3 6.4 × 10−3

Without aeration, O •− and e− cb are dominant, making similar contributions to the
Without aeration, O2·−2 and e−cb are dominant, making similar contributions to the me-
methyl orange removal. With these conditions, they are more important than h+ and •OH.
thyl orange removal. With these conditions, they are more important than h+ and ‧OH.
The large decrease in the methyl orange removal efficiency when using pBQ in air
The large decrease in the methyl orange removal efficiency when using pBQ in air
aeration and O2 aeration shows that the dominant reactive species of methyl orange
aeration and O2 aeration shows that the dominant reactive species of methyl orange deg-
degradation in an oxygenated environment was O2 •− , in accordance with other reports
radation in
(Table 3). an oxygenated environment was O2·−, in accordance with other reports (Table

3).
Catalysts 2021, 11, 511 8 of 14

Table 3. Comparison of effect of different reactive species in other studies.

Contaminant Photocatalyst Scavenger Target Reactive Species Removal Efficiency (%) Conditions References
- - 60.3 ± 3.4
KI h+ and •OH 28.2
Methyl orange 120 min 14.7 W UVA irradiation,
P25 TiO2 (2 g/L) tert-butyl alcohol (TBA) •OH 47.0 this study
(20 mg/L) without bubbling, 2 L solution
NaNO3 e− cb 33.75
pBQ O2 •− 36.3
- - 95.0 (air-equilibrated)
benzoquinone (BQ) O2 •− 13.0
Methyl orange 4 W UV lamps (centered at 365 nm),
P25 TiO2 (0.53 g/L) AgNO3 e− cb 55.0 [38]
(6.1 × 10−5 M) 120 min irradiation, 150 mL solution
TBA •OH 91.0
ammonium oxalate h+ 64.0
- - ≈92.0
Methyl orange 5% SnSO4 -modified TiO2 2 mM BQ O2 •− ≈19.3 14 h visible light irradiation,
[41]
(20 mg/L) (0.2 g/L) 2 mM KI h+ and •OH ≈28.3 150 mL solution
40 mM isopropanol •OH ≈49.1
- - 88.0
Methyl orange 60 min visible light irradiation,
g-C3 N4 @MoS2 /TiO2 (1 g/L) TBA •OH 70.0 [42]
(1 × 10−5 M) 50 mL solution
BQ O2 •− 10.0
Catalysts 2021, 11, 511 9 of 14

Therefore, we conclude that photogenerated h+ and •OH together make the main
contribution towards oxidizing methyl orange, both with and without nano-bubbling,
while O2 •− was the main reactive oxidizing reagent in a dissolved oxygen-rich environment.
In N2 nanobubble photocatalytic degradation, •OH contributed most to the degradation
of methyl orange. A study by Temesgen et al. showed that the surfaces of nanobubbles
are negatively charged with OH− from the water molecules [22], which might provide the
reactive species in a low dissolved oxygen environment.
Wang et al. [25] reported over 60% of oxytetracycline (OTC) was directly photode-
graded (k = 3.92 × 10−3 min−1 ) in the presence of only O2 nanobubbles with sizes in the
range from 100 to 500 nm after 240 min of visible light. In their study, •OH was shown to
be the main reactive species of OTC degradation, and 20% of OTC would degrade with
only photolysis. The main reactive species for degrading methyl orange was found to be
O2 •− in the present work; our study showed no degradation with only O2 nanobubbles
and photolysis. This might suggest that different pollutants undergo different degrada-
tion mechanism, and that adding O2 nanobubbles for water treatment may not affect the
degradation of all pollutants similarly.

2.4. Effect of pH
The pH value had a critical effect on the efficiency of photocatalytic reactions. The
influence of solution pH on the process was determined using a constant concentration
of methyl orange at 20 mg L−1 , 2 g L−1 TiO2 with O2 nanobubbles, and without
Catalysts 2021, 11, x FOR PEER REVIEW 9 ofbubbling
14
by varying pH from 2 to 10. The results are shown in Figure 5 and Table 4. The lowest
removal efficiency for methyl orange was detected at pH = 10 with and without bubbling,
and thethe
and highest
highestremoval
removalefficiency
efficiency was
was found at pH
found at pH==22and
andpH
pH= = 5 for
5 for nono bubbling
bubbling andand air
air bubbling,
bubbling, respectively.
respectively.

100
No Aeration
80
pH = 2
60 pH = 5
pH = 7
C/C0 / %

40
pH = 10
20
0 20 40 60 80 100 120
100
O2 Nanobubbles
80

60
pH = 2
40 pH = 5
20 pH = 7
pH = 10
0
0 20 40 60 80 100 120
Time / min
Figure 5. Photocatalytic degradation of methyl orange at different pH values with oxygen nanobubbles (conditions:
Figure 5. Photocatalytic degradation of methyl orange at different pH values with oxygen nanobubbles (conditions: 20 mg
20 mg L−1−1 methyl orange, 2−1g L−1 TiO2 , 14.7 W UVA irradiation).
L methyl orange, 2 g L TiO2, 14.7 W UVA irradiation).

The methyl orange (MO) adsorption efficiency of TiO is significantly impacted by

The methyl orange (MO) adsorption efficiency of TiO2 is 2significantly impacted by
thethe
changing
changingelectrostatic interactionbetween
electrostatic interaction between TiO
TiO 2 and
2 and MOMO under
under the different
the different pH con-
pH con-
ditions [43]. The adsorption efficiency values at different pH values are summarized
ditions [43]. The adsorption efficiency values at different pH values are summarized in in
Table 5. The highest adsorption capacity (31.0 ± 4.2%) was observed at pH = 5, while no
MO adsorption occurred on the surface of TiO2 at pH = 10. These differences resulted from
the changes in the charge of MO and the surface charge of TiO2 particles. The point of zero
charge of TiO2 is at pH = 5.8 ± 0.1 [44]; if the pH is more acidic than this value, the surface
is positively charged, TiO2 + H+ →TiO2H+, and if pH is above this value, it is negatively
− −
Catalysts 2021, 11, 511 10 of 14

Table 5. The highest adsorption capacity (31.0 ± 4.2%) was observed at pH = 5, while no
MO adsorption occurred on the surface of TiO2 at pH = 10. These differences resulted from
the changes in the charge of MO and the surface charge of TiO2 particles. The point of zero
charge of TiO2 is at pH = 5.8 ± 0.1 [44]; if the pH is more acidic than this value, the surface
is positively charged, TiO2 + H+ →TiO2 H+ , and if pH is above this value, it is negatively
charged, TiO2 + OH− → TiO2 OH− [45]. Thus, at acidic pH values, negatively charged
nanobubbles will be attracted to the surface. The methyl orange indicator has a pKa value
of 3.47. At pH values above this value, the molecule is negatively charged [46]. In this form
there is electrostatic repulsion between the negatively charged TiO2 and negatively charged
sulfate group on the azo-form methyl orange, leading to no methyl orange adsorption on
the TiO2 surface. Under conditions with pH below pKa, methyl orange is better adsorbed
since the RSO3 − is attracted by positively charged surface functionalities. According to
the scavenger test the main reactive species for degrading methyl orange is O2 •− , while at
high pH, the high concentration of OH− may limit the separation of electron–hole pairs,
which will further inhibit photocatalytic activity. Since pKa of the O2 •− /HO2 • was 4.8,
HO2 may act as a stronger oxidant than O2 •− , which could be contributing to the faster MO
degradation at pH = 2. Compared to other studies (Table 5), at lower pH, the photocatalytic
reaction presented the highest removal efficiency in most cases. The trend of the effect of
pH did not change because of higher oxygen dissolved in solution.
At pH = 10, the removal decreased compared to no aeration. Nanobubbles were
proved to be negatively charged from pH 2 to 12 [22], and the magnitude of the negative
zeta potential of nanobubbles increased monotonically as a function of pH. At pH = 10, the
zeta potential of oxygen nanobubbles could reach to −32 mV, resulting in a negative charge
on nanobubble’s surface. At low pH, nanobubbles are expected to have a short lifetime due
to the lack of OH− ions needed to form a stable electric layer around the bubble surface,
while in alkaline solutions, the bubbles are more stable and have a longer lifetime [47].
Agrawal et al. [48] showed that lower pH enhances the generation of free radicals. Our
experimental results confirm these findings.

Table 4. Summary of results for methyl orange photodegradation as a function of pH (conditions: 20 mg L−1 methyl orange,
2 g L−1 TiO2 , UVA).

Methyl Orange Degradation Methyl Orange Photodegradation Methyl Orange Adsorption

pH
Efficiency without Aeration/% Efficiency with O2 Bubbling/% Efficiency (%)
2 70.8 ± 0.4 75.6 ± 1.0 29.4 ± 2.1
5 66.4 ± 0.7 83.1 ± 2.3 31.0 ± 4.2
7 60.1 ± 0.4 71.9 ± 0.6 18.3 ± 2.5
10 53.9 ± 0.5 39.4 ± 1.0 −0.4 ± 1.3

Table 5. Comparison of pH effect with other studies.

Contaminant Photocatalyst pH Removal Efficiency/% Conditions Reference

2 70.8 ± 0.4
Methyl orange 5 66.4 ± 0.7 120 min 14.7 W UVA irradiation,
P25 TiO2 (2 g/L) this study
20 mg/L 7 60.1 ± 0.4 without bubbling, 2 L solution
10 53.9 ± 0.5
2 93.2 300 W medium-pressure mercury
Methyl orange
TiO2 /PW12 4 54.5 lamp (MPML, λmax = 365 nm), [49]
10 mg/L
6.4 10.0 60 min irradiation, 20 mL solution
3 93.7
Methyl orange 45 W fluorescent lamp, 60 min
TiO2 /Cs–MT 6.3 98.0 [50]
20 mg/L irradiation, 20 mL solution
9 94.3
3 43.0
medium-pressure mercury vapor
Methyl orange 5 72.0
Ag-DP25 (0.16 g/L) lamp (350–400 nm), 60 min [51]
10 mg/L 6.6 100.0
irradiation, 250 mL solution
9 51.0
Catalysts 2021, 11, 511 11 of 14

3. Materials and Methods

3.1. Chemical and Reagents
UV-A light from 340 to 400 nm was generated using 1 PL-L 24W/10/4P lamp with
light intensity of 4.9 W of UV-A output from Philips with a maximum intensity at 365 nm.
The concentration of methyl orange (pH 3.0–4.4, Sigma-Aldrich, St. Louis, MO, USA)
was 20 mg/L. The P25 TiO2 was purchased from Sigma-Aldrich (St. Louis, MO, USA,
21 nm primary particle size, ≥99.5% purity on a trace metals basis) and added at a nominal
concentration of 2 g/L. O2 (Air Liquide, Alphagaz−1, 99.5%, Taastrup, Denmark), and
N2 (Air Liquide, Alphagaz−1, 99.995%) were used without further purification. Filtered
compressed technical air was used as supplied by university facilities. Ceramic micro
bubble diffusers (PMBD 75, Point Four Systems, Airoxi, India) were used to produce
uniform fine bubbles from 100 to 500 nm, with gas pressures from 1.7 to 2.4 bar [52].

3.2. Sample Characterization

The gas bubble size distribution was measured using a Zetasizer (Brookhaven In-
struments, Holtsville, NY, USA). The DO concentration and pH were measured using the
Multiparameter Meter edge® from Hanna Instruments, Kungsbacka, Sweden.

3.3. Experiment Setup

The photocatalytic activity of TiO2 nanoparticles was quantified by monitoring the
photodegradation of methyl orange in aqueous solution with continuous supply of nanobub-
bles, under UVA irradiation. Photocatalytic tests were carried out using a beaker filled
with an aqueous suspension (2 L) containing methyl orange, TiO2 , and the nanobubble
generator with different types of gas; without aeration, pure N2 , pure O2 , and with clean
technical air.
Initially, 20 mg/L of methyl orange was put into a beaker with Milli-Q water and
stirred for 10 min. The pH of the solution was adjusted using NaOH or HCl and measured
with the pH meter. TiO2 (2 g/L) was added into a stirred beaker under dark conditions
for 30 min. Keeping it in the dark, the nanobubble generator with the selected gas (pure
N2 , pure O2 , or clean technical air; flow rate: 100 mL min−1 ) generates nanobubbles
with inherently different DO levels. After 30 min, the system was irradiated under UVA
light until the initial dissolved oxygen concentration reached a constant level, keeping the
solution in a water bath at 23 ± 2 ◦ C with continuous magnetic stirring. The UV lamps
were immersed in the solution with a light path of 12 cm. Next, samples were taken at
specific time intervals. After centrifugal separation, twice at 5000 rpm for 20 min (Labofuge
200, Heraeus Sepatech GmbH, Oesterode, Germany ), the absorption spectra of methyl
orange in supernatant were analyzed with a UV–VIS spectrophotometer (UV−2401 PC,
Shimadzu Inc., Columbia, MD, USA).

4. Conclusions
We studied the synergistic effect of nanobubbles and TiO2 photocatalysis on the
degradation of methyl orange under UVA light for the first time. By adding oxygen
nanobubbles, we increased photocatalytic degradation from 58.2 ± 3.5% (N2 aeration)
to 71.9 ± 0.6%, whereas without aeration, the removal efficiency was 60.3 ± 3.4%. This
may have been due to increased DO, increased oxygen gas/water surface area, or the
presence of oxygen bubbles on the photocatalyst surface. Methyl orange could not be
directly degraded by nanobubbles without irradiation or without the photocatalyst, while
during the photocatalytic reaction, the consumption of DO may enhance the generation of
reactive species, thus improving the removal efficiency. The removal efficiency was greater
at acidic pH. Scavenger tests showed that h+ , •OH, O2 •− , and e− cb were the reactive species
in the methyl orange degradation. The dominant active species in the reaction with high
dissolved oxygen condition was O2 •− /HO2 • , while in low dissolved oxygen solution, h+
and •OH were the main reactive species. This study suggests that nanobubbles may be a
novel method for enhancing the photocatalytic degradation of organic pollutants.
Catalysts 2021, 11, 511 12 of 14

Author Contributions: Conceptualization, M.S.J., M.A. and W.Y.; methodology, M.S.J., M.A. and
W.Y.; experiments, J.C. and W.Y.; validation, M.S.J., M.A. and E.L.C.; formal analysis, J.C., W.Y. and
M.A.; writing—original draft preparation, W.Y.; writing—review and editing, W.Y., J.C., E.L.C., M.S.J.
and M.A.; supervision, M.S.J., M.A. and E.L.C. All authors have read and agreed to the published
version of the manuscript.
Funding: This paper was funded by the Chinese Scholarship Council and the Department of Chem-
istry of the University of Copenhagen.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author. The data are not publicly available due to privacy.
Conflicts of Interest: The authors are aware of no conflicts of interest.

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