Trends in Analytical Chemistry 156 (2022) 116715

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Trends in Analytical Chemistry

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

Dielectric barrier discharge plasma for nanomaterials: Fabrication,

modification and analytical applications
Juan He a, Xiaohui Wen a, Lan Wu a, Hanjiao Chen a, Jing Hu a, *, Xiandeng Hou a, b, **
a
Analytical & Testing Center, Sichuan University, Chengdu, Sichuan, 610064, China
b
Key Lab of Green Chem & Tech of MOE at College of Chemistry, Sichuan University, Chengdu, Sichuan, 610064, China

a r t i c l e i n f o a b s t r a c t

Article history: Recently, blooming studies of nanomaterials have attracted great interest of scientists for developing
Received 11 May 2022 diverse applications in analytical chemistry. Among the various methods available today for nano-
Received in revised form materials synthesis, the ones by use of dielectric barrier discharge (DBD) plasma are relatively new,
9 June 2022
which is a typical low-temperature atmospheric pressure non-thermal plasma, composed of abundant
Accepted 9 June 2022
Available online 14 June 2022
active free radicals, high-energy electrons and excited species. With a series of unique advantages of
being prone to chemical reactions, low power consumption, simple construction and atmospheric
operation at room temperature, the DBD plasma technology has been widely used in the synthesis and
modification of various nanomaterials. This review first highlights the recent updates on DBD plasma-
based synthesis and modification of nanomaterials; then, the applications are summarized concerning
plasma-synthesized nanomaterials and DBD plasma in analytical chemistry; and finally, further appli-
cations are prospected for DBD plasma-assisted synthesis of nanomaterials and related analytical
chemistry.
© 2022 Elsevier B.V. All rights reserved.

1. Introduction discharge, radio frequency discharge, corona discharge, sliding arc

Plasma is known as the “fourth state” of the substance apart
from solid, liquid and gas, which is generally described as a
collection of excited electrons, ions, atoms, radical species, photons
and nonionized neutral particles, and the overall state of the
plasma is generally electrically neutral. It can be classified as high-
temperature plasma and low-temperature plasma based on the
temperature level. In high-temperature plasma, the gas is almost all
ionized, the electron temperature is almost equal to the ion tem-
perature. The gas temperature can be more than 10,000
Celsius,
which is in a state of thermodynamic equilibrium and generally
refers to nuclear fusion plasma. Compared with high-temperature
plasma, low-temperature plasma has a much lower particle tem-
perature and density, the gas in the low-temperature plasma is
partially ionized, and the electron temperature is much higher than
the ion temperature, which is in a state of non-thermodynamic
equilibrium. At present, it is known that various discharge
schemes including dielectric barrier discharge, jet discharge, glow
* Corresponding author.
** Corresponding author. Analytical & Testing Center, Sichuan University,
Chengdu, Sichuan, 610064, China.
E-mail addresses: hujing2019@scu.edu.cn (J. Hu), houxd@scu.edu.cn (X. Hou).
discharge, etc. can generate low-temperature plasmas.
Dielectric barrier discharge (DBD) is known as dielectric barrier
corona discharge or silent discharge [1], which is originally reported
with coaxial cylindrical electrode structure to generate ozone by
Siemens [2]. Typical DBD devices can be divided into flat plate type
(Fig. 1aec) and coaxial type configuration (Fig. 1def), where at least
one piece of dielectric barrier is inserted between the two electrodes
to limit the discharge current and prevent complete breakdown.
Thus, the sustained plasma generated by DBD is distributed across
the electrode area, effectively expanding the plasma size and their
coverage. The discharge zone/area is filled with working gas (argon,
helium, nitrogen or air). When a high-voltage alternating current is
applied to both ends of the electrodes, DBD will discharge and
generate high-energy electrons that inelastic collide with sur-
rounding gas molecules, which could excite or dissociate them to
produce plasma containing a variety of substances, including high-
energy and high-density electrons, a large number of free radicals,
UV photons, excited atomic and molecular species, excimer mole-
cules and excited state particles with active chemical properties.
Thus, some reactions requiring high temperature or noble metal
catalysis in conventional chemistry could be easily realized under the
low temperature DBD conditions.

https://doi.org/10.1016/j.trac.2022.116715
0165-9936/© 2022 Elsevier B.V. All rights reserved.
J. He, X. Wen, L. Wu et al.
Fig. 1. Different types of DBD plasma configurations [3]. Electrode: metals such as aluminum and copper; Dielectric: materials such as glass, quartz, polymer or ceramic.
Most importantly, among different sources of plasma, DBD is a
typical ‘‘cold’’ non-equilibrium low-temperature plasma with the
characteristics of high electron temperature (103e104 K) and low
macroscopic temperature. Since DBD plasma can be generated
under normal room temperature and atmospheric pressure
without the need for vacuum, it is a relatively simple, cost-effective,
and maintainable technique to create non-equilibrium plasma in
the laboratory. This non-equilibrium of DBD plasma is of great
significance to chemical reactions. On the one hand, the energy of
electrons can effectively activate relatively stable (or even inert)
small molecules to initiate chemical reactions, while the entire
reaction system can be kept at lower temperature, which is bene-
ficial for industrial acceptance, popularization and application. On
the other hand, different from other nonthermal plasmas, the
uniformity of DBD plasma is very conducive to the modification of
nanomaterials.
Therefore, DBD has demonstrated attractive properties including
strong excitation capability, simple configuration, atmospheric
pressure working conditions, low power consumption, and the
presence of a diversity of reactive species. These extraordinary
chemical characteristics have made DBD plasma profoundly useful in
diverse applications including instrument miniaturization [4,5],
atomic spectrometry [6e8], nanomaterials production [9e12], sur-
face modification [13,14], and pollution degradation [15e22] in
recent years. Besides, DBD is also an attractive and efficient way for
the generation of light or the excitation of excimer radiation based on
the UV or VUV photons emitted from the plasma [23], which are
developed as new light sources, especially ideally suited for excimer
lamps for many photophysical and photochemical applications [24].
The previous reviews have summarized the generation [25],
characteristics [25], and applications of DBD in ozone generation
[26], catalyst synthesis [27], heterocatalysis [28], medicine [25],
biomedical application [29] and analytical spectrometry [4,30,31].
DBD also plays an extremely important role in the miniaturization
of analytical instruments as the excimer radiation sources [32], the
excitation sources or ion sources [33]. Benefited from unique op-
tical, electrical, magnetic, and special physical or chemical prop-
erties, nanomaterials have developed rapidly in various fields of
science and technology over the past few decades [34]. Low-
temperature DBD plasma is now widely used in research
regarding the rapid synthesis and processing of nanomaterials,
which has received increasing attention in the field of analytical
chemistry, extending the use of nanomaterials for various appli-
cations such as sensor, adsorption, separation, and photocatalysis.
Therefore, this review mainly aims to sum up the analytical appli-
cations of nanomaterials prepared with DBD in recent years,
involving nanomaterial synthesis, nanomaterial modification, and
their applications in analytical chemistry as shown in Fig. 2.
2. Applications for nanomaterial synthesis
Owing to the attractive chemical and physical properties
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Trends in Analytical Chemistry 156 (2022) 116715
different from bulk materials, nanomaterials have drawn extensive
attention in recent years. To meet the increasing demand for
nanomaterials in science and industry, there is an urgent need to
develop green, cost-effective, energy-saving methodologies for
nanomaterial synthesis. DBD plasma technique is a powerful
method for the rapid synthesis of diverse nanomaterials originated
from the highly tunability of plasma properties. Any of the common
gases such as H2, O2, N2, air, I2, CO2, Ar, NH3 and H2S or conventional
solvent can be used to generate DBD plasma. The composition and
proportion of the plasma species differ in the different discharge
medium, and thus different nanomaterials can be prepared.
Therefore, by fine-tuning the discharge feeding gas such as H2
(reducing), Ar (inert) and O2 (oxidizing), the properties of the
plasma can be modulated to achieve diverse nanomaterial
synthesis.
2.1. Inorganic nanomaterials
2.1.1. Metal nanomaterials
DBD has been widely used for the preparation of metal nano-
particles (NPs) with nano size and great dispersibility owing to the
high-energy electron reduction (normally in inert gas plasma such
as Ar and He), or high-energy hydrogen radicals and other reducing
substances in the hydrogen plasma. The former plasma can reduce
metal ions with positive standard electrode potential such as Ag,
Au, Pt, Pd, Ir, Rh, etc., while the latter plasma, which is more
effective than electron reduction, can not only reduce metal ions
with positive standard electrode potential, but also some metal
ions with negative standard electrode potential, such as Co and Ni
[35]. For instance, a compact bench-top DBD argon plasma reactor
was developed to generate active electrons by Fortin for the
continuous-flow and automated preparation of gold nanoparticles
[36]. Over 99% of the gold ions was reduced by Ar plasma treatment
within 30 min, which can be monitored by UVevisible spectrom-
etry in real time. With higher reducibility compared to Ar plasma,
Ar/H2 mixture plasma has been reported to prepare Pt, Pd, and Rh
nanoparticles by reducing the metal ions in aqueous solution [37].
It was proved to be an efficient and green way to the recovery of
metal elements (Au and Pd) from wastewater as nanoparticles
(Fig. 3) [38]. Xu et al. used Ar/H2 plasma to synthesize Cu nano-
particles by reduction of CuO [39]. H2 content in the mixture gas
plays an important role in the reduction efficacy since excited-state
hydrogen molecules are effective reducing agents other than high-
energy electrons or heating effect. Therefore, metal nanoparticles
can be prepared not only by the reduction of metal ions but also by
the direct reduction of metal oxides by DBD plasma.
2.1.2. Metal oxide nanomaterials
Argon and hydrogen plasmas mainly generate reductive elec-
trons and active species for the reduction of materials, thereby
resulting in the preparation of metal NPs; in contrast, argon and
oxygen will generate more reactive oxygen species to realize the
J. He, X. Wen, L. Wu et al. Trends in Analytical Chemistry 156 (2022) 116715

Fig. 2. Schematic representation of the fabrication, modification and analytical application of nanomaterials by use of DBD plasma. NMs: nanomaterials.

Fig. 3. The reduction of metal ions to metal NPs by Ar/H2 DBD plasma. Reproduced with copyright permission from Ref. [38].

oxidation of metal, which helps the stoichiometric formation of Besides, air-DBD plasma is applied for direct oxidation of the
metal oxide nanomaterials. Mok's research team prepared a variety surface of NieFe foam to generate active metal oxides sites (e.g.,
of oxide nanomaterials including SiO2, CuO, RuO2, and RuO2 based NiO, Fe2O3) for further preparation of crosslinked trimetallic CoS/
nanocomposites [40] with good crystallinity from treating their salt Ni3S2eFeS nanopetals [42]. With the combination of air-DBD
solution precursors using DBD argon plasma. It was noted that plasma with sol-gel method, Liu et al. synthesized MnOx, CeO2
plasma constituents interact differently with various materials, and MnCeOx composite oxides catalysts [43], which possess
giving rise to different metal oxide nanomaterials with diverse enhanced surface active oxygen concentration and higher NO
surface morphologies (Fig. 4). During the growing process of semi- oxidation efficiency compared with traditional calcined catalysts.
conductor, the electron accumulation and the potential gradient
drove the one-dimensional growth of CuO and RuO2 NPs. On the
2.1.3. Metal-based other nanomaterials
other hand, the energy dissipation mechanism in insulator particle
In addition to common gases, iodine vapors can also be intro-
favors the growth of SiO2 into spherical shapes morphology. They
duced into DBD reactors as discharge gases to produce abundant
also found the surface morphology of Ag2O NPs change from
active iodine substances. In Xia's work [44], active iodine plasma
“garland-like” to “flower-like” and “leaf-like” at different NaOH
was used to rapidly react with metal substrates to obtain metal
concentrations, while the change of discharge voltage does not
iodide. Interestingly, copper wire was used as both inner electrode
affect the morphology of Ag2O since electrons are highly mobile
and metallic precursors to prepare CuI particles via 10-min treat-
over the entire surface of nucleated Ag2O [41]. The composition of
ment by iodine DBD plasma without additional metal ion solution.
DBD gas also plays crucial roles in controlling the morphological
Based on the same mechanism, CuI nanosheet arrays could be
structures of metal oxides nanomaterials. RuO2 nanomaterials with
formed within 1 min on Cu foam by iodine DBD plasma treatment,
various morphologies were synthesized by controlling the feed gas
which was followed by an anion exchange reaction between S2
such as Ar or Ar/O2 mixture, which created an inert or oxidation
and the CuI to prepare a 3D Cu2S/CF OER catalyst in the work of He
atmosphere, respectively. Therefore, DBD plasma can also realize
et al. [44].
the morphology control of various metal oxides nanomaterials.
The discharge medium of the liquid phase plasma is much more
3
J. He, X. Wen, L. Wu et al.
Fig. 4. Schematic illustration of the growth of SiO2, CuO, and RuO2 in the presence of Ar DBD plasma. Reproduced with copyright permission from Ref. [40].
complex, and there are higher requirements for the liquid
discharge. The application of liquid-phase plasma for the synthesis
of inorganic nanomaterials is less common compared with the gas-
phase plasma as mentioned above. However, the types of active
substances produced by liquid-phase plasma are also abundant,
possessing higher density of radicals and electrons [45], making it
outstanding in the synthesis of some types of nanomaterials
especially nano-composite materials. Therefore, in recent years, it
has received more and more attention and been utilized in the
synthesis of various nanomaterials such as metal nanoparticles [46]
and layered double hydroxides (LDHs) [47,48]. Huang and co-
workers introduced Ni2þ, Fe3þ and carbonate (Ci) solution into the
DBD microplasma device with a piece of carbon cloth (CC) inside,
and carbonate-modified NiFe LDH-Ci nanosheets array on CC with
excellent oxygen evolution reaction (OER) catalytic performance
was obtained after 1 h plasma treatment [48]. Later, they used the
same liquid DBD plasma strategy to prepare 3D CoO supported NiFe
LDH nanosheets array on Ni foam (NF) [47]. It is worth mentioning
that cationic defect and anion dual-regulated layered double hy-
droxide can be easily realized via a modified water DBD plasma
treatment. Plasma treatment of pristine CoAl LDHs by introducing
sulfide ions to the aqueous solution was used to obtain S2 regu-
lated CoAl LDHs with abundant Al3þ vacancies, resulting in
improved conductivity and OER performance [49]. Compared to the
majority of conventional synthesis strategies of metal and metal-
oxide nanoparticles, plasma synthesis avoids the use of poten-
tially biologically and environmentally toxic reducing reagents,
stabilizer and dispersants, making it a reliable, eco-friendly, cost-
effective, and rapid strategy for synthesis of metallic NPs.
2.2. Organic nanomaterials
Organic nanomaterials [50] such as carbon nanomaterials
(CNMs), porous carbons (PCs), carbon nanotubes (CNTs), reduced
graphene oxide (rGO), carbon quantum dot (CQDs) have attracted
great interest in supercapacitors, batteries, microextraction and
sensing areas [51]. With the sprouting of organic materials with
excellent physical and chemical properties, it is necessary to
develop more synthesis and modification methods to further
explore their applications in diverse fields.
With the continuous development of plasma synthesis tech-
nology, a series of different organic nanomaterials have been
successfully synthesized by DBD plasma. For instance, Lin et al.
reported that one-step in situ preparation of porous carbons on
4
Trends in Analytical Chemistry 156 (2022) 116715
different metal surfaces could be achieved in a room-temperature
DBD plasma at atmospheric pressure [52]. In their work, a coaxial
cylindrical DBD was developed with different metal electrodes,
including copper, aluminum, iron, gold, silver, platinum and
stainless-steel fiber, as both the substrate for deposition of the PCs
and the inner electrode, and ethanol vapor introduced by argon
gas serving as an environmentally friendly carbon precursor. PCs
with high specific surface areas and thermal stability was ob-
tained in less than 40 min. In addition, a one-pot strategy was
used to synthesize carbon quantum dots by DBD by He et al. [53].
Different from the gas discharge strategy used for PCs synthesis,
liquid-phase DBD discharge was applied with N, N-dime-
thylformamide (DMF) as the sole carbon source and discharge
medium, which was demonstrated to be a novel, fast and simple
method to synthesize carbon dots with high fluorescence
performance.
Based on the same mechanism as reducing metallic ions to form
metallic nanoparticles, graphene oxide powder can be directly
exfoliated and reduced to rGO by air DBD plasma [54] or H2 DBD
plasma [55] at atmospheric pressure. When a dopant such as boric
acid, ammonium bicarbonate or a mixture of both was mixed with
GO samples and followed by DBD plasma treatment, boron doped
rGO (B-rGO) [56], nitrogen doped rGO (N-rGO) [55], as well as
boron and nitrogen co-doped rGO (BN-rGO) [55] can also be readily
obtained. In addition to element doping, the composite of metal
NPs or metal oxides NPs can also be used to improve the perfor-
mance of graphene-based nanomaterials. Furthermore, DBD
plasma can induce simultaneous reduction of metal ions and gra-
phene oxide, thus easily achieving the one-step preparation of
metallic NieCo/graphene catalysts [57], Fe3O4/rGO [58], Pt/rGO
[59], Pt/rGO-MoS2 [59] and Ag/GO composites [60].
Like graphene, the graphite phase carbon nitride (g-C3N4) has a
one-dimensional planar structure. The traditional solvothermal
synthesis of g-C3N4 requires high temperature of over 500 ℃ to
calcinate the melamine precursor for several hours, while it can be
facilely prepared using DBD plasma in a H2 atmosphere at room
temperature and atmospheric pressure [61]. In addition, active sites
from nitrogen vacancies can be introduced into the g-C3N4 struc-
ture to increase the catalytic activity by trapping and promoting the
transfer of photoelectrons. Under H2S atmosphere, DBD plasma
treatment is also a new strategy for in situ preparation of hetero-
atoms S-doped g-C3N4 with more effective charge transfer, higher
visible light absorption, promoted specific surface area and nar-
rower band gap [62].
J. He, X. Wen, L. Wu et al.
2.3. Nanoporous frameworks
Metal organic frameworks (MOFs) and covalent organic frame-
works (COFs) are new types of nanoporous framework materials
[63], which are a class of porous crystalline materials with periodic
network structure obtained through crystal engineering and mo-
lecular design [64]. Benefiting from the advantages of composition
and structure diversity, structural tunability, large specific surface
area, great thermal stability and physical and chemical stability,
nanoporous framework materials have attracted widespread
attention in the fields of chemistry, physics and materials, which
have a favorable foreground in the fields of gas adsorption and
storage, separation and enrichment, sensing, catalysis, drug de-
livery, and photoelectricity [65]. Most of the synthesized nano-
porous frameworks are obtained via solvothermal synthetic
methods which are usually time-consuming, and may require
advanced facility and cumbersome operation. Many research
groups have attempted to expand the synthetic possibility in
different ways including microwave synthesis, mechanical syn-
thesis, ultrasonic synthesis methods [66]. However, those devel-
oped synthetic methods are always limited to specific types of
nanoporous frameworks. In order to expand the application of
nanoporous frameworks to analytical chemistry, facile synthesis
methods of nanoporous frameworks need to be further developed.
2.3.1. Metal organic frameworks
It is well known that MOFs are a kind of inorganic-organic
hybrid material with extended crystalline structures formed by
coordination bond between metal clusters and organic ligands. Hou
and coworkers [67] firstly proposed a novel power-saving, rapid,
and green method for diverse MOFs synthesis under mild condi-
tions by liquid DBD plasma [68]. In their work, a simple and
portable coaxial cylinder DBD reactor was designed (Fig. 5a), which
can be used for the generation of liquid-phase DBD plasma with
power exerted on the precursors. The generated DMF and elec-
trons could greatly accelerate the deprotonation of organic linkers,
thus leading to fast nucleation and crystal growth (down to 1 min)
of MOFs from different subfamilies (Fig. 5c), including UiO-66, UiO-
66-NH2, MOF-5, ZIF-8, HKUST-1, Mn3(BDC)3(DMF)2 and
Tb(BTC)(DMF). By fine-tunning the synthetic conditions, the yield,
morphology and particle size of these MOFs could also be
controlled. To further promote large scale production, a modified
reactor was designed for continuous synthesis as shown in Fig. 5b.
Compared to single-metal counterparts, mixed-metal MOFs
Fig. 5. Schematic illustration of the synthesis of MOFs by using DBD plasma. Reproduced with copyright permission from Ref. [68].
5
Trends in Analytical Chemistry 156 (2022) 116715
possess superior properties for diverse applications. Using this DBD
method, bimetallic MOFs such as UiO-66(Zr/Ce) [69] and
Tb1.7Eu0.3(BDC)3(H2O)4 [69] can be one-pot synthesized within
20 min, which is much faster than traditional hydrothermal syn-
thesis. Subsequently, with the successful preparation of MOF-235
[70], Ce-MOFs [71], Fe-MOF [72], Ce-based bimetallic MOFs [73],
and Ln-MOFs [9] in greatly shortened preparation time, the appli-
cation of DBD plasma in the synthesis of MOFs has been expanded.
2.3.2. Covalent organic frameworks
Water stability is one of the most important properties of
nanoporous frameworks in regards to future applications. None-
theless, due to the easy hydrolysis of the coordination bond, most
MOFs materials are water/moisture-labile, which precludes their
applications to some degree [74]. COFs are a novel class of porous
crystalline materials composed of organic ligands linked by cova-
lent bonding [75]. With permanent porosity, low density, high
surface area and exceptional stability, COFs are very promising for
diverse applications [76]. Liquid-phase plasma can promote the
formation of coordination bond, and lately, Hou and coworkers [77]
firstly demonstrated that DBD plasma is also an effective reaction
environment to promote polymerization and trigger the formation
of covalent bonds [78]. In detail, liquid DBD technology is proven to
be a novel, fast and facile approach to produce diverse COFs in less
than 1 h under mild conditions, including boronate ester-linkage
(COF-5, COF-8 and COF-10), azine-linkage (NUS-2), b-ketoen-
amine-linkage (TpPa, TPBD), imine-linkage (ILCOF-1, Py-COF), and
3DeCOFe102 (boroxine linkage). On the other hand, the proposed
methodology also allows the crystal regulation of the packing
phase of COF-1. By fine-tuning the synthetic solvents, the fast
construction of well-ordered AB staggered COF-1 and AA eclipsed
COF-1 can be facilely realized (Fig. 6). Compared with previously
reported synthetic methods, their DBD plasma strategy features
simplicity, fast reaction, low power, mild condition and green
chemistry, making it a very promising new method for COFs syn-
thesis and crystal regulation.
2.4. Nanocomposites
The nature of plasma makes it easy to interact with the surface
of nanomaterial. Therefore, in addition to the synthesis of single-
phase nanomaterials, in-situ, simple and rapid synthesis of com-
posite nanomaterial can also be accomplished in a plasma to
modulate the performance of nanomaterials. The most commonly
J. He, X. Wen, L. Wu et al.
Fig. 6. Schematic illustration of the crystal regulation of COF-1 by using DBD plasma. Reproduced with copyright permission from Ref. [78].
used method for synthesis of metal nanoparticle composites is
plasma reduction combined with incipient impregnation, which is
different from the above-mentioned plasma-liquid interaction for
the reduction of aqueous cations. In the study of Pham and co-
workers, Pd (NH4)4(NO3)2 salt solution was impregnated into Al2O3
support, and after a drying stage, PdNPs well dispersed on the Al2O3
carrier was processed by argon DBD plasma [79]. Many supported
metal NPs such as Ag/NeTiO2 [35], Pd/P25 [80], Pt/rGO-MoS2 [59],
Ag/cotton [81], Pd/FeOx [82], Pd/Al2O3 [83], metallic NieCo/gra-
phene [57], and Ni/CeO2eAl2O3 with higher Ni dispersion and NiO
reduction [84] have been synthesized with higher catalytic or
antibacterial activity based on the combination of incipient
impregnation with treatment by atmospheric pressure reductive
DBD plasma. However, the preparation of these composite requires
a two-step strategy. Jiang et al. developed a one-pot synthesis
method for the preparation of MOF-based composites (e.g., ZIF-8
encapsulated with nano-Au/Ag) with liquid phase plasma
discharge [68]. Without extra chemicals or complex procedures,
the electrons in the plasma could reduce Au/Ag cations together
with the plasma catalysis of the formation of MOFs, and this greatly
simplified the composite material preparation.
3. Plasma for nanomaterial modification
Surface modification has always been a research focus in the
field of materials. Plasma modification technology uses the chem-
ical active species such as electrons, ions, free radicals, excited state
and meta-stable particles, monatomic oxygen, ozone, atomic
groups produced in gas or liquid discharge plasma to interact with
the surface of nanomaterials, leading to their physical and chemical
changes, which can expose more active sites, optimize the elec-
tronic structure, endow desirable properties, or modify the surface
properties such as improving the catalytic performance, lumines-
cence performance and enhancing the adsorption capacity of the
modified material. Among all the plasma treatment techniques,
DBD has attracted wide attention because of its advantages of
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Trends in Analytical Chemistry 156 (2022) 116715
simplification, low cost, easy industrialization and easy regulation.
Most solid nanomaterials can be modified by DBD plasma treat-
ment without surface functionalization. In addition, the uniformity
of DBD discharge is well suitable for the plasma surface modifica-
tion, easily achieving the uniform modification of the material. The
mild, non-thermodynamic equilibrium discharge characteristics of
DBD make the plasma act on the surface of the material without
affecting the bulk properties, and this is hard to be achieved via
other techniques. Besides, the modification process based on
various gas discharges does not involve solvents, and almost no
waste is generated. In short, DBD plasma treatment is a promising,
high-efficiency, environmentally friendly and novel alternative
technique to traditional modification methods for surface modifi-
cation of nanomaterials. Depending on the DBD plasma type, the
interaction of plasma species with material differs, including
chemical reduction [59], oxidation [85], surface etching [49],
doping [86], grafting of active groups [87], decomposition [88],
exfoliation [89], and other plasma processing [90] as well as syn-
ergistic effect [91].
3.1. Plasma induced doping
Doping heteroatoms with different electronegativity into the
structure of materials is a classical and effective way to tune the
charge distribution of nanomaterial intrinsically, thereby endowing
nanomaterials with new properties. However, the doping of het-
erogeneous atoms is always a challenge task. Usually, the heter-
oatomic precursor is mixed with the nanomaterial followed by
calcination at high temperature. For example, the preparation of
nitrogen-doped carbon materials requires the mixing of activated
carbon, NaHCO3 and NH4HCO3, and then calcined at 700
C for 1 h
under the protection of nitrogen gas. This traditional method not
only requires high temperature and long time, but also results in
uneven distribution of the doped nitrogen element. However, with
DBD plasma, effective and uniform doping can be achieved through
simple discharge at room temperature and atmospheric pressure.
J. He, X. Wen, L. Wu et al.
Among various doping atoms, nitrogen [92], boron [55] and
sulfur [62] are the most representative dopants owning to their
multiple electron nature and special electron deficiency. For
instance, single atom (B, N, etc.) or multi-element doping is widely
used in the modification of carbon materials like rGO to enhance
photocatalytic performance. By using dopant such as boric acid,
ammonium bicarbonate as the dopant precursor of boron and ni-
trogen, respectively, following H2 DBD plasma treatment for just
around 3 min, B-doped rGO, N-doped rGO and B,N-co-doped rGO
have been successfully prepared, respectively, with significantly
improved capacitance of these heteroatoms doped materials [55].
The above plasma modification method is simple, quick and highly
efficient, but still requires additional chemical reagents as pre-
cursors to the doped heteroatom [93]. Discharge gas can also be
used as the dopant precursor. Reniers et al. [94] developed a simple
method for the fabrication of nitrogen doped titanium dioxide by
using NH3 gas as both discharge gas and doping precursors, and
NH3 concentration played a key role in controlling the doping de-
gree. With the doping of nitrogen, the band gap of NeTiO2 was
obviously reduced, resulting in enhanced photocatalytic activity for
dye degradation. Qiu et al. studied and compared the modification
effects of different discharge gases on the same nanomaterial. They
modified TiO2 nanosheets for enhanced visible light photocatalytic
activity by DBD plasma with various working gas (Ar, H2, and NH3)
[95]. The types of dopants such as surface Ti3þ, oxygen vacancy and
substituted N vary with different feeding gas. Therefore, the type of
discharge gas will affect the surface properties of the material.
According to previous reports [96], N2 plasma can also be applied
for the N-doping [97], O2 plasma treatment is efficient for the O-
doping [98], H2S DBD plasma can be used for the S-doping of C3N4
[62], and H2eCCl4 mixture plasma can be applied for the C/Cl co-
doping of RTiO2 [99]. A simple solvent-free scale-up synthesis of
fluorine-doped graphene oxide (FGO) can be achieved in a
H2eN2eNF3 mixture DBD plasma to improve the supercapacitor
performance (Fig. 7) [100]. Besides doping of non-metal elements,
the reduction of metal elements-containing precursors by DBD
plasma can also be used for successful synthesis of nanomaterials
doped with metal ions such as Nb-doped NiFe phosphides [101]
and Fe,N-doped graphene [102].
3.2. Plasma etching
Producing new type of defects, vacancies in existent frameworks
could substantially tune their intrinsic properties, but this remains
an arduous task. Plasma etching refers to the partial structural
defects or vacancies that occur when the surface of material is
bombarded by high-energy electrons or active species in a plasma
and covalent bonds are broken to generate vacancies by ejecting
partial surface atoms, which sheds a new light on the vacancy en-
gineering. On the one hand, plasma etching can occur in edges to
prepare edge-rich and dopant-free graphene and carbon nanotubes
by Ar plasma treatment, which increases the active edge sites, thus
resulting in enhanced oxygen reductive reaction (ORR) electro-
catalysis activity [103]. On the other hand, DBD plasma etching
could also occur in frameworks to create anion or cation vacancies.
Wang et al. created coordinately unsaturated metal sites in
missing-linker ZIF-67 (Fig. 8a) by removing part of the organic li-
gands under N2 plasma etching [104], leading to larger surface area,
mesopores formation and mono-dispersion of active sites for the
oxygen evolution reaction. Yu et al. [105] reported that uncon-
ventional CN vacancies are incorporated to Prussian blue analogues
by breaking iron-carbon-nitrogen-nickel units under the
bombardment of N2 plasma (Fig. 8c). Similarly, gas plasma etching
has also been applied to generate defect-rich MoS2 [98], N-vacancy-
doped g-C3N4 [61] and O-vacancy-doped FeCo@NC [92].
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Trends in Analytical Chemistry 156 (2022) 116715
Apart from the above-mentioned anionic regulation, the intro-
duction of cation vacancies are also effective approaches to regulate
the intrinsic activity. Metal cations are generally the actual active
sites, especially in metal-based catalysts. Due to the multifarious
electronic structure and orbital distribution of metal cation va-
cancies, cationic defects can expose more active sites, which is
more important in enhancing catalytic activity compared to anionic
defects. However, to overcome the high formation energy of
cationic defects is still arduous. By taking full advantage of the
etching effect of the water DBD plasma, Wang et al. [49] success-
fully prepared cationic defect and anion dual-regulated CoAl LDHs
in just a few minutes (Fig. 8b), which possess both abundant Al3þ
vacancies and S2 regulation and exhibit improved OER perfor-
mance with a synergistic effect. Different from gas plasma etching,
liquid plasma etching can also facilitate the removal of the inactive
oxide overlayers of NiFe phosphide to accelerate the formation of
metal hydroxides and lead to a remarkably enhanced OER activity
[106]. Additionally, liquid DBD plasma was also used by Jiang et al.
to etch nickel foam to prepare Ni3S2 nanosheet with sodium sulfide
aqueous solution as the discharge medium [107].
Notably, in the practical application of plasma engineering for
material modification, the doping of heteroatoms on the surface of
the material is often accompanied by partial etching of the surface
structure of the material [98]. For example, Dai et al. prepared
Co9S8/graphene hybrid for electrocatalysis by simultaneously
etching and nitrogen doping via the NH3 plasma treatment [108].
Heteroatom doping can effectively modify the electronic properties
of Co9S8/graphene, and surface etching helps to generate a large
number of physical and chemical defects and expose more reactive
sites. The synergistic effect has a significant effect on tuning surface
properties of nanomaterials [109].
3.3. Plasma induced grafting
Based on the chemical reaction between the plasma active
species and the nanomaterial structure, functional groups can be
successfully grafted into the surface microstructure, thus improving
the physical and chemical properties of the nanomaterials. Qiu et al.
employed an Ar DBD plasma treatment as an effective way to
introduce oxygenated functionalization into edge-enriched gra-
phene nanoribbons to increase the capacitance for supercapacitors
[87]. Similarly, air DBD plasma can also be used to induce different
oxygen-containing functional groups like eOH, eCOOH into skel-
eton of C3N4 [110], and carbon particles and carbon nanotubes
[111]. Moreover, compared with the plasma of a single feeding gas,
the types of active substances in the air plasma are more abundant,
mainly including e*, OH, H, O, O2, O3, N, NOx [112]. Therefore,
the air plasma can introduce both oxygen-containing and nitrogen-
containing functional groups into polymers simultaneously [113],
and with the change of plasma treatment time and conditions, the
types of modified functional groups will change accordingly
(Fig. 9a) [91]. Different from the strategy of using oxygen DBD
plasma to introduce abundant hydroxyl groups on the surface of
Au/TiO2 catalysts [114], liquid DBD plasma can also achieve the
hydroxylation of MOFs (UiO-66) with enhanced fluorescence
properties via the covalent binding of organic ligands and hydroxyl
radicals generated during discharge of aqueous solutions (Fig. 9b)
[115]. In addition to directly tuning the surface properties of
nanomaterials, the introduction of functional groups is also
exploited in the preparation of nanocomposites to enhance the
interface adhesion and binding strength between different mate-
rials [116]. Nowadays, plasma induced grafting of functional groups
has received increasing interest, profiting from its simple equip-
ment, easy operation and low energy-consumption process
without producing chemical wastes.
J. He, X. Wen, L. Wu et al. Trends in Analytical Chemistry 156 (2022) 116715

Fig. 7. Schematic illustration of the synthetic procedure of F-Doped GO. Reproduced with copyright permission from Ref. [100].

Fig. 8. Illustration of the preparation of the CUMSs-ZIF-67 by N2 plasma etching (a), CoAl LDHs with Al3þ vacancies by water DBD plasma (b) and Prussian blue analogue with CN
vacancies (c). Reproduced with copyright permission from Ref. [104], Ref. [49] and Ref. [105].

The universality of DBD plasma lies not only in the grafting of
functional groups, but also the grafting of polymer on the surface of
nanomaterials. Plasma induced polymerization is based on the
activation of some common monomers to initiate polymerization
with the energy provided by DBD plasma. Wang et al. synthesized
graphene oxide/polypyrrole (GO/PPy) composites via N2 DBD
plasma induced polymerization [117]. Within the nitrogen DBD, N2
molecules first dissociates under the excitation of the electric field
to produce abundant nitrogen-containing active species such as
radicals (N*, Nþ*), atomic species (N, Nþ) and molecular ions (Nþ2 ),

8
J. He, X. Wen, L. Wu et al.
Fig. 9. Schematic illustration of the mechanism of treating the g- C3N4 by air DBD plasma (a) and the grafting of eOH on UiO-66 by using DBD liquid plasma (b). Reproduced with
copyright permission from Ref. [91] and Ref. [115].
which activate the surface of GO nanosheets to generate active
carbon sites (-C*). The reaction between the active carbon sites of
GO nanosheets with the olefin double bonds of pyrrole molecules
can induce the excitation of pyrrole, which further acts as binding
sites and induces the polymerization of pyrrole molecules. Then,
polypyrrole is polymerized on the GO nanosheets with abundant
oxygen-containing functional groups and positively charged ni-
trogen atoms via DBD plasma induced grafting of polymer. Similar
to the case of polypyrrole, the same group has also successfully
applied the plasma-induced polymerization technique to the syn-
thesis of polyacrylamide grafted graphene oxide nanosheets [118],
further demonstrating that plasma is an efficient way to trigger the
monomer polymerization.
3.4. Plasma exfoliation
Due to the destroy of electrostatic interactions [119] and the
break of chemical bonds or the instantaneous release of formed gas
[120] under the bombardment by plasma active substances, DBD
treatment can also induce layer-by-layer exfoliation of the
stacking-structured two-dimensional layered nanomaterial into
single layer or few layer structure to expose more active sites.
Different from traditional approach, the advantage of plasma
exfoliation lies in not only the absence of toxic chemicals, but also
the process of plasma doping, etching, surface functionalization
occurred during the exfoliation, which can synergetically regulate
the chemical composition and properties of nanomaterials. For
example, the N-doping plasma exfoliated graphene oxide (Fig. 10a)
was obtained with air DBD treatment [120]. The preparation of
ultrathin MoS2 and g-C3N4 nanosheets can be achieved by H2/Ar
DBD plasma treatment of (NH4)2MoS4 powder and bulk g-C3N4
powder, respectively [121]. When gas-phase plasma is used for
exfoliation, gas etching, gas expansion, and electron repulsion may
be the key factors for plasma exfoliation of layered nanomaterials.
For the liquid-phase plasma exfoliation, on the other hand, the
interlayer van der Waals force, p-p stacking interactions, etc. could
be destroyed by the plasma treatment, thereby obtaining layered
nanomaterial. The ultrathin CoFe LDH nanosheets with multi-
vacancy (Fig. 10b) [119] and vacancy-abundant CoFePi nanosheets
[122] can be prepared by water-plasma-enabled exfoliation, which
could destroy the electrostatic interactions, resulting in fast exfo-
liation, and plasma etching produce multi-vacancy in the exfoliated
LDHs nanosheets, simultaneously. Therefore, plasma exfoliation
plays an important role in the preparation of ultrathin lamellar
materials.
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Trends in Analytical Chemistry 156 (2022) 116715
4. Applications for analytical chemistry
4.1. Applications for sensing
Chemical sensors have been widely used in analytical chemistry,
including environmental monitoring, security guarding, food and
water quality controlling, and disease diagnosis. Generally, chem-
ical sensors can selectively bind target analytes with changes in
electrical, optical, or mechanical properties for qualitative or
quantitative analysis. Today, thanks to the advantages of fast
response, high sensitivity, miniaturization and online detection of
chemical sensors, the demand for efficient detection of various
analytes can be met for diverse applications with high-efficiency
chemical sensor materials prepared by DBD plasma.
4.1.1. Catalytic luminescence sensing
For decades, catalytic luminescence sensors have been widely
developed for molecular recognition. The interaction between an-
alyte gases with different materials to produce cataluminescence
(CTL) is a simple and effective way to construct gas sensors. Lv et al.
used geC3N4eMn3O4 composite for the cataluminescent sensing of
gaseous H2S with high selectivity and sensitivity [123]. As shown in
Fig. 11, geC3N4eMn2þ precursor was first formed through the
electrostatic binding, physisorption, coordination effect between
Mn2þ and functional groups of g-C3N4, followed by the oxidation of
highly active oxygen-containing species produced in the air DBD
plasma treatment. Then, geC3N4eMn3O4 with enhanced specific
surface area and decreased uniform size was obtained in 10 min
with the synergistic effect of plasma oxidation and plasma etching
without any solvent or any extra oxidant/reductant. In the presence
of H2S gas, the geC3N4eMn3O4 composite catalyzes the oxidation
of H2S, accompanied by significantly improved CTL emission
compared to pure Mn3O4, pristine geC3N4eDBD and their physical
mixture with quick response and recovery (within 0.6 s), over-
matching most reported H2S-sensing materials. The characteristic
CTL spectral response was linear towards H2S with a low limit of
detection (0.13 mg mL1) and an impressive RSD (within 1e3%),
indicating speediness, stability, high sensitivity and great repeat-
ability of the sensor. Hou et al. established a CTL sensor for acetic
acid equipped with in situ growth of nano/micro CuO/ZnO in DBD
[124], in which brass was applied as the inner electrode and a
unique precursor, directly reacting with DBD discharge gas (I2/Ar)
to produce CuI/ZnI2 particles and then put into the CTL reaction cell,
where the nano/micro CuO/ZnO composites were produced in situ
by heating the CuI/ZnI2 particles in room air atmosphere. The CuO/
J. He, X. Wen, L. Wu et al.
Fig. 10. Schematic illustration of the exfoliation of N-doping GO by air plasma (a) and the exfoliation of CoFe LDH by H2O plasma (b). Reproduced with copyright permission from
Ref. [120] and Ref. [119].
Fig. 11. Schematic illustration of the synthesis of geC3N4eMn3O4 and CTL reaction process on its surface. Reproduced with copyright permission from Ref. [123].
ZnO composites possess highly selective and sensitive CTL signal
towards CH3COOH with a LOD of 3 mg L1.
4.1.2. Electrochemical sensing
Unlike the CTL emission accompanied with the chemical reac-
tion process, an electrochemical sensor is constructed by reacting
with an analyte to generate an electrical signal proportional to the
concentration of the analyte, which provides a crucial analytical
method. Jiang et al. proposed the synthesis of Co(OH)F nanoflower
for an effective non-enzymatic glucose electrochemical sensor
[125]. Co(OH)F nanoflower on carbon cloth (Co(OH)F NF/CC) was
synthesized by DBD plasma treatment of the aqueous mixture so-
lution of Co(NO3)26H2O, urea and NH4F with a piece of carbon
cloth inside for 1.5 h. A standard three-electrode system was built
with Co(OH)F NF/CC as the working electrode, platinum wire and
Hg/HgO as the counter electrode and the reference electrode,
respectively. Co(OH)F NF/CC has been proven to be an excellent
catalyst electrode for glucose electrooxidation with good sensing
performance: a linear range of 1.0 mMe3.5 mM and a LOD of
0.75 mM, and this has been successfully used in the determination
of glucose in human serum. Subsequently, in order to further
improve the glucose sensing sensitivity, the research group used
the same DBD method to synthesize a nickel based sensing material
Ni(OH)2 NA/CC simply by replacing Co(NO3)26H2O with
Ni(NO3)2$6H2O precursor, exhibiting great electrode reproduc-
ibility, stability and selectivity [126]. Compared to Co(OH)F NF/CC,
Ni(OH)2 NA/CC has better electrochemical performance of glucose
sensing with a wider linear range of 0.001e5.45 mM and a lower
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Trends in Analytical Chemistry 156 (2022) 116715
limit of detection of 62 nM. They also developed a high-sensitivity
nonenzymatic electrochemical sensor for formaldehyde detection
using Ni3S2 nanosheet, which was synthesized by DBD plasma
etching with sodium sulfide directly on the nickel foam [107]. These
strategies show the important usefulness of DBD microplasma in
the high-efficiency preparation of nanomaterials and in the
exploration of real-time and in situ electrochemical sensors.
4.1.3. Fluorescence sensing
Different from the CTL sensing or electrochemical sensing that
accompanies the chemical or electrochemical reaction process,
fluorescence is a cold luminescence phenomenon of photo-
luminescence, and it is also a crucial analytical tool for rapid, se-
lective and sensitive determination of analytes. Wu et al. proposed
a selective and sensitive fluorescent probe for the detection of H2O2
and glucose based on carbon quantum dots, which was fabricated
by DBD treatment using DMF as the liquid discharge medium and
carbon source [53]. Compared to carbon fluorescent quantum dots,
MOFs, as a new generation of porous crystalline materials, have
demonstrated obvious advantages in fluorescent sensing, especially
bimetallic lanthanide metal centers-based MOFs. With a tedious
procedure, however, the production of bimetallic MOFs by sol-
vothermal or microwave-assisted synthesis takes hours or even
days. To address the problem, Long et al. proposed a liquid DBD-
based strategy for the energy-saving, facile and fast synthesis of
bimetallic MOFs in 20 min with a one-pot manner for the first time
[69]. The obtained Tb1.7Eu0.3(BDC)3(H2O)4 showed characteristic
ratiometric fluorescent emission at 616 and 544 nm corresponding
J. He, X. Wen, L. Wu et al.
to Eu and Tb, respectively. In the presence of dipicolinic acid (DPA)
with gradient concentration ranging from 2 to 100 mM, there is a
gradual increase of the Tb emission and a decrease of the Eu
emission, with the I544/I616 value increasing in a linear manner,
causing the fluorescent color of Tb1.7Eu0.3(BDC)3(H2O)4 change
from orange-red to yellow-green gradually (Fig. 12). Thus, a ratio-
metric fluorescent probe based Tb1.7Eu0.3(BDC)3(H2O)4 for sensing
DPA was constructed with satisfactory performance, also proving
that the MOFs prepared by the quick DBD method possess the same
fluorescent function as those prepared by the traditional synthesis
method.
It is worth noting that use of DBD plasma can not only directly
synthesize MOF materials with good luminescence performance,
but also modify the properties of MOF materials with low fluo-
rescence activity, so that materials that is not capable of fluores-
cence sensing can be successfully applied to the construction of
fluorescence sensing platform after DBD processing. For example,
an atmospheric low-temperature plasma-based post-synthetic
modification method was developed by our research group for
directly introducing the hydroxy into UiO-66, endowing UiO-66
with greatly enhanced fluorescence properties [115]. The experi-
mental results showed that direct hydroxylation of UiO-66 or MIL-
101(Cr) can be realized simply by capturing the plasma-induced
hydroxyl radicals with aqueous solution as a dielectric medium.
The obtained functionalized UiO-66 was demonstrated a reliable
fluorescence enhanced sensing platform for arsenic in a linear
range of 0.05e10 mg mL1 with a limit of detection as low as
28 ng mL1, which is comparable to or even better than other
similar sensing methods. The DBD plasma synthesis and modifi-
cation procedure features simplicity, low power, low temperature,
environmental friendliness and free of chemical reagents, and it is
important in the screening of functional nanomaterial for fluores-
cence sensing application.
4.1.4. Colorimetric detection
Unlike electrochemical and fluorescent sensing, colorimetric
detection can be easily adapted for identifying various chemical
hazards with visible signal transduction, while it remains simple,
portable, miniaturized, inexpensive and visual without any addi-
tional instrumentation, meeting the demand for real-time analysis
of analytes in the field. Xia et al. exemplified colorimetric detection
of trace mercury (Hg) via the visual chromogenic reaction between
mercury vapor with CuI particles, prepared via 10-min treatment of
copper wire inner electrode in iodine DBD plasma [44]. The
Fig. 12. PL sensing of DPA with Tb1.7Eu0.3(BDC)3(H2O)4. Reproduced with copyright permission from Ref. [69].
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Trends in Analytical Chemistry 156 (2022) 116715
prepared CuI wire was assembled with a mercury cold vapor gen-
eration reactor by hanging in the cap of the reactor. KBH4eNaOH
system was used to in site generate mercury vapor by the reduction
of Hg2þ and the CuI on the wire surface gradually transferred to
Cu2HgI4 after contacting the volatile mercury vapor, along with
color changes from white to yellow, orange and finally deep orange,
which corresponded with the concentration of mercury vapor.
According to the visual color changes, colorimetric detection of
trace mercury in the range of 1 ng mL1 to 1 mg mL1 was achieved
by naked eyes.
4.2. Applications for separation and removal
4.2.1. Adsorption and removal
Environmental pollution has caused widespread concern
around the whole world because it poses risks to public health and
environmental safety. Therefore, it is not only necessary to conduct
accurate analysis of various samples for environment pollutants,
but also to develop reliable sorbent with excellent sorption ca-
pacities and high selectivity for removal of pollutants. Nano-
materials have garnered increasing attention in the adsorption and
removal of environmental pollutants owing to their advantages of
easy modification, and strong adsorption performance on various
organic and inorganic contaminants.
Jiang et al. found that bimetallic UiO-66(Zr/Ce) prepared by
liquid DBD strategy was a good absorbent for Se(IV) preconcen-
tration, so that the high sensitivity and selectivity determination of
Se(IV) can be achieved by hydride generation-atomic fluorescence
spectrometry (HG-AFS) combined with solid-phase extraction
(SPE) with an LOD of 0.005 mg L1. More interestingly, UiO-66(Zr/
Ce) exhibits completely discrepant adsorption capacity for Se(IV)
and Se(VI) at pH value of 10. Taking advantage of this discrepancy in
alkaline media, speciation analysis of Se was accomplished by
inductively coupled plasma-mass spectrometry (ICP-MS) [69]. Due
to the carcinogenicity, long half-life of radionuclides, eliminating
trace radionuclides from radioactive wastes is of scientific and
technical importance. Via DBD plasma induced polymerization,
graphene oxide/polypyrrole (GO/PPy) composites were synthe-
sized to highly selectively extract U(VI) from aqueous solutions
[117]. Owing to the abundant oxygen- and nitrogen-containing
functional groups, and positively charged nitrogen atoms, GO/PPy
composite exhibits strong affinity toward U(VI) with high sorption
capacities of 85.7 mg g1, high selectivity, good chemical stability
and reusability. And later, they further applied a similar DBD
J. He, X. Wen, L. Wu et al.
plasma induced polymerization technique to modify poly-
acrylamide on the surface of graphene oxide nanosheets (PAM/GO).
The PAM/GO is efficient for simultaneous removal of diverse ra-
dionuclides including U(VI), Eu(III) and Co(II) from radioactive
wastewater with maximum sorption capacities of 0.698, 1.245 and
1.621 mmol g1, respectively [127]. Besides the removal of radio-
nuclide, the research group also found that toxic aromatic pollut-
ants like phenol and aniline could be effectively extracted by GO/
PPy composite via the hydrophobic interaction, electron donor-
acceptor interaction and acid-base interaction [128]. Zheng et al.
developed a method for solid-phase microextraction (SPME) of
polycyclic aromatic hydrocarbons (PAHs) using porous carbons
(PCs) synthesized in situ on a metal surface by using DBD plasma.
The generated PCs possess nestlike morphology and large surface
area, which was used as an SPME fiber to preconcentrate PAHs,
followed by the ultra-sensitive determination by gas chromatog-
raphy with flame ionization detection (GC-FID).
Majorly originated from the textile, leather, and paper in-
dustries, the problem of dye pollution in color effluents has become
increasingly prominent. Dye is a class of strong carcinogenic com-
pounds and the most common bio-refractory organics in waste-
water, which must be removed for ecosystem and public health. Tao
synthesized Fe-MOFs via a DBD method to extract methyl orange
with an adsorption capacity of 750 mg g1 [70]. They also applied
air DBD plasma for the modification of ZnMgAl-LDHs to improve
the adsorption capacity of methyl orange [129]. Plasma treatment
for 30 min can lead to smaller particle size, increased pore size and
volume, which has better dispersion, higher surface area and more
sorption sites, resulting in significant improvement in methyl or-
ange adsorption with an adsorption capacity of 1327 mg/g, much
higher compared to other similar adsorbents. Therefore, DBD
plasma technique is a valuable approach to develop functional
sorbents for separation and detection of various pollutants.
4.2.2. Photocatalytic degradation
Photocatalytic degradation is another important means of
pollutant removal, which ideally degrades organic pollutants into
carbon dioxide and water via the oxidation-reduction capability of
a nano-photocatalyst under light irradiation without the produc-
tion of secondary pollution. Therefore, as an efficient and safe
environment-friendly environmental purification technology,
photocatalytic technology has opened a new pathway in environ-
mental governance. DBD plasma plays an important role in nano-
photocatalyst preparation and nanostructural engineering for the
modification of photocatalytic activity performance. For example,
Tao et al. employed liquid DBD plasma to fabricate Ce-MOFs, which
acted as a precursor for derivation of CeO2 photocatalysts with high
photocatalytic degradation performance towards methyl orange
(98% degradation rate) under irradiation of an ultraviolet lamp,
owing to the abundant oxygen vacancy defects, wide range of UV-
light absorption and strong adsorption capacity [71]. They also
applied DBD plasma to modify NiAlCeeLDH to improve the pho-
tocatalytic performance, resulting in nearly 100% MO degradation
within 1 h under ultraviolet light irradiation, which was attributed
to the smaller particle size, higher crystallinity, the formation of
heterostructure and decreased band gap [90]. However, the pho-
todegradation processes must rely on ultraviolet light excitation,
while ultraviolet light accounts for only a small part of the solar
energy. In order to overcome the limitation of ultraviolet light and
improve the utilization efficiency of solar energy, Zhang et al. re-
ported the manufacture of 2D ultrathin g-C3N4 nanosheets by H2/Ar
DBD plasma induced exfoliation via gas etching and expansion,
which exhibited enhanced photocatalytic activity (1.3-fold)
compared to bulk materials and can successfully degrade rhoda-
mine B in 2 h under visible light irradiation [121]. To further
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Trends in Analytical Chemistry 156 (2022) 116715
increase the degradation efficacy, Mao et al. demonstrated air-
plasma treatment was an effective way to modify the surface
properties of g-C3N4 by introducing hydrophilic oxygen-containing
functional groups, such as eOH and eCOOH, resulting in an
enhanced hydrophilicity and 2.0 times increase of degradation ef-
ficiency of rhodamine B under visible light irradiation [110].
Although plasma exfoliation and functional group grafting can
effectively improve the photocatalytic degradation capability of
C3N4, the band gap of C3N4 remains unchanged. Dong et al. boosted
visible light photodegradation activity of C3N4 by coupling g-C3N4
with GO to fabricate boron doped rGO/g-C3N4 using H2 DBD plasma
(Fig. 13) [93]. The band gap of the nanocomposite was greatly
reduced, and thus significantly increased photocurrent in com-
parison with that of g-C3N4 (20-fold), resulting in enhanced pho-
tocatalytic performance for RhB degradation.
TiO2 is a star and popular material in the field of photocatalysis
with excellent ultraviolet photocatalytic activity. In order to
improve its visible-light photocatalytic activity, DBD plasma has
been widely used in the activity regulation. Zhang et al. used DBD
plasma to regulate the energy band gap of TiO2 by the decoration of
Pd NPs, resulting in the transfer of photogenerated electrons from
TiO2 to Pd, thus improving the photocatalytic efficiency for MB dye
degradation [130]. N2/Ar plasma was applied by Geng et al. to
construct Cu2O/NeTiO2 [96], and they found that plasma treatment
enabled the doping of nitrogen, the generation of pen hetero-
junction and the formation of Ti3þ as well as Cu2O species syner-
gistically increased the photodegradation efficiency of methyl
orange under both the visible and full-spectrum light irradiation.
Similarly, wide-spectrum light absorption and visible light photo-
catalytic degradation of methyl blue was demonstrated by using
anatase TiO2 nanosheets treated by plasma under varied working
gas (Ar, H2, or NH3) [95], and the results showed (Fig. 14) that Ar gas
plasma helped the formation of oxygen vacancy owing to the high-
energy electrons/ions, while more oxygen vacancies and Ti3þ ions
were created in the case of H2 plasma, thus possessing higher
reduction capability. As for NH3 plasma, owing to the synergistic
effect of nitridation and simultaneous reduction, TiO2 was doped
with both substituted N and surface Ti3þ, which remarkably
impeded the recombination of the photogenerated carriers and
reduced the energy band gap. Therefore, NH3eTiO2 presented a
green color and the highest visible-light photocatalytic activity over
Ar-TiO2, H2eTiO2 and pristine TiO2.
4.3. Application of DBD in atomic spectrometry
In addition to the above applications, with high excitation and
dissociation capacities, DBD can provide enough energy to directly
atomize analytes into free atoms in their ground states, and even
excite the free atoms to higher excited states. Therefore, DBD has
also been widely used as a new vapor generation technique [131] or
an atomizer/excitation source in atomic spectrometry, including
atomic emission spectrometry (AES), atomic absorption spec-
trometry (AAS) and atomic fluorescence spectrometry (AFS), which
greatly reduces the sample volume and energy consumption, and
provides a new tool for portable/miniaturized, sensitive and in-
field analysis. For instance, Jiang et al. [132] constructed a
portable DBD-AES by the introduction of a miniature electro-
thermal vaporizer (ETV) for less sample consumption, high injec-
tion efficiency, good separation effect, simple device and easy
automation. Multielement analysis with high sensitivity has been
achieved with LODs ranged from 0.16 to 11.65 mg L1 for Zn, Pb, Ag,
Cd, Au, Cu, Mn, Fe, Cr, and As. Our research group [133] further
coupled a miniaturized DBD-AES with a tungsten coil for on-line
hydride generation trapping-electrothermal vaporization, which
greatly improved the total sample throughput and detection
J. He, X. Wen, L. Wu et al.
Fig. 13. Schematic illustration for the degradation of RhB by B-rGO/g-C3N4. Reproduced with copyright permission from Ref. [93].
Fig. 14. The surface modification of TiO2 through DBD-plasma with different working gases. Reproduced with copyright permission from Ref. [95].
sensitivity for trace elements. DBD has also been proved a novel
transportation and preconcentration technique by Mao et al. [134].
They designed a novel integrated DBD reactor built with two in-
dependent discharging zones to fulfill gas-phase enrichment of
arsenic based on ETV-DBD-AFS, where the DBD atomizer tube was
applied to atomize arsenic nanoparticles to free atoms, while the
DBD trap tube can efficiently trap and release arsenic oxide or
arsenic atoms under different atmospheres. Except for the physical
vapor generation method, chemical vapor generation (CVG) is also
an important method of DBD sampling, including hydride genera-
tion (HG), catalytic oxidation vapor generation (COVG), photo
chemical vapor generation (PVG), chelate vapor generation and so
forth. A HG-DBD-AAS setup was developed by Borges [7] for the
analysis of methylmercury with fast reaction speed and high vapor
generation efficiency. By utilizing a DBD plasma for the COVG of
organic compounds into CO2 and a point discharge (PD) plasma to
excite the optical emission spectra of atomic carbon, DBD-COVG-
PD-OES were developed by Jiang et al. [135] as a miniaturized
TOC analyzer with excellent accuracy and practicality for TOC field
analysis as shown in Fig. 15. What's more, benefiting from the UV
irradiation and highly potent chemical oxidizing species, DBD has
been developed as a novel sample digestion method. Zheng et al.
[136] demonstrated a DBD microplasma digester arrays as an
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Trends in Analytical Chemistry 156 (2022) 116715
effective, eco-friendly and one-step sample digestion method for
the sensitive determination of trace elements in rice samples
without any chemicals. DBD digestion was later further applied for
the decomposition of volatile organic compounds for solid sam-
pling and mercury analysis [137].
DBD has also been applied in mass spectrometry (MS) as a
sample introduction method [138], an atomizer [8] or an ionization
source [139]. For instance, nebulized film dielectric barrier
discharge combined with chelate vapor generation was developed
by Zhang et al. [140] as a new sample introduction method for ICP-
MS, which lead to 8e9 folds sensitivity enhancement of trace rare
earth elements determination. Zhu et al. [138] proposed liquid
spray DBD plasma to induce CVG, which was coupled with multi-
collector inductively coupled plasma mass spectrometry (MC-ICP-
MS) for high-precision Pb isotopic analysis. Apart from highly
sensitive elemental or isotopic analysis, Zenobi et al. [141] reported
a homebuilt in-line dielectric barrier discharge ionization (DBDI)
source, which can be coupled to any mass spectrometer. By the
combination of laser ablation with mass spectrometer equipped
with this DBDI source, a flexible LA-DBDI-MSI platform was con-
structed with significantly enhanced ionization efficiency, high
spatial resolution and sensitivity for MS imaging. And later, they
further combined DBDI with nanoelectrospray ionization to
J. He, X. Wen, L. Wu et al.
Fig. 15. Schematic diagram of the TOC analyzers with DBD-COVG unit (a) and PD-OES unit (b). Reproduced with copyright permission from Ref. [135].
develop a hybrid ionization source for single-cell analysis [142],
which further broadened the application scope of DBD.
5. Conclusion and future perspectives
This review has summarized recent progress in the synthesis
and modification of nanomaterials based on DBD plasma technique,
and their representative applications in analytical chemistry. The
unique physical properties of DBD plasma make it capable of syn-
thesizing a wide range of nanomaterials including metals, metals
oxides, metal hydroxides, metal iodides, carbon-containing organic
materials, polymers, covalent organic frameworks, metal organic
frameworks and composites. Compared with other strategy, DBD
plasma technology has attracted great interest owing to its
tunability, miniaturization, high efficiency, cost-effectiveness and
mild conditions (green chemistry), and thus has promising pros-
pects in the field of material synthesis. DBD plasma has also been
proven to be an efficient, environmentally friendly method for
modification of the properties of nanomaterials via plasma induced
doping, etching, exfoliation, polymerization, grafting of functional
group, while these progresses always occur simultaneously; and
various plasma functions have been presented here separately for
better understanding. Applications from chemical sensor devel-
opment, adsorption and separation to catalytic degradation were
summarized, and recent direct application of DBD in analytical
atomic spectrometry including sample digestion was also briefly
summarized. The great opportunities offered by DBD preparation
and modification technologies foreshadow rapid future progress in
analytical chemistry. More work based on nanomaterials for
application in analytical chemistry seems to be very promising and
hail further studies:
(1) First, to expand the scope of nanomaterials that can be
synthesized by DBD. The adjustable structural and physical
properties of DBD make it a class of versatile techniques.
However, as summarized in Table 1, currently plasma syn-
thesis is mainly applied to the preparation of inorganic
nanomaterials, such as metal NPs and metal oxides NPs. The
research on the synthesis of some new-generation porous
nanocrystalline frameworks is still insufficient, and further
exploration is highly expected for preparing more types of
nanomaterials.
14
Trends in Analytical Chemistry 156 (2022) 116715
(2) To bridge the gap between plasma synthesis and modifica-
tion, realizing the simultaneous synthesis and modification
of nanomaterials based on the non-thermal plasma tech-
nology. Compared with gas phase plasma, the mechanisms of
liquid phase plasmas are rarely explored. It is also necessary
to further expand the applications of liquid phase plasma, or
to develop a novel discharge system by combining liquid
phase with gas phase discharge to produce gas-liquid inter-
face reaction, which may allow new applications.
(3) To achieve large-scale synthesis of nanomaterials by DBD
plasma. DBD plasma has benefited from miniaturization and
low cost, which also brings an inevitable problem of low
product output, limited productivity, making it difficult to
realize large-scale production. Therefore, in order to seek the
advantages of high efficiency, eco-friendliness and versatility
of the plasma synthesis and extend the strategy to industrial
applications, it is necessary to design new DBD devices such
as a continuously flowing plasma reactor or microplasma
arrays, which can produce nanomaterials in large batch
quantities.
(4) To further gain deeper insight into the mechanism of DBD-
assisted synthesis and modification processes. Although it
is well-known that there are diversified active species in
plasma such as high energy electrons, free radicals, active
molecules, etc., it is not fully understood what specific forms
of the active substance exist in different types of plasmas and
what roles the diversified active species play in most plasma
synthesis and modification cases. Therefore, it is highly
desired to conduct thorough investigation for related
mechanisms to disclose the underlying secrets of DBD syn-
thesis, eventually facilitating applications and developments
of DBD plasma in synthetic and analytical chemistry. For
instance, to develop in-situ real-time monitoring and char-
acterization technology. To date, although many achieve-
ments on the DBD plasma-induced synthesis of
nanomaterials have been accomplished, ex-situ methods are
relied on the characterization of the structure of products,
the spatial and temporal evolutions of processes in the
plasma are still unclear. In-situ probing is indispensable to
continuously monitoring and detecting the detailed pro-
cesses taking place in the plasma without disturbing the
reaction system.
J. He, X. Wen, L. Wu et al. Trends in Analytical Chemistry 156 (2022) 116715

Table 1
List of nanomaterials produced by DBD plasma techniques.

Nanomaterials Precursors Plasma type Discharge Time/ Application Ref.

medium min

Cu NPs CuO Gas-phase AreH2 50 s/4 e [11,39]

Au NPs HAuCl4 Gas-liquid Ar 30 e [36]
interaction
Au, Pd NPs Au þ Sn and Pd solution Gas-liquid AreH2 5e15 NPs Extraction [38]
interaction
Pt, Pd, Rh NPs H2PtCl6, PdCl2, RhCl3 Gas-liquid AreH2 30 Recuperate metal ions [37]
interaction
RuO2 RuCl3xH2O, NaOH Gas phase Ar or Ar/O2 3h MB degradation [143]
ZnO Zn(OH)2 Gas phase Air 45 Removal of H2S [144]
Ag2O/RuO2 AgNO3, RuCl3 xH2O and NaOH Gas phase Ar 3h Redox properties [41]
SiO2, CuO and RuO2 TEOS, CuCl2 and RuCl3$nH2O þ NH3OH Gas phase Ar 3-h e [40]
CuO NS/CF NaOH, (NH4)2S2O8, copper foam Liquid phase H2O 10 Non-enzymatic glucose [145]
sensor
CuI copper wire electrode Gas phase Ar/I2 10 Colorimetric sensor for Hg [44]
CuI/ZnI2 brass mesh Gas phase I2 10 CTL sensor for acetic acid [124]
CuCl, CuBr, CuBr0$5I0.5, copper substrateþ1,2-dichloro-4-X benzene Gas phase N2 5 e [146]
CuI0$9Cl0.1 (X ¼ Cl, Br, I)
NiMoO4$xH2O nanowires (NH4)6Mo7O24$4H2O, urea, Liquid phase H2O 30 Electrochemical sensor for [147]
Ni(CH3COO)2$4H2O þ CC glucose
Ni(OH)2 NA/CC Ni(NO3)2$6H2O, urea, NH4F þ CC Liquid phase H2O 1.5 h Glucose sensor [126]
Co(OH)F NF/CC Co(NO3)26H2O, urea, NH4F þ CC Liquid phase H2O 1.5 h Glucose sensor [125]
CoO@NiFe LDH/NF Ni(NO3)2,6H2O, Fe(NO3)3,9H2O, urea, NH4F, Liquid phase H2O 1h Oxygen evolution reaction [47]
CoO NWs/NF
NiFe LDH-Ci/CC Fe(NO3)39H2O, NH4F, CH4N2O, Liquid phase H2O 1h Oxygen evolution reaction [48]
Ni(NO3)26H2O and a piece of CC
rGO GO Gas phase Air 60 Electro-catalysis [54]
CNTs CO2 Gas phase H2 e e [148]
Porous Carbons ethanol vapor Gas phase argon 40 HS-SPME for PAHs detection [52]
carbon QDs DMF Gas phase argon flowSyn Fluorescence sensor for H2O2 [53]
and glucose
Fe-MOFs FeSO4 7H2O þ TA Liquid phase DMF/ethanol 90 MO removal [72]
Ce-MOFs Ce(NO3)36H2O þ BTC Liquid phase Ethanol/H2O 120 MO degradation [71]
Tb1.7Eu0.3(BDC)3(H2O)4 Tb(NO3)3$6H2O þ Eu(NO3)3$6H2O þ BDC Liquid phase DMF 20 Fluorescent sensor for DPA [69]
Tb(BTC), Eu(BTC), Tb(BDC) Eu3þ/Tb3þþ BDC/BTC Liquid phase DMF 0e50 Crystallization process study [9]
UiO-66(Zr/Ce) ZrCl4þCe(NH4)2(NO3)6 þBDC Liquid phase DMF 15 SPE-HG-AFS analysis for [69]
Se(IV)
bimetallic Fe/Ce-MOFs Ce3þ/Fe3þþtrimesic acid Liquid phase H2O/ethanol 90 MO degradation [73]
COFs Organic ligands Liquid phase organic 2e60 e [78]
solvent
MOF-5, HKUST-1, UiO-66, MIL-53 (Fe), ZIF-8, Mnþþ L Liquid phase DMF 3e10 e [68]
Mn3(BDC)3(DMF)2
Ag/Cotton AgNO3/Cotton Gas phase Ar/H2 6 Antibacterial [81]
Ag/NeTiO2 AgNO3/TiO2/NH4Cl Gas phase Ar/H2 5 e [35]
Pd/g-Al2O3 Pd (NH4)4(NO3)2/Al2O3 Gas phase Air/Ar e CO oxidation [79]
Pd/Al2O3 Pd(NO3)2/Al2O3; H2PdCl4/Al2O3 Gas phase Ar/H2 6 CO oxidation [83]
Pd/FeOx Pd/Fe(OH)x Gas phase Ar/H2 e CO oxidation [82]
Pd/TiO2eP TiO2þH2PdCl4 Gas phase Ar/H2 6 MB oxidation [130]
Pd/P25 Pd(NO3)2/P25 Gas phase Ar/ethanol 9 CO oxidation [80]
Pd/C H2PdCl4/activated carbon Gas phase Ar/H2 6 CO oxidation [149]
Pt/rGO-MoS2 K2PtCl4/GO-MoS2 Gas phase H2 40 Electrocatalysts for methanol [59]
oxidation
Ni/ᵧ-Al2O3 Ni(NO3)2/ᵧ-Al2O3 Gas phase H2, CO2, N2 20 CO2 reforming of methane [150]
Ni/CeO2eAl2O3 Ni(NO3)2/CeO2eAl2O3 Gas phase Ar/H2 e CO2 methanation [84]
NieCo/graphene sheets Ni(CH3COOH)2$4H2O Gas phase H2 e Catalytic [57]
eCo(CH3COOH)2$4H2O/graphite oxide hydrodesulfurization
Fe3O4/rGO FeOOH/GO Gas phase H2 30 Lithium storage [58]
Mn3O4-g-C3N4 geC3N4eMn2þ Gas phase air 5 CTL sensor for H2S [123]
Au/ZIF-8, Ag/ZIF-8 AuCl4, AgNO3 þZn2þþMEI Liquid phase DMF/H2O 10 - [68]

NPs: nanoparticles; NA: nanoflake array; CC: carbon cloth; CF: copper foam; NF: Ni foam; LDH: layered double hydroxide; QDs: quantum dots.

(5) To further broaden the analytical applications of nano-
material quickly prepared with DBD plasma. At present,
compared with the field of catalysis, the analytical applica-
tion of plasma-synthesized materials is still limited. DBD
plasma is a new promising technique for the development of
multifunctional nanomaterials, and we believe that the
analytical application of the nanomaterials can be further
expanded beyond sensing and adsorption (as shown in
Table 2). Furthermore, most studies in analytical applications
have been performed only as proof-of-concept at analytical
laboratories, mostly lack of real sample analysis. Therefore, it
is of significant importance to accomplish the transition from
proof-of-concept studies to practical use-guided
applications.
To sum up, techniques of DBD plasma for nanomaterial syn-
thesis and modification remain an area of very promising research,
including expansion of the scope of functional nanomaterials,
process scale-up, mechanism investigation, in-situ probing, and
new applications of produced nanomaterials, especially in

15
J. He, X. Wen, L. Wu et al. Trends in Analytical Chemistry 156 (2022) 116715

Table 2
A summary of nanomaterials with plasma treatment.

Plasma roles Nanomaterials Presusor Plasma Discharge Time/min Application Ref.

type medium

Doping C,Cl-doped TiO2 TiO2 Gas phase H2þCCl4 15 Photocatalytic oxidation of [99]
benzene and toluene
Doping N- Doped Pd/C dopant: NH3 Gas phase Ar þ NH3 30 Improved HCOOH [97]
dehydrogenation activity
Doping N-Doped TiO2 TiO2þdopant (NH3) Gas phase NH3/Ar 20 Visible light photocatalyst [94]
Doping S doped g-C3N4 melamine þ dopant (H2S) Gas phase H2S 20e50 Photocatalytic RhB degradation [62]
Etching Ni3S2 nanosheet Na2S on nickel foam Liquid H2O 40 Formaldehyde detection [107]
phase
Etching NiFeP NiFeP powders Liquid H2O 5e20 Enhanced OER activity [106]
phase
Etching NiFe/NiSe2 rich in oxygen NiFe@NCNT Gas phase air 5 Rechargeable batteries [13]
vacancies
Etching NieFe PBA with CN vacancies NiMoO4þK4Fe(CN)63H2O Gas phase N2 10e120 Enhanced OER activity [105]
Etching FeCo@NC with defect sites FeCo@NC Gas phase Ar 30 Enhanced ORR activity [92]
Etching CUMS-rich ZIF-67 ZIF-67 Gas phase N2 9 Enhanced OER activity [104]
Etching Edge-rich and dopant-free graphene Gas phase Ar 30e90 Advanced ORR electrocatalytic [103]
graphene activity
Etching Defects rich MoS2 MoS2 on Ti foil Gas phase Ar or O2 8 Improved HER activity [98]
Grafting Edge rich graphene with GO nanoribbons Gas phase Ar 20 s-10 High performance [87]
oxygen groups supercapacitors
Grafting Au/TiO2 with hydroxyl groups Au/TiO2 Gas phase O2 30 CO oxidation [114]
Grafting Pt/Al2O3 with carboxylate Al2O3þH2PtCl6$6H2O Gas phase Ar, CH4, SO2, HAc 15 Dehydrogenation [14]
groups
Grafting UiO-66-OH UiO-66 Liquid H2O 5e180 Fluorescence sensing for [115]
phase arsenic
Exfoliation MoS2 nanosheets (NH4)2MoS4 Gas phase H2þAr 60 Photodegradation of dye [121]
Exfoliation g-C3N4 nanosheets bulk g-C3N4 Gas phase air 60 Photodegradation of dye [121]
Polymerization GO/Polyacrylamide GO þ acrylamide Gas phase Ar 30 Removal of radionuclides [151]
Polymerization GO/polypyrrole GO þ pyrrole Gas phase N2 30 Pollutant removal [128]
Doping/Reduction B-doped rGO/g-C3N4 GO þ g-C3N4þH3BO3 Gas phase H2 20 Photodegradation of RhB [93]
Doping/Reduction Cu2O/NeTiO2 CuO/TiO2 Gas phase N2/Ar 20 Photodegradation of MO [96]
Doping/Reduction B, N-co Doped rGO GO þ NH4HCO3þH3BO3 Gas phase H2 3 Improves the capacitance [55]
Doping/Reduction Fe,N-doped rGO GO þ forroporphyrin Gas phase NH3 30 Improved ORR activity [102]
Doping/ HCl-doped PANI/PET yarn aniline and HCl Gas phase Air 1.5e6 s Boosted conductivity [113]
polymerization
Doping/Etching Ti3þ and N doped TiO2 with TiO2 Gas phase Ar, H2, NH3 15 Photocatalytic MB Degradation [95]
oxygen vacancy
Doping/Etching Etched and Doped Co9S8/ Co9S8/Graphene Gas phase NH3 60 Enhanced electrocatalytic [108]
Graphene performance
Doping/Exfoliation N-Doping of exfoliated GO GOþ (NH4)2CO3 Gas phase air 10 ORR activity [120]
Exfoliation/Etching Exfoliated CoFe LDHs with CoFe LDHs Liquid H2O 5 OER activity [119]
multivacancies phase
Exfoliation/Etching CoFePi NS with vacancies CoFe LDHs þ NaH2PO4 Liquid H2O 1e5 OER activity [122]
phase
Exfoliation/Grafting g-C3N4 nanosheets with O- g-C3N4 powder Gas phase Air 2.5e20 Enhanced photocatalytic RhB [110]
containing groups degradation
Exfoliation/Reduction graphene NS GO powder Gas phase H2, Ar or CO2 2 min Supercapacitor electrodes [152]
Etching/Grafting carbon particles with defect carbon particles Gas phase Air 3e5 s Increased hydrophilic character [111]
sites, N-/O-containing groups
Etching/Grafting PET with N-/O-groups polyethylene Gas phase Air 3e300 s Increasing drag force [112]
terephthalate
Doping/Etching O vacancies rich Ni/NiO/N Ni(x)Ti Gas phase NH3 3e20 Photocatalytic hydrogen [109]
/Oxidation eTiO2-x production
Doping/Reduction B-doped rGO GO powders þ H3BO3 Gas phase H2 3 Improved capacitance [56]
/Exfoliation

CUMS: coordinately unsaturated metal sites; NS: nanosheets; NCNT: nitrogen-doped carbon nanotubes.

analytical chemistry. We hope that this review will help to lead the
way for analytical chemistry development by use of nanomaterials
fast prepared with DBD techniques.
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.
the National Natural Science Foundation of China (U21A20283),
1.3.5 Project for Disciplines of Excellence, West China Hospital,
Sichuan University, China (ZY2016204), Science & Technology
Department of Sichuan Province, China (No.2019ZDZX0035, and
No.2019ZDZX0046), Natural Science Foundation of Sichuan Prov-
ince, China (2022NSFSC1210) and the Fundamental Research Funds
for the Central Universities, China.
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