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Microfluidic plasma: Novel process intensification strategy

  • Liangliang Lin EMAIL logo , Ziyi Zhang and Yuanping Min
Published/Copyright: November 23, 2022
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Abstract

Microfluidic plasma is a novel process intensification strategy that integrates microfluidic and plasma together and uses their synergistic effects to provide new pathways for chemistry and chemical engineering. In this work, the unique properties and synergistic advantages of microfluidic plasma are introduced. According to the reactor configuration, three types of microfluidic plasmas are elaborated, including chip-based microfluidic plasma, tubular-based microfluidic plasma, and jet-based microfluidic plasma. Selected examples in nanofabrication, chemical synthesis, water treatment, etc., are provided to show their applications in diverse fields. Finally, the existing challenges of this technique have prospected.

1 Introduction

Process intensification (PI) is defined as any chemical engineering development that leads to substantially smaller, cleaner, safer, and more energy-efficient technology [1]. It can be divided into two sub-domains: equipment and methods. The former deals with PI from the reactor engineering view, such as static mixers, membrane distillation, spinning disc reactors, and microreactors, while the latter handles PI from the process view, like hybrid separations, integrated reaction and separation, heat exchange, phase transition, and techniques using alternative energy sources (e.g., microwave, ultrasound, electric field, centrifugal field) [2]. As yet, many disruptive strategies or devices have been designed and implemented in the chemical industry to improve process efficiency and economic sustainability. The cardinal principle governing PI can be improved by utilizing molecular interactions at optimized conditions of driving forces and synergistic effects of different unit operations [3]. Indeed, most chemical reactions are mass or heat-transfer-controlled rather than kinetically controlled [4]. There is an increasing trend of applying microreactors to realize PI by maximizing the specific surface areas as well as the effectiveness of intra- and intermolecular events. Microfluidics, featuring fluid manipulation at submillimeter level, has attracted great attention over the past decade. Thanks to the specificities of small-scale physics, microfluidic allows the rapid mixing of reagents, the precise controls over flows, the accurate regulation of reaction conditions, and the handling of hazardous chemicals [5,6,7]. These features along with the continuous operation mode make microfluidic a powerful platform for chemical synthesis or nanofabrication with good stability and reproducibility [8].

In addition to overcoming mass and heat transfer limitations from the reactor engineering view, the concept of novel process windows was also proposed to speed up kinetics through the use of harsh conditions from the process view [4,9]. In this manner, reaction times can be further reduced from an hour or minute to the second level. Plasma is perceived as an exciting PI technique that uses diverse energetic species (e.g., electrons, ions, photons, free radicals, excited atoms, or molecules) to intensify reactions [10,11]. In plasma media, traditional solvents are not necessitated; thus, it not only avoids chemical residues or diffusion pathways caused by solvents but also gets rid of additional steps for the removal of solvents. Besides, since different gases (e.g., Ar, He, O2, N2, air, NH3, CO, CO2, H2, CH4, fluorine, and chlorine) or their mixtures can be incorporated as working gas, with diverse precursors as reagents, plasma offers great flexibility in reactions ranging from oxidation, nitration, carbonation, hydrogenation, to sulfuration, chlorination, and polymerization.

Inspired by the encouraging achievements, novel ideas naturally come out: By merging microfluidics with plasma technology, is it possible to create an efficient and completely new PI strategy? If so, can we use their synergistic advantages to open new pathways in chemistry and chemical engineering fields? In the constant pursuit of fascinating ideas, the integration of microfluidic and plasma (i.e., microfluidic plasma) has been explored, aiming to use their synergistic advantages to solve formidable challenges that cannot be solved by each alone or by conventional technology [12]. According to Paschen’s law, the breakdown voltage of plasma is a function of the ambient pressure and the gap between two electrodes [13,14]. Thus, miniaturization of plasma reactors not only has practical potential for low power operation at high pressures but also leads to small portable devices with fascinating synergistic effects. Figure 1 summarizes the advantages of microfluidic, plasma, and microfluidic plasma. Typically, microfluidic plasma is strongly nonequilibrium, where gas temperature is much lower than electron temperature. This is particularly favored by nanomaterial synthesis due to the much-reduced particle agglomeration and growth [15]. The high-pressure chemistry contributes to enhanced radical collisions and densities, which further accelerates chemical reactions and intensifies processes. Another important feature of microfluidic plasma is the great flexibility in precursor choice, configuration design, and process control. The wide operational spaces may open up new possibilities for chemistry and chemical engineering.

Figure 1 
               The advantages of microfluidic, plasma, and microfluidic plasma.
Figure 1

The advantages of microfluidic, plasma, and microfluidic plasma.

In this timely Mini-Review, we discussed microfluidic plasma in terms of synergistic effects, configurations, applications, and challenges, aiming to bring this new PI strategy to academic and industrial communities and to offer innovative solutions to approach intractable challenges that cannot be solved by conventional techniques.

2 Representative microfluidic plasma configurations

Driven by their fascinating properties, different types of microfluidic plasmas have been designed and developed, with materials ranging from glass, quartz, silicon, ceramics, metals, polymers, or composite materials. Due to the high degree of flexibility, they come in many shapes and sizes. Based on the microreactor configuration, they can be roughly classified into three categories: chip-based microfluidic plasma, tubular-based microfluidic plasma, and jet-based microfluidic plasma. Selected configurations are shown in Figure 2.

Figure 2 
               Representative microfluidic plasma configurations: (a) chip-based microfluidic plasma, (b) tubular-based microfluidic plasma, and (c) jet-based microfluidic plasma. (a) Reprinted with permission from [26,27,28], Copyright 2018 The Royal Society of Chemistry, Copyright 2018 Springer Nature, Copyright 2022 The Royal Society of Chemistry. (b) Reprinted with permission from [16,29], Copyright 2022 American Chemical Society, Copyright 2018 Springer Nature. (c) Reprinted with permission from [30,31,32], Copyright 2022 American Chemical Society, Copyright 2018 PCCP Owner Societies, and Copyright 2020 IOP Publishing.
Figure 2

Representative microfluidic plasma configurations: (a) chip-based microfluidic plasma, (b) tubular-based microfluidic plasma, and (c) jet-based microfluidic plasma. (a) Reprinted with permission from [26,27,28], Copyright 2018 The Royal Society of Chemistry, Copyright 2018 Springer Nature, Copyright 2022 The Royal Society of Chemistry. (b) Reprinted with permission from [16,29], Copyright 2022 American Chemical Society, Copyright 2018 Springer Nature. (c) Reprinted with permission from [30,31,32], Copyright 2022 American Chemical Society, Copyright 2018 PCCP Owner Societies, and Copyright 2020 IOP Publishing.

2.1 Chip-based microfluidic plasma

Chip-based microfluidic plasmas refer to the configuration where plasmas are generated and confined in chip-form microreactors. They are typically manufactured using glass, quartz, silicon, or certain polymers like polydimethylsiloxane, Teflon, polymethylmarthacrylate (PMMA), polyetheretherketone (PEEK), perfluoroalkoxy (PFA), and polycarbonate by micromachining, etching, lithography, and photolithography methods. Glass or indium tin oxides (ITO) are the most commonly used materials, since they are transparent and chemically inert, allowing visual observation of microchannels. These devices are characteristically comprised of two parts, on which the surfaces are engraved with fluidic channels of various widths and depths, before being fused by thermal bonding to form a compact vessel (Figure 2a). Capillaries are connected to the reactor via fluidic connections, so that gas or liquid precursors can be delivered into the reactor. The electrical connection between the electrodes and high voltage power supply can be realized with the assistance of metal strips or paints. Upon imposing high voltage on the electrodes, plasma discharges are generated within the chip microreactor.

Chip-based configuration gives a very high degree of control over the chemical reactions and can integrate multiple processes into a single device while maintaining a small overall size. It also provides great flexibility in the design of channel patterns without dead volume. Furthermore, due to the high surface-to-volume ratio, it offers several advantages including rapid heat and mass transfer, high reaction rates, low reagent consumption, and high efficiency. On the other hand, the complicated fabrication process along with the expensive fabrication facilities may limit their industrial use.

2.2 Tubular-based microfluidic plasma

Tubular-based microfluidic plasmas refer to the configuration that employs capillary tubes as the reactors, and plasma discharges are generated inside the capillary tubes. They are commonly made by commercially available micrometer-sized capillaries such as metal tubing (e.g., stainless steel, nickel, and copper), fused-silica tubing, quartz tubing, Teflon tubing, PFA tubing, and PEEK tubing. As a consequence, this configuration is often longer in one dimension. A representative design is shown in Figure 2b, where a PFA capillary tube (O.D. = 1/16 inch, I.D. = 0.03 inch) is wrapped around a stainless steel grounded electrode [16]. A copper or an ITO foil serves as the high-voltage electrode and is wrapped outside the coiled PFA capillary. Both electrodes are connected to a sinusoidal alternate current power supply. A continuous helium flow is incorporated into the PFA capillary tube as the plasma gas. Once the high voltage is applied to the electrodes, plasma discharges are formed inside the capillary. By varying the length of the outer electrode, the discharge region can be tuned, making it possible to adjust the residence time.

The tubular-based configuration is modular and adaptable by extending the length of the tube capillary and electrodes in one dimension to control the residence time in the plasma region. Complex and expensive processing (e.g., micromachining, lithography, etching, electroplating, and molding) is not required for manufacturing microreactors, since the capillary tubes are commercially available. Besides, reactors are easily connected with other microfluidic devices or in-situ characterization techniques (optical emission spectroscopy, chromatography, mass spectrometry, or electrophoresis) for real-time process monitoring and product analysis [17,18]. In comparison to the chip-based reactors, this configuration is much cheaper to be fabricated, easier to be scaled up, and can produce a larger quantity of products.

2.3 Jet-based microfluidic plasma

Jet-based microfluidic plasmas are the most intensively studied and frequently used configurations till now. They typically operate as dielectric barrier discharges (DBD) with a central needle as the inner electrode and an outer ring electrode, or a single electrode with capacitive coupling [19]. Each of the electrodes is either grounded or connected to high power supply, with the distance ranging from tens of microns to several millimeters. Another common configuration consists of two concentric tubes with the same diameter as the electrodes, which are inserted in a larger tube and separated by a certain distance. Each electrode composes of a copper ring that connects to the high power supply. A continuous gas is coupled in the electrodes as working gas and flows into the ambient to ensure low-temperature character. In general, noble gases such as Ar or He are used, while the admixture of reactive gases like O2, N2, H2, and CH4 offers the opportunity to tune the plasma chemistry. Therefore, the jet-based configuration is capable of generating diverse short-living reactive species depending on the working gas and precursor. With the supply of high voltage to electrodes, it launches a stable plasma plume to the ambient air. According to the electrode arrangement, jet-based plasmas can be further categorized as dielectric-free electrode jets, single electrode jets, DBD jets, and DBD-like jets [20]. Representative configurations are provided in Figure 2c.

Compared with the chip-based or tubular-based configuration, jet-based microfluidic plasmas have a higher degree of flexibility in configuration. This type of microfluidic plasma can be driven by direct current, pulsed direct, or high-frequency alternating currents like radio frequency (RF) or microwave frequency power supplies, offering more alternative ways to couple the power supply. Another important feature is that plasma jets can directly contact objects, which open up many possibilities for practical applications, like plasma additive manufacturing [21,22], nanomaterials deposition [23], plasma medicine [24], or portable plasma devices [25].

The selection of microfluidic plasma configuration mainly depends on applications. Chip-based configuration allows precise control over process parameters, which is suitable for fundamental studies like kinetics, dynamics, or mechanisms. Tubular-based configuration is more adaptable to diverse processes, with the ability to continuously produce a larger quantity of products. Thus, it is favored by chemical synthesis or nanofabrication purposes. As to the jet-based configuration, it has a high degree of design flexibility, rendering it possible to be applied for surface modification, water treatment, and biomedical science.

3 Applications of microfluidic plasmas

Owing to the synergistic effects of microfluidics and plasma technology, microfluidic plasma has demonstrated itself as an efficient PT strategy, with rapidly expanding applications in chemistry and chemical engineering fields. In this section, we highlight several promising areas in which this technique may pave.

The strong nonequilibrium state of microfluidic plasmas makes them particularly suitable for nanomaterials synthesis and processing since low background temperature would suppress particle nucleation and growth. In some cases, particles are also charged in plasma, which further reduces aggregation. Another benefit of nanomaterials synthesis is electrons can replace chemical reductants to avoid contaminations (e.g., NO 3 , Cl, and SO 4 2 ). Such a capability could guarantee product purity yet minimize the use of solvents or stabilizers [33]. As a proof-of-demonstration, a jet-based microfluidic plasma system was developed for the continuous in-flight synthesis of ligand-free AuNPs [34]. By transporting a stream of HAuCl4 precursor through a cold plasma jet in a quartz capillary, Au3+ ions were rapidly reduced by electrons to form AuNPs of small diameters (∼4 nm) within 150 μs, and the synthesis rates were many orders of magnitude greater than radiolysis, electron beam irradiation, or colloidal chemical synthesis approaches. Recently, Pho et al. [35] reported the synthesis of N-doped carbon dots with 35% quantum yield from Vitamin B9 using a non-thermal microplasma jet, which proved to achieve PI by optimizing plasma jet-liquid distance, metal–plasma interaction, and recycling, bringing the throughput toward 1 g per day [36].

Compared with conventional batch reactions, microfluidic plasmas have better control and versatility both in terms of reactor configuration and operational space. The combination of physical (heat, light, electrical field) and chemical (electrons, ions, photons, metastable atoms, or excited radicals) effects provides a highly reactive environment at mild conditions, leading to new chemical routes without catalysts. Thus, they were also explored for chemical synthesis. A smart Biflow 2.7 chip-based microfluidic plasma reactor was designed by Lepoetre et al. and applied for various chemical reactions, such as cyclohexane amination [37], CO2 carbonylation [38], amine N-acylation [28], and 1-hexene oligomerization [39]. Results showed the reactor has a high degree of flexibility and versatility and can trigger reactions at rather low temperatures (close to room temperature) and atmospheric pressure. Furthermore, the substantially intensified heat and mass transfer enabled the reactor to produce target products in good to excellent yields. Another salient example was reported by Cameli et al. [16], where a tubular-based microfluidic plasma was developed for intensified H2O2 production. A water stream together with a helium gas flow was delivered in a tubular capillary. When high voltage was supplied to the electrodes around the microreactor, plasma discharges were generated within the capillary, leading to the formation of H2O2 through the below reactions:

(1) H 2 O ( g ) OH + H

(2) OH ( g ) + OH ( g ) H 2 O 2 ( g ) H 2 O 2 ( aq )

(3) OH ( aq ) + OH ( aq ) H 2 O 2 ( aq )

(4) OH + H H 2 O

(5) 2 H 2 O H 2 O 2 + H 2

With rapid industrial development, the continued production of pollution remains inevitable. Environmental monitoring has become increasingly important to minimize the adverse impacts on human health and the environment. Nitrosamines are a class of strong carcinogens that widely exist in cosmetics, like N-nitrosodiethanolamine, N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), N-nitrosodibutylamine, N-nitrosodiphenylamine, and N-nitrosodicyclohexylamine. In the study of Lin et al. [40], the ion beam technique was utilized to fabricate 1,2-ethanedithiol-modified gold nanorods for surface-enhanced Raman scattering detection of NDMA and NDEA. Characteristic peaks of NDMA/NDEA were observed, a detection limit of 10−8 M for both molecules. In a recent study, a jet-based microfluidic plasma system was developed for the continuous synthesis of glucose-functionalized gold nanoparticles (G-AuNPs) and their use for real-time Pb2+ detection [41]. Results showed the whole process took less than 30 s, including the G-AuNPs synthesis and colorimetric Pb2+ detection. This reveals the high efficiency of the microfluidic plasma system and is very promising for the detection of hazardous materials like nitrosamines and heavy metal ions.

Microfluidic plasmas also have been applied for water treatment to remove microbial and chemical contaminants. This is because high energy electrons (1–10 eV) and reactive species in plasma have the potential to oxidize organic pollutants to their less toxic forms and enhance their potential for degradation. Meanwhile, plasma also supplies the water with ultraviolet light and reactive radicals, which further penetrate and interact with the microorganism to repel or kill bacteria. The integration of microfluidics for plasma water treatment provides additional benefits like continuous operation, enhanced treatment efficiency, portable devices, and shorter distances for the transfer of plasma species from a gas into a liquid. This may overcome limitations such as mass transfer in bulk reactors. Sun et al. [29] reported a jet-based microfluidic plasma device for the control and removal of biofilms in drinking water. A 9 × 9 array of microchannels with an overall area of 125.4 mm2 were adopted to conduct experiments. Results showed biofilms vanished rapidly after plasma exposure, which was attributed to the generation of oxygen-bearing species like hydroxyl radical (OH), singlet oxygen (1O2), hydrogen peroxide (H2O2), and ozone (O3). In addition to the jet-based configuration, chip-based microfluidic plasma was also used for water treatment. Specifically, a DBD chip microreactor with 100 or 50 µm depths and 390 or 330 µm channel widths was fabricated by Patinglag et al. [27] for the degradation of methylene blue. They found the degradation rates were related to the residence time of the sample in the plasma zone, the plasma working gas, the channel depth, and flow rate. At the optimum condition, the degradation level of methylene blue was greater than 97%.

Apart from the aforementioned applications, there are studies exploiting microfluidic plasmas for surface modification of materials or biomedical science applications. For instance, by incorporating suitable precursors in microchannels and igniting plasma discharges inside the chip microreactor, Wu et al. [42] successfully modified the inner surface of microfluidic platforms with hydrophobicity or hydrophilicity. The developed strategy is surface-material-independent, including sapphire, PET, PMMA, and silicon wafers. A similar method was reported by Escobedo and Sinton [43] to actuate liquids in microchannels by tuning the surface energy of microchannels by plasma impacts. In the study of Neretti et al. [44], jet-based microfluidic plasma arrays were developed for biomedical applications. Results revealed the existence of nitrogen species as well as helium metastable excited states, which exhibited a remarkable disinfectant effect against bacteria and fungi. To show the wide applications of microfluidic plasma in diverse fields, Table 1 summarizes selected examples reported in recent years.

Table 1

Typical examples of microfluidic plasma in diverse fields

Applications Examples Configurations References
Nanofabrication Au nanoparticles Chip-based reactor [34]
Nanodiamonds Chip-based reactor [45]
Ag–Au nanoalloys Jet-based reactor [30]
Bimetallic Fe–Ni nanoparticles Tubular-based reactor [46]
Chemical synthesis Amination of cyclohexane Chip-based reactor [37]
Carbonylation of CO2 Chip-based reactor [38]
N-Acylation of amines Chip-based reactor [28]
H2O2 production Tubular-based reactor [16]
Water treatment Methylene blue degradation Chip-based reactor [27]
Biological compounds degradation Chip-based reactor [47]
Biofilm control and removal Jet-based reactor [29]
Surface modification Corrosion resistance Jet-based reactor 10.1016/j.jtice.2022.104467
Liquid actuation Chip-based reactor [43]
Wettability effects Jet-based reactor [48]
Biomedical science Wound healing Chip-based reactor [49]
Microbiological inactivation Jet-based reactor [50]
Sterilization of human biofilm Jet-based reactor [44]

4 Conclusion and outlook

PI through microfluidic plasma technology is an emerging field, paving an efficient way for chemical reactions and processes at mild conditions (low temperature, atmospheric pressure, without catalysts). Many researchers are exploiting the synergistic effects of both techniques to address challenges that cannot be solved by conventional approaches. Despite the indisputable advantages, microfluidic plasmas still face several problems. Currently, they are only suitable for fundamental research rather than large-scale industrial use due to the low throughput. We believe this technique has promising commercial applications in the synthesis of nanomaterials and chemicals, as long as the throughput can be enhanced. Adding devices in parallel or enhancing the productivity of each device may be an answer. The influence of the electrical field and plasma species on fluids and their transportation in microchannels is not clear yet, requiring both modeling and experiments to reveal their interactions. Also, microfluidic plasma is a multidisciplinary field of research at the intersection of physics, chemistry, engineering, and materials, but has been applied in rather limited areas. Active collaborations among diverse fields are needed to further expand their applications.

  1. Funding information: This work was supported by the Natural Science Foundation of Jiangsu Province (BK20190605), National Natural Science Foundation of China (22078125, 52004102), China Postdoctoral Science Foundation (2021M690068), Fundamental Research Funds for the Central Universities (JUSRP221018, JUSRP622038), and NMPA Key Laboratory of Cosmetic Safety Assessment, Guangdong Institute for Drug Control (KF2021014).

  2. Author contributions: Liangliang Lin: conceptualization, formal analysis, writing – original draft, writing – review and editing; Ziyi Zhang: review and writing; Yuanping Min: review and writing.

  3. Conflict of interest: The corresponding author (Liangliang Lin) is a member of the Editorial Board of Green Processing and Synthesis.

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Received: 2022-07-21
Revised: 2022-10-03
Accepted: 2022-10-25
Published Online: 2022-11-23

© 2022 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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