Direct Current Pulse Atmospheric Pressure Plasma Jet Treatment on Electrochemically Deposited NiFe/Carbon Paper and Its Potential Application in an Anion-Exchange Membrane Water Electrolyzer.

An atmospheric pressure plasma jet (APPJ) is used to process electrochemically deposited NiFe on carbon paper (NiFe/CP). The reactive oxygen and nitrogen species (RONs) of the APPJ modify the surface properties, chemical bonding types, and oxidation states of the material at the self-sustained temperature of the APPJ. The APPJ treatment further enhances the hydrophilicity and creates a higher disorder level in the carbon material. Moreover, the metal carbide bonds of NiFe/CP formed in the electrochemical deposition (ED) process are converted to metal oxide bonds after APPJ processing. The potential application of APPJ treatment on NiFe/CP in alkaline water electrolysis is demonstrated. With more oxygen-containing species and better hydrophilicity after APPJ treatment, APPJ-treated NiFe/CP is applied as the electrocatalyst for the oxygen evolution reaction (OER) in alkaline water electrolysis. APPJ-treated NiFe/CP is also used in a custom-made anion-exchange membrane water electrolyzer (AEMWE); this should contribute toward realizing the practical large-scale application of AEM for hydrogen production.

A low-cost microplasma generation unit allowing for the on-site processing of ZnO-based gas sensors.

In this study, a low-cost gas-sensing device that integrates a zinc-oxide (ZnO)-based gas sensor with a microplasma generation unit is presented. By the proper connection of different sets of electrodes to the desired power sources or the measurement circuit, the device can be operated in the microplasma mode (MPM) or the gas-sensing mode (GSM), respectively. Due to the device design, microplasma can be generated at the same location where the precursor for the sensing materials, namely Zn(NO3)2 solution, is coated. Such an arrangement allows for low temperature and the on-site conversion of the precursor materials to ZnO particles upon microplasma treatment under MPM. GSM can be used to detect ethanol vapor with a concentration between 100 and 18 000 ppm at room temperature. We observed that the sensor can be operated under a wide range of ethanol concentrations with stable sensing behavior for over 80 test cycles.

Online, Continuous, and Interference-Free Monitoring of Trace Heavy Metals in Water Using Plasma Spectroscopy Driven by Actively Modulated Pulsed Power.

This work presents the development of an online continuous heavy metals monitoring system using optical emission spectroscopy of plasma in water. The plasmas were driven by actively modulated pulsed power (AMPP) to control the plasma and its emission behavior in solutions with a wide range of conductivity. The AMPP quantified in situ the solutions' conductivity and modulated in real time the pulse width based on the conductivity. We demonstrated the online monitoring of the metallic elements. The results show that multiple metallic elements, namely Pb and Zn, can be independently and simultaneously detected with less than a 10% variation in the corresponding optical emission lines in solutions with a wide range of conductivity. An alert system was integrated to demonstrate the capability of an instant warning via e-mail once metallic elements were detected. Finally, we demonstrated that this system was robust even with the existence of several interferences and able to perform online continuous monitoring for days. We believe the system using plasma spectroscopy with AMPP for online monitoring of metals in water will have a significant impact on the fields of environmental monitoring and protection.

A Photoactivated Gas Detector for Toluene Sensing at Room Temperature Based on New Coral-Like ZnO Nanostructure Arrays.

A photoactivated gas detector operated at room temperature was microfabricated using a simple hydrothermal method. We report that the photoactivated gas detector can detect toluene using a UV illumination of 2 µW/cm². By ultraviolet (UV) illumination, gas detectors sense toluene at room temperature without heating. A significant enhancement of detector sensitivity is achieved because of the high surface-area-to-volume ratio of the morphology of the coral-like ZnO nanorods arrays (NRAs) and the increased number of photo-induced oxygen ions under UV illumination. The corresponding sensitivity (ΔR/R0) of the detector based on coral-like ZnO NRAs is enhanced by approximately 1022% compared to that of thin-film detectors. The proposed detector greatly extends the dynamic range of detection of metal-oxide-based detectors for gas sensing applications. We report the first-ever detection of toluene with a novel coral-like NRAs gas detector at room temperature. A sensing mechanism model is also proposed to explain the sensing responses of gas detectors based on coral-like ZnO NRAs.

Battery-operated, portable, and flexible air microplasma generation device for fabrication of microfluidic paper-based analytical devices on demand.

A portable microplasma generation device (MGD) operated in ambient air is introduced for making a microfluidic paper-based analytical device (µPAD) that serves as a primary healthcare platform. By utilizing a printed circuit board fabrication process, a flexible and lightweight MGD can be fabricated within 30 min with ultra low-cost. This MGD can be driven by a portable power supply (less than two pounds), which can be powered using 12 V-batteries or ac-dc converters. This MGD is used to perform maskless patterning of hydrophilic patterns with sub-millimeter spatial resolution on hydrophobic paper substrates with good pattern transfer fidelity. Using this MGD to fabricate µPADs is demonstrated. With a proper design of the MGD electrode geometry, µPADs with 500-µm-wide flow channels can be fabricated within 1 min and with a cost of less than $USD 0.05/device. We then test the µPADs by performing quantitative colorimetric assay tests and establish a calibration curve for detection of glucose and nitrite. The results show a linear response to a glucose assay for 1-50 mM and a nitrite assay for 0.1-5 mM. The low cost, miniaturized, and portable MGD can be used to fabricate µPADs on demand, which is suitable for in-field diagnostic tests. We believe this concept brings impact to the field of biomedical analysis, environmental monitoring, and food safety survey.

Observation of the rose petal effect over single- and dual-scale roughness surfaces.

Rose petals exhibit superhydrophobicity with strong adhesion to pin water drops, known as the 'petal effect.' It is generally believed that the petal effect is attributed to dual-scale roughness, that is, the surface possesses both a nanostructure and a microstructure (Feng et al 2008 Langmuir 24 4114). In this study, we demonstrate that the dual-scale roughness is not a necessary condition for a surface of the petal effect. A surface of single-scale roughness, either at the nanoscale or the microscale alone, within a certain roughness region may also exhibit the petal effect. The surface roughness plays the essential role on the wetting behavior and governs the contact angle in the Wenzel or Cassie state, as well as the contact angle hysteresis. A water drop on the surface of the petal effect under the condition of the advancing and receding contact angle would fall into, respectively, the Cassie and Wenzel state, which leads to a contact angle hysteresis large enough to pin the water drop. On both single and dual textured hydrophobic surfaces, a sequence of wetting transitions: Wenzel state → petal state (sticky superhydrophobic state) → lotus state (slippery superhydrophobic state) is consistently observed by simply increasing the surface roughness.

Development of a real-time and multitasking system for long-term monitoring of aqueous metallic elements using plasma spectroscopy.

In this work, we integrated a Raspberry Pi (RPi) board, an open-sourced hardware, with a spectrometer, a high voltage DC power source, and a plasma system to develop a multi-tasking monitoring system for metallic elements in solution. In this system, RPi precisely controls voltage pulses, synchronizes them with the spectrometer, and performs real-time analysis using data acquired in real-time. This integration enables continuous monitoring of multiple metallic elements in solutions of varying conductivities. Synchronization of voltage pulses and spectrometer triggering is crucial for reliable measurements and prolongs the lifetime of the electrode. This multitasking capability significantly improves the quality of the overall spectroscopic data and enables operation in a long-term manner. Two operating modes are proposed, namely regular detection mode (RDM) and event-based mode (EBM). RDM is used to identify the existence of metallic elements and EBM is used for quantification upon detection. A 24-h long-term test shown in this work demonstrates the system capability in of utilizing RDM to monitor the presence of Pb and Mg every 30 min. Injection of Pb- and/or Mg-containing solutions is performed to activate EBM for quantification analysis. Instant warning messages can be sent upon metal detection showcasing the system potential for real-time monitoring and efficient quantification. We believe this work can contribute to multiple fields such as environmental monitoring, industrial quality control, or process monitoring.

Modulation of cell attachment and collagen production of anterior cruciate ligament cells via submicron grooves/ridges structures with different cell affinity.

This study aimed to investigate the effects of submicron-grooved topography and surface cell affinity on the attachment, proliferation and collagen synthesis of anterior cruciate ligament (ACL) cells. Two grooved polystyrene (PS) surfaces (equal groove/ridge width of 800 nm) with a groove depth of 100 or 700 nm were fabricated and modified by oxygen plasma treatment, dopamine deposition and conjugation of RGD-containing peptides to enhance cell affinity. The elongation and alignment of ACL cells was enhanced by grooved structures with increasing groove depths regardless of surface chemistry. On the other hand, cell spreading and proliferation mainly depended on surface chemistry, in accordance with surface cell affinity: O(2) plasma < dopamine deposition < RGD conjugation. The synthesis of type I collagen was the highest by the ACL cells cultured on the 700 nm grooved surface conjugated with RGD peptides, indicating that both surface grooved topography and chemistry play a role in modulating collagen production of ACL cells. Furthermore, the type I collagen deposited on the 700 nm PS surface was aligned with grooves/ridges. Our results indicated that both ligand presentation and cell alignment are important in the physiological activities of ACL fibroblasts. Such information is critical for design of biomaterials for ACL tissue engineering.

Ultrafast Fabrication of H2SO4, LiCl, and Li2SO4 Gel Electrolyte Supercapacitors with Reduced Graphene Oxide (rGO)-LiMnOx Electrodes Processed Using Atmospheric-Pressure Plasma Jet.

Pastes containing reduced graphene oxide (rGO) and LiCl-Mn(NO3)2·4H2O are screen-printed on a carbon cloth substrate and then calcined using a nitrogen atmospheric-pressure plasma jet (APPJ) for conversion into rGO-LiMnOx nanocomposites. The APPJ processing time is within 300 s. RGO-LiMnOx on carbon cloth is used to sandwich H2SO4, LiCl, or Li2SO4 gel electrolytes to form hybrid supercapacitors (HSCs). The areal capacitance, energy density, and cycling stability of the HSCs are evaluated using electrochemical measurement. The HSC utilizing the Li2SO4 gel electrolyte exhibits enhanced electrode-electrolyte interface reactions and increased effective surface area due to its high pseudocapacitance (PC) ratio and lithium ion migration rate. As a result, it demonstrates the highest areal capacitance and energy density. The coupling of charges generated by embedded lithium ions with the electric double-layer capacitance (EDLC) further contributed to the significant overall capacitance enhancement. Conversely, the HSC with the H2SO4 gel electrolyte exhibits better cycling stability. Our findings shed light on the interplay between gel electrolytes and electrode materials, offering insights into the design and optimization of high-performance HSCs.

Interpreting convolutional neural network for real-time volatile organic compounds detection and classification using optical emission spectroscopy of plasma.

This study presents the investigation of optical emission spectroscopy of plasma using interpretable convolutional neural network (CNN) for real-time volatile organic compounds (VOCs) classification. A microplasma-generation platform was developed to efficiently collect 64 k spectra from various types of VOCs at different concentrations, as training and testing sets for machine learning. A CNN model was trained to classify VOCs with accuracy of 99.9%. To interpret the CNN model and its predictions, the spectral processing mechanism of the CNN was visualized by feature maps and the critical spectral features were identified by gradient-weighted class activation mapping. Such approaches brought insights on how CNN analyzes the spectra and enables the CNN operation to be explainable. Finally, the CNN model was incorporated with the microplasma platform to demonstrate the application of real-time VOC monitoring. The type of VOCs can be identified and reported via messages within 10 s once the microplasma is ignited. We believe that using CNN brings a novel route for plasma spectroscopy analysis for VOC classification and impacts the fields of plasma, spectroscopy, and environmental monitoring.

Suppressing Defect Formation in Metal-Organic Framework Membranes via Plasma-Assisted Synthesis for Gas Separations.

Metal-organic frameworks (MOFs) are considered as promising materials for membrane gas separations. Structural defects within a pure MOF membrane can considerably reduce its selectivity and possibly result in a nonselective separation. This work proposes a solution-phase synthesis with dielectric barrier discharge (DBD) plasma to suppress the formation of defects in the pure MOF membrane of CPO-8-BPY. Through comprehensive solid-state characterization with XRD, SEM, XPS, solid-state NMR, and XAFS, DBD plasma is demonstrated to facilitate deprotonation in the H2aip linker, which leads to a smaller and more uniform particle size of CPO-8-BPY. The narrow grain size distribution effectively reduces the pinhole-type defects in the pure CPO-8-BPY membrane and endows it with good ideal selectivity for H2/CH4 (αH2/CH4 = 28.2) and N2/CH4 (αN2/CH4 = 5.4). The selectivity for H2/CH4 of this membrane from a mixed-gas permeation test is found to be 15.4. Molecular simulations are also performed to gain insights into the gas transport properties of this MOF. The results suggest that ligand rotation plays an important role in CPO-8-BPY when being applied to the membrane separation of N2/CH4.

Dielectric Barrier Discharge Plasma Jet (DBDjet) Processed Reduced Graphene Oxide/Polypyrrole/Chitosan Nanocomposite Supercapacitors.

Reduced graphene oxide (rGO) and/or polypyrrole (PPy) are mixed with chitosan (CS) binder materials for screen-printing supercapacitors (SCs) on arc atmospheric-pressure plasma jet (APPJ)-treated carbon cloth. The performance of gel-electrolyte rGO/CS, PPy/CS, and rGO/PPy/CS SCs processed by a dielectric barrier discharge plasma jet (DBDjet) was assessed and compared. DBDjet processing improved the hydrophilicity of these three nanocomposite electrode materials. Electrochemical measurements including electrical impedance spectroscopy (EIS), cyclic voltammetry (CV), and galvanostatic charging-discharging (GCD) were used to evaluate the performance of the three types of SCs. The Trasatti method was used to evaluate the electric-double layer capacitance (EDLC) and pseudocapacitance (PC) of the capacitance. The energy and power density of the three types of SCs were illustrated and compared using Ragone plots. Our experiments verify that, with the same weight of active materials, the combined use of rGO and PPy in SCs can significantly increase the capacitance and improve the operation stability.

The Influence of Helium Dielectric Barrier Discharge Jet (DBDjet) Plasma Treatment on Bathocuproine (BCP) in p-i-n-Structure Perovskite Solar Cells.

A bathocuproine (BCP) layer is typically used as the hole-blocking layer in p-i-n-structure perovskite solar cells (PSCs) between PC61BM and Ag electrodes. Before evaporating the Ag, we used a low-temperature (<40 °C) atmospheric-pressure dielectric barrier discharge jet (DBDjet) to treat the BCP with different scan rates. The main purpose of this was to change the contact resistance between the BCP layer and the Ag electrodes through surface modification using a DBDjet. The best power conversion efficiency (PCE) of 13.11% was achieved at a DBDjet scan rate of 2 cm/s. The He DBDjet treatment introduced nitrogen to form C-N bonds and create pits on the BCP layer. This deteriorated the interface between the BCP and the follow-up deposited-Ag top electrode. Compared to the device without the plasma treatment on the BCP layer, the He DBDjet treatment on the BCP layer reduced photocurrent hysteresis but deteriorated the fill factor and the efficiency of the PSCs.

Low-Temperature (<40 °C) Atmospheric-Pressure Dielectric-Barrier-Discharge-Jet Treatment on Nickel Oxide for p-i-n Structure Perovskite Solar Cells.

A scan-mode low-temperature (<40 °C) atmospheric-pressure helium (He) dielectric-barrier discharge jet (DBDjet) is applied to treat nickel oxide (NiO) thin films for p-i-n perovskite solar cells (PSCs). Reactive plasma species help reduce the trap density, improve the transmittance and wettability, and deepen the valence band maximum (VBM) level. A NiO surface with the lower trap density surface of NiO allows better interfacial contact with the MAPbI3 layer and increases the carrier extraction capability. MAPbI3 can better crystallize on a more hydrophilic NiO surface, thereby suppressing charge recombination from the grain boundary and the interface. Further, the deeper VBM allows better band alignment and reduces the probability of nonradiative recombination. NiO treatment using He DBDjet with a scan rate of 0.3 cm/s can improve PSC efficiency from 13.63 to 14.88%.

How critical is geometrical confinement? Analysis of spatially and temporally resolved particulate matter removal with an electrostatic precipitator.

This study investigates the spatial and temporal dispersion of particulate matter (PM) when using a needle-type electrostatic precipitator (ESP). The ESP is installed in tubes of 3 and 10 cm diameter. A simple light scattering setup integrated with image processing is built to evaluate and quantify the spatial and temporal dispersion of PM. The ESP is operated under stationary and continuous flowing modes to test its PM removal capability. Under the stationary mode, PM is removed efficiently in 10 and 45 seconds when using a 3 and 10 cm tube, respectively. In a more geometrically confined system, a large spatial particulate concentration gradient is seen from 18 to 24 cm, indicating that the cleaning capability can be controlled within a localized space. By modulating the applied voltage from direct current (DC) to a low-frequency pulse with 50% duty, the ozone concentration can be reduced by nearly 50% while maintaining the cleaning efficiency. The analysis with spatially and temporally resolved particulate dispersion provides a novel strategy for testing the performance of an ESP. Furthermore, physical confinement enhances both the spatial and temporal removal efficiency, which is crucial for indoor and personal air cleaning devices. These results will contribute to air purification and environmental monitoring.

Atmospheric Pressure Plasma Jet-Assisted Synthesis of Zeolite-Based Low-k Thin Films.

Zeolites are ideal low-dielectric constant (low-k) materials. This paper reports on a novel plasma-assisted approach to the synthesis of low-k thin films comprising pure-silica zeolite MFI. The proposed method involves treating the aged solution using an atmospheric pressure plasma jet (APPJ). The high reactivity of the resulting nitrogen plasma helps to produce zeolite crystals with high crystallinity and uniform crystal size distribution. The APPJ treatment also remarkably reduces the time for hydrothermal reaction. The zeolite MFI suspensions synthesized with the APPJ treatment are used for the wet deposition to form thin films. The deposited zeolite thin films possessed dense morphology and high crystallinity, which overcome the trade-off between crystallinity and film quality. Zeolite thin films synthesized using the proposed APPJ treatment achieve low leakage current (on the order of 10-8 A/cm2) and high Young's modulus (12 GPa), outperforming the control sample synthesized without plasma treatment. The dielectric constant of our zeolite thin films was as low as 1.41. The overall performance of the low-k thin films synthesized with the APPJ treatment far exceed existing low-k films comprising pure-silica MFI.

Atmospheric-pressure-plasma-jet processed carbon nanotube (CNT)-reduced graphene oxide (rGO) nanocomposites for gel-electrolyte supercapacitors.

This study evaluates DC-pulse nitrogen atmospheric-pressure-plasma-jet processed carbon nanotube (CNT)-reduced graphene oxide (rGO) nanocomposites for gel-electrolyte supercapacitor applications. X-ray photoelectron spectroscopy (XPS) indicates decreased oxygen content (mainly, C-O bonding content) after nitrogen APPJ processing owing to the oxidation and vaporization of ethyl cellulose. Nitrogen APPJ processing introduces nitrogen doping and improves the hydrophilicity of the CNT-rGO nanocomposites. Raman analysis indicates that nitrogen APPJ processing introduces defects and/or surface functional groups on the nanocomposites. The processed CNT-rGO nanocomposites on carbon cloth are applied to the electrodes of H2SO4-polyvinyl alcohol (PVA) gel-electrolyte supercapacitors. The best achieved specific (areal) capacitance is 93.1 F g-1 (9.1 mF cm-2) with 15 s APPJ-processed CNT-rGO nanocomposite electrodes, as evaluated by cyclic voltammetry under a potential scan rate of 2 mV s-1. The addition of rGOs in CNTs in the nanoporous electrodes improves the supercapacitor performance.

Investigating the effects of plasma pretreatment on the formation of ordered aggregates of lysozyme.

We investigated the influence of plasma pretreatment on fibril formation and aggregation properties of lysozyme by using the Congo red binding assay, transmission electron microscopy, sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE), far-ultraviolet circular dichroism, and 1-anilinonaphthalene-8-sulfonic acid (ANS) fluorescence spectroscopy. Our Congo red binding and transmission electron microscopy findings indicated that plasma pretreatment may suppress the formation of ordered fibrillar lysozyme aggregates. The inhibitory effect triggered by plasma pretreatment was observed to be positively correlated with the duration of plasma pretreatment. Compared to the untreated controls, our ANS fluorescence results suggested that fewer solvent-exposed hydrophobic clusters in lysozymes were formed upon pretreatment with plasma. Moreover, HEWL samples with and without plasma pretreatment showed considerably different molecular profiles. We believe the outcome from this work may not only help develop potential strategies for the attenuation of ordered protein aggregation, which is implicated in amyloid pathology, but also present a nice example of plasma-based medicine.

Ultra-low-cost and flexible paper-based microplasma generation devices for maskless patterning of poly(ethylene oxide)-like films.

This work presents the use of an ultra-low-cost and flexible paper-based microplasma array to perform maskless patterning of poly(ethylene oxide)-like (PEO-like) thin films with a feature size down to submillimeter scale. In this process, the liquid precursor was directly applied to the paper substrate, gradually vaporized, and dissociated in the microplasma cavity, which leads to plasma polymerization. The FTIR and XPS spectra of the deposited film confirm the PEO-like structures. The protein adsorption test using the absorption of fluorescence-labeled fibrinogen conjugates on the treated surface shows the deposited films possessed the antifouling property with decent pattern transfer fidelity defined by the geometry of the microplasma array.

Rapid atmospheric pressure plasma jet processed reduced graphene oxide counter electrodes for dye-sensitized solar cells.

In this work, we present the use of reduced graphene oxide (rGO) as the counter electrode materials in dye-sensitized solar cells (DSSCs). rGO was first deposited on a fluorine-doped tin oxide glass substrate by screen-printing, followed by post-treatment to remove excessive organic additives. We investigated the effect of atmospheric pressure plasma jet (APPJ) treatment on the DSSC performance. A power conversion efficiency of 5.19% was reached when DSSCs with an rGO counter electrode were treated by APPJs in the ambient air for a few seconds. For comparison, it requires a conventional calcination process at 400 °C for 15 min to obtain comparable efficiency. Scanning electron micrographs show that the APPJ treatment modifies the rGO structure, which may reduce its conductivity in part but simultaneously greatly enhances its catalytic activity. Combined with the rapid removal of organic additives by the highly reactive APPJ, DSSCs with APPJ-treated rGO counter electrode show comparable efficiencies to furnace-calcined rGO counter electrodes with greatly reduced process time. This ultrashort process time renders an estimated energy consumption per unit area of 1.1 kJ/cm(2), which is only one-third of that consumed in a conventional furnace calcination process. This new methodology thus saves energy, cost, and time, which is greatly beneficial to future mass production.