Vasculature-on-a-Chip with a Porous Membrane Electrode for In Situ Electrochemical Detection of Nitric Oxide Released from Endothelial Cells.

Vasculature-on-a-chip is a microfluidic cell culture device used for modeling vascular functions by culturing endothelial cells. Porous membranes are widely used to create cell culture environments. However, in situ real-time measurements of cellular metabolites in microchannels are challenging. In this study, a novel microfluidic device with a porous membrane electrode was developed for the in situ monitoring of nitric oxide (NO) released by endothelial cells in real time. In this system, a porous Au membrane electrode was placed directly beneath the cells for in situ and real-time measurements of NO, a biomarker of endothelial cells. First, the device was electrochemically characterized to construct a calibration plot for NO. Next, NO released by human umbilical vein endothelial cells under l-arginine stimulation was successfully quantified. Furthermore, the changes in NO release with culture time (in days) using the same sample were successfully recorded by exploiting minimally invasive measurements. This is the first report on the combination of a microfluidic device and porous membrane electrode for the electrochemical analysis of endothelial cells. This device will contribute to the development of organ-on-a-chip technology for real-time in situ cell analyses.

Selective and high-rate CO2 electroreduction by metal-doped covalent triazine frameworks: a computational and experimental hybrid approach.

The electrochemical CO2 reduction reaction (CO2RR) has attracted intensive attention as a technology to achieve a carbon-neutral society. The use of gas diffusion electrodes (GDEs) enables the realization of high-rate CO2RRs, which is one of the critical requirements for social implementation. Although both a high reaction rate and good selectivity are simultaneously required for electrocatalysts on GDEs, no systematic study of the relationship among active metal centers in electrocatalysts, reaction rate, and selectivity under high-rate CO2RR conditions has been reported. In the present study, we employed various metal-doped covalent triazine frameworks (M-CTFs) as platforms for CO2 reduction reaction (CO2RR) electrocatalysts on GDEs and systematically investigated them to deduce sophisticated design principles using a combined computational and experimental approach. The Ni-CTF showed both high selectivity (faradaic efficiency (FE) > 98% at -0.5 to -0.9 V vs. reversible hydrogen electrode) and a high reaction rate (current density < -200 mA cm-2) for CO production. By contrast, the Sn-CTF exhibited selective formic acid production, and the FE and partial current density reached 85% and 150 mA cm-2, respectively. These results for the CO2RR activity and selectivity at high current density with respect to metal centers correspond well with predictions based on first-principles calculations. This work is the first demonstration of a clear relationship between the computational adsorption energy of intermediates depending on metal species and the experimental high-rate gaseous CO2RR.

Electrochemical microwell sensor with Fe-N co-doped carbon catalyst to monitor nitric oxide release from endothelial cell spheroids.

Endothelial cells have been widely used for vascular biology studies; recent progress in tissue engineering have offered three-dimensional (3D) culture systems for vascular endothelial cells which can be considered as physiologically relevant models. To facilitate the studies, we developed an electrochemical device to detect nitric oxide (NO), a key molecule in the vasculature, for the evaluation of 3D cultured endothelial cells. Using an NO-sensitive catalyst composed of Fe-N co-doped reduced graphene oxide, the real-time monitoring of NO release from the endothelial cell spheroids was demonstrated.

Are Redox-Active Organic Small Molecules Applicable for High-Voltage (>4 V) Lithium-Ion Battery Cathodes?

While organic batteries have attracted great attention due to their high theoretical capacities, high-voltage organic active materials (> 4 V vs Li/Li+ ) remain unexplored. Here, density functional theory calculations are combined with cyclic voltammetry measurements to investigate the electrochemistry of croconic acid (CA) for use as a lithium-ion battery cathode material in both dimethyl sulfoxide and γ-butyrolactone (GBL) electrolytes. DFT calculations demonstrate that CA dilitium salt (CA-Li2 ) has two enolate groups that undergo redox reactions above 4.0 V and a material-level theoretical energy density of 1949 Wh kg-1 for storing four lithium ions in GBL-exceeding the value of both conventional inorganic and known organic cathode materials. Cyclic-voltammetry measurements reveal a highly reversible redox reaction by the enolate group at ≈4 V in both electrolytes. Battery-performance tests of CA as lithium-ion battery cathode in GBL show two discharge voltage plateaus at 3.9 and 3.1 V, and a discharge capacity of 102.2 mAh g-1 with no capacity loss after five cycles. With the higher discharge voltages compared to the known, state-of-the-art organic small molecules, CA promises to be a prime cathode-material candidate for future high-energy-density lithium-ion organic batteries.

Activity switching of Sn and In species in Heusler alloys for electrochemical CO2 reduction.

The electrochemical CO2 reduction reaction (CO2RR) activity of Ni2MnIn and Ni2MnSn Heusler alloys was investigated. Although pure In, Sn and Ni2MnIn generated formate as the major product, Ni2MnSn generated H2 as the major product. The CO2RR selectivity could be controlled by selecting the constituent elements of the intermetallic catalysts.

Copper Aluminum Layered Double Hydroxides with Different Compositions and Morphologies as Electrocatalysts for the Carbon Dioxide Reduction Reaction.

Electrochemical CO2 reduction (CO2 RR) is a key technology to convert greenhouse gas CO2 to value-added products, such as CO and formic acid (HCOOH). In the present study, two-dimensional Cu- and Al-based layered double hydroxides (Cu-Al/LDHs) were applied as CO2 RR catalysts. The catalysts were synthesized using a simple co-precipitation method employing sodium carbonate solutions with different pH and synthesis temperatures. The elemental ratio of Cu and Al, and sheet size were controlled. The most active Cu-Al/LDH showed a faradaic efficiency for CO generation of 42 % and one for formate generation of 22 % at the current density of 50 mA using a gas diffusion electrode system under galvanostatic conditions. Our result indicates that the sheet size of the LDH sheet is a critical parameter for determining CO2 RR activity.

A photo-curable gel electrolyte ink for 3D-printable quasi-solid-state lithium-ion batteries.

3D printing technologies have been adapted to enable the fabrication of lithium-ion batteries (LIBs), allowing flexible designs such as micro-scale 3D shapes. Here, we demonstrate 3D-printable gel electrolytes, printed at room temperature. The electrolyte gel solidified by UV irradiation maintains its structural integrity and high lithium-ion conductivity, enabling fully 3D-printed quasi-solid-state LIBs.

Effect of Cobalt Speciation and the Graphitization of the Carbon Matrix on the CO2 Electroreduction Activity of Co/N-Doped Carbon Materials.

The electroreduction of carbon dioxide is considered a key reaction for the valorization of CO2 emitted in industrial processes or even present in the environment. Cobalt-nitrogen co-doped carbon materials featuring atomically dispersed Co-N sites have been shown to display superior activities and selectivities for the reduction of carbon dioxide to CO, which, in combination with H2 (i.e., as syngas), is regarded as an added-value CO2-reduction product. Such catalysts can be synthesized using heat treatment steps that imply the carbonization of Co-N-containing precursors, but the detailed effects of the synthesis conditions and corresponding materials' composition on their catalytic activities have not been rigorously studied. To this end, in the present work, we synthesized cobalt-nitrogen co-doped carbon materials with different heat treatment temperatures and studied the relation among their surface- and Co-speciation and their CO2-to-CO electroreduction activity. Our results reveal that atomically dispersed cobalt-nitrogen sites are responsible for CO generation while suggesting that this CO-selectivity improves when these atomic Co-N centers are hosted in the carbon layers that cover the Co nanoparticles featured in the catalysts synthesized at higher heat treatment temperatures.

Supercritical hydrothermal synthesis of MoS2 nanosheets with controllable layer number and phase structure.

Molybdenum disulfide (MoS2), an attractive material for energy conversion devices, is known to exhibit varying properties depending on the number of layers and the phase structure. In this study, we developed a supercritical hydrothermal process that allows the controllable synthesis of MoS2 nanosheets with various structural and morphological characteristics. Detailed characterization of the synthesized materials confirmed that the number of layers in the MoS2 nanosheets could be controlled by varying the organic reducing agent under supercritical hydrothermal conditions. In addition, the MoS2 phase could be controlled kinetically by varying the reaction time with ascorbic acid as the reducing agent. Because water and elemental sulfur were respectively used as the solvent and sulfur source and as the reaction time was minimal, the developed hydrothermal process represents a facile processing method for different types of MoS2 nanosheets.

Aqueous Electrochemical Partial Oxidation of Gaseous Ethylbenzene by a Ru-Modified Covalent Triazine Framework.

Aqueous electrochemical oxidation of hydrocarbons into valuable compounds, such as alcohols and carbonyl compounds, has attracted much attention because these systems can operate under mild conditions without toxic oxidants or flammable solvents. The key requirements to achieve such oxidation reactions are (1) highly reactive species on an electrocatalyst for the activation of C-H bonds and (2) efficient transportation pathway for water-insoluble hydrocarbons to an electrode surface. We have determined that a gas diffusion electrode (GDE) supporting Ru atom-modified covalent triazine frameworks (Ru-CTF) has an activity for the electrooxidation of gaseous ethylbenzene to acetophenone using an aqueous electrolyte. A high-valency Ru═O species was formed in Ru-CTF as an effective active site for O-atom insertion into stable C-H bonds. Furthermore, Ru-CTF showed excellent stability during four consecutive cycles with the replacement of the electrolyte every 12 h, although the reactive Ru═O species is generated. As for the transportation pathway for substrates, the amount of acetophenone generated from gaseous ethylbenzene was much larger than that from ethylbenzene dissolved in an electrolyte. This result indicates that the three-dimensional microstructures in the GDE maximize the transportation of gaseous hydrocarbons and the oxidation reaction occurs at the triple-phase boundary, which enables the use of aqueous electrolytes.

'Click' conjugated porous polymer nanofilm with a large domain size created by a liquid/liquid interfacial protocol.

A liquid/liquid interfacial method is used to synthesize a conjugated porous polymer nanofilm with a large domain size. Copper-catalyzed azide-alkyne cycloaddition between a triangular terminal alkyne and azide monomers at a water/dichloromethane interface generates a 1,2,3-triazole-linked polymer nanofilm featuring a large aspect ratio and robustness against heat and pH.

Covalent triazine framework modified with coordinatively-unsaturated Co or Ni atoms for CO2 electrochemical reduction.

The electrochemical reduction of carbon dioxide (CO2) has attracted considerable attention as a means of maintaining the carbon cycle. This process still suffers from poor performance, including low faradaic efficiencies and high overpotential. Herein, we attempted to use coordination number as a control parameter to improve the electrocatalytic performance of metal species that have previously been thought to have no CO2 reduction activity. Covalent triazine frameworks (CTF) modified with coordinatively-unsaturated 3d metal atoms (Co, Ni or Cu) were developed for efficient electroreduction of CO2. Co-CTF and Ni-CTF materials effectively reduced CO2 to CO from -0.5 V versus RHE. The faradaic efficiency of the Ni-CTF during CO formation reached 90% at -0.8 V versus RHE. The performance of Ni-CTF is much higher than that of the corresponding metal-porphyrin (using tetraphenylporphyrin; TPP). First principles calculations demonstrated that the intermediate species (adsorbed COOH) was stabilized on the metal atoms in the CTF due to the low-coordination structure of this support. Thus, the free energy barriers for the formation of adsorbed COOH on the metal atoms in the CTF supports were lower than those on the TPP supports.

Nickel-Nitrogen-Modified Graphene: An Efficient Electrocatalyst for the Reduction of Carbon Dioxide to Carbon Monoxide.

Nickel-nitrogen-modified graphene (Ni-N-Gr) is fabricated and Ni-N coordination sites on Ni-N-Gr as active centers effectively reduce CO2 to CO. The faradaic efficiency for CO formation reaches 90% at -0.7 to -0.9 V versus RHE, and the turnover frequency for CO production comes up to ≈2700 h-1 at -0.7 V versus RHE.

Copper-modified covalent triazine frameworks as non-noble-metal electrocatalysts for oxygen reduction.

The electrochemical oxygen reduction reaction (ORR) is an important cathode reaction of various types of fuel cells. The development of electrocatalysts composed only of abundant elements is a key goal because currently only platinum is a suitable catalyst for ORR. Herein, we synthesized copper-modified covalent triazine frameworks (CTF) hybridized with carbon nanoparticles (Cu-CTF/CPs) as efficient electrocatalysts for the ORR in neutral solutions. The ORR onset potential of the synthesized Cu-CTF/CP was 810 mV versus the reversible hydrogen electrode (RHE; pH 7), the highest reported value at neutral pH for synthetic Cu-based electrocatalysts. Cu-CTF/CP also displayed higher stability than a Cu-based molecular complex at neutral pH during the ORR, a property that was likely as a result of the covalently cross-linked structure of CTF. This work may provide a new platform for the synthesis of durable non-noble-metal electrocatalysts for various target reactions.