The Implications of Coupling an Electron Transfer Mediated Oxidation with a Proton Coupled Electron Transfer Reduction in Hybrid Water Electrolysis.

Invited for this month's cover are the groups of Menny Shalom at the Ben-Gurion University of the Negev, Israel and Dr. Biswajit Mondal at Indian Institute of Technology Gandhinagar, India. The image shows the connection between two half-cells: an electron transfer-mediated [(2,2,6,6-tetramethyl-1-piperidin-1-yl)oxyl] (TEMPO)-catalyzed benzylamine oxidation at the anode and a proton-coupled electron transfer at the cathode for hydrogen generation. The difference in pH dependence of the anodic and cathodic processes enables hybrid water electrolysis at low cell potential (∼1.0 V) by adjusting only the pH value of the electrolytic medium. The Research Article itself is available at 10.1002/cssc.202202271.

The Implications of Coupling an Electron Transfer Mediated Oxidation with a Proton Coupled Electron Transfer Reduction in Hybrid Water Electrolysis.

Electrolysis of water is a sustainable route to produce clean hydrogen. Full water-splitting requires a high applied potential, in part because of the pH-dependency of the H2 and O2 evolution reactions (HER and OER), which are proton-coupled electron transfer (PCET) reactions. Therefore, the minimum required potential will not change at different pHs. TEMPO [(2,2,6,6-tetramethyl-1-piperidin-1-yl)oxyl], a stable free-radical that undergoes fast electro-oxidation by a single-electron transfer (ET) process, is pH-independent. Here, we show that the combination of PCET and ET processes enables hydrogen production from water at low cell potentials below the theoretical value for full water-splitting by simple pH adjustment. As a case study, we combined the HER with the oxidation of benzylamine by anodically oxidized TEMPO. The pH-independent electrocatalytic oxidation of TEMPO permits the operation of a hybrid water-splitting cell that shows promise to perform at a low cell potential (≈1 V) and neutral pH conditions.

Polarity governed selective amplification of through plane proton shuttling in proton exchange membrane fuel cells.

Graphene oxide (GO) anisotropically conducts protons with directional dominance of in plane ionic transport (σ IP) over the through plane (σ TP). In a typical H2-O2 fuel cell, since the proton conduction occurs through the plane during its generation at the fuel electrode, it is indeed inevitable to selectively accelerate GO's σ TP for advancement towards a potential fuel cell membrane. We successfully achieved ∼7 times selective amplification of GO's σ TP by tuning the polarity of the dopant molecule in its nanoporous matrix. The coexistence of strongly non-polar and polar domains in the dopant demonstrated a synergistic effect towards σ TP with the former decreasing the number of water molecules coordinated to protons by ∼3 times, diminishing the effects of electroosmotic drag exerted on ionic movements, and the latter selectively accelerating σ TP across the catalytic layers by bridging the individual GO planes via extensive host guest H-bonding interactions. When they are decoupled, the dopant with mainly non-polar or polar features only marginally enhances the σ TP, revealing that polarity factors contribute to fuel cell relevant transport properties of GO membranes only when they coexist. Fuel cell polarization and kinetic analyses revealed that these multitask dopants increased the fuel cell performance metrics of the power and current densities by ∼3 times compared to the pure GO membranes, suggesting that the functional group factors of the dopants are of utmost importance in GO-based proton exchange membrane fuel cells.

Galvanic Cell Type Sensor for Soil Moisture Analysis.

Here we report the first potentiometric sensor for soil moisture analysis by bringing in the concept of Galvanic cells wherein the redox energies of Al and conducting polyaniline are exploited to design a battery type sensor. The sensor consists of only simple architectural components, and as such they are inexpensive and lightweight, making it suitable for on-site analysis. The sensing mechanism is proved to be identical to a battery type discharge reaction wherein polyaniline redox energy changes from the conducting to the nonconducting state with a resulting voltage shift in the presence of soil moisture. Unlike the state of the art soil moisture sensors, a signal derived from the proposed moisture sensor is probe size independent, as it is potentiometric in nature and, hence, can be fabricated in any shape or size and can provide a consistent output signal under the strong aberration conditions often encountered in soil moisture analysis. The sensor is regenerable by treating with 1 M HCl and can be used for multiple analysis with little read out hysteresis. Further, a portable sensor is fabricated which can provide warning signals to the end user when the moisture levels in the soil go below critically low levels, thereby functioning as a smart device. As the sensor is inexpensive, portable, and potentiometric, it opens up avenues for developing effective and energy efficient irrigation strategies, understanding the heat and water transfer at the atmosphere-land interface, understanding soil mechanics, forecasting the risk of natural calamities, and so on.