Here we show a surrogate strategy for power production, wherein light is used to actuate a discharge chemistry in the cathode of an aqueous rechargeable battery (ARB). The proposed photo battery consists of a titanium nitride photoanode, promising cathode material iron(III) hexacyanoferrate(II) as the battery active species and Na 2 S 2 O 8 as the chemical charging agent. The photo battery delivered negligible capacity in the dark and the capacity shot up to 77.8 mAh/g when artificially shined light, confirming that the battery chemistry is light driven. In the ambient light, the device retained 72% of its artificial light discharge capacity with a stable cycling for more than 100 cycles. Further, an unprecedented means for charging the battery rapidly is presented using Na 2 S 2 O 8 and it revitalized the battery in 30 s without any external bias. This methodology of expending a photoanode extends to a battery that is free from dissolution of active materials, irreversible structural changes, spontaneous deinsertion reactions, and safety concerns commonly encountered in the state of the art anode materials in ARBs. Apart from bringing out a sustainable way for power production, this device opens up avenues for charging the battery in the likely events of electrical input unavailability, while solving the critcial issues of longer charging time and higher charging voltage.
Graphene oxide (GO) is impermeable to H2 and O2 fuels while permitting H(+) shuttling, making it a potential candidate for proton exchange membrane fuel cells (PEMFC), albeit with a large anisotropy in their proton transport having a dominant in plane (σIP) contribution over the through plane (σTP). If GO-based membranes are ever to succeed in PEMFC, it inevitably should have a dominant through-plane proton shuttling capability (σTP), as it is the direction in which proton gets transported in a real fuel-cell configuration. Here we show that anisotropy in proton conduction in GO-based fuel cell membranes can be brought down by selectively tuning the geometric arrangement of functional groups around the dopant molecules. The results show that cis isomer causes a selective amplification of through-plane proton transport, σTP, pointing to a very strong geometry angle in ionic conduction. Intercalation of cis isomer causes significant expansion of GO (001) planes involved in σTP transport due to their mutual H-bonding interaction and efficient bridging of individual GO planes, bringing down the activation energy required for σTP, suggesting the dominance of a Grotthuss-type mechanism. This isomer-governed amplification of through-plane proton shuttling resulted in the overall boosting of fuel-cell performance, and it underlines that geometrical factors should be given prime consideration while selecting dopant molecules for bringing down the anisotropy in proton conduction and enhancing the fuel-cell performance in GO-based PEMFC.
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.
Here we report an ON–OFF effect on electrocatalytic amplification when the molecules are connected to each other on an electrode surface. When the molecular connection is achieved, the redox potential of the catalytic redox entity is significantly upshifted with concurrent experience of a more electron-withdrawing atmosphere, and the electron transfer to and from the catalytic center is accelerated, rendering the molecules with strong electroreducing character; however, the overall outcome is dictated by the surface charge. Outer sphere redox probes and X-ray photoelectron spectroscopy evidently revealed that a positive surface charge is preserved in acidic and neutral media after molecular connection which is in parallel with the corresponding electrocatalytic amplifications toward oxygen reduction reaction (ORR), suggesting the electrodics after molecular connection is extremely pH dependent. Surface charge present after molecular connection is significantly neutralized by the abundant hydroxyl groups in alkaline media, making the central metal ion’s atmosphere less electron deficient and downshifting its redox potential (compared to the case in acidic and neutral media), thereby reducing the disparity in electroactivity before and after molecular connection. This study underlines that after molecular connection surface charge is the key as it can turn on and turn off the redox entity responsible for electrochemical amplifications. The solvent dependence and redox potential upshift outlined here for monolayer electrodes are nullified during bulk polymerization, indicating the circumstances leading to molecular connection are different from bulk polymerization. Since the surface charge can be modulated by connecting the molecules and tuning the surrounding media, the proposed strategy brings forward a way to tune the interfacial activity and is expected to have implications in electrocatalysis, selective sensing, ion screening, and so on.
Electrode structure plays an important role in the performance of proton exchange membrane fuel cells. To get high electrochemical active area in the electrode, perfluorosulfonate-ionomer is loaded in stage wise. Single-wall carbon nanohorns (SWCNHs) are synthesized by DC arc-discharge method in Helium atmosphere and these synthesized SWCNHs were functionalized with Nafion. Platinum was reduced onto Nafion functionalized SWCNHs through colloidal method. Pt/Nafion-SWCNHs catalysts were prepared by varying deposition times. Detailed characterization of the catalyst was carried out using Transmission Electron Microscopy (TEM), X-ray diffraction (XRD), infrared spectroscopy (IR), and Thermo Gravimetric Analysis (TGA). TEM of Pt decorated SWCNHs revealed uniformly dispersed Pt nano particles with an average particle size of 3 nm in the SWCNHs. IR studies of catalyst confirm the presence of Nafion on Pt/Nafion-SWCNHs. Nafion membrane and Pt/Nafion-SWCNHs catalyst were used to construct fuel cell in decal method and tested in fuel cell testing facility. Cyclic voltammetry tests of the catalyst also confirm the high electrochemical active area of the catalyst. Pt reduction onto Nafion functionalized SWCNHs leads to an increase in electrochemically active surface area. High platinum utilization due to increased electrochemical surface area with efficient SWCNHs support of Pt/Nafion-SWCNHs catalyst makes it a promising electrocatalyst for fuel cells.
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