Ligand Isomerization Driven Electrocatalytic Switching.

The prevailing view about molecular catalysts is that the central metal ion is responsible for the reaction mechanism and selectivity, whereas the ligands mainly affect the reaction kinetics. Here, we question this paradigm and show that ligands have a dramatic influence on the selectivity of the product. We show how even a seemingly small change in ligand isomerization sharply alters the selectivity of the well-researched oxygen reduction reaction (ORR) Co phthalocyanine catalyst from an indirect 2e- to a direct 4e- pathway. Detailed analysis reveals that intramolecular hydrogen-bond interactions in the ligand activate the catalytic Co, directing the oxygen binding and thus deciding the final product. The resulting catalyst is the first example of a Co-based molecular catalyst catalyzing a direct 4e- ORR via ligand isomerization, for which it shows an activity close to the benchmark Pt in an actual H2-O2 fuel cell. The effect of the ligand isomerism is demonstrated with different central metal ions, thus highlighting the generalizability of the findings and their potential to open new possibilities in the design of molecular catalysts.

Electrochemical energy storage in an organic supercapacitor via a non-electrochemical proton charge assembly.

Contrary to conventional beliefs, we show how a functional ligand that does not exhibit any redox activity elevates the charge storage capability of an electric double layer via a proton charge assembly. Compared to an unsubstituted ligand, a non-redox active carboxy ligand demonstrated nearly a 4-fold increase in charge storage, impressive capacitive retention even at a rate of 900C, and approximately a 2-fold decrease in leakage currents with an enhancement in energy density up to approximately 70% via a non-electrochemical route of proton charge assembly. Generalizability of these findings is presented with various non-redox active functional units that can undergo proton charge assembly in the ligand. This demonstration of non-redox active functional units enriching supercapacitive charge storage via proton charge assembly contributes to the rational design of ligands for energy storage applications.

Cellulose graphitic carbon directed iron oxide interfaced polypyrrole electrode materials for high performance supercapacitors.

The rising demand for green and clean energy urges the enlargement of economical and proficient electrode materials for supercapacitors. Herein, we designed a novel electrode material by porous cellulose graphitic carbon (CC) derived from bio-waste cornhusk via the pyrolysis route, and α-Fe2O3 decorated nanostructure with CC (CCIO) was achieved in situ pyrolysis of corn-husk and Fe(NO3)3·9H2O metal salt followed by a coating of polypyrrole (CCIOP). The CC, CCIO, and CCIOP nanocomposite electrodes were characterized by XRD, Raman, FTIR, FE-SEM/EDX, FE-TEM, XPS, and BET analysis. The CCIOP nanocomposite electrode exhibits an enhanced specific capacitance (Csp) of 290.9 F/g, which is substantial to its pristine CC (128.3 F/g), PPy (140.3 F/g), and CCIO (190.7 F/g). The Csp of CCIOP in a three-electrode system, using 1 M Na2SO4 electrolyte exhibits excellent capacity retention of 79.1 % even at a high current density of 10 A/g. The as-fabricated asymmetric supercapacitor (ASC) delivered a remarkable capacity retention of 88.7 % with a coulombic efficiency of 98.8 % even after 3000 cycles. The study shows successful utilization of cellulose from bio-waste cornhusk into a substantial template applicable in future alternative energy storage devices.

Unprecedented energy storage in metal-organic complexes via constitutional isomerism.

The essence of any electrochemical system is engraved in its electrical double layer (EDL), and we report its unprecedented reorganization by the structural isomerism of molecules, with a direct consequence on their energy storage capability. Electrochemical and spectroscopic analyses in combination with computational and modelling studies demonstrate that an attractive field-effect due to the molecule's structural-isomerism, in contrast to a repulsive field-effect, spatially screens the ion-ion coulombic repulsions in the EDL and reconfigures the local density of anions. In a laboratory-level prototype supercapacitor, those with ß-structural isomerism exhibit nearly 6-times elevated energy storage compared to the state-of-the-art electrodes, by delivering ∼535 F g-1 at 1 A g-1 while maintaining high performance metrics even at a rate as high as 50 A g-1. The elucidation of the decisive role of structural isomerism in reconfiguring the electrified interface represents a major step forward in understanding the electrodics of molecular platforms.

Regio-isomerism directed electrocatalysis for energy efficient zinc-air battery.

We have investigated the role of ligand isomerism in modulating the mechanisms and kinetics associated with charge/discharge chemistry of an aqueous metal-air battery. The dominant electron-withdrawing inductive effect (-I effect) and the diminished electron-withdrawing resonance effect (-R effect) in the α-NO2 isomer noticeably diminishes the rate of oxygen reduction (ORR) and oxygen evolution reactions (OER) on the catalytic Co-center. In their ß-counterpart, the cumulative -I and -R effects noticeably enhance the OER and ORR kinetics on the same catalytic Co-center. Therefore, the regioisomerism of the -NO2 functionality amplifies the kinetics of ORR/OER without influencing their mechanistic pathways. When isomeric electrocatalysts are integrated to aid the charge chemistry of a Zn-air battery, the overpotential could be decreased by ∼250 mV with ß-NO2 isomer leading to a round-trip efficiency as high as 60%. This work contributes to the design of novel molecular platforms to target the overall round-trip efficiency of energy storage and conversion devices.

Unprecedented Isomerism-Activity Relation in Molecular Electrocatalysis.

The role of electrocatalysts in energy storage/conversion, biomedical and environmental sectors, green chemistry, and much more has generated enormous interest in comprehending their structure-activity relations. While targeting the surface-to-volume ratio, exposing reactive crystal planes and interfacial modifications are time-tested considerations for activating metallic catalysts; it is primarily by substitution in molecular electrocatalysts. This account draws the distinction between a substituent's chemical identity and isomerism, when regioisomerism of the -NO2 substituent is conferred at the "α" and "ß" positions on the macrocycle of cobalt phthalocyanines. Spectroscopic analysis and theoretical calculations establish that the ß isomer accumulates catalytically active intermediates via a cumulative influence of inductive and resonance effects. However, the field effect in the α isomer restricts this activation due to a vanishing resonance effect. The demonstration of the distinct role of isomerism in substituted molecular electrocatalysts for reactions ranging from energy conversion to biosensing highlights that isomerism of the substituents makes an independent contribution to electrocatalysis over its chemical identity.

A zinc-quinone battery for paired hydrogen peroxide electrosynthesis.

Hydrogen peroxide is a commodity chemical with immense applications as an environmentally benign disinfectant for water remediation, a green oxidant for synthetic chemistry and pulp bleaching, an energy carrier molecule and a rocket propellant. It is typically synthesized by indirect batch anthraquinone process, where sequential hydrogenation and oxidation of anthraquinone molecules generates H2O2. This highly energy demanding catalytic sequence necessitates the advent of new reaction pathways with lower energy expenditure. Here we demonstrate a Zn-quinone battery for paired H2O2 electrosynthesis at the three phase boundary of its cathodic half-cell during electric power generation. The catalytic quinone half-cell of the Zn-quinone battery, mediates proton coupled electron transfer with molecular oxygen during its chemical regeneration thereby pairing peroxide electrosynthesis with electricity generation. Hydrogen peroxide synthesizing Zn-quinone battery (HPSB) demonstrated a peak power density of ~90 mW/cm2 at a peak current density of ~145 mA/cm2 while synthesizing ~230 mM of H2O2. HPSB offers immense opportunities as it distinctly couples electric power generation with peroxide electrosynthesis which in-turn transforms energy conversion in batteries truly multifunctional.

An Electrochemical Wind Velocity Sensor.

Electrochemical interfaces invariably generate unipolar electromotive force because of the unidirectional nature of electrochemical double layers. Herein we show an unprecedented generation of a time varying bipolar electric field between identical half-cell electrodes induced by tailored interfacial migration of magnetic particles. The periodic oscillation of a bipolar electric field is monotonically correlated with velocity-dependent torque, opening new electrochemical pathways targeting velocity monitoring systems.

Fuel Exhaling Fuel Cell.

State-of-the-art proton exchange membrane fuel cells (PEMFCs) anodically inhale H2 fuel and cathodically expel water molecules. We show an unprecedented fuel cell concept exhibiting cathodic fuel exhalation capability of anodically inhaled fuel, driven by the neutralization energy on decoupling the direct acid-base chemistry. The fuel exhaling fuel cell delivered a peak power density of 70 mW/cm2 at a peak current density of 160 mA/cm2 with a cathodic H2 output of ∼80 mL in 1 h. We illustrate that the energy benefits from the same fuel stream can at least be doubled by directing it through proposed neutralization electrochemical cell prior to PEMFC in a tandem configuration.

Redox Active Binary Logic Gate Circuit for Homeland Security.

Bipolar junction transistors are at the frontiers of modern electronics owing to their discrete voltage regulated operational levels. Here we report a redox active binary logic gate (RLG) which can store a "0" and "1" with distinct operational levels, albeit without an external voltage stimuli. In the RLG, a shorted configuration of half-cell electrodes provided the logic low level and decoupled configuration relaxed the system to the logic high level due to self-charge injection into the redox active polymeric system. Galvanostatic intermittent titration and electrochemical quartz crystal microbalance studies indicate the kinetics of self-charge injection are quite faster and sustainable in polypyrrole based RLG, recovering more than 70% signal in just 14 s with minor signal reduction at the end of 10000 cycles. These remarkable properties of RLGs are extended to design a security sensor which can detect and count intruders in a locality with decent precision and switching speed.

Stereochemistry-Dependent Proton Conduction in Proton Exchange Membrane Fuel Cells.

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.

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.