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.

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.

Unusual Ligand Assistance in Molecular Electrocatalysis via Interfacial Proton Charge Assembly.

We show that the ability of the ligand to reorganize the electric double layer (EDL) often dominates the electrocatalysis contrary to their inductive effect in the spectrochemical series, leading to counterintuitive electrocatalysis. With water oxidation and chlorine evolution as the probe reactions, the same catalytic entity with carboxy functionalized ligand exhibited surprisingly higher electrochemical activity in comparison to the aggressively electron-withdrawing nitro functionalized ligands, which is contrary to their actual location in the spectrochemical series. Spectroscopic and electrochemical analyses suggest the enrichment of catalytically active species in the carboxy substituted ligand via proton charge assembly in the EDL that in turn enhances the kinetics of the overall electrochemical process. This demonstration of less obvious ligands becoming indispensable in electrocatalysis suggests a blind designing of ligands solely based on their inductive effect should be reconsidered as it will prevent the utilization of the maximum potential of the molecule in electrocatalysis.

Foldamer Nanotubes Mediated Label-Free Detection of Protein-Small Molecule Interactions.

Development of miniaturized lab-on-chip devices for the detection of rapid and specific small molecule-protein binding interactions at very low concentrations holds significant importance in drug discovery and biomedical applications. Here, the label-free detection of small molecule-protein interactions is reported on the surface functionalizable nanotubes of α,γ-hybrid peptide helical foldamers using nanoscale capacitance and impedance spectroscopy. The 12-helix conformation of the α,γ-hybrid peptide observed in the single crystals, self-assembled into nanotubes in an aqueous environment with exposed cysteine thiols for small molecule conjugation. The binding of streptavidin to the covalently linked biotin on the surface of nanotubes was detected at the picomolar concentrations. No change in the capacitance and impedance were observed in the absence of either immobilized biotin or protein streptavidin. The functionalizable hybrid peptide nanotubes reported here pave the way for the label-free detection of various small molecule protein interactions at very low concentrations.

Aqueous OH- /H+ Dual-Ion Zn-Based Batteries.

Aqueous Zn-based batteries hold multiple advantages of eco-friendliness, easy accessibility, high safety, easy fabrication, and fast kinetics, while their widespread applications have been greatly limited by the relatively narrow thermodynamically stable potential windows (i. e., 1.23 V) of water and the mismatched pH conditions between cathode and anode, which presents challenges regarding how to maximize the output voltage and the energy density. Recently, aqueous OH- /H+ dual-ion Zn-based batteries (OH- /H+ -DIZBs), where the Zn anode reacts with hydroxide ions (OH- ) in alkaline electrolyte while hydrogen ions (H+ ) are involved in the cathode reaction in the acidic electrolyte, have been reported to be capable of broadening the working voltage and improving the energy density, which offers practical feasibility toward overcoming the above limitations. This Review thus takes this chance to investigate the recent progress on aqueous OH- /H+ -DIZBs. First, the concept and the history of such OH- /H+ -DIZBs are introduced, and then special emphasis is put on the working mechanisms, the progress of the development of new batteries, and how the electrolytes improve their performance. Finally, the challenges and opportunities in this field are discussed.

Aqueous OH-/H+ dual-ion gradient assisted electricity effective electro-organic synthesis of 2,5-furandicarboxylic acid paired with hydrogen fuel generation.

The OH-/H+ dual-ion gradient has a hidden electromotive force of 0.82 V under standard conditions; however, its non-redox nature completely prevents its direct interconversion as electrical driving force. We show by using organic molecules whose heterogeneous electron transfer is pH dependent, OH-/H+ dual-ion energy can be directly harvested as electrical driving force for performing simultaneous electro-organic synthesis and hydrogen fuel production in an electricity effective manner. To demonstrate this dual-ion gradient assisted electro-organic synthesis, 5-hydroxymethylfurfural (HMF) is chosen as the model molecule because of the immense techno commercial applications of its oxidized products. This dual-ion assisted device only required âˆ¼1 V to provide a current density of 50 mA/cm2 and for achieving the same rate; the traditional state-of-the-art electrolytic cell required a doubling of the applied potential. The dual-ion gradient assisted device can convert biomass-derived HMF to economically important FDCA with âˆ¼90 % yield and âˆ¼87 % Faradaic efficiency with simultaneous H2 fuel production at a potential as low as 1 V.

A multi-chromic supercapacitor of high coloration efficiency integrating a MOF-derived V2O5 electrode.

Modern technological trends in smart electronic devices demand more intelligent automation. Simultaneous integration of energy storage and multicolor electrochromism in a single device improves user-device interfacing based on a salient human-readable output. In this work, primarily metal-organic framework (MOF) derived V2O5 was synthesized which, as an electrochromic material, shows high optical modulation of 35% at 485 nm, with very fast switching speeds (2.9/3.4 s for coloring/bleaching). The multiple coloration states of the V2O5 electrode make it worthy for further integration as a smart negative electrode in a multicolored electrochromic asymmetric supercapacitor, where the electrochromic polyaniline electrode serves as the counter electrode. The device demonstrates a high coloration efficiency of 137.2 cm2 C-1 and an areal capacitance of 12.27 mF cm-2 and an energy density of 2.21 × 10-3 mW h cm-2 at a current density of 0.05 mA cm-2. By virtue of its different chromatic states during charging and discharging, smart visual tracking of the state of charge of the supercapacitor can be realized. Such a design of energy storage devices will have promising practical application in futuristic smart multifunctional electronic devices.

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.

Hydrogels Based on Poly([2-(acryloxy)ethyl] Trimethylammonium Chloride) and Nanocellulose Applied to Remove Methyl Orange Dye from Water.

Bio-based hydrogels that adsorb contaminant dyes, such as methyl orange (MO), were synthesized and characterized in this study. The synthesis of poly([2-(acryloyloxy)ethyl] trimethylammonium chloride) and poly(ClAETA) hydrogels containing cellulose nanofibrillated (CNF) was carried out by free-radical polymerization based on a factorial experimental design. The hydrogels were characterized by Fourier transformed infrared spectroscopy, scanning electron microscopy, and thermogravimetry. Adsorption studies of MO were performed, varying time, pH, CNF concentration, initial dye concentration and reuse cycles, determining that when the hydrogels were reinforced with CNF, the dye removal values reached approximately 96%, and that the material was stable when the maximum swelling capacity was attained. The maximum amount of MO retained per gram of hydrogel (q = mg MO g-1) was 1379.0 mg g-1 for the hydrogel containing 1% (w w-1) CNF. Furthermore, it was found that the absorption capacity of MO dye can be improved when the medium pH tends to be neutral (pH = 7.64). The obtained hydrogels can be applicable for the treatment of water containing anionic dyes.

Coulombic Force Gated Molecular Transport in Redox Flow Batteries.

The interfacial electrochemistry of reversible redox molecules is central to state-of-the-art flow batteries, outer-sphere redox species-based fuel cells, and electrochemical biosensors. At electrochemical interfaces, because mass transport and interfacial electron transport are consecutive processes, the reaction velocity in reversible species is predominantly mass-transport-controlled because of their fast electron-transfer events. Spatial structuring of the solution near the electrode surface forces diffusion to dominate the transport phenomena even under convective fluid-flow, which in turn poses unique challenges to utilizing the maximum potential of reversible species by either electrode or fluid characteristics. We show Coulombic force gated molecular flux at the interface to target the transport velocity of reversible species; that in turn triggers a directional electrostatic current over the diffusion current within the reaction zone. In an iron-based redox flow battery, this gated molecular transport almost doubles the volumetric energy density without compromising the power capability.

Biologically inspired catalyst for electrochemical reduction of hazardous hexavalent chromium.

An indirect electrochemical detoxification and detection platform has been demonstrated for toxic hexavalent chromium (Cr(vi)) based on the biologically important N-4 macrocycle. The research work describes a simple, green, low-cost and potential way for the synthesis of a new N-4 macrocyclic molecule and the molecule is characterized by various analytical and spectroscopic techniques like elemental analysis, TGA, FT-IR, UV-visible, mass spectrometry and NMR spectroscopies, and cyclic voltammetry. The synthesized molecule was explored for the electrochemical reduction of Cr(vi) using both voltammetric and amperometric methods. Amperometric studies exhibited 50 to 2500 nM linear range and the detection limit and quantification limit are 18 and 50 nM, respectively. The common coexisting metal ions did not interfere with Cr(vi) even in the presence of 40-fold excess interfering ions. The real sample analysis was carried out with the fabricated sensor and successfully quantified a recovery result (98-104%) of Cr(vi) in water. This proposed sensor is helpful in the detection of chromium ions in drinking water and is capable of detecting Cr(vi) in the limits set by the World Health Organization (WHO). In addition, this sensor satisfactorily demonstrated considerable stability and reproducibility.

Geometrical Isomerism Directed Electrochemical Sensing.

We report the independent role of isomerism of secondary sphere substituents over their nature, a factor often overlooked in molecular electrocatalysis pertaining to electrochemical sensing, by establishing that isomerism redefines the electronic structure at the catalytic reaction center via geometrical factors. UV-vis spectroscopy and X-ray photoelectron spectroscopy suggest that a substituent's isomerism in molecular catalysts conjoins molecular planarity and catalytic activation through competing field effects and resonance effects. As a classical example, we demonstrate the influence of isomerism of the -NO2 substituents for the electrocatalytic multi electron oxidation of As(III), a potentially important electrochemical pathway for water remediation and arsenic detection. The isomerism dependent oxidative activation of catalytic center leads to a nonprecious molecular catalyst capable for direct As(III) oxidation with an experimental detection limit close to WHO guidelines. This work opens up an unusual approach in analytical chemistry for developing various sensing platforms for challenging chemical and electrochemical reactions.

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.

Metal Coordination Polymer Framework Governed by Heat of Hydration for Noninvasive Differentiation of Alkali Metal Series.

We illustrate that the extent of hydration and consequently the heat of hydration of alkali metal ions can be utilized to control their insertion/deinsertion chemistry in a redox active metal coordination polymer framework (CPF) electrode. The formal redox potential of CPF electrode for cation intercalation is inversely correlated to hydrated ionic radii, with clear distinction between the intercalation of ions across alkali metal series. This leads to noninvasive identification and differentiation of cations in the alkali metal series by utilizing a single sensing platform.

A hybrid hydrazine redox flow battery with a reversible electron acceptor.

Hydrazine is a pollutant with high hydrogen content, offering tremendous possibilities in a direct hydrazine fuel cell (DHFC) as it can be converted into electricity via benign end products. Due to the inner sphere nature of half-cell chemistries, hydrazine cross over triggers parasitic chemistry at the Pt-based air cathode of a state-of-the-art DHFC, overly complicating the already sluggish electrode kinetics at the positive electrode. Here, we illustrate that by altering the interfacial chemistry of the catholyte from inner sphere to outer sphere, the parasitic chemistry can be dissociated from the redox chemistry of the electron acceptor and the hybrid fuel cell can be driven by simple carbon-based cathodes. The reversible nature of an outer sphere catholyte leads to a hybrid fuel cell redox flow battery with performance metrics ∼4 times higher than a Pt-based DHFC-air configuration.

A Rechargeable Hydrogen Battery.

We utilize proton-coupled electron transfer in hydrogen storage molecules to unlock a rechargeable battery chemistry based on the cleanest chemical energy carrier molecule, hydrogen. Electrochemical, spectroscopic, and spectroelectrochemical analyses evidence the participation of protons during charge-discharge chemistry and extended cycling. In an era of anthropogenic global climate change and paramount pollution, a battery concept based on a virtually nonpolluting energy carrier molecule demonstrates distinct progress in the sustainable energy landscape.

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.