A Silver-Based Integrated System Showing Mutually Inclusive Super Protonic Conductivity and Photoswitching Behavior

Abstract

Photoinduced electricity and proton conductivity led fuel cells have emerged, inter alia, as highly promising systems for unconventional energy harvesting. Notwithstanding their individual presence with widely acclaimed results, an integrating system with mutually inclusive manifestation of both features has hitherto not been reported in the literature. To achieve this objective, our approach was to design a ligand system incorporating prerequisite features of both systems, like extended conjugation instigating photophysical activity and functional groups facilitating ionic conduction. As such, we report herein the design, synthesis, and characterization of a pyridyl-pyrazole-based silver compound that exhibits an excellent photocurrent generation and very high proton conductivity. The X-ray single-crystal structure of the Ag complex fully supports our notion, showing extensive π–π conjugated aromatic rings with a protruding free sulfonic group, facing toward solvent-filled channels with numerous supramolecular interactions. The nanoscopic silver metallogel induces semiconductive features in the system which ultimately result in photoresponse behavior in terms of photocurrent generation with an whopping photocurrent gain (I on/I off) of 21.2. To complete the idea of an integrated system, the proton conductivity values were also measured for both gel and crystalline states, while the former state yields a better result. The maximum proton conductivity value turns out to be 1.03 × 10–2 S cm–1 at 70 °C, which is higher than or comparable to those of well-known systems in the literature for proton conductivity.

Proton‐Conducting Hierarchical Composite Hydrogels Producing First Soft Memcapacitors with Switchable Memory

“…[3][4][5] Some recent works reported strikingly high conductivity values for an Ag + metallogel (1.03 × 10 -2 S cm -1 ; at 70 °C) and Zn 2+ /Cu 2+ metallogels assisted by Li + (1.02 × 10 -2 and 1.14 × 10 -2 S cm -1 ). [24] Unambiguously, our developed networks with their conductivities ranging between (1.66-4.34) × 10 -2 S cm -1 under environmental conditions defines new benchmark for the conductivity shown by soft gel materials (Table S3, Supporting Information).…”

The synthesis and combined electrical–magnetic and toxic dye sequestration properties of a Cr(iii)-metallogel

“…Interestingly, the azide-functionalized metallogel provides us with a unique opportunity to explore the role of immobilized functionalities, which can exist as distinctly charge-separated resonance structures, in improving proton conductivity, the most important parameter required for an efficient fuel cell membrane. 57,58 Accordingly, detailed proton conductivity experiments were carried out on a xerogel sample using alternating current (ac) impedance spectroscopy under variable temperature and relative humidity conditions. As illustrated in the inset of Fig.…”

Exploring the Water Oxidation Catalytic Activity of a Mn-Based Magnetic Metal–Organic Framework: The Role of Proton Conductivity and Oxygen Evolution Reaction Overpotential

“…On the other hand, H 2 STA with an ortho-oriented sulfonic moiety, came as a natural choice to excel the electrical conductivity of the resulting MOF. The grafted sulfonic groups tend to instigate partial charge species formation that facilitate easier proton mobility and henceforth enhance the conductivity. , Furthermore, strategic immobilization of highly polar sulfonic groups also favors extensive supramolecular interaction with polar solvents like water. Employment of H 2 STA is therefore expected to favor highly periodic accumulation of lattice water molecules, which in other words, facilitates easy storage and supply of the sole substrate to reduce the overpotential of OER as well as outweigh the sluggish kinetics …”