Copper foam supported g-C3N4-metal-organic framework bacteria biohybrid cathode catalyst for CO2 reduction in microbial electrosynthesis.

Microbial electrosynthesis (MES) presents a versatile approach for efficiently converting carbon dioxide (CO2) into valuable products. However, poor electron uptake by the microorganisms from the cathode severely limits the performance of MES. In this study, a graphitic carbon nitride (g-C3N4)-metal-organic framework (MOF) i.e. HKUST-1 composite was newly designed and synthesized as the cathode catalyst for MES operations. The physiochemical analysis such as X-ray diffraction, scanning electron microscopy (SEM), and X-ray fluorescence spectroscopy showed the successful synthesis of g-C3N4-HKUST-1, whereas electrochemical assessments revealed its enhanced kinetics for redox reactions. The g-C3N4-HKUST-1 composite displayed excellent biocompatibility to develop electroactive biohybrid catalyst for CO2 reduction. The MES with g-C3N4-HKUST-1 biohybrid demonstrated an excellent current uptake of 1.7 mA/cm2, which was noted higher as compared to the MES using g-C3N4 biohybrid (1.1 mA/cm2). Both the MESs could convert CO2 into acetic and isobutyric acid with a significantly higher yield of 0.46 g/L.d and 0.14 g/L.d respectively in MES with g-C3N4-HKUST-1 biohybrid and 0.27 g/L.d and 0.06 g/L.d, respectively in MES with g-C3N4 biohybrid. The findings of this study suggest that g-C3N4-HKUST-1 is a highly efficient catalytic material for biocathodes in MESs to significantly enhance the CO2 conversion.

Diffusion controlled electrochemical analysis of MoS2 and MOF derived metal oxide-carbon hybrids for high performance supercapacitors.

In the context of emerging electric devices, the demand for advanced energy storage materials has intensified. These materials must encompass both surface and diffusion-driven charge storage mechanisms. While diffusion-driven reactions offer high capacitance by utilizing the bulk of the material, their effectiveness diminishes at higher discharge rates. Conversely, surface-controlled reactions provide rapid charge/discharge rates and high power density. To strike a balance between these attributes, we devised a tri-composite material, TiO2/Carbon/MoS2 (T10/MoS2). This innovative design features a highly porous carbon core for efficient diffusion and redox-active MoS2 nanosheets on the surface. Leveraging these characteristics, the T10/MoS2 composite exhibited impressive specific capacitance (436 F/g at 5 mV/s), with a significant contribution from the diffusion-controlled process (82%). Furthermore, our symmetrical device achieved a notable energy density of ~ 50 Wh/kg at a power density of 1.3 kW/kg. This concept holds promise for extending the approach to other Metal-Organic Framework (MOF) structures, enabling enhanced diffusion-controlled processes in energy storage applications.

Recent advances on surface mounted metal-organic frameworks for energy storage and conversion applications: Trends, challenges, and opportunities.

Establishing green and reliable energy resources is very important to counteract the carbon footprints and negative impact of non-renewable energy resources. Metal-organic frameworks (MOFs) are a class of porous material finding numerous applications due to their exceptional qualities, such as high surface area, low density, superior structural flexibility, and stability. Recently, increased attention has been paid to surface mounted MOFs (SURMOFs), which is nothing but thin film of MOF, as a new category in nanotechnology having unique properties compared to bulk MOFs. With the advancement of material growth and synthesis technologies, the fine tunability of film thickness, consistency, size, and geometry with a wide range of MOF complexes is possible. In this review, we recapitulate various synthesis approaches of SURMOFs including epitaxial synthesis approach, direct solvothermal method, Langmuir-Blodgett LBL deposition, Inkjet printing technique and others and then correlated the synthesis-structure-property relationship in terms of energy storage and conversion applications. Further the critical assessment and current problems of SURMOFs have been briefly discussed to explore the future opportunities in SURMOFs for energy storage and conversion applications.

Evaluation of local oxygen flux produced by photoelectrochemical hydroxide oxidation by scanning electrochemical microscopy.

Several in-situ electrochemical approaches have been developed for performing a localized photoelectrochemical investigation of the photoanode. One of the techniques is scanning electrochemical microscopy (SECM), which probes local heterogeneous reaction kinetics and fluxes of generated species. In traditional SECM analysis of photocatalysts, evaluation of the influence of radiation on the rate of studied reaction requires an additional dark background experiment. Here, using SECM and an inverted optical microscope, we demonstrate the determination of O2 flux caused by light-driven photoelectrocatalytic water splitting. Photocatalytic signal and dark background are recorded in a single SECM image. We used an indium tin oxide electrode modified with hematite (α-Fe2O3) by electrodeposition as a model sample. The light-driven flux of oxygen is calculated by analysis of SECM image recorded in substrate generation/tip collection mode. In photoelectrochemistry, the qualitative and quantitative knowledge of oxygen evolution will open new doors for understanding the local effects of dopants and hole scavengers in a straightforward and conventional manner.

A novel zinc sulfide impregnated carbon composite derived from zeolitic imidazolate framework-8 for sodium-ion hybrid solid-state flexible capacitors.

The pyrolysis of metal-organic frameworks (MOFs) is an easy approach to prepare metal oxides as well as nanoporous carbon with high specific surface area. In the present work, for the first time, ZIF-8 (zeolitic imidazolate framework-8) has been pyrolyzed under different conditions to derive two products, i.e., highly porous carbon (C) and zinc sulfide (ZnS) infused carbon (ZnS@C). These two materials, i.e., nanoporous C and ZnS@C, have been investigated as a negative and a positive electrode, respectively, for potential application in a hybrid asymmetrical solid-state supercapacitor device (HASD). The controlled pyrolysis approach for the preparation of ZnS@C has yielded uniformly distributed ZnS nanoparticles inside the carbon structure. A 1.8 V HASD has been assembled, which delivered an excellent energy density of 38.3 W h kg-1 (power density of 0.92 kW kg-1) along with the greatly desirable feature of cycling stability. The proposed selection of materials as electrodes is promising to develop futuristic hybrid capacitors.

High-Performance Symmetrical Supercapacitor with a Combination of a ZIF-67/rGO Composite Electrode and a Redox Additive Electrolyte.

The synthesis of a highly porous composite of ZIF-67 and reduced graphene oxide (rGO) using a simple stirring approach is reported. The composite has been investigated as an electrode to be assembled in a supercapacitor. In the presence of an optimized redox additive electrolyte (RAE), that is, 0.2 M K3[Fe(CN)6] in 1 M Na2SO4, the ZIF-67/rGO composite electrode has combined the properties of improved conductivity, high specific surface area, and low resistance. The proposed composite electrode in the three-electrode system shows an ultrahigh specific capacitance of 1453 F g-1 at a current density of 4.5 A g-1 within a potential window of -0.1 to 0.5 V. Further, the ZIF-67/rGO composite electrode was used to fabricate a symmetrical supercapacitor whose operation in the presence of the RAE has delivered high values of specific capacitance (326 F g-1 at a current density of 3 A g-1) and energy density (25.5 W h kg-1 at a power density of 2.7 kW kg-1). The device could retain about 88% of its initial specific capacitance after 1000 repeated charge-discharge cycles. The practical usefulness of the device was also verified by combining two symmetrical supercapacitors in series and then lighting a white light-emitting diode (illumination for 3 min). This study, for the first time, reports the application of a ZIF-based composite (ZIF-67/rGO) in the presence of an RAE to design an efficient supercapacitor electrode. This proposed design is also scalable to a flexible symmetric device delivering high values of specific capacitance and energy density.