Metal organic frameworks as electrocatalysts: Hydrogen evolution reactions and overall water splitting

The development of clean energy technologies to protect the environment is an important demand of the times. Electrocatalysis is emerging as a promising method for evolution of hydrogen and overall water splitting. Nowadays, metal organic frameworks (MOFs) have emerged as electrocatalysts having uniformly distributed active sites and high electrical conductivity. This review summarizes the latest advances in heterogeneous catalysis by MOFs and their composite/derivatives for efficient hydrogen evolution reaction (HER) and water splitting. Pristine MOFs with their recent development are summarized first followed by composites of MOFs with their enhanced electrocatalytic performances. Overall water splitting by using bifunctional electrocatalysts derived from MOFs with different synthetic approaches is provided and this review gives the metal-based categorisation of precursor MOFs. Different strategies to improve chemical stability, conductivity, and overall electrocatalytic properties have been discussed. In the last, perspectives on the synthesis of efficient MOF-based electrocatalyst materials are provided.     

Water Seepage Mapping in an Underground Coal-Mine Barrier Using Self-potential and Electrical Resistivity Tomography

Mine Water and the Environment - Seepage of water through an underground coal-mine barrier is a common indicator of a potential hydrogeological hazard. The Jharia coalfield has witnessed several...     

Synthesis of CuTi-LDH supported on g-C3N4 for electrochemical and photoelectrochemical oxygen evolution reactions

A nanocomposite CuTi layered double hydroxide (LDH) supported on g-C₃N₄ (15 wt% of g-C₃N₄) is facilely synthesized by hydrothermal method. There are electrostatic interactions between positive layers of CuTi-LDH and negatively charged inner g-C₃N₄ sheets. The nanocomposite and its precursors are characterized through various analytical techniques, which affirmed the presence of both g-C₃N₄ and CuTi-LDH characteristic features. The pore-enriched hybrid geometry of CuTi-LDH@g-C₃N₄ with high specific surface area (146 m²/g), and suitable band gap of 2.46 eV enables the nanocomposite to act as both an electrocatalyst and photoelectrocatalyst for oxygen evolution reaction (OER). Both the electrochemical and photoelectrochemical studies are done using 1 M KOH (pH = 13.6) with applied potential of ?0.2 V to 1.5 V vs. Ag/AgCl. The onset potential of CuTi-LDH@g-C₃N₄ for OER appears at η = 0.36 V in dark and η = 0.32 V under visible light illumination of 30 min. Also, Mott-Schottky analysis shows n-type semiconductor behaviour for CuTi-LDH@g-C₃N₄ and its precursors. The photoelectrochemical water oxidation proceeds by charge transfer across a Type II heterojunction formed between the CuTi-LDH and g-C₃N₄ materials.     

Platinum nanoparticles decorated on graphitic carbon nitride-ZIF-67 composite support: An electrocatalyst for the oxidation of butanol in fuel cell applications

In the present study, we report an eco-friendly and simple route to design and synthesize novel nanocomposite catalyst based on platinum nanoparticles anchored on binary support of graphitic carbon nitride (g-C₃N₄) and cobalt-metal-organic framework (ZIF-67). For this purpose, ZIF-67 was prepared by precipitation method and g-C₃N₄ was prepared through thermal polymerization method. Later, ZIF-67 and g-C₃N₄ were hybridized through sonication to get homogeneous g–C₃N₄–ZIF-67 nanocomposite support material. Platinum nanoparticles (PtNPs) were uniformly deposited on g–C₃N₄–ZIF-67 by an electrochemical method. The as-developed nanocatalyst was characterized by morphological, structural and electrochemical techniques. The electrocatalytic activity of PtNPs@g–C₃N₄–ZIF-67 nanocatalyst towards butanol oxidation was evaluated via CV, CA, LSV and EIS in an alkaline medium. Results revealed that the proposed catalyst showed greatly enhanced electrooxidation of butanol in terms of high magnificent current density, lower oxidation potential, excellent long-term stability, large surface area, low charge transfer resistance and less toxic ability. Enhanced catalytic performance of the proposed catalyst could be ascribed to the synergistic effect of g–C₃N₄–ZIF-67 nanocomposite and PtNPs. The PtNPs@g–C₃N₄–ZIF-67 catalyst holds promising potential applications to be used as an anodic electrocatalyst for the development of high-performance alkaline fuel cells.     

Ionic liquid-based deep eutectic solvents as novel solvent-cum-catalyst media for thermal dehydrogenation of chemical hydrides

The current work explores the usage of novel synthesized Deep Eutectic Solvent (DES) as a catalyst cum solvent media for the thermal dehydrogenation of chemical hydrides, namely Ammonia Borane (AB) and Ethylene diamine bisborane (EDAB). In the first instance, the quantum chemistry based COSMO-SAC (COnductor like Screening MOdel Segment Activity Coefficient) model was used for the selection of the pertinent solvent. 1-Butyl-3-methylimidazolium methanesulfonate: Imidazole ([BMIM][MeSO₃]:[Im]) turned out to be an ideal eutectic mixture with the highest predicted solubility with amine boranes. The DES was synthesized by combining the Hydrogen Bond Acceptor (HBA), namely 1-Butyl-3-methylimidazolium methanesulfonate and Imidazole as Hydrogen Bond Donor (HBD) at a molar ratio of 1:2 and T = 70 °C. The formation of DES was confirmed by recording the NMR spectra. Further, the thermal dehydrogenation study was performed at a vacuum of 4 × 10^?2 mbar (gauge pressure) of AB/DES and EDAB/DES systems at 105 °C, where a hydrogen equivalent of 1.40 and 2.55 was produced, respectively. The residual samples were further analyzed through ¹H NMR analysis for the reaction mechanism and to confirm the role of Ionic Liquid-based DES as catalyst cum solvent media.     

Graphene-based electrocatalysts: Hydrogen evolution reactions and overall water splitting

Recently, carbon-based materials (e.g., graphene, carbon nanotubes, carbon quantum dots) have been used as electrocatalysts to catalyze the reactions such as hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). Among them, graphene has attracted attention as an electrocatalyst, and its electrocatalytic performances have been improved by doping with metals and non-metals, surface and defect engineering, and hybrid development. In this perspective, the present paper reviewed the recent advances (2018 onwards) on the progress of graphene-based electrocatalysts for HER and overall water splitting (OWS). It is emphasizing strategies for optimizing electrocatalytic properties followed by challenges and future outlook. This review will provide the essential ideas and strategies that can help design graphene-based electrocatalysts of high performance that can be implemented for sustainable energy application.