Balancing elementary steps enables coke-free dry reforming of methane.

Balancing kinetics, a crucial priority in catalysis, is frequently achieved by sacrificing activity of elementary steps to suppress side reactions and enhance catalyst stability. Dry reforming of methane (DRM), a process operated at high temperature, usually involves fast C-H activation but sluggish carbon removal, resulting in coke deposition and catalyst deactivation. Studies focused solely on catalyst innovation are insufficient in addressing coke formation efficiently. Herein, we develop coke-free catalysts that balance kinetics of elementary steps for overall thermodynamics optimization. Beginning from a highly active cobalt aluminum oxide (CoAl2O4) catalyst that is susceptible to severe coke formation, we substitute aluminum (Al) with gallium (Ga), reporting a CoAl0.5Ga1.5O4-R catalyst that performs DRM stably over 1000 hours without observable coke deposition. We find that Ga enhances DRM stability by suppressing C-H activation to balance carbon removal. A series of coke-free DRM catalysts are developed herein by partially substituting Al from CoAl2O4 with other metals.

General Strategy for Incorporation of Functional Group Handles into Covalent Organic Frameworks via the Ugi Reaction.

The library of imine-linked covalent organic frameworks (COFs) has grown significantly over the last two decades, featuring a variety of morphologies, pore sizes, and applications. An array of synthetic methods has been developed to expand the scope of the COF functionalities; however, most of these methods were designed to introduce functional scaffolds tailored to a specific application. Having a general approach to diversify COFs via late-stage incorporation of functional group handles would greatly facilitate the transformation of these materials into platforms for a variety of useful applications. Herein, we report a general strategy to introduce functional group handles in COFs via the Ugi multicomponent reaction. To demonstrate the versatility of this approach, we have synthesized two COFs with hexagonal and kagome morphologies. We then introduced azide, alkyne, and vinyl functional groups, which could be readily utilized for a variety of post-synthetic modifications. This facile approach enables the functionalization of any COFs containing imine linkages.

Electrochemical detection of methyl parathion via a novel biosensor tailored on highly biocompatible electrochemically reduced graphene oxide-chitosan-hemoglobin coatings.

A quick electrochemical sensing tool by utilizing novel bioelectrode based on redox active protein hemoglobin (Hb) has been offered here for the determination of methylparathion (MP). The bioelectrode has been designed by immobilizing Hb on electrochemically reduced graphene oxide-chitosan (ERGO-CS/Hb/FTO) based biocompatible coatings. Fourier transform-infrared analyses (FTIR), field emission scanning electron microscopy (FESEM), UV-visible and electrochemical characterization reveal the successful grafting of ERGO-CS/Hb/FTO. A detailed impedimetric analysis shows low charge transfer resistance (RCT) and solution resistance (Rs) for the fabricated biosensor, thus pointing towards improved electrochemical performance and sensitivity. In-depth elucidation of redox analysis has been presented in terms of surface concentration of redox moiety (2.92 × 10-9 mol cm-2) and heterogeneous electron transfer rate constant (0.0032 s-1) which indicate enhanced surface coverage and better charge transfer properties of the proposed electrochemical biosensor. The sensor is equipped with a low limit of detection of 79.77 nM and a high sensitivity of 45.77 Acm-2 µM-1 with excellent reproducibility. The modified biosensor also offered its credibility towards detection of MP in vegetable samples with recovery (%) ranging from 94% to 101%. The designed biosensor hereby, evolves as a promising approach for the recognition of MP.