Nanoengineering Metal–Organic Frameworks and Derivatives for Electrosynthesis of Ammonia

Abstract

Electrocatalytic synthesis under mild conditions has become increasingly important as one of the practical alternatives for industrial applications, especially for the green ammonia (NH3) industry. A properly engineered electrocatalyst plays a vital role in the realization of superior catalytic performance. Among various types of promising nanomaterials, metal–organic frameworks (MOFs) are competitive candidates for developing efficient electrocatalytic NH3 synthesis from simple nitrogen-containing molecules or ions, such as N2 and NO3−. In this review, recent advances in the development of electrocatalysts derived from MOFs for the electrosynthesis of NH3 are collected, categorized, and discussed, including their application in the N2 reduction reaction (NRR) and the NO3− reduction reaction (NO3RR). Firstly, the fundamental principles are illustrated, such as plausible mechanisms of NH3 generation from N2 and NO3−, the apparatus of corresponding electrocatalysis, parameters for evaluation of reaction efficiency, and detection methods of yielding NH3. Then, the electrocatalysts for NRR processes are discussed in detail, including pristine MOFs, MOF-hybrids, MOF-derived N-doped porous carbons, single atomic catalysts from pyrolysis of MOFs, and other MOF-related materials. Subsequently, MOF-related NO3RR processes are also listed and discussed. Finally, the existing challenges and prospects for the rational design and fabrication of electrocatalysts from MOFs for electrochemical NH3 synthesis are presented, such as the evolution of investigation methods with artificial intelligence, innovation in synthetic methods of MOF-related catalysts, advancement of characterization techniques, and extended electrocatalytic reactions. "Image missing"

Multifunctional Ni-NPC Single-Atom Nanozyme for Removal and Smartphone-Assisted Visualization Monitoring of Carbamate Pesticides

“…Metal–nitrogen-doped carbon (M–N–C) materials, derived from metal–organic frameworks (MOFs), have garnered substantial attention as a class of sophisticated multifunctional materials with applications spanning diverse disciplines, including adsorption, sensing, drug delivery, gas storage, and heterogeneous catalysis, among others. − On one hand, M–N–C materials exhibited a high surface area and porous structure, enriched with nitrogen dopants within the carbon matrix, rendering them suitable for pesticide adsorption. On the other hand, the synergistic interplay between transition metals with nitrogen-doped carbon nanomaterials has shown the potential to enhance the catalytic activity of nanozyme .…”

Enhancing Green Ammonia Electrosynthesis Through Tuning Sn Vacancies in Sn-Based MXene/MAX Hybrids

“…Ammonia (NH 3 ), as an important inorganic chemical, is not only widely used in industrial manufacture such as fertilizer, plastics and refrigerants, but also in the field of energy storage and conversion, especially the hydrogen storage [ 1 – 3 ]. Up to now, the industrial NH 3 production mainly relies on the Haber Bosch (H-B) process, which requires harsh reaction conditions (300–600 °C, 150–350 atm), simultaneously generates enormous energy consumption and CO 2 emission [ 4 – 7 ]. Considering energy and environmental factors, it is necessary to explore a sustainable and green method for NH 3 synthesis [ 8 , 9 ].…”

Construction of a CoNiHHTP MOF/PHI Z-Scheme Heterojunction for ppb Level NO2 Photoelectric Sensing with 405 nm Irradiation at RT

“…As for PHI, the construction of a heterojunction with an energy band-matched semiconductor is a potential strategy to promote the charge separation. , Significantly, a bioinspired artificial Z-scheme heterojunction that enhances charge separation and retains sufficient thermodynamic reaction capacities of the electrons, coupled with well-defined charge transfer pathways, is a preferable candidate for improving sensing performances. , Recent research has implied that metal–organic frameworks (MOFs) have superior gas sensing capabilities due to their high specific surface areas, ultrahigh porosity, adjustable structures, and abundant metal sites. ,− It is feasible to incorporate suitable MOFs with PHI to construct dimensionally matched 2 D /2D Z-scheme heterojunctions to address the obstacle. , Among numerous MOFs, hexahydroxytriphenylene-based 2D MOFs, known as the M 3 (HHTP) 2 MOF, is an ideal coupler choice for PHI due to their strong metal–ligand orbital hybridization, which results in the formation of a wide range of π-d conjugated planar and π–π conjugated stacking structures and a suitable energy-band structure for the construction of a Z-scheme heterojunction. − Moreover, the open metal nodes of the M 3 (HHTP) 2 MOF show strong selectively adsorption capacity toward NO 2 . ,, For example, Campbell et al were the pioneers in reporting the chemiresistive sensing of ammonia using the Cu 3 (HITP) 2 MOF. Building on this, Jo and colleagues fabricated the Fe 2 O 3 –Cu 3 (HHTP) 2 MOF heterojunctions that, when activated by visible light, displayed a significant RT response to NO 2 , as well as rapid response and recovery …”