Rational Design of Graphene Derivatives for Electrochemical Reduction of Nitrogen to Ammonia.

The conversion of nitrogen to ammonia offers a sustainable and environmentally friendly approach for producing precursors for fertilizers and efficient energy carriers. Owing to the large energy density and significant gravimetric hydrogen content, NH3 is considered an apt next-generation energy carrier and liquid fuel. However, the low conversion efficiency and slow production of ammonia through the nitrogen reduction reaction (NRR) are currently bottlenecks, making it an unviable alternative to the traditional Haber-Bosch process for ammonia production. The rational design and engineering of catalysts (both photo- and electro-) represent a crucial challenge for improving the efficiency and exploiting the full capability of the NRR. In the present review, we highlight recent progress in the development of graphene-based systems and graphene derivatives as catalysts for the NRR. Initially, the history, fundamental mechanism, and importance of the NRR to produce ammonia are briefly discussed. We also outline how surface functionalization, defects, and hybrid structures (single-atom/multiatom as well as composites) affect the N2 conversion efficiency. The potential of graphene and graphene derivatives as NRR catalysts is highlighted using pertinent examples from theoretical simulations as well as machine learning based performance predictive methods. The review is concluded by identifying the crucial advantages, drawbacks, and challenges associated with principal scientific and technological breakthroughs in ambient catalytic NRR.

Emerging MXene@Metal-Organic Framework Hybrids: Design Strategies toward Versatile Applications.

Rapid progress on developing smart materials and design of hybrids is motivated by pressing challenges associated with energy crisis and environmental remediation. While emergence of versatile classes of nanomaterials has been fascinating, the real excitement lies in the design of hybrid materials with tunable properties. Metal-organic frameworks (MOFs) are the key materials for gas sorption and electrochemical applications, but their sustainability is challenged by limited chemical stability, poor electrical conductivity, and intricate, inaccessible pores. Despite tremendous efforts towards improving the stability of MOF materials, little progress has made researchers inclined toward developing hybrid materials. MXenes, a family of two-dimensional transition-metal carbides, nitrides and carbonitrides, are known for their compositional versatility and formation of a range of structures with rich surface chemistry. Hybridization of MOFs with functional layered MXene materials may be beneficial if the host structure provides appropriate interactions for stabilizing and improving the desired properties. Recent efforts have focused on integrating Ti3C2Tx and V2CTx MXenes with MOFs to result in hybrid materials with augmented electrochemical and physicochemical properties, widening the scope for emerging applications. This review discusses the potential design strategies of MXene@MOF hybrids, attributes of tunable properties in the resulting hybrids, and their applications in water treatment, sensing, electrochemical energy storage, smart textiles, and electrocatalysis. Comprehensive discussions on the recent efforts on rapidly evolving MXene@MOF materials for various applications and potential future directions are highlighted.