As a fascinating conjugated polymer, graphitic carbon nitride (g-C3N4) has become a new research hotspot and drawn broad interdisciplinary attention as a metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability, and “earth-abundant” nature. This critical review summarizes a panorama of the latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites, including (1) nanoarchitecture design of bare g-C3N4, such as hard and soft templating approaches, supramolecular preorganization assembly, exfoliation, and template-free synthesis routes, (2) functionalization of g-C3N4 at an atomic level (elemental doping) and molecular level (copolymerization), and (3) modification of g-C3N4 with well-matched energy levels of another semiconductor or a metal as a cocatalyst to form heterojunction nanostructures. The constructi...

Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer To Achieving Sustainability?

Semiconductor-based photocatalysis is considered to be an attractive way for solving the worldwide energy shortage and environmental pollution issues. Since the pioneering work in 2009 on graphitic carbon nitride (g-C3N4) for visible-light photocatalytic water splitting, g-C3N4 -based photocatalysis has become a very hot research topic. This review summarizes the recent progress regarding the design and preparation of g-C3N4 -based photocatalysts, including the fabrication and nanostructure design of pristine g-C3N4 , bandgap engineering through atomic-level doping and molecular-level modification, and the preparation of g-C3N4 -based semiconductor composites. Also, the photo-catalytic applications of g-C3N4 -based photocatalysts in the fields of water splitting, CO2 reduction, pollutant degradation, organic syntheses, and bacterial disinfection are reviewed, with emphasis on photocatalysis promoted by carbon materials, non-noble-metal cocatalysts, and Z-scheme heterojunctions. Finally, the concluding remarks are presented and some perspectives regarding the future development of g-C3N4 -based photocatalysts are highlighted.

Polymeric Photocatalysts Based on Graphitic Carbon Nitride

Metal-organic frameworks (MOFs) are an emerging class of porous materials with potential applications in gas storage, separations, catalysis, and chemical sensing. Despite numerous advantages, applications of many MOFs are ultimately limited by their stability under harsh conditions. Herein, the recent advances in the field of stable MOFs, covering the fundamental mechanisms of MOF stability, design, and synthesis of stable MOF architectures, and their latest applications are reviewed. First, key factors that affect MOF stability under certain chemical environments are introduced to guide the design of robust structures. This is followed by a short review of synthetic strategies of stable MOFs including modulated synthesis and postsynthetic modifications. Based on the fundamentals of MOF stability, stable MOFs are classified into two categories: high-valency metal-carboxylate frameworks and low-valency metal-azolate frameworks. Along this line, some representative stable MOFs are introduced, their structures are described, and their properties are briefly discussed. The expanded applications of stable MOFs in Lewis/Bronsted acid catalysis, redox catalysis, photocatalysis, electrocatalysis, gas storage, and sensing are highlighted. Overall, this review is expected to guide the design of stable MOFs by providing insights into existing structures, which could lead to the discovery and development of more advanced functional materials.

Stable Metal-Organic Frameworks: Design, Synthesis, and Applications.

Among the large family of metal–organic frameworks (MOFs), Zr-based MOFs, which exhibit rich structure types, outstanding stability, intriguing properties and functions, are foreseen as one of the most promising MOF materials for practical applications. Although this specific type of MOF is still in its early stage of development, significant progress has been made in recent years. Herein, advances in Zr-MOFs since 2008 are summarized and reviewed from three aspects: design and synthesis, structure, and applications. Four synthesis strategies implemented in building and/or modifying Zr-MOFs as well as their scale-up preparation under green and industrially feasible conditions are illustrated first. Zr-MOFs with various structural types are then classified and discussed in terms of different Zr-based secondary building units and organic ligands. Finally, applications of Zr-MOFs in catalysis, molecule adsorption and separation, drug delivery, and fluorescence sensing, and as porous carriers are highlighted. Such a review based on a specific type of MOF is expected to provide guidance for the in-depth investigation of MOFs towards practical applications.

Zr-based metal-organic frameworks: design, synthesis, structure, and applications.

We developed two-step solution-phase reactions to form hybrid materials of Mn3O4 nanoparticles on reduced graphene oxide (RGO) sheets for lithium ion battery applications. Mn3O4 nanoparticles grown selectively on RGO sheets over free particle growth in solution allowed for the electrically insulating Mn3O4 nanoparticles wired up to a current collector through the underlying conducting graphene network. The Mn3O4 nanoparticles formed on RGO show a high specific capacity up to ~900mAh/g near its theoretical capacity with good rate capability and cycling stability, owing to the intimate interactions between the graphene substrates and the Mn3O4 nanoparticles grown atop. The Mn3O4/RGO hybrid could be a promising candidate material for high-capacity, low-cost, and environmentally friendly anode for lithium ion batteries. Our growth-on-graphene approach should offer a new technique for design and synthesis of battery electrodes based on highly insulating materials.

Mn3O4-Graphene Hybrid as a High Capacity Anode Material for Lithium Ion Batteries

Metal–organic frameworks (MOFs) have received a lot of attention because of their diverse structures, tunable properties and multiple applications such as gas storage, catalysis and magnetism. Recently, there has been a rapidly growing interest in developing MOF-based materials for electrochemical energy storage. MOFs have proved to be particularly suitable for electrochemical applications because of their tunable chemical composition that can be designed at the molecular level and their highly porous framework in which fast mass transportation of the related species is favorable. In this review, the recent progress in fabricating MOFs and MOF-derived nanostructures for electrochemical applications is presented. The review starts with an introduction of the principles and strategies for designing targeted MOFs followed by a discussion of some novel MOF-derived structures and their potential applications in electrochemical energy storage and conversion. Finally, major challenges in electrochemical energy storage are highlighted and prospective solutions from current progress in MOF-based nanostructure research are given.

Metal–organic frameworks and their derived nanostructures for electrochemical energy storage and conversion

Replacing the rare and precious platinum (Pt) electrocatalysts with earth-abundant materials for promoting the oxygen reduction reaction (ORR) at the cathode of fuel cells is of great interest in developing high-performance sustainable energy devices. However, the challenging issues associated with non-Pt materials are still their low intrinsic catalytic activity, limited active sites, and the poor mass transport properties. Recent advances in material sciences and nanotechnology enable rational design of new earth-abundant materials with optimized composition and fine nanostructure, providing new opportunities for enhancing ORR performance at the molecular level. This Review highlights recent breakthroughs in engineering nanocatalysts based on the earth-abundant materials for boosting ORR.

Earth-Abundant Nanomaterials for Oxygen Reduction.

Metal-organic frameworks (MOFs) with high surface area and tunable chemical structures have attracted tremendous attention. Recently, there has been increasing interest in deriving advanced materials from MOFs for electrochemical energy storage and conversion. This progress report highlights recent breakthroughs in electrocatalysis by using MOF-based novel catalysts, such as in oxygen reduction and evolution, hydrogen evolution and carbon dioxide reduction. The advantages of preparing electrocatalysts from MOFs are introduced and discussed. Then, the development of MOF derived electrocatalysis-active products, such as heteroatom-doped carbon, metal oxide (MO), metal sulfide (MS), metal carbide (MC), metal phosphide (MP) and their hybrids with carbon, are summarized. The detailed functions of these materials in representative electrocatalysis systems are also reviewed. The demonstrated examples will provide understanding in preparing highly active and stable electrocatalysts. The progress report concludes with the future applications of MOF-based materials in the field of electrocatalysis.

Metal‐Organic Framework‐Based Nanomaterials for Electrocatalysis

The technological evolution has been progressing for centuries and will possibly increase at a higher rate in the 21st century. Currently, in this age of nanotechnology, the discovery of more economical and sustainable novel materials has considerably increased. The abundance of two-dimensional (2D) materials has endowed them with a broad material platform in technical studies and in the expansion of nano- and atomic-level applications. The innovation of graphene has motivated considerable attention to the study of other novel 2D materials, known as modern day “alchemy”, by which scientists are trying to convert most possible periodic table elements into 2D material structures and forms. 2D material devices with high quality and good optical encoder performance have a multitude of industrial applications. However, their stability and large size restrict their applications, but these problems can be overcome by functionalization and substrate-based formation of 2D materials. Therefore, via this review, first, basic attributes of 2D materials are described, and the mechanisms to further enhance their properties are also summarized. Second, the applications of 2D materials are discussed, along with their advantages and disadvantages. Finally, some effective device-fabrication approaches, such as heterostructure approaches, are applied to further enhance the properties of 2D materials; their novel device applications and opportunities are also presented. This updated review may provide new avenues for 2D material synthesis and development of more efficient devices compared to conventional devices in different fields.

Recent developments in emerging two-dimensional materials and their applications

Phase change materials (PCMs) have been extensively characterized as constant temperature latent heat thermal energy storage (TES) materials. Nevertheless, the widespread utilization of PCMs is limited due to the flow of liquid PCMs during melting, phase separation, supercooling and low heat transfer rate. In order to overcome these inherent problems and to improve thermo-physical properties, the confinement of PCMs at the nanoscale has been identified as a versatile strategy, which ensures the encapsulation of PCMs in much smaller nano-containers. Such strategies including core–shell, longitudinal, interfacial and porous confinement have been widely presented in recent years to efficiently encapsulate PCMs in nanospaces and are presenting attractive ways to enhance thermal performance. This review summarizes the recent advancement and critical issues of nanoconfinement technologies of PCMs from the point of view of material design. In addition, the potential applications of nanoconfined PCMs in diverse fields, including energy conversion and storage, thermal rectification and temperature controlled drug delivery systems, are presented in detail. Finally, the major drawbacks associated with nanoconfined PCMs and their prospective solutions are also provided.

Asif Mahmood

Papers

Metal–organic frameworks and their derived nanostructures for electrochemical energy storage and conversion

Earth-Abundant Nanomaterials for Oxygen Reduction.

Metal‐Organic Framework‐Based Nanomaterials for Electrocatalysis

Recent developments in emerging two-dimensional materials and their applications

Nanoconfined phase change materials for thermal energy applications