Ultrathin 2D Rare-Earth Nanomaterials: Compositions,Syntheses, and Applications

Ultrathin 2D nanomaterials possess promising properties due to electron confinement within single or a few atom layers. As an emerging class of functional materials, ultrathin 2D rare-earth nanomaterials may incorporate the unique optical, magnetic, and catalytic behaviors of rare-earth elements into layers, exhibiting great potential in various applications such as optoelectronics, magnetic devices, transistors, high-efficiency catalysts, etc. Despite its importance, reviews on ultrathin 2D rare-earth nanomaterials or related topics are rare and only focus on a certain family of ultrathin 2D rare-earth nanomaterials. This work is the first comprehensive review in this impressive field, which covers all families of ultrathin 2D rare-earth nanomaterials, illustrating their compositions, syntheses, and applications. After summarizing the current achievements, the challenges and opportunities of future research on ultrathin 2D rare-earth nanomaterials are evaluated.     

Multifunctional Cellular Materials Based on 2D Nanomaterials: Prospects and Challenges

Recent advances in emerging 2D nanomaterial‐based cellular materials (2D‐CMs) open up new opportunities for the development of next generation cellular solids with exceptional properties. Herein, an overview of the current research status of 2D‐CMs is provided and their future opportunities are highlighted. First, the unique features of 2D nanomaterials are introduced to illustrate why these nanoscale building blocks are promising for the development of novel cellular materials and what the new features of 2D nanoscale building blocks can offer when compared to their 0D and 1D counterparts. An in‐depth discussion on the structure–property relationships of 2D‐CMs is then provided, and the remarkable functions that can be achieved by engineering their cellular architecture are highlighted. Additionally, the use of 2D‐CMs to tackle key challenges in different practical applications is demonstrated. In conclusion, a personal perspective on the challenges and future research directions of 2D‐CMs is given.     

2D V‐V Binary Materials: Status and Challenges

2D phosphorene, arsenene, antimonene, and bismuthene, as a fast‐growing family of 2D monoelemental materials, have attracted enormous interest in the scientific community owing to their intriguing structures and extraordinary electronic properties. Tuning the monoelemental crystals into bielemental ones between group‐VA elements is able to preserve their advantages of unique structures, modulate their properties, and further expand their multifunctional applications. Herein, a review of the historical work is provided for both theoretical predictions and experimental advances of 2D V‐V binary materials. Their various intriguing electronic properties are discussed, including band structure, carrier mobility, Rashba effect, and topological state. An emphasis is also given to their progress in fabricated approaches and potential applications. Finally, a detailed presentation on the opportunities and challenges in the future development of 2D V‐V binary materials is given.     

Mid-infrared photonics and optoelectronics in 2D materials

With intriguing properties that are different from the conventional bulk materials, two-dimensional (2D) materials have attracted numerous and widespread research interests, including its applications in photonics and optoelectronics. Devices based on 2D materials have been demonstrated in a wide spectral range, from the ultraviolet to the terahertz, and the microwave wavelength range. The mid-infrared (MIR) region (about 2–20 μm) bears a particular scientific and technological significance because, for instance, many molecules have their spectral fingerprints and there are atmosphere transparent windows in this region. Nevertheless, the MIR region remains underdeveloped compared to the visible and the near-infrared telecommunication regimes, mainly due to the lack of suitable materials, such as narrow bandgap materials, and proper photonic designs for building high performance optoelectronic devices in this wavelength regime. Therefore, researchers have been exploring the possibility and opportunity of 2D materials to fill up the gap. Here, we review the key recent developments of 2D materials in the MIR photonic and optoelectronic applications, including photodetection, light modulation, surface plasmon polaritons, phonon polaritons, and their nonlinearities and provide an outlook on the challenges and opportunities that lie ahead for MIR optoelectronic research fields with 2D materials.     

3D printed architected lattice structures by material jetting

High-precision 3D printing technology opens to almost endless opportunities to design complex shapes present in tailored architected materials. The scope of this work is to review the latest studies regarding 3D printed lattice structures that involve the use of photopolymers fabricated by Material Jetting (MJ), with a focus on the widely used Polyjet and MultiJet techniques. The main aspects governing this printing process are introduced to determine their influence during the fabrication of 3D printed lattices. Performed experimental studies, considered assumptions, and constitutive models for the respective numerical simulations are analyzed. Furthermore, an overview of the latest extensively studied 3D printed architected lattice materials is exposed by emphasizing their achieved mechanical performances through the use of Ashby plots. Then, we highlight the advantages, limitations, and challenges of the material jetting technology to manufacture tunable architected materials for innovative devices, oriented to several engineering applications. Finally, possible approaches for future works and gaps to be covered by further research are indicated, including cost and environmental-related issues.     

Smart polymers and nanocomposites for 3D and 4D printing

Smart materials, also known as intelligent materials, which are responsive to the external stimuli including heat, moisture, stress, pH, and magnetic fields, have found extensive applications in sensors, actuators, soft robots, medical devices and artificial muscles. Using three-dimensional (3D) printing techniques for fabrication of smart devices allows for complex designs and well-controlled manufacturing processes. 4D printing is attributed to the 3D printing of smart materials that can be significantly transformed over time. Herein the smart materials including hydrogels and polymeric nanocomposites used in 4D printing were reviewed and the fundamental mechanisms responsible for the functionalities were discussed in detail. In this report, 4D printing of smart systems and their applications in sensors, actuators and biomedical devices were reviewed to provide a deeper understanding of the current development and the future outlook.     

Confinement Catalysis with 2D Materials for Energy Conversion

The unique electronic and structural properties of 2D materials have triggered wide research interest in catalysis. The lattice of 2D materials and the interface between 2D covers and other substrates provide intriguing confinement environments for active sites, which has stimulated a rising area of “confinement catalysis with 2D materials.” Fundamental understanding of confinement catalysis with 2D materials will favor the rational design of high‐performance 2D nanocatalysts. Confinement catalysis with 2D materials has found extensive applications in energy‐related reaction processes, especially in the conversion of small energy‐related molecules such as O₂, CH₄, CO, CO₂, H₂O, and CH₃OH. Two representative strategies, i.e., 2D lattice‐confined single atoms and 2D cover‐confined metals, have been applied to construct 2D confinement catalytic systems with superior catalytic activity and stability. Herein, the recent advances in the design, applications, and structure–performance analysis of two 2D confinement catalytic systems are summarized. The different routes for tuning the electronic states of 2D confinement catalysts are highlighted and perspectives on confinement catalysis with 2D materials toward energy conversion and utilization in the future are provided.     

Interface Characterization and Control of 2D Materials and Heterostructures

2D materials and heterostructures have attracted significant attention for a variety of nanoelectronic and optoelectronic applications. At the atomically thin limit, the material characteristics and functionalities are dominated by surface chemistry and interface coupling. Therefore, methods for comprehensively characterizing and precisely controlling surfaces and interfaces are required to realize the full technological potential of 2D materials. Here, the surface and interface properties that govern the performance of 2D materials are introduced. Then the experimental approaches that resolve surface and interface phenomena down to the atomic scale, as well as strategies that allow tuning and optimization of interfacial interactions in van der Waals heterostructures, are systematically reviewed. Finally, a future outlook that delineates the remaining challenges and opportunities for 2D material interface characterization and control is presented.     

Current status of 4D printing technology and the potential of light-reactive smart materials as 4D printable materials

The onset of multi-material 3D printing and the combination of smart materials into the printable material has led to the development of an exciting new technology called 4D printing. This paper will introduce the background and development into 4D printing, discuss water reactive 4D printing methods and temperature reactive 4D printing, modelling and simulation software, and future applications of this new technology. Smart materials that react to different external stimuli are described, along with the benefits of these smart materials and their potential use in 4D printing applications; specifically, existing light-reactive smart materials. 4D printing has the prospective to simplify the design and manufacturing of different products and the potential of automating actuation devices that naturally react to their environment without the need for human interaction, batteries, processors, sensors, and motors.     

Robust Catalysis on 2D Materials Encapsulating Metals: Concept,Application, and Perspective

Great endeavors are undertaken to search for low‐cost, rich‐reserve, and highly efficient alternatives to replace precious‐metal catalysts, in order to cut costs and improve the efficiency of catalysts in industry. However, one major problem in metal catalysts, especially nonprecious‐metal catalysts, is their poor stability in real catalytic processes. Recently, a novel and promising strategy to construct 2D materials encapsulating nonprecious‐metal catalysts has exhibited inimitable advantages toward catalysis, especially under harsh conditions (e.g., strong acidity or alkalinity, high temperature, and high overpotential). The concept, which originates from unique electron penetration through the 2D crystal layer from the encapsulated metals to promote a catalytic reaction on the outermost surface of the 2D crystal, has been widely applied in a variety of reactions under harsh conditions. It has been vividly described as “chainmail for catalyst.” Herein, recent progress concerning this chainmail catalyst is reviewed, particularly focusing on the structural design and control with the associated electronic properties of such heterostructure catalysts, and also on their extensive applications in fuel cells, water splitting, CO₂ conversion, solar cells, metal–air batteries, and heterogeneous catalysis. In addition, the current challenges that are faced in fundamental research and industrial application, and future opportunities for these fantastic catalytic materials are discussed.     

Supramolecular Chiral 2D Materials and Emerging Functions

Chiral materials are widely applied in various fields such as enantiomeric separation, asymmetric catalysis, and chiroptical effects, providing stereospecific conditions and environments. Supramolecular concepts to create the chiral materials can provide an insight for emerging chiro-optical properties due to their well-defined scaffolds and the precise functionalization of the surfaces or skeletons. Among the various supramolecular chiral structures, 2D chiral sheet structures are particularly interesting materials because of their extremely high surface area coupled with many unique chemical and physical properties, thereby offering potential for the next generation of functional materials for optically active systems and optoelectronic devices. Nevertheless, relatively limited examples for 2D chiral materials exhibiting specific functionality have been reported because incorporation of molecular chirality into 2D architectures is difficult at the present stage. Here, a brief overview of the recent advances is provided on the construction of chiral supramolecular 2D materials and their functions. The design principles toward 2D chirality and their potential applications are also discussed.     

3D Printed Graphene-Based Metamaterials: Guesting Multi-Functionality in One Gain

Advanced functional materials with fascinating properties and extended structural design have greatly broadened their applications. Metamaterials, exhibiting unprecedented physical properties (mechanical, electromagnetic, acoustic, etc.), are considered frontiers of physics, material science, and engineering. With the emerging 3D printing technology, the manufacturing of metamaterials becomes much more convenient. Graphene, due to its superior properties such as large surface area, superior electrical/thermal conductivity, and outstanding mechanical properties, shows promising applications to add multi-functionality into existing metamaterials for various applications. In this review, the aim is to outline the latest developments and applications of 3D printed graphene-based metamaterials. The structure design of different types of metamaterials and the fabrication strategies for 3D printed graphene-based materials are first reviewed. Then the representative explorations of 3D printed graphene-based metamaterials and multi-functionality that can be introduced with such a combination are further discussed. Subsequently, challenges and opportunities are provided, seeking to point out future directions of 3D printed graphene-based metamaterials.     

Ultrathin 2D Photocatalysts: Electronic‐Structure Tailoring,Hybridization, and Applications

As a sustainable technology, semiconductor photocatalysis has attracted considerable interest in the past several decades owing to the potential to relieve or resolve energy and environmental‐pollution issues. By virtue of their unique structural and electronic properties, emerging ultrathin 2D materials with appropriate band structure show enormous potential to achieve efficient photocatalytic performance. Here, the state‐of‐the‐art progress on ultrathin 2D photocatalysts is reviewed and a critical appraisal of the classification, controllable synthesis, and formation mechanism of ultrathin 2D photocatalysts is presented. Then, different strategies to tailor the electronic structure of ultrathin 2D photocatalysts are summarized, including component tuning, thickness tuning, doping, and defect engineering. Hybridization with the introduction of a foreign component and maintaining the ultrathin 2D structure is presented to further boost the photocatalytic performance, such as quantum dots/2D materials, single atoms/2D materials, molecular/2D materials, and 2D–2D stacking materials. More importantly, the advancement of versatile photocatalytic applications of ultrathin 2D photocatalysts in the fields of water oxidation, hydrogen evolution, CO₂ reduction, nitrogen fixation, organic syntheses, and removal pollutants is discussed. Finally, the future opportunities and challenges regarding ultrathin 2D photocatalysts to bring about new opportunities for future research in the field of photocatalysis are also presented.     

Emerging 2D Materials Produced via Electrochemistry

2D materials are important building blocks for the upcoming generation of nanostructured electronics and multifunctional devices due to their distinct chemical and physical characteristics. To this end, large-scale production of 2D materials with high purity or with specific functionalities represents a key to advancing fundamental studies as well as industrial applications. Among the state-of-the-art synthetic protocols, electrochemical exfoliation of layered materials is a very promising approach that offers high yield, great efficiency, low cost, simple instrumentation, and excellent up-scalability. Remarkably, playing with electrochemical parameters not only enables tunable material properties but also increases the material diversities from graphene to a wide spectrum of 2D semiconductors. Here, a succinct and critical survey of the recent progress in this research direction is presented, comprising the strategic design, exfoliation principles, underlying mechanisms, processing techniques, and potential applications of 2D materials. At the end of the discussion, the emerging trends, challenges, and opportunities in real practice are also highlighted.     

Laws of 4D Printing

Three-dimensional (3D) printing is an additive manufacturing process. Accordingly, four-dimensional (4D) printing is a manufacturing process that involves multiple research fields. 4D printing conserves the general attributes of 3D printing (such as material waste reduction, and elimination of molds, dies, and machining) and further enables the fourth dimension of products to provide intelligent behavior over time. This intelligent behavior is encoded (usually by an inverse mathematical problem) into stimuli-responsive multi-materials during printing, and is enabled by stimuli after printing. The main difference between 3D- and 4D-printed structures is the presence of one additional dimension, which provides for smart evolution over time. However, currently there is no general formula for modeling and predicting this additional dimension. Herein, by starting from fundamentals, we derive and validate a general bi-exponential formula with a particular format that can model the time-dependent behavior of nearly all 4D (hydro-, photochemical-, photothermal-, solvent-, pH-, moisture-, electrochemical-, electrothermal-, ultrasound-, etc. responsive) structures. We show that two types of time constants are needed to capture the correct time-dependent behavior of 4D multi-materials. We introduce the concept of mismatch-driven stress at the interface of active and passive materials in 4D multi-material structures, leading to one of the two time constants. We develop and extract the other time constant from our unified model of time-dependent behavior of nearly all stimuli-responsive materials. Our results starting from the most fundamental concepts and ending with governing equations can serve as general design principles for future research in the field of 4D printing, where time-dependent behaviors should be properly understood, modeled, and predicted.     

Heterostructures Based on 2D Materials: A Versatile Platform for Efficient Catalysis

The unique structural and electronic properties of 2D materials, including the metal and metal‐free ones, have prompted intense exploration in the search for new catalysts. The construction of different heterostructures based on 2D materials offers great opportunities for boosting the catalytic activity in electo(photo)chemical reactions. Particularly, the merits resulting from the synergism of the constituent components and the fascinating properties at the interface are tremendously interesting. This scenario has now become the state‐of‐the‐art point in the development of active catalysts for assisting energy conversion reactions including water splitting and CO₂ reduction. Here, starting from the theoretical background of the fundamental concepts, the progressive developments in the design and applications of heterostructures based on 2D materials are traced. Furthermore, a personal perspective on the exploration of 2D heterostructures for further potential application in catalysis is offered.     

Strain Engineering of 2D Materials: Issues and Opportunities at the Interface

Triggered by the growing needs of developing semiconductor devices at ever‐decreasing scales, strain engineering of 2D materials has recently seen a surge of interest. The goal of this principle is to exploit mechanical strain to tune the electronic and photonic performance of 2D materials and to ultimately achieve high‐performance 2D‐material‐based devices. Although strain engineering has been well studied for traditional semiconductor materials and is now routinely used in their manufacturing, recent experiments on strain engineering of 2D materials have shown new opportunities for fundamental physics and exciting applications, along with new challenges, due to the atomic nature of 2D materials. Here, recent advances in the application of mechanical strain into 2D materials are reviewed. These developments are categorized by the deformation modes of the 2D material–substrate system: in‐plane mode and out‐of‐plane mode. Recent state‐of‐the‐art characterization of the interface mechanics for these 2D material–substrate systems is also summarized. These advances highlight how the strain or strain‐coupled applications of 2D materials rely on the interfacial properties, essentially shear and adhesion, and finally offer direct guidelines for deterministic design of mechanical strains into 2D materials for ultrathin semiconductor applications.     

Nanoscale Assembly of 2D Materials for Energy and Environmental Applications

Rational design of 2D materials is crucial for the realization of their profound implications in energy and environmental fields. The past decade has witnessed significant developments in 2D material research, yet a number of critical challenges remain for real-world applications. Nanoscale assembly, precise control over the orientational and positional ordering, and complex interfaces among 2D layers are essential for the continued progress of 2D materials, especially for energy storage and conversion and environmental remediation. Herein, recent progress, the status, future prospects, and challenges associated with nanoscopic assembly of 2D materials are highlighted, specifically targeting energy and environmental applications. Geometric dimensional diversity of 2D material assembly is focused on, based on novel assembly mechanisms, including 1D fibers from the colloidal liquid crystalline phase, 2D films by interfacial tension (Marangoni effect), and 3D nanoarchitecture assembly by electrochemical processes. Relevant critical advantages of 2D material assembly are highlighted for application fields, including secondary batteries, supercapacitors, catalysts, gas sensors, desalination, and water decontamination.     

Development of Bioimplants with 2D, 3D,and 4D Additive Manufacturing Materials

Over the past 30 years, additive manufacturing (AM) has developed rapidly and has demonstrated great potential in biomedical applications. AM is a materials-oriented manufacturing technology, since the solidification mechanism, architecture resolution, post-treatment process, and functional application are based on the materials to be printed. However, 3D printable materials are still quite limited for the fabrication of bioimplants. In this work, 2D/3D AM materials for bioimplants are reviewed. Furthermore, inspired by Tai Chi, a simple yet novel soft/rigid hybrid 4D AM concept is advanced to develop complex and dynamic biological structures in the human body based on 4D printing hybrid ceramic precursor/ceramic materials that were previously developed by our group. With the development of multi-material printing technology, the development of bioimplants and soft/rigid hybrid biological structures with 2D/3D/4D AM materials can be anticipated.     

Retrieving Grain Boundaries in 2D Materials

The coalescence of randomly distributed grains with different crystallographic orientations can result in pervasive grain boundaries (GBs) in 2D materials during their chemical synthesis. GBs not only are the inherent structural imperfection that causes influential impacts on structures and properties of 2D materials, but also have emerged as a platform for exploring unusual physics and functionalities stemming from dramatic changes in local atomic organization and even chemical makeup. Here, recent advances in studying the formation mechanism, atomic structures, and functional properties of GBs in a range of 2D materials are reviewed. By analyzing the growth mechanism and the competition between far-field strain and local chemical energies of dislocation cores, a complete understanding of the rich GB morphologies as well as their dependence on lattice misorientations and chemical compositions is presented. Mechanical, electronic, and chemical properties tied to GBs in different materials are then discussed, towards raising the concept of using GBs as a robust atomic-scale scaffold for realizing tailored functionalities, such as magnetism, luminescence, and catalysis. Finally, the future opportunities in retrieving GBs for making functional devices and the major challenges in the controlled formation of GB structures for designed applications are commented.