Surface characterization of 2D transition metal carbides (MXenes)

Surface characterization of 2D transition metal carbides (MXenes) PDF Author: Ingemar Persson
Publisher: Linköping University Electronic Press
ISBN: 9176850854
Category :
Languages : en
Pages : 91

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Book Description
Research on two-dimensional (2D) materials is a rapidly growing field owing to the wide range of new interesting properties found in 2D structures that are vastly different from their three-dimensional (3D) analogues. In addition, 2D materials embodies a significant surface area that facilitates a high degree of surface reactions per unit volume or mass, that is imperative in many applications such as catalysis, energy storage, energy conversion, filtration, and single molecule sensing. MXenes constitute a family of 2D materials consisting of transition metal carbides and/or nitrides, which are typically formed after selective etching of their 3D parent MAX phases. The latter, are a family of nanolaminated compounds that typically follow the formula Mn+1AXn (n=1-3), where M is a transition metal, A is a group 13 or 14 element, and X is C and or N. Selective etching by aqueous F- containing acids removes the A layer leaving 2D Mn+1Xn slabs instantly terminated by a mix of O-, OH- and F-groups. The first and most investigated MXene is Ti3C2TX, where TX stands for surface termination, which has shown record properties in a range of applications (eg. electrode in Li-batteries, supercapacitors, sieving membrane, electromagnetic interference shielding, and carbon capture). Adding to that, over 30 different MXenes have been discovered since 2011, exhibiting alternative or superior properties. Most importantly, elegant routes for property design in the MXene family has been demonstrated, by means of either varying the chemistry in the Mn+1Xn compound, by alloying two M elements, or by changing the structure of the MXene by introducing vacancies. The present work has a led to an additional route for post synthesis property tuning in MXenes by manipulation of surface termination elements. This enables a unique toolbox for property tuning which is not available to other 2D materials and is highly beneficial for applications that is dependent on surface reactions. Furthermore, chemical and structural characterization of terminations on single sheets is essential to rule out the influence of intercalants or contamination that is typically present in multilayer MXene samples or thin films. For that purpose, a method for preparing isolated contamination free single sheets of MXene samples for transmission electron microscopy (TEM) characterization was established. In order to determine vacancy and termination sites, atomically resolved scanning (S)TEM imaging and image simulations was carried out. Two main processes were employed to substitute the termination elements. 1) An initial thermal treatment in vacuum facilitates F desorption and it was shown that O-terminations rearranges on the evacuated sites. H2 gas exposure in a controlled environment demonstrated a removal of the remaining O-terminations. As a result, termination-free MXene is possible to realize under vacuum conditions. 2) CO2 was introduced as a first non-inherent termination on MXene by in situ CO2 gas exposure at low temperatures. That was a first demonstration of Ti3C2TX as promising material for carbon capture. Additionally, O-saturated surfaces were demonstrated after introduction of O2 gas on the F-depleted Ti3C2TX MXene, which is highly relevant for hydrogen evolution reactions where fully O-terminated Ti3C2TX are predicted to improve efficiency. A Lewis acid melt synthesis method was used to realize the first MXene exclusively terminated with Cl. Moreover, this was the first report of a MXene directly synthesised with terminations other than O, OH, and F. Furthermore, we have expanded the space of property tuning by introduction of chemical ordering, by selective etching of Y in an alloyed (Mo2/3Y1/3)2CTX MXene. This either produced chemical ordering with one M (Mo) element and vacancies, or ordering between two M (Mo and Y) elements. This was further reported to significantly increase volumetric capacitance because of the increased number of active sites around vacancies, leading to an increasing charge density. As a final note, the stability of Nb2CTX MXene under ambient conditions was investigated. It was found that the surface Nb adatoms, present after etching, got oxidized over time which resulted in local clustering and effectively degraded the MXene. This work has demonstrated reproducible surface characterization methods for determining termination elements and sites in 2D MXenes, that is ultimately governing MXene properties. Most importantly, we report on a new approach for MXene property tuning as well as contributing to several existing property tuning approaches.

Surface characterization of 2D transition metal carbides (MXenes)

Surface characterization of 2D transition metal carbides (MXenes) PDF Author: Ingemar Persson
Publisher: Linköping University Electronic Press
ISBN: 9176850854
Category :
Languages : en
Pages : 91

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Book Description
Research on two-dimensional (2D) materials is a rapidly growing field owing to the wide range of new interesting properties found in 2D structures that are vastly different from their three-dimensional (3D) analogues. In addition, 2D materials embodies a significant surface area that facilitates a high degree of surface reactions per unit volume or mass, that is imperative in many applications such as catalysis, energy storage, energy conversion, filtration, and single molecule sensing. MXenes constitute a family of 2D materials consisting of transition metal carbides and/or nitrides, which are typically formed after selective etching of their 3D parent MAX phases. The latter, are a family of nanolaminated compounds that typically follow the formula Mn+1AXn (n=1-3), where M is a transition metal, A is a group 13 or 14 element, and X is C and or N. Selective etching by aqueous F- containing acids removes the A layer leaving 2D Mn+1Xn slabs instantly terminated by a mix of O-, OH- and F-groups. The first and most investigated MXene is Ti3C2TX, where TX stands for surface termination, which has shown record properties in a range of applications (eg. electrode in Li-batteries, supercapacitors, sieving membrane, electromagnetic interference shielding, and carbon capture). Adding to that, over 30 different MXenes have been discovered since 2011, exhibiting alternative or superior properties. Most importantly, elegant routes for property design in the MXene family has been demonstrated, by means of either varying the chemistry in the Mn+1Xn compound, by alloying two M elements, or by changing the structure of the MXene by introducing vacancies. The present work has a led to an additional route for post synthesis property tuning in MXenes by manipulation of surface termination elements. This enables a unique toolbox for property tuning which is not available to other 2D materials and is highly beneficial for applications that is dependent on surface reactions. Furthermore, chemical and structural characterization of terminations on single sheets is essential to rule out the influence of intercalants or contamination that is typically present in multilayer MXene samples or thin films. For that purpose, a method for preparing isolated contamination free single sheets of MXene samples for transmission electron microscopy (TEM) characterization was established. In order to determine vacancy and termination sites, atomically resolved scanning (S)TEM imaging and image simulations was carried out. Two main processes were employed to substitute the termination elements. 1) An initial thermal treatment in vacuum facilitates F desorption and it was shown that O-terminations rearranges on the evacuated sites. H2 gas exposure in a controlled environment demonstrated a removal of the remaining O-terminations. As a result, termination-free MXene is possible to realize under vacuum conditions. 2) CO2 was introduced as a first non-inherent termination on MXene by in situ CO2 gas exposure at low temperatures. That was a first demonstration of Ti3C2TX as promising material for carbon capture. Additionally, O-saturated surfaces were demonstrated after introduction of O2 gas on the F-depleted Ti3C2TX MXene, which is highly relevant for hydrogen evolution reactions where fully O-terminated Ti3C2TX are predicted to improve efficiency. A Lewis acid melt synthesis method was used to realize the first MXene exclusively terminated with Cl. Moreover, this was the first report of a MXene directly synthesised with terminations other than O, OH, and F. Furthermore, we have expanded the space of property tuning by introduction of chemical ordering, by selective etching of Y in an alloyed (Mo2/3Y1/3)2CTX MXene. This either produced chemical ordering with one M (Mo) element and vacancies, or ordering between two M (Mo and Y) elements. This was further reported to significantly increase volumetric capacitance because of the increased number of active sites around vacancies, leading to an increasing charge density. As a final note, the stability of Nb2CTX MXene under ambient conditions was investigated. It was found that the surface Nb adatoms, present after etching, got oxidized over time which resulted in local clustering and effectively degraded the MXene. This work has demonstrated reproducible surface characterization methods for determining termination elements and sites in 2D MXenes, that is ultimately governing MXene properties. Most importantly, we report on a new approach for MXene property tuning as well as contributing to several existing property tuning approaches.

Synthesis and transport properties of 2D transition metal carbides (MXenes)

Synthesis and transport properties of 2D transition metal carbides (MXenes) PDF Author: Joseph Halim
Publisher: Linköping University Electronic Press
ISBN: 9176852199
Category :
Languages : en
Pages : 82

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Book Description
Since the isolation and characterization of graphene, there has been a growing interest in 2D materials owing to their unique properties compared to their 3D counterparts. Recently, a family of 2D materials of early transition metal carbides and nitrides, labelled MXenes, has been discovered (Ti2CTz, Ti3C2Tz, Mo2TiC2Tz, Ti3CNTz, Ta4C3Tz, Ti4N3Tz among many others), where T stands for surface-terminating groups (O, OH, and F). MXenes are mostly produced by selectively etching A layers (where A stands for group A elements, mostly groups 13 and 14) from the MAX phases. The latter are a family of layered ternary carbides and/or nitrides and have a general formula of Mn+1AXn (n = 1-3), where M is a transition metal and X is carbon and/or nitrogen. The produced MXenes have a conductive carbide core and a non-conductive O-, OH- and/or F-terminated surface, which allows them to work as electrodes for energy storage applications, such as Li-ion batteries and supercapacitors. Prior to this work, MXenes were produced in the form of flakes of lateral dimension of about 1 to 2 microns; such dimensions and form are not suitable for electronic characterization and applications. I have synthesized various MXenes (Ti3C2Tz, Ti2CTz and Nb2CTz) as epitaxial thin films, a more suitable form for electronic and photonic applications. These films were produced by HF, NH4HF2 or LiF + HCl etching of magnetron sputtered epitaxial Ti3AlC2, Ti2AlC, and Nb2AlC thin films. For transport properties of the Ti-based MXenes, Ti2CTz and Ti3C2Tz, changing n from 1 to 2 resulted in an increase in conductivity but had no effect on the transport mechanism (i.e. both Ti3C2Tx and Ti2CTx were metallic). In order to examine whether the electronic properties of MXenes differ when going from a few layers to a single flake, similar to graphene, the electrical characterization of a single Ti3C2Tz flake with a lateral size of about 10 μm was performed. These measurements, the first for MXene, demonstrated its metallic nature, along with determining the nature of the charge carriers and their mobility. This indicates that Ti3C2Tz is inherently of 2D nature independent of the number of stacked layers, unlike graphene, where the electronic properties change based on the number of stacked layers. Changing the transition metal from Ti to Nb, viz. comparing Ti2CTz and Nb2CTz thin films, the electronic properties and electronic conduction mechanism differ. Ti2CTz showed metallic-like behavior (resistivity increases with increasing temperature) unlike Nb2CTz where the conduction occurs via variable range hopping mechanism (VRH) - where resistivity decreases with increasing temperature. Furthermore, these studies show the synthesis of pure Mo2CTz in the form of single flakes and freestanding films made by filtering Mo2CTz colloidal suspensions. Electronic characterization of free-standing films made from delaminated Mo2CTz flakes was investigated, showing that a VRH mechanism prevails at low temperatures (7 to ≈ 60 K). Upon vacuum annealing, the room temperature, RT, conductivity of Mo2CTx increased by two orders of magnitude. The conduction mechanism was concluded to be VRH most likely dominated by hopping within each flake. Other Mo-based MXenes, Mo2TiC2Tz and Mo2Ti2C3Tz, showed VRH mechanism at low temperature. However, at higher temperatures up to RT, the transport mechanism was not clearly understood. Therefore, a part of this thesis was dedicated to further investigating the transport properties of Mo-based MXenes. This includes Mo2CTz, out-of-plane ordered Mo2TiC2Tz and Mo2Ti2C3Tz, and vacancy ordered Mo1.33CTz. Magneto-transport of free-standing thin films of the Mo-based MXenes were studied, showing that all Mo-based MXenes have two transport regimes: a VRH mechanism at lower temperatures and a thermally activated process at higher temperatures. All Mo-based MXenes except Mo1.33CTz show that the electrical transport is dominated by inter-flake transfer. As for Mo1.33CTz, the primary electrical transport mechanism is more likely to be intra-flake. The synthesis of vacancy ordered MXenes (Mo1.33CTz and W1.33CTz) raised the question of possible introduction of vacancies in all MXenes. Vacancy ordered MXenes are produced by selective etching of Al and (Sc or Y) atoms from the parent 3D MAX phases, such as (Mo2/3Sc1/3)2AlC, with in-plane chemical ordering of Mo and Sc. However, not all quaternary parent MAX phases form the in-plane chemical ordering of the two M metals; thus the synthesis of the vacancy-ordered MXenes is restricted to a very limited number of MAX phases. I present a new method to obtain MXene flakes with disordered vacancies that may be generalized to all quaternary MAX phases. As proof of concept, I chose Nb-C MXene, as this 2D material has shown promise in several applications, including energy storage, photothermal cell ablation and photocatalysts for hydrogen evolution. Starting from synthetizing (Nb2/3Sc1/3)2AlC quaternary solid solution and etching both the Sc and Al atoms resulted in Nb1.33C material with a large number of vacancies and vacancy clusters. This method may be applicable to other quaternary or higher MAX phases wherein one of the transition metals is more reactive than the other, and it could be of vital importance in applications such as catalysis and energy storage.

2D Metal Carbides and Nitrides (MXenes)

2D Metal Carbides and Nitrides (MXenes) PDF Author: Babak Anasori
Publisher: Springer Nature
ISBN: 3030190269
Category : Technology & Engineering
Languages : en
Pages : 530

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Book Description
This book describes the rapidly expanding field of two-dimensional (2D) transition metal carbides and nitrides (MXenes). It covers fundamental knowledge on synthesis, structure, and properties of these new materials, and a description of their processing, scale-up and emerging applications. The ways in which the quickly expanding family of MXenes can outperform other novel nanomaterials in a variety of applications, spanning from energy storage and conversion to electronics; from water science to transportation; and in defense and medical applications, are discussed in detail.

MXenes and their Composites

MXenes and their Composites PDF Author: Kishor Kumar Sadasivuni
Publisher: Elsevier
ISBN: 0128225866
Category : Technology & Engineering
Languages : en
Pages : 796

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Book Description
MXenes and their Composites: Synthesis, Properties and Potential Applications presents a state of the art overview of the recent developments on the synthesis, functionalization, properties and emerging applications of two-dimensional (2D) MXenes and their composites.The book systematically describes the state-of-the-art knowledge and fundamentals of MXene synthesis, structure, surface chemistry and functionalization. The book also discusses the unique electronic, optical, mechanical and topological properties of MXenes. Besides, this book covers the various emerging applications of MXenes and their composites across different fields such as energy storage and conversion, gas sensing and biosensing, rechargeable lithium and sodium-ion batteries, lithium-sulphur and multivalent batteries, electromagnetic interference shielding, hybrid capacitors and supercapacitors, hydrogen storage, catalysis and photoelectrocatalysis, gas separation and water desalination, environmental remediation and medical and biomedical applications. All these applications have been efficiently discussed in the specific chapters and in each case, the processing of MXene composites has also been discussed.This book will be an excellent reference for scientists and engineers across various disciplines and industries working in the field of highly promising 2D MXenes and their composites. The book will also act as a guide for academic researchers, material scientists, and advanced students in investigating the new applications of 2D MXenes based materials. - Covers fundamentals of technologically important MAX phases, MXene derivatives, MXene synthesis methods, intercalation and delamination strategies, surface functionalization, fundamental characteristics and properties - Demonstrates major application areas of MXenes, including catalytic, energy storage and energy generation, flexible electronics, EMI shielding, sensors and biosensors, medical and biomedical, gas separation and water desalination - Presents a detailed discussion on the processing and performance of various MXenes towards different applications

Metal and Ceramic Matrix Composites

Metal and Ceramic Matrix Composites PDF Author: Brian Cantor
Publisher: CRC Press
ISBN: 1420033972
Category : Science
Languages : en
Pages : 432

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Book Description
With contributions from leading experts in their respective fields, Metal and Ceramic Matrix Composites provides a comprehensive overview of topics on specific materials and trends. It is a subject regularly included as a final year option in materials science courses and is also of much industrial and academic interest. The book begins wit

MAX Phases

MAX Phases PDF Author: Michel W. Barsoum
Publisher: John Wiley & Sons
ISBN: 3527654607
Category : Technology & Engineering
Languages : en
Pages : 436

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Book Description
In this comprehensive yet compact monograph, Michel W. Barsoum, one of the pioneers in the field and the leading figure in MAX phase research, summarizes and explains, from both an experimental and a theoretical viewpoint, all the features that are necessary to understand and apply these new materials. The book covers elastic, electrical, thermal, chemical and mechanical properties in different temperature regimes. By bringing together, in a unifi ed, self-contained manner, all the information on MAX phases hitherto only found scattered in the journal literature, this one-stop resource offers researchers and developers alike an insight into these fascinating materials.

Layered 2D Materials and Their Allied Applications

Layered 2D Materials and Their Allied Applications PDF Author: Inamuddin
Publisher: John Wiley & Sons
ISBN: 1119654963
Category : Technology & Engineering
Languages : en
Pages : 400

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Book Description
Ever since the discovery of graphene, two-dimensional layered materials (2DLMs) have been the central tool of the materials research community. The reason behind their importance is their superlative and unique electronic, optical, physical, chemical and mechanical properties in layered form rather than in bulk form. The 2DLMs have been applied to electronics, catalysis, energy, environment, and biomedical applications. The following topics are discussed in the book’s fifteen chapters: • The research status of the 2D metal-organic frameworks and the different techniques used to synthesize them. • 2D black phosphorus (BP) and its practical application in various fields. • Reviews the synthesis methods of MXenes and provides a detailed discussion of their structural characterization and physical, electrochemical and optical properties, as well as applications in catalysis, energy storage, environmental management, biomedicine, and gas sensing. • The carbon-based materials and their potential applications via the photocatalytic process using visible light irradiation. • 2D materials like graphene, TMDCs, few-layer phosphorene, MXene in layered form and their heterostructures. • The structure and applications of 2D perovskites. • The physical parameters of pristine layered materials, ZnO, transition metal dichalcogenides, and heterostructures of layered materials are discussed. • The coupling of graphitic carbon nitride with various metal sulfides and oxides to form efficient heterojunction for water purification. • The structural features, synthetic methods, properties, and different applications and properties of 2D zeolites. • The methods for synthesizing 2D hollow nanostructures are featured and their structural aspects and potential in medical and non-medical applications. • The characteristics and structural aspects of 2D layered double hydroxides (LDHs) and the various synthesis methods and role of LDH in non-medical applications as adsorbent, sensor, catalyst, etc. • The synthesis of graphene-based 2D layered materials synthesized by using top-down and bottom-up approaches where the main emphasis is on the hot-filament thermal chemical vapor deposition (HFTCVD) method. • The different properties of 2D h-BN and borophene and the various methods being used for the synthesis of 2D h-BN, along with their growth mechanism and transfer techniques. • The physical properties and current progress of various transition metal dichalcogenides (TMDC) based on photoactive materials for photoelectrochemical (PEC) hydrogen evolution reaction. • The state-of-the-art of 2D layered materials and associated devices, such as electronic, biosensing, optoelectronic, and energy storage applications.

Tribology of Graphene

Tribology of Graphene PDF Author: Oleksiy V. Penkov
Publisher: Elsevier
ISBN: 0128187387
Category : Technology & Engineering
Languages : en
Pages : 268

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Book Description
Tribology of Graphene: Simulation Methods, Preparation Methods, and Their Applications provides an exhaustive reference guide on the tribology of graphene-based materials. The book begins with a discussion on the selection of the proper graphene-based material and then segues into how to choose a deposition method, how to control of its structure and properties, and the most effective working conditions and applications. The latest developments in theoretical simulations of graphene friction, preparation methods, and effective applications are all reviewed, as are the ways various graphene coatings can be successfully employed to decrease friction and wear in nano-, micro- and macro-mechanical applications. - Synthesizes the broad current research in tribological applications of graphene all in one place - Covers theoretical simulations and preparation methods, including insights on how to put them into practice, allowing for quicker and more effective selection of graphene-based material - Provides a broader perspective by discussing both graphene-based composites and additives

Fundamentals of Ceramics

Fundamentals of Ceramics PDF Author: Michel Barsoum
Publisher: CRC Press
ISBN: 9780750309028
Category : Technology & Engineering
Languages : en
Pages : 642

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Book Description
Updated and improved, this revised edition of Michel Barsoum's classic text Fundamentals of Ceramics presents readers with an exceptionally clear and comprehensive introduction to ceramic science. Barsoum offers introductory coverage of ceramics, their structures, and properties, with a distinct emphasis on solid state physics and chemistry. Key equations are derived from first principles to ensure a thorough understanding of the concepts involved. The book divides naturally into two parts. Chapters 1 to 9 consider bonding in ceramics and their resultant physical structures, and the electrical, thermal, and other properties that are dependent on bonding type. The second part (Chapters 11 to 16) deals with those factors that are determined by microstructure, such as fracture and fatigue, and thermal, dielectric, magnetic, and optical properties. Linking the two sections is Chapter 10, which describes sintering, grain growth, and the development of microstructure. Fundamentals of Ceramics is ideally suited to senior undergraduate and graduate students of materials science and engineering and related subjects.

MXene-Based Photocatalysts

MXene-Based Photocatalysts PDF Author: Zuzeng Qin
Publisher: CRC Press
ISBN: 1000541304
Category : Technology & Engineering
Languages : en
Pages : 179

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Book Description
MXene, a two-dimensional (2D) transition metal carbide, nitride, and carbonitride, was discovered in 2011. MXene has great potential as a cocatalyst in the field of photocatalysis due to its unique properties and structure. MXene-Based Photocatalysts: Fabrication and Applications introduces readers to the fundamentals, preparation, microstructure characterization, and a variety of applications of MXene-based photocatalysts. The book is a comprehensive reference for MXene materials and provides an overview of the current literature on MXene-based photocatalysts. FEATURES Discusses preparation methods of MXenes Describes the morphology and microstructure of MXenes Offers strategies for fabricating MXene-based photocatalysts Details the reaction mechanism of MXene-based photocatalysts Covers applications in photocatalytic water-splitting, photocatalytic CO2 reduction, photocatalytic degradation, photocatalytic nitrogen fixation, and photocatalytic H2O2 production This book serves as an invaluable guide for advanced students, industry professionals, professors, and researchers in the field of materials science and engineering, photocatalysis, energy, and environmental applications.