Graphdiyne E-Book
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- Sprache: Englisch
Graphdiyne
Discover the most cutting-edge developments in the study of graphdiyne from a pioneer of the field
In Graphdiyne: Fundamentals and Applications in Renewable Energy and Electronics, accomplished chemist Dr. Yuliang Li delivers a practical and insightful compilation of theoretical and experimental developments in the study of graphdiyne. Of interest to both academics and industrial researchers in the fields of nanoscience, organic chemistry, carbon science, and renewable energies, the book systematically summarizes recent research into the exciting new material.
Discover information about the properties of graphdiyne through theoretical simulations and experimental characterizations, as well as the development of graphdiyne with appropriate preparation technology. Learn to create new graphdiyne-based materials and better understand its intrinsic properties. Find out about synthetic methodologies, the controlled growth of aggregated state structures, and structural characterization.
In addition to demonstrating the interdisciplinary potential and relevance of graphdiyne, the book also offers readers:
- A thorough introduction to basic structure and band gap engineering, including molecular and electronic structure, mechanical properties, and the layers structure of bulk graphdiyne
- Explorations of Graphdiyne synthesis and characterization, including films, nanotube arrays and nanowires, nanowalls, and nanosheets, as well as characterization methods
- Discussions of the functionalization of graphdiyne, including heteroatom doping, metal decoration, and absorption of guest molecules
- Rigorous treatments of Graphdiyne-based materials in catalytic applications, including photo- and electrocatalysts
Perfect for organic chemists, electronics engineers, materials scientists, and physicists, Graphdiyne: Fundamentals and Applications in Renewable Energy and Electronics will also find its place on the bookshelves of surface and solid-state chemists, electrochemists, and catalytic chemists seeking a one-stop reference on this rising-star carbon material.
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Veröffentlichungsjahr: 2021
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Table of Contents
Cover
Title Page
Copyright
Preface
1 Introduction
1.1 The Development of Carbon Materials
1.2 Models and Nomenclature
1.3 Brief Introduction of Graphdiyne
References
2 Basic Structure and Band Gap Engineering: Theoretical Study of GDYs
2.1 Structures
2.2 Electronic Structures
2.3 Mechanical Properties
2.4 Layers Structure of Bulk GDYs
2.5 Band Gap Engineering of GDYs
References
3 GDY Synthesis and Characterization
3.1 Synthesis
3.2 Characterization
3.3 Summary
References
4 Functionalization of GDYs
4.1 Heteroatom Doping
4.2 Metal Decoration
4.3 Absorption of Guest Molecules
References
5 Graphdiyne‐Based Materials in Catalytic Applications
5.1 Graphdiyne‐Based Zero‐Valent Metal Atomic Catalysts
5.2 GDY‐Based Heterojunction Catalysts
5.3 Graphdiyne‐Based Metal‐Free Catalysts
References
6 Graphdiyne‐Based Materials in Rechargeable Batteries Applications
6.1 Introduction
6.2 Lithium‐Ion Battery Anodes
6.3 Graphdiyne Derivatives for LIB Anodes
6.4 Sodium Ion Battery Anodes
6.5 Electrochemical Interface
6.6 Lithium–Sulfur Battery
6.7 Lithium Metal Anodes
6.8 Supercapacitor Electrodes
6.9 Fuel Cells
References
7 Graphdiyne‐Based Materials in Solar Cells Applications
7.1 Perovskite Solar Cells
7.2 Organic Solar Cells
7.3 Others
7.4 Future Perspectives
References
8 Graphdiyne: Electronics, Thermoelectrics, and Magnetism Applications
8.1 Electronic Devices
8.2 Optic Devices
8.3 Thermoelectric Materials
8.4 Magnetism
References
9 Graphdiyne‐Based Materials in Sensors and Separation Applications
9.1 Sensors
9.2 Separation
9.3 Conclusion and Perspective
References
10 Perspectives
10.1 Chemical Synthesis Methodology and Aggregate Structures of Graphdiyne
10.2 Controllable Preparation of Highly Ordered Graphdiyne
10.3 Fundamental Physical Properties and Applications of Graphdiyne
Index
End User License Agreement
List of Tables
Chapter 2
Table 2.1 Cohesive energies and geometric parameters. Lattice constants and ...
Table 2.2 Calculated band gap, effective mass (
m
h
* and
m
e
*), DP constants fo...
Table 2.3 Fracture stresses, strains, and Young's moduli of graphynes and gr...
Table 2.4 Summary of calculated mechanical properties for extended graphynes...
Table 2.5 Fracture stresses and strains of graphynes and graphene with and w...
Table 2.6 Calculated results for TM‐GDY/GY.
Table 2.7 Calculated bandgap and position of valence band maximum (VBM) and ...
Table 2.8 Summary of calculatedband gaps (in eV) for graphyne sheet and its ...
Chapter 8
Table 8.1 NLO parameters of 2D GDY at different wavelengths.
List of Illustrations
Chapter 1
Figure 1.1 The development of carbon materials.
Figure 1.2 Schematic structures of graphene, carbyne, and graphynes, which c...
Figure 1.3 Structural motifs of some 2D carbon networks:
1.1
: pentaheptites ...
Figure 1.4 Ideal atomic models [10] of possible graphynes (GY1–GY7). The thr...
Figure 1.5 Some possible atomic motifs of graphyne‐like structures, which ar...
Figure 1.6 Graphdiyne with special properties and the related potential appl...
Chapter 2
Figure 2.1 (a) A mixed‐carbon configuration, which is classified as sp
h
(1 <...
Figure 2.2 (a) α‐, (b) β‐, and (c) γ‐graphyne structures with the armchair e...
Figure 2.3 Structures of (a) α‐, (b) β‐, and (c) 6,6,12‐graphyne. Dirac cone...
Figure 2.4 Schematic representation of unit cell defined by the vectors
X
1
a...
Figure 2.5 (a) Geometrical structure (red diamond dashed) and first Brilloui...
Figure 2.6 Band structures and total density of states (DOS) for (a) α‐, (b)...
Figure 2.7 (a) Schematic representation of three GDNRs: (I) an armchair‐like...
Figure 2.8 Γ‐point HOMO (a) and LUMO (b) for the GDNRs with armchair edge (A...
Figure 2.9 The graphene and graphyne nanotubes with zigzag and armchair edge...
Figure 2.10 Band structures for the stretched (top panel) and compressed (bo...
Figure 2.11 Current voltage characteristics for (a) transport on the
X
1
dire...
Figure 2.12 (a) Energy curves of uniaxial strains on y‐axis maintaining
ɛ
...
Figure 2.13 Schematic and stress–strain results of uniaxial tension tests in...
Figure 2.14 Atomic corrugated configurations of GyNRs with a width of
n
= 2 ...
Figure 2.15 Evolution of lattice fracture of graphdiyne film: (a) initial st...
Figure 2.16 (a) Representative stress–strain response for graphdiyne (
n
= 2)...
Figure 2.17 (a) A 10 nm × 10 nm
γ
‐graphyne sheet, along with the defini...
Figure 2.18 Fracture mechanics of graphynes. (a) Stress–strain results for e...
Figure 2.19 (a) In‐plane linear thermal expansion coefficient of graphyne, (...
Figure 2.20 (a–f) Six different stacking configurations for bilayer α‐graphy...
Figure 2.21 (a–f) Band structures near the
K
point (
K
x
,
K
y
) for different st...
Figure 2.22 (a) Illustration of the Gyne/Gyne bilayers with different stacki...
Figure 2.23 (a) Geometrical structures of AB‐1, AB‐2, and AB‐3 stacked graph...
Figure 2.24 Two possible configurations of graphdiyne bilayers from top view...
Figure 2.25 (a–c)
Scanning electron microscopy
(
SEM
) image,
high resolution
...
Figure 2.26 Band structures of (a) pristine and N‐doped γ‐graphyne with (b) ...
Figure 2.27 Band structures of (a) pristine and B‐doped γ‐graphyne with (b) ...
Figure 2.28 (a) Optimized structure of BN pair codoped graphyne (BN‐yne). Th...
Figure 2.29 The band structures of (a) pristine GDY, (b) 2BN‐GDY, (c) 4BN‐GD...
Figure 2.30 Atomic structures of hydrogen or halogen atoms adsorbed graphyne...
Figure 2.31 Atomic structures of hydrogen and halogen atoms adsorbed graphyn...
Figure 2.32 (a) Geometry structure of γ‐graphyne.
a
a
and
a
z
are the lattice ...
Figure 2.33 Schematic structures of graphdiyne (a) under a symmetrical biaxi...
Figure 2.34 (a) Geometric structure of γ‐graphyne sheet where the primitive ...
Figure 2.35 (a) Schematic representation of graphyne nanoribbons with armcha...
Chapter 3
Scheme 3.1 Cu‐Mediated coupling reaction toward GDY synthesis. (a) Glaser co...
Figure 3.1 (a) Synthesis and structures of precursor HEB and GDY, (b) scanni...
Figure 3.2 (a) Schematic presentation of the synthesis process of GDY nanowa...
Figure 3.3 (a) Schematic illustration of the GDY‐grown Cu foam and its SEM i...
Figure 3.4 (a) The introduction of π–π/CH–π interactions for controlling the...
Figure 3.5 (a) Synthetic route of H‐GDY, Me‐GDY, and CN‐GDY, (b) magnified S...
Figure 3.6 (a) Schematic of large‐scale CEY synthesis [35]. (i) Synthesis of...
Figure 3.7 (a) Formation of the 2D TzF at the flat Cu interface via Cu‐media...
Figure 3.8 (a) Illustration of the synthetic strategy of PTEB nanofibers on ...
Figure 3.9 (a) Schematic illustration of the synthesis of 2D fluorescent fil...
Figure 3.10 (a) Synthetic scheme with the molecular structure of TEP and PDY...
Figure 3.11 Synthesized benzannellated, and perethynylated dehydroannulene‐d...
Figure 3.12 (a−c) Large‐scale STM images of the formation of molecular chain...
Figure 3.13 (A) The stepwise intermolecular and intramolecular Glaser–Hay co...
Figure 3.14 (a) The process to fabricate GDY nanotube arrays, (b–d) SEM and ...
Figure 3.15 Synthesis of GDY nanowalls on arbitrary substrates via Cu envelo...
Figure 3.16 Representation of GDY and analogues in situ growth on carbon clo...
Figure 3.17 Synthetic process of single‐crystalline GDY on graphene film. (a...
Figure 3.18 (a) Schematic illustration of the in situ synthesis of GDY patte...
Figure 3.19 Interfacial synthesis of GDY. (a) The liquid/liquid interfacial ...
Figure 3.20 Interfacial synthesis of GDY analogues. (a) N‐GDYs, (b) CN‐GDY, ...
Figure 3.21 (a, b) Illustration of the growth process of GDY film on ZnO nan...
Figure 3.22 (a) Experimental setup of the CVD system for the growth of linke...
Figure 3.23 Illustrations of the explosion approach preparation processes. (...
Figure 3.24 Raman spectra and vibrational modes of GDY. (a) Predicted Raman ...
Figure 3.25 Raman spectra of GDY. (a) Raman spectra of GDY films on Cu foil ...
Figure 3.26 XPS spectra of GDY. (a) Elements survey scan, (b) High‐resolutio...
Figure 3.27 Comparison of C K‐edge XANES spectra of GDY‐1w and GDY‐3m normal...
Figure 3.28 Direct imaging of the crystal structure of a GDY nanosheet, (a) ...
Figure 3.29 (a) HRTEM image of multilayer GDY films, (b) SAED pattern of the...
Figure 3.30 (a) XRD pattern of GDY film, (b) 2D GIWAXS pattern of few‐layer ...
Chapter 4
Figure 4.1 Heteroatom doping of GDY.
Figure 4.2 Nitrogen‐doped GDY prepared through (a) thermal annealing, (b) so...
Figure 4.3 Doping of the sp‐hybridized nitrogen to GDY.
Figure 4.4 Phosphor doping of GDY.
Figure 4.5 (a) Preparation of F‐GDY; (b) F1s‐XPS spectrum to characterize th...
Figure 4.6 (a) Preparation of Cl‐GDY. (b) The theoretical analysis of Li sto...
Figure 4.7 (a) Preparation of S‐GDY with as BDS as sulfur source. (b) The ap...
Figure 4.8 (a) Preparation of B‐GDY. (b) Atomic structure of C12B2 B‐GDY. (c...
Figure 4.9 (a) Preparation of HGDY through bottom‐up method; (b) the images ...
Figure 4.10 GDY oxide used as (a) catalyst supporter for Pd clusters. (b) Aq...
Figure 4.11 Dual heteroatom doping GDY: (a) hydrogen and nitrogen. (b) Hydro...
Figure 4.12 Anchoring the single Ni and Fe atom to the GDY.
Figure 4.13 The energy‐level illustration of TiO
2
@GDY composite.
Figure 4.14 Preparing MoS
2
@GDY composite.
Figure 4.15 Electron densities GDY‐adsorbed guest molecules.
Chapter 5
Figure 5.1 Protocols for the synthesis of Ni
0
/GDY and Fe
0
/GDY. A two‐step st...
Figure 5.2 (a) Possible adsorption sites for Ni/Fe atoms between GDY layers ...
Figure 5.3 HAADF images of (a–d) Ni
0
/GDY, (e–h) Fe
0
/GDY, (i, j, m, and n) Pd
Figure 5.4 Ex situ EXAFS spectra of (a) Ni/GD and Ni foil at the Ni K‐edge, ...
Figure 5.5 (a) Ex situ EXAFS and (b) the normalized XANES spectra at the Ni ...
Figure 5.6 (a) The 3d orbital energies for the targeted Ni site in (a) NiO, ...
Figure 5.7 HER activities and stabilities of Ni
0
/GDY and Fe
0
/GDY. (a) Polari...
Figure 5.8 (a) Synthesis and structural configuration evolution of catalysis...
Figure 5.9 (a) Schematic of the synthesis (central green circle) and resuabi...
Figure 5.10 (a) Schematic illustration of the synthesis of GDY/G heterostruc...
Figure 5.11 (a) Illustration showing different hydrogenation processes of ph...
Figure 5.12 (a) Fabrication process of the Cu@GD NA/CF, including enlarged m...
Figure 5.13 (a) Schematic illustration of the hydrogen production on eGDY/MD...
Figure 5.14 (a) Schematic representation of the synthetic strategy for the p...
Figure 5.15 (a) Schematic diagram of the PEC cell, consisting of the assembl...
Figure 5.16 (a) Preparation of CdS/GD composite and its photocatalytic proce...
Figure 5.17 (a) Schematic illustration of the fabrication process of the NiC...
Figure 5.18 (a) Comparison of CoAl‐LDH (CO
3
2−
) assembled hydrophobic a...
Figure 5.19 Electrocatalytic performance of e‐ICLDH@GDY/NF. (a) OER CV curve...
Figure 5.20 (a) Schematic of the synthesis of CoN
x
@GDY NS/NF via an in‐site ...
Figure 5.21 SEM images of (a) micropyramidal structure of silicon, (b) silic...
Figure 5.22 (A) Schematic representation of the Ag
3
PO
4
/GDY‐based emulsion fo...
Figure 5.23 (a) Schematic representation of the OWS process of e‐ICLDH@GDY/N...
Figure 5.24 SEM images of (a) BiVO
4
and (b) the as‐prepared GDY/BiVO
4
. (c) E...
Figure 5.25 (a) Preparation of the Pd/Pyr‐GDY composite and its catalytic re...
Figure 5.26 (a) Formation of MG/GDY nanosheets: (i) sp–sp
2
‐hybridized carbon...
Figure 5.27 (a) Schematic of the structure of FGDY. (b) The photograph of th...
Figure 5.28 (a) Two‐dimensional TEM image of
boron‐doped graphdiyne
(
B
...
Figure 5.29 (a) Schematic illustration of the preparation process for the hy...
Figure 5.30 Proposed structure of (a) N1‐GDY, (b) N2‐GDY, and (c) N3‐GDY; Ex...
Figure 5.31 (a) Photocurrent response spectrum of g‐C
3
N
4
/GDY photoelectrode;...
Chapter 6
Figure 6.1 (a) Structural character of the precursors for the graphdiyne der...
Figure 6.2 Performance of graphdiyne anode in LIB. (a) Morphology of the gra...
Figure 6.3 (a) Structure of graphdiyne; (b) SEM and (c, d) TEM images of gra...
Figure 6.4 SEM images of graphdiyne film treated at different temperatures: ...
Figure 6.5 Morphologies of graphdiyne nanowall: (a–c) Top view of graphdiyne...
Figure 6.6 Morphologies of the ultrathin graphdiyne catalyzed by the Cu nano...
Figure 6.7 (a–d) SEM images and (e) nitrogen adsorption–desorption isotherms...
Figure 6.8 (a–d) SEM images of samples; (e) Scheme showing the N‐doping of g...
Figure 6.9 Schematic illustrations of the possible metallization/demetalliza...
Figure 6.10 The electrochemical performance of
H‐graphdiyne
(
H‐GDY
...
Figure 6.11 Electrochemical performance of Cl‐graphdiyne in half‐cell testin...
Figure 6.12 The interaction between Li atom and F‐graphdiyne. (a) The ex sit...
Figure 6.13 (a) Structure of N‐doped graphdiyne with well‐defined N‐configur...
Figure 6.14 (a) Schematic representation and photo of a carbon ene‐yne‐based...
Figure 6.15 (a) Formation of polytetraethynylmethane via the Eglinton coupli...
Figure 6.16 (a) In situ Raman spectra during the first discharge process; (b...
Figure 6.17 (a) Calculated binding energies at five storage sites. (b) The g...
Figure 6.18 The application potential of graphdiyne in constructing the inte...
Figure 6.19 Electrochemical performance of the freestanding silicon anode. (...
Figure 6.20 (a–c) Schematic illustration of the preparation of large‐scale s...
Figure 6.21 Schematic illustrations showing (a) the pulverization of the bar...
Figure 6.22 (a) Top and (b) side views of the heterostructure between graphd...
Figure 6.23 (a) Advantages and the disadvantages of organic‐based cathodes f...
Figure 6.24 Morphological characterization of electrodes before and after in...
Figure 6.25 (a) Schematic representation of the preparation of Nafion@graphd...
Figure 6.26 (a) Schematic illustration of the
H‐graphdiyne
(
HsGY
) elec...
Figure 6.27 Characterization of graphdiyne film. (a) Photograph of large‐sca...
Figure 6.28 Possible mechanism for suppressing lithium dendrites. (a) The di...
Figure 6.29 (a–c) Coulombic efficiency of
copper nanowire
(
CuNW
) electrode w...
Figure 6.30 Electrochemical performance of capacitor based on graphdiyne. (a...
Figure 6.31 Supercapacitor performance based on N‐doped graphdiyne electrode...
Figure 6.32 SEM images of the graphdiyne nanostructures on the nickel foam: ...
Figure 6.33 (a, b) Morphologies of the MnO
2
@
graphdiyne oxide
(
GDYO
); (c) CV ...
Figure 6.34 (a–d) Molecular structures of the graphyne with different side l...
Figure 6.35 (a) Typical quantum configuration of trans‐membrane H
5
O
2
+
co...
Figure 6.36 (a–c) Possible interaction between Nafion on NH
2
‐GDY; (d, e) the...
Chapter 7
Figure 7.1 Quantitative statistics of research interests in solar cells as o...
Figure 7.2 (a) Mesoporous n–i–p structure. (b) Planar n–i–p structure. (c) P...
Figure 7.3 (a) Device architecture of perovskite solar cell and chemical str...
Figure 7.4 (a) Device structure of the photovoltaic device with GDY doped el...
Figure 7.5 (a) Molecule structures of PCBSD and graphdiyne and schematic ill...
Figure 7.6 Characterization of GDY and GDY–SnO
2
ETLs. (a) TEM image and clos...
Figure 7.7 (a) Preparation route and photograph of ClGD–PCBM solution. (b) S...
Figure 7.8 (a) Schematic diagram of perovskite solar cells with P3HT hole tr...
Figure 7.9 (a) In situ contact potential difference (CPD) of perovskite (PSK...
Figure 7.10 XPS spectra of Pb 4f in (a) PbI
2
, PbI
2
(GDY) and (b) perovskite....
Figure 7.11 (a) Device structure and (b) cross‐sectional SEM image of the pl...
Figure 7.12 Quantum transport structure for (a) the GDY/PbI
2
and (b) the GDY...
Figure 7.13 (a) SEM, (b) AFM, (c, d)
High‐resolution transmission electron m
...
Figure 7.14 (a) Schematic illustration of GDY quantum dots (QDs). (b) Device...
Figure 7.15 Introduction to OSCs. (a) Cross‐section of the conceptual device...
Figure 7.16 Chemical structure of (a) P3HT, (b) PCBM, and (c) GDY, and (d) c...
Figure 7.17 (a) XPS spectra of Zn 2p
3/2
and (b) O 1s in ZnO and GDZO. (c) Th...
Figure 7.18 Chemical structures of (a) PM6, (b) Y6, (c) GCl. UV–Vis spectra ...
Figure 7.19 AFM height images of PM6:Y6 blend films with (a) CN and (b) GCl,...
Figure 7.20 Device architecture of GCl‐containing organic solar cells and ce...
Figure 7.21 (a) Schematic illustration of the PbS CQD solar cells with GDY a...
Figure 7.22 (a) Mayer bond‐order analysis and maps of localized orbital loca...
Chapter 8
Figure 8.1 (a) Structure of GDY and its first Brillouin zone. (b) Band struc...
Figure 8.2 (a) Schematic representation of the GDY transistor. (b) Optical m...
Figure 8.3 (a) Schematic diagram of electric field temperature regulated GTF...
Figure 8.4 (a) Schematic of a GDY‐based FET device with an ionic liquid diel...
Figure 8.5 (a) Chemical structures of GDY and PFC. (b) Schematic illustratio...
Figure 8.6 (a) Illustration of the preparation process of GDY nanowalls. (b)...
Figure 8.7 Nonlinear optical responses of 2D GDY to fs pulses. (a) Open‐aper...
Figure 8.8 (a–f) Mode‐locked pulse output performance of the GDY–PVP nanocom...
Figure 8.9 (a) The experimental setup for the proposed graphdiyne/SnS
2
‐based...
Figure 8.10 (a–c) Random laser performance of GDY nanosheets. The typical em...
Figure 8.11 (a) Schematic diagram of the device based on s‐SWNTs and GDY. (b...
Figure 8.12 (a) GDY powders and (b) the as‐prepared GDY nanosheets. SEM imag...
Figure 8.13 (a) Schematic illustration of the preparation route of nanocompo...
Figure 8.14 (a) Fabrication process for the TiO
2
:GDY nanocomposites. (b)
I
‐
V
Figure 8.15 The room temperature (a) Seebeck coefficient
S
, (b) electrical c...
Figure 8.16 (a) Magnetic moment
ΔM
(after subtracting linear diamagneti...
Figure 8.17 (a) Magnetic moment Δ
M
(after subtracting linear diamagnetic bac...
Figure 8.18 Typical
χ
−1
(
T
) curves of (a) HsGDY, (b) FsGDY, and (...
Chapter 9
Figure 9.1 (a) Schematic illustration of the GDY‐based fluorometric DNA assa...
Figure 9.2 (A) Schematic illustration of PEC biosensor based on AuNPs‐GDY mo...
Figure 9.3 (a) Top and side views of HCHO adsorbed on GDY sheet. (b) Top and...
Figure 9.4 Adsorption process of VOCs mixtures on (a) C
2
N monolayer, (b) GDY...
Figure 9.5 (a)
Cyclic voltammetry
(
CV
s) of the PB/GDYO‐modified
glassy carbo
...
Figure 9.6 Geometry structure of (a) graphdiyne, (b) graphyne, (c) rhombic‐g...
Figure 9.7 (a) Minimum energy pathway for H
2
, CO, and CH
4
diffusion through ...
Figure 9.8 (a) Schematic illustration of graphdiyne for separating oxygen fr...
Figure 9.9 (a) MD‐simulated configurations of the equimolar CO
2
/N
2
/CH
4
gas m...
Figure 9.10 (a) Molecular structures used to study the nanopores of graphdiy...
Figure 9.11 (a) Schematic illustration of fabrication procedure of GDY‐coate...
Guide
Cover Page
Table of Contents
Title Page
Copyright
Preface
Begin Reading
Index
WILEY END USER LICENSE AGREEMENT
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Graphdiyne
Fundamentals and Applications in Renewable Energy and Electronics
Edited byYuliang Li
Editor
Prof. Yuliang Li
Institute of Chemistry
Chinese Academy of Sciences
Zhongguancun North First Street 2
100190 Beijing
P.R. China
Cover Design: Wiley
Cover Image: © LAGUNA DESIGN/Getty Images
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Preface
In 2010, a new carbon allotrope was born, which brought a new member to the family of carbon materials. Its unique chemical and electronic structures provide unlimited space for scientific innovation of scientists. It shows infinite charm and great potential to promote the development of fundamental and applied science. Chinese scientists named the material “Shimoque.” New materials have become one of the keys to break through the bottleneck of science and technology. Inspired by this, many researchers are committed to discover or develop new materials in nontraditional architectures. The hybridization of carbon allotrope with sp‐hybridization is a very interesting research topic, because the acetylenic bond of sp can cause significant changes in the properties of carbon. The sp and sp2 hybrid structures, and its intrinsic properties and performances illustrate that graphdiyne exhibits transformative properties and performances in the fields of catalysis, energy, optoelectronic and intelligent information, and so on.
Graphdiyne (GDY) shows the characteristics of sp‐ and sp2‐hybridized carbon atoms, which are fundamentally different from the sp3 and sp2 hybridization of traditional carbon materials. It is rich in chemical bonds, highly conjugated, superlarge π structures, and has infinitely distributed cavities on the surface. GDY shows also high chemical activity and the functions of chemical reaction, chemical and physical doping, and chemical modification. Due to these exclusive structural features, GDY is expected to be a perfect and peculiar new carbon allotrope. As an important material, if you want to expand its application space, the material must be able to do “chemistry.” GDY represents a great advantage in chemical modification. Several methods have been developed to obtain GDY‐based materials such as invoke strains, B and N‐doping, halogen doping, as‐prepared nanostructures, controllable growth of aggregate structure with different dimensions, and hydrogenation, bromination, and fluorination have been developed for regulating band gap of GDY. As a new kind of carbon material, GDY's chemical and physical properties are of great concern to scientists. Therefore, many studies have focused on its basic properties for understanding the physical and chemical properties of GDY. These fundamental studies provide very important informations for GDY's further basic and applied research. Researchers can truly understand the structural and natural advantages of GDY and its development trend. Early fundamental and applied research gave researchers great confidence, that is, GDY demonstrated excellent and potential performance in catalysts, lithium ion batteries, sodium ion batteries, zinc water batteries, and fuel cells photoelectric conversion, optical devices and electrochemical intelligent and information devices, gas separation, and water purification. The infinite π bond on the GDY surface leads to high surface activity, which can interact with many units of organisms and can be used efficiently in life science–related research. So many biological and life scientists are also actively engaged in the field of research, aiming at toxicity, drug delivery, and therapy.
On the 10th anniversary of GDY discovery, at the invitation of Wiley publishers, we are very happy to write this book, which records the course and achievements of GDY research since 2010, from preliminary research to maturity, from fundamental research to application. The results demonstrate that GDY has strong potential for fundamental and applied researches. Preparation determines the future! In this book, we try to describe GDY‐related theoretical calculations and simulations, chemical and physical models, synthetic methodologies, controlled growth of aggregated state structures, structural characterization, fundamental physical and chemical properties, and GDY applications in many fields. After nearly 10 years of persistent work, scientific researches in different regions have shown that GDY has strong advantages in the fields of energy, catalysis and photoelectricity, electrochemical intelligent devices, and so on. We believe that in the next 10 years, GDY‐based materials should move rapidly toward the route of interdiscipline with different disciplines, and it is possible to show a powerful role in multidisciplinary crossing, and to become a model of cross‐fusion in important fields such as chemistry, physics, information science, material science, and environmental science. GDY demonstrated potential and exciting results, which prompted us to better complete this book and convey graphdiyne's theoretical and practical progress to students, teachers, and practitioners who wish to participate in the exciting development of the subject.
December 2020
Yuliang Li
Beijing
1Introduction
Yongjun Li and Yuliang Li
Institute of Chemistry, Chinese Academy of Sciences, Zhongguancun North First Street 2, 100190, Beijing, PR China
1.1 The Development of Carbon Materials
The pursuit of new materials with nontraditional architecture is one of the hot spots in current research [1–3]. Carbon‐based nanomaterials (such as fullerenes, carbon nanotubes, and graphene) have attracted much attention due to their special structures and chemical and physical properties [4–7]. Carbon materials have experienced a long history of development. The contact of carbon materials with humans can be traced back to the earliest appearance of humans on the earth.
The first known existence of carbon was charcoal and soot. Diamond is a famous allotype of carbon, which was discovered by humans as early as 4000 BCE. Graphite is the most widely used allotrope of carbon and was found in the sixteenth century. Although carbon is one of the oldest elements, it is surprising that it constantly shows great vitality for the discovery of new allotropes (Figure 1.1), such as fullerene (1985), carbon nanotubes (1991), graphene (2004), and graphdiyne (GDY) (2010). The application of carbon materials can even be considered to promote the progress of human society and the development of other materials. In fact, the unique valence bond hybrid forms of carbon molecules, namely sp, sp2, and sp3, ensure that carbon allotropes can be constructed in various possible forms and exhibit different intrinsic properties. Diamond is composed of sp3‐hybridized carbon, while graphite, fullerene, carbon nanotubes, and graphene are composed of sp2‐hybridized carbon. sp2 hybrid carbon can enhance the conjugation of materials and exhibit good electrical conductivity, while sp3 hybrid carbon has three‐dimensional (3D) spatial configuration in carbon materials, which can further improve the rigidity of related materials. The sp hybrid carbon has a linear structure, which can improve the porosity and provide enough active or storage sites for other atoms. At present, the reasonable design of carbon materials and the full use of the advantages of the three hybrid carbon materials are of great significance in many research fields.
An interesting family of carbon allotropes is represented by the so‐called graphynes (GYs) and GDYs. In general, these allotropes are flat one‐atom‐thin carbon networks (such as graphene), which can be constructed by replacing some;CC bonds in graphene by uniformly distributed acetylenic bonds C≡C (graphynes) or diacetylenic bonds C≡CC≡C (GDYs). In both cases, the resulting network consists of two nonequivalent types of carbon atoms: threefold coordinated sp2‐hybridized atom and twofold coordinated sp‐hybridized atom. In this context, these flat carbon networks can be regarded as the “intermediate” (sp2 + sp) systems between two famous carbon allotropes: graphene (containing only sp2‐like atoms) and carbyne (containing only sp‐like atoms) [8], see Figure 1.2. We can simply classify these materials according to the number of “C≡C” bonds connecting two adjacent sp2‐hybridized carbon atoms. As shown in Figure 1.2, they are called graphyne, GDY, and graphyne‐n [9].
Figure 1.1 The development of carbon materials.
Figure 1.2 Schematic structures of graphene, carbyne, and graphynes, which comprise exclusively sp‐atoms, sp2‐atoms, and both types: (sp + sp2) atoms, respectively.
The history of systematic study of (sp + sp2) allotrope family began in 1987, when Baughman et al. [10] first proposed the structural model of graphynes and discussed some macrocyclic subunits suitable for creating these networks. Ten years later (1997), the structure of GDY was predicted and many small diacetylene molecules had been synthesized, which had become the “hot” spot of synthetic chemistry for a period of time. These studies started in the mid‐1990s and continued into the new millennium. The chemists began some computational simulation and theoretical studies during this period, and the related materials with different sizes and dimensions [11–16], as well as some of their B–N and B–C–N analogues [15], [17–19] were also experimented by theoretical simulation. On the other hand, the experimental efforts in the synthesis of subunits of these systems were closely related to organic chemistry, that is, new synthetic routes in annulene chemistry [20]. However, research in these areas has not advanced much because of the serious lack of innovation in synthetic methods, leading to the study of the synthesized GDY in the synthesis and properties of some small‐molecule diacetylene. It was in 2010 that the synthesized bottleneck of GDY was broken, and this was a great success. A new allotrope of carbon was born, which opened up a new field for research in carbon materials.
1.2 Models and Nomenclature
In 1968, Balaban et al. first proposed a rich and diverse planar carbon network (consisting of only sp2‐bonded atoms with a threefold coordination) [21]. The search line was actively extended, and then a large number of related two‐dimensional periodic carbon networks were constructed from non‐C6 carbon polygons. For example, so‐called pentaheptites [22], [23] (formed by periodically distributed pentagons C5 and heptagons C7) or haeckelites [24] (including pentagons C5, hexagons C6, and heptagons C7, see Figure 1.3), as well as some other related types of carbon networks, sometimes referred to as graphene allotropes [9], [27–35], were proposed and successfully investigated. Here, the so‐called two‐dimensional supracrystals [25], [36] can also be mentioned, Figure 1.3. These hypothetical low‐stable polycyclic networks are composed of strained cycles such as C3, C4, and C12; therefore, their synthesis seems very suspicious. The recently studied 2D “square carbon” [25] also belongs to this category.
Figure 1.3 Structural motifs of some 2D carbon networks: 1.1: pentaheptites [22], [23], 1.2: haeckelites [24], and 1.3–1.7: some hypothetical so‐called 2D carbon supracrystals – polycyclic networks (based on Kepler's nets) composed of strained cycles such as C3, C4, and C12 [25].
Source: Ivanovskii [26]. © 2013, Elsevier.
Figure 1.4 Ideal atomic models [10] of possible graphynes (GY1–GY7). The threefold coordinated sp2 atoms (forming hexagons, pairs, or as isolated atoms) are marked. On the left: thermal ripples of GY1 network according to molecular dynamics (MD) simulation at T = 300 K [37].
Source: Ivanovskii [26]. © 2013, Elsevier.
Graphynes are a series of stable two‐dimensional crystalline carbon allotropes composed of sp‐ and sp2‐hybridized carbon atoms. Their structural models were first proposed by R. H. Baughman et al. [10]. They have a two‐dimensional structure similar to graphite and contain acetylenic linkages (sp components), referred to as graphyne. Accordingly, sp‐ and sp2‐hybridized carbon atoms can be connected to each other according to certain hybrid rules, producing a variety of 2D structures [26]. Some of such GYs are depicted in Figure 1.4. These (and related) networks fall into four categories: I–IV, see Figure 1.4. Therefore, the structure of group I (GY1) includes hexagons C6, which are connected to each other by C≡C linkages. The two networks (GY2, GY3) of the second family consist of hexagonal C6 and a pair of sp2 atoms (CC bonds), which are interconnected by C≡C linkages. The three networks of group III (GY4–GY6) have no hexagonal C6 and only contain paired sp2 atoms (CC bond). They are connected by C≡Cbonds (GY4, GY5), or by paired sp2 atoms and isolated sp2 atoms (GY6). Finally, the network of group IV (GY7) consists of isolated sp2 atoms, which are connected to each other by C≡C linkages. This network (so‐called supergraphene) can be seen as a graphene‐like structure, in which all CC bonds are replaced by acetylenic linkages C≡C. Therefore, GY7 has the same hexagonal p6m symmetry as graphene.
Today, there is still no standard classification of such graphyne systems. In the first work, Baughman et al. [10] designated the GY networks to be considered in the simplified nomenclature, which defines the number of carbon atoms in different rings forming a given network. According to this method, graphynes can be named as a, b, and g‐graphyne, where a and b represent the number of carbon atoms in the smallest ring of the graphynes (a ring) and number of carbon atoms in the adjacent smallest ring of the graphynes (b ring), respectively. Among them, rings a and b are connected by C(sp2)C(sp)C(sp)C(sp2). The index g is the number of carbon atoms in the third ring of graphynes, which is connected to ring b by C(sp2)C(sp)C(sp)C(sp2). For example, GY2 network is called 6,6,12‐graphyne, GY4 is named 12,12,12‐graphyne, and supergraphene (GY7) is called 18,18,18‐graphyne. In addition, for convenience, several kinds of graphynes are commonly named after the Greek alphabet [36], which can be called as the customary nomenclature: α‐graphyne (GY7) [38], β‐graphyne (GY4) [39], and γ‐graphyne (GY1) [12].
Figure 1.5 Some possible atomic motifs of graphyne‐like structures, which are termed in the text as GY1′–GY5′.
Source: Ivanovskii [26]. © 2013, Elsevier.
Coming back to possible types of graphynes, the structures of GY1′ and GY2′ (Figure 1.5) can be easily constructed from pentaheptite or haeckelite networks by simple replacement of all CC bonds by acetylenic linkages C≡C; the structures of GY3 and GY4′ are graphyne‐like analogues of some 2D carbon supracrystals depicted in Figure 1.3. Besides, various graphene/graphyne “hybrids” can be supposed. A simple example is GY5′, which includes “stripes” of hexagons C6 bonded by acetylenic linkages C≡C, etc. On the other hand, in all of the described graphynes, the sp2 atoms are bonded by “single” C≡C linkages. Therefore, one more way of construction of graphyne‐like networks is to increase the length of linear carbine‐like atomic chains between sp2 atoms, i.e. to replace (C≡C) by (C≡CC≡C) or (C≡CC≡CC≡C) chains, etc. which connect either hexagons C6, or pairs of sp2 atoms, or individual sp2 atoms.
Figure 1.6 Graphdiyne with special properties and the related potential applications. EMI; 1‐ethyl‐3methylimidazolium, PVdF; poly(vinylidene fluoride), BF4; tetrafluoroborate, GD NS; Graphdiyne nanosheets, P3HT; poly(3‐hexylthiophene‐2,5‐diyl), HOMO; highest occupied molecular orbital, LUMO; lowest unoccupied molecular orbital.
Source: (a) Gao et al. [40]. © 2016, John Wiey & Sons, (b) Xue et al. [41]. ©2018, Springer Nature/CC License 4.0, (c) Wang et al. [42]. ©2012, John Wiley & Sons, (d) Xiao et al. [43]. ©2015, John Wiley & Sons, (e) Jia et al. [44]. ©2017, Elsevier, (f) Parvin et al. [45]. John Wiley & Sons, (g) Lu et al. [46]. ©2018, Springer Nature/CC License 4.0.
1.3 Brief Introduction of Graphdiyne
The chemical study of carbon‐rich molecules has and will continue to produce significant structures in size, topology, and spatial direction. Nevertheless, the achievements of early chemists were indeed remarkable in the current synthetic and analytical techniques that modern chemists take for granted. Advanced synthesis methods for alkyne chemistry have been developed through Sonogashira cross‐coupling reactions or oxidative acetylenic coupling reactions catalyzed by Cu‐[47], [48] or Pd/Cu [49]. The on‐surface chemistry also provides a new way for the development of GDY.
GDY has butadiyne linkage between two adjacent aromatic rings. The development of GDY prepared by in situ Glaser coupling reaction of hexaethynylbenzene (HEB) monomers on a copper (Cu) substrate by Professor Yuliang Li's group [50] in 2010, is widely recognized as a great breakthrough regarding the structure of carbon materials. One of the most important features of the chemical structure of GDY is the presence of quantitative sp carbon, which gives it some characteristics that other carbon materials do not have [51], [52].
Theoretical analysis shows that GDY has a direct natural bandgap (0.46 eV) [53] and a Dirac cone structure, which can be attributed to the inhomogeneous π‐bonding between the sp and sp2‐hybridized carbon (Figure 1.6). GDY has excellent electrical properties, such as high carrier mobility and small carrier effective mass, which make it promising for nanoelectronics [54]. Both the intrinsic holes and electrons mobility of GDY at room temperature can reach up to 105 cm2 V−1 s−1[55]. As the number of GDY layers increases, the band gap of GDY decreases and the direct band gap remain unchanged. The mechanical properties of GYs are considered as a function of the number and arrangement of acetylenic linkages [9], [56]. The expanded pores surrounded by the butadiyne linkers and benzene rings in the structure provide additional space for the storage and diffusion of metal atoms such as lithium and sodium. Moreover, the uniformly distributed in‐plane pores of GDY can also promote the vertical transfer of ions [57].
Another unique feature of GDY ‐based materials is that they can be prepared by chemical methods, which is conducive to adjusting and optimizing their morphology and some fundamental chemical properties, including the conductivity, size and distribution of the pores, and affinity to certain metal atoms. In addition, the position and number of heteroatoms introduced in GDY can be well controlled by this preparation method [58]. GDY has been synthesized under different experimental conditions in the forms of films, nanowires, nanotube arrays, nanowalls, 3D foams, nanosheets and ordered stripe arrays, etc.
The above structural features and performance advantages make it possible and convenient to adjust and optimize the electrochemical properties of GDY, leading to the wide application of GDY in efficient separation, energy storage, photoelectric and energy conversion (Figure 1.6). The abundant distribution of alkyne bonds makes the charge distribution on the GDY surface extremely uneven, which endows it with more active sites, leading to higher intrinsic activity, which can effectively promote the catalytic reaction process. Therefore, GDY should be a valuable complement to popular sp2‐hybridized carbon materials for constructing new concepts and highly active metal‐free catalysts and understanding their catalytic mechanisms.
In Chapters 2–4, we will introduce the fundamental characteristics of GDY in terms of experiment and theory, namely electrical, mechanical, and optical properties [51], [52], [58], [59]. More importantly, we will focus on the application of GDY in catalysis [41], [42] (Chapter 5), energy conversion and storage [43], [44] (Chapters 6, 7), electronic devices [46] (Chapter 8), detectors, biomedicine and treatment [45], and water purification [40] (Chapter 9).
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2Basic Structure and Band Gap Engineering: Theoretical Study of GDYs
Feng He
Institute of Chemistry, Chinese Academy of Sciences, Zhongguancun North First Street 2, Beijing, 100190, PR China
2.1 Structures
2.1.1 Theoretical Prediction and Classification
In 1987, Baughman et al. [1] predicted a new carbon material, consisting of sp2‐ and sp‐hybrid carbon atoms, which was called graphyne (GY). It has 2D planar structure and symmetry similar to layered graphite, which can be constructed by replacing one‐third of CC bonds in graphite by C≡C linkages. Compared to other carbon phases containing sp‐atoms as the major structural elements, graphyne has much higher density and much lower formation energy. Although the formation energy of graphyne is higher than that of graphite, it is predicted to have high kinetic stability in the process of graphitization. Combining the retention of stabilized aromatic rings in the network backbone, graphyne shows more attractive thermal stabilities and synthesis possibilities than other carbon phases. Using the semiempirical self‐consistent‐field method, the lattice parameters of energy‐minimized graphyne unit cell (containing 24 carbon atoms) were calculated to be a = b = 6.86 Å, c = 6.72 Å, γ = 120°.
The original structure of graphdiyne (GDY) was proposed as a large molecular one. This is unlike our concept of material design today where we aim at finding an advanced material with a two‐dimensional (2D), layered, superlarge cavity structure. As a result, we have named it “shimoque” in Chinese since the date of discovery. In fact, it is quite different from the “graphdiyne” in English, because in our proposed material, we pay more attention to its layered, two‐dimensional atomic arrangement and its electronic structure with uneven charge distribution, band structure, and so on. The difference is the number (n) of acetylenic linkages (C≡C) between two nearest‐neighboring aromatic rings, for example, n = 1 in graphyne and n = 2 in GDY. GDY is the most stable carbon allotrope containing diacetylenic linkages and has large pores (about 2.5 Å) in the planar sheets, which can accommodate various large metal ions and favor the through‐sheet transport of small ions. In addition, GDY could provide the intrasheet intercalation, which is not available for graphite with this type of dopant storage.
Narita et al. [2] systematically studied the atomic geometries of graphyne and GDY using a full‐potential linear combination of atomic orbitals (LCAOs) method in the local density approximation. These structures consist of hexagons connected by linear carbon chains with different lengths. The binding energies are 7.95 eV atom−1 for graphyne and 7.78 eV atom−1 for GDY, respectively, and the corresponding lattice parameters are 6.86 and 9.44 Å, respectively. As the lengths of acetylenic chains in these graphyne allotropes expand, the binding energies are decreased, while the lattice parameters and lattice space are uniformly increased. For example, when adding each acetylenic connection unit, the lattice space is regularly increased by about 0.266 nm. More importantly, the extension of acetylenic chain does not lead to the obvious structural change. In addition, it is estimated theoretically that the formation energies of graphyne (i.e. 12.4 kcal mol−1 carbon) and GDY (i.e. 18.3 kcal mol−1 carbon) are much lower than those of any other carbon allotropes containing acetylenic linkages, thereby having the thermodynamic stability.
Using the density functional theory tight‐binding (DFT‐TB) calculations, Buehler and coworkers [3] systematically studied the relative stabilities and structural properties of each 2D planar graphynes network. Graphene and carbyne (the linear acetylenic carbon) consist of pure sp2‐ and pure sp‐hybridization, respectively, while the graphyne structures are a mixed configuration of sp2‐ and sp‐hybridization (Figure 2.1a). The differential energy per carbon atom (δE) can be used to assess the relative stability of each graphyne, which is defined as the difference in the total energies between the graphyne allotropes (En‐yne) and pristine graphene (Egraphene):
The energy of graphynes can be predicted theoretically through the number of acetylenic groups, n (Figure 2.1b) or the hybridization, h (Figure 2.1c). The geometries of graphene (n = 0) and a few graph‐n‐ynes (namely n = 1, 2, 3, and 4) are shown in Figure 2.1d–h. With the increase of the number of acetylenic connection units [C≡C] in the network, the graphyne structures tend to be less stable since it approaches pure sp1‐hybridization (e.g. carbyne) with an ultimate δEcarbyne of 1.17 eV atom−1. However, it is noted that the graphynes have much lower ranges of energy differences (<1.17 eV atom−1) than other possible carbon allotropes containing acetylenic linkages [2], [4], thereby being relatively more stable.
The graphyne family can be divided into α‐graphyne, β‐graphyne, γ‐graphyne, 6,6,12‐graphyne, etc. [5]. All these graphynes have two‐dimensional layered planar structures, which are the combination of aromatic rings, large hexagons, or truncated triangular pores. Due to the multiple carbon bonds such as single bond, aromatic bond, and triple bond, the structural variability of graphynes is much stronger than that of graphene, thereby easily forming the curved nanowires or nanotubes with high stability [6]. The cohesion energies of various sp–sp2 hybridized graphyne allotropes (e.g. α‐, β‐, and γ‐graphyne) were studied using quantum Monte Carlo (QMC) calculations with full description of electron–electron correlation [7]. It is found that the cohesive energies of different types of graphynes decrease systematically as the ratio of sp‐carbon atoms increases. Among them, γ‐graphyne is the most energetically stable graphyne structure with a cohesive energy of 6.766(6) eV atom−1. However, the cohesive energy is still smaller than that of graphene by 0.698(12) eV atom−1, which could explain the experimental difficulty in synthesizing graphynes.
Figure 2.1 (a) A mixed‐carbon configuration, which is classified as sph (1 < h < 2), according to the fraction of sp1 and sp2 hybridization. The energy of graphynes vs. (b) the number of acetylenic groups, n, or (c) the hybridization, h. For comparison, previous first‐principles results [2], [4] are plotted with black crosses. Constructed full atomistic models of (d) graphene, (e) graphyne, (f) graphdiyne, (g) graphtriyne, and (h) graphtetrayne with approximately 100 Å × 100 Å in dimensions.
Source: Cranford et al. [3]. © 2012, Royal Society of Chemistry.
In 2010 year, Li's group successfully synthesized large‐area γ‐GDY films for the first time on the surface of copper foil via the cross‐coupling reaction using hexaethynylbenzene [8]. The γ‐GDY is the most widely studied graphyne structure and attracts wide attention. As a new 2D nanomaterial, GDY not only has much variable and controllable carbon atoms combination (i.e. sp‐ and sp2 hybridization), but also can grow in situ on any substrate surface under low temperature and mild conditions. Arising from the abundant chemical bonds, large specific surface area, wide interplanar distance, high carrier mobility, good electrical conductivity, excellent chemical stability, and unique porous structures, GDY possesses excellent electrical, mechanical, optical, magnetic, and thermal properties. Therefore, it is successfully applied in many research fields such as photoelectric catalysis [9]–12], energy storage [13]–15], photoelectric conversion [16]–19], solar–thermal conversion [20], oil–water separation [21], biological detection [22], [23], photoelectric detection [24], and electrochemical drives [25].
2.1.2 Geometric Structures of GDYs
The geometric structures of GDYs (such as α‐, β‐, and γ‐graphyne) can be obtained by inserting the acetylenic linkages between two individual sp2 carbon atoms (Figure 2.2
