Tuning the Properties of Graphdiyne by Introducing Electron-Withdrawing/Donating Groups

Article abstract of DOI:10.1002/anie.202004454

The properties of graphdiyne (GDY), such as energy gap, morphology, and affinity to alkali metals, can be adjusted by including electron-withdrawing/donating groups. The push–pull electron ability and size differences of groups play a key role on the partial property adjusting of GDY derivatives MeGDY, HGDY, and CNGDY. Cyano groups (electron-withdrawing) and methyl groups (electron-donating) decrease the band gap and increase the conductivity of the GDY network. The cyano and methyl groups affects the aggregation of GDY, providing a higher number of micropores and specific surface area. These groups also endow the original GDY additional advantages: the stronger electronegativity of cyano groups increase the affinity of GDY frameworks to lithium atoms, and the larger atomic volume of methyl groups increases the interlayer distance and provides more storage space and diffusion tunnels.

Full text of DOI:10.1002/anie.202004454

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
International Edition
www.angewandte.org
Accepted Article
Title: Tuning the Properties of Graphdiyne through Introducing Electron
Withdrawing/Donating Groups
Authors: Chipeng Xie, Xiuli Hu, Zhaoyong Guan, Xiaodong Li, Fuhua
Zhao, Yuwei Song, Yuan Li, Xiaofang Li, Ning Wang, and
Changshui Huang
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202004454
Link to VoR: https://doi.org/10.1002/anie.202004454

10.1002/anie.202004454
Angewandte Chemie International Edition
COMMUNICATION
Tuning the Properties of Graphdiyne through Introducing Electron
Withdrawing/Donating Groups
Chipeng Xie,[a] Xiuli Hu,[a] Zhaoyong Guan,[b] Xiaodong Li,[a] Fuhua Zhao,[a] Yuwei Song,[a] Yuan Li,[a]
Xiaofang Li,*[c] Ning Wang*[b] and Changshui Huang*[a]
Abstract: Herein, properties of graphdiyne (GDY) such as energy gap, graphene, which can be prepared by wet chemical reaction or
morphology, and affinity to alkalis metals are efficiently adjusted
through including electron withdrawing/donating groups. The
experimental and theoretical results indicate that the push-pull
electron ability and size differences of groups play a key role on the
partial property adjusting of as-prepared GDY derivatives named
MeGDY, HGDY, and CNGDY. Typically, cyano group with electron
withdrawing ability and methyl group with electron donating
characteristic have successfully reduced the band gap and increased
the conductivity of the GDY network within an obvious range.
Meanwhile, the inclusion of cyano and methyl groups affects the
aggregation of GDY, thus providing a higher number of micropores
and specific surface area. Moreover, the fascinating properties of
these groups endow the original GDY additional advantages in
following aspects: the stronger electronegativity of cyano groups
increase the affinity of GDY frameworks to lithium atoms; the larger
atomic volume of methyl groups increases the interlayer distance and
provide more storage space and diffusion tunnels. These results
provide an inspiring idea to design and synthesize novel
functionalized GDY based materials for high stability, high
conductivity and controllable functionality.
annealing.[11] Furthermore, the infinitely adjustable D–A systems
built through surface modified graphene with electron donating or
electron withdrawing molecules, providing more opportunities for
the preparation of high efficiency solar cells.[12] However, it is hard
to precise control the number and position of heteroatoms or
groups following above methods, which limits the systematic
regulation of the structures and properties of carbon materials.
Therefore, it is necessary to develop a new method to tailor the
structure and modulate the properties of carbon materials.
Studying the relationship between the functionality of the group
and the properties of the carbon material is not only conducive to
the preparation of new carbon materials with excellent
performance, but also opens up new platforms for the theoretical
and experimental research of carbon materials.
Recently, facile approach is developed to prepare
heteroatomic substituted GDY films through
a bottom-up
synthetic strategy, such as fluorine-substituted GDY[13] and
nitrogen-substituted GDY[14]. At the same time, the electronic
structure and lithium storage properties of GDY derivatives are
significantly tuned by precisely modifying the number and position
of heteroatoms. Compare to heteroatoms, the structure variability
of functional groups is distinct, and the characteristic difference of
introduced functional groups can be an important positive factor
to realize the systematical adjustment of the partial properties of
GDY, such as charge density distribution, interlayer distance and
morphology, etc. [15] In detail, the electrode materials modified by
the electron withdrawing or the electron donating groups can
decrease or increase the oxidation-reduction potential,
respectively.[16] For example, a strong electron withdrawing group,
cyano group has a lower lowest empty molecular orbital (LUMO)
energy level and higher electrochemical stability than other
electron donating groups, thereby greatly improves the potential
range and cycle stability for high energy metal ion batteries.[17] On
the other hand, methyl group is an electron donating group that
provides a wider charge/discharge platform and better cycle
stability for the organic polymer negative electrode.[18]
Carbon allotropes composed of three kinds of hybrid carbons
(including sp, sp2 and sp3 carbon) exhibit varied structure and
properties, such as fullerenes,[1] carbon nanotubes,[2] graphene,[3]
graphdiyne (GDY),[4] have been widely applied in the fields of drug
delivery,[5] sensors,[6] biomaterials,[7] catalysis,[8] energy storage
and conversion[9]. Recently, the structure modification of
strategies such as doping heteroatoms and including surface
covalently groups have been developed for adjusting the
electronic structure and related properties of carbon allotropes.[10]
For example, oxygen reduction catalytic performance has been
significantly improved by doping high content of nitrogen in
[a]
C. Xie,[+] X. Hu,[+] X. Li, F. Zhao, Y. Song, Y. Li, and Prof. C. Huang.
Qingdao Institute of Bioenergy and Bioprocess Technology
Chinese Academy of Sciences
No. 189 Songling Road, Qingdao 266101, China
Center of Materials Science and Optoelectronics Engineering，
University of Chinese Academy of Sciences, Beijing 100049, China
E-mail: huangcs@qibebt.ac.cn
Dr. Z. Guan and Prof. N. Wang
School of Chemistry and Chemical Engineering
Shandong University
No. 27 Shanda Nanlu, Jinan, 250100, China
Prof. X. Li
School of Chemistry and Chemical Engineering
Hunan University of Science and Technology
Xiangtan 411100, P.R. China
In this work, via a bottom-up synthetic strategy, methyl group
substituted GDY (MeGDY), hydrogen substituted GDY (HGDY)
and cyano group substituted GDY (CNGDY) were synthesized
successfully by choosing the pentaethynyl-benzyl, pentaethynyl-
benzene and pentaethynyl-benzonitrile as monomers,
respectively. Moreover, the effects of electron withdrawing and
electron donating groups on the basic properties of carbon
materials were systematically studied. The experimental results
and first-principles calculations indicate that cyano groups with
electron withdrawing ability can increase conductivity by reducing
the band gap of GDY. In addition, the microstructure, interlayer
[b]
[c]
[+]
These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/anie.202004454
Angewandte Chemie International Edition
COMMUNICATION
Figure 1. Synthetic route and characterizations of HGDY, MeGDY and CNGDY. (a) Synthetic route of HGDY, MeGDY and CNGDY. (b) Comparison of group
properties, including electronegativity and volume. Chemical structure and electronic properties of (c) CNGDY, (d) HGDY, (e) MeGDY (Top to bottom). (f) Solid-
state 13C NMR spectrum of HGDY. (g) FT-IR spectrum of HGDY, MeGDY and CNGDY. (h) Raman spectrum of HGDY, MeGDY and CNGDY.
spacing and morphology of three GDY derivatives were found to
be related to the size and coplanarity of the groups. At the same
time, three GDY derivatives worked as anode material assembled
Three GDY derivatives have two identical broaden peaks at 132
ppm and below 100ꢀppm, which correspond to C(sp2)-C(sp2) on
the benzene ring and the carbon atoms of butadiyne (including
C(sp)-C(sp2) and C(sp)-C(sp)), respectively.[19] The broaden
peaks below 100 ppm maybe due to the coexistence of multiple
configurations in GDY derivatives. Precursors of three GDY
derivatives with low molecular symmetry lead to complex coupling
modes, thus producing a variety of configurations of GDY during
the polymerization process. However, under the bottom-up
strategy, the groups will be evenly distributed over the GDY planar.
Notably, the peaks located around at 30 ppm (Figure S2g) and
126.6 ppm (Figure S2h) are the characteristic peaks of carbon
atoms attached to the methyl group and the cyano group.[20] The
carbon and nitrogen species were further characterized by X-ray
photoelectron spectroscopy (XPS) (Figure S3-S5), which
confirmed the components and structures of three GDY
derivatives. FT-IR and Raman spectra are also used to
characterize the components and structures of three GDY
derivatives (Figure 1g and 1h). In their structures, adjacent
aromatic rings are connected by diacetylenic bonds, while a group
replaces one acetylenic bond on any aromatic ring (Figure 1a).
The detailed XPS, FT-IR and Raman analysis are shown in
Supporting Information.
lithium-ion battery showed
a
regular improvement in
electrochemical properties, demonstrating the favorable
regulation of the group on the properties of GDY. CNGDY exhibits
the best electrochemical performance when applied to a negative
electrode for lithium ion batteries. As a result, the high reversible
capacity of 1612 mAh g-1 was achieved at a current density of 50
mA g-1, and maintained more than 495 mAh g−1 at a current
density of 2 A g−1 after 6000 cycles.
HGDY, MeGDY and CNGDY films are prepared on the
surface of copper foil using group modified precursors, which are
synthesized by simple chemical procedures including connecting
alkyne and desiliconization (Figure 1a and Figure S1). As shown
in Figure 1b, there is a clear difference between cyano and methyl
groups in the aspects of electronegativity and group volume, so
that the electronic structure and layer spacing of these GDY
derivatives can be effectively tuned. Moreover, Figure 1c-e shows
the electron transfer around the group and the adjacent benzene
ring. It is expected that the electron density on the benzene ring
will be decreased and increased after modifying the electron
withdrawing group (cyano) and the electron donating group
(methyl) on GDY planar, respectively. As shown in Figure 1f and
Figure S2, the 13C solid-state nuclear magnetic resonance (NMR)
indicates the chemical structure of HGDY, MeGDY and CNGDY.
With respect to the influence of different groups upon the
microstructure of GDY, the morphologies and crystal structures of
three GDY derivatives were characterized and discussed in
This article is protected by copyright. All rights reserved.

10.1002/anie.202004454
Angewandte Chemie International Edition
COMMUNICATION
Figure 2. The top-view SEM images of (a) HGDY, (b) MeGDY and (c) CNGDY.
The magnified SEM images of (d) HGDY, (e) MeGDY and (f) CNGDY. The
formation process of (g) HGDY, (h) MeGDY and (i) CNGDY. The TEM images
of (j) HGDY, (k) MeGDY and (l) CNGDY. The high-resolution TEM images of
(m) HGDY, (n) MeGDY and (o) CNGDY.
Figure 3. (a) UV-vis absorption spectrum of HGDY, MeGDY andCNGDY and
plots of (Ahν)2 versus photon energy (hν) (inset). (b) The Band structures of
HGDY, MeGDY and CNGDY along the S-Γ-Y direction, respectively. The
optimized configurations of (c) MeGDY and (d) CNGDY. The charge densities
of (e) MeGDY and (f) CNGDY, the accumulation and loss of charge are
represented by red and blue regions, respectively. (g) The X-ray diffraction
patterns of samples. (h) The conductivity of different samples.
detailed, As shown in Figure 2a-f and S6, the scanning electron
microscopy (SEM) images clearly show different morphologies
about three GDY derivatives, all of them are composed of
nanoparticles of different sizes. It is expected that the change in
morphology is attributed to the size, coplanarity and
electronegativity of groups. Figure S7 showed the diameter
distribution of nanospheres of GDY derivatives under micro
conditions. Subsequently, the simulated formation processes of
microstructures are shown in Figure 2g–i. The electron donating
group represented by methyl group not only reduces the size of
the MeGDY nanospheres, but also provides an ordered porous
structure by limiting the growth direction of the MeGDY
nanospheres (Figure 2h). The electron withdrawing group
represented by a cyano group tends to inhibit the aggregation of
CNGDY nanospheres (Figure 2i).
Transmission electron microscopy (TEM) images present
uniform films for HGDY, MeGDY and CNGDY, confirming the
regular structure of GDY derivatives. Furthermore, layer spacings
of GDY derivatives were obtained by high-resolution transmission
electron microscopy (HRTEM) and X-ray diffraction (XRD). As
shown in Figure 2m-o, HRTEM shows that the layer spacing of
HGDY, MeGDY and CNGDY are 0.36nm, 0.38nm and 0.37nm,
respectively. The SAED images (Figure S8) indicating the as-
prepared GDY derivatives might contains polycrystal. At the
same time the results of X-ray diffraction XRD (Figure 3g) are
consistent with HRTEM, according to the different peak angles of
three material (HGDY:MeGDY:CNGDY = 23.35°:24.20°:23.98°).
Therefore, larger group could increase the layer spacing of GDY
by a simple replacement process. Notably, the methyl provided
the largest layer spacing for GDY, which can be attributed to the
larger volume and non-planarity. The specific surface areas of
HGDY, MeGDY and CNGDY powder calculated by nitrogen
adsorption and desorption isotherms are 207 m2/g, 559 m2/g and
636 m2/g, respectively (Figure S9). This confirms that the
microstructure can be adjusted by changing the size and
electronegativity of the group, predicting that unexpected results
can be achieved in some areas. Moreover, three GDY derivatives
exhibit a highly similar pore size distribution by the corresponding
nitrogen adsorption-desorption isotherm (Figure S10).
As shown in Figure 3a and S11, the optical energy gap of
HGDY, MeGDY and CNGDY, which calculated by ultraviolet-
visible (UV-vis) and the formula of α ∝ (hν−Eg)1/2/hν, were
measured to be 1.73 eV, 1.62 eV and 1.53 eV, respectively
(CNGDY< MeGDY < HGDY). As the optimized configurations
shown in Figure 3 c-d, the methyl group is not planar since the
angel of C1-C2-H is about 110° and the distance of C2-H is about
This article is protected by copyright. All rights reserved.

10.1002/anie.202004454
Angewandte Chemie International Edition
COMMUNICATION
Figure 4. The electrochemical performance of HGDY, MeGDY and CNGDY electrodes in Li metal half-cell format. (a) (b) (c) The rate performance of HGDY,
MeGDY and CNGDY, respectively. (d) The calculated adsorption energies of single Li occupied mode of different samples and corresponding storage sites. (e) The
different adsorption configurations of single Li atom on the CNGDY with the adsorption energy marked. (f)The model of lithium ion battery. (g) The initial
configurations of C32H2-Li20, C34H6-Li24 and C34N2-Li34, respectively. (h) The cycle performance of HGDY, MeGDY and CNGDY.
1.10 Å, which will observably increase the layer spacing. It is
worth noting that the cyano group is collinear while the two cyano
group in CNGDY protruded in up and down directions slightly due
to the interaction of them. Therefore, the methyl group and the
cyano group increased the layer spacing, which is consistent with
the layer spacings of HGDY, MeGDY and CNGDY obtained from
HRTEM are 0.36 nm, 0.38 nm, 0.37 nm, respectively.
To provide more insight difference of three samples, Figure
3e-f and Figure S12 show charge densities for different materials.
Together with the bader analysis, the hydrogen and methyl group
lose 0.12e and 0.13e while the cyano group gains 0.21e,
confirming the cyano group has the high electronegativity as an
electron withdrawing group while the methyl group and hydrogen
have the low electronegativity as the electron donating group. The
band structures of GDY modified with different groups along the
high symmetry points Γ-X-S-Γ-Y-S are slightly different. The
calculated direct band gaps of HGDY, MeGDY and CNGDY
monolayers by PBE functional are predicted to be 0.79ꢀeV,
0.77ꢀeV and 0.73ꢀeV, respectively (Figure 3b and S13), which is
consistent with the changing trend of measured optical energy
gap.[21] The narrower band gap will improve the conductivity, so it
is often considered to provide better conductance and easier to
overcome harsh experimental conditions. The current-voltage (I-
V) curves of HGDY, MeGDY and CNGDY are in Figure 3h. the
conductivity of HGDY and MeGDY are calculated by the
conductivity formula (σ=L/RS) are about 1.14×10-2 s/m and
4.25×10-2 s/m while the conductivity of CNGDY can up to 5.41×10-
1 s/m. Hence, the properties and performance for CNGDY should
also be highly expected.
We further studied the lithium storage of three GDY
derivatives as the LIB anode, including lithium storage
mechanism, rate performance and cycle performance, etc. Figure
4a and 4b indicate the charge/discharge capacities of
HGDY/MeGDY are 510.7/915.5 mAh g-1 with 55.7%,
997.3/1785.1 mAh g-1 with 55.87%, respectively. However, the
first charge/discharge capacities of CNGDY are 1612 / 2420 mAh
g-1 with the Coulombic efficiency (CE) of 66.6% (Figure 4c). It is
notable that the electron withdrawing group has a stronger lithium
storage ability and a higher coulombic efficiency. In addition,
when the current density was reduced from 5 A g-1 to 0.05 A g-1,
all three materials completely recovered to the initial reversible
capacity. The stability of three GDY derivatives were further
characterized by long term cycling performances at a high current
density (5 A g-1) (Figure 4e), CNGDY shows the highest specific
capacity (495 mAh g-1) and stability when as the anode.
Furthermore, we analyzed the lithium storage behavior of GDY by
the cycling performance, cyclic voltammetry curves and capacity
voltage curves, which were discussed in Supporting Information
This article is protected by copyright. All rights reserved.

10.1002/anie.202004454
Angewandte Chemie International Edition
COMMUNICATION
[2]
[3]
S. Iijima, Nature 1991, 354, 56-58.
(Figure S14 and S15). Moreover, in Supporting Information, we
used the first principles to calculate the lithium storage
characteristics of three GDY derivatives, including the adsorption
energy at different sites and maximum theoretical capacity of
lithium (Figure 4d, e, g and S16). The excellent electrochemical
properties of CNGDY are mainly attributed to the reasonable
adjustment of the physical and chemical properties, including the
microscopic morphology, specific surface area, pore size
distribution and interlayer spacing. The result of experiment and
first-principles DFT calculations demonstrated the reduction of
band gap (HGDY, 1.73 eV; MeGDY, 1.62 eV; CNGDY, 1.53 eV),
the increase of volume or interlayer spacing （HGDY, 0.36 nm;
CNGDY, 0.37 nm; MeGDY, 0.38 nm）, indicating a remarkable
influence of group on the Li-storage capabilities. Expectedly,
CNGDY with the stronger electronegativity ultimately increased
the Li-storage capabilities through the increased reaction sites
and the improved electron distribution environment. Moreover,
MeGDY with larger interlayer distance provide more space for the
storage and diffusion of lithium atom and ion, respectively.
However, the improved layer spacing also acts unstable factors
while the electrochemical process going on, causing low cycle
stability of MeGDY based electrode (Figure 4h).
In summary, we synthesized a series of GDY derivatives with
groups such as hydrogen, methyl and cyano through a novel
cross-coupling reaction using chemically modified precursors.
With the introduction of different groups, the properties including
energy gap, layer spacing and microstructure, etc. would alter
naturally. Expectedly, the regulation of the basic properties of
GDY by these groups is beneficial to observe the change of
lithium storage capacity in terms of reversible capacity, cycle
stability and rate performance. Meanwhile, compared to those of
GDY, HGDY and MeGDY, the improved electrochemical
properties of CNGDY are released. Accurate control of energy
gap, electron mobility, layer spacing, crystalline packing and
specific surface area impacts the performance of lithium-ion
storage. This in-depth investigation provides an effective strategy
for precise regulation the electronic structure and properties of
carbon materials and would leads to novel types of highly efficient
carbon-based materials for energy storage.
K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V.
Dubonos, I. V. Grigorieva, A. A. Firsov, Science 2004, 306, 666-669.
a) C. Huang, Y. Li, N. Wang, Y. Xue, Z. Zuo, H. Liu, and Y. Li, Chem.
Rev. 2018, 118, 16, 7744-7803. b) Y. Xue, B. Huang, Y. Yi, Y. Guo, Z.
Zuo, Y. Li, Z. Jia, H. Liu, Y. Li, Nat. Commun. 2018, 9, 1460.
X. Sun, Z. Liu, K. Welsher, J. T. Robinson, A. Goodwin, S. Zaric, H. Dai,
Nano Res. 2008, 1, 203-212.
[4]
[5]
[6]
[7]
[8]
Y. Shao, J. Wang, H. Wu, J. Liu, I. A. Aksay, Y. Lin, Electroanalysis 2010,
22, 1027-1036.
S. Polizu, O. Savadogo, P. Poulin, L. H. Yahia, J. Nanoscience and
Nanotechnology 2006, 6, 1883-1904.
a) X. Li, J. Yu, S. Wageh, A. A. Al-Ghamdi, J. Xie, Small 2016, 12, 6640-
6696. b) L. Hui, Y. Xue, H. Yu, Y. Liu, Y. Fang, C. Xing, B. Huang, and
Y. Li, J. Am. Chem. Soc. 2019, 141, 10677-10683. c) L. Hui, Y. Xue, B.
Huang, H. Yu, C. Zhang, D. Zhang, D. Jia, Y. Zhao, Y. Li, H. Liu and Y.
Li, Nat. Commun., 2018, 9, 5309.
[9]
F. Bonaccorso, L. Colombo, G. Yu, M. Stoller, V. Tozzini, A. C. Ferrari,
R. S. Ruoff, V. Pellegrini, Science 2015, 347, 6217.
[10] a) C. N. R. Rao, K. Gopalakrishnan, A. Govindaraj, Nano Today 2014, 9,
324-343; b) Z. H. Xiang, Q. B. Dai, J. F. Chen, L. M. Dai, Adv. Mater.
2016, 28, 6253-6261; c) Q. L. Yan, M. Gozin, F. Q. Zhao, A. Cohen, S.
P. Pang, Nanoscale 2016, 8, 4799-4851; d) Y. Li, T. Liu, H. Liu, M. Tian,
and Y. Li, Acc. Chem. Res. 2014, 47, 1186-1198.
[11] Q. Tang, Z. Zhou, Z. F. Chen, Nanoscale 2013, 5, 4541-4583.
[12] a) N. Wang, J. He, Z. Tu, Z. Yang, F. Zhao, X. Li, C. Huang, K. Wang, T.
Jiu, Y. Yi and Y. Li, Angew. Chem. 2017, 129, 1-5; Angew. Chem.-Int.
Edit. 2017, 56, 10740-10745. b) H. Zheng, Y. Li, H. Liu, X. Yin and Y. Li,
Chem. Soc. Rev. 2011, 40, 4506-4524.
[13] X. Shen, J. He, K. Wang, X. Li, X. Wang, Z. Yang, N. Wang, Y. Zhang,
C. Huang, ChemSusChem 2019, 12, 1342-1348.
[14] Z. Yang, R. Liu, N. Wang, J. He, K. Wang, X. Li, X. Shen, X. Wang, Q.
Lv, M. Zhang, J. Luo, T. Jiu, Z. Hou, C. Huang, Carbon 2018, 137, 442-
450.
[15] a) H.-J. Yen, H. Tsai, M. Zhou, E. F. Holby, S. Choudhury, A. Chen, L.
Adamska, S. Tretiak, T. Sanchez, S. Iyer, H. Zhang, L. Zhu, H. Lin, L.
Dai, G. Wu, H.-L. Wang, Adv. Mater. 2016, 28, 10250-10256. b) G. Li, Y.
Li, H. Liu, Y. Guo, Y. Li and D. Zhu. Chem. Commun. 2010, 46, 3256-
3258. c) Y. Li, L. Xu, H. Liu, Y. Li, Chem. Soc. Rev. 2014, 43, 2572-2586.
[16] M. S. Strano, C. A. Dyke, M. L. Usrey, P. W. Barone, M. J. Allen, H. Shan,
C. Kittrell, R. H. Hauge, J. M. Tour, R. E. Smalley, Science 2003, 301,
1519-1522.
[17] P. Hu, J. Chai, Y. Duan, Z. Liu, G. Cui, L. Chen, J. Mater. Chem. A 2016,
4, 10070-10083.
[18] D. J. Kim, S. H. Je, S. Sampath, J. W. Choi, A. Coskun, RSC Adv. 2012,
2, 7968-7970.
[19] a) W. A. Chalifoux, R. R. Tykwinski, Nature Chemistry 2010, 2, 967; b)
W. A. Chalifoux, R. McDonald, M. J. Ferguson, R. R. Tykwinski, Angew.
Chem. 2009, 121, 7241-7250; Angew. Chem.-Int. Edit. 2009, 48, 7915-
7919.
Acknowledgements
This study was supported by the National Natural Science
Foundation of China (51822208, 21790051, 21771187,
21875274), the Hundred Talents Program, the Frontier Science
Research Project (QYZDB-SSW-JSC052) of the Chinese
Academy of Sciences, and the Natural Science Foundation of
Shandong Province (China) for Distinguished Young Scholars
(JQ201610). The authors are grateful to Beijing PARATERA Tech
Corp., Ltd. for the computation in the National Supercomputer
Center of Guangzhou.
[20] a) L. Zhu, X. Cao, Mater Lett. 2015, 150, 16-19; b) A. E. Lakraychi, F.
Dolhem, F. Djedaïni-Pilard, A. Thiam, C. Frayret, M. Becuwe, J. Power
Sources 2017, 359, 198-204.
[21] a) B. Mortazavi, M. Shahrokhi, M. E. Madjet, M. Makaremi, Rabczuk. A.
S, Carbon 2019, 141, 291-303; b) S. Yang, W. Li, C. Ye, G. Wang, H.
Tian, C. Zhu, P. He, G. Ding, X. Xie, Y. Liu, Y. Lifshitz, S.-T. Lee, Z. Kang,
M. Jiang, Adv. Mater. 2017, 29, 1605625.
Keywords: graphdiyne • cyano • methyl • groups • lithium Ion
battery
[1]
H. W. Kroto, J. R. Heath, S. C. Obrien, R. F. Curl, R. E. Smalley, Nature
1985, 318, 162-163.
This article is protected by copyright. All rights reserved.

10.1002/anie.202004454
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
CNGDY, HGDY and MeGDY are
Chipeng Xie, Xiuli Hu, Zhaoyong Guan,
Xiaodong Li, Fuhua Zhao, Yuwei Song,
Yuan Li, Xiaofang Li*, Ning Wang* and
Changshui Huang*
prepared through
a
bottom-to-up
synthesis strategy. The push-pull
electron ability and size differences of
groups play a key role on the partial
property adjusting of as-prepared GDY
derivatives, such as energy gap,
morphology, and affinity to alkalis
metals.
Page No. – Page No.
Tuning the Properties of Graphdiyne
through Introducing Electron
Withdrawing/Donating Groups
This article is protected by copyright. All rights reserved.