Programmable Triboelectric Nanogenerators Dependent on the Secondary Building Units in Cadmium Coordination Polymers

Article abstract of DOI:10.1021/acs.inorgchem.0c02946

Precisely controlling the coordination microenvironment and electronic features of polynuclear secondary building units (SBUs) in coordination polymers (CPs) is an efficient approach to governing their fundamental performance. Here, different multinuclear

Full text of DOI:10.1021/acs.inorgchem.0c02946

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Programmable Triboelectric Nanogenerators Dependent on the
Secondary Building Units in Cadmium Coordination Polymers
Chao Huang,* Guizhen Lu, Yingying Zhang, Kaifang Zhu, Siwen Cui, Weihua Chen, Zijie Wu,
Mei Qiu,* and Liwei Mi*
Cite This: Inorg. Chem. 2021, 60, 550−554
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ABSTRACT: Precisely controlling the coordination microenvironment and electronic features of polynuclear secondary building
units (SBUs) in coordination polymers (CPs) is an efficient approach to governing their fundamental performance. Here, different
multinuclear SBUs (binuclear, trinuclear, and pentanuclear SBUs for 1−3, respectively) were introduced into Cd-based CPs, which
were used as frictional electrode materials, to clarify the contributions of polynuclear Cd-SBUs through the output of triboelectric
nanogenerators (TENGs). The results demonstrated that 1-TENG with binuclear Cd-SBUs possessed the highest output, whereas
3-TENG with the pentanuclear Cd-SBUs indicated the minimum output, suggesting that the binuclear Cd-SBUs in 1 lost electrons
most readily and generated much more charge, which was further confirmed by density functional theory calculations. This work
opened a new prospect to confirm the gaining/losing capability of polynuclear Cd-SBUs in CPs and provided an effective approach
to tuning both the stability and functionality of polynuclear CPs as frictional pair materials to regulate the output of CPs-based
TENGs.
oordination polymers (CPs), composed of polynuclear
clusters [secondary building units (SBUs)] and organic
ance of TENGs is extremely determined by the structure of the
device, environmental factors, frictional motions, and partic-
ularly the nature of the triboelectric active materials.36,37,39−42
Developing steady and highly efficient triboelectrode active
materials with molecular or electronic structures that can
facilitate the gain/loss of charges to tune the output of TENGs
is of ongoing interest.43−48 Therefore, benefiting from the
unique electronic properties and highly tunable platform for
polynuclear SBUs, we sought to explore the potential utility of
CPs with polynuclear SBUs and TENGs that could achieve the
gain/loss capability of electrons of different polynuclear SBUs
in CPs and expand the application range of polynuclear CPs.
Herein, we report a platform CP that affords the direct
incorporation of different polynuclear SBUs into its Cd-CPs-
based frameworks at accurate positions, resulting in Cd-CPs
1−3, wherein the arrangement of the polynuclear Cd-SBUs
(binuclear, trinuclear, and pentanuclear SBUs for 1−3,
respectively) controls the geometry and electronic structure.
Furthermore, the Cd-CPs-based TENGs demonstrated that 1-
TENG with the binuclear Cd-SBUs possessed the highest
output, while 3-TENG with the pentanuclear Cd-SBUs had the
lowest output. The results confirmed that the binuclear Cd-
SBUs in 1 were capable of losing electrons and transferring
charges much easier than the trinuclear and pentanuclear Cd-
SBUs in 2 and 3, respectively. The DFT calculations further
C
linkers, have been explored as functional molecular materials
for many applications, owing to their structural diversity within
the principles of reticular chemistry.1−9 To achieve an
improved structural performance, the overall connectivity
and well-defined platform of SBUs play a crucial role in tuning
the various chemical and physical properties of CPs, such as
the reduction potential, critical steric thermodynamic stability,
and kinetic inertness, to accomplish the catalytic as well as gas
adsorption and separation with open-metal centers, thermo-
electrics, molecular magnets, and others.10−21 Meanwhile,
polynuclear SBUs in CPs not only are considered to be
nanoscale models of metal oxides that control the electronic
characteristics of the primary structure but also are promising
in that they create electrically conducting pathways that
facilitate evaluation of their gain/loss electronic capability
through experiments and density functional theory (DFT)
calculations, in which structure−function relationships could
be established to develop polynuclear SBU design principles
for engineering CPs with desired properties.22−31 Therefore,
incorporating the atomically polynuclear SBUs into CPs
through realm reticular chemistry provides a promising
strategy to tailor the electronic structure of CPs and may
open up new opportunities for precisely controlling the
internal structure of CPs to manipulate the output of
triboelectric nanogenerators (TENGs).
Received: October 3, 2020
Published: December 31, 2020
TENGs have recently attracted increasing attention because
they can directly convert various mechanical energies into
electricity owing to its simple, cost-effective, and competent
technique with the coupling of triboelectrification and
electrostatic induction, since it was first presented by Wang
and co-workers in 2012.32−38 Generally, the output perform-
https://dx.doi.org/10.1021/acs.inorgchem.0c02946
© 2020 American Chemical Society
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illustrated that the electrons in binuclear Cd-SBUs were the
most active and the most likely to escape.
A single-crystal X-ray diffraction (SCXRD) study showed
that complex 1 crystallized in the triclinic crystal system space
bridging coordination mode to link [Cd4(μ4-O)] units and
Cd2 ions, generating crown-shaped pentanuclear [Cd5(μ4-
O)(COO)12] SBUs (Figure S3f). Meanwhile, the [Cd5(μ4-
O)(COO)12] SBUs were extended by CBBD4− ligands to
construct a neutral 3D framework (Figure S3g). As a result,
structural conversions from the neutral framework with
binuclear Cd-SBUs of 1 to the anionic framework of 2 with
trinuclear Cd-SBUs and back to the neutral architecture with
pentanuclear Cd-SBUs were achieved.
̅
group P1 with the binuclear SBUs (Figure 1a). In 1, the
To develop a clearer understanding of the impact of
incorporating different SBUs in 1−3, TENGs were fabricated
to clarify the contributions of the electronic structure in
different Cd-SBUs. The use of materials that possess molecular
or electronic structures that facilitate charge transfer in the
fabrication of TENGs improves their output.49−51 Correspond-
ingly, the electron gaining/losing capabilities, polarities, and
morphologies of the frictional pair materials were carefully
evaluated to optimize the operating conditions (Figures S4−
S9). After extensive examination of the morphologies,
polarities, and electron gain/loss characteristics of polynuclear
Cd-SBUs, a simple TENG was constructed with a pair of
opposite triboelectric polarities. The powered Cd-CPs acted as
electron donors, releasing electrons into their backbones, while
poly(vinylidene fluoride) spin-coated onto a Kapton film was
used as the electron acceptor. The working principle of
TENGs synthesized from these materials was their vertical
contact and separation mode, which would provide the
electricity by the coupling effect of triboelectrification and
electrostatic induction (Figure 2a).52,53
Figure 1. Crystal structures of 1−3: (a) 2D framework of 1 with
binuclear Cd-SBUs; (b) 3D network of 2 with trinuclear Cd-SBUs;
(c) 3D architecture of 3 with pentanuclear Cd-SBUs.
carboxylic groups of the ligands were completely deprotonated
and took the bridging/chelating coordination modes to
connect two Cd ions to form binuclear [Cd2(COO)4] SBUs
(Figures S1a−f). Furthermore, these binuclear SBUs were
linked with four CBBD4− ligands (Scheme S1), and each
ligand bridged with four binuclear SBUs, leading to a 2D
network structure (Figure S1b).
When the process of synthesis was slightly changed,
structural transformations occurred between the neutral
framework of 1 and the anionic framework of 2. SCXRD
analysis revealed that complex 2 crystallized in the monoclinic
system P21/n and possessed a 3D structure with trinuclear Cd-
SBUs in an anionic framework (Figure 1b). In 2, three
deprotonated carboxyl groups took the bis-monodentate and
chelate coordination modes to bridge two Cd ions (Cd1 and
Cd2), while the remaining deprotonated carboxyl group
adopted the chelating/bridging bidentate coordination mode
to link two Cd ions (Cd1 and Cd2), generating the trinuclear
[Cd3(COO)8] SBUs (Figure S2a−e). Furthermore, each
[Cd3(COO)8] SBU was bridged with eight CBBD4− ligands,
and each ligand was connected with four [Cd3(COO)8] SBUs,
resulting in a 3D network (Figure S2f).
As anticipated, the catenation isomerism could be further
controlled by regulating the reaction conditions. Unlike the
anion framework 2, 3 crystallized in the tetragonal space group
I4/m and demonstrated a neutral 3D architecture with
pentanuclear Cd-SBUs (Figure 1c). On the basis of the
coordination mode, the symmetrical Cd1, Cd1a, Cd1b, and
Cd1c were bridged together by a μ4-O atom to give a
tetranuclear [Cd4(μ4-O)] plane unit, and the O atom was
present at the center of the quadrilateral (Figure S3a−f).
Furthermore, the deprotonated carboxylic groups took the
Figure 2. Output performances of Cd-based TENGs: (a) working
principle of Cd-based TENGs. (b−d) Isc, Vo, and σ of ligand L-, 1-, 2-,
and 3-TENG, respectively.
Ligand L and Cd-CPs 1−3 triboelectrodes were employed
to engineer TENGs of dimensions 5 cm × 5 cm, which were
regarded as L-, 1-, 2-, and 3-TENG. The TENGs were
controlled via a linear motor at a frequency of 5 Hz to imitate
the mechanical energy in the environment. The short-circuit
current (Isc) and output voltage (Vo) of these TENGs were
measured under identical conditions (Figure 2b,c). It was
found that 1-TENG demonstrated the highest output among
all of the samples. The peak values of Isc and Vo for 1-, 2-, and
3-TENG were 78.2 μA and 548 V, 69.5 μA and 502 V, and 55
μA and 453 V, respectively, which indicated that the output
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performance decreased with an increase in the nuclear number
in the SBUs of Cd-based CPs. The triboelectric surface charge
density (σ), as one of the most important parameters for
evaluating the material performance in the TENG, produced
by 1-TENG was up to 132.8 μC/m2, which was about 1.3 and
1.7 times that produced by 2-TENG (99 μC/m2) and 3-
TENG (80 μC/m2), respectively (Figure 2d). Notably, σ of
1−3-TENGs was close to that of a wide range of materials
used in TENG fabrication (e.g., polymers, metals, etc.).54−56
Therefore, the output performance of Cd-CPs-based TENGs
followed the order 1-TENG > 2-TENG > 3-TENG > L-
TENG, which revealed that the binuclear Cd-CP 1 lost
electrons more readily and generated more charge than 2 and
3. Meanwhile, the results further demonstrated that the
readiness of polynuclear Cd-SBUs in 1−3 to lose electrons
was in the following order: binuclear SBUs in 1 > trinuclear
SBUs in 2 > pentanuclear SBUs in 3.
Having compared the electron-losing abilities of polynuclear
Cd-SBUs in CPs, we performed DFT calculations to acquire
deep insight into the effect of the electron escape probability
on polynuclear Cd-SBUs at the atomic level. The optimal
structure confirmed that the highest occupied molecular orbital
(HOMO) of polynuclear Cd-SBUs was located at the
coordination O atoms and the corresponding HOMO energies
of three polynuclear Cd-SBUs were −1.51, −2.40, and −3.20
eV, respectively (Figures 3a−c and Table S4). Consequently,
Figure 4. (a) Isc and (b) Vo from 1 to 8 Hz of 1-TENG. (c) Isc of 1-
TENG after working 50000 cycles.
was approximately 20.22 mW at a load resistance of 20 MΩ
(Figure S11).
In conclusion, we successfully designed and synthesized a
series of Cd-CPs (1−3), including SBUs with different
structures (binuclear, trinuclear, and pentanuclear SBUs for
1−3, respectively), in required compositions and controllable
arrangements to explore their electron gaining/losing capa-
bilities through the output of TENGs. The results revealed that
the magnitude of the outputs generated by the 1−3-based
TENGs were in the order 1-TENG > 2-TENG > 3-TENG,
which further confirmed the electron-losing capability of
polynuclear Cd-SBUs in CPs with the same order of binuclear
SBUs in 1 > trinuclear SBUs in 2 > pentanuclear SBUs in 3.
Meanwhile, this order was also consistent with the DFT
calculations. This work provided a sample and feasible strategy
to explore the gain/loss electronic capability of polynuclear
Cd-SBUs in CPs and endowed polynuclear CPs as a well-
defined platform for tuning the output performance of CPs-
based TENGs.
Figure 3. DFT calculation results: (a−c) HOMO and LUMO
energies of binuclear, trinuclear, and pentnuclear SBUs in 1−3,
respectively. (d) Calculated DOSs of polynuclear SBUs in 1−3.
ASSOCIATED CONTENT
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electrons were much more likely to escape from the binuclear
SBUs in 1 than from the trinuclear and pentanuclear SBUs in 2
and 3, respectively. The density of states (DOS) also revealed
that the electrons on the HOMO of the binuclear SBUs in 1
and the pentanuclear SBUs in 3 were the most active and inert,
respectively (Figure 3d). Moreover, the electrical conductivity
experiments further confirmed that the charges and electrons
generated during the vertical contacting process could be more
easily transported within 1-TENG (Table S5). Thus, 1 with
binuclear SBUs possessed the easiest ability to lose electrons
and held the highest output based on TENG.
Subsequently, the output of 1-TENG under periodic
impacts of 1−8 Hz was also measured. As the operating
frequencies increased, Isc and Vo increased, with maximum
values of Isc and Vo reaching 118 μA and 605 V, respectively
(Figure 4a,b). Furthermore, the stability of both Isc and Vo for
1-TENG was examined (Figures 4c and S10). The results
demonstrated that 1-TENG possessed good stability and
durability. Meanwhile, the highest output powder of 1-TENG
Detailed information for the experimental procedures,
methods, and figures (PDF)
The commercial red LEDs driven by 2-TENG (MP4)
Accession Codes
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tallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
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Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Authors
■
Chao Huang − Center for Advanced Materials Research,
Henan Key Laboratory of Functional Salt Materials,
Zhongyuan University of Technology, Zhengzhou 450007,
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(6) Chen, Z.; Jiang, H.; Li, M.; O’Keeffe, M.; Eddaoudi, M. Reticular
Chemistry 3.2: Typical Minimal Edge-Transitive Derived and Related
Nets for the Design and Synthesis of Metal−Organic Frameworks.
Chem. Rev. 2020, 120, 8039−8065.
(7) Deria, P.; Mondloch, J. E.; Karagiaridi, O.; Bury, W.; Hupp, J. T.;
Farha, O. K. Beyond post-synthesis modification: evolution of metal−
organic frameworks via building block replacement. Chem. Soc. Rev.
2014, 43, 5896−5912.
(8) Li, M.; Li, D.; O’Keeffe, M.; Yaghi, O. M. Topological Analysis
of Metal−Organic Frameworks with Polytopic Linkers and/or
Multiple Building Units and the Minimal Transitivity Principle.
Chem. Rev. 2014, 114, 1343−1370.
(9) Kirchon, A.; Feng, L.; Drake, H. F.; Joseph, E. A.; Zhou, H.-C.
From fundamentals to applications: a toolbox for robust and
multifunctional MOF materials. Chem. Soc. Rev. 2018, 47, 8611−
8638.
China; orcid.org/0000-0001-8576-8024;
Email: huangchao@zut.edu.cn
Mei Qiu − Department of Chemistry, College of Science,
Jiangxi Agricultural University, Nanchang, Jiangxi 330045,
China; Email: 523473836@qq.com
Liwei Mi − Center for Advanced Materials Research, Henan
Key Laboratory of Functional Salt Materials, Zhongyuan
University of Technology, Zhengzhou 450007, China;
orcid.org/0000-0001-9239-6599; Email: mlwzzu@
163.com
Authors
Guizhen Lu − Center for Advanced Materials Research, Henan
Key Laboratory of Functional Salt Materials, Zhongyuan
University of Technology, Zhengzhou 450007, China
Yingying Zhang − Center for Advanced Materials Research,
Henan Key Laboratory of Functional Salt Materials,
Zhongyuan University of Technology, Zhengzhou 450007,
China
Kaifang Zhu − Center for Advanced Materials Research,
Henan Key Laboratory of Functional Salt Materials,
Zhongyuan University of Technology, Zhengzhou 450007,
China
Siwen Cui − Center for Advanced Materials Research, Henan
Key Laboratory of Functional Salt Materials, Zhongyuan
University of Technology, Zhengzhou 450007, China
Weihua Chen − College of Chemistry and Green Catalysis
Center, Zhengzhou University, Zhengzhou 450001, China
Zijie Wu − North West Composites Center, School of
Materials, The University of Manchester, Manchester
M139PL, U.K.
(10) Bai, Y.; Dou, Y.-B.; Xie, L.-H.; Rutledge, W.; Li, J.-R.; Zhou, H.-
C. Zr-based metal−organic frameworks: design, synthesis, structur-
e,and applications. Chem. Soc. Rev. 2016, 45, 2327−2367.
(11) Kim, E. J.; Siegelman, R. L.; Jiang, H. Z. H.; Forse, A. C.; Lee,
J.-H.; Martell, J. D.; Milner, P. J.; Falkowski, J. M.; Neaton, J. B.;
Reimer, J. A.; Weston, S. C.; Long, J. R. Cooperative carbon capture
and steam regeneration with tetraamine-appended metal−organic
frameworks. Science 2020, 369, 392−396.
(12) Ni, K.; Luo, T.; Nash, G. T.; Lin, W. Nanoscale Metal−Organic
Frameworks for Cancer Immunotherapy. Acc. Chem. Res. 2020, 53,
1739.
(13) Park, S. S.; Hendon, C. H.; Fielding, A. J.; Walsh, A.; O’Keeffe,
̌
M.; Dinca, M. The Organic Secondary Building Unit: Strong
Intermolecular π Interactions Define Topology in MIT-25, a
Mesoporous MOF with Proton-Replete Channels. J. Am. Chem. Soc.
2017, 139, 3619−3622.
(14) Islamoglu, T.; Chen, Z.; Wasson, M. C.; Buru, C. T.;
Kirlikovali, K. O.; Afrin, U.; Mian, M. R.; Farha, O. K. Metal−Organic
Frameworks against Toxic Chemicals. Chem. Rev. 2020, 120 (16),
8130−8160.
Complete contact information is available at:
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(15) Sheberla, D.; Bachman, J. C.; Elias, S.; Sun, C.-J.; Shao-Horn,
Notes
̌
Y.; Dinca, M. Conductive MOF electrodes for stable supercapacitors
The authors declare no competing financial interest.
with high areal capacitance. Nat. Mater. 2017, 16, 220−224.
(16) Zhao, D.; Cheetham, A.; Furukawa, J. S.; Kitagawa, S.; Xu, Q.;
Zhang, W.; Zou, R. Open framework materials for energy applications.
APL Mater. 2020, 8, No. 040401.
ACKNOWLEDGMENTS
■
This work was financially supported by the National Natural
Science Foundation of China (Grants 21701201, 21601212,
and 21671205), Centaline Science and Technology Innovation
Leading Talents Support Plan (Grant 204200510014),
Program for Interdisciplinary Direction Team, the independent
innovation application research project (K2019YY002), and
Young Backbone Teacher of Zhongyuan University of
Technology.
(17) Thorarinsdottir, A. E.; Harris, T. D. Metal−Organic Framework
Magnets. Chem. Rev. 2020, 120 (16), 8716−8789.
(18) Abednatanzi, S.; Gohari Derakhshandeh, P.; Depauw, H.;
Coudert, F.-X.; Vrielinck, H.; Van Der Voort, P.; Leus, K. Mixed-
metal metal−organic frameworks. Chem. Soc. Rev. 2019, 48, 2535−
2565.
(19) Zhao, W.; Li, G.; Tang, Z. Metal-organic frameworks as
emerging platform for supporting isolated single-site catalysts. Nano
Today 2019, 27, 178−197.
(20) Masoomi, M. Y.; Morsali, A.; Dhakshinamoorthy, A.; Garcia, H.
Mixed-Metal MOFs:Unique Opportunities in Metal−Organic Frame-
work (MOF) Functionality and Design. Angew. Chem., Int. Ed. 2019,
58, 15188−15205.
REFERENCES
■
(1) Yaghi, O. M.; O'Keeffe, M.; Ockwig, N. W.; Chae, H. K.;
Eddaoudi, M.; Kim, J. Reticular synthesis and the design of new
materials. Nature 2003, 423, 705−714.
(21) Jumpathong, W.; Pila, T.; Lekjing, Y.; Chirawatkul, P.; Boekfa,
B.; Horike, S.; Kongpatpanich, K. Exploitation of missing linker in Zr-
based metal-organic framework as the catalyst support for selective
oxidation of benzyl alcohol. APL Mater. 2019, 7, 111109.
(22) Ejegbavwo, O. A.; Martin, C. R.; Olorunfemi, O. A.; Leith, G.
A.; Ly, R. T.; Rice, A. M.; Dolgopolova, E. A.; Smith, M. D.;
Karakalos, S. G.; Birkner, N.; Powell, B. A.; Pandey, S.; Koch, R. J.;
Misture, S. T.; Loye, H.-C. Z.; Phillpot, S. R.; Brinkman, K. S.;
Shustova, N. B. Thermodynamics and Electronic Properties of
Heterometallic Multinuclear Actinide-Containing Metal−Organic
Frameworks with “Structural Memory. J. Am. Chem. Soc. 2019, 141,
11628−11640.
(2) Yaghi, O. M.; O’Keeffe, M.; Kanatzidis, M. Design of Solids from
Molecular Building Blocks: Golden Opportunities for Solid State
Chemistry. J. Solid State Chem. 2000, 152, 1−2.
(3) Castillo-Blas, C.; de la Pena-O’Shea, V. A.; Puente-Orench, I.; de
̃
́
́
́
Paz, J. R.; Saez-Puche, R.; Gutierrez-Puebla, E.; Gandara, F.; Monge,
́
A. Addressed realization of multication complex arrangements in
metal-organic frameworks. Sci. Adv. 2017, 3, 1700773.
(4) Kalmutzki, M. J.; Hanikel, N.; Yaghi, O. M. Secondary Building
Units as the Turning Point in the Development of the Reticular
Chemistry of MOFs. Sci. Adv. 2018, 4, 9180.
̌
(5) Dinca, M.; Long, J. R. Introduction: Porous Framework
Chemistry. Chem. Rev. 2020, 120, 8037−8038.
553
https://dx.doi.org/10.1021/acs.inorgchem.0c02946
Inorg. Chem. 2021, 60, 550−554

Inorganic Chemistry
pubs.acs.org/IC
Communication
(23) Calvo, J. J.; Angel, S. M.; So, M. C. Charge transport in metal−
organic frameworks for electronics applicationsl. APL Mater. 2020, 8,
No. 050901.
(24) Qian, Q.; Asinger, P. A.; Lee, M. J.; Han, G.; Mizrahi
Rodriguez, K.; Lin, S.; Benedetti, F. M.; Wu, A. X.; Chi, W. S.; Smith,
Z. P. MOF-Based Membranes for Gas Separations. Chem. Rev. 2020,
120, 8161−8266.
(25) Mancuso, J. L.; Mroz, A. M.; Le, K. N.; Hendon, C. H.
Electronic Structure Modeling of Metal−Organic Frameworks. Chem.
Rev. 2020, 120, 8641−8715.
(26) Kamakura, Y.; Chinapang, P.; Masaoka, S.; Saeki, A.;
Ogasawara, K.; Nishitani, S. R.; Yoshikawa, H.; Katayama, T.;
Tamai, N.; Sugimoto, K.; Tanaka, D. Semiconductive Nature of Lead-
Based Metal−Organic Frameworks with Three-Dimensionally Ex-
tended Sulfur Secondary Building Units. J. Am. Chem. Soc. 2020, 142,
27−32.
(27) Bigdeli, F.; Lollar, C. T.; Morsali, A.; Zhou, H.-C. Switching in
Metal−Organic Frameworks. Angew. Chem., Int. Ed. 2020, 59, 4652−
4669.
stabilize the β-phase of PVDF for flexible piezoelectric nano-
generators. Nanoscale 2019, 11, 22989−22999.
(42) Wang, Y.; Chao, M.; Wan, P.; Zhang, L. A wearable breathable
pressure sensor from metal-organic framework derived nano-
composites for highly sensitive broad-range healthcare monitoring.
Nano Energy 2020, 70, 104560.
(43) Khandelwal, G.; Maria Joseph Raj, N. P.; Kim, S. J. Zeolitic
Imidazole Framework: Metal−Organic Framework Subfamily Mem-
bers for Triboelectric Nanogenerators. Adv. Funct. Mater. 2020, 30,
1910162.
(44) Khandelwal, G.; Chandrasekhar, A.; Maria Joseph Raj, N. P.;
Kim, S. J. Metal−Organic Framework: A Novel Material for
Triboelectric Nanogenerator−Based Self−Powered Sensors and
Systems. Adv. Energy Mater. 2019, 9, 1803581.
(45) Wen, R.; Guo, J.; Yu, A.; Zhai, J.; Wang, Z. L. Humidity−
Resistive Triboelectric Nanogenerator Fabricated Using Metal
Organic Framework Composite. Adv. Funct. Mater. 2019, 29 (20),
1807655.
(46) Guo, Y.; Cao, Y.; Chen, Z.; Li, R.; Gong, W.; Yang, W.; Zhang,
Q.; Wang, H. Fluorinated metal-organic framework as bifunctional
filler toward highly improving output performance of triboelectric
nanogenerators. Nano Energy 2020, 70, 104517.
(28) Barona, M.; Snurr, R. Q. Exploring the Tunability of Trimetallic
MOF Nodes for Partial Oxidation of Methane to Methanol. ACS
Appl. Mater. Interfaces 2020, 12, 28217−28231.
(47) Zhang, Y.; Wu, J.; Cui, S.; Wei, W.; Chen, W.; Pang, R.; Wu, Z.;
Mi, L. Organosulfonate Counteranions−A Trapped Coordination
Polymer as a High-Output Triboelectric Nanogenerator Material for
Self-Powered Anticorrosion. Chem. - Eur. J. 2020, 26, 584−591.
(48) Zhai, L.; Cui, S.; Tong, B.; Chen, W.; Wu, Z.; Soutis, C.; Jiang,
D.; Zhu, G.; Mi, L. Bromine−Functionalized Covalent Organic
Frameworks for Efficient Triboelectric Nanogenerator. Chem. - Eur. J.
2020, 26, 5784−5788.
(29) Peng, L.; Asgari, M.; Mieville, P.; Schouwink, P.; Bulut, S.; Sun,
D. T.; Zhou, Z.; Pattison, P.; van Beek, W.; Queen, W. L. Using
Predefined M3(μ3-O) Clusters as Building Blocks for an Isostructural
Series of Metal−Organic Frameworks. ACS Appl. Mater. Interfaces
2017, 9, 23957−23966.
(30) Castells-Gil, J.; Padial, N. M.; Almora-Barrios, N.; da Silva, I.;
́
́
Mateo, D.; Albero, J.; GarcIa, H.; MartI-Gastaldo, C. De novo
synthesis of mesoporous photoactive titanium(IV)−organic frame-
works with MIL-100 topology. Chem. Sci. 2019, 10, 4313−4321.
(49) Fan, F. R.; Tang, W.; Wang, Z. L. Flexible Nanogenerators for
Energy Harvesting and Self-Powered Electronics. Adv. Mater. 2016,
28, 4283−4305.
̌
(31) Bour, J. R.; Wright, A. M.; He, X.; Dinca, M. Bioinspired
chemistry at MOF secondary building units. Chem. Sci. 2020, 11,
1728−1737.
(50) Yang, Y.; Lin, L.; Zhang, Y.; Jing, Q.; Hou, T.-C.; Wang, Z. L.
Self-Powered Magnetic Sensor Based on a Triboelectric Nano-
generator. ACS Nano 2012, 6, 10378−10383.
(32) Fan, F.-R.; Tian, Z.-Q.; Wang, Z. L. Flexible triboelectric
generator. Nano Energy 2012, 1, 328−334.
(51) Feng, Y.; Zheng, Y.; Zhang, G.; Wang, D.; Zhou, F.; Liu, W. A
new protocol toward high output TENG with polyimide as charge
storage layer. Nano Energy 2017, 38, 467−476.
(33) Zi, Y.; Wang, J.; Wang, S.; Li, S.; Wen, Z.; Guo, H.; Wang, Z. L.
Effective energy storage from a triboelectric nanogenerator. Nat.
Commun. 2016, 7, 10987.
(52) Zhu, G.; Pan, C.; Guo, W.; Chen, C.-Y.; Zhou, Y.; Yu, R.;
Wang, Z. L. Triboelectric-Generator-Driven Pulse Electrodeposition
for Micropatterning. Nano Lett. 2012, 12, 4960−4965.
(34) Zhao, H.; Xiao, X.; Xu, P.; Zhao, T.; Song, L.; Pan, X.; Mi, J.;
Xu, M.; Wang, Z. L. Dual-Tube Helmholtz Resonator−Based
Triboelectric Nanogenerator for Highly Efficient Harvesting of
Acoustic Energy. Adv. Energy Mater. 2019, 9, 1902824.
(35) Liu, Z.; Li, H.; Shi, B.; Fan, Y.; Wang, Z. L.; Li, Z. Wearable and
Implantable Triboelectric Nanogenerators. Adv. Funct. Mater. 2019,
29, 1808820.
(36) Zhu, G.; Chen, J.; Zhang, T.; Jing, Q.; Wang, Z. L. Radial-
arrayed rotary electrification for high performance triboelectric
generator. Nat. Commun. 2014, 5, 3426.
(53) Zi, Y.; Niu, S.; Wang, J.; Wen, Z.; Tang, W.; Wang, Z. L.
Standards and figure-of-merits for quantifying the performance of
triboelectric nanogenerators. Nat. Commun. 2015, 6, 8376.
(54) Cui, S.; Zheng, Y.; Liang, J.; Wang, D. Conducting polymer
PPy nanowire-based triboelectric nanogenerator and its application
for self-powered electrochemical cathodic protection. Chem. Sci. 2016,
7, 6477−6483.
(55) Cheng, L.; Xu, Q.; Zheng, Y.; Jia, X.; Qin, Y. A self-improving
triboelectric nanogenerator with improved charge density and
increased charge accumulation speed. Nat. Commun. 2018, 9, 3773.
(56) Cui, S.; Zheng, Y.; Zhang, T.; Wang, D.; Zhou, F.; Liu, W. Self-
powered ammonia nanosensor based on the integration of the gas
sensor and triboelectric nanogenerator. Nano Energy 2018, 49, 31−39.
(37) Khandelwal, G.; Maria Joseph Raj, N. P.; Kim, S.-J.
Triboelectric nanogenerator for healthcare and biomedical applica-
tions. Nano Today 2020, 33, 100882.
(38) Kim, W. J.; Vivekananthan, V.; Khandelwal, G.; Chandrasekhar,
A.; Kim, S.-J. Encapsulated Triboelectric−Electromagnetic Hybrid
Generator for a Sustainable Blue Energy Harvesting and Self-Powered
Oil Spill Detection. ACS Appl. Electro. Mater. 2020, 2, 3100.
(39) Zhao, J.; Li, H.; Li, C.; Zhang, Q.; Sun, J.; Wang, X.; Guo, J.;
Xie, L.; Xie, J.; He, B.; Zhou, Z.; Lu, C.; Lu, W.; Zhu, G.; Yao, Y.
MOF for template-directed growth of well-oriented nanowire hybrid
arrays on carbon nanotube fibers for wearable electronics integrated
with triboelectric nanogenerators. Nano Energy 2018, 45, 420−431.
(40) Khandelwal, G.; Raj, N. P. M. J.; Kim, S.-J. ZIF-62: a mixed
linker metal−organic frameworkfor triboelectric nanogenerators. J.
Mater. Chem. A 2020, 8, 17817−17825.
(41) Ojha, S.; Paria, S.; Karan, S. K.; Si, S. K.; Maitra, A.; Das, A. K.;
Halder, L.; Bera, A.; De, A.; Khatua, B. B. Morphological interference
of two different cobalt oxides derived from a hydrothermal protocol
and a single two-dimensional metal organic framework precursor to
554
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Inorg. Chem. 2021, 60, 550−554