Revie On Synthesis and Conversion

Materials Science and Engineering B 272 (2021) 115341
Contents lists available at ScienceDirect
Materials Science & Engineering B

journal homepage: www.elsevier.com/locate/mseb
Carbon nanomaterials: Synthesis, properties and applications in

electrochemical sensors and energy conversion systems
Govindhan Maduraiveeran a, *, Wei Jin b, *
a
Materials Electrochemistry Laboratory, Department of Chemistry, SRM Institute of Science and Technology, Kattankulathur, Chennai 603 203, Tamil Nadu, India
b
State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai
200092, China
A R T I C L E I N F O A B S T R A C T
Keywords: Carbon materials secure to progress a plenty of real-world technologies. In particular, they are emerging ma
Carbon terials in numerous electrochemical applications, including electrochemical sensor and biosensor platforms, fuel
Nanomaterials cells, water electrolyzers, etc. Nanostructured carbon materials (NCMs) offer integrated advantages, including
Electrochemical sensors
upright electrical conductivity, built-in and structural flexibility, flimsy, huge chemical and thermal stability,
Energy conversion systems
Energy storage systems
alleviate of chemical functionalization, potential mass production, etc., allowing them to be emergent candidate
materials for various electrochemical employments. In consequent, enormous research efforts are dedicated to
the structure-, dimension- and pore-size/structure controlled synthesis carbon nanomaterials with unique
characteristics for uses in next-generation electrochemical devices. Herein we systematically discuss the recent
developments carbon nanomaterials (carbon nanotubes, graphene, carbon dot, biomass-derived carbon, etc.)
their synthetic strategies, surface active sites, and other surface characteristics, electrode fabrication methods,
working hypothesis, electrochemical activity and the state-of-the-art electrochemical applications. Development
of numerous carbon nanomaterials with rational design of controlled nano-/micro-scale structures, structur
e–property correlation and mechanistic conception for high performance electrochemical devices are introduced.
The figure-of-merit, emerging challenges, future perspectives, and vital aspects integrated with the invention of
new class of nanoscale carbon nanomaterials in electrochemical technologies furthermore are described.
1. Introduction interactions with other materials in nanoscale dimensions [8]. Accord

ingly, considerable recent research efforts have been made to the bulk
Carbon (C) is one of the most abundant elements in the Earth’s crust synthesis of structurally homogeneous materials and their assembly in
which has been acknowledged for a long time. The conception of carbon bulk-scale with competently-controlled surfaces and interfaces [9–11].
materials has aggressively reached an another milestone level from the Over last few decades, owing to the invention of the outstanding
macro-scale to the nano-scale with the incessant evolution in nano characteristics, the tasks of carbon nanomaterials have been increas
science and technology [1]. In recent advances, the nanostructured ingly extended from electrode materials to building blocks in electro
carbon materials (NCMs) provide miscellaneous allotropes such as dia chemical applications [12–15]. Though the high-flying uniqueness of
mond, graphene (GR), amorphous carbon, C60, carbon nanotubes the diverse NCMs diverge, their widespread features deliver them
(CNTs) and carbon dot (CDs) towards the numerous electrochemical exceptionally smart for the assembly of electrochemical technological
applications. These carbon nanomaterials can be arranged based on the applications as described below: (i) Owing to the intrinsic or artistic
number of dimensions, such as zero-dimensional (0-D) nanodots, one- electrochemical activity, NCMs and their nanocomposites may demon
dimensional (1-D) nanotubes, two-dimensional (2-D) and three- strate high electrochemical performance [16]; (ii) Due to the high
dimensional (3-D) materials [2,3]. They have been employed in electrical conductivity, NCMs secures that they provide as an ideal
diverse fields, including electronics, chemical sensors and biological electron transfer medium in numerous electrochemical systems [17];
sensors, energy conversion and storage devices, etc. [4–7]. Carbon (iii) The NCMs offer high electrocatalytic and storage performances by
nanomaterials are often sturdily reliant on their atomic structures and possessing of large surface area and small pore dimension [18]; (iv)
* Corresponding authors.
E-mail addresses: [email protected] (G. Maduraiveeran), [email protected] (W. Jin).
https://doi.org/10.1016/j.mseb.2021.115341
Received 10 January 2021; Received in revised form 1 June 2021; Accepted 28 June 2021
Available online 7 July 2021
0921-5107/© 2021 Elsevier B.V. All rights reserved.
G. Maduraiveeran and W. Jin Materials Science & Engineering B 272 (2021) 115341
Because of ease of functionalization, NCMs can easily be altered, which

may improve their functions significantly in electrochemical activity
[19,20]; and (v) Because of the biocompatibility, the NCMs facilitate the
numerous applications in biological fields [21,22]. Due to those ratio
nale, the NCMs are effectively considered as emergent materials which
induce us to review at length with the various synthesis strategies,
structure dependent reactivity and the state-of-the-art electrochemical
applications such as electrochemical sensors and biosensors, electro
chemical energy conversion and electrochemical energy storage sys
tems. This review aims to facilitate advance research and development
of high performance electrochemical devices, transfiguring the labora
tory strategies to the marketplace.
In this review, recent advancements in design of carbon nano
materials for electrochemical sensors/biosensors, electrochemical en
ergy conversion and electrochemical energy storage devices is
summarized. The developments in synthetic routes, functionalization
approaches and activation processes of NCMs such as carbon nanotubes,
graphene, carbon dot, biomass-derived carbon, etc., their nano
composits are briefly presented in Section 2. The structure–char
acteristic correlation and mechanistic conception of NCMs towards the
development of high performance electrochemical devices is discussed
in Section 3. The state-of-the-art electrochemical applications of NCMs,
including electrochemical sensors/biosensors, fuel cells, water electro
lyzers, supercapacitors and batteries is described in Section 4. Moreover,
the challenges, opportunities and decisive aspects associated with the Fig. 1. Pictorial representation of carbon allotropes and their properties of
discovery of potential new in carbon based nanomaterials for electro hybridization (black), crystal system (white), dimension (blue), specific surface
chemical sensor and energy related applications are presented in Section area (lavender), and density (red) [3]. (For interpretation of the references to
5, offering anticipate for coherent design and electrode materials prep colour in this figure legend, the reader is referred to the web version of
aration with high electrochemical activity and outstanding durability this article.)
for numerous technological processes.
2.1. Zero-dimensional (0-D) carbon nanomaterials
2. Synthesis and properties of carbon nanomaterials
Vast empty space among organic molecules and nature-abundant
Carbon-derived nanomaterials have been considered as emergent carbon materials has being partly occupied through the discovery of
materials owing to their exceptional chemical and physical character wide range of new materials with unique properties. Fullerenes, C60
istics such as high thermal and electrical conductivity, huge mechanical molecule with various sizes (30–3000 carbon atoms) was discovered in
potency, and optical possessions, extending applications in biosensor, early of 1980′ s. Apiece C60 molecule contains of 60 sp2 carbon atoms,
energy conversion and energy storage devices [23–25]. It is fascinated which are prearranged in a sequence of hexagons and pentagons to
that carbon debatably promising element possessing the capability to shape a spherical, known as truncated icosahedral structure (stable
bind afar and to almost all elements. Carbon can often be formed carbon nanostructures) [31]. In particular, C60 can rationally be shown
numerous crystalline disordered structures due to its existence in three as a large spherical organic molecule given, which soluble in organic
different sp1, sp3 and sp2 hybridizations as shown in Fig. 1 [3]. The solvents. Hence, C60 and other fullerenes (C70, C76, C82, and C84) may
carbon atoms are often connected with linear, trigonal, and tetrahedral also be considered as a carbon nanoallotrope with hybridization be
geometries, respectively which may be integrated in many routes to tween sp2 and sp3 [32]. There are two types of bonds lengths discovered
build a new allotropes with exceptional physical and chemical proper with the aid of X-ray diffraction pattern with a length of 1.38 Å attaching
ties. As presented in Fig. 2, presents the vertices of the ternary phase C atoms ordinary to a couple of adjacent hexagons and a length of 1.45 Å
diagram signify the three important hybridization states of carbon [26]. involving C atoms frequent to the pentagon-hexagon pair. The C60
Graphite is most broadly employed natural materials candidate, represents the face-centered cubic (fcc) lattice structures in a solid
utilizing in many large-scale industrial technological concerns. In recent phase. It has stable structure and the cage destroys at temperatures of
years, the utilization of synthetic graphite is considerably amplified ˃1000 ◦ C. The geometries of numerous fullerenes are presented in Fig. 3
because of its huge demand in market [27–29]. Widespread scientific in- [33]. The proposed all the graphyne model compounds and fullerenes
depth research into graphite has suggested that its exclusive integration are optimized in view of their molecular symmetries where the perme
of physical and chemical properties of stacked layers of hexagonal sp2 ation of a species via a membrane chiefly relays on two structural fac
carbon arrays. Over last two decades, graphite has been employed as a tors, the molecular diameter of the permeating species and the pore size
preliminary material to persuade numerous variety of carbon nano of the membrane. Numerous research papers have described prepara
materials with advanced development of fabrication techniques and tion, characterization and properties of fullerenes-based carbon allo
nanostructured materials, including majorly fullerenes, single- and tropes [31,32,34–36].
multi-walled nanotubes, and graphene (Fig. 1). Well-controlled nano Primarily, Kroto et al. [1] have produced durable carbon cluster
structures of carbon materials offer improved technological advance containing of 60 carbon atoms via laser irradiation for the clear
ments in numerous field, which will be attained via the ability to perceptive the mechanisms through the long-chain carbon molecules
synthesize and assemble carbon into controlled dimension and other form in the interstellar space. This study led a lot of attention in the
geometries at the nanoscale [15,30]. The synthesis of most carbon fullerene science. Numerous efforts were attended for the searching new
nanomaterials is from 2D- hexagonal carbon lattices. A list of carbon strategy for the preparation of larger fullerenes and specific isomers.
nanomaterials and their electrochemical energy applications are sum Nevertheless, at the moment, the vaporization of graphite via pyrolysis,
marized in Table 1. radio-frequency-plasma, or arc discharge-plasma techniques are highly
employed for production of fullerenes in commercial scale. Fig. 4 depicts
2
Fig. 2. Ternary phase diagram presenting carbon materials in a single hybridization state at the vertices, carbon materials containing two hybridization states along
the edges mixture, and materials with all three hybridization states within the triangle [26].
Table 1
Comparison of recent carbon-based electrocatalysts for energy applications.
Catalysts System Reactions Activity Durability Selectivity Ref
CoOx in N-doped graphitic carbon 0.1 M KOH RT ORR E1/2 = 0.84 V – n = 3.9 [210]
H2-O2/air; Fuel cells 100 mA cm− 2 at 0.85 V 15% current decay-15 h –
65 ◦ C
Fe-N-C 0.1 M KOH RT ORR E1/2 = 0.899 V 16 mV E1/2 shift-5000 n = 3.95–3.99 [211]
cycles
B/N-doped graphene QDs/graphene 0.1 M KOH RT ORR Eonset ~ 15 mV more positive than 27% current decay- n = 3.93–3.95 [212]
Pt/C 20,000 s
3D graphene nanoribbon 1 M KOH RT ORR E1/2=0.84 V 10% decay-12 h n = 3.95 [163]
1 M KOH RT OER η = 360 mV <10% decay-24 h n=4
6 M KOH RT Zinc-air 873 mAh g− 1 and 65 mW cm− 2 200 mV increase-150 –
battery cycles
Porous N/P-doped NiFe2O4/SWCNT 1 M KOH RT OER η = 247 mV No decay − 1000 cycles – [213]
W-SAC on N-doped carbon 0.1 M KOH RT HER η = 85 mV No decay − 10,000 cycles – [214]
53 mV dec-1
2D Mo2CTx 0.5 M H2SO4 RT HER η = 283 mV η = 305 mV-30 cycles – [215]
N-doped CNTs 0.1 M KHCO3 CO2RR CO formation from − 0.7 V – 80% FE − 1.05 V [216]
RT
N-doped nanoporous carbon/CNT 0.1 M KHCO3 CO2RR − 0.18 V onset overpotential No decay-36 h 81% FE − 0.9 V [196]
membranes RT
Cobalt sulfide/graphene 0.05 M H2SO4 N2RR 25 μg h− 1⋅mg-1cat at − 0.2 V Negligible decay-10 h 25.9% FE at − 0.05 [209]
RT V
− 1
B4C nanosheet 0.1 M HCl RT N2RR 26.57 μg h ⋅mg-1cat at − 0.75 V 8% decay-30 h 15.95% FE at − 0.75 [217]
V
the pure fullerenes, and chemical functionalization of fullerenes [36]. In product. The fullerenes show its basic property of capability to act as an
this study, a couple of strategy such as plasma and pyrolysis were electron acceptor in the donor–acceptor units in energy conversion
employed for the preparation of fullerenes. The plasma approach needs systems, connecting to its elevated electron affinity and low reorgani
a huge amount of electricity over 7–10 times higher energy in fullerene zation energy. Various number of donor–acceptor dyads were made and
3
Fig. 3. Optimized numerous fullerenes geometries and structural characteristics of fullerenes and graphynes [33].
Fig. 4. Structure of fullerene (a) and its derivatives (b-d); the fullerenes derivatives based organic solar cells diagram (e) [36].
investigated, presenting C60 as a classical electron donor. It is reported majorly engages the electroreduction of C60 to its dianion, creating a
by Balch co-workers [37] that the electrochemical performance of ful thin film which was comparable to, the film prepared by electrochemical
lerenes is noticeably modified in the presence of small amount of reduction of C60O. It is noticed that a switching potential of − 1.1 V is
dioxygen concentrations. This proposed electrochemical approach adequate to attain film growth and a maximum potential of − 1.4 V
4
necessity be attained for achieving a reasonable film growth under strategy which is treated mixtures of graphite powder and cement. This
dioxygen atmosphere. In addition, various chemical synthetic methods method develops the primary structure of the carbon dots which will be
are being employed for the preparation of C60. Though, a universal treated with oxidative for enriching the carbon dots surfaces with
preparation approaches for the chemical synthesis of fullerenes is silent reactive oxygen groups. The surface-passivation step is occurred with a
to be revealed. It is basically necessary the inclusive conception and the variety of organic molecules and oligomers, which are usually
choice of precursor molecules of the cyclization practice is a vital step to embedded on the carbon dots. Owing to the numerous merits of the
rationalize the preparation of fullerenes. electrochemical etching strategy such as abundant conductive carbo
Carbon nanodot (CD), later of fullerene study, with effective naceous substrates (graphite rod), highly abundant resources in nature
advancement of carbon nanomaterials, carbon nanodot (CD) is discov and less cost, the electrochemical etching method, a top-down approach
ered relatively new and one of the most auspicious carbon nano is a promising method to prepare carbon nanodots (Fig. 5(A)) [40]. The
materials. Carbon nanodot with a diameter of 2–10 nm principally dimension and chemical compositions of carbon nanodots may be
contains of a carbonized carbon core with organic functional groups. It expediently altered via changing a lot of synthetic parameters such as
has huge amount of oxygen contents and comprise of integrations of pH, concentration, electrolyte composition, and electrochemical
graphitic and turbostratic carbon in various volumetric ratios. The car method of electrolysis (potentiostatic, galvanostatic, and potential
bon nanodots present various interesting characteristics, in terms of varying techniques, etc.). As depicted in Fig. 5(B), the average distance
tunable excitation/emission, high chemical inertness, photo-durability, (ΔE) among the spaced peaks in differential pulse voltammetric (DPV)
relatively low toxicity, good biocompatibility, alleviate handling, and curves steadily increased with decreased size of the carbon nanodots
environment-friendly [38]. They have effectively been utilized in broad [40]. It is suggested that ΔE is inversely proportional to the geometrical
range of concerns in the area of biosensing, bio-imaging, photocatalysis, capacitance. These obtained well-defined electrochemical redox peaks,
optoelectronics, electrocatalysis, etc. [39,40]. In general, carbon nano sharp, reversible and highly reproducible, which are similar to single-
dots comprise of almost sp3-hybridized carbon which are mostly in electron transfer processes quantum dots, revealing the multivalent
amorphous nature. The carbon nanodots show quite strong photo species. Moreover, the carbon nanodots demonstrated the exciting op
luminescence, and rely on their dimension/structure, the excitation portunities in numerous applications in the field of single-electron
wavelength, and functionalization of the surface. transistors, molecular switches, and resonant tunneling diodes.
Carbon nanodots are produced using a lot of techniques with a huge Other approaches based on thermal decomposition or carbonization
interest in carbon nanomaterials over recent years. In typical, the carbon of organic compounds in high boiling solvents, water in oil emulsions,
nanodots are prepared using top-down method based on laser ablation the pyrolysis of polymer–silica nanocomposites, ultrasonic
Fig. 5. Schematic picture of the electrochemical approach for the synthesis of carbon nanodots using an appropriate intercalation compounds (A). Electrochemical
characteristics of the carbon nanodots under various scan rates and electrolytes (B) [40].
5
carbonization, or the hydrothermal, electrochemical, solvothermal, can easily be altered by modifying their dimension, morphology, ge
microwave, etc. with the treatment of carbohydrates, polymers, organic ometry, edges, etc. [25,46,48].
compounds, etc. [41–43]. Very recently Shan Co-workers [39] have Significant research investigations have been made for the homo
developed carbon nanodots with average of ~6.0 nm using a simple geneous and well-dispersed graphene quantum dots via top-down and
hydrothermal method. For instance, as shown in Fig. 6, the prepared bottom-up strategies [50–52]. Cutting and exfoliation of single graphitic
carbon nanodots exhibited a height of ~2.7 nm, highly uniform in crystallite through physical or chemical process are involved in top-
dimension (~6.0 nm) and distribution. The carbon core showed a down method. It is known that the strong oxidants (KClO3, KMnO4,
crystalline lattice structure with an interlayer spacing of 0.21 nm (d etc.) and acids are utilized for the chemical cutting of sp2 carbon ma
spacing of the graphene (1 0 0) planes). The average particle size was terials. Removing the by-products, including inorganic salts and acids
calculated to be 2.3 nm. The carbon nanodots displayed the stretching through application of the chemical cutting approach limited for large
vibrations of C-OH (3430 cm− 1), N–H (3412 cm− 1), stretching vibra scale production of graphene quantum dots. Conversely, physical cut
tional absorption band of C–C (1513 cm− 1), stretching vibrational ab ting approaches likely impossible due to the low efficiency in large-scale
sorption band of C-O/C-N (1635 cm− 1), and C-N (1290 cm− 1). A number production. Bottom-up methods signify to a series of reactions from
of efforts have been made for the dimension and morphology-controlled polycyclic aromatic compound, aromatic structures of molecules, etc.
synthesis of monodispersed carbon nanodots [44–46]. Generally, for the preparation of graphene quantum dots, which may exactly
bottom-up methods are presently facing following major issues for the gearshift the characteristics of the final graphene quantum dots. In un
mono-dispersed preparation of carbon nanodots [47–49]: (i) Aggrega fortunate, the traditional solvothermal bottom-up strategies are inade
tion via a carbonization, difficulty correlated to dimension-control; (ii) quate due to its low crystallinity of graphene quantum dots. Very
Required post-treatments process, including filtration, centrifugation, recently, Yang Co-workers [53] have demonstrated a facile, clean and
dialysis, gel electrophoresis, etc. (iii) Confined pyrolysis and electro highly proficient approach using ultraviolet irradiation (Fig. 7(a)) for
chemical strategies are likely suited to overcome those problems on the the synthesis of graphene quantum dots with ease of by-products
other hand. removal. The developed graphene quantum dots exhibited the size dis
Graphene quantum dot (GOD), is described the cutting a graphene tribution of ~1–5 nm with an average diameter of ~3 nm (Fig. 7(b)),
monolayer into small pieces in the dimensions of a few nanometers and perfect lattice structure (Fig. 7(c)). The graphene quantum dots
(2–20 nm), which are majorly comprised of sp2-hybridized carbon and showed low oxygen content offers a support of having a good crystal
in crystalline nature. Owing to the quantum confinement and edge ef linity and less surface oxygen-containing groups (Fig. 7(d)). The high
fects in graphene nanosheets in the dimension ranges from less than that intensity of the D and G band with a peak intensity ratio of ID/IG ≈ 0.25
of ~100 nm, eventually sheet the sheets become smaller (~10 nm). relatively, revealed the existence of defects in the graphene quantum
Interestingly, the graphene quantum dot shows non-zero band gaps due dots. It is highly suggested that the design of integrated approaches of
to those mentioned effects whereas graphene nanosheet presents band synthetic strategies, unique physico-chemical properties and potential
gap of zero width. This effect makes them promising electronic, optical applications with enhanced performance leads unlocking the challenge
and electrochemical properties. The band gap of graphene quantum dot for materials scientists and technologist.
Fig. 6. AFM (a), TEM (b), HRTEM (c), SAED (d), XRD (e) and FI-IR (f) measurements of the carbon nanodots [39].
6
Fig. 7. (a) Schematic illustration of graphene quantum dots. (b) TEM, (c) HRTEM, (d) XPS, and (f) The Raman spectrum of the produced graphene quantum
dots [53].
2.2. One-dimensional (1-D) carbon nanomaterials Wang Co-workers have demonstrated very recently that the sorting
of long nanotubes (>10 μm) which can be realized by “self-sorting” in
Carbon nanotubes (CNT) and carbon nanofibers (CNF), are majorly aqueous solutions [60]. The separation of SWCNTs was occurred owing
considered as the 1-D carbon nanomaterials, which were identified and to the length-dependent interactions among the SWCNTs themselves
successfully characterized many years before the segregation of gra (Fig. 8). This method completely contrasts to other published mecha
phene. Carbon nanotubes possess a cylindrical carbon structure and nisms that depend on SWCNT interactions with other media, including
offer broad range of tunable electrical, optical and physical properties gels, density gradients, porous membranes, etc. The developed SWCNTs
such as diameter, length, single-/multi-walled, surface functionaliza acts as a thin-film transistors (TFTs) exhibited a current on/off ratio of
tion, etc. Single walled carbon nanotubes (SWCNT) devise diameters in ˃1000 with the carrier mobility of ~90 cm2 V− 1 s− 1, beyond the con
the range of ~0.4–2 nm, and are numerous micro-meters long, with an ventional TFT materials. The development of a facile and versatile
empty internal space. Single- or multi-walled carbon nanotubes strategy for fabricating nanocomposites based on carbon nanotubes. The
(MWCNT) dependent on the graphenic layers number in the walls of the catalytically active nanoparticles in carbon nanotube matrix (NCN)
cylindrical structure. In addition, carbon atoms nearby the nanotube exhibit the high electrochemical performance via altering the electron
edge may be organized in numerous routes such as armchair, zigzag, and structure of the catalysts, led to improved conductivity, altering ener
chiral patterns, which are purely depending on the chirality. Due to the getics, etc. Wu et al. [56] have presented the fabrication of nano
substantial van der Waals interactions, carbon nanotubes are not composites based on Cr-doped FeNi–P/NCN using single-step heating
completely dispersible in organic or aqueous environments, frequently treatment by transition metal oxide, DCDA, and (NH4)3PO4 as pre
alleged sturdily organized in bundles. Numerous well-established ap cursors, as shown in Fig. 9. The Fe, Ni, and Cr solid solution metals
proaches are made for the production of carbon nanotubes [54–57]. An primarily reacted with phosphorus to create Cr-doped FeNi–P. In the
arch discharge of a couple of carbon electrodes in a chamber with an moment, the related carbons were catalytically converted to carbon
inert environment is a simple method among other developed methods. nanotubes in the existence of transition metals. Thus, it prevents the
Based on the individuality and pressure of the inert gas, the yield, aggregation of active nanoparticles, forming a very small dimension
clarity, and quality of the nanotubes are grown where various other (Fig. 9). The developed nanocomposites have elevated conductivity and
gases, including He, CH4, and H2, etc. may be injected into the working profuse mesopore structure, resulting in high activity, fast mass/charge
chamber for influencing the characteristics of the forming nanotubes. transport, easy release of formed gas bubbles, and favorable stability.
Graphite target generally composes catalytic nanoparticles such as Ni or It is understood that the preparation parameters often directly cause
Co or a mixture of the two, and the ablation is carried out through either on the length and density of the carbon nanotubes. With increase the
Nd:YAG or CO2 lasers. The quality, yield, purity, and properties of the catalyst concentration and catalyst exposure time, the carbon resources
CVD derived carbon nanotubes are majorly based on the composition are optimistically exaggerated the density and length of carbon nano
and morphology of the catalytic nanoparticles, the carbon resource, the tube grown. Many reports have shown that the nanocomposites of car
substrate nature, etc. [58,59]. bon nanotubes/other 2-D carbon nanostructures presented the
7
Fig. 8. (a) Scheme for the self-sorting method of long SWCNTs with a nematic phase. (b) SWCNTs are dispersed in superacid and the neutralized with NaOH [60].
exceptional electrochemical performance in comparison to commercial the carbon matrix. The resulting NCN nanocomposites exhibited high
carbon materials [61–63]. It is highly recommended that the growth of catalytic activity, rapid mass or charge transport process, and encour
carbon nanostructure with an organic environment facilitates the shape aging durability for electrocatalytic applications. It has been suggested
and various composition of 2-D carbon nanomaterials for improved that the environment of the precursor effects the texture of the carbon
electrical, electrocatalytic and storage properties [64–66]. nanofibers.
Carbon nanofibers (CNFs) are classified as a non-continuous 1D Carbon nanohorns (CNH), is a tubule- or cone-like morphology
carbon nanomaterials of cylindrical mostly in shape, involving of through a single graphenic layer. It is observed that ~0.4 nm is the wall-
stacked and curved graphene sheets settled in countless methods to-wall distance among contiguous single walled carbon nanohorns. The
[67–70]. In general, they are often explained as sp2-based hybridization cones-based structures were assembled via cutting a block from the
in a diameter extending in the range of ~50–200 nm with a high aspect single graphenic thin layer and the unprotected edges are then associ
ratio of ˃100. It has been understood that numerous types of carbon ated in a seamless manner. The carbon nanohorns are majorly prepared
nanofibers such as platelet carbon nanofibers, herringbone carbon via CO2 laser ablation of a graphite target or through the arc-discharge
nanofibers, ribbon (or tubular) carbon nanofibers, cone-helix carbon technique. The dimension of carbon nanohorns is easily aggregated by
nanofibers, etc. were acknowledged up to now. However, carbon using a method of the arc-discharge technique. By using CO2 laser
nanofibers absence the hollow structure, revealing one of the major ablation technique, the dimension of carbon nanohorns is generally
differences from carbon nanotubes. The cone and tilted graphene sheets small. The carbon nanohorns may be prepared in high yield and purity
structure of carbon nanofibers present an angle (α) ˃ 0, which defines even in the nonexistence of metal catalyst in comparison to carbon
the physicochemical characteristics of carbon nanofibers. Numerous nanotube preparation, suggesting that carbon nanohorns are in usual
synthetic methods were employed for producing carbon nanofibers, entirely metal impurities-free and relatively less cost to produce or
which are similar techniques for carbon nanotubes. In specific, majorly manufacture. As depicted in Fig. 10(top), the atomistic structure of
both catalytic chemical vapor deposition and catalytic plasma-enhanced graphene is provided in the formation of one pentagon per 60◦ wedge
chemical vapor deposition strategies permit for the controlled- [71]. Fig. 10 (bottom) shows the TEM and HRTEM images of the carbon
preparation of carbon nanofibers in terms of alignment, shape, dimen nanohorns [72]. The morphology of the individual nanocorns and
sion, and structures. As shown in Fig. 9, many steps are involved for the dimension of the aggregates may be affected with the application of
production of carbon nanofibers [56]. The hydrocarbon molecules such different types and pressures of the ambient gas, utilized in laser abla
as acetylene, ethylene, etc. are initially adsorbed and decomposed on the tion strategy. Density functional simulations study highlights the spatial
metal catalyst (Fe, Ni, Co, Mn, Cu, Mo, Pd, MgO, etc.) surface. The variations in chemistry of nanocone as displayed in Fig. 11, similar to
growth of carbon nanofibers occurs on the appropriate substrate via that of fullerenes and cone sidewall chemistry which is more reminiscent
dissolution, diffusion and precipitation. The stabilization progressions of graphene and large diameter nanotubes. This investigation revealed
involve, the oxidation process, promoting the graphitization of elec that the oxygen addition to graphenic sidewalls is an endothermic; as
trospun polymer nanofibers. The as-prepared nanocomposites of Cr- well as the epoxide oxygen may preferentially be found at nanocone tips
doped FeNi–P/NCN represents a pea-like structure with a diameter of [73]. The single-walled nanohorn (SWNH) nanocomposites with
35 nm which are highly immobilized with the carbon matrix. The ex phenolic resins and polymers presented a high electrical conductivity. It
istence of the elements such as C, N, P, Fe, Ni, and Cr evenly dispersed in has been shown that the nanocomposites of SWNHs/PANI nanobrushes
8
Fig. 9. (a) Pictorial representation of the preparation of Cr-doped FeNi–P/NCN and SEM image of the Cr-doped FeNi–P/NCN; (b & c) TEM and HRTEM images of the
developed nanocomposites; (d) Corresponding enlarged lattice image of (c); (e–k) HAADF-STEM elemental mapping of the nanocomposites [56].
also exhibited a key enhancement in capacitance values [74]. The for numerous electrochemical applications. For the bulk production of
capability to facilitate fast mass-transport kinetics by the generation of high purity graphene derivatives, a chemical approach is one of the
well-controlled structure with low level of aggregation and small pore promising strategies.
dimension spans the alternative energy conversion and storage sources. In particular, Hummers methods [78] and modified Hummers
With the significant development advances and current breakthroughs, methods [79] are broadly being used for various electrochemical ap
furthermore optimization of individualization process is necessary over plications. There are a couple of problems remain in many modified
functionalization mechanisms and spatially targeted functionalization Hummers method such as (i) huge usage of the oxidants and inter
strategies, may enhance the employment of carbon nanohorns in elec calating agents was unavoidable, and (ii) long time to produce graphene
trochemical technological area. based derivates, resulting in high cost and poor scalability. As a result,
there is a well-built demand to design a strategy with cost-effective and
performance-efficient route for producing graphene oxide (GO). Xing
2.3. Two-dimensional (2-D) carbon nanomaterials Co-workers have developed a method for NaNO3-free Hummers
methods through partial replacement of KMnO4 with K2FeO4 and
Graphene is one of the latest carbon nanomaterial and highly concentrated H2SO4 [80]. As shown in Fig. 12, the produced graphene
abundant candidate due to its building block of natural graphite and it oxide sheets initially are very irregular in morphological structure and
shows exceptional electrical characteristics. Graphene and carbon encompass a lateral dimension of a few microns with a thickness of
nanotubes are having the very comparable electrical, optical, thermal 1.5–2 nm, associating to 2–3 layers of carbon atoms. The produced
and other properties, however, graphene, a two-dimensional atomic graphene oxide (GA2) offered a highly porous nature with abundant
sheet-like structure, empowers more miscellaneous electronic charac macropores of ~10–20 μm in size. In the meantime, a remarkable vol
teristics via the presence of quantum Hall effect and massless Dirac ume of reduced GO2 nanosheets self-assemble into three-dimensional
fermions. Moreover, graphene is structurally flexible, marks it smart for conducting networks. Besides from 2-D graphene, a 3-D graphene
engineering thin and very stretchy material. Several synthetic ap structure presents improved heterogeneous electron transfer kinetics in
proaches have been established, including mechanical, solution, and comparison to 2-D graphene derivatives and 3-D porous carbon mate
chemical based strategies for the production of 2-D carbon materials of rials [27]. Over recent years, a lot of researches have attended to build 3-
graphene and others. Though, each synthetic approach varies in scal D graphene through template-assisted chemical vapor deposition (CVD),
ability and characteristics, influencing the characteristics of producing lithography, and chemical methods. On the other hand, it is understood
graphene [27,75–77]. In relation to pristine graphene, the intrinsic that the interconnectivity of graphene nanosheets with covalent link
restacking of graphene layers at the surface of the electrodes majorly ages is a crucial for forming of durable 3-D graphene morphology by
reduces the electroactive surface area and electrochemical performance
9
Fig. 10. (Top) Construction presentation of carbon nanohorns using cutting a wedge from graphene. (a) A simple single-pentagon cone. (b) four-pentagon cone. (c)
Possible cones with their cone tip angle and number of pentagons [71]. (Bottom) TEM and HRTEM images of the carbon nanohorns [72].
Fig. 11. DFT studies on reaction enthalpies for oxygen bridging among C60 and C60O, which oxidized 84◦ nanocone tip, or an epoxide on grapheme [73].
using several network linkers such as glutaraldehyde, resorcinol, poly high porous nature (Fig. 13 (bottom)). The value of interlayer spacing of
allylamine, etc. The resulting 3-D graphene may show poor electro graphite was extensively increased to 0.79 from 0.33 nm because of the
chemical performance because the attached linkers are negatively existence of oxygen functional groups and possessed a similar XRD
impacting the electrochemical activity, which are unavoidable [81–83]. pattern of rGO. The produced 3-D RGO possessed a lot of merits such as
Chen Co-workers have demonstrated a strategy for building of inter (i) oxygen functional groups are eliminated without the application of
connected 3-D graphene structures in the without the use of any network reducing agents; (ii) in the absence of external linkers, the intercon
linkers for improved supercapacitors applications [27]. Fig. 13 (top) nection is developed using covalent linkages via the formation of ether
presents synthesize of 3-D RGO from graphite through improved Hum and ester; and (iv) this method is economical and ease of bulk produc
mers strategy. The resulting 3-D RGO was highly interconnected with tion of 3-D graphene.
10
Fig. 12. Picture of (a) GO2 paper (Inset: GO1 and GO2 in water) and (b) GA2, (c) AFM image of GO2, and (d,e) FESEM images of GA2 [80].
Fig. 13. (Top) Scheme for the production of 3-D reduced graphene oxide; (Bottom) FE-SEM (A), TEM (B) images of 3-D RGO and XRD pattern of graphite, GO and
RGO (C) [27].
On the other hand, many researchers have demonstrated graphene- were developed in the concept of waste to wealth for improved water
like hierarchical porous nanosheets carbon materials which are splitting and supercapacitance applications. As depicted in Fig. 14,
derived from numerous natural sources. Many natural resources, graphene-like hierarchical porous nanosheets were derived from dry
including orange peel, aloevera, food waste, soya-bean, rice husks, spathe-pollen waste of palm plant and effectively employed as an effi
peanut root nodules, etc. have been studied for the mass production of cient hydrogen evolution reaction catalyst “energy from waste”
carbon nanostructures via chemical activation with many reagents offers approach [23]. DFT investigation presents that the hydrogen binding
activated carbon nanomaterials with attractive morphological and energy of the produced sheet-like carbon nanostructures possessed
textural features [23,84,85]. Recently, graphene-like carbon materials exquisite properties, which can be associated unique integration of high
11
Fig. 14. Schematic illustration of the preparation of porous and nanosheet structured carbon materials from palm waste [23].
surface area, simplistic electrolyte percolation within hierarchical prepared on template from other nanoscale materials via a CVD
bimodal pore model, stout electrode/electrolyte interface as well as the approach. For instance, Wang et al. have prepared micrometer long
N-dopant. boron-doped diamond nanowire electrodes where boron-doped dia
Owing to exceptional characteristics, including high surface area, mond (BDD) films were grown by microwave plasma-enhanced chemi
ultra-thin thickness, brilliant electrical conductivity, mechanical flexi cal vapor deposition from methane/hydrogen mixtures (1% CH4) in an
bility, and lofty chemical functionality, graphene can be considered as ASTeX 6500 reactor is employed [93]. Fig. 15 shows the morphology
an ideal 2D platform for forming or assembling nanocomposites with and overall substrate coverage of the BBD nanowires formed on a highly
small nanoparticles for numerous electrochemical applications boron-doped polycrystalline diamond thin films using mask less reactive
[24,77,86,87]. A variety of graphene-based materials with anchored, ion etching (RIE) with oxygen plasma.
wrapped, embedded, layered, sandwich, mixed structures, etc., have It is understood that the obtained electrical and electrochemical
established for greatly enhanced electrochemical performance for sen characteristics of the diamond electrodes locally or by the characteristics
sors, energy conversion and energy storage devices in terms of improved difference of macroscopic bulk-diamond electrodes from their nano
catalytic activity, capacitance, rate capability, and durability. The well- structures is clarified clearly. The influence of morphology, composition
controlled dimension, surface morphology, high dispersion of functional (the ratio of graphite to diamond), doping in diamond, boundary in
groups and enhanced interfacial interactions among graphene and fluence, and surface functionalization of diamond surface on their
functional building blocks must be focused for the further improved
electrochemical performance.
2.4. Three-dimensional (3-D) carbon nanomaterials
Three-dimensional structured nanodiamonds (ND) is also created a

much interest in various field over recent years, which are produced via
high-energy conduction of graphite, maximum usually by detonation.
Interestingly, they devour analogous physical possessions as bulk dia
mond in terms of fluorescence and photoluminescence and biocompat
ibility. They are mostly composed of sp3 carbon, and the numerous
functional groups have been employed for the surface functionalization
of diamond in practical. Numerous research studies [88–92] have
showed the effective employment of planar macroscopic diamond,
graphite, etc. based electrodes in the field of bio-electrochemistry,
electroanalytical chemistry, electrocatalysis, etc. Nanodiamonds were
prepared using top-down, bottom-up, template-free, and related ap
proaches. The diamond is etched with reactive ions via an etching mask
in the top-down strategy. The dimension and structures of the nano
diamonds majorly depends on the etching mask, etching conditions, etc. Fig. 15. SEM images obtained for the prior to- (a) and after oxygen etching (b)
On the other hand, in a bottom-up strategy, the nanodiamonds are BDD film, S-BDD NWs (c), and L-BDD NWs (d) [93].
12
electrochemical characteristics may be explained in brief. The interfa demonstrated that the CNPs usually possess both the fluorescent and
cial properties of the diamond nanostructures or textures were usually electrochemical response. With different electrode modifications as
studied with voltammetry and impedance techniques in the presence of shown in Fig. 17 [97], the CNPs fabricated electrochemical biosensor
redox probes. The electrochemical characteristics of the short and long can have good cell permeability and intracellular solubility, high target
BDD nanowires were studied with CV techniques (Fig. 16) [93]. As affinity (π-π interactions) and nontoxicity. Consequently, it can be used
depicted in Fig. 16, the hydrogen-terminated electrode depicts the for the fast and highly sensitive detection of O2, H2O2, glucose and even
reversible redox-behavior and showed the currents ~2.4 times over on cancer markers in the blood, urine, body tissues/fluids of potential pa
S-BDD nanowires and ~3.5 times on L-BDD nanowires in comparison to tients. Goyal et al. [99] reported the dopamine detection in the presence
the flat BDD. Nanoscale diamond materials have demonstrated of concentrated ascorbic acid at C60-coated gold electrode, in which the
enhanced electrochemical active sites, electrocatalytic activity, oxidation of these two analytes is split into two well-defined peaks due
electron-transfer rates, etc. Thus, nanodiamonds based electrodes have to the strong electrocatalytic performance. Li et al. [100] developed the
been considered as the promising electrode materials for various ap carbon quantum dots/Cu2O nanocomposite for the non-enzymatic
plications in the field of electroanalysis, catalysis, fuel cells, energy amperometric detection of glucose and hydrogen peroxide.
conversion and storage. Recent advancements on nanodiamonds have There are also many emerging advances of 0-D carbon sensing
revealed that their exception and durable electrochemical performance nanomaterials, such as the development of novel architectures and
in many sensors, energy conversion and energy storage platforms, combination of nanomaterials/devices. Ugarte [101] developed the
creating them substitute possibilities to metal-based materials. multi-layer fullerenes of carbon nano-onions (CNOs), and then many
functional groups have been introduced at the surface of CNOs to further
3. Electrochemical applications improve the solubility and mobility in the solvents. Bartolome et al.
[102] reported there is 4.3-fold sensitivity increase and a factor of 7
3.1. Electrochemical Sensor/Biosensor platforms reduction in limit of detection (LOD) at the CNOs modified electrode as
compared to the corresponding carbon nanodiamonds modified elec
The carbon-based electrode was initiated by Adams in 1958, nowa trode. On the other hand, the miniaturization of microfluidic devices is
days carbon nanomaterials (CNMs) are widely employed for electro another pathway to enhance the detection performance. As illustrated in
chemical sensors due to their superiorities of low cost, large surface area, Fig. 18, Opallo [103] reported a CNPs microfluidic channels for the
high electrochemical activity, good chemical durability, enhanced sensitive and selective determination of dopamine in the presence of
molecules adsorption and favorable biocompatibility [94,95]. interfering ascorbic acidic and uric acid with ultra-low detection limit of
Currently, the successful detected analytes include neurochemicals/ 3.5 nm.
biomarkers (dopamine, ascorbic acid, hydrogen peroxide, proteins and Carbon nanotubes (CNTs) are hollow rolled-up graphene sheets,
DNA) and environmental pollutants (heavy metals, persistent organic ranging from single walled (SWCNTs) to multi-walled (MWCNTs) with
pollutants and gaseous pollutants), even under the complicated in vivo different thickness and metallic/semiconducting features [104,105].
and real-time monitoring conditions[96]. These carbon sensing nano With acidic treatment, the pristine CNTs can be purified and endowed
materials can be mainly classified into zero-dimensional (0-D) nano with defect sites/oxygen functional groups, which is beneficial for the
particles, one-dimensional (1-D) nanotubes/nanofiber, two-dimensional analyte adsorption and electron transfer [106,107]. It has been
(2-D) layered graphene/diamond film and three-dimensional (3-D) demonstrated that dip coating or drop casting CNTs often suffer from the
porous structures. surface agglomerations, while directly fabricated aligned CNTs can
Generally, the zero-dimensional carbon nanoparticles (CNPs) are generate more reproducible and amenable surfaces. As shown in Fig. 19,
consist of nanodiamonds, fullerenes (C60), carbon dots (CDs, carbon Gooding [108] identified the aligned shortened SWNTs array for the
nanodots and carbon quantum dots with quantum confinement) and direct electron transfer with enzyme of miroperoxidase MP-11, resulting
graphene quantum dots (GQDs, the p-conjugated mono-sheet of carbon in high efficiency of similar heterogeneous rate constant to that for the
nanodots) with a size 10–100 nm [97,98]. Since the discovery of laser corresponding one at cysteamine-modified or 3-mercaptopropionic acid
ablation at carbon target, many preparation methods of pyrolysis, hy (MPA)-modified gold electrodes. Rius [109], Vashist [104] and Wang
drothermal/electrochemical treatments and microwave have been re [105], Gooding [106] and Jacobs [110] have systematically summa
ported for the CNPs from a wide variety of carbon resources. It has been rized the advances of CNTs electrochemical sensors. And recently, Yang
Fig. 16. CV curves of the BDD film (grey), S-BDD NWs (black) and L-BDD-NWs (blue): (A) H-terminated electrodes; experimental data (dotted lines), Digi Sim fitted
data (full lines); (B) oxidized electodes: Electrolyte solution: 10 mM of Fe(CN)6 + 0.1 M KCl at a scan rate of 50 mVs− 1; (C) Change of peak current with square root of
scan rate for BDD (grey), S-BDD NWs (black) and L-BDD NWs (blue) for anodic and cathodic currents [93]. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
13
Fig. 17. Schematic diagram of surface modified CNPs electrodes. Reproduced with permission from Ref. [97] Copyright Elsevier 2019.
Fig. 18. (a) Schematic diagram of the microfluidic amperometric detection system. (b) Digital photograph of the microfluidic experimental setup. Reproduced from
Ref. [103]. Copyright Royal Society of Chemistry 2014.
[111] reported a photo-refreshable electrochemical 5-hydroxyltrypt widely used as the electrochemical sensing materials towards small
amine and dopamine sensor at the composite of CNTs and TiO2 nano molecules, proteins and cells. Liu [115] reported a renewable electro
particles, offering further understanding of the synergistic effect spun Ni nanoparticle-decorated CNFs paste electrode for the nonenzy
between photocatalytic and electrochemical activity at CNTs-based matic glucose sensors, resulting in 1 μM detection limit and 2 μM to 2.5
electrodes. mM linear range. Additionally, there is good operational durability due
Carbon nanofibers (CNFs) are consist of closed graphitic shells along to the favorable resistance to surface fouling. As shown in Fig. 20, Mao
the tube axis. They have comparable conductivity and stability to CNTs, et al. [116] developed the continuous electrospun carbon nanofibers
but more edge sites on the outer wall due to the stacking graphene sheets with ultra-wide-range electrochemical dopamine sensing performance,
of varying shapes [112–114]. The vertically aligned CNFs have been in which ~105 greater dynamic range than that of many other carbon-
14
Fig. 19. Schematic diagram of aligned shortened SWNT arrays for direct electron transfer with MP-11. Reproduced from Ref. [108]. Copyright American Chemical
Society 2003.
Fig. 20. Electrospun carbon nanofibers for the ultra-wide-range electrochemical sensing. Reproduced from Ref. [116]. Copyright American Chemical Society 2014.
based sensors is achieved. functional groups in the GO. Although Lin, Pumera, Bahadır, Roy,
Since the discovery in 2004, graphene is an emerging rising-star Chen and et al. [121–126] have published review articles about the
nanomaterial of one-atom-thick planar carbon sheet with sp2-bonds electrochemical sensing performance of graphene-based nanomaterials,
[117]. It has many advantages of high crystal and electronic quality, there are still many research advances in the most recent 3–5 years. As
large specific surface area (theoretically 2630 m2/g for monolayer gra illustrated in Fig. 21, Amani et al. [127] reported a screen-printed
phene), strong mechanical toughness, great thermal and electrical electrodes modified with poly p-phenylenediamine and graphene
conductivities, offering promising applications for the sensitive elec nanocomposite as enzyme and label free electrochemical immunosensor
trochemical detection and related device miniaturization [118–120]. of protein biomarker neuron-specific enolase. The fabricated immuno
Graphene can be produced by many methods, and it has been demon sensor exhibited a wide linear range of 1.0–1000 ng⋅mL− 1 and a low
strated that the pathway of chemical graphite oxide reduction obtains detection limit of 0.3 ng⋅mL− 1 even in human serum samples. Xuan et al.
graphene with abundant structural defects and functional groups. [128] developed a wearable electrochemical glucose sensor based upon
Interestingly, this graphene oxide (GO) precursor to graphene is an also the micro-patterned reduced GO on flexible substrate to achieve high
interesting material in itself, which has various oxygen-containing sensitivity of 45 μA⋅mM− 1 cm− 1 and low detection limit of 5 μM. It
15
Fig. 21. Electrochemical immunosensor based on screen-printed electrodes modified with PPD-GR nanocomposite. Reproduced from Ref. [127]. Copyright Elsev
ier 2018.
should be noted that there is short response time of 20 s and can be

applied in the human sweat-based glucose.
As compared to graphene, reduced graphene oxide (rGO) with rich
active sites and function groups has been widely employed to be able to
detect NO2, NH3, H2 and organic vapors [129]. Nitric oxide (NO) is one
of the smallest and important biologically signaling molecules in the
nervous and cardiovascular systems. As shown in Fig. 22, Shahid et al.
[130] reported a reduced graphene oxide-cobalt oxide nano
cube@platinum (rGO-Co3O4@Pt) nanocomposite for the electro
chemical NO detection. The nanocomposite modified electrode
presented better catalytic performance as compared to those of rGO,
Co3O4 nanocubes and rGO-Co3O4 nanocomposite modified electrodes.
And there is great NO detection selectivity in the presence of other 100-
fold higher concentration analytes. Li et al developed rGO devices for
NO detection by alternating current dielectrophoresis (ac-DEP), result
ing in highly sensitive, reproducible and reliable detection of NO gas
ranging from 2 to 420 ppb at room temperature. Besides, the rGO
nanocomposite can also be employed in the electrochemical heavy
metal monitoring. Guo et al. [131] reported a rGO-chitosan/poly-l-
lysine nanocomposite modified electrode for the simultaneously detec
tion of trace Cd(II), Pb(II) and Cu(II) with detection limits of 0.01 μg⋅L-1,
0.02 μg⋅L-1, and 0.02 μg⋅L-1, respectively.
Nowadays, transition-metal single-atom catalysts (SACs) present the
superb specific activity due to the maximum atom efficiency and low-
coordinated surface nature [132–134]. As illustrated in Fig. 23, due to
the typically high surface free energy at single atom, single transition
metal atoms anchored at single vacancies of graphene attracts increasing
attentions. Taking advantages of both experimental and theoretical in
vestigations, it has been demonstrated there is completely different re
action pathway at the SACs embedded in graphene, leading to excellent
electrocatalytic activity, durability and selectivity. Therefore, after
solving the issues of cost-effectiveness and fabrication simplicity in the
near future, it is expected that there is great potential for these novel
nanomaterials for the electrochemical sensor.
The 3D and porous carbon (PC) with high surface area, accessible
surface chemistry, and improved mass transfer has attracted consider
able interest for electrochemical sensors [135]. Cheng [136] identified Fig. 22. (A) Amperometric i-t curves obtained at bare GC, Co3O4 nanocubes,
that there are significantly different performance of 3D and 2D structure rGO, rGO-Co3O4 nanocomposite and rGO-Co3O4@Pt nanocomposite for NO2;
of carbon nanocomposite, in which the H2O2 detection limit of 3D (B) the corresponding calibration plots of current versus concentration of NO2.
graphene aerogel-supported and 2D rGO-supported Cu2O are 0.37 μM Reproduced from Ref. [130]. Copyright Royal Society of Chemistry 2015.
and 3.78 μM, respectively. Many methods including soft/hard
16
Fig. 23. (Upper) Morphology and composition characterization of isolated Ni single atoms in graphene nanosheets. Reproduced from Ref. [133]. Copyright Royal
Society of Chemistry 2018 [133]; (Below) theoretical calculation of the single metal atoms embedded in grapheme. Reproduced from Ref. [134]. Copyright from
American Chemical Society 2017.
templates, chemical vapor deposition et al. have been developed to Organization (WHO).
fabricate porous CNTs sponge, graphene foam, and CNTs/graphene Besides, the porous carbon derived from the low-cost biomass is
aerogel [137]. As shown in Fig. 24, Jiao et al. [138] reported a dual another promising strategy for the electrochemical sensor platform
templating method to prepare the hierarchically porous carbon fabrics construction, leading to simultaneous high value-added exploration of
with both macro- and meso-porous features. These novel nanomaterials biomass resources and better understanding of the structure-
presents superhydrophilicity and highly conductive, which is benefit for performance relationship [140,141]. With the rational design of nar
the sensitive electrochemical detection of methanol or H2O2. Besides, row pore distribution and abundant oxygen doping, Wang et al. [142]
the emerging metal–organic frameworks (MOFs) have been widely reported a 3D microporous carbon derived from kenaf stem for the
explored as the porous carbon precursor, due to their rational tailorable electrochemical detection of H2O2, glucose and amino acid (as shown in
cavities and open channels. Ju et al. [139] developed a nitrogen-doped Fig. 25), while Zhou et al. [143] identified a carbon nanorods assembled
PC material from polypyrrol-doped Al-bearing metal–organic gel and meso-macroporous carbons aerogels from apples for the electrochemical
the as-prepared sensor has a 2.2 nM Cd ions detection limit, which is monitoring of ascorbic acid and H2O2. Zeinu et al. [144] developed a
much lower than the limited value of 26 nM set by the World Health hollow sphere Bi2O3 doped mesoporous carbon nanosphere as the
17
Fig. 24. (a) Water and H2O2 liquid drops and b) methanol on the pristine PET; c) spread water drop on HC-PET; d) the CAs of different liquids on various samples in
ambient condition.. Reproduced from Ref. [138]. Copyright Wiely 2018.
Fig. 25. Electrochemical sensing using biomass-derived microporous carbon. Reproduced from Ref. [143]. Copyright American Chemical Society 2014.
picomolar electrochemical sensing of Pb and Cd, resulting in ultra-low pyrrolic, graphitic N) with an extra electron and better electro-
detection limit of 1.72 pM Pb2+ and 1.58 pM Cd2+ as well as good negativity is most popular dopant for carbon, which can change the
linear range, reproducibility and selectivity. And increasing sources of band gap and effectively tune the charge distribution for electrocatalysis
biomass have been reported as the porous carbon precursor, Yu et al. (as shown in Fig. 26) [148].
[140] reported the systematic design of bacterial cellulose-derived car Metal-doped carbon nitrides (M-N-C) or transition metal carbides
bon nanofiber aerogel (CNF), while Dutta [145] well summarized the (TMCs): The synergistic effect between metal and carbon can provide
interconnected pores control of hierarchically porous carbon stemmed beneficial effects towards the electrochemical performance as well as
from polymer and biomass. the high hardness/melting points/thermal conductivity for the
durability.
2D/3D structures: The rational design of emerging 2D carbon (such
3.2. Electrochemical energy conversion systems as graphene, MXene et al.) and the hierarchically porous structure offer
promising potential to improve the specific surface areas, electronic/
In electrochemical energy applications, the carbon-based materials ionic conductivity, active sites and mass transport.
have been widely employed as gas diffusion layer, electrocatalyst sup Defect/strain/interface engineering: With precise control of surface-
port and electrocatalyst itself [146,147]. It has been identified that the related properties, the intrinsic activity, electronic states and chemical
amorphous carbon black support usually suffer from the corrosion issue bonds can be significantly enhanced for the target-specific reactions.
under high-potential condition, thus resulting in many alternatives of
carbon nanotubes, fibers, graphene, etc. [148] Recently, considerable 3.2.1. Fuel cells and metal-air batteries
efforts have been carried out in the development of novel carbon-based Oxygen reduction reaction (ORR) and evolution reaction (OER) are
metal-free to replace noble metal (e.g., Pt) catalysts, which can be one pair electrochemical reactions of significant importance for the
mainly classified into the following strategies: energy technologies of fuel cells and metal-air batteries. Qiao
Heteroatom-doping (e.g., N, B, P, S). Nitrogen (i.e. pyridinic,
18
Fig. 26. (a) Charge density distribution at nitrogen-doped CNTs (N-CNTs); (b) Possible oxygen adsorption modes on CNTs (top) and N-CNTs (bottom); (c) Atomic-
resolution transmission electron microscopy (AR-TEM) image of the SeGnP edge; (d) IRR mimetic diagram on the SeGnP surface; (e) Schematic illustration of charge
transfer and of ORR process on PDDA-CNT; (f) Free energy values for ORR of different kinds of defects; (g) AR-TEM image of DG. Reproduced from Refs. [142,153].
Copyright American Chemical Society 2019.
[149–151], Dai [152,153], Lin [154], Guo [146], Shao [155,156] et al. interest in the promising cost-effective alternatives of nitrogen-doped
summarized the carbon-based nanomaterials for these two important carbon nanocomposites and transition metal-derived M-N-C (M = Fe,
half-reactions. The sluggish ORR and OER kinetics lead to large con Co or Ni). It should be noted that the selectivity of 4e- reaction mecha
sumption of precious metal (e.g., Pt, Ir, Ru), thus there is increasing nism in ORR is also a key consideration for the electrocatalyst design,
Fig. 27. (a) Atomic configuration of various dopants at the graphene matrix; (b) Free energy diagram of doped graphene; (c) Tafel plots for different electrocatalysts;
(d) Free energy diagram and adsorbed species at the g-C3N4 surface with different pathways; (e) Typical TEM image and (f) ORR performance of the obtained g-
C3N4@CMK-3 composite. Reproduced with permission form Ref. [149]. Copyright Royal Society of Chemistry 2015.
19
otherwise the side-reaction of 2e- pathway to H2O2 (in acidic solution) containing nitrogen-doped carbide-derived carbon materials for the
or HO–2 (in alkaline solution) significantly decrease the activity and ORR cathode catalysts in an alkaline direct methanol fuel cell, resulting
facilitate the hazardous corrosion issue. As shown in Fig. 27, Qiao et al. in comparable performance to that of Pt/C in both rotating disk elec
[149] identified that the heteroatoms doping can endow the carbon trodes (RDE) and fuel cell measurements. And the emerging 2D TMCs,
materials with modulated electronic characters and defect structures, also known as MXenes, have increasing applications in the hydrogen
and there is also synergistic effects among different doping elements. evolution reaction (HER) in the following sections of water
The functionalized carbon can have improved performance due to the electrolyzers.
more active sites, enhanced oxygen and intermediate OOH* adsorption Furthermore, considerable efforts have been carried out toward the
for better oxygen electrocatalysis, particularly in the N-graphene (usu novel carbon materials for both OER and ORR processes. It has been
ally 2–5 atom% N content). Murdachaew et al. [157] systematically predicted that N-graphene has the potential for this bifunctional elec
investigated the OER on N-doped defective carbon nanotubes and gra trocatalysis, while the different active sites (zigzag carbon–nitrogen for
phene, and found that the presence of 0.3–1% N with simple lattice ORR, armchair carbon near nitrogen for OER) significantly hinder the
defects (atomic substitution, vacancy and Stone-Wales rotation) can exploration. Recently, Liu and Dai [163] reported the 3D nitrogen-
significantly reduce the overpotentials. For example, the graphitic ni doped graphene nanoribbon networks (N-GRW) for the superb bifunc
trogen atom doping can decrease the overpotential of single-walled tional electrocatalyst, in which the electron-donating quaternary N sites
carbon nanotubes (SWNTs) from 1.17 V to 0.43 V. and electro-withdrawing pyridinic N moieties are responsible for the
Besides, there is also considerable efforts in the transition-metal ORR and OER, respectively (as illustrated in Fig. 29). Therefore, the as-
addition to improve the electrocatalysis performance of carbon nano prepared N-GRW exhibited 1.46 V open-circuit voltage, 873 mAh g− 1
materials as illustrated in Fig. 28. Inspired from the pioneer FeN4 elec specific capacity, 65 mW cm− 2 peak power density and excellent cycling
trocatalyst of Lefevre and Dodelet [158], Wu et al. [159] reported the durability in the rechargeable zinc-air batteries. And Loh et al. [164]
fabrication of Fe-N-C from polyaniline (PANI) and transition metal (Fe also reported a wood-derived hierarchically porous carbon plates for the
or Co) precursors, leading to increased active sites, and comparable comparable bifunctional performance, indicating the facilitating effect
performance with benchmark Pt/C. As a result, this material can of porous structures. Besides, the hybrid nanomaterials of transition
generate sufficient activity/durability for practical fuel cell applications. metal/carbon [165–167], N, S-doping [168] are also good strategies for
The nearly 5 at% transition metal cations can coordinate with pyridinic the bifunctional electrocatalyst design. Most recently, Li et al.[169] re
nitrogen (up to 8 at%), and encapsulate itself into the carbon plane as ported a defect-rich and ultrathin N-doped carbon nanosheets for the
the additional active sites. Artyushkova and Chen [160] also illustrated even tri-functional ORR, OER and HER electrocatalysts, benefiting from
that the M-N-C catalysts can facilitate the ORR selectivity via blocking the synergistic effect of defect, 2D and nitrogen doping methods.
the protonated and hydrogenated N, which are responsible for the
partial 2e- reduction of oxygen to H2O2. On the other hand, Mustain 3.2.2. Electrochemical and photoelectrochemical water splitting
et al. [161] demonstrated that transition metal carbides are excellent Electrochemical and photoelectrochemical (PEC) water splitting
electrocatalyst support materials, which have similar electronic struc have been widely demonstrated as carbon–neutral promising energy
tures to Pt near the Fermi level for better electron transfer and stability conversion technologies from electric/solar into clean H2 fuels. As
at catalyst-support interface. Ratso [162] developed the Co- and Fe- shown in Fig. 30, it consists of two half reactions, i.e., water reduction of
Fig. 28. Superior ORR activity (a) and durability (b) in acidic media; (c) activity and (d) durability in alkaline media at Fe-N-C catalyst. Reproduced with permission
from Ref [168]. Copyright Elsevier 2016.
20
Fig. 29. Electronic characteristics and ORR/OER active sites of N-doped graphene catalysts; (A) UPS spectra and inset of enlarged view about the secondary electron
tail threshold; (B and C) Carbon and nitrogen K-edge XANES spectra of N-GRW catalyst; (D) Schematic diagram of ORR and OER occurring at different active sites on
the n- and p-type domains of the NGRW catalyst. Reproduced with permission from Ref. [163]. Copyright American Association for the Advancement of Sci
ence 2016.
Fig. 30. (a) Schematic diagram of the electrolytic and fuel cells; (b) typical polarization curves of the hydrogen- and oxygen-involving reactions. Reproduced from
Ref. [155]. Copyright American Chemical Society 2018.
HER and water oxidation of OER [155]. Recently, the noble platinum- dev− 1 are obtained. Besides, it has been demonstrated that the 2D
group metals, RuO2/IrO2 are the most efficient electrocatalysts for transition metal carbides/nitrides of MXenes is a new group of prom
HER and OER, respectively. There are tremendous efforts for the ising electrocatalysts for HER [183–185], owing to the nearly 0 eV (the
development of earth-abundant 2D/3D transition metal-based oxides, ideal value) atomic hydrogen adsorption Gibbs free energy (ΔGH*), rich
sulfides, phosphides, nitrides for these two half-reactions, leading to the oxygen vacancy, and the weak binding strength between terminated O*/
successful hybrid structures between transition metal-based nano Hads (as illustrated in Fig. 31 [186]. These are systematically screened
materials and carbon nanomaterials [170–175]. the 72 different MXenes for electrochemical HER using density func
According to previous summarizations [176–180], the functional tional theory calculations, and identified that the HER performance can
ized carbon nanomaterials also can exhibit great performance for the be easily tuned via controlling the MXenes layer structures. Qiao et al.
water splitting. Zhao et al.[181] reported that the simple surface- [187] reported an interacting carbon nitride and Ti carbide nanosheets
oxidized MWCNTs has a low overpotential of 0.3 V for the OER, due with electroactive Ti–Nx motifs and hydrophilic porous structure for the
to the C–– O effects towards the electronic structures and intermediates OER, resulting in excellent electrocatalytic ability comparable to that of
adsorption. Tsiakaras [182] developed the N-doped porous Mo2C precious-/transition-metal catalysts and superior to that of most avail
nanobelts for HER, in which small onset potential of − 52 mV, low able free-standing films.
overpotential of 110 mV at 10 mA cm− 2, and low Tafel slope of 49.7 mV Since Fujishima and Honda’s pioneer study of the
21
Fig. 31. (Upper) Negative overpotential of carbide and nitride MXenes; (below) ΔH versus ΔGH plot for MXenes that have |ΔGH| ≤ 0.5 eV. Reproduced from
Ref. [186]. Copyright American Chemical Society 2017.
photoelectrochemical water splitting into H2 and O2 at TiO2 [188], H2 production rate of 474.7 μmol g− 1 h− 1 and approximate quantum
semiconductor-based PEC nanomaterials attract increasing attentions as yield (AQY) of 3.2% at 435 nm. Wang et al. [191] reported the Pt-CoP/g-
illustrated in Fig. 32. It has been shown that the PEC light-harvesting C3N4 for overall water splitting, which can improve catalytic kinetics
performance suffers from the wide band gap of traditional TiO2, WO3 and charge separation/migration to achieve better photocatalytic effi
and ZnO. The α-Fe2O3 of hematite has a narrower Eg for good photo ciency. Ajayan et al. [192] developed the 2D α-Fe2O3/g-C3N4 Z-scheme
current density, while it still limited by the issue of large bulk recom catalysts for the PEC water splitting, achieving a large H2 evolution rate
bination losses. Graphitic carbon nitride materials, particularly the g- above 3 × 104 µmol g-1 h-1 and remarkable external quantum efficiency
C3N4, have emerged as alternative photocatalysts due to the cost- of 44.35% at λ = 420 nm.
effectiveness, tunable band gap, favorable energy-band position and
great durability [189]. Peng [190] reported a sub-15 nM Ni2P nano 3.2.3. The CO2 and N2 reduction reaction (CO2RR and N2RR)
particles immobilized on porous g-C3N4 as a 0D-2D heterostructure for In order to fulfill the commitment of the Paris Climate Conference,
photocatalytic hydrogen evolution, leading to a remarkable efficient and clean conversion of large-scale inert small molecules (CO2
Fig. 32. Bandgap energies and CB (green) and VB (red) edge positions of the selected oxides, nitrides and chalcogenides. Reproduced from Ref. [188]. Copyright
2016 Wiley. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
22
and N2) is also highly important as compared to energy structure transition-metal atoms (M = Ag, Au, Co, Cu, Fe, Ir, Ni, Os, Pd, Pt, Rh, or
transformation and low-carbon society development. And it has been Ru) can insert into the surface defect sites of TiC, while the Ir-doped TiC
demonstrated that electrochemical reduction into value-added products has an extremely low overpotential of − 0.09 V.
(e.g. CO, CH4, CH3OH, C2H4, and NH3) is an effective strategy. However, The annual production of 200 million tons with Haber-Bosch tech
the conversion rate, efficiency, and selectivity are largely hindered by nology needs 1–3% of global energy production and possess a significant
the high dissociation energy of C–– O/N– – N bonds and the side reduction
– concern to climate change. Similar to CO2RR, many transition metals of
reaction of HER, addressing the necessity to search for highly efficient Fe, Ni, Mo, Ru, Pt and their alloys/nitrides exhibits great performance
and robust electrocatalysts with desirable selectivity. for the electrochemical nitrogen fixation to NH3. And as for a multistep
The electrochemical CO2 reduction reaction (CO2RR) is multi- proton-electron transfer process, the initiate 1 or 2 electrons reactions
electron transfer process to C1 and C2 products, which is mainly in are usually the rate-determining step. However, due to the weak tran
volves the CO2 adsorption, C-O bonds cleavage and products desorption sition metal-N2 bind and favorable metal-H bonds via d orbital electrons,
steps. The Au, Ag and Cu based nanomaterials are widely employed for the side reaction of HER is a bottlenecks for the metal-based electro
the CO2RR, where the size, alloy, interface and defect effects are highly catalysts [206,207]. Zhao et al. reported the N-doped porous carbon as
important to decrease the overpotential, improve faradic efficiency and the efficient N2RR catalysts, resulting a high production rate of 1.40
enhance the durability. As for the carbon-based CO2RR, the nitrogen- mmol g-1h− 1 owing to the favorable N2 adsorption and N– – N cleavage
–
doping, porous defect, and rational hybrid are general methods for the [208]. Sun et al. reported the Mo2C nanorod, Ti3C2Tx (T = F, OH)
electrocatalysts design [193]. Ajayan et al. [194] reported there is a low nanosheets, B4C nanosheets with Faradic efficiency of 8.13% at − 0.3 V,
onset potential of − 0.19 V (vs. RHE) and a high Faradic efficiency above 9.3% at − 0.4 V, and 15.95% at − 0.75 V, respectively. Recently, as
85% at N-doped graphene foam, which is better than the corresponding shown in Fig. 34, Xie et al. [209] developed a cobalt sulfide/graphene
ones at Au and Ag. Similar investigations can also be found at poly hybrids with strong bridging bonds (Co-N/S-C) at the interface between
ethylenimine modified N-doped carbon nanotubes [195], N-doped CoSx nanoparticles and NS-G (nitrogen- and sulfur-doped reduced gra
nanoporous carbon/carbon nanotube membranes [196], N-doped gra phene), leading to a high NH3 Faradaic efficiency of 25.9% at − 0.05 V.
phene/CNT [197]. Besides, it has been identified that the transition
metal carbides are the most promising selective CO2 to CH4 electro 4. Figure-of-the-merit of carbon nanomaterials
catalysts [198–200], such as Cr3C2, WC and Mo3C2. As illustrated in
Fig. 33, Kolpak et al. [201] calculated that there is smaller COH binding Design of advanced highly electrochemically active, durable, and
energy barrier with the introduction of WC. Most recently, there is low-cost electrode materials is of massive impact towards the evolution
increasing interest in the single atom transition metal supported on and practical concerns in sensor/biosensor, electrochemical energy
carbon-based nanomaterials for the CO2RR [202,203]. Liu et al. [204] conversion and storage devices. It is aimed that the brief figures-of-the-
reported the Ni SACs on niterogenated graphene as an efficient elec merit of carbon derived nanomaterials in state-of-the-art electro
trocatalysts with a specific current of 350 A g-1
catalyst, turnover frequency chemical technologies to prompt the massive prospective for accom
of 14,800 h− 1 and a low overpotential of 0.61 for CO production at even plishing extraordinary atom-utilization productivity, series of hybrid
97% Faradic efficiency. And Jung et al. [205] calculated that single architectures and other distinctive possessions will be described in this
section, as follows.
(i) Cost-effective: Owing to low Earth abundance, high price, and
harmful in biological platforms of noble- and non-noble metals derived
electrode materials (Pt-, Ru-, Ir-, Co-, Ni-, etc.), the engineering industry
build-ups are severely stuck. Nanostructured carbon-based electrode
materials, as an alternate, the deployment of tremendously less expen
sive and high Earth-abundance (4th most abundant element in the
universe by mass), electrochemical active, high performance, long-term
durable and great biocompatible materials have converted emergent as
a first-hand frontline in electrochemical technologies.
(ii) Maximum atom-utilization efficiency: High surface area, huge
number of active sites, the characteristic electronic structure, unsatu
rated coordination surroundings of the electrochemically active axes can
easily uncovered by using the maximum utilization of carbon atom. The
inherent electrochemical activity can also be value-added through the
quantum-size belongings, facilitating to validate an admirable electro
chemical performance at a low-slung ingestion.
(iii) Carbon nanomaterials effect: Exceptional capability of the car
bon atoms to contribute in stout covalent bonds with other carbon atoms
in miscellaneous hybridization states (sp, sp2, sp3) or with non-metallic
elements qualifies them to create an extensive series of structures,
starting from small molecules to long chains. This character reinforces
the giant prominence of organic chemistry, materials chemistry and
biology, identifying a choice of new materials with unique characteris
tics and various electrochemical applications in sensors, catalysis,
supercapcitors, batteries, etc.
(iv) Ease of functionalization: Appropriate functionalization of
organic or biological molecules creates them solid employment for
various functional components of electronic devices include in vitro cell
imaging, sensing, fuel cells, batteries, etc. through high water solubility,
Fig. 33. Transition-metal-coated tungsten carbides for the efficient and selec non-toxic, biocompatible, ease of cell permeable, etc. and
tive electro-reduction of CO2 to methane. Reproduced with permission from (v) Support materials: Owing to the extraordinary optical, electrical
Ref. [201]. Copyright Wiely 2015. and mechanical characteristics, carbon and its derivatives are expected
23
Fig. 34. Catalytic performance of CoSx/NS-G during the electrocatalytic nitrogen reduction. (A) NH3 yield rate and Faradaic efficiency; (B) NMR spectra of 1H for the
electrolytes after NRR test; (C) Comparison of NH3 yield rate at − 0.2 V and particle size; (D) Faradaic efficiency of well-developed NRR electrocatalysts. Reproduced
with permission from Ref. [209]. Copyright National Academy of Sciences of the United States of America (NAS) 2019.
to devise extensive support candidates for multiplicity of noble and non- care and other in-vivo and in-vitro studies, on-time determination and
noble metal particles or metal oxides, sulfides, phosphides, etc. Carbon monitoring emerging biomarkers will get-up-and-go the advent of
nanomaterials allow a lot of nanocomposites towards the construction of advanced devices. It is highly understood that there will be a substantial
robust thin films, field-effect transistors, photosensitive transistors, and mandate for the progress of advanced technologies for environmental
high conductive plates in supercapacitor, lithium and sodium batteries. issues as well as for the invention of substitute energy conversion and
High electrochemical activity of carbon based nanomaterials in sensing, storage devices due to the amassed environmental anxieties and the
catalytic, storage activity, and atom economy effects are significantly augmented reduction of fossil. Owing to those reasons, the development
stimulated via various special effects, including their structure, allo of advanced catalysts, sensing and storage materials based on carbon to
tropes, dimension, functionalization, purity, coordination site, confine reduce the noble and non-noble metals, while improving the electro
ment, etc. chemical performance and durability.
Though, a lot of major challenges persist to be set preceding to the
5. Conclusion, challenges and outlook wide-ranging fabrication of electrochemical technologies by the
employment of carbon nanomaterials. The major downsides of carbon
Nanostructured carbon-based materials have materialized as an nanomaterials are their isolation and dispersion, solubility, volume
exceptional sensing, catalytic and storage platform due to their miscel contraction, purity issues when large scale production, etc. Disputes to
laneous and stout inherent optical, electronic and mechanical charac cogitate in the establishment of novel carbon nanomaterials compre
teristics. The tractability of these carbon based nanomaterials is hend (i) pore volume and morphology control- to attain prime active
demonstrated with the application of carbon nanodots (0-D), carbon sites, (ii) ease of isolation and dispersion method- to commendably
nanotubes (1-D) and graphene (2-D) as whichever distinct single carbon adapt the feasibility of the reactions/adsorptions, (iii) control of volume
atom derived or as assembled and hybrid/composite, integrated into shrinkage for improved durability, (iv) appropriate functionalization- to
numerous electrochemical platforms or devices. With an eternally high dispersion and creation of bio-compatible environments, (v) reac
emergent diversity of carbon-based material candidates, this stimulates tive edge sites creation- to improve the electrochemical active sites, (vi)
in the field of electrochemical sensor, energy conversion and storage optimization and high yield- to enrich the electrochemical activity and
being advanced year on year. In this Review, we describe structure-, stability, (vii) central correlation among morphology, pore-structure,
dimension- and pore-size/structure-controlled synthesis and structur composition and electrochemical activity- to build a competent candi
e–property correlation and mechanistic conception-based characteris date, and (viii) discover novel hybrid materials based on multiple carbon
tics of various allotropes of carbon such as carbon dot, carbon allotropes- to obtain the integrated characteristics of their component
nanotubes, graphene, biomass-derived carbon, etc. towards the state-of- carbon allotropes. As the wide-range of hybrid carbon derived archi
the-art electrochemical applications. In particular, the chemical func tectures using multiple carbon allotropes grows, it is expected that
tionalization, biocompatibility, activation, electrode fabrication, elec carbon nanomaterials to discover even more real-world technologies
trochemical activity and advances of the numerous carbon where they were formerly collegial with further conservative sub
nanomaterials are well-discussed. Over next decade, the intention and stitutes. We strongly believe that the present review has offered a solid
execution of high electrochemical performance of carbon nanomaterials charter to expedite the advent of novelties to discourse the challenges
are expected to raise extensively. With growing prerequisite for point-of- which are presently obstruct the employment of carbon nanomaterials
24
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The authors declare that they have no known competing financial [45] J. Feng, G. Liu, S. Yuan, Y. Ma, Phys. Chem. Chem. Phys. 19 (2017) 4997–5003.
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Materials Science and Engineering B 272 (2021) 115341

Contents lists available at ScienceDirect

Materials Science & Engineering B

Carbon nanomaterials: Synthesis, properties and applications in

1. Introduction interactions with other materials in nanoscale dimensions [8]. Accord

Because of ease of functionalization, NCMs can easily be altered, which

2.4. Three-dimensional (3-D) carbon nanomaterials

Three-dimensional structured nanodiamonds (ND) is also created a

should be noted that there is short response time of 20 s and can be

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Revie On Synthesis and Conversion

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Revie On Synthesis and Conversion

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Materials Science and Engineering B 272 (2021) 115341

Contents lists available at ScienceDirect

Materials Science & Engineering B

Carbon nanomaterials: Synthesis, properties and applications in

1. Introduction interactions with other materials in nanoscale dimensions [8]. Accord­

Because of ease of functionalization, NCMs can easily be altered, which

2.4. Three-dimensional (3-D) carbon nanomaterials

Three-dimensional structured nanodiamonds (ND) is also created a

should be noted that there is short response time of 20 s and can be

You might also like

1. Introduction interactions with other materials in nanoscale dimensions [8]. Accord