PROGRESS REPORT
Carbon Nanoreactors
Nanoengineering Carbon Spheres as Nanoreactors
for Sustainable Energy Applications
Hao Tian, Ji Liang, and Jian Liu*
Colloidal carbon sphere nanoreactors have been explored extensively as
a class of versatile materials for various applications in energy storage,
electrochemical conversion, and catalysis, due to their unique properties
such as excellent electrical conductivity, high specific surface area, controlled
porosity and permeability, and surface functionality. Here, the latest updated
research on colloidal carbon sphere nanoreactor, in terms of both their
synthesis and applications, is summarized. Various synthetic strategies are
first discussed, including the hard template method, the soft template method,
hydrothermal carbonization, the microemulsion polymerization method, and
extension of the Stöber method. Then, the functionalization of colloidal carbon
sphere nanoreactors, including the nanoengineering of compositions and
the surface features, is discussed. Afterward, recent progress in the major
applications of colloidal carbon sphere nanoreactors, in the areas of energy
storage, electrochemical conversion, and catalysis, is presented. Finally, the
perspectives and challenges for future developments are discussed in terms
of controlled synthesis and functionalization of the colloidal carbon sphere
nanoreactors with tunable structure, and the composition and properties that
are desirable for practical applications.
1. Introduction
The design and synthesis of functional colloidal carbon spheres
has recently attracted great attention because of their wide
applications in a number of research areas such as energy
storage and conversion, catalysis, water and air purification, and
Dr. H. Tian, Prof. J. Liu
State Key Laboratory of Catalysis
Dalian Institute of Chemical Physics
Chinese Academy of Sciences
457 Zhongshan Road, Dalian 116023, China
E-mail: jian.liu@dicp.ac.cn
Dr. J. Liang
Institute for Superconducting and Electronic Materials
Australian Institute of Innovative Materials
University of Wollongong
Innovation Campus, Squires Way, North Wollongong, NSW 2500, Australia
Prof. J. Liu
DICP-Surrey Joint Centre for Future Materials
Department of Chemical and Process Engineering
and Advanced Technology Institute
University of Surrey
Guildford, Surrey GU2 7XH, UK
E-mail: jian.liu@surrey.ac.uk
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.201903886.
DOI: 10.1002/adma.201903886
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adsorption.[1–4] Their suitability for these
application is attributed to the very unique
properties of colloidal carbon spheres such
as tunable porous structures, controllable
particle size, large surface area, and con-
trollable surface chemistry.[5,6] All these
properties of colloidal carbon spheres are
highly dependent on their synthesis meth-
odology. Over the past decades, great efforts
have been made on the synthesis, char-
acterization, and extension of the appli-
cation of porous carbon spheres. More
research advances on colloidal carbon
spheres would provide new opportunities
to understand their physical and chemical
properties, as well as for the design and
preparation of new structured carbon
spheres built up from the molecular level,
which can further provide guidelines for
practical applications.
To mimic the structure of cells, the as-
prepared artificial cells should own some
properties such as spatial compartmen-
talization and selective permeability. Until
now, polymersomes,[7] liposomes,[8] and multiple emulsions[9]
have been used to imitate the structures and properties of
natural cells. However, the softness, poor mechanical strength,
and chemical robustness have hindered their practical applica-
tions. The carbon spheres are potentially promising candidates
for construction of cell-like structures. The ideal colloidal carbon
spheres should possess all or most of the following properties:
a) large surface area and controllable surface functionalities
for effective dispersion and loading of metal nanoparticles or
other active species on their surface; b) superior conductivity
to provide electron pathways; c) tunable porosity and particle
size for facile mass transport; d) high stability for long term
operation.[10–13] To achieve this goal, a series of synthetic strate-
gies for these nanostructured carbon spheres have been devel-
oped, such as the Stöber method,[13] the template method,[14,15]
hydrothermal carbonization (HTC),[16] and microemulsion
polymerization.[17] To further modify the carbon spheres with
various porous structures and functionalities, novel technolo-
gies for pore size control, surface modification, heteroatom
doping, and graphitization engineering have also been devel-
oped and widely utilized.
A number of excellent reviews on colloidal carbon spheres
have been published in recent years, especially for energy
storage applications.[1,5,18,19] In this context, this review article
aims to systematically summarize the latest works, mainly
focusing on synthetic approaches to optimized properties of
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porous carbon spheres toward electrochemical storage, conver-

sions, and catalysis (Figure  1), with nanoreactors as a clue. In Hao Tian received his B.S.
the first part, different strategies of the preparation of nano­ and M.S. from Lanzhou
porous carbon spheres are summarized. Following that, various University in 2009 and 2012,
approaches for tuning the particle size, porous structure, pore his M.S. from the University
orientation, morphology, and surface properties of carbon of New South Wales in 2014,
spheres are appraised. Subsequently, the major applications and his Ph.D. from Curtin
of carbon spheres in the areas of the secondary batteries, elec- University in 2018, under the
trochemical conversion, and catalysis are presented. General supervision of Prof. Jian Liu
guidelines are provided to help select suitable methods for and Prof. Shaomin Liu. He is
synthesizing carbon spheres with the desired structures and now a postdoctoral research
functionalities for targeted applications. Finally, we will discuss associate at the Center for
the current challenges and present the prospects for the fabri- Clean Energy Technology,
cation of superior colloidal carbon spheres and its utilization as University of Technology Sydney. His current research
nanoreactors. mainly focuses on hollow, core–shell, and yolk–shell
structured nanoparticles in the field of catalysis, energy
storage, and conversion.
2. Synthesis of Porous Carbon Spheres
Ji Liang received his Ph.D.
2.1. Synthetic Strategies degree from the University
of Adelaide in 2014. After a
The fabrication of carbon spheres with well–defined structures two-year T. S. Ke fellowship
is an important research area and current hotspot in mate- at the Institute of Metal
rials science. Figure  2 illustrates typical transmission electron Research of the Chinese
microscopy (TEM) images of carbon materials with different Academy of Sciences, he
particle sizes, pore sizes, porous structures, and spherical deriv- was appointed as an ARC
atives with hierarchical structures. For instance, microporous DECRA research fellow at the
carbon spheres, mesoporous carbon spheres, hollow carbon Institute for Superconducting
spheres (HCS), yolk–shell carbon spheres, multiple-cavities and Electronic Materials of
carbon spheres, asymmetric bowl-like mesoporous carbon the University of Wollongong,
particles, and asymmetric flask-like hollow carbon particles Australia. His research interests focus on the design of
have been successfully prepared. Various methods have been functional carbon-based materials for electrochemical
used to prepare colloidal carbon spheres, including the Stöber catalysis and energy storage applications.
method (Figure 3a), the hard template method (Figure 3b), the
microemulsion polymerization method (Figure 3c), the soft
template method, (Figure 3d) and the hydrothermal carboniza- Jian Liu received his Ph.D.
tion method (Figure 3e), which will be highlighted in this sec- degree in physical chemistry
tion. On the basis of these methods, new synthetic approaches from the Dalian Institute of
to colloidal carbon spheres with various functionalities await Chemical Physics, Chinese
discovery. Academy of Science, China,
in 2008, and worked at
the Australian Institute
2.1.1. Hard Template Method for Bioengineering and
Nanotechnology (AIBN),
Rigid structure-directing materials such as polymers including University of Queensland
polystyrene (PS), resorcinol–formaldehyde (RF) polymer, (UQ) as a research fellow.
poly(methyl methacrylate) (PMMA), and SiO2, have been used After working at Curtin
as hard templates to prepare porous or hollow carbon spheres. University as a senior lecturer from 2013 to 2017, he then
The hard template method includes several steps: 1) the syn- joined DICP as a full professor and group leader of micro–
thesis of hard template materials, 2) the preparation of the nanoreactor and reaction engineering. He also held an
intermediate composite material containing both the carbon adjunct Reader position in the Department of Chemical
precursor and the hard template, 3) the carbonization of the and Process Engineering, University of Surrey, UK. His
formed material in an inert atmosphere, and 4) the removal research focuses on the design of micro–nanoreactors,
of hard template. To successfully incorporate the carbon energy materials, CO2 utilization, anisotropic particles with
precursor and the hard template (i.e., to “assemble”), the surface patchy, multicompartment, and Janus architectures.
of the hard templates usually needs to be modified to have
the appropriate surface charge and polarity features. To prepare sol–gel or hydrothermal method. For the removal of the
the carbon spheres, a shell of the carbon precursor is depos- hard template, chemical etching and thermal decomposition
ited on the surface of the hard template through the traditional methods are commonly used, depending on the nature of

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Figure 1.  Design of colloidal carbon spheres as nanoreactors toward catalysis, energy storage, and conversion. Image for catalytic hydrogenation reaction:
Reproduced with permission.[2] Copyright 2016, Springer Nature. Image for ORR: Reproduced with permission.[20] Copyright 2016, American Chemical Society.
Image for OER: Reproduced with permission.[21] Copyright 2016, Elsevier. Image for HER: Reproduced with permission.[22] Copyright 2019, Wiley-VCH. Image
for Li–S: Reproduced with permission.[23] Copyright 2017, Wiley-VCH. Image for Li/Na metal: Reproduced with permission.[24] Copyright 2016, Springer Nature.
Image for Li/Na ion: Reproduced with permission.[25] Copyright 2017, Wiley-VCH. Image for catalytic oxidation reaction: Reproduced with permission.[240]
Copyright 2010, American Chemical Society. ORR = oxygen evolution reaction; HER = hydrogen evolution reaction; OER = oxygen evolution reaction.

the hard templates. The as-obtained porous or hollow carbon
spheres usually must be further treated to enhance certain
properties, such as the degree of carbonization.
The typical hard templates including PS, resin polymer (RF),
PMMA, latex particles, and SiO2 particles; the common carbon
precursors that are used for the fabrication of carbon spheres;
the respective physical properties of the obtained carbon
spheres are summarized in Table  1. PS sphere templates can
be easily removed by organic solvent dissolution (e.g., tet-
rahydrofuran (THF) and dimethylformamide) or the thermal
annealing procedure. White et al. reported the preparation of
hollow carbon spheres via PS spheres as hard templates.[15]
RF colloidal spheres, which can be synthesized by the Stöber
method,[13] also can be used as the hard templates to fabricate
carbon spheres.[28] SiO2 spheres have been commonly used as
hard templates due to their easily tunable size, surface func-
tionality, low cost, and high uniformity. SiO2 solid spheres are
usually synthesized through Stöber method, where hydrolysis
of the silica precursor takes place in a mixture of ethanol and
water with ammonia as the catalyst.[36] Hollow carbon spheres
can be achieved through coating different carbon precursors on
the surface of SiO2 particles by a following carbonization and
etching process. The hard template method to prepare hollow
carbon spheres is usually easy to control and the obtained
structure is often homogeneous and well-defined. Nevertheless,
the major drawback of hard template method is that it may
involve a multi-step coating process and the subsequent tem-
plate removal requires harsh conditions (e.g., using HF and
NaOH), which restricts its widespread application. In addi-
tion, the particle size, pore structure, and morphology of the
obtained carbon spheres are predominantly dependent on the
properties of the hard templates.
2.1.2. Soft Template Method
Mesoporous carbon spheres also can be synthesized through
an organic–organic assembly approach (i.e., the soft template

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Figure 2. Typical transmission electron microscopy images of various spherical-like carbon nanoparticles synthesized by different methods.
a) Microporous carbon spheres. Reproduced with permission.[13] Copyright 2011, Wiley-VCH. b) Mesoporous carbon spheres. Reproduced with
permission.[14] Copyright 2013, Springer Nature. c) N-doped mesoporous carbon nanospheres with large pores. Reproduced with permission.[26]
Copyright 2015, Wiley-VCH. d) Porous carbon spheres with inner surface protuberance. Reproduced with permission.[27] Copyright 2017, Wiley-VCH.
e) Yolk–shell carbon spheres. Reproduced with permission.[28] Copyright 2015, The Royal Society of Chemistry. f) Hollow carbon spheres. Reproduced
with permission.[29] Copyright 2015, The Royal Society of Chemistry. g) Hollow carbon spheres with ultrahigh surface area. Reproduced under the
terms of the CC-BY Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/).[30] Copyright 2015,
Springer Nature. h) Asymmetric bowl-like mesoporous carbon particles. Reproduced with permission.[31] Copyright 2016, American Chemistry Society.
i) Multichamber carbon microspheres. Reproduced with permission.[32] Copyright 2018, Wiley-VCH. j) Multiple-cavities carbon spheres. Reproduced
with permission.[33] Copyright 2017, Wiley-VCH. k) Walnut-shaped carbon particles. Reproduced with permission.[34] Copyright 2018, Wiley-VCH.
l) Asymmetric flask-like hollow carbon particles. Reproduced with permission.[35] Copyright 2017, American Chemistry Society.

method) by using emulsion droplets, micelles, or surfactant
as soft templates. There are four important requirements for
successfully synthesizing porous carbon materials through the
soft template method. First, the soft template precursors should
be able to assemble themselves into nanostructures. Second,
the generation of intermediate composites with both the
carbon precursor and the soft template are necessary. The soft
templates should not only tolerate the temperature of carbon
formation, but also be easily decomposed during the subse-
quent carbonization period. Last, the carbon precursors should
become thermosetting before reaching the decomposition tem-
perature of soft templates during the carbonization process.[75]
In the past decade, significant attention has been paid on
the synthesis of ordered mesoporous carbon materials.[75,76]
Due to the insufficient self-assembly of the carbon precursors
and the high tendency toward the crosslinking of neighboring
nanospheres; however, it is still a great challenge to achieve
monodispersed mesoporous carbon spheres.[1] Until now, only
a few reports have been published about successful fabrica-
tion of monodispersed mesoporous carbon spheres using soft
template method.[11,14,26] For example, self-polymerization of
dopamine and spontaneous co-assembly of di-block copolymer
micelles could assist the formation of mesopores. By using
aerosol-spraying and the spray-drying pyrolysis method, mono-
dispersed mesoporous carbon spheres could be fabricated
on a large scale, but their particle size was very large and not
uniform.[77,78] Hollow mesoporous carbon spheres can also be
achieved on the basis of a soft template strategy.[79] They were

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Figure 3.  Synthetic methods for colloidal carbon spheres. a) Extended Stöber method; b) hard template method; c) microemulsion polymerization;
d) soft template method; e) hydrothermal carbonization method.
prepared by the hydrothermal treatment of α-cyclodextrin with
Pluronic F127 as the soft template, and the particle size and
morphology could also be controlled.
Compared with hard template method, soft template method
always involves the co-assembly of the carbon precursors and soft
templates for the formation of meso-structures without requiring
the harsh conditions needed to remove the hard templates.
In addition, this simple method can be applied to synthesize
mesoporous carbon spheres. Nevertheless, the high cost of
soft templates, low yield of carbon spheres, limited types of
usable soft templates, and difficulty in controlling the particle
size distribution are the major challenges for the soft template
method at the current stage. Therefore, it is desirable to further
design and synthesize mesoporous carbon spheres with lower
cost, more uniform particle size, and suitability for large-scale
production.
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2.1.3. HTC Method
The HTC method at low temperatures (160–200 °C) is also
suitable for the preparation of monodispersed colloidal carbon
spheres from biomass-based precursors.[80,81] There are four
steps during the HTC process for preparing carbon spheres:
dehydration, condensation, polymerization, and aromatization.
The physical properties of various biomass-derived carbon
precursors are summarized in Table  2. As shown, biomass-
derived carbohydrate sources such as glucose, fructose, and
sucrose have been used to prepare colloidal carbon spheres.
For example, microporous carbon spheres with pore size of
about 0.4 nm were prepared through hydrothermal carboniza-
tion of glucose at 190 °C for 5 h. By introducing iron ions and
oxide during the HTC process, the carbonization rate could
be accelerated.[16] Combined with the hard and soft template
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Table 1.  Physical properties, templates, and precursors for carbon spheres obtained through the hard template method.

Template Carbon precursor Structure; pore size [nm]; surface area [m2 g−1] Reference
Latex nanoparticles Glucose Microporous; –; 360–470 [15]
RF spheres Phenolic resin Hierarchical micro, meso and macroporous; –; 90–280 [28]
SiO2 spheres Dopamine –; –; – [37]
SiO2 spheres Resorcinol and formaldehyde Microporous;1; 720 [38]
Si@SiO2 spheres Resorcinol and formaldehyde –; –; – [39]
SiO2 spheres Resorcinol and formaldehyde Mesoporous; 2, 20; 1124 [40]
SiO2 spheres Petroleum pitch Mesoporous; 3; 648 [41]
Latex nanoparticles Glucose Hierarchical micro and mesoporous; 0.2–0.35, 2.5; 410 [42]
Polystyrene (PS) spheres Aniline Hierarchical micro and mesoporous; –; 1567 [43]
SiO2 spheres Aniline Hierarchical micro, meso, and macroporous; –, 2.6,4.0; 53–2239 [44]
SiO2 sphere Aniline Mesoporous; 13.4–23.2; 115–670 [45]
RF spheres Phenolic resin Mesoporous; 2.14; 1038 [46]
PMMA spheres Phenolic resin Mesoporous; 2.6; 532 [47]
PMMA spheres Resorcinol and formaldehyde Microporous; –; 486.5 [48]
Polyacrylonitrile nanospheres (PAN) Polyacrylonitrile Mesoporous; 4.6; 718 [49]
Mesoporous hollow silica spheres Dopamine Mesoporous; 2.9; 370–440 [50]
SiO2 spheres Petroleum pitch Hierarchical micro, meso and macroporous; –; 90–280 [51]
SiO2 spheres Dopamine hydrochloride Hierarchical micro, meso and macroporous; 0.59, 1.87, 3.8,9.6, [52]
50–100; 396
SiO2 spheres Pyrrole Micro and mesoporous; –; 95 [53]
SiO2 spheres Polybenzoxazine Mesoporous; 2.5; 760–2160 [54]
SiO2 spheres Dopamine Mesoporous; 2; 457 [55]
SiO2 spheres Dopamine hydrochloride Mesoporous; 30; 340 [56]
SiO2 spheres Iron-phthalocyanine Mesoporous; 3.7; 297 [57]
SiO2 spheres Phenolic resin Hierarchical micro and mesoporous; 1–25; 1520 [58]
MCM-48 spheres Furfuryl alcohol Mesoporous; 2.4; 2034 [59]
SiO2 opals Resol Mesoporous; 3.1, 6.0; 2445 [60]
MCM-48 spheres Glucose Mesoporous; 2.3; 1442 [61]
SiO2 opals Resol Mesoporous; 7–10; 500–1100 [62]
SiO2 spheres 1,4-bis(triethoxysilyl)Benzene Mesoporous; 3.8; 646 [63]
SiO2 spheres 1-Alkyl-3-methylimidazolium bromide Mesoporous; 2.4, 3.6,13; 67–281 [64]
SiO2 spheres Resorcinol and formaldehyde Microporous; –; 639 [65]
SiO2 spheres Resorcinol and formaldehyde Microporous; –; 219 [66]
SiO2 spheres Resorcinol and formaldehyde Microporous; 1.1; 407 [67]
SiO2 spheres Resorcinol and formaldehyde Hierarchical micro, meso and macroporous; –; 767 [68]
SiO2 spheres Organic moiety Mesoporous; 4.3; 1620 [69]
SiO2 spheres Dopamine Mesoporous; 3.2; 1538 [70]
SiO2 spheres Glucose –; –; – [71]
Fe3O4@SiO2 Glucose –; –; – [72]
SnO2 hollow spheres Glucose –; –; 748 [73]
ZIF-8 ZIF-8 Microporous; 1.1; 1038 [74]

method, various spherical carbon particles with different
porosity can be achieved through the HTC process.[82] Com-
pared with hard and soft template methods, the HTC method
has its own merits such as low toxicity, environmental friend-
liness and mild reaction conditions.[83] Although microporous
carbon spheres can be obtained through HTC method, it
still requires effort to prepare colloidal carbon spheres with
uniform particle size and well-defined porosity. In addition,
the choice of biomass-derived carbon precursors is very
limited.

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Table 2. The Physical properties and molecular structure of carbon To increase the amount of crosslinking, Wu and co-workers
precursor for carbon spheres obtained through HTC method. introduced carbon tetrachloride (CCl4) as the crosslinker during
the polymerization of styrene, which was followed by hydro-
Chemical name Structure, pore size [nm], References thermal treatment at 180 °C for 5 h for the synthesis of mono­
surface area [m2 g−1]
dispersed porous PS spheres.[17] The hydrothermal treatment
Sugar Microporous; 0.4; 400 [84] can improve the thermal stability of the crosslinking of polymers.
Glucose N/A [81] After annealing at 900 °C for 5 h under N2 atmosphere, highly
–; –; 3 [85] monodispersed carbon nanospheres with particle size of 224 nm
and surface area of about 1357 m2 g−1 were obtained. Moreover,
N/A [86]
the second method to enhance the crosslinking is to coat the
Microporous; –; 630–730 [87] carbon precursor such as polymer with a layer of an aluminosili-
N/A [88] cate. For example, Xiao and co-workers synthesized hierarchical
Hierarchical micro and meso; 0.4–1.0, 4; 1670 [89] porous carbon spheres via a facile anion exchange process with
the assistance from aluminosilicate coating to prevent structural
Microporous; –; ≈50 [90]
collapse.[107] Another possible method is to use temperature
N/A [91] programming with holding at relatively low temperature such as
–; –; 15.43 [92] 200 °C for a certain time before reaching the final temperature
Hierarchical micro and meso; –; 600–1200 [93] and with a slow ramping rate. In addition, a facile hyper-
Hierarchical micro and meso; 0.5,0.8.1.3; 914 [94]
crosslinking strategy was developed to prepare hollow micro­
porous carbon nanospheres by using SiO2 as the hard tem-
Fructose N/A [95]
plate, divinylbenzene (DVB) as the pre-crosslinking agent, and
Mesoporous; 4; 296–996 [96] styrene as the carbon precursor.[108] The carbon shell structures
N/A [97] with micropores were well-maintained during the carbonization
Xylose N/A [95] because of excellent stability of the as-formed hyper-crosslinked
polymer shell. By tuning the hyper-crosslinking and carboni-
Furfural Mesoporous; 4.5; 180–380 [82]
zation conditions, the porous structure, the size of the hollow
Sucrose N/A [98] sphere and their morphology could be finely modified.
Cellulose Microporous; –; 2220–2300 [99] The difference between soft template method and the
N/A [91] microemulsion method can be described as follows. For the
soft template method, it usually involves the use of structure-
N/A [100]
directing agents (soft-templates) such as triblock copolymer poly
Lignocellulose N/A [91]
(ethylene oxide)-poly (propylene oxide)-poly (ethylene oxide)
Starch –; –; 104–402 [16] (PEO–PPO–PEO). Ordered polymer-polymer nanocomposites
N/A [98] through organic–organic interactions with some thermosetting
N/A [100]
polymers (mainly phenolics resins) can be formed. For example,
when PEO–PPO–PEO surfactant was used as the soft templates
Hierarchical micro, meso and macroporous; [101]
to synthesis resin polymer spheres, low molecular weight resols
0.4–0.7,0.9–1.3, 1.3–3.4 and 50–95; 3251
and phenolic formaldehyde compound can interact with the
Cyclodextrin Microporous; –; – [102] PEO block through hydrogen bonding.[109] Thus, after carboni-
N/A [103] zation of polymeric sphere composites carbon spheres with
Chitosan Microporous; –; 30–50 [104] ordered mesopores can be achieved. For the emulsion polym-
erization method, the nucleation and growth of emulsion drop-
lets usually consist of multiple different routes. The degree of
2.1.4. Microemulsion Polymerization Method polymer cross-linking should usually be improved due to struc-
tural collapse during carbonization and low carbonization yield.
Emulsion polymerization has been considered as a versatile Therefore, the obtained carbon spheres are usually disordered
and scalable method for synthesizing monodispersed polymer porous structures.
spheres such as from PS, PMMA, and poly(hydroxyethyl
methacrylate). The process of micro­­emulsion polymerization
usually involves monomers, initiators, a dispersion medium, 2.1.5. Extension of the Stöber Method
and a colloid stabilizer, which can form a homogeneous system
for the synthesis of colloidal polymers. The as-formed colloidal Nanostructured phenolic resins have attracted considerable
spheres are hard to convert to carbon spheres; however, because attentions due to their facile functionalities of their size and
of thermal decomposition and serious agglomeration.[105] The porosity.[109] Among the various synthetic approaches, the fabri-
main drawbacks of this method are structural collapse during cation of monodisperse RF resin has been considered as a major
carbonization and low carbonization yield due to the insuffi- breakthrough in our previous work on the development of resin
cient polymer cross-linking, which have limited utilization of nanospheres.[13] Monodispersed carbon spheres can be obtained
the microemulsion method for the synthesis of porous carbon through the carbonization of the monodisperse RF resin
spheres.[106] polymer spheres. In this part, the main research progress on

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Table 3. Physical properties of carbon spheres by using phenolic Table 3. Continued.

resin-based carbon precursors.
Chemical name Morphology; pore size [nm]; surface References
area [m2 g−1]
Chemical name Morphology; pore size [nm]; surface References
area [m2 g−1] Mesoporous; 2; 362–582 [153]
Resorcinol Microporous; –; 504 [13] 3-Aminophenol Microporous; –; 368–482 [110]

Microporous; 1; 550 [38] Microporous; –; 366 [111]

Microporous; –; 639 [65] Hierarchical micro and meso; –; 343–394 [117]

Microporous; –; 219 [66] Dopamine Mesoporous; 5.4–16; 343–363 [26]

Microporous; 1.1; 407 [67] Hierarchical micro and meso; –; 422 [154]

Hierarchical micro, meso and [68] N/A [155]

macroporous; –; 767 Sulfonyldiphenol N/A [156]
Mesoporous; 3.5; 857 [14] 4-Amino-3-nitrophenol Microporous; –; 416 [110]
Mesoporous; 10–20; 430–540 [113] 4-Aminophenol Microporous; –; 344 [110]
Mesoporous; 2.4; 1129 [114] Phloroglucinol –; –; 461–2123 [157]

Microporous; –; 540–671 [124] Mesoporous; 7.0–18.7; 476–517 [158]

Microporous; –; 440–518 [118] Tannic acid Hierarchical micro, meso [159]

and macro; –; 520–920
Mesoporous; 0.7; 79–360 [125]
Hierarchical micro and meso; –; 270–560 [160]
Mesoporous; 4.7–5.3; 633–1483 [126]
Hierarchical micro and meso; [161]
N/A [127]
0.9, 2.2, 3.3; 540
Microporous; –; 500–552 and 1100–1250 [128]
−; –; 328–477 [162]
Hierarchical micro and meso; [129]
Hierarchical micro and meso; 1.6, 2.6, [163]
1.1,3.7; 460–525
5.3; 16–202
Microporous; –; 495–1610 [130]
Mesoporous; 6.0–8.8; 38–101 [164]
Microporous; –; 780–840 [131] Mesoporous; –; 327–470 [165]
Microporous; 0.5–1.5; 530–2400 [132] Melamine – [152]
Microporous; –; 390–2930 [133] Microporous; –; 753 [166]
Mesoporous; 3.1,6.4; 1704 [134] Mesoporous; 29; 1330 [167]
N/A [135] Mesoporous; 31; 1460 [168]
Hierarchical micro, meso and [136] Mesoporous; 2.7–5.3; 662–996 [169]
macroporous; –; 450–1080
Microporous; 0.64; 419 [137]
resin polymer spheres and carbon spheres will be summarized.
Mesoporous; 4.3–5.0; 760–1800 [138]
The phenolic resin-based carbon precursors and their features
N/A [139] for the synthesis of carbon spheres are included in Table 3.
N/A [140] In 2011, it was found that resorcinol and formaldehyde can
Microporous; –; 160–766 [141] polymerize together under basic conditions in a similar manner
Hierarchical micro and meso; –; 15–239 [142] to the Stöber method.[13] By changing the synthetic parameters
such as the molar ratio of resorcinol to formaldehyde, the sol-
Hierarchical micro and meso; –; 25–686 [143]
vent, and the amount of ammonia, the particle size of RF
Mesoporous; 2.4,4.5; 2464 [144] spheres can be adjusted from 200 to 1000 nm. In addition, the
Microporous and mesoporous; –; 1584 [145] prepared RF spheres can be easily converted into monodispersed
Mesoporous; 3; 1230 [146] and microporous carbon spheres, which can be used as catalyst
Hierarchical micro and meso; 3.6–26.2; [27] supports for the oxygen reduction reaction (ORR). Inspired
679–837 by this successfully extended Stöber method, mesoporous RF
nanospheres (MRF) with pore size of about 3.5 nm were then
Mesoporous; 3.8–11.9; 916–2385 [115]
obtained after introducing a suitable surfactant, and their par-
– [147]
ticle size could also be tuned from 80 to 400 nm. Importantly,
– [148] the pore size of these spheres could be further enlarged by
Mesoporous; 3.6–3.8; 663 [149] changing the concentration of ethanol and 1,3,5-trimethylben-
Microporous; –; 130 [150] zene (TMB) as the swelling agent. After the carbonization of the
MRF spheres, mesoporous carbon spheres were shown to be an
Microporous; –; 82 [151]
excellent material when used in lithium–sulfur (S) batteries.[14]
Phenol Mesoporous; 2.6–3.0; 940–1130 [11]
Additionally, other phenol derivatives have also been used
Microporous; –; – [152] to prepare resin polymers and the carbon spheres derivatives.

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Table 3 summarizes the phenolic resins-based carbon pre-
cursors that have been reported. On this basis, a series of
heteroatom-containing phenol derivatives (such as nitrophenol,
aminophenol, and halide-substituted phenols) have been
used to prepare phenolic resin spheres, which can be further
converted to heteroatom-doped carbon spheres.[110] It has been
found that the phenolic precursors including 3-aminophenol
and 4-amino-3-nitrophenol could be used to synthesize mono-
dispersed carbon spheres with high nitrogen (N) content,
ranging from 5.5 to 11.9 wt% in the carbon framework. The
inductive effect of the substitution group in phenol derivatives
and the orientation effect of the aromatic ring toward electro-
philic addition have played important roles in the successful
formation of phenol resin spheres.[110] Additionally, Zhao et al.
also found that 3-methlyphenol and 1,3,5-trihydroxybenzene
cannot polymerize with formaldehyde to produce resin colloidal
spheres because of steric hindrance.[111]
In addition, due to the similarity between resin polymer
spheres and silica spheres, this facile method has been extended
to prepare highly monodispersed and core–shell structured
silica–RF spheres and silica–carbon spheres.[38,40,66,112–116] Dai
and co-workers reported the synthesis of mesoporous carbon
nanospheres, hollow mesoporous carbon nanospheres, and yolk–
shell mesoporous carbon nanospheres through co-assembling
phenolic resols and silicate oligomers with hexadecyl trimeth-
ylammoniumchloride as the soft template.[114] Following this
work, by tri-constituent co-assembly of 3-aminophenol, formal-
dehyde, and bis[3-(triethoxysilyl)propyl]tetrasulfide, N,S-doped
carbon–silica nanospheres with either smooth or rough sur-
faces could be obtained by direct carbonization of the polymer–
silica nanospheres.[116] Based on the above developments in
this extended Stöber method to fabricate carbon spheres, more
versatile strategies have been proposed for the fabrication of
core–shell and yolk–shell metal-oxide–carbon composites with
unique core@void@shell structures and various morphologies
such as polymer@polymer,[117] Ag@polymer,[118] α-Fe2O3 nano-
spindle@polymer,[119] Fe2O3box@polymer,[120] Cu/Fe@γ-Fe2O3@
polymer,[121] yolk–shell carbon nanospheres,[23] and zeolitic imida-
zolate framework-8 (ZIF-8)@polymer.[122]
Colloidal carbon spheres are also usually considered as an
excellent candidate for catalyst support and the tunable porous
structure for carbon spheres is one of the most predominate
factor related to this task. The pore size distribution, pore struc-
ture, and pore length have a great impact for the transport of
reactants and products during catalytic reactions. These porous
carbon spheres have been successfully designed and synthe-
sized with particle sizes from nanometers to micrometers and
different pore structures, ranging from micropores (<2 nm),
mesopores (2–50 nm) to macropores (>50 nm). Microporous
carbons could offer a high surface area to enhance reaction
rate, but macroporous carbon materials could more efficiently
facilitate mass transfer and diffusion of reactants and products
in the reaction. Mesoporous carbons can be used to support
metal nanoparticles with high dispersion when used as
catalysts. Hierarchical structured carbon materials with com-
bined micropores, mesopores, and macropores will provide the
opportunity for the large-scale production of carbon catalyst.
As shown in Tables 1–3, microporous carbon spheres
can be synthesized by hydrothermal carbonization of
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biomass-derived carbon precursors. Recently, carbonization of
phenolic-resin-derived polymer spheres obtained from various
precursors including resorcinol, phenol, aminophenol, and
other phenol derivatives can also achieve microporous carbon
sphere. Furthermore, based on the organic–inorganic self-
assembly approach by using cationic fluorocarbon surfactant
FC4 and triblock copolymer Pluronic F127 as templates,
mesoporous carbon spheres with pore size of about 3.5 nm can
be obtained with RF as carbon precursors.[14] Mesoporous carbon
spheres can also be prepared through a hard-template method
by filling the mesopores of silica template with a carbon pre-
cursor. For example, double-shelled carbon spheres with par-
ticle size of about 300 nm and pore size of about 2 and 20 nm
were successfully synthesized by using SiO2 spheres as the hard
templates.[40] Macroporous carbon spheres with pore size of
about 250 nm also can be synthesized by using colloidal silica
crystal beads as the hard templates with glucose as the carbon
precursor.[123] Hierarchical micro, meso and macroporous carbon
spheres can be obtained by carbonization of core–shell struc-
tured SiO2@dopamine with the following HF etching process.[52]
2.2. Functionalization of Colloidal Carbon Spheres
2.2.1. Heteroatom Doping Effect
To create active sites and further enhance the conductivity,
catalytic activity, and interaction between carbon composites
and reactants, doping with heteroatoms such as boron (B),
fluorine (F), S, N, and phosphorus (P) or their combination
such as boron with nitrogen and nitrogen with sulfur, has
been commonly adopted (Figure  4a,b). Particularly, great
attention has been paid to nitrogen incorporation because
the resultant nitrogen-doped carbon spheres feature better
chemical reactivity, electrical conductivity, adsorption affinity
toward CO2 adsorption and specific capacitance for supercapac-
itors than their pure carbon counterparts.[128,172] Two different
routes are usually employed to prepare N-doped carbon nano-
composites: a) direct pyrolysis of nitrogen-containing precursors
such as melamine foam, carbon nitride, and polymer frame-
work. Reproduced with permission[117] and b) post-synthesis
incorporation of nitrogen atoms into the carbon framework
via chemical vapor deposition (CVD),[173] or thermal treatment
in ammonia or polyaniline.[173,174] In the post-treatment
method; however, one of the major problems is the non-even
heteroatom distribution in the carbonaceous structure due to
the limitations of surface modification. Therefore, tremendous
efforts have been made to prepare heteroatom doped carbon
nanospheres with uniform heteroatom distribution. To date,
great progress has been reported in the preparation of heter-
oatom doped carbon nanospheres based on molecular-level
design of porous carbon spheres, especially by using phenolic
resin polymer precursors. For example, nitrogen containing
compounds such as melamine,[167,175] aminophenol,[110,111,117]
4-amino-3-nitrophenol,[110] 4-aminophenol,[110] hexamethylene­
tetramine,[176] and 1,6-diaminohexane[12] have been used to prepare
nitrogen-doped carbon spheres. Nitrogen-containing monomers
such as aniline,[43–45,177] pyrrole,[53,127,178] and dopamine[37,50,55]
can also be introduced for preparing the nitrogen-doped carbon
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Figure 4.  a) Typical different types of dopants and different doping sites in carbon matrix. Reproduced with permission.[211] Copyright 2015, The
Royal Society of Chemistry. b) DFT-calculated free-energy diagram. Reproduced under the terms of the ACS AuthorChoice/CC-BY Creative Com-
mons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/).[170] Copyright 2014, American Chemistry Society. c) TEM
image of Au loaded carbon spheres. TEM image: Reproduced under the terms of the CC-BY Creative Commons Attribution 4.0 International License
(http://creativecommons.org/licenses/by/4.0/).[143] Copyright 2016, Springer Nature. d) Fourier-transform infrared (FT-IR) spectra of the synthesized
carbon spheres. FTIR spectrum: Reproduced with permission.[171] Copyright 2015, Elsevier.

spheres. In addition, it is worth mentioning that the N content
in the obtained carbonaceous framework can be well controlled
by tuning the amounts of precursors, pyrolysis temperatures,
and reaction efficiency. When preparing N-, S-, and B-doped
carbon spheres, the N-, S-, and B-containing precursors such
as dibenzyl disulfide and boric acid have been respectively
used.[117] The particle size of the N-doped mesoporous carbon
spheres can be tuned from 40 to 750 nm and the carbon
spheres with particle size of about 150 nm showed the highest
activity among the catalysts. Through the addition of urea and
cysteine to assist the synthesis of polymer spheres through the
Stöber method, N-doped and S-doped carbon spheres can be
further achieved.[124,179]
2.2.2. Surface Modification
Modification of the surface of porous carbon material is essential
because carbon materials are usually used as catalysts support to
enhance the application performance of the catalytically active spe-
cies. There are two main ways to functionalize the surface of car-
bons: deposition of nanoparticles and grafting of functional groups.
Nanoparticle Decoration: Nanoparticle deposition on the
surface of carbons is often considered as a very effective method
to adjust the interfacial properties and improve the interac-
tion among molecules for the desired electrochemical behavior
and catalytic process.[180] Due to the effectiveness of surface
modification in tuning the materials’ electrical and catalytic
properties, the electronic conductivity and electrochemical
activity can be improved through the incorporation of nanoparti-
cles on the surface of porous carbon materials. It is believed that
highly dispersed metal nanoparticles or metal compounds with
a narrow particle size distribution on the carbon surface can
increase the active surface area of the metal, further enhancing
its electrochemical performance and catalytic properties.
Many methods have been developed for the deposition of
metal nanoparticles onto carbon spheres through one-pot
synthesis or post-synthesis modification in the presence of
metal salts. Several methods including directly impregnating
metal salts with carbon precursor, spray pyrolysis, hydrothermal
synthesis, microwave synthesis, and CVD have been used for
the preparation of carbon spheres decorated with metal nano-
particles.[139,143,181] The most popular way to achieve metal-
loaded carbon spheres is to impregnate carbon spheres with

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metal salts, followed by thermal or chemical reduction process.
To prevent noble metal nanoparticles from sintering/coalescing
at high temperatures and leaching from the surface of carbon
spheres during catalytic reactions, yolk–shell structured and
hollow structured carbon spheres with a permeable shell have
been recognized as very promi­ sing candidates. Ag,AgBr@
carbon core–shell spheres were prepared through an extended
Stöber method with simultaneous reduction of AgNO3 and a fol-
lowing carbonization process.[118] In addition, small and fine Pt
nanoparticles can be carefully confined in the mesoporous hollow
carbon spheres and the as-prepared catalysts showed excellent
stability for electrochemical oxygen reduction reactions.[10,182]
The synthesis of Au-decorated carbon nanospheres through the
extended Stöber method (Figure 4c) and the particle size of the
as-formed Au nanoparticles was about 6 nm.[143] In addition,
Jaroniec and co-workers reported the synthesis of carbon spheres
with gold nanoparticles decorated on the surface.[139] By using
aminopropylsilane to enhance the absorption ability of gold pre-
cursors, the finally obtained carbon–gold core–shell structures
were composed of the carbon spheres with particle size of about
500 nm and densely packed gold nanoparticles on their surfaces.
After that, various metal nanoparticles such as Au, Ag, Ru, and
Fe with high dispersion could be loaded on the surfaces of carbon
spheres by using a cysteine-assisted strategy.[141]
Functional Group Grafting: Functional groups on the surfaces
of carbon materials can be utilized as anchoring sites for metal
catalysts and can assist metal adsorption on the carbon surface.
This usually leads to high dispersion of metallic species on
the surface and enhanced chemical performance.[3] Various
methods including oxidation, KOH activation, sulphonation,
halogenation, polymer decoration, and grafting are usually used
for functional group modification of carbon surfaces. Oxygen
containing functional groups such as anhydride, carboxylic
acid, ether, ketone, and phenol groups are introduced on the
carbon surface through covalent, electrostatic, and hydrogen
bonding interactions, resulting in enhanced wettability of the
pore surface by the various polar solvents and improved electro-
chemical capacitance of the porous carbon material.[183]
The polarity of carbon spheres can also be tuned by intro-
ducing a variety of polar groups (such as carboxylic, nitric,
sulfonic, and hydroxyl groups) or nonpolar groups (fluorine)
on their surface.[137,184] For example, Xiao and co-workers
prepared sulfonated hollow carbon spheres through carboni-
zation, HF etching of SiO2@Carbon, and treatment by chloro-
sulfonic acid.[137] The microporous carbon spheres with SO3H
groups on the surface showed a larger surface area than the
unfunctionalized carbon spheres, leading to high catalytic
performance toward the acetalization of glycerol with acetone.
Guo and co-workers reported the synthesis of arylsulfonic-acid-
functionalized hollow mesoporous carbon spheres by the hard
template method, using furfural alcohol as the carbon precursor
via diazonium coupling (Figure 4d).[171] The ArSO3H loadings
and inner diameters of the hollow carbon spheres can also be
controlled by adjusting the amount of sulfanilic acid and the
particle size of SiO2 spheres. It was found that the prepared
carbon spheres showed high catalytic performances toward
furfuryl alcohol ethanolysis and levulinic acid esterification
reactions; a higher ArSO3H loading or smaller diameter of the
hollow carbon spheres resulted in higher ethanolysis activity.
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3. Application
3.1. Energy Storage on Carbon Nanospheres
The open structures of carbon nanospheres are especially
favorable to achieve a high rate of mass diffusion, which is desir-
able for battery applications that require the rapid migration of
ions. In addition to this, the high tunability of the carbon nano-
spheres’ structure, in terms of their porous structure and core–
shell or yolk–shell structure, also provides additional versatility
to satisfy the various specific requirements of different types of
batteries. For example, by tuning the pore size of the carbon
nanospheres, sulfur can be physically restricted into a small-
molecule form, completely avoiding the formation of the unde-
sirable soluble polysulfides for Li–S batteries. By confining the
various high capacity active species inside the hollow spheres,
their cycling stability can be greatly enhanced, when the com-
posites are used as anodes/cathodes for Li-ion/Na-ion batteries.
Very recently, state-of-the-art Li or Na metal has also been
integrated into the carbon nanospheres, with the purpose of
suppressing detrimental dendrite formation, which can signifi-
cantly push forward the practical application of high capacity
Li/Na-metal batteries. Based on these considerations, in this
section, we will summarize and discuss the rational design of
the structure and chemical composition of carbon nanospheres
and their applications in different types of batteries.
3.1.1. Carbon Nanospheres as Nanoreactors of Sulfur Host
for Li–S Batteries
In a typical Li–S sulfur battery, energy is stored and released
through the reversible redox reactions between lithium metal
and elemental sulfur. Due to the high capacity of both Li
metal anode (3850 mAh g−1) and elemental sulfur cathode
(1675 mAh g−1), a very high gravimetric energy density
of 2600 Wh kg− can be achieved in this battery system, in
theory.[185,186] During the discharge of a Li–S battery, sulfur,
normally in a S8 molecule, is stepwise reduced to form lithium
polysulfide intermediate products in different forms (i.e., Li2Sx,
x = 2, 4, 6, 8) and then finally Li2S.[185,186] When being charged,
the reverse process occurs. Among these intermediate prod-
ucts, the ones with longer chain lengths (e.g., Li2S8, Li2S6, and
Li2S4) are soluble in the common ether-based electrolytes (e.g.,
dimethoxyethane and dioxolane), which would migrate from the
cathode to the anode under the gradient of both concentration
and electric field, resulting in the so-called “shuttle effect.” This
issue will then lead to the decrease in the battery capacity, rapid
self-discharge, and low coulombic efficiency. To deal with it,
sulfur/polysulfide species have to be trapped within the cathode
region in a Li–S battery, either physically or chemically. As men-
tioned above, the very high controllability of the carbon spheres’
nanostructure can be greatly desirable to achieve this goal.
To host sulfur, mesoporous carbon is the most frequently
used candidate, due to its relatively high pore volume, which
is needed to host a satisfactory amount of sulfur, and its
large surface area that is able to physically adsorb the soluble
polysulfides. In this regard, carbon nanospheres with an
ordered mesoporous structure were prepared by a two-step
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Figure 5.  a) Scanning electron microscopy (SEM) image of PMMA@nanosphere hard template with enlargement (inset). b) SEM image of silica
template with a reverse opal structure obtained from the PMMA template with enlargement (inset). c,d) SEM and transmission electron microscopy
(TEM) image of the mesoporous carbon nanosphere obtained from the silica template with the reverse opal structure. a–d) Reproduced with permis-
sion.[60] Copyright 2012, Wiley-VCH. e) SEM images of the nitrogen-doped carbon nanospheres and high-magnification TEM images of the connecting
section of two spheres (inset). f) Nitrogen adsorption–desorption isotherms, magnified high-pressure section (left inset), and pore size distribution
of the N-doped carbon nanospheres (right inset). g) Adsorption capability of N-doped nanospheres in comparison with carbon black (Super P).
e–g) Reproduced with permission.[187] Copyright 2017, Wiley-VCH. h) Schematic illustration of the fabrication of carbon spheres with both nitrogen
and oxygen species. Reproduced with permission.[188] Copyright 2015, Wiley-VCH.

impregnation and multiple template method (Figure 5a–c).[60]
On these carbon nanospheres (diameter of ≈300 nm), a
bimodal pore structure was obtained, with both ordered
mesopores ≈6 nm in size, which were derived from the tri-
block copolymer softer template and non-ordered mesopores
of ≈3.1 nm, which is from the introduced silica during the
evaporation-induced self-assembly (EISA) process (Figure 5d).
Due to this unique bimodal pore structure with relatively
large pore size, this material possessed a very high pore
volume, as high as 2.32 cm3 g−1. As a result, a high content
of sulfur (70 wt%) can be accommodated inside the pore
structure of this material. Moreover, its very high specific sur-
face area (2445 m2 g−1) was favorable for physical adsorption
of the soluble polysulfides, leading to moderate cycling sta-
bility. Despite this, such mesoporous structure can hardly
completely suppress the shuttling of polysulfides; this was
reflected by the continuously dropping capacity (initially
≈1050 mAh g−1 to ≈850 mAh g−1 after 100 cycles, tested at
1675 mA g−1) and relatively low Coulombic efficiency of ≈90%
throughout the test.
One solution to this issue is to anchor these soluble poly-
sulfides onto the surface of the carbon host through chemical
interactions. Nitrogen is a very commonly selected heteroatom
for doping into these porous carbon spheres to tune the surface
electronic structure of the carbon and to achieve such inter-
actions.[189] For example, N-doped carbon nanospheres with

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a uniform particle size (≈350 nm) were fabricated by directly
carbonizing phenolic resin nanospheres (Figure 5e).[187] On
these spheres, a bi-modal pore structure existed, with narrowly
distributed micropores ≈1 nm in size and broadly distributed
pore sizes of 1–2.5 nm (Figure 5f). The material’s large pore
volume (2.3 cm3 g−1) enabled it to host a high sulfur content
(70 wt%) and the nitrogen species (5 wt%) introduced good
chemical adsorption of the polysulfides (Figure 5g), leading
to a reasonably good cycling stability (56% capacity retention
after 500 cycles, equal to a decay rate of 0.1% per cycle), even
at a high areal sulfur density of 5 mg cm−2. To more effec-
tively adsorb the polysulfides, extra oxygen species (≈3.73 wt%)
were also introduced into the carbon spheres, besides nitrogen
(≈4.85%), by annealing a melamine formaldehyde resin pre-
cursor sphere that was fabricated through an EISA process
(Figure 5h).[188] On this material, the oxygen species, in the
forms of CO or COOH groups, can accept the electrons
from the neighboring N atoms, which can result in a more
negative charge on these oxygen groups to enable stronger
binding with the Li+ ions in the lithium polysulfide interme-
diates. Consequently, despite its large pore size (≈28 nm), this
material can still deliver very good capacity retention up to 90%
after 200 cycles (initial capacity 1480 mAh g−1, tested at 0.2 C,
with an areal sulfur density of 5 mg cm−2).
Another solution to deal with this issue is to further decrease
the pore size to physically confine the sulfur species, which
are hosted inside the pores, into small molecule forms (S2–S4)
rather than the conventional S8 form. By doing this, the soluble
long-chain polysulfide species would not be formed during the
charge/discharge process, and their shuttling will thus be elim-
inated.[185] To achieve this, microporous carbon nanospheres
have been fabricated by hydrothermal treatment of sucrose
with subsequent carbonization (Figure 6a).[190] On this material,
there are worm-like micropores with a very narrow pore size
distribution (0.7 nm) (Figure 6b,c), which can accommodate a
sulfur content of ≈42 wt%. Due to the molecular confinement
effect, a fairly good cycling stability can be achieved on it, with
capacity retention of over 80% after 500 cycles as well as a high
coulombic efficiency of nearly 100% when tested at 0.4 A g−1.
In comparison with the solid carbon nanospheres, trans-
forming them into hollow ones might bring about bonus to
the materials’ feasibility. First, the thin and porous shell, with
a short pore depth, can achieve a shortened diffusion length
for the lithium ions during the charge and discharge processes.
In this regard, a number of attempts have been conducted,
including microporous, mesoporous, double-shell hollow
carbon nanospheres, and others.[41,138] The main issue for such
hollow structures, however, is the relative low sulfur accommo-
dation content on their thin shell and the related low tap den-
sity, making them hard to be used for practical application. One
solution is to make use of the large internal void space as a host
to achieve a larger loading of sulfur, thus improving the overall

Figure 6.  a,b) TEM images of microporous carbon nanospheres at different magnifications; c) the nitrogen adsorption–desorption isotherms of the
microporous carbon nanospheres and their corresponding pore size distribution (inset). a–c) Reproduced with permission.[190] Copyright 2010, The Royal
Society of Chemistry. d) TEM image of the “double-shell” carbon nanosphere and e) schematic illustration of its fabrication protocol. d,e) Reproduced
with permission.[191] Copyright 2015, Wiley-VCH.

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capacity of the material. To ensure that the sulfur species is
inside the hollow structure, rather than merely on the shell,
management of the pore structure is critical. By continuously
tuning the pore size, this influence has been comprehensively
studied.[192] In this regard, a comprehensive study has been
conducted in terms of determining the most suitable pore size
for such hollow carbon materials.[192] It has been found that
sulfur can be stably and effectively hosted inside the internal
voids only when the pore size is small enough (i.e., 2.8 nm). On
the contrary, in the case of larger pores (i.e., 2.3 and 4.1 nm),
the sulfur species that was partially impregnated inside the
voids tended to be unstable and easily sublimed, even under
a TEM electron beam. Consequently, the one with the smallest
pore size not only could accommodate a high content of sulfur
(85 wt%) but also delivered the best cycling stability, with 88%
capacity retention after being cycled for 100 cycles.
As aforementioned, even when small, such pores are still
too large to intercept the soluble polysulfide intermediates,
and are thus unable to avoid the shuttle effect. To deal with
this, a series of strategies has been proposed to further modify
such hollow carbon nanospheres. One very straightforward
approach is to fabricate an additional mesoporous shell on the
outside of the hollow carbon, which is expected to provide extra
confinement of the polysulfide species, in comparison with
single-shelled counterparts (Figure 6d).[191] This was achieved
by coating both the outer and inner surfaces of a hollow titania
oxide nanosphere template with carbon, followed by the sub-
sequent removal of the template (Figure 6e). Such a “dual-
confinement” mechanism is effective for maintaining the
sulfur species inside the internal voids, and a very low capacity
decay rate of 0.19% per cycle could be obtained when tested
at 0.5 C for 200 cycles. Similarly, a coating of polydopamine
was also applied to such hollow carbon nanospheres after the
impregnation of sulfur, to provide additional immobilization
for the sulfur species.[70] Such a polymer coating can effectively
confine the polysulfide intermediates inside the hollow carbon
nanosphere and thus significantly enhance the cycling stability
of the resultant material. As a result, very high capacity reten-
tion of 85.1% was achieved after 600 cycles for this material, as
well as a high Coulombic efficiency of over 99%.
Apart from the post-impregnation of sulfur into the internal
voids of the hollow carbon nanospheres, metal sulfides can also
be used as the sulfur precursors, which could be first coated
with carbon and then converted into sulfur. For instance, ZnS
nanoparticles were first coated with a phenolic resin, which was
then thermally converted into a carbon shell on the outside of
these ZnS particles.[193] The ZnS species inside the ZnS@C
nanospheres was then mildly oxidized into elemental sulfur
particles using Fe(NO3)3 as the oxidant (Figure 7a). Due to the
leaching of the Zn species from ZnS, the obtained S particles
were smaller than the original void spaces (Figure 7b), which
can be favorable for buffering the huge volume variation

Figure 7.  a) Schematic illustration of the fabrication of sulfur nanoparticles encapsulated inside a hollow carbon nanosphere. b) The corresponding
TEM image of the material. a,b) Reproduced with permission.[193] Copyright 2015, The Royal Society of Chemistry. c) Schematic illustration of the
fabrication of the “yolk–shell” carbon nanospheres. d) The corresponding TEM image of the spheres. e,f) TEM images of the shell and yolk sections
of the spheres, respectively. g,h) The pore size distribution showing the existence of micropores and mesopores. c–h) Reproduced with permission.[23]
Copyright 2017, Wiley-VCH.

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(i.e., up to 80%) between charge and discharge. It is interesting
to find that the actual battery performance of this material is
heavily related to the thickness of the carbon shell, which can
be tuned by the thickness of the initial coating of the phenolic
resin on the outside of the ZnS particles. The best S/C ratio of
was found to be ≈1:1. A too thin shell is favorable for achieving
the high initial capacity, which, however, fades quickly as well.
In contrast, a too thick shell, although good for maintaining
excellent cycling stability, results in a relatively low capacity,
which might be because of the difficult lithium ion transport
during battery operation.
These sulfur species inside the hollow structures, normally
in a particle form with a diameter of few hundred nanometers,
may suffer from the intrinsic poor electronic and ionic conduc-
tivity. Addressing this issue, our group has proposed “yolk–shell”
carbon nanospheres, which are composed of a mesoporous
yolk inside a microporous shell, thorough a dual template
route (Figure 7c).[23] In this material, the outer shell is very thin
(≈15 nm) to provide rapid lithium transport and the very narrow
micropores (≈0.6 nm) in it can effectively impede the migration
of any soluble polysulfides. On the other hand, the yolk inside
the shell has large mesopores (≈9.7 nm), which can adequately
accommodate a high content of sulfur and provide sufficient
electronic conductivity as well. The space between the yolk and
the shell can also provide an effective buffer for the volume
variation, which is desirable for good stability (Figure 7d–h).
Consequently, these merits not only enabled this material to
host a large amount of sulfur (76 wt%) but also led to stable
cycling stability of up to 1000 cycles at a high rate of 0.5 C.
Briefly, for state-of-the-art Li–S batteries, the carbon nano-
spheres have recently been intensively studied, as a host for
sulfur to deal with the critical shuttle effect. Among them, the
hollow/yolk–shell ones are especially favorable, and their shells
can act as a natural barrier against polysulfide migration. On this
basis, structural (e.g., designing hierarchical structures) and/or
compositional (e.g., surface modification by heteroatoms) com-
bination of materials has been proven a very effective strategy to
achieve high efficiency in suppression of the shuttling effect.
3.1.2. Carbon Nanospheres as a Catalytic Nanoreactor
for Polysulfide Redox
Apart from being used as a host for sulfur for suppressing the
shuttle of the soluble polysulfide species. These carbon nano-
spheres, especially the hollow-structured ones, have also been
utilized as a nanoreactor to confine the various active species
inside them to chemically absorb the soluble polysulfides, to
accelerate the electrochemical redox of polysulfides, and to fur-
ther enhance the performance of a Li or Na sulfur battery.
Similar to the previous reports, doping of the carbon frame
with various non-metal heteroatoms, such as N and P, have been
considered to be able to provide catalytic activity for a number of
reactions, for instance, oxygen reduction reaction. Recently, such
concept has also been utilized to accelerate the electrochemical
redox of the polysulfides in a Li–S battery. For instance, a double-
shelled hollow carbon nanosphere was fabricated through the
double-shelled and porous SiO2 hollow capsule as the hard tem-
plate and RF resin as the carbon precursor (Figure  8a).[194] By
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introducing NH4H2PO4 during the annealing of the RF resin,
the obtained carbon nanosphere, obtained after the removal of
the template, was simultaneously doped with nitrogen and phos-
phorus (denoted as NPDSCS, Figure 8b). By using this material
as a host of sulfur, which resides both inside sphere as a solid
core and in between the double shells, a much-enhanced capacity
and cycling stability was achieved, in comparison with the coun-
terparts doped with only nitrogen or non-doped (Figure 8c). This
improved performance was attributed to the combined effect in
terms of the materials’ structural and chemical characteristics,
including the efficient physical trapping, good chemical affinity,
and high adsorption for polysulfides, as well as the bifunctional
catalyzing effect of the sulfur redox processes that was brought
from the dual dopants of N and P.
Based on the carbon hollow nanospheres, additional species
with a strong affinity to the lithium polysulfides have been
formed on the inert or outer surface of the carbon nanosphere
as well, with the purpose of both immobilizing the polysulfide
shuttling and promoting their redox reactions in a confined
space. For example, by simply treating a porous carbon hollow
sphere with an aqueous solution of KMnO4, MnO2 nanoparticles
can be homogeneously formed and anchored on both sides of
the carbon shell.[196] The dual encapsulation effect of this mate-
rial, including the physical confinement from the carbon hollow
structure and the chemical adsorption from the MnO2 nano-
particles, endowed it with fairly good cycling stability for up to
1000 cycles with a low average capacity decay of 0.041% per cycle.
To overcome the short come of low electronic conductivity
of for the metal oxides, metal oxides have been converted into
nitrides, with much-improved conductivity and strong affinity
to the polysulfides as well. One of the most frequently adopted
strategies of metal nitrogenization is to anneal the respective
oxides in an ammonia atmosphere. For example, a C@TiO2
composite nanosphere, on which carbon is coated outside a
hollow TiO2 nanosphere, was converted into a hollow C@TiN
nanosphere, which was able to load a high content (71 wt%)
of sulfur and delivered a good cycling stability for 300 cycles
at a high rate of 2 C (Figure 8d,e).[195] This performance
enhancement was attributed to the rapid redox reactions of
lithium polysulfides over the conductive TiN and its catalytic
capability. Similarly, tungsten oxide particles, which were coated
outside a hollow carbon nanosphere, has been nitrogenized as
well and used to host sulfur.[197] The strong chemical binding
ability and the high electronic conductivity of tungsten nitride
toward the lithium polysulfides can effectively suppress their
shuttling and accelerate the kinetics of their redox reactions.
Consequently, a high capacity of 1351 mAh g−1 (0.1 C) and
superior long-term cycling stability with 80% capacity retention
after 500 cycles (0.5 C) were achieved on this material, at a high
areal sulfur loading of 3 mg cm−2.
In order to further improve the number of active sites to
adsorb/catalyze the lithium polysulfide redox, the “single-
atom catalysis” concept has been introduced into the func-
tional sulfur host materials. Based on this consideration, a
cobalt-doped and yolk–shell-structured vanadium nitride nano-
sphere coated by a thin layer of N-doped carbon was fabri-
cated through a multiple-stepped process (denoted Co-VN@C,
Figure  9a,b).[198] With a high sulfur loading of 70 wt% on the
material and a high areal sulfur loading of 4.07 mg cm−2, a high
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Figure 8.  a) Schematic illustration of the fabrication of NPDSCS material. b) TEM image of NPDSCS and the corresponding elemental mapping (red:
carbon, green: nitrogen, cyan: phosphorus, yellow: sulfur). c) Cycling performance of the material. a–c) Reproduced under the terms of the CC-BY
Creative Commons Attribution 4.0 International License (https://creativecommons.org/licenses/by/4.0/).[194] Copyright 2018, The authors, published
by Wiley-VCH. d) Schematic illustration of the fabrication of C @ TiN and its composite with sulfur (C @ TiN-S). e) The TEM image of C @ TiN-S and
the corresponding elemental mappings. d,e) Reproduced with permission.[195] Copyright 2019, Elsevier.

capacity of ≈830 mAh g−1 can be still achieved at 0.2 C after
100 cycles (Figure 9c). This excellent performance was ascribed
to the yolk–shell structure to physically confine the soluble poly­
sulfides and the synergistic effect of vanadium nitride, cobalt
dopants, and N-doped carbon to provide chemical affinity for
the soluble polysulfides. Recently, cobalt single atoms or clus-
ters have been homogeneously decorated on hollow carbon
nanosphere (Con-HC), through a post treatment as shown in
Figure 9d.[199] These atomic cobalt species were found to be
able to catalyzing the decomposition of the long chain poly-
sulfides, both experimentally and theoretically, due to the strong
polar–polar interaction between them, which leads to not only
enhanced cycling stability but also better utilization of the sulfur
active species. Consequently, this material, when used as a
sulfur host for sodium sulfur batteries, delivered a high initial
capacity of 1081 mAh g−1 (i.e., 64.7% sulfur utilization) and a
high remaining capacity of 508 mA h g−1after 600 cycles when
tested at 100 mAh g−1.
Briefly, carbon nanospheres, especially the hollow ones, have
provided a very convenient confined space that can not only
host sulfur, but also more importantly, load various catalytically
active species on their walls or inside their internal void. This
is essential from further enhancing the materials’ performance
from several aspects: 1) the carbon nanospheres themselves, as
aforementioned, can physically confine the soluble polysulfides;
2) the active species, either inside them or on their walls, can
have more efficient contact with the polysulfides to chemically
anchor them or to kinetically accelerate their electrochemical
conversion process; 3) in a closed environment, these active
species can also be well kept in the sphere, which is essential to
prevent them from being detached from the material and help
enhance their stability.

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Figure 9.  a) Schematic illustration of the fabrication of Co-VN@C and the structure of Co-VN@C after loading sulfur into it. b) TEM image of Co-VN@C.
c) Cycling performance of the material. a–c) Reproduced with permission.[198] Copyright 2018, American Chemistry Society. d) Schematic illustration
of the fabrication of Con-HC and the subsequent composite with sulfur (S@Con-HC). Reproduced under the terms of the CC-BY Creative Commons
Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/).[199] Copyright 2018, The Authors, published by Springer Nature.

3.1.3. Carbon Nanospheres for Electrochemical Ion Storage
For lithium-ion or sodium-ion batteries (LIBs/SIBs), the electro­
chemical storage of these ions is essential, especially in the case
of the anode materials. On the one hand, the porous carbon
nanospheres themselves can be used as the anode, and their
advantage of facile structural tailoring is also quite desirable to
achieve a high ion diffusion rate. On the other hand, the hollow
carbon nanospheres possess the additional merits of being able
to accommodate the various high-capacity active species (e.g.,
Si, Sn, SnO2, Fe3O4, and others), which generally suffer from
huge volume variation upon charge and discharge.[18] This

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has thus significantly broadened the application of the carbon
nanosphere materials in LIBs/SIBs.
First, the carbon nanospheres can be readily used to store
lithium ions, although their versatile microstructures and
chemical compositions could lead to different lithium-ion
storage mechanisms from their graphite counterparts and
thus a higher capacity. For example, N-doped carbon
nanospheres with a relatively small particle size (60–70 nm)
and a turbostratic structure were prepared by pyrolyzing poly­
pyrrole nanospheres.[200] The short range graphitic structure
with abundant defect sites endowed this material with a high
capacity that was close to those of the hard carbon materials
(≈420 mAh g−1) but much better cycling stability. On the other
hand, the very small particle size of this material also ensured
the rapid intercalation and deintercalation of lithium ions
into/from the material. Thus, an excellent rate performance
(≈180 mAh g−1 @ 3 A g−1) was achieved for this material,
outperforming other commercial carbonaceous anode mate-
rials. In addition, by reducing CHCl3 with potassium metal,
hydrogenated carbon nanospheres were obtained, which were
about 40–90 nm in diameter and abundant in surface defects
(i.e., open graphitic structures), which can be confirmed by the
presence of a substantial content of sp3 hybridized carbons.[201]
In this case, the unclosed graphitic structure, which ended with
a hydrogen atom, would lead to “dangling bonds” and could
thus contribute to a much higher lithium ion storage capacity
and, shortened lithium ion pathways, as well as more accessible
sites for lithium ions. In total, these merits led to a high dis-
charge capacity (978 mA h g−1 after 50 cycles) and good cycling
stability. However, the coulombic efficiency in the initial few
cycles, especially in the first cycle, was not satisfactory, which
might be caused by the irreversible surface reactions between
the hydrogen species and lithium ions.
Apart from being directly used for lithium-ion storage, as
mentioned above, such carbon nanospheres can also be used
as a host for the high capacity yet unstable active species
for the storage of lithium ions. One typical high capacity
lithium-ion storage material is silicon, which possesses a very
high capacity of 4200 mAh g−1 and a huge volume expan-
sion of up to 400%. This characteristic thus makes silicon
suffer from rapid capacity fading when used alone, mainly
due to the structural collapse during the repeated cycling.[202]
To deal with this issue, silicon nanoparticles are commonly
confined inside carbon nanostructures to improve their struc-
tural stability, and carbon nanospheres in different forms
have been a popular candidate for this purpose. For example,
silicon nanoparticles have been confined inside a double-
shell carbon nanosphere through a multi-step coating and
etching process (Figure  10a).[25] In this material, tiny silicon
nanoparticles were uniformly distributed inside the double-
shelled carbon nanospheres (Figure 10b). The inner carbon
shell provided finite inner voids for buffering the large volume
variation of silicon nanoparticles, while the outer shell could
facilitate the formation of a stable solid electrolyte interphase
(SEI). Moreover, the intershell space was also believed to be
able to further buffer the volume changes and thus alleviate
mechanical stress from inner carbon shell (Figure 10c). Conse-
quently, this material delivered a high capacity of 1802 mAh g−1
@ 0.2 C and good cycling performance for up to 1000 cycles.
Remarkably, the full cell, with this material as the anode and
lithium nickel cobalt manganese oxide (LiNCM) as the cathode,
exhibited a very high energy density of 473.6 Wh kg−1 and

Figure 10.  a) Schematic illustration of the fabrication of silicon nanoparticles confined in double-shell carbon nanoparticles. b) The corresponding
TEM image of the material, with the selected area electron diffraction (SAED) pattern in the inset. c) Schematic illustration of the structural change of
the material during the charge–discharge process. a–c) Reproduced with permission.[25] Copyright 2017, Wiley-VCH. d) Schematic illustration of the
fabrication of silica nanospheres embedded in the walls of hollow carbon nanospheres. e) TEM images of the material in the un-lithiated, fully lithiated,
and fully delithiated states, from left to right. f) Schematic illustrations of the material’s structures in these states. d–f) Reproduced with permission.[203]
Copyright 2017, The Royal Society of Chemistry.

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good cycling stability with capacity retention of 93.8% after
200 cycles.
Apart from silicon, its oxide, silica, has also been used as the
anode for lithium-ion batteries and similar strategies have also
been applied to deal with the stability issues. In this case, silica
nanoparticles were first assembled into hollow spheres and then
infiltrated with carbon (Figure 10d).[203] Silica nanospheres were
then evenly embedded on the walls of the carbon hollow
spheres (Figure 10e), which not only enhances the conductivity
but also improves the structural stability of the silica nanopar-
ticles during repeated charge–discharge processes (Figure 10f),
making it able to be stably cycled for up to 500 cycles. More-
over, similar strategies have also been successfully utilized to
stabilize other active species with the same stability problems,
such as tin (Sn), tin oxide (SnO2), or molybdenum (Mo)
disulfide (MoS2), by anchoring them in the internal voids,
inside the walls, or on the outer surface of hollow carbon
nanoparticles.[71,142,203]
As for the sodium ions, the most frequently used material to
store them is hard carbon that is composed of partially cross-
linked (i.e., sp3 hybridized) carbon atoms.[204] Compared with
the commercial hard carbon with random particle sizes and
morphologies, making it into microspheres can not only
improve the actual tap density but also homogenize the current
density for smoother Na ion insertion and SEI formation.[205]
In particular, the ones with a hollow structure or open struc-
ture would further reduce the diffusion distance for Na ion
insertion and extraction, which is very desirable for this kineti-
cally sluggish process and thus, can significantly enhance its
rate capacity for Na ion storage.[42] Compared with its coun-
terpart with a solid core, the hollow structure with a very thin
shell (<12 nm) guarantees a very short sodium diffusion dis-
tance, which plays a critical role in the rate performance of the
material. As a result, a much-enhanced performance, especially
in the case of the rate performance (≈100 mAh g−1 @ 2A g−1
or ≈50 mAh g−1 @ 10 A g−1), was achieved on this material,
greatly outperforming its solid carbon nanosphere counter-
part (≈20 A g−1 @ 2 A g−1). Similar to the solutions for storing
lithium ions, high capacity materials, such as molybdenum dis-
elenide (MoSe2) and molybdenum disulfide (MoS2), have also
been confined inside or grafted onto hollow carbon nanostruc-
tures, which were quite effective in enhancing their electro-
chemical Na ion storage performance, particularly their cycling
stability.[206]
3.1.4. Carbon Nanospheres as a Host for Lithium/Sodium Metal
Unlike storing lithium ions in the anode material in a lithium-
ion battery, a lithium metal battery directly utilizes lithium
metal as the anode material. Compared with the conventional
graphite anode material for LIBs, lithium metal possesses a
much high specific capacity (3860 mAh g−1 vs 375 mAh g−1).[207]
When a lithium metal anode is coupled with other high
capacity cathode materials, such as oxygen and sulfur, a very
attractive energy density can be expected (e.g., 3500 Wh kg−1
for Li-O2 batteries and 2600 Wh kg−1 for Li–S batteries).[208]
Despite these merits, the intrinsic shortcomings of lithium
metal are also significant, including its high reactivity, its
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enormous volume variation during cycling, and its dendrite
formation.
To deal with this, the surface protection of lithium metal is
essential and hollow carbon nanospheres can be readily utilized
for this purpose.[208,209] It is only very recently that the successful
accommodation of lithium metal inside the hollow carbon
nanospheres has been achieved, due to the difficulties in regu-
lating the position or the morphology of lithium disposition.
To address this, selective and controllable lithium deposition
was achieved by using gold nanoparticles, which were located
inside the hollow carbon spheres, as the seeds for the preferen-
tial deposition of lithium inside the spheres (Figure  11a,b).[24]
For the first time, such selective deposition and confine-
ment of lithium metal inside carbon hollow nanospheres was
directly observed (Figure 11c). Such confinement can effectively
improve the stability of the electrochemical cycling for lithium
metal and minimize the undesirable side reactions with electro-
lyte because the direct contact between the lithium metal and
the electrolyte was significantly eliminated. As a result, much-
improved cycling performance was achieved, including a high
Coulombic efficiency of up to 98% in carbonate electrolyte and
excellent cycling stability for over 300 cycles.
3.2. Electrochemical Conversion
Electrocatalysis is an important process in the field of clean
energy conversion such as in fuel cells, water splitting, and
metal–air batteries.[210,211] Nevertheless, the electrochemical
performance of these devices is limited, mainly by the sluggish
kinetics of the hydrogen evolution reaction (HER), the oxygen
evolution reaction (OER), the ORR, and some other electro-
catalytic reaction processes such as CO2 reduction, methanol
oxidation, and nitrogen reduction, which are the key factors
in the electrochemical processes for renewable energy conver-
sion (Figure  12).[211] For these applications, the high conduc-
tivity of colloidal carbon spheres could improve the efficiency
of the charge transfer. Additionally, the transfer of electrolyte
ions also can be facilitated because porous carbon structures
with high active surface areas can be tuned and further modi-
fied for electrochemical reactions, leading to enhanced and
even optimal electrochemical properties. Benefiting from all
the above unique structural features, the carbon spheres have
been proven to be one of the superior candidates for electroca-
talysis with high activity and stability. Bearing all this in mind,
the rational design and fabrication of carbon nanospheres with
controllable structure and composition for various electrochem-
ical reactions will be summarized and discussed in this section.
3.2.1. Carbon Sphere as Nanoreactors for Oxygen
Reduction Reaction
The ORR plays an important role in fuel cells and metal–air
batteries.[212] The state-of-the-art Pt electrocatalysts have exhib-
ited excellent ORR electrocatalytic activity in both basic and
acidic solutions.[213] Although the use of these sorts of noble
metal catalysts have been limited in terms of widespread pro-
duction and further practical applications due to their high cost,
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advmat.de

Figure 11.  a) TEM images of gold nanoparticles trapped inside hollow carbon nanospheres; b) schematic illustration of the lithium deposition process
inside the hollow carbon structure; c) the corresponding TEM images of the lithium disposition at different stages. a–c) Reproduced with permission.[24]
Copyright 2016, Springer Nature.

low tolerance to methanol crossover and CO poisoning, and and stability that would be comparable to platinum catalysts.
poor stability.[214] Increasing efforts have been made to fabricate Since they are metal-free, and especially, precious-metal-free,
more cost-effective materials with high electrocatalytic activity carbon spheres have received great research attention due to

Figure 12. a) Schematic diagram of ORR catalytic process. b) Illustration of N-doped mesoporous carbon spheres. c) SEM image of NMCS-3.
a–c) Reproduced with permission.[26] Copyright 2015, Wiley-VCH. d) Schematic diagram of OER catalytic process. e) Illustration of hollow carbon spheres
N-HMSC. f) TEM image of N-HMSC particles. d–f) Reproduced with permission.[21] Copyright 2016, Elsevier. g) Schematic diagram of HER catalytic process.
h) Illustration of mC-Mo-850 carbon spheres. i) SEM image of mC-Mo-850 particles. g–i) Reproduced with permission.[22] Copyright 2019, Wiley-VCH.

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their good catalytic activity toward the ORR, low cost, and good
durability.[31,215] In spite of the tremendous research that has
been conducted on metal-free and nonprecious metal catalysts,
it is still challenging to explore relatively cheaper metal-free or
transition-metal-based carbon spheres as electrocatalysts for the
ORR with high catalytic activity and durability.
Metal free carbon spheres are promising candidates as ORR
catalysts because they have high current densities and high
onset potential via a 4e− reduction pathway similar to that for
platinum catalysts (Figure 12a).[216] To further improve the
ORR activity of carbon spheres, various strategies including
hetero atom doping,[117,154,217] and hierarchical porosity
control,[26,218,219] have been widely explored. Their electronic
structures and chemical activities can be modified through
doping with various atoms such as N and P because their
differences in electronegativity facilitate electron transfer and
enhance their ORR activity. More active sites can be exposed
through tuning the porosity of the carbon spheres, which is
beneficial for the transfer of reactants to active sites and for the
further improvement of the ORR activity. The synergetic effects
between the heteroatom doping and porosity can be highly
effective to achieve active carbon spheres.
For example, nitrogen-doped colloidal carbon nanospheres
presented a cathodic peak about −0.22 V and onset poten-
tial at −0.1 V, which was superior to those for N-free polymer-
based carbon spheres.[154] Our group have also developed a
facile method to prepare mesoporous nitrogen-doped carbon
nanospheres (Figure 12b,c), which have a microporous
shell with a mesoporous interior, through a dual surfactant
template method. These nanospheres exhibited excellent ORR
performance due to their unique mesoporous structure and
nitrogen doping.[107]Based on the results from linear sweep
voltammetry curves (LSV), our N-doped mesoporous hollow
carbon nanosphere particles (N-MHCNSs-700) exhibited great
potential as an ORR catalyst. It was found that the onset poten-
tial became higher after 15 h, indicating that the prepared
catalyst was very stable and could be further activated during
the ORR tests. In addition, the pore size of the colloidal carbon
spheres could be finely tuned through soft template method to
achieve the optimal electrochemical behavior for the ORR.[26]
In another work, N-doped carbon spheres (NMCS-3) with
large mesopores of about 16 nm and small particle sizes of
about 200 nm have been successfully prepared.[26] When used
as ORR electrocatalysts, the NMCS-3 particles with relatively
larger pore size showed a higher diffusion-limiting current and
a more positive onset potential compared with the micropo-
rous carbon spheres and commercial Pt/C catalyst. Their excel-
lent electroactivity can be attributed to the open porous carbon
framework, which is advantageous for mass transportation and
ion diffusion. Among the various potential doping elements,
nitrogen has been widely investigated because of its ability to
enhance the electrocatalytic activity of the nanospheres toward
the ORR.[220] The main problems for N-doped metal-free carbon
spheres as electrocatalysts are their poor performance and
poor stability in acidic media because of the degradation of the
carbon matrix.[221] Indeed, excellent N-doped electrocatalysts
have been reported in alkaline media,[117,217,218] but only very
few groups have reported a good electrochemical behavior in
acid media.[219]
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To overcome these difficulties, the cooperative effect between
N-doping and nonprecious metals such as cobalt or iron have
inspired efforts to design metal–N–carbon spheres with high
activity, long-term stability, and better tolerance to poisons
than solely doped carbon spheres.[20,154,222] The most common
approach to prepare metal–N–carbon spheres as ORR catalysts
is to incorporate the metal species into/onto the N-doped carbon
nanostructures. For instance, Fe/N/C hollow carbon spheres have
been prepared through impregnating polydopamine spheres
with iron salts and the following carbonization process.[154] It is
believed that the primary active sites for the ORR are the metal-N
moieties on the surface of the material. Titirici and co-workers
also prepared Fe–N-doped carbon catalyst, which exhibited
outstanding electrocatalytic activity toward the ORR in both
alkaline and acidic media.[20] This excellent electrochemical
performance was attributed to the combination effects of active
N-doping, Fe–N coordination sites, large surface area, and open
mesoporous structure.
Recently, isolated single atomic site catalysts have attracted
tremendous interest due to their maximum metal utilization
efficiency, their homogeneous distribution of catalytically
active sites and the low co-ordination environment of the metal
atoms.[223] These features have promoted the use of single atom
catalysts with high electrochemical catalytic behavior, stability
and selectivity.[224] Hollow N-doped carbon spheres with isolated
single Co atomic sites have been successfully prepared and also
exhibited the high half-wave potential of 0.773 V in acid media,
which is comparable to the performance of commercial Pt/C
materials.[225] In addition, only a very small ORR polarization
curve shift was found after 10 000 cycles and superior stability
against methanol poison could also be achieved in the presence
of 1.0 m methanol.
3.2.2. Carbon Sphere as Nanoreactors for Oxygen
Evolution Reaction
As the reverse procedure from the ORR, OER is considered
as a bottleneck half reaction in energy-conversion and storage
devices such as overall water splitting and metal–air batteries
(Figure 12d).[226] It is well-known that noble-metal catalysts
such as RuO2 and IrO2 are among the most effective OER elec-
trocatalysts. Nevertheless, their high cost and limited availa-
bility in the earth’s crust have greatly restricted their widespread
application in the energy industry. Therefore, great attentions
have been paid to exploring relatively cheap and abundant OER
catalysts with high catalytic performances, especially transition-
metal- and N-doped carbon spheres. These kinds of materials
have shown high activity because of the synergistic effects of
the heterometallic ions, although only a few examples have
been reported that involve using colloidal carbon spheres as
catalysts for the OER.[21,227]
Hierarchically porous graphitized carbon spheres deco-
rated with NiFe layered double hydroxides (NiFe-LDHs) on
their surfaces were successfully constructed.[227] The prepared
carbon spheres exhibited excellent OER properties, including
superior stability, low onset potential, and a low overpotential
of 265 mV, which were superior to those of the noble-metal
IrO2/C catalyst. This excellent electrochemical behavior was
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www.advancedsciencenews.com
ascribed to the synergistic effects between the NiFe-LDHs
and the unique carbon structure with optimal exposure of the
active sites. To further understand impact of metal species in
metal–N carbon spheres, Fe–N-doped hollow mesoporous
shelled carbon (N-HMSC) was prepared through the hard tem-
plate method using Fe phthalocyanine as the carbon precursor
(Figure 12e,f).[21] It was found that nitrogen doping is necessary
for effective OER electrocatalysis rather than Fe species while
more effective N species with high edge exposure and the gra-
phitization degree can be further increased through incorpora-
tion of Fe species.
3.2.3. Carbon Sphere as Nanoreactors for Hydrogen Evolution
Reaction
Hydrogen is considered as a very promising alternative energy
carrier to replace fossil fuels for a sustainable economy. The
utilization of electrocatalysts to produce hydrogen from aqueous
solutions such as water through a HER process is an especially
attractive and sustainable approach (Figure 12g). Compared
with OER process, even though the overpotential of the HER
process is lower, an efficient HER catalyst is still required.
Although noble metals and their derivatives such as Pt are
the most active catalysts to promote the HER half-reaction of
water splitting, their broad utilization in energy systems has
been severely limited by the high costs. Therefore, non-noble
metal catalysts with relatively low prices and high abundance
in nature have been widely explored with various compositions
and structures.[228]
Among the current transition metal catalysts, Mo-based
colloidal carbon spheres, such as Mo2C,[22,229,230] MoS2,[230,231]
and MoP,[230] and FeCo alloy-based colloidal carbon spheres[232]
have shown promising catalytic activity and stability. For
example, molybdenum-based (MoP, Mo2C, MoS2) carbon
spheres was fabricated by carbonization of glucose and various
Mo precursors.[230] In the case of MoS2 decorated carbon
spheres, excellent HER catalytic properties were achieved
in both acid and alkaline media, while MoP decorated carbon
spheres showed the best HER behavior among the as-prepared
catalysts in acid solution with a low overpotential of 136 mV
at 10 mA cm−2. Mo2C decorated carbon spheres exhibited the
lowest overpotential for the HER in alkaline solution. A facile
and scalable synthesis of Mo2C-based carbon spheres with
hierarchically mesoporous structure was reported using a
metal–organic framework (MOF) precursor for efficient electro-
catalytic HER (Figure 12h,i).[22] High HER activity and stability
with a low overpotential of 222 mV at 100 mA cm−2, which was
even smaller than that of Pt/C (263 mV), were achieved for this
material, due to the formation of Mo2C/Mo2N heterojunction
and mesoporous structures.
3.2.4. Carbon Sphere for Bifunctional Electrocatalysts
In the practical electrochemical devices, multiple electrochem-
ical processes often occur. For instance, overall water splitting
usually involves both HER and OER processes. In the recharge-
able metal–air batteries, both the OER and the ORR take place.
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Thus, bifunctional catalysts are required, which should have low
cost and high electrochemical activity as well. Since the doping
atoms, porous structure, and components of the colloidal
carbon spheres are inherently beneficial for bifunctional electro-
catalysis, manipulation of the complementary components with
particular porous structures is necessary to achieve enhanced
electrochemical performances. Hollow carbon microspheres
with encapsulation of cobalt nitride (Co–N) and cobalt oxide
(Co–O) was designed and it was found that both the molar ratio
of the carbon to the cobalt precursors and the annealing tem-
perature were the key factors for the formation of this unique
hybrid structure.[233] Oxygen adsorption properties could be
optimized by finely tuning the electronic interaction between
the carbon layers and the encapsulated cobalt species, leading
to a high onset potential of 0.93 V and a limiting current
density of 5.6 mA cm−2 with a 4-electron ORR process, com-
bined with excellent OER electrocatalytic activity and stability
comparable to those of commercial electrocatalysts. Manthiram
and co-workers also reported Co3O4-coated hollow graphitic
carbon spheres with high OER and ORR electrocatalytic activi-
ties, which could be attributed to the strong interaction between
the adsorbed O2 molecule and the surface structure and to their
high electrical conductivity.[234]
3.3. Carbon Sphere Nanoreactors for Catalysis
It is of highly important to design appropriate reactors in
chemical reaction engineering. To achieve optimized operating
conditions, one has to consider the flow dynamics, mass transfer,
heat transfer, and reaction kinetics. With the development of
nanotechnology, it is possible to design and fabricate reactors
from the meter scale to the micro and nanoscale. The term
“Nanoreactors” was first used around 1990s, and now it has been
used in connection with potential candidates for catalytic appli-
cations.[235] From the perspective of chemical engineering, the
designed and prepared catalysts are considered as nano­reactors.
Compared with the conventional reactors, nanoreactors have
several advantages, including the capability of performing
parallel chemical reactions, removing undesirable products,
and enhancing the catalytic behavior. Multiple reaction sites can
be controllably located on different spatially positions of nano-
reactors such as, the exterior and interior surfaces of the carbon
shell, the void of carbon particles and anisotropic positions
to obtain the optimal catalytic behaviors.[236] Therefore, great
efforts have been devoted to the fundamental understanding
and rational design of these nanoreactors, especially the rela-
tionship between the materials’ architecture and their catalytic
performance. In this section, an overview of chemical reactions
by using carbon nanoreactors is provided. Three categories
including oxidation, hydrogenation, and biphasic catalytic reac-
tions have been classified for these carbon nanoreactors.
The most commonly used catalysts are yolk–shell carbon
spheres, referring to hollow carbon spheres with a void space
between the catalytically active core and a void space between
them, in which the cores are free to move inside the shell.[237]
The preparation of this kind of yolk–shell carbon nanoreactor
has been shown in the Section 2 through using selectively
removing the template method. Until now, various yolk–shell
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www.advancedsciencenews.com
carbon spheres, with different core compositions and a wide
range of particle sizes, have been successfully prepared.[2] Yolk–
shell carbon spheres have received great attention because of
their properties such as low density, high surface-to-volume
ratio, large specific surface area, and interior void. Compared
with the solid carbon nanoreactors, hollow carbon nanoreactors
have their unique advantages: i) catalytically active species can
be loaded within the void to stabilize particles against sintering;
ii) the selectivity of catalytic reactions can be further enhanced
through controlling the pore size of the shell; iii) mass transfer
during catalytic process can also be improved compared with
the same mass of bulk catalysts; iv) the catalytic reaction rate
can also be increased through adjusting the hydrophobicity/
hydrophilicity to enrich the reactants within the void.[238]
3.3.1. Oxidation Catalytic Reaction
Catalytic oxidation reaction in aqueous solution is of great
significance for the synthesis of carbonyl compounds and carbox-
ylic acids as the organic intermediates in chemical industry.[239]
Therefore, noble metal catalysts such as Pd has received consid-
erable interest in the development of aerobic oxidations.[240,241]
For example, the core–shell Pd@hmC catalysts with confined
Pd particles within a mesoporous carbon shell, was successfully
prepared by Ikeda and co-workers[240] Compared with those
of Pd/activated carbon (turnover frequency (TOF) = 2090 h−1)
and the Pd/hmC composite (TOF = 1528 h−1), the as-prepared
catalysts presented high catalytic activity (TOF = 2940 h−1) for
oxidation of benzyl-alcohol. This was derived from the protec-
tion of the carbon shell to the active Pd particles and inhibi-
tion of aggregation of Pd particles at high temperature reaction.
Coville and co-workers also reported the boron-doped hollow
carbon spheres encapsulating Pd nanoparticles, which showed
excellent catalytic oxidation of alcohols into aldehydes; it was
found that boron atoms can stabilize the Pd nanoparticles on
the carbon support.[241] Recently, due to the high cost and scar-
city of noble metal, transitional-based carbon sphere catalysts
such as Mn-and Mo-related catalysts have been obtained and
proved to be highly efficient, selective and recyclable.[242,243]
Yang and co-workers prepared carbon spheres with decorated
molybdenum oxides (MoOx/CS), which showed high catalytic
activity in aerobic oxidation of fructose (nearly 78% yield of
2,5-diformylfuran at 100% conversion).[242] The acid and oxide
sites in the MoOx/CS catalysts played an important role for
dehydration of fructose and aerobic oxidation
3.3.2. Hydrogenation Catalytic Reactions
Selective hydrogenation reaction are essential for organic
synthesis, such as the fabrication of epoxides.[244] Most such
catalytic reactions are carried out at relatively high tempera-
tures, leading to the sintering of metal-based active species and
finally the deactivation of catalysts. One of the representative
work reported by Schüth and co-workers demonstrated a facile
method to prepare PtCo bimetallic nanoparticles with diameters
about 4 nm that are confined inside HCS (Figure  13a–c).[2]
Using this material as the catalyst, the conversion from
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5-hydroxymethylfurfural to 2,5-dimethylfuran (DMF) reached
100% in just 10 min and the yield of DMF reached 98% after
2 h. In another work, through the hydrothermal treatment and
the following pyrolysis of an emulsion containing P123/sodium
oleate/PdCl42− and the polymer precursors of 2,4-dihydroxyben-
zoic acid and hexamethylentetramine, a scalable preparation of
yolk–shell structured Pd@carbon catalysts can be achieved.[245]
Recently, our group also reported the yolk–shell structured
sub-microreactors with loaded metal nanoparticles into ZnO-
microporous carbon core–shell structures (Figure 13d).[122]
When used as the catalysts for hydrogenation of phenylacety-
lene to phenylethylene, the prepared sub-microreactor showed
a higher conversion and selectivity than the Pd/ZnO and Pd/C
catalysts with a similar Pd loading. Moreover, a high selec-
tivity (99%) and superior catalytic stability were achieved on
this catalyst (Figure 13e). Telfer and co-workers reported the
ZIF-derived hollow carbon capsules with monometallic or
bimetallic nanoparticles confined in them and found that the
formation of hollow structures could avoid the sintering and
detachment of the metal nanoparticles, which assured the
efficient mass transport and excellent catalytic activity for the
hydrogenation of nitroarenes.[159] After this work, the same
group also developed a universal synthesis strategy to encapsu-
late multi-metallic particles in the porous carbon framework,
which exhibited superior electrocatalytic properties toward
HER and OER catalysis.[160]
3.3.3. Biphasic Catalytic Reactions
To date, a few papers have been published in the area of
biphasic catalytic reactions.[246–248] For such interfacial catalysis,
the Janus carbon nanoreactors have shown great advantages,
such as superior emulsion stability, enhanced interfacial areas,
improved mass transfer among the two phases, and effective
separation of catalysts and products. Janus nanoreactors, which
are considered as one new generation of smart functional
materials, have been utilized for promising applications such as
catalysis.[249] The asymmetric structures of Janus nanoreactors
provide the possibility to design nanoparticles with multifunc-
tional properties and synergistically enhanced performances,
especially for catalytic processes.[250] The synthesis of Janus
carbon nanoreactors usually involves the surface-controlled
nucleation and growth, which depends on the controlled het-
ero-epitaxial growth or anisotropic attachment of one nanopar-
ticle on another.
Recently, Lu and co-workers reported an anisotropic and
dumbbell-shaped mesoporous carbon@organosilica Janus struc-
ture with asymmetric hydrophilic/hydrophobic properties.[246]
During the synthesis, mesoporous RF spheres were first
prepared and then periodic mesoporous organosilica (PMO)
particles were grown on the RF spheres. The formation of these
Janus particles was highly dependent on the molar ratio of the
cationic surfactant hexadecyltrimethylammonium bromide
(CTAB) and PMO precursors (Figure  14a–c). After selectively
loading of Pt nanoparticles and subsequent carbonization in
a N2 atmosphere, this Janus Pt/C&PMO carbon nanoreactor
showed higher interfacial activity toward stabilizing in a water-
in-oil Pickering emulsions and greater catalytic stability than
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advmat.de

Figure 13. a) Schematic illustration of the synthesis of uniform HCS. b,c) TEM image of PtCo@HCS-500. a–c) Reproduced with permission.[2]
Copyright 2014, Springer Nature. d) TEM image of Pd&ZnO@carbon. e) Conversion and selectivity to phenylacetylene hydrogenation. d,e) Reproduced
with permission.[122] Copyright 2018, Wiley-VCH.

the Pt/C catalyst (Figure 14d–f). Zhao and co-workers also syn-
thesized dual-mesoporous Fe3O4@mC&mSiO2 Janus nanoreac-
tors through a surface-charge-mediated selective encapsulation
approach with controllable wettability, which could be adjusted
through the volume ratio of carbon and silica precursors
(Figure 14g).[247] The obtained Pt-modified Janus carbon nanore-
actors with the optimal hydrophilic/hydrophobic ratio presented
high a catalytic efficiency (100%) in the biphasic reduction of
4-nitroanisole and the cascade synthesis of cinnamic acid with
a high turnover frequency of 700 h−1 (Figure 14h).
4. Conclusions and Perspectives
Significant advances have been made in the development of
colloidal carbon spheres with well-designed morphologies,
controllable morphologies, manipulated porosity, and adjust-
able functionalities. This review has summarized the advances
on colloidal carbon spheres from their synthetic and modifica-
tion strategies to the various applications. A special focus has
been placed on the synthetic strategies and functionalization
of carbon spheres with controllable sizes, architectures, and
surface properties, and their utilization as nanoreactors for
energy storage, electrochemical catalysis, and conversion.
The synthetic strategies for carbon spheres include the
templating method, hydrothermal carbonization, microemulsion
polymerization, and extension of the Stöber method. Table  4
presents a comparison of the various synthetic methods for
colloidal carbon spheres. Colloidal carbon spheres with a
well-defined and highly tunable particle size, controllable mor-
phology, and good mono-dispersity can be achieved through
the hard template method, which usually involves multiple
steps including the template-etching. Compared with the hard
template method, the mesoporous colloidal carbon spheres
obtained from the soft template method involve easier template
removal, but such carbon spheres are normally nonuniform in
size and morphology, and the limited types of the templates are
high-cost as well. Although hydrothermal carbonization pro-
vides an environmentally friendly and low-toxic method to pre-
pare carbon spheres, the irregular particle sizes, random pore
sizes, and the lack of choices of carbon precursors have impeded
the preparation of carbon spheres in this way. On the other
hand, microemulsion polymerization is a versatile and scalable
method, but structural collapse and low yield issues usually

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Figure 14.  a) Graphic illustration of the synthesis of the Janus nanoparticles. b) TEM image and c) high-angle annular dark-field scanning transmission
electron microscopy (HAADF-STEM) image of a single Pt/C&PMO particle; d) the kinetic profile for nitrobenzene reductions over Pt/C&PMO, Pt/C,
Pt/PMO, and Pt/C&PMO double sides under stir-free conditions. e) Conversions of five different substrates in the catalysis reaction under stir-free
conditions over Pt/C&PMO or Pt/C, and their reaction times corresponding to 7, 5, 5, 4, and 4 h. f) Microscopic scenario of the reaction occurring in the Janus
particle-stabilized emulsion, where A, B, and C represent NaBH4, nitroarene, and aniline molecules, respectively. a–f) Reproduced with permission.[246]
Copyright 2017, Wiley-VCH. g) Fabrication scheme of the dual-mesoporous Fe3O4@mC&mSiO2 Janus nanoparticles. h) Conversion−time plot of
different Pt-loaded catalysts: Pt loaded on the dual-mesoporous Fe3O4@mC&mSiO2 Janus nanoparticles (Pt/C&SiO2), mesoporous Fe3O4 &mSiO2
Janus nanoparticles (Fe3O4&SiO2/Pt), and Pt/C. g,h) Reproduced with permission.[247] Copyright 2018, American Chemical Society.

occur during the carbonization process. The recently developed
Stöber method has opened up a facile and novel strategy to
prepare uniform carbon spheres with high uniformity, thermal
stability, and a high carbonization yield; however, toxic phenol
carbon precursors have to be used during the synthesis of the
carbon precursors. Manipulation of the pore size, heteroatoms,
surface functional groups, and graphitization degree of the
colloidal carbon spheres plays an important role in the prop-
erties relevant to electrochemical performance and catalytic
behaviors. Additionally, to further precisely control the syn-
thesis of porous carbon spheres, it is necessary to design the
methodologies from the molecular level.
Precise characterization of carbon spheres is of great sig-
nificance to fully understand the physical properties of carbon
spheres. So far, advanced characterization techniques such as
TEM, high angle annular dark field scanning transmission
electron microscopy (HAADF-STEM) imaging and elemental
mapping, have been widely involved in carbon spheres. More
in situ or operando characterization methods are expected to
be developed for measurement of the catalytic process in one
single carbon sphere nanoreactors, their electron transferring,
mass transfer, diffusion, and reaction kinetics.
As for the various types of batteries, carbon sphere nanoreac-
tors have been extensively employed because they are versatile
and it is easy to tune their porosity and other structural
parameters. Among them, the ones with a hollow structure
and porous shells are especially attractive, because they are
able to host a series of active species, which are used in both
the anode and cathode of a battery, inside their internal voids,
stabilizing them and providing them with sufficient electronic/
ionic conductivity. This is essential for maintaining the stable
cycling of these species and their full utilization as well. On
the other hand, to enhance the electrochemical catalytic activity
and stability of colloidal carbon spheres, the pore size, par-
ticle size, and morphological structure of the carbon spheres
with surface modification should be controllably tailored, so

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Table 4.  Comparison of various synthetic methods for colloidal carbon spheres. great importance. This should become one of
the future directions for designing the high-
Advantages Disadvantages efficiency carbon sphere nanoreactors, even
Hard template •  Easy to control •  Multi-step coating process for the design atomic reactors.
• Homogeneous and well-defined • Harsh conditions Moreover, to meet the requirements for
porous structure for template removal industrial-scale applications, more attention
• Porous structure restricted needs to be paid to the development of new
by template methods with improved physical and chem-
Soft template • Removal of template under mild •  High cost of soft templates ical properties to fabricate such materials
conditions •  Low yield of carbon spheres with more economic viability and on a larger
• Facile synthesis of mesoporous •  Limited suitable soft templates scale, especially considering that almost all
structure •  Broad particle size distribution of the current reports require the use of dif-
Hydrothermal carbonization •  Low toxicity •  Irregular particle size ferent types of hard and soft templates that
•  Environmentally friendly •  Random pore size distribution tend to be expensive and need subsequent
•  Mild reaction conditions • Limited choices of carbon treatments to remove them. From this aspect,
precursors several critical challenges still exist, such
Microemulsion polymerization Versatile and scalable • Structural collapse during as the production cost and environmental
carbonization impact. Future research on the colloidal
•  Low carbonization yield carbon spheres should be focused on both
Extension of the Stöber method •  Easy to prepare Usage of toxic phenol precursor the basic synthetic methods and the related
•  High thermal stability applications. A deeper understanding of the
•  High carbonization yield synthesis of carbon sphere will be beneficial
in many different fields of application and for
that the number of exposed active sites can be optimized and scaling up the production of carbon spheres in the future in an
mass transfer can be improved. The synergetic effects of het- environmentally friendly and cost-effective way.
eroatom doping and increased porosity could be further used
to enhance the electroactivity of colloidal carbon spheres. By
controllably adjusting the morphology of carbon spheres, the Acknowledgements
reactive sites can be finely controlled on different positions on
the carbon spheres such as anisotropic positions, the exterior J.L. gratefully acknowledges support from the Chinese Government
and interior surfaces of the carbon shell, and the voids of the 1000 Young Talent Plan. H.T. gratefully acknowledges support from a
Curtin Strategic International Research Scholarship, a Curtin University
carbon particles to optimize their catalytic behavior. To further Mobility Scholarship, and a Chinese Government Award for Outstanding
deeply understand the electron/ion transfer during the dis- Self-Financed Students Abroad. J.L. would like to acknowledge support
charge–charge process, carbon sphere nanoreactors could be from the Australian Research Council under a Discovery Early Career
one of the potential candidates. Researcher Award (DECRA, No. DE170100871). The authors would like
To achieve the superior catalytic properties such as electro- to thank Dr. Tania Silver for proof reading. The authors are grateful to
chemical CO2 and N2 reduction, the effects including doping Prof. Qihua Yang and Prof. Can Li for fruitful discussions.
atoms, conductivity, and porosity should be fully considered,
ensuring the maximum exposure of active sites from the
carbon sphere nanoreactors. Through delicately design and Conflict of Interest
synthesis of carbon sphere nanoreactors, high-value chemicals
The authors declare no conflict of interest.
can be produced and some important chemical intermediates
can be controlled. However, the complexity of the surface prop-
erties and the heteroatoms resulted in the effective develop-
ment of carbon sphere nanoreactors. Therefore, it is still a great Keywords
challenge to molecularly control the active sites and catalytic carbon spheres, catalysis, energy conversion, energy storage,
properties, especially for isolated catalytically active sites. The nanoreactor
deeply understanding of experimental and theoretical results
becomes necessary to elucidate the nature of the active sites, Received: June 19, 2019
which can provide some guidelines for the design and synthesis Revised: July 24, 2019
novel carbon sphere nanoreactors. Published online: September 26, 2019
From a practical point of view, the catalytic performance
that the carbon nanoreactors can achieve so far still needs to
be further improved. Indeed, some strategies including the
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