Energy Storage Materials 19 (2019) 446–463

Contents lists available at ScienceDirect

Energy Storage Materials

journal homepage: www.elsevier.com/locate/ensm

Two dimensional bismuth-based layered materials for

energy-related applications
Kang Xu a, b, 1, Liang Wang a, 1, Xun Xu a, **, Shi Xue Dou a, Weichang Hao b, ***, Yi Du a, b, *
a
Institute for Superconducting and Electronic Materials (ISEM), Australian Institute for Innovative Materials (AIIM), University of Wollongong, Wollongong, NSW, 2525,
Australia
b
School of Physics, and BUAA-UOW Joint Research Centre, Beihang University, Beijing, 100191, China

A R T I C L E I N F O A B S T R A C T

Keywords: Owing to unique structures and properties, 2D layered materials have exhibited great potentials for energy-related
2D materials applications. Among these, 2D Bi-based layered materials which possess intriguing characteristics for energy
Bismuth-based layered materials conversion and storage systems have attracted tremendous attention. In this review, the structural and electronic
Energy conversion
properties of 2D Bi-based layered materials classified into four categories (unitary, binary, ternary and multinary)
Energy storage
Catalysis
are introduced. Their promising applications in energy conversion and storage are reviewed in details, with
particular emphasis on photocatalysis, electrocatalysis, solar cells, thermoelectrics, optoelectronics and
rechargeable batteries. Finally, based on current research progress, future perspectives for exploring and devel-
oping advanced 2D Bi-based layered energy conversion and storage materials are presented.

1. Introduction
The exploration of two-dimensional (2D) materials can be traced back
to decades, but from 2004, Novoselov et al. used scotch tape to suc-
cessfully strip graphene from graphite to trigger a research boom in 2D
materials [1]. In recent years, 2D layered materials developed with
unique structures and properties have delivered great potentials for ap-
plications in various aspects [2–5]. Among these, 2D layered materials
are of great significance in exploring energy conversion and storage
materials [6–10]. For instance, bismuth-based 2D materials layered
materials has demonstrated excellent characteristics as a new component
family for building electronic, optoelectronic and energy conversion and
storage devices [11–15].
Bismuth is an excellent eco-friendly metal that has a wide range of
applications [16–19]. It possesses many interesting features that have
been applied in energy related applications [20–22]. Firstly, a part of the
pivotal properties (correspondence of light) of a semiconductor is
determined by its band gap, yet the size of the band gap is closely related
to the crystal structure [23,24]. As shown in Table 1, in bismuth-based
layered compounds, the band structure can be manipulated through by
introduction of distinct anions and cations into the intrinsic layered
structure. The band gap can be tuned from 0.3 eV to 3.6 eV, so that the
corresponding absorption range is from ultraviolet to near infrared [25,
26]. Secondly, our recent theoretical and experimental studies proved
that the spatially anisotropic p and s-p hybrid states in bismuth-based
materials lead to a high-dispersion band structure [27–29]. It can be
seen from the Table 1 that the valance band maximum and the valence
band bottom of the Bi layered materials belong to the anisotropic p and
s-p hybridization. The highly dispersed electronic structure does not only
reduces effective mass of photoexcited charge carriers and promote their
mobility, but also enhances the charge separation and transmission ef-
ficiency in photoexcitation process [28,29]. Additional benefit of high
carrier mobility includes enhancements of performance in applications
such as solar cell, thermoelectric and optoelectronic conversion devices
[30,31]. Thirdly, Bi layered components have a stable skeleton structure
and a large interlayer space [32]. It allows foreign ions to intercalate and
to form multicomponent stable compounds without significant structural
deformation. This structure facilitate bismuth-based layered compounds
a promising material family for developing energy storage devices, such
as ion batteries.

* Corresponding author. Institute for Superconducting and Electronic Materials (ISEM), Australian Institute for Innovative Materials (AIIM), University of Wol-
longong, Wollongong, NSW, 2525, Australia.
** Corresponding author.
*** Corresponding author.
E-mail addresses: xun@uow.edu.au (X. Xu), whao@buaa.edu.cn (W. Hao), yi_du@uow.edu.au (Y. Du).
1
Kang Xu and Liang Wang contributed equally to this work.

https://doi.org/10.1016/j.ensm.2019.03.021
Received 18 January 2019; Received in revised form 26 February 2019; Accepted 25 March 2019
Available online 28 March 2019
2405-8297/© 2019 Elsevier B.V. All rights reserved.
K. Xu et al. Energy Storage Materials 19 (2019) 446–463

Table 1
Crystal and energy structures of 2D Bi-based layered materials.
2D Bi-layered Crystal VBM CBM Band Gap
materials Systems (eV)

Unitary Bi rhombohedral 0.3–0.5

Binary Bi2Te3, Bi2Se3 Rhombohedral Bi-6s, Bi-6p, 0.3
Te-4p/ Te/
Se-4s Se-4p
Bi2S3 orthorhombic S-3p Bi-6p 1.2–1.7
BiI3 rhombohedral I-5p Bi-6p 1.8
Ternary Bi2O2M (M ¼ S, tetragonal M-p, Bi-p 0.8–1.1
Se, Te) O-p
CuBiS2 orthorhombic Cu-3d, Bi-p 1.65–1.80
S-3p
Bi2SiO5, Bi2CO5 orthorhombic O-2p Bi-6p 3.5
BiOX (X ¼ F, Br, Tetragonal X-p, O- Bi-6p 1.7–3.5
Cl, I) Bi3O4Cl, 2p
Bi3O4Br,
BiO(IO3)
Cs3Bi2I9 hexagonal I-5p Bi-6p 1.89
Bi2WO6, orthorhombic O-2p Mo- 2.9
Bi2MoO6 4d/W-
5d
Multinary MBiO2X orthorhombic O-2p Bi-6p 2.8–3.6
(X ¼ Br, Cl;
M ¼ Ca, Sr, Ba)
Bi4MO8X orthorhombic O-2p Bi-6p 2.5
(M ¼ Nb, Ta;
X ¼ Br, Cl)
Fig. 1. An overview diagram showing 2D Bi-based layered materials for energy-
related applications.
In this review, as shown in Fig. 1, we will introduce the structural
properties of 2D Bi-based layered materials in four categories (unitary, bismuth and halogen, or chalcogen are p-block elements, these binary 2D
binary, ternary and multinary). The potential applications in energy Bi-based layered materials belong to p-block semiconductors. And p
conversion and storages including photocatalysis, electrocatalysis, solar states or s-p states in their disperse band structures lead to the
cells, thermoelectrics, optoelectronics and batteries are reviewed in de- ultra-narrow band gaps and ultra-high carrier motilities [28]. Hence,
tails. As awareness of the environment continues to increase and the these binary Bi-based semiconductors can be promising to be utilised in
demand for energy, the use of green metals such as bismuth will be photo-convention and thermoelectric applications. For binary 2D bis-
greatly improved. muth chalcogenides (Fig. 2c), Bi2Se3 taken as an example crystallizes in
an orthorhombic layered structure, consisting of five atomic layers con-
2. Crystal and electronic band structures of 2D Bi-based layered nected by weak van der Waals forces parallel to the z-axis [41]. And in
materials each layer, Bi atoms are bonded with two non-equivalent Se atoms by the
relatively stronger covalent bonds. And the ultralow electronegativity of
Up to now, multiple 2D Bi-based layered materials have been Se atoms makes Bi2Se3 possess an ultra-narrow band gap with strong
exploited for a variety of applications [26,27]. Here, the crystal and infrared absorption.
energy structures of 2D Bi-based layered materials are displayed espe-
cially for those intensively explored and developed as promising candi-
2.3. Ternary 2D Bi-based layered materials
dates for energy-related applications. And based on their elemental
compositions, these Bi-based materials are classified into four different
Ternary 2D Bi-based layered materials can be mainly obtained by
categories: unitary, binary, ternary, and multary.
inserting various anionic groups including simple or oxacid anions into
[Bi2O2]-based framework [26,42]. For these layered compounds, the
2.1. Unitary 2D Bi-based layered material interactions between positively charged Bi-based layers and anionic
layers are by van der Waals force or weak electrostatic force [43].
For unitary 2D bismuth (Fig. 2a), it has a rhombohedral layered Among these Bi-based materials, binary Bi-based p-block semi-
structure [16]. And its vertical interlayer spacing is 3.10 Å (Fig. 2b) [33], conductors can designed and explored via the introduction of simple
which much larger than many radii of alkali cations such as Liþ, Naþ, and anions (halogen or chalcogen anions) into [Bi2O2]2þ layers [44]. Like
Kþ [34,35]. So it can provide enough interlayer space for the insertion of bismuth oxyhalides (BiOX, X ¼ Cl, Br, and I) as Sillen-phase compounds,
these alkali cations. In addition, there are a large number of coor- they possess typical 2D layered structures, made up of [Bi2O2]-based
dinatively unsaturated Bi atoms on its exposed surfaces, which can be as fluorite-like layers interleaved with halogen layers [45]. And p-states of
catalytic sites to activate the reactant molecules and also offer “open halogen elements contribute mainly to their valence band maximum
tunnels” for ion insertions [21,36]. Moreover, the metallic property en- (VBM). The reduced electronegativity (Cl > Br > I) can result in negative
dows it with high conductivity [37]. These advanced properties shift of VBM, and further decrease their band gaps from 3.5 to 1.7 eV
mentioned above suggest their potential energy-related applications, [46]. So the band structures of bismuth oxyhalides can be adjusted by
especially on electrocatalysis and rechargeable batteries [36,38]. tuning halogen anions. In addition, the similar trend was also observed
for bismuth oxychalcogenide-Bi2O2X (X ¼ S, Se, Te) (Fig. 2d). However,
2.2. Binary 2D Bi-based layered materials the lower electronegativity of chalcogen atoms locates their p-orbitals at
higher energies than that of halogen atoms, leading to a reduction of
Binary 2D Bi-based layered materials including bismuth chalcogen- band gaps relative to corresponding bismuth oxyhalides [47,48]. For
ides and bismuth halides are mainly constructed via the combination of these binary Bi-based p-block semiconductors with tunable band struc-
bismuth with halogen or chalcogen elements [39,40]. Because both of tures, they can be utilised as promising candidates for kinds of

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K. Xu et al. Energy Storage Materials 19 (2019) 446–463

Fig. 2. (a) Photograph of layered bulk Bi. Reproduced with permission [16]. Copyright 2010, Nature Publishing Group. Crystal structures of (b) bismuth, (c) Bi2Se3
(Reproduced with permission [41]. Copyright 2014, Wiley-VCH), (d) Bi2O2Se (Reproduced with permission [143]. Copyright 2017, Nature Publishing Group), (e)
Bi2MoO6 (Reproduced with permission [152]. Copyright 2017, Wiley-VCH), and (f) Bi4MO8X (M ¼ Nb, Ta and X ¼ Cl, Br) (Reproduced with permission [46].
Copyright 2016, American Chemical Society).

Table 2
2D Bi-based layered materials for energy-related catalysis.
2D Bi-based layered materials Synthetic strategies Energy-related Final Catalytic activity Reference
catalysis products

Bi3TiNbO9 nanosheets molten salt photocatalytic H2 342.6 μmol h1 g1 under simulated solar [64]
method H2 evolution light
monolayer Bi2WO6 nanosheets surfactant-assisted hydrothermal photocatalytic H2 2.67 μmol h1 g1 under visible light [49]
synthesis H2 evolution
1 1
monolayer Bi12O17Cl2 ultrasonic exfoliation photocatalytic H2 0.86 mmol h g under visible light [65]
nanosheets H2 evolution
CoOx-loaded liquid-solid-state reaction photocatalytic H2 70 μmol h1 g1 under visible light [66]
BiVO4 H2 evolution
(040)-crystal facet engineered hydrothermal synthesis Photoelectrocatalysis H2 0.02 mmol h1 at 1.23 V vs. RHE under AM [67]
BiVO4 H2 evolution 1.5 G illumination
defect-mediated surfactant-assisted hydrothermal photocatalytic CO 87.4 μmol h1 g1 under visible light [68]
BiOBr atomic layers synthesis and ultrasonic exfoliation CO2 reduction
1 1
BiOIO3 nanosheets hydrothermal synthesis photocatalytic CO 5.42 μmol g h under visible light [56]
CO2 reduction
single unit cell Bi2WO6 layers surfactant-assisted hydrothermal photocatalytic CH3OH 75 mmol g1 h1 simulated solar light [53]
synthesis CO2 reduction
defective single-unit-cell BiVO4 surfactant-assisted solvothermal photocatalytic CH3OH 398.3 μmol g1 h1 [69]
synthesis CO2 reduction
1 1
BiOBr nanosheets with oxygen solvothermal synthesis photocatalytic NH3 104.2 μmol g h under visible light [70]
vacancies N2 fixation
ultrathin BiOBr nanosheets solvothermal synthesis photocatalytic NH3 24.5 μmol g1 h1 under visible light [71]
with oxygen vacancies N2 fixation
ultrathin Bi nanosheets in situ topotactic transformation of BiOI electrocatalytic HCOOH 95% (faradaic efficiency), 11 mA cm2 [21]
CO2 reduction (current density) at 1.5 V vs. RHE
ultrathin Bi nanosheets BiOBr-templated electrocatalytic electrocatalytic HCOOH 90%, 200 mA cm2 [72]
reduction CO2 reduction
defect-rich Bi Bi2S3-templated electrocatalytic electrocatalytic HCOOH 84% at 0.75 V vs RHE [73]
reduction CO2 reduction
Bi nanodendrites electrochemical deposition electrocatalytic HCOOH 96.4%, 15.2 mA cm2 at 0.8 V vs. SCE [74]
CO2 reduction
Bi dendrite electrochemical deposition electrocatalytic HCOOH 89%, 2.7 mA cm2 at 0.74 V vs. RHE [75]
CO2 reduction
2
BiOx/C solvothermal synthesis electrocatalytic HCOOH 93.4%, 13.0 mA cm at 1.75 V vs. RHE [76]
CO2 reduction
ultrathin Bi2O2CO3 nanosheets electrochemical exfoliation method electrocatalytic HCOOH 85%, ~11 mA cm2 at 0.7 V vs. RHE [77]
CO2 reduction
Bi nanoparticles organic solution chemical reduction electrocatalytic CO 96.1%, ~16 mA mg1 at 2.0 V vs. SCE [78]
CO2 reduction

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K. Xu et al. Energy Storage Materials 19 (2019) 446–463

Fig. 3. (a) Crystal structure of monolayer Bi2WO6. (b) Schematic illustration of visible-light-driven photocatalytic mechanism over monolayer Bi2WO6 nanosheets. (c)
Photocatalytic H2 evolution under visible-light irradiation over Bi2WO6 nanoparticles, monolayers and monolayers sensitized by Rh.B. Reproduced with permission
[49]. Copyright 2015, Nature Publishing Group. (d) The side-view atomic-resolution HAADF-STEM image of Bi12O17Cl2/MoS2 heterostructures with its EELS
elemental mapping. (e) Schematic illustration of the interfacial separation of charge carriers within Bi12O17Cl2/MoS2 heterostructures along Bi–S bonds. (f) Cycling
tests of photocatalytic H2 evolution over Bi12O17Cl2/MoS2 heterostructures and monolayer Bi12O17Cl2. Reproduced with permission [65]. Copyright 2016, Nature
Publishing Group.

photo-conversion applications [29].
By the insertion of TM-based oxacid anions into [Bi2O2]2þ layers,
simple Aurivillius phase oxides with the general formula of (Bi2O2)(TM)
Ox (TM ¼ Mo, W, Sn, Nb, Ta, Ti, etc.) can be developed, composed of
corner-sharing connected (TM)Ox octahedral layers sandwiched between
[Bi2O2]-based layers (Fig. 2e) [49–51]. And the typical layered structures
enable them with high chemical and thermal stability. The polarization
of the non-uniform charge distribution between (TM)Ox and [Bi2O2]--
based layers can induce the internal electric field, which can facilitate
effectively the separation and migration of charge carriers [52]. And
their VBM is mainly composed of O-2p orbitals. Due to the relatively high
electronegativity of O, these compounds often have wide band gaps
compared with binary Bi-based p-block semiconductors [53]. In addition,

other non-metal oxacid anions (for example, CO2 2
3 , SiO3 , IO3 ) also can
be inserted into [Bi2O2]2þ layers to form Bi-based layered semi-
conductors [54–56].
2.4. Multinary 2D Bi-based layered materials
Multinary 2D Bi-based layered materials often possess complicated
compositions, including complex Aurivillius-phase compounds [49],
Aurivillius-Sillen compounds composed of both Aurivillius-phase and
Sillen-phase structures [57,58], and those obtained via the partial
replacement of Bi atoms in [Bi2O2]2þ layers of ternary Bi-based layered
compounds with some metal atoms such as Ca, Sr, and Ba [59,60]. Due to
their complicated compositions, these compounds are difficult to be
synthesized with facile wet chemical methods. Therefore, the intensive
exploration and development of these compounds have been consider-
ably hindered and their research is still in fancy.
Here, taking Sillen-Aurivillius compounds with a general formula of
[(Bi2O2)2X]3þ[An-1BnO3nþ1]3- (X as halogen elements, n ¼ 1, 2, 3, etc.) as
an example (Fig. 2f), they consist of Aurivillius [An-1BnO3nþ1]-based
perovskite and Sillen (Bi2O2)2X layers, which are alternately stacked with
each other along [001] direction [57,61]. Furthermore, the band struc-
tures of these Bi-based materials can be finely and extensively controlled
by the manipulation of (Bi2O2)2X blocks as well as perovskite blocks.
These compounds possess advantages of both Aurivillius-phase and
Sillen-phase semiconductors on light absorption, charge separation and
transfer, and photo-stability, suggesting their potential applications on
photocatalysis [46].
3. Energy-related applications of 2D bismuth-based layered
materials
3.1. Energy-related catalysis
To address the global energy challenge, energy-related photo/electro-
catalysis such as H2 evolution, CO2 reduction, N2 fixation has offered
significant opportunities [14,18,62]. Owing to widely chemical and
structural varieties, 2D Bi-based layered materials present competitive

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K. Xu et al.
with other 2D materials in energy-related catalysis [13,26,63]. Table 2
illustrates the recent achievements in development of 2D Bi-based
layered materials for energy-related catalysis.
3.1.1. Photocatalytic reduction
Photocatalytic reductions are viewed as ideal chemical reactions for
fuels production through harvesting the energy of solar light. A variety of
2D Bi-based layered semiconductors as photo-catalysts for energy con-
version have been widely investigated [38,79]. However, photocatalytic
efficiencies of these semiconductors are mainly limited by some draw-
backs, such as poor photoabsorption ability, sluggish separation/tran-
sport of charge carriers, and a relatively high activation barrier for the
dissociation of reactant molecules [17]. To overcome these limitations in
2D Bi-based layered photocatalysts, some efficient strategies such as
thickness control, facet and defect engineering have been developed to
construct high-performance photocatalytic systems on energy conversion
[26,27].
The atomically thin thickness of 2D materials could not only
tremendously prompt transfer of charge carriers from bulk to exposed
surfaces via shortened diffusion pathway in photocatalytic processes, but
also help to introduce abundant active sites into exposed surfaces
through the enlargement of the surface area [80,81]. Recently, mono-
layer Bi2WO6 has been successfully fabricated through a
surfactant-assisted self-assembly strategy, as shown Fig. 3a [49].
Ascribed to ultrafast separation of charge carriers and highly active
surfaces (Fig. 3b), it exhibited high photocatalytic efficiency of H2 evo-
lution under visible-light irradiation, although pure Bi2WO6 nanocrystals
were considered as photocatalysts with no visible-light-driven activity
for H2 production (Fig. 3c). Meanwhile, the improvement of internal
electric field induced by the non-uniform charge distribution of different
stacked layers via the decrease in thickness can be a feasible strategy to
develop high-performance photocatalytic systems [80]. It was reported
that under visible-light illumination, the separation of photogenerated
electrons and holes in monolayer Bi12O17Cl2 can be efficiently promoted
by the enhanced internal electric field to (Bi12O17) and (Cl2) end-faces,
respectively [65]. After building a 2D Janus (Cl2)-(Bi12O17)-(MoS2) ver-
tical heterojunctions (Fig. 3d), the separated photon-induced electrons
are allowed to induce to MoS2. These charge carriers can be further
proceed via Bi–S bonds formed between coordinatively unsaturated Bi
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Energy Storage Materials 19 (2019) 446–463
Fig. 4. (a) Advantages of BiOBr atomic layers with
oxygen defects as visible-light-driven photocatalyst
for CO2 reduction. (b) Photocatalytic CO evolution
rate of oxygen-deficient BiOBr atomic layers, pure
atomically thin BiOBr nanosheets, and pristine bulk
BiOBr nanosheets under visible-light irradiation.
Reproduced with permission [68]. Copyright 2018,
Wiley-VCH. (c) Schematic diagram of photocatalytic
N2 fixation model over BiOBr nanosheets with oxygen
vacancies. (d) Visible-light-driven photocatalytic NH3
generation over BiOBr nanosheets with oxygen va-
cancies. Reproduced with permission [70]. Copyright
2015, American Chemical Society.
atoms in (Bi12O17) and exposed surface S atoms in MoS2 monolayers to
activate absorbed H2O (Fig. 3e). The ultrahigh visible-light-driven H2
evolution rate was achieved consequently in such the heterostructures
(Fig. 3f).
Defect engineering can efficiently enhance photocatalytic reduction
activity of 2D Bi-based layered semiconductors by accelerating the sep-
aration of charge carriers and promoting the adsorption and activation of
reactant molecules [45,53,82]. For example, BiOBr atomic layers with
abundant oxygen vacancies created via UV-light irradiation were fabri-
cated and new defect levels resulting from oxygen vacancies extended the
photoresponse of BiOBr into visible light region (Fig. 4a) [68]. In pho-
tocatalytic reactions, the conversion of CO2 into COOH* intermediate
was facilitated by the charge delocalization induced by oxygen vacancies
in these BiOBr samples, verified by in situ Fourier-transform infrared
spectroscopy. As a result, atomically thin BiOBr nanosheets with oxygen
vacancies achieved much better visible-light-driven photocatalytic per-
formance for CO evolution than atomically thin BiOBr nanosheets and
pristine bulk BiOBr nanosheets (Fig. 4b). In addition to aforementioned
photoreduction application, defect engineering is also employed to
improve photocatalytic performance for N2 fixation. Owing to a strong
N–N triple bond in single N2 molecule, conventional Haber-Bosch pro-
cess must be carried out under harsh conditions, like high-temperature
and -pressure [83]. It was realized that oxygen vacancies can facilitate
photocatalytic N2 fixation proceed under ambient conditions via the
reduction of Gibbs free energy for the absorption and activation N2
molecules [62]. For BiOBr with oxygen vacancies under visible light
irradiation, the catalytic centers of oxygen vacancies could activate N2
molecules and efficiently promote the transfer of photogenerated elec-
trons to adsorbed N2 for fixation reactions (Fig. 4c) [84]. Hence, BiOBr
nanosheets with oxygen vacancies exhibited significantly enhanced vis-
ible-light-driven N2 fixation activity compared with pure BiOBr nano-
sheets (Fig. 4d).
Besides the thickness control and defect engineering, facet engi-
neering is another attractive strategy to enhance the photocatalytic
reduction activity of 2D Bi-based layered photocatalysts [85–87]. Via the
manipulation of facet junctions, the efficient spatial separation of pho-
togenerated holes and electrons to different facets can be achieved, and
then photo-reduction and photo-oxidation reactions could proceed on
the specific facets. Recently, it was found that the ratio of (010)/(100) in
K. Xu et al.
Fig. 5. (a) The spatial separation of photogenerated electrons and holes on (010) and (100) facets of BiOIO3. Reproduced with permission [56]. Copyright 2018,
Wiley-VCH. (b) CO evolution rates over samples synthesized under different synthesis conditions. (c) Schematic illustration of H2O splitting via H2 and O2 evolution on
different facets of Bi3TiNbO9 nanosheets. Reproduced with permission [64]. Copyright 2018, Elsevier.
2D layered BiO(IO3) nanoplates can be modulated precisely by
wet-chemical routes [56]. The various separation rate of photogenerated
carriers was verified subject to various (010)/(100) ratios (Fig. 5a). It
showed the highest photocatalytic CO evolution rate from CO2 reduction,
reaching 5.42 μmol g1 h1 can be achieved at the optimal ratio of
(010)/(100) (3:1) (Fig. 5b). In addition, the similar trend was also
observed in multinary 2D Bi-based layered photocatalysts. Here, taking
ferroelectric Bi3TiNbO9 as an example (Fig. 5c), photogenerated elec-
trons and holes tended to migrate to (001) and (110) facets, respectively
[64]. So by tuning the ratio of (001) and (110), the photocatalytic ac-
tivity of Bi3TiNbO9 would be correspondingly changed and Bi3TiNbO9
with highest (001) exposed facet showed most efficient H2 activity.
In addition to those 2D Bi-based layered photocatalysts mentioned,
BiVO4, one of famous Bi-based semiconductors, with unique structural
and electronic properties has also been widely developed as high-
performance photoelectrodes or photocatalytic systems for energy-
related catalysis [88–90]. And the modification strategies of 2D
Bi-based layered materials were also applied on BiVO4 to improve its
photochemical or photoelectrochemical H2O splitting or CO2 reduction
[26]. For example, ultrathin BiVO4 nanosheets with tunable concentra-
tions of oxygen or vanadium vacancies exhibited excellent photocatalytic
activity for H2 evolution or CO2 reduction, benefiting from the enhanced
photoabsorption and electronic conductivity induced by defect states
[69,91]. Besides, it was also found the overpotential of BiVO4 photo-
anode for H2 evolution reaction could be significantly reduced by
well-controlled oxygen vacancies and high photocurrent densities were
largely achieved [92]. Additionally, due to co-existence of oxidation and
reduction facets in single BiVO4 nanoparticle, photogenerated electrons
and holes can be spatially separated and accumulated onto different
facets of BiVO4 via engineering high-index surfaces [93] or crystal facet
orientation [94], or selective deposition of redox co-catalysts onto the
certain functional facets [66,95], hence the charge separation and
transport efficiency can be remarkably enhanced, resulting in its excel-
lent energy-related catalytic activity.
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Energy Storage Materials 19 (2019) 446–463
3.1.2. Electrocatalytic reduction
Due to ambient reaction conditions and efficient energy-conversion
performances, electrochemical reduction on energy-conversion applica-
tions (for example, CO2 reduction to value-added liquid or gaseous fuels)
has been considered as a significant way to alleviate the aggravated en-
ergy crisis [96,97]. With high activity and selectivity for CO2 electro-
reduction, 2D Bi-based layered materials as electrocatalysts have gained
considerable attention [98,99].
In the periodic table, unitary Bi is located close to some traditional
metals with highly electrocatalytic activity for CO2 reduction, implying
its potential application for CO2 conversion [21]. And the prominent
advantages of environmental friendliness and less toxic make it more
appealing as electrocatalyst for CO2 reduction in contrast to these metals
[100]. Recently, it was reported that ultrathin Bi nanosheets generated
via in-situ topotactic electroreduction of 2D layered bismuth oxyhalide
(BiOX, X ¼ Cl, Br, I) nanosheets showed excellent electrocatalytic per-
formance for CO2 reduction to formate (Fig. 6a) [72]. And the structural
evolution of BiOX-templated catalyst in electroreduction processes was
investigated at the atomic level by operando grazing-incidence
wide-angle X-ray scattering (GIWAXS) (Fig. 6b), demonstrating that Bi
could be in-situ formed via the full transformation of BiOX templates in
electrocatalytic reaction. Based on theoretical results, CO2 reduction re-
action could take place preferably on Bi (110) facet compared with Bi
(121) facet (Fig. 6c and d), contributing to the high electrocatalytic ac-
tivity of ultrathin Bi nanosheets. From the Gibbs free-energy diagrams for
formation of HCOO, CO, and H2, it was further confirmed that CO2
reduction to formate would occur prior to other electrocatalytic re-
ductions on ultrathin Bi nanosheets, while hydrogen evolution reaction
could be suppressed due to the too positive free energy of H adsorption
(Fig. 6e). Thanks to its advantageous 2D nanostructure and the exposure
of active facets, metallic Bi exhibited high selectivity for CO2 reduction to
formate under large current density over a broad potential (Fig. 6f). In
addition, other 2D Bi-based layered materials such as Bi2S3 were also
employed as templates to form metallic Bi nanosheets via electrocatalytic
K. Xu et al. Energy Storage Materials 19 (2019) 446–463

Fig. 6. (a) Schematic illustration of the fabrication of ultrathin Bi nanosheets from the transformation of bismuth oxybromide nanosheets. (b) EXAFS spectra of Bi-
based samples, in which the contribution of Bi–O bonds in BiOBr-derived samples increases with the compression of interplane Bi–Bi distances. Schematic diagram
of adsorption sites of H* and HCOO* on (c) Bi (110) and (d) Bi (121) facets. Reproduced with permission [72]. Copyright 2018, Wiley-VCH. (e) Gibbs free-energy
diagrams of formation of HCOO, CO, and H2 on Bi. (f) Faradaic efficiencies of different products on atomically thin Bi nanosheets, in comparison with that of HCOO
on commercial Bi nanopowder. Reproduced with permission [21]. Copyright 2018, Nature Publishing Group.

reduction strategy [73].
The edge sites of nanostructured electrocatalysts have been proven to
be as the active sites in electrocatalytic processes. Therefore morphology-
controlled strategy to introduce large number of edge sites into 2D Bi-
based catalytic systems has been widely applied to enhance the ele-
trocatalytic activity for CO2 reduction. Besides ultrathin Bi nanosheets
mentioned above, metallic Bi with various morphologies such as nano-
dendrites [74,75], nanoflakes [101], nanowires [102], mesoporous
nanosheets [103], and nanoparticles [78] were also successfully
designed and synthesized for electrocatalytic CO2 reduction.
The electrical conductivity of electrocatalysts is one of the vital fac-
tors in determining their catalytic activity. Because of the low electrical
conductivity resulting from their intrinsic semiconducting properties,
normal 2D Bi-based layered compounds often suffer from relatively low
electro-catalytic activities [78]. Hence, the introduction of highly
conductive carbon-based materials or metallic Bi into Bi-based electro-
catalytic systems can be an efficient approach to overcome the problem.
For example, the heterostructures of carbon-supported BiOx
nanoparticles (BiOx/C) were explored as promising electrocatalysts for
CO2 reduction (Fig. 7a) [76]. With the suppression of CO and H2 evo-
lution, efficient electro-conversion of CO2 to formate (a high Faradaic
efficiency of 93.4%) was achieved by BiOx/C electrocatalyst in bicar-
bonate solutions, (Fig. 7b). Besides, the heterostructures of 2D Bi-based
layered compounds and metallic Bi could be created via part electro-
reduction of pristine Bi-based catalysts in the catalytic process. It was
reported that ultrathin Bi2O2CO3 nanosheets which were controllably
synthesized via an electrochemical exfoliation method could develop to
Bi/Bi2O2CO3 heterostructures under catalytic turnover conditions
(Fig. 7c) [77]. Benefiting from atomically thin 2D structures and coupling
of Bi and Bi2O2CO3, these nanosheets exhibited high faradaic efficiency
for electrocatalytic CO2 reduction to formate with large current density at
a low overpotential (Fig. 7d). Moreover, two-electron transfer and the
protonation of CO⋅-2 on Bi/Bi2O2CO3 nanosheets as the determining steps
of electrocatalytic rate for CO2 reduction were revealed by
Fourier-transformed alternating current voltammetry (FTacV).

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K. Xu et al. Energy Storage Materials 19 (2019) 446–463

Fig. 7. (a) STEM image and schematic model of obtained carbon-supported BiOx nanoparticles. (b) Potential-dependent Faradaic efficiencies for HCOO, H2, and CO
production on carbon-supported BiOx nanoparticles and commercial Bi2O3 nanopowder. Reproduced with permission [76]. Copyright 2018, American Chemical
Society. (c) XRD patterns of few-layer Bi2O2CO3 nanosheets obtained after 30 min electrolytic reaction at an applied potential of 0.65 V. Inset: TEM image of the
same sample. (d) Faradaic efficiencies for kinds of products with few-layer Bi2O2CO3 nanosheets as the electrode at different applied potentials. Reproduced with
permission [77]. Copyright 2018, Wiley-VCH.

3.2. Energy conversion in solar cells, thermoelectric devices and
photodetectors
The conversion of photo energy and thermal energy into electrical
energy is one of the means to solve the current energy crisis [47,104].
Bi-based layered materials have high electron mobility and strong lattice
scattering interlayer, which leads to high electrical conductivity, low
thermal conductivity and stable structures simultaneously. This unique
structural nature and wide adjustable bandgap make them the important
application potential in the field of solar cells, thermoelectric devices and
photodetectors [105,106]. The energy conversion performances of 2D
Bi-based layered materials in solar cells, thermoelectric devices and
photodetectors are summarized in Table 3.
region of the solar spectrum and a high photocurrent without light-
shielding. Interestingly, theoretical studies have shown that the inter-
face of electroactive graphene with a single layer of BiI3 nanosheets ex-
hibits enhanced light absorption compared to a single layer of BiI3 [123].
The BiOI nanosheet combines with a thin nanoparticle titanium dioxide
layer to form a visible light responsive photoanode that can be used with
liquid electrolyte solar cells and has a conversion efficiency of 1.03%
[108]. The calculations show that CuBiS2 semiconductor has a high ab-
sorption coefficient of ~105 cm1 in the visible spectrum which makes it
a sensitizer for quantum dot solar cells [109]. By measuring the perov-
skite structure solar cell Cs3Bi2I9, the light absorption and conversion
efficiency showed a very small change after one month, which indicates
that it has considerable stability [110].

3.2.1. Solar cells 3.2.2. Thermoelectric devices

Solar cell technology is one of the most attractive ways to address
environmental and energy crises based on semiconductor-based solar
light utilization [121,122]. Solar cells are devices that can directly
convert solar energy into electrical energy. The energy conversion effi-
ciency is determined by the absorption of sunlight by the PN junction and
the movement of photoexcitation electrons and holes in the PN junction.
PN junction materials with a band gap of 1.1–1.7 eV have the best ab-
sorption of the solar spectrum. Recently, Bi-based 2D materials with
less-toxic, stable structure and suitable band gap for light absorber,
including BiI3 [123,124], BiOI [105,125], CuBiS2 [109], and Cs3Bi2I9
[126], have drawn great attention in the application of solar cells.
BiI3 exhibits an absorption coefficient of > 105 cm1 in the visible
Thermoelectric materials (TE materials) can achieve the mutual
conversion between thermal energy and electronic energy which are
widely used in thermoelectric power generation and refrigeration
equipment [127]. They provides an opportunity to address the energy
crisis by saving waste heat into available electric energy [128]. The
important index to measure the performance of TE materials is the ZT
value, which determines the TE conversion rate of TE materials. ZT ¼
(S2σ/к)T, among them, к, σ, S, T, S2σ are the thermal conductivity,
electrical conductivity, Seebeck coefficient (thermoelectric potential),
absolute temperature and power factor, respectively [31]. A bigger S2σ
and a small к usually brings excellent TE performance. Theoretical and
experimental studies have shown that 2D TE materials can exhibit high

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K. Xu et al. Energy Storage Materials 19 (2019) 446–463

Table 3
2D Bi-based layered materials for energy conversion in solar cells, thermoelectric devices and photodetectors.
2D Bi-based layered materials Synthetic strategies Energy conversion application Energy conversion efficiency Reference

BiI3 nanosheets hydrothermal synthesis solar cells 3.5% (conversion efficiency), [107]
0.56 V (open-circuit voltage), 10.4 mA cm2
(short-circuit current density), 0.601 (fill factor)
BiOI nanoflakes chemical vapor transport solar cells 1.03%, 0.61 V, 3.8 mA cm2, [108]
0.45
CuBiS2 nanoparticles chemical bath solar cells 0.62%, 0.25 V, 6.87 mA cm2, 0.361 [109]
deposition
Cs3Bi2I9 spin-coating and annealing solar cells 1.09%, 0.85 V, 2.15 mA cm2, 0.60 [110]
Bi2Se3 nanosheets microwave-heated thermoelectric devices 0.48 (ZT, thermoelectric figure of merit), [111]
solvothermal 0.41 W m1 K1 (κ, thermal conductivity)
synthesis
Bi2Te2.7Se0.3 solvothermal thermoelectric devices 1.23 at 480 K [112]
synthesis
Bi2Te3-xSex colloidal nanocrystals solvothermal thermoelectric devices ~1.31 at 438 K [113]
synthesis
1 1
BiSbSe3 melting method thermoelectric devices ~1.4 at 800 K, 0.4–0.6 W m K (300–800 K) [114]
Bi2Te3/graphene quantum dots solvothermal thermoelectric devices 0.55 at 425 K [115]
synthesis
La doped Bi2O2Se ball-milling and melting method thermoelectric devices 0.35 at 823 K [116]
Bi2O2Se with defects / thermoelectric devices / [117]
Bi2O2Se chemical vapor deposition (CVD) photodetectors 65 A W1 at 1200 nm [118]
Bi2O2Se CVD photodetectors 2000 A W1 at 532 nm [106]
ultrathin Bi2S3 solvothermal synthesis photodetectors 4.4 A W1 in visible-near-infrared light range [119]
nanosheets
Bi2S3 nanosheets liquid phase exfoliation photodetectors 210 μA W1 under simulated light [120]

Fig. 8. (a) TE characteristics as a function of tem-

perature for pellets sintered from corresponding as-
synthesized nanosheets as well as commercial
Bi2Se3. Reproduced with permission [111]. Copyright
2015, Wiley-VCH. (b) Temperature dependence of
power factor of the ultra-thin Bi2Se3 nanosheets.
Reproduced with permission [11]. Copyright 2012,
American Chemical Society. (c) Room-temperature
thickness-dependent TE properties of individual
Bi2Te3 nanoplates. Reproduced with permission
[137]. Copyright 2013, American Chemical Society.
(d) TE properties of single-layer Bi2Se3 was eight
times that of bulk Bi2Se3. Reproduced with permission
[136]. Copyright 2014, The Royal Society of
Chemistry.

TE efficiency. It is found that the 6s lone pair electrons of bismuth can
also lead to a low thermal conductivity [129,130]. Nowadays, binary and
ternary layered bismuth containing Bi2Se3, Bi2Te3, Bi2O2Se and Bi2O2Te
have attracted widely attention due to their excellent TE performance.
Bi2Se3 and Bi2Te3 are kind of layered material which widely used as
three-dimensional topological materials with nontrivial surface states
and traditional TE materials at the room temperature range [131–133].
Bi2Te3 and Bi2Se3 were widely used as a TE device from the 1950s and
1960s with a narrow gap of ~0.15 and ~0.3 eV [134]. Even through as
one of the best TE materials at room temperature, their relatively low
energy conversion efficiency limits the practical application of TE ma-
terials as generators [135].
Dresselhaus et al. demonstrated that the ZT value of low-dimensional
materials is higher than the ZT value of the same bulk material, which is
attributed to lower thermal conductivity and quantum confinement ef-
fects by low-dimensional materials [11,136]. It is possible to improve the
TE performance of TE materials by thickness regulation. From Min et al.,
highly crystallized Bi2Se3 nanosheets of different thicknesses (1, 4, 7, and
13 nm) were confirmed by the AFM test and the Raman spectrum. A
significantly reduced κ (0.41 W m 1 K-1) and an enhanced S2σ

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K. Xu et al.
(4.71  104 W m1 K2 with S ¼ 155.32 μV K1 and
σ ¼ 1.96  104 S m1) were assessed of single layered Bi2Se3 nanosheets
in Fig. 8a. This significant improvement of S2σ is attributed to the opti-
mized Fermi level (Ef) position in the ultra-thin Bi2Se3 nanosheet with a
wider Eg Ref. [111]. Xu et al. obtained ultra-thin Bi2Se3 nanosheets by
microwave-assisted solvothermal method with power factor of
15.7  105 W m1 K1 at 523 K, which was got by improving their
electrical transport properties (Fig. 8b) [136]. From Fig. 8c, TE properties
related to temperature and thickness have also been found in Bi2Te3
nanocrystals in thickness of 9–15 nm [137]. Yi et al. unearthed that the
ZT value of single-layer Bi2Se3 which was obtained by the inter-
calation/stripping method was eight times that of bulk materials (Fig. 8d)
[11]. The reason is that the scattering of phonons is enhanced and the
conductivity is increased in single-layer Bi2Se3.
Defects in nanomaterials can have a significant impact on their per-
formance. Due to the Fermi level moving to deeper conduction band, a
decreased S2σ inevitably appearing in pure n-type Bi2Te3 with Intrinsic
Te vacancies. Incorporating Se into Bi2Te3 to adjust anion vacancies
becomes a strategy to improve S2σ. From Fig. 9a, n-type Bi2Te2.7Se0.3
nanoplates with high ZT of 1.23 at 480 K in the thicknesses about 30 nm
were obtained by reducing κ significantly and shifting the peak of S2σ to
high temperature, which was driven by broadband phonon scattering
and coordinated carrier scattering [112]. In Fig. 9b, a supernal ZT value
(1.31) of the Bi2Te2.7Se0.3 nanomaterial with an average thickness of
35  8 nm was investigated in the pressing direction, which gained a ca.
40% ZT enhancement from commercial ingots [113]. BiSbSe3, a product
of alloying 50% Sb on Bi site, exhibited excellent electron and phonon
transport, in which extremely low thermal conductivity
(0.6–0.4 W m1 K1, 300–800 K) was found in Fig. 9c [114].
Bi2Te3 based hybrid thermoelectric materials can also achieve great
thermoelectric properties. A ZT value of 0.55 was obtained at 425 K for
graphene quantum dots embedding in Bi2Te3 nanosheets with the
thicknesses of 20 nm, which is much higher than that of Bi2Te3 without
mixed nanostructures. The high-density Bi2Te3/GQDs nanointerface with
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Energy Storage Materials 19 (2019) 446–463
Fig. 9. (a) N-type Bi2Te2.7Se0.3 nanoplates with high
ZT of 1.23 at 480 K. Reproduced with permission
[112]. Copyright 2016, American Chemical Society.
(b) A supernal ZT value (1.31) of the Bi2Te2.7Se0.3
nanomaterial in the pressing direction. Reproduced
with permission [113]. Copyright 2018, American
Chemical Society. (c) Extremely low thermal conduc-
tivity (0.6–0.4 W m1 K1, 300–800 K) of BiSbSe3.
Reproduced with permission [114]. Copyright 2019,
Wiley-VCH. (d) A ZT value of 0.55 was obtained at
425 K for graphene quantum dots embedding in
Bi2Te3 nanosheets. Reproduced with permission
[115]. Copyright 2017, American Chemical Society.
atomic scale defects greatly enhances phonon scattering, resulting in a
much small κlatt, which was shown in Fig. 9d [115].
By replacing the M atom in Bi2M3 (M ¼ Se, Te) with an oxygen atom,
one can obtain a new layered ternary bismuth compound Bi2O2M. They
all belong to n-type semiconductors with band gaps of 0.80 eV (Bi2O2Se)
[47] and 0.23 eV (Bi2O2Te) [138]. Experiment confirmed that bulk
Bi2O2Se has low lattice thermal conductivity with 1.1 W m1 K1 at room
temperature and ZT value about 0.2 at 800 K due to the low electrical
conductivity. Theoretical and experimental results show that Bi2O2Se
nanosheets have high electrical conductivity and thus achieve higher ZT
value [47]. Tan et al. verified that isovalent doping of Bi2O2Se exalts ZT
value by pressing thermal conductivity [116]. Thermal conductivity of
Bi2O2Te is 0.91 W m1 K1 at room temperature, and the predicted ZT
value of p-doped Bi2O2Te run up to 1.27 at 600 K from Tran et al. [117].
3.2.3. Photodetectors
Photodetector material is a semiconductor with the ability to convert
light into electrical signals. The principle of photoelectric detection is
that when photons with energy larger than bandgap are absorbed by
semiconductor, electrons in valence band are stimulated into conduction
band to form free electrons which transformed into electrical signals that
can be detected [139,140]. Finally, the conversion of light and electricity
is realized. This photo-electric conversion capability has great applica-
tion prospects in sensor, communication, environmental monitoring, and
imaging, detection of tumors, astronomical exploration and so on [121].
In virtue of the extreme size limitation and strong optical-material
interaction in 2D plane, the rise of 2D layered materials in recent years
has provided more possibilities for high performance optical detection.
Among them, the binary bismuth layered compound Bi2S3 and ternary
bismuth layered compounds Bi2O2Se have attracted supernal attention
due to high sensitivity, high-speed IR detection and high air stability
[106].
Bi2S3 is a typical thin-layered chalcogenide semiconductor with a
direct band gap of 1.3 eV [39]. Because its highly anisotropic orthotropic
K. Xu et al. Energy Storage Materials 19 (2019) 446–463

Fig. 10. (a) The photocurrent as function of time under 1.6 mW cm2 illumination at bias voltage of 0.5 V of Bi2S3. (b) The wavelength-dependent photoresponsivity
and photodetectivity of Bi2S3. Reproduced with permission [119]. Copyright 2015, Wiley-VCH. (c) Photocurrent density profiles of Bi2S3 nanosheets illuminated by
simulated light as a function of light power density. (d) Photoresponsivity profiles of Bi2S3 nanosheets illuminated by simulated light as a function of light power
density. Reproduced with permission [120]. Copyright 2018, The Royal Society of Chemistry.

phase which is composed of an infinite band of Bi4S6 polymers con-
necting together, it can be made into spheres, rods, tubes, lines, flowers
and sheets [141]. Gui et al. have successfully demonstrated a simple
solvothermal method of ethanol, from the reaction of triphenyl bismuth
with dibenzyl disulfide at 180  C for 8 h, to obtain ultra-thin Bi2S3
nanosheets with a thickness of 2.2 nm for the first time. Ultra-thin Bi2S3
nanosheet has good light response characteristics from visible light to
near infrared (405–780 nm), i.e. a 4.4 A W1 response, a high detection
rate up to ~1011 Jones (Fig. 10a), and ultrafast response times of 10 μs,
which is better than that of some other two-dimensional materials
including graphene, few-layer GaSe, few-layered MoS2 and so on [119].
In practical optoelectronic device applications of atomic-scale thin

Fig. 11. (a) Comparison of photodetectors based on Bi2O2Se,

graphene, black phosphorus, and transition metal dichalco-
genides (TMDs). Reproduced with permission [118]. Copy-
right 2018, Nature Publishing Group. (b) Photocurrent and
detectivity of Bi2O2Se nanosheet under various light in-
tensities. The fitting linear shows the relationship Iph ~ Pα.
Reproduced with permission [144]. Copyright 2018,
Wiley-VCH. (c) Linear Ids–Vds curves of an individual Bi2O2Se
photosensitive unit with/without the illumination of 532 nm
incident laser, showing excellent environmental stability
even exposed to air for six months. Reproduced with
permission [106]. Copyright 2017, Wiley-VCH.

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K. Xu et al. Energy Storage Materials 19 (2019) 446–463

Table 4
2D Bi-based layered materials for energy storage in rechargeable batteries.
2D Bi-based layered Synthetic strategies Rechargeable Electrochemical performance: reversible capacity (current density), Reference
materials batteries cycle number

Bi-based composites mechanical milling Li-ion battery 310 mAh g1, 100 cycles [148]
Bi2S3/carbon nanotube controlled hydrolysis reaction Li-ion battery 405 mAh g1 (1 A g1), 100 cycles [149]
hybrid
BiOCl hydrothermal synthesis Li-ion battery 254 mAh g1 (500 mA g1), 15 cycles [150]
BiOBr hydrothermal synthesis Li-ion battery 230 mAh g1 (500 mA g1), 15 cycles [150]
BiOI thermal treatment Li-ion battery ~5678 mAh cm3 [151]
ultrathin Bi2MoO6 surfactant-assisted hydrothermal Li-ion battery 478 mAh g1 (2000 mA g1), 1500 cycles [152]
nanosheets synthesis
Bi particles commercial bismuth particles Na-ion battery 400 mAh g1 (400 mA g1), 2000 cycles [153]
Bi/graphene hydrothermal synthesis Na-ion battery 561 mAh g1 (40 mA g1), 50 cycles [154]
nanocomposite
Bi/graphite commercial bismuth particles Na-ion battery 142 mAh g1 (3.2 A g1), [155]
10000 cycles
Bi2S3 nanorods refluxing Na-ion battery 658 mAh g1 (100 mA g1) [156]
process 264 mAh g1 (2000 mA g1)
Bi commercial bismuth particles K-ion battery 407 mAh g1 (400 mA g1), 100 cycles [157]
Bi commercial bismuth particles K-ion battery 108.1 Wh kg1 (566 W kg1), 350 cycles [158]
Bi/rGO roomtemperature K-ion battery 290 mAh g1 (50 mA g1), 50 cycles [159]
solution synthesis
colloidal Bi nanocrystals in-situ formed metal long-chain Mg-ion battery 325 mAh g1 (770 mA g1), 150 cycles [160]
amides
1 1
Bi nanoparticles commercial bismuth particles Mg-ion battery 92 mAh g (0.2 A g ), 200 cycles [161]
BiOCl particles commercial BiOCl particles Cl-ion battery 60 mAh g1 [162]

crystals, water and oxygen molecules physically adsorbed from the air
can be used as surface trap states and affect their charge carrier transport
due to high surface area to volume ratio. Therefore, surface adsorption
has an important influence on the photoelectric properties of 2D mate-
rials. Photoelectrochemical (PEC) measurements by Huang et al., showed
that photodetectors based on Bi2S3 nanosheets (4.2–9.9 nm) prepared by
liquid-phase exfoliation (LPE) method have a highly photocurrent den-
sity (42 μA cm2) (Fig. 10b) [119], an enhanced photoresponsivity
(210 μA W1) (Fig. 10c and d) [120], a broad absorption range ranging
from 300 nm to 800 nm in alkaline solution. Compared to other 2D
nanomaterial photodetectors illuminated by light. Moreover, the
long-term stability of the ON/OFF switch behavior can be demonstrated
without any external protection in an alkaline solution. Its stability in
0.1 M KOH only reduced 14.6% of the Iph value after one month without
any protection.
The substitution of oxygen atoms for selenium atoms results in a
significant change from low conductivity of Bi2Se3 to high mobility of
Bi2O2Se [106]. Such little change leads to the transformation of Bi2Se3

Fig. 12. (a) Distribution of interface electric field in atomically thin Bi2MoO6. (b) A representation of the effect of the electric field on the transfer kinetic process of Li
ions in (c) atomically thin Bi2MoO6 and (d) bulk Bi2MoO6. Reproduced with permission [152]. Copyright 2017, Wiley-VCH.

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K. Xu et al. Energy Storage Materials 19 (2019) 446–463

Fig. 13. (a) Schematic illustration of the intercalation process of Na–Bi system. Reproduced with permission [167]. Copyright 2016, American Chemical Society. (b)
Density of states for Na3Bi. Reproduced with permission [154]. Copyright 2015, Elsevier. (c) Ex situ XRD of sodiation/desodiation of Bi in the second discharge/charge
cycle. (d) Schematic diagram of morphological evolution of Bi electrode during cycling test. (e) SEM images of discharged and charged Bi electrodes after different
number of cycles. (f) Cycling stability of Bi electrode at 400 mA g1. (g) Discharge/charge curves of Bi electrode at different current densities in the fifth cycling test.
Reproduced with permission [153]. Copyright 2017, Wiley-VCH.

from an excellent thermoelectric conversion material to an excellent
photoelectric conversion material Bi2O2Se. Its unique band structure
makes it have an in-plane electron mass (m* ¼ 0.14) lower than most
materials [142]. Bi2O2Se is an air-stable semiconductor with proper
electron band gap (~0.8 eV) and high carrier mobility [143]. Yin et al.
certified that main characteristics of Bi2O2Se nanosheets are excellent in
the entire 2D series: high sensitivity of 65 A W1 at 1200 nm and
ultra-fast photo response of about 1 ps at room temperature, which
means an intrinsic material-limited bandwidth up to 500 GHz (Fig. 11a)
[118]. Li et al. studied the near-infrared response of ultra-thin Bi2O2Se
nanosheet (below 10 nm) by temperature-varying measurement system
in Fig. 11b [144]. Response time, responsiveness and detection rate are
close to 2.8 ms, 6.5 A W1 and 8.3  1011 Jones. From Fig. 11c, the 2D
Bi2O2Se photodetector shows excellent environmental stability: negli-
gible changes in Ids-Vds (darkness and light) even after exposure to air for
about 6 months [106].
3.3. Energy storage in rechargeable batteries
To meet continuously increasing energy demands, the exploration
and development of rechargeable batteries with desirable features such
as high energy density and safety, abundant natural resources, and
environmental friendliness have been urgently required [145,146]. 2D
Bi-based layered materials are of great interest as anode materials for
various kinds of rechargeable batteries due to their multiple advantages,
including low cost and toxicity, chemical stability, ion conductivity, large
interlayer space, and high theoretical capacity values [147,148]. 2D
Bi-based layered materials as anodes for various rechargeable batteries
and their electrochemical performances are outlined in Table 4.
3.3.1. Lithium-ion batteries (LIBs)
Among battery energy storage systems, LIBs have been extensively
utilised in kinds of electronic devices. And 2D Bi-based layered materials
as anodes for LIBs were widely studied. Unitary Bi was found to be a
novel candidate for LIBs [163]. Despite the relatively low gravimetric
capacity of 386 mA h g1 resulting from its high atomic mass, it could
deliver high theoretical volumetric capacity (3765 mA h cm3), much
higher than that of graphite (840 mA h cm3) [22,34,164]. Moreover, the
reaction between Bi and Li could take place via alloying/dealloying
processes of LiBi and Li3Bi at relatively low potential ~0.8 V vs Liþ/Li0.
Besides unitary Bi, 2D Bi-based layered compounds were also
explored successfully as electrode materials for Li-ion batteries. As a
typical example, benefiting from 2D configuration, the coupling effects of
interlayers, and inherent structural stability (Fig. 12a), atomically thin
Bi2MoO6 nanosheets exhibited high-rate capability and cycling stability
in LIBs (Fig. 12b) [165]. The built-in electric fields of Bi2MoO6 induced
by the unbalanced charge distribution also significantly boosted Li ion
transfer dynamics, and the charge transport would be further promoted
by the extra charge transport channels created on open surfaces, as
shown in Fig. 12c and d. Moreover, other 2D Bi-based layered materials,
such as BiOX (X ¼ Cl, Br, I) [150,151] and Bi2X3 (X ¼ S, Se) [149,166],
were also extensively investigated as anode materials for LIBs.
3.3.2. Sodium-ion batteries (SIBs)
As sodium (Na) shares similar chemical properties with Li and has
more abundant natural resources than Li, SIBs are expected to be the

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K. Xu et al. Energy Storage Materials 19 (2019) 446–463

Fig. 14. (a) Alloying and dealloying processes of Bi electrode in potassium-ion battery. Reproduced with permission [157]. Copyright 2018, Wiley-VCH. (b) The
cycling performance of Bi electrodes. (c) Schematic illustration of Bi//Prussian blue (PB) full KIBs. Reproduced with permission [158]. Copyright 2018, Wiley-VCH.
(d) Electrochemical processes of magnesiation reaction of Bi with the relevant crystal structures of different phases: elemental Bi (hexagonal), α-Mg3Bi2 (trigonal), and
β-Mg3Bi2 (cubic). Reproduced with permission [160]. Copyright 2018, American Chemical Society.

most potential substitute for LIBs [22]. Owing to the large interlayer
distance of metallic Bi crystal, enough space can be provided for the
insertion and storage of Na ions [155]. After the formation of Na3Bi via
the reaction of Bi and Na, the theoretical gravimetric energy density can
reach 385 mA h g1 (Fig. 13a) [167]. As shown in Fig. 13b, calculated
density of states (DOS) was conducted to investigate Na-ion intercalation
processes in Bi crystal [154]. It could be observed that the majority of
DOS curves of Na and Bi overlapped, suggesting that the diffusion and
accommodation of Na-ions could proceed via the sites provided by Bi. Ex
situ XRD was utilised to monitor the sodiation/desodiation of Bi in
charge-discharge operations (Fig. 13c), displaying the reversible con-
version processes among the pristine rhombohedral Bi, the intermediate
phase of tetragonal NaBi, and the final new phase of hexagonal Na3Bi
[153]. To demonstrate the evolution of Bi electrode after repeated
charge-discharge operations, the schematic diagrams for proposed
morphological evolution and SEM images are depicted in Fig. 13d and e.
The porous integrity of Bi could be gradually formed and sustained from
bulk, allowing facile transport of electrons and Naþ ions and realizing fast
kinetics and long cycling stability. The high reversible Na-ion storage
capacity of bulk Bi can be achieved reaching 400 mA h g1, and SIBs with
Bi anode also exhibited a remarkable cycling stability (94.4% initial
capacitance after 2000 cycles) (Fig. 13f and g) [153].
3.3.3. Other types of rechargeable batteries
Besides LIBs and SIBs, 2D Bi-based layered materials have also been
identified as potential electrode materials in other types of rechargeable
batteries, such as potassium (K), manganese (Mg), chloride (Cl) ion
batteries.
As the radius of Kþ ion (1.38 Å) is much larger than that of Liþ
(0.76 Å) and Naþ (1.02 Å), anode materials for potassium ion batteries
(PIBs) usually suffer from low capacity and short cycle life due to slow Kþ
diffusion and their large volume expansion. The unique layered structure
and large interlayer space of Bi can be beneficial for the insertion and the
accommodation of guest K elements with small volume change [159]. So
bulk Bi anode could showed promising electrochemical performance in
PIBs system with excellent capacity of ~400 mA h g1 [157]. During
alloying and dealloying processes of PIBs (Fig. 14a), Bi anode would
undergo three reversible two-phase reactions: Bi ↔ KBi2 ↔ K3Bi2 ↔ K3Bi.
Meanwhile, its morphology also evolved gradually from bulk into a 3D
porous network, contributing to fast Kþ interaction kinetics and enabling
a large volume change of Bi anode (Fig. 14b). And the similar working
mechanism was also proposed and elucidated in Bi//Prussian blue (PB)
full KIBs (Fig. 14c) [158].
Mg-ion batteries could offer good alternatives to Li-ion systems,
because of highly abundant and environmentally friendly Mg resources.
Metallic Bi can be an optimal anode material for applications in Mg-ion

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K. Xu et al.
batteries, which can achieve the operation with a broad range of Mg-ion
electrolytes [160]. Based on an alloying mechanism, the intercalation of
Mg within Bi nanocrystals occurred with reversible phase transitions of
α-Mg3Bi2 and β-Mg3Bi2, as illustrated in Fig. 14d. In the initial electro-
chemical discharge, Bi nanocrystals evolved into smaller amorphous
particles, because their monodispersed and crystalline properties were
disturbed in the active process [161]. And during the subsequently
repeated discharge-charge cycles, the electrode structure and the elec-
trochemical capacity could keep almost unchanged.
Owing to the advantages of broadly various potential electrochemical
couples and high theoretical energy density of 2500 W h L1, recharge-
able chloride (Cl) ion batteries were proposed [162]. BiOCl, one signif-
icant member of metal oxychlorides, was applied as a cathode material in
rechargeable Cl-ion batteries and its reversible capacity reached
60 mA h g1 (60% of its theoretical capacity) [162]. The intercalation
reaction of BiOCl-based Cl-ion batteries was further investigated in
cycling test. In the discharge process, BiOCl losing the Cl ion would
transform to Bi metal and amorphous Bi2O3 with a considerable
morphology change, while the recovery of BiOCl phase would proceed at
the cathode side with the return of Cl ion during charge reaction.
4. Summary and perspective
In this review, the crystal structures of a variety of 2D Bi-based
layered materials (unitary, binary, ternary and multinary) are pre-
sented in detail. And benefiting from their tunable structural and elec-
tronic properties, 2D Bi-based layered materials could offer promising
opportunities for the construction of advanced energy-related systems
and devices, with particular emphasis on energy-related catalysis (photo/
electrochemical reduction), energy conversion in solar cells and thermal-
electronic devices, and energy storage in rechargeable batteries.
In future prospect, the directions for the development and exploration
of novel 2D Bi-based layered materials on energy-related applications can
be focused on the following aspects.
For lack of large-scale synthesis methods, energy-related industrial
applications of 2D Bi-based layered materials have been practically
restricted. To tackle this challenge, it is necessary to develop new ap-
proaches for the formation of 2D Bi-based layered materials with large-
scale production. In addition, the physicochemical properties of mono-
layers or few layers of 2D layered materials often differ dramatically from
those of parent bulk. The weak inter-layer interaction between stacked
layers in 2D Bi-based layered materials permits the theoretical and
experimental preparation of monolayers or atomically thin layers, which
can be expected to exhibit superior energy-related properties. And the
atomic termination on exposed surfaces for 2D Bi-based layered materials
as a key factor on energy conversion and storage performances is still a
matter for controversy, which should be computationally and experi-
mentally confirmed, particularly for those consisting of ternary or mul-
tinary elements.
The exploration of new 2D Bi-based layered materials with controlled
size and morphology such as multinary compounds or metal organic
framework (MOF) can offer new possibilities for applications in energy
conversion and storage. Moreover, interface engineering of 2D Bi-based
layered vertical or lateral heterostructures by introduction of different
anion groups into [Bi2O2]2þ-based frames also holds huge potential for
tuning properties for the energy-related applications.
To fundamentally understand the operation of 2D Bi-based layered
materials on the atomic scales in energy conversion and storage pro-
cesses, in-situ high-technologies like in-situ X-ray absorption spectroscopy
(XAS), in-situ infrared radiation (IR), and in-situ scanning transmission
electron microscopy (STEM) can be utilised. The reaction processes, such
as compositional and structural changes of Bi-based materials, the
interaction between reactant molecules and 2D Bi-based layered mate-
rials, and the transfer of charge carriers may be in-situ observed. It can be
much helpful to guide continuing research in energy-related applications
of 2D Bi-based layered materials.
460
Energy Storage Materials 19 (2019) 446–463
Acknowledgements
This work was supported by the Australian Research Council (ARC)
through Discovery Projects (DP160102627, DP170101467 and
FT180100585) and Linkage Infrastructure, Equipment and Facilities
(LIEF) grants (LE100100081, LE110100099 and LE120100104). The
work was also supported by the National Natural Science Foundation of
China (NSF) (51272015, 51472016, and 51672018), Beiijing Natural
Science Foundation (Z180007), and the Fundamental Research Funds for
the Central Universities (YWF-16-JCTD-B-03 and YWF-16-BJ-J-44).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://do
i.org/10.1016/j.ensm.2019.03.021.
References
[1] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos,
I.V. Grigorieva, A.A. Firsov, Electric field effect in atomically thin carbon films,
Science 306 (2004) 666–669.
[2] M. Xu, T. Liang, M. Shi, H. Chen, Graphene-like two-dimensional materials, Chem.
Rev. 113 (2013) 3766–3798.
[3] A. Gupta, T. Sakthivel, S. Seal, Recent development in 2D materials beyond
graphene, Prog. Mater. Sci. 73 (2015) 44–126.
[4] S. Zhang, S. Guo, Z. Chen, Y. Wang, H. Gao, J. Gomez-Herrero, P. Ares, F. Zamora,
Z. Zhu, H. Zeng, Recent progress in 2D group-VA semiconductors: from theory to
experiment, Chem. Soc. Rev. 47 (2018) 982–1021.
[5] J. Zhuang, C. Liu, Q. Gao, Y. Liu, H. Feng, X. Xu, J. Wang, J. Zhao, S.X. Dou, Z. Hu,
Bandgap modulated by electronic superlattice in blue phosphorene, ACS Nano 12
(2018) 5059–5065.
[6] F. Bonaccorso, L. Colombo, G. Yu, M. Stoller, V. Tozzini, A.C. Ferrari, R.S. Ruoff,
V. Pellegrini, 2D materials. Graphene, related two-dimensional crystals, and
hybrid systems for energy conversion and storage, Science 347 (2015) 1246501.
[7] C. Tan, X. Cao, X.J. Wu, Q. He, J. Yang, X. Zhang, J. Chen, W. Zhao, S. Han,
G.H. Nam, M. Sindoro, H. Zhang, Recent advances in ultrathin two-dimensional
nanomaterials, Chem. Rev. 117 (2017) 6225–6331.
[8] J. Zhuang, X. Xu, G. Peleckis, W. Hao, S.X. Dou, Y. Du, Silicene: a promising anode
for lithium-ion batteries, Adv. Mater. 29 (2017) 1606716.
[9] Z. Li, J. Zhuang, L. Wang, H. Feng, Q. Gao, X. Xu, W. Hao, X. Wang, C. Zhang,
K. Wu, Realization of flat band with possible nontrivial topology in electronic
Kagome lattice, Sci. Adv. 4 (2018) eaau4511.
[10] Z. Meng, J. Zhuang, X. Xu, W. Hao, S.X. Dou, Y. Du, Electronic band engineering in
elemental 2D materials, Adv. Mater. Interfaces 5 (2018) 1800749.
[11] Y. Sun, H. Cheng, S. Gao, Q. Liu, Z. Sun, C. Xiao, C. Wu, S. Wei, Y. Xie, Atomically
thick bismuth selenide freestanding single layers achieving enhanced
thermoelectric energy harvesting, J. Am. Chem. Soc. 134 (2012) 20294–20297.
[12] J. Li, Y. Yu, L. Zhang, Bismuth oxyhalide nanomaterials: layered structures meet
photocatalysis, Nanoscale 6 (2014) 8473–8488.
[13] J. Di, J. Xia, H. Li, S. Guo, S. Dai, Bismuth oxyhalide layered materials for energy
and environmental applications, Nano Energy 41 (2017) 172–192.
[14] J. Li, H. Li, G. Zhan, L. Zhang, Solar water splitting and nitrogen fixation with
layered bismuth oxyhalides, Acc. Chem. Res. 50 (2017) 112–121.
[15] J. Ni, X. Bi, Y. Jiang, L. Li, J. Lu, Bismuth chalcogenide compounds Bi2X3 (X¼O, S,
Se): applications in electrochemical energy storage, Nano Energy 34 (2017)
356–366.
[16] R. Mohan, Green bismuth, Nat. Chem. 2 (2010) 336.
[17] Z. Wang, S. Yan, Y. Sun, T. Xiong, F. Dong, W. Zhang, Bi metal sphere/graphene
oxide nanohybrids with enhanced direct plasmonic photocatalysis, Appl. Catal., B
214 (2017) 148–157.
[18] D.D. Zhu, J.L. Liu, S.Z. Qiao, Recent advances in inorganic heterogeneous
electrocatalysts for reduction of carbon dioxide, Adv. Mater. 28 (2016)
3423–3452.
[19] Y. Cheng, H. Zhang, Novel bismuth-based nanomaterials used for cancer diagnosis
and therapy, Chem. Eur J. 24 (2018) 17405–17418.
[20] S.M. Beladi-Mousavi, M. Pumera, 2D-Pnictogens: alloy-based anode battery
materials with ultrahigh cycling stability, Chem. Soc. Rev. 47 (2018) 6964–6989.
[21] N. Han, Y. Wang, H. Yang, J. Deng, J. Wu, Y. Li, Y. Li, Ultrathin bismuth
nanosheets from in situ topotactic transformation for selective electrocatalytic CO2
reduction to formate, Nat. Commun. 9 (2018) 1320.
[22] X. Li, J. Ni, S.V. Savilov, L. Li, Materials based on antimony and bismuth for
sodium storage, Chem. Eur J. 24 (2018) 13719–13727.
[23] J. Zhang, J. Sun, K. Maeda, K. Domen, P. Liu, M. Antonietti, X. Fu, X. Wang, Sulfur-
mediated synthesis of carbon nitride: band-gap engineering and improved
functions for photocatalysis, Energy Environ. Sci. 4 (2011) 675–678.
[24] S. Mathew, A. Yella, P. Gao, R. Humphry-Baker, B.F. Curchod, N. Ashari-Astani,
I. Tavernelli, U. Rothlisberger, M.K. Nazeeruddin, M. Gratzel, Dye-sensitized solar
cells with 13% efficiency achieved through the molecular engineering of
porphyrin sensitizers, Nat. Chem. 6 (2014) 242–247.
K. Xu et al.
[25] X. Li, Y. Sun, T. Xiong, G. Jiang, Y. Zhang, Z. Wu, F. Dong, Activation of
amorphous bismuth oxide via plasmonic Bi metal for efficient visible-light
photocatalysis, J. Catal. 352 (2017) 102–112.
[26] R. He, D. Xu, B. Cheng, J. Yu, W. Ho, Review on nanoscale Bi-based
photocatalysts, Nanoscale Horiz. 3 (2018) 464–504.
[27] D. Cui, L. Wang, Y. Du, W. Hao, J. Chen, Photocatalytic reduction on bismuth-
based p-block semiconductors, ACS Sustain. Chem. Eng. 6 (2018) 15936–15953.
[28] H. Feng, Y. Du, C. Wang, W. Hao, Efficient visible-light photocatalysts by
constructing dispersive energy band with anisotropic p and s-p hybridization
states, Curr. Opin. Green Sustain. Chem. 6 (2017) 93–100.
[29] Z. Xu, K. Xu, H. Feng, Y. Du, W. Hao, Sp orbital hybridization: a strategy for
developing efficient photocatalysts with high carrier mobility, Sci. Bull. 63 (2018)
465–468.
[30] R.A. Schlitz, F.G. Brunetti, A.M. Glaudell, P.L. Miller, M.A. Brady, C.J. Takacs,
C.J. Hawker, M.L. Chabinyc, Solubility-limited extrinsic n-type doping of a high
electron mobility polymer for thermoelectric applications, Adv. Mater. 26 (2014)
2825–2830.
[31] Y. Pei, H. Wang, G.J. Snyder, Band engineering of thermoelectric materials, Adv.
Mater. 24 (2012) 6125–6135.
[32] S. Zhang, M. Xie, F. Li, Z. Yan, Y. Li, E. Kan, W. Liu, Z. Chen, H. Zeng,
Semiconducting group 15 monolayers: a broad range of band gaps and high
carrier mobilities, Angew. Chem. Int. Ed. 55 (2016) 1666–1669.
[33] X. Li, W. Zhang, W. Cui, Y. Sun, G. Jiang, Y. Zhang, H. Huang, F. Dong, Bismuth
spheres assembled on graphene oxide: directional charge transfer enhances
plasmonic photocatalysis and in situ DRIFTS studies, Appl. Catal., B 221 (2018)
482–489.
[34] S. Liu, J. Feng, X. Bian, J. Liu, H. Xu, Advanced arrayed bismuth nanorod bundle
anode for sodium-ion batteries, J. Mater. Chem. A 4 (2016) 10098–10104.
[35] H. Yin, Q. Li, M. Cao, W. Zhang, H. Zhao, C. Li, K. Huo, M. Zhu, Nanosized-
bismuth-embedded 1D carbon nanofibers as high-performance anodes for lithium-
ion and sodium-ion batteries, Nano Res. 10 (2017) 2156–2167.
[36] J. Sun, M. Li, J.A.S. Oh, K. Zeng, L. Lu, Recent advances of bismuth based anode
materials for sodium-ion batteries, Mater. Technol. 33 (2018) 563–573.
[37] F. Dong, T. Xiong, Y. Sun, Z. Zhao, Y. Zhou, X. Feng, Z. Wu, A semimetal bismuth
element as a direct plasmonic photocatalyst, Chem. Commun. 50 (2014)
10386–10389.
[38] L. Wang, D. Lv, Z. Yue, H. Zhu, L. Wang, D. Wang, X. Xu, W. Hao, S.X. Dou, Y. Du,
Promoting photoreduction properties via synergetic utilization between plasmonic
effect and highly active facet of BiOCl, Nano Energy 57 (2019) 398–404.
[39] Y. Cheng, Y. Chang, Y. Feng, H. Jian, Z. Tang, H. Zhang, Deep-level defect
enhanced photothermal performance of bismuth sulfide-gold heterojunction
nanorods for photothermal therapy of cancer guided by computed tomography
imaging, Angew. Chem. Int. Ed. 57 (2018) 246–251.
[40] Y. Cheng, H. Zhang, Novel bismuth-based nanomaterials used for cancer diagnosis
and therapy, Chem. Eur J. 24 (2018) 17405–17418.
[41] A. Zhuang, J.J. Li, Y.C. Wang, X. Wen, Y. Lin, B. Xiang, X. Wang, J. Zeng, Screw-
dislocation-driven bidirectional spiral growth of Bi2Se3 nanoplates, Angew. Chem.
Int. Ed. 53 (2014) 6425–6429.
[42] M. Li, H. Huang, S. Yu, N. Tian, Y. Zhang, Facet, junction and electric field
engineering of bismuth-based materials for photocatalysis, Chem. Cat. Chem. 10
(2018) 4477–4496.
[43] L. Ye, Y. Su, X. Jin, H. Xie, C. Zhang, Recent advances in BiOX (X¼ Cl, Br and I)
photocatalysts: synthesis, modification, facet effects and mechanisms, Environ.
Sci.: Nano 1 (2014) 90–112.
[44] H. Feng, Z. Xu, L. Wang, Y. Yu, D. Mitchell, D. Cui, X. Xu, J. Shi, T. Sannomiya,
Y. Du, Modulation of photocatalytic properties by strain in 2D BiOBr nanosheets,
ACS Appl. Mater. Interfaces 7 (2015) 27592–27596.
[45] D. Cui, L. Wang, K. Xu, L. Ren, L. Wang, Y. Yu, Y. Du, W. Hao, Band-gap
engineering of BiOCl with oxygen vacancies for efficient photooxidation
properties under visible-light irradiation, J. Mater. Chem. A 6 (2018) 2193–2199.
[46] H. Fujito, H. Kunioku, D. Kato, H. Suzuki, M. Higashi, H. Kageyama, R. Abe,
Layered perovskite oxychloride Bi4NbO8Cl: a stable visible light responsive
photocatalyst for water splitting, J. Am. Chem. Soc. 138 (2016) 2082–2085.
[47] J. Yu, Q. Sun, Bi2O2Se nanosheet: an excellent high-temperature n-type
thermoelectric material, Appl. Phys. Lett. 112 (2018), 053901.
[48] M. Wu, X.C. Zeng, Bismuth Oxychalcogenides: a new class of ferroelectric/
ferroelastic materials with ultra high mobility, Nano Lett. 17 (2017) 6309–6314.
[49] Y. Zhou, Y. Zhang, M. Lin, J. Long, Z. Zhang, H. Lin, J.C.-S. Wu, X. Wang,
Monolayered Bi2 WO6 nanosheets mimicking heterojunction interface with open
surfaces for photocatalysis, Nat. Commun. 6 (2015) 8340.
[50] A. Al-Keisy, L. Ren, X. Xu, W. Hao, S.X. Dou, Y. Du, Selective ferroelectric BiOI/
Bi4Ti3O12 heterostructures for visible light-driven photocatalysis, J. Phys. Chem. C
123 (2018) 517–525.
[51] H. Huang, X. Li, J. Wang, F. Dong, P.K. Chu, T. Zhang, Y. Zhang, Anionic group
self-doping as a promising strategy: band-gap engineering and multi-functional
applications of high-performance CO2– 3 -doped Bi2O2CO3, ACS Catal. 5 (2015)
4094–4103.
[52] S. Cao, B. Shen, T. Tong, J. Fu, J. Yu, 2D/2D heterojunction of ultrathin MXene/
Bi2WO6 nanosheets for improved photocatalytic CO2 reduction, Adv. Funct.
Mater. 28 (2018) 1800136.
[53] L. Liang, F. Lei, S. Gao, Y. Sun, X. Jiao, J. Wu, S. Qamar, Y. Xie, Single unit cell
bismuth tungstate layers realizing robust solar CO2 reduction to methanol, Angew.
Chem. Int. Ed. 54 (2015) 13971–13974.
[54] A. Al-Keisy, L. Ren, T. Zheng, X. Xu, M. Higgins, W. Hao, Y. Du, Enhancement of
charge separation in ferroelectric heterogeneous photocatalyst Bi4(SiO4)3/Bi2SiO5
nanostructures, Dalton Trans. 46 (2017) 15582–15588.
461
Energy Storage Materials 19 (2019) 446–463
[55] F. Dong, T. Xiong, Y. Sun, H. Huang, Z. Wu, Synergistic integration of
thermocatalysis and photocatalysis on black defective (BiO)2CO3 microspheres,
J. Mater. Chem. A 3 (2015) 18466–18474.
[56] F. Chen, H. Huang, L. Ye, T. Zhang, Y. Zhang, X. Han, T. Ma, Thickness-dependent
facet junction control of layered BiOIO3 single crystals for highly efficient CO2
photoreduction, Adv. Funct. Mater. 28 (2018) 1804284.
[57] X. Tao, Y. Zhao, L. Mu, S. Wang, R. Li, C. Li, Bismuth tantalum oxyhalogen: a
promising candidate photocatalyst for solar water splitting, Adv. Energy Mater. 8
(2018) 1701392.
[58] H. Kageyama, K. Hayashi, K. Maeda, J.P. Attfield, Z. Hiroi, J.M. Rondinelli,
K.R. Poeppelmeier, Expanding frontiers in materials chemistry and physics with
multiple anions, Nat. Commun. 9 (2018) 772.
[59] D. Kato, K. Hongo, R. Maezono, M. Higashi, H. Kunioku, M. Yabuuchi, H. Suzuki,
H. Okajima, C. Zhong, K. Nakano, Valence band engineering of layered bismuth
oxyhalides toward stable visible-light water splitting: madelung site potential
analysis, J. Am. Chem. Soc. 139 (2017) 18725–18731.
[60] S. Tu, Y. Zhang, A.H. Reshak, S. Auluck, L. Ye, X. Han, T. Ma, H. Huang,
Ferroelectric polarization promoted bulk charge separation for highly efficient
CO2 photoreduction of SrBi4Ti4O15, Nano Energy 56 (2019) 840–850.
[61] H. Kunioku, M. Higashi, O. Tomita, M. Yabuuchi, D. Kato, H. Fujito, H. Kageyama,
R. Abe, Strong hybridization between Bi-6s and O-2p orbitals in Sillen–Aurivillius
perovskite Bi4MO8X (M ¼ Nb, Ta; X ¼ Cl, Br), visible light photocatalysts enabling
stable water oxidation, J. Mater. Chem. A 6 (2018) 3100–3107.
[62] C. Guo, J. Ran, A. Vasileff, S.-Z. Qiao, Rational design of electrocatalysts and photo
(electro) catalysts for nitrogen reduction to ammonia (NH3) under ambient
conditions, Energy Environ. Sci. 11 (2018) 45–56.
[63] H. Wang, W. Zhang, X. Li, J. Li, W. Cen, Q. Li, F. Dong, Highly enhanced visible
light photocatalysis and in situ FT-IR studies on Bi metal@ defective BiOCl
hierarchical microspheres, Appl. Catal., B 225 (2018) 218–227.
[64] X. Yin, X. Li, H. Liu, W. Gu, W. Zou, L. Zhu, Z. Fu, Y. Lu, Realizing selective water
splitting hydrogen/oxygen evolution on ferroelectric Bi3TiNbO9 nanosheets, Nano
Energy 49 (2018) 489–497.
[65] J. Li, G. Zhan, Y. Yu, L. Zhang, Superior visible light hydrogen evolution of Janus
bilayer junctions via atomic-level charge flow steering, Nat. Commun. 7 (2016)
11480.
[66] A. Iwase, S. Yoshino, T. Takayama, Y.H. Ng, R. Amal, A. Kudo, Water splitting and
CO2 reduction under visible light irradiation using Z-scheme systems consisting of
metal sulfides, CoOx-loaded BiVO4, and a reduced graphene oxide electron
mediator, J. Am. Chem. Soc. 138 (2016) 10260–10264.
[67] C.W. Kim, Y.S. Son, M.J. Kang, D.Y. Kim, Y.S. Kang, (040)-crystal facet
engineering of BiVO4 plate photoanodes for solar fuel production, Adv. Energy
Mater. 6 (2016) 1501754.
[68] J. Wu, X. Li, W. Shi, P. Ling, Y. Sun, X. Jiao, S. Gao, L. Liang, J. Xu, W. Yan,
Efficient visible-light-driven CO2 reduction mediated by defect-engineered BiOBr
atomic layers, Angew. Chem. Int. Ed. 130 (2018) 8855–8859.
[69] S. Gao, B. Gu, X. Jiao, Y. Sun, X. Zu, F. Yang, W. Zhu, C. Wang, Z. Feng, B. Ye,
Y. Xie, Highly efficient and exceptionally durable CO2 photoreduction to methanol
over freestanding defective single-unit-cell bismuth vanadate layers, J. Am. Chem.
Soc. 139 (2017) 3438–3445.
[70] H. Li, J. Shang, Z. Ai, L. Zhang, Efficient visible light nitrogen fixation with BiOBr
nanosheets of oxygen vacancies on the exposed {001} facets, J. Am. Chem. Soc.
137 (2015) 6393–6399.
[71] X. Xue, R. Chen, H. Chen, Y. Hu, Q. Ding, Z. Liu, L. Ma, G. Zhu, W. Zhang, Q. Yu,
J. Liu, J. Ma, Z. Jin, Oxygen vacancy engineering promoted photocatalytic
ammonia synthesis on ultrathin two-dimensional bismuth oxybromide
nanosheets, Nano Lett. 18 (2018) 7372–7377.
[72] F.P. Garcia de Arquer, O.S. Bushuyev, P. De Luna, C.T. Dinh, A. Seifitokaldani,
M.I. Saidaminov, C.S. Tan, L.N. Quan, A. Proppe, M.G. Kibria, S.O. Kelley,
D. Sinton, E.H. Sargent, 2D metal oxyhalide-derived catalysts for efficient CO2
electroreduction, Adv. Mater. 30 (2018) 1802858.
[73] Y. Zhang, F. Li, X. Zhang, T. Williams, C.D. Easton, A.M. Bond, J. Zhang,
Electrochemical reduction of CO2 on defect-rich Bi derived from Bi2S3 with
enhanced formate selectivity, J. Mater. Chem. A 6 (2018) 4714–4720.
[74] H. Zhong, Y. Qiu, T. Zhang, X. Li, H. Zhang, X. Chen, Bismuth nanodendrites as a
high performance electrocatalyst for selective conversion of CO2 to formate,
J. Mater. Chem. A 4 (2016) 13746–13753.
[75] J.H. Koh, D.H. Won, T. Eom, N.-K. Kim, K.D. Jung, H. Kim, Y.J. Hwang, B.K. Min,
Facile CO2 electro-reduction to formate via oxygen bidentate intermediate
stabilized by high-index planes of Bi dendrite catalyst, ACS Catal. 7 (2017)
5071–5077.
[76] C.W. Lee, J.S. Hong, K.D. Yang, K. Jin, J.H. Lee, H.-Y. Ahn, H. Seo, N.-E. Sung,
K.T. Nam, Selective electrochemical production of formate from carbon dioxide
with bismuth-based catalysts in an aqueous electrolyte, ACS Catal. 8 (2018)
931–937.
[77] Y. Zhang, X. Zhang, Y. Ling, F. Li, A.M. Bond, J. Zhang, Controllable synthesis of
few-layer bismuth subcarbonate by electrochemical exfoliation for enhanced CO2
reduction performance, Angew. Chem. Int. Ed. 57 (2018) 13283–13287.
[78] Z. Zhang, M. Chi, G.M. Veith, P. Zhang, D.A. Lutterman, J. Rosenthal,
S.H. Overbury, S. Dai, H. Zhu, Rational design of Bi nanoparticles for efficient
electrochemical CO2 reduction: the elucidation of size and surface condition
effects, ACS Catal. 6 (2016) 6255–6264.
[79] J. Shang, W. Hao, X. Lv, T. Wang, X. Wang, Y. Du, S. Dou, T. Xie, D. Wang,
J. Wang, Bismuth oxybromide with reasonable photocatalytic reduction activity
under visible light, ACS Catal. 4 (2014) 954–961.
K. Xu et al.
[80] Y. Dou, L. Zhang, X. Xu, Z. Sun, T. Liao, S.X. Dou, Atomically thin non-layered
nanomaterials for energy storage and conversion, Chem. Soc. Rev. 46 (2017)
7338–7373.
[81] Y. Sun, S. Gao, F. Lei, C. Xiao, Y. Xie, Ultrathin two-dimensional inorganic
materials: new opportunities for solid state nanochemistry, Acc. Chem. Res. 48
(2015) 3–12.
[82] J. Li, X. Wu, W. Pan, G. Zhang, H. Chen, Vacancy-rich monolayer BiO2-x as a highly
efficient UV, visible, and near-infrared responsive photocatalyst, Angew. Chem.
Int. Ed. 57 (2018) 491–495.
[83] H. Li, J. Shang, J. Shi, K. Zhao, L. Zhang, Facet-dependent solar ammonia synthesis
of BiOCl nanosheets via a proton-assisted electron transfer pathway, Nanoscale 8
(2016) 1986–1993.
[84] H. Li, J. Shang, Z. Ai, L. Zhang, Efficient visible light nitrogen fixation with BiOBr
nanosheets of oxygen vacancies on the exposed {001} facets, J. Am. Chem. Soc.
137 (2015) 6393–6399.
[85] X. Wu, Y.H. Ng, L. Wang, Y. Du, S.X. Dou, R. Amal, J. Scott, Improving the photo-
oxidative capability of BiOBr via crystal facet engineering, J. Mater. Chem. A 5
(2017) 8117–8124.
[86] J. Jiang, K. Zhao, X. Xiao, L. Zhang, Synthesis and facet-dependent photoreactivity
of BiOCl single-crystalline nanosheets, J. Am. Chem. Soc. 134 (2012) 4473–4476.
[87] J. Li, Y. Sun, W. Cen, F. Dong, Facet-dependent interfacial charge separation and
transfer in plasmonic photocatalysts, Appl. Catal., B 226 (2018) 269–277.
[88] T.W. Kim, K.-S. Choi, Nanoporous BiVO4 photoanodes with dual-layer oxygen
evolution catalysts for solar water splitting, Science 343 (2014) 990–994.
[89] R. Li, H. Han, F. Zhang, D. Wang, C. Li, Highly efficient photocatalysts constructed
by rational assembly of dual-cocatalysts separately on different facets of BiVO4,
Energy Environ. Sci. 7 (2014) 1369–1376.
[90] Y. Qiu, W. Liu, W. Chen, G. Zhou, P.-C. Hsu, R. Zhang, Z. Liang, S. Fan, Y. Zhang,
Y. Cui, Efficient solar-driven water splitting by nanocone BiVO4-perovskite
tandem cells, Sci. Adv. 2 (2016), e1501764.
[91] C. Dong, S. Lu, S. Yao, R. Ge, Z. Wang, Z. Wang, P. An, Y. Liu, B. Yang, H. Zhang,
Colloidal synthesis of ultrathin monoclinic BiVO4 nanosheets for Z-scheme overall
water splitting under visible light, ACS Catal. 8 (2018) 8649–8658.
[92] S. Wang, P. Chen, Y. Bai, J.H. Yun, G. Liu, L. Wang, New BiVO4 dual photoanodes
with enriched oxygen vacancies for efficient solar-driven water splitting, Adv.
Mater. 30 (2018), e1800486.
[93] P. Li, X. Chen, H. He, X. Zhou, Y. Zhou, Z. Zou, Polyhedral 30-faceted BiVO4
microcrystals predominantly enclosed by high-index planes promoting
photocatalytic water-splitting activity, Adv. Mater. 30 (2018).
[94] S. Wang, P. Chen, J.H. Yun, Y. Hu, L. Wang, An electrochemically treated BiVO4
photoanode for efficient photoelectrochemical water splitting, Angew. Chem. Int.
Ed. 56 (2017) 8500–8504.
[95] R. Li, F. Zhang, D. Wang, J. Yang, M. Li, J. Zhu, X. Zhou, H. Han, C. Li, Spatial
separation of photogenerated electrons and holes among {010} and {110} crystal
facets of BiVO4, Nat. Commun. 4 (2013) 1432.
[96] R.G. Mariano, K. McKelvey, H.S. White, M.W. Kanan, Selective increase in CO2
electroreduction activity at grain-boundary surface terminations, Science 358
(2017) 1187–1192.
[97] Y. Song, W. Chen, C. Zhao, S. Li, W. Wei, Y. Sun, Metal-free nitrogen-doped
mesoporous carbon for electroreduction of CO2 to ethanol, Angew. Chem. Int. Ed.
129 (2017) 10980–10984.
[98] M.C. Thompson, J. Ramsay, J.M. Weber, Solvent-driven reductive activation of
CO2 by bismuth: switching from metalloformate complexes to oxalate products,
Angew. Chem. Int. Ed. 55 (2016) 15171–15174.
[99] J. Medina-Ramos, S.S. Lee, T.T. Fister, A.A. Hubaud, R.L. Sacci, D.R. Mullins,
J.L. DiMeglio, R.C. Pupillo, S.M. Velardo, D.A. Lutterman, J. Rosenthal, P. Fenter,
Structural dynamics and evolution of bismuth electrodes during electrochemical
reduction of CO2 in imidazolium-based ionic liquid solutions, ACS Catal. 7 (2017)
7285–7295.
[100] W. Zhang, Y. Hu, L. Ma, G. Zhu, Y. Wang, X. Xue, R. Chen, S. Yang, Z. Jin, Progress
and perspective of electrocatalytic CO2 reduction for renewable carbonaceous
fuels and chemicals, Adv. Sci. 5 (2018) 1700275.
[101] S. Kim, W.J. Dong, S. Gim, W. Sohn, J.Y. Park, C.J. Yoo, H.W. Jang, J.-L. Lee,
Shape-controlled bismuth nanoflakes as highly selective catalysts for
electrochemical carbon dioxide reduction to formate, Nano Energy 39 (2017)
44–52.
[102] A. Ananthi, S.S. Kumar, K.L. Phani, Facile one-step direct electrodeposition of
bismuth nanowires on glassy carbon electrode for selective determination of folic
acid, Electrochim. Acta 151 (2015) 584–590.
[103] H. Yang, N. Han, J. Deng, J. Wu, Y. Wang, Y. Hu, P. Ding, Y. Li, Y. Li, J. Lu,
Selective CO2 reduction on 2D mesoporous Bi nanosheets, Adv. Energy Mater. 8
(2018) 1801536.
[104] F. Bonaccorso, L. Colombo, G. Yu, M. Stoller, V. Tozzini, A.C. Ferrari, R.S. Ruoff,
V. Pellegrini, Graphene, related two-dimensional crystals, and hybrid systems for
energy conversion and storage, Science 347 (2015) 1246501.
[105] R.L. Hoye, L.C. Lee, R.C. Kurchin, T.N. Huq, K.H. Zhang, M. Sponseller,
L. Nienhaus, R.E. Brandt, J. Jean, J.A. Polizzotti, Strongly enhanced photovoltaic
performance and defect physics of air-stable bismuth oxyiodide (BiOI), Adv.
Mater. 29 (2017) 1702176.
[106] J. Wu, Y. Liu, Z. Tan, C. Tan, J. Yin, T. Li, T. Tu, H. Peng, Chemical patterning of
high-mobility semiconducting 2D Bi2O2Se crystals for integrated optoelectronic
devices, Adv. Mater. 29 (2017) 1704060.
[107] K.M. Boopathi, S. Raman, R. Mohanraman, F.-C. Chou, Y.-Y. Chen, C.-H. Lee, F.-
C. Chang, C.-W. Chu, Solution-processable bismuth iodide nanosheets as hole
transport layers for organic solar cells, Sol. Energy Mater. Sol. Cells 121 (2014)
35–41.
462
Energy Storage Materials 19 (2019) 446–463
[108] S. Sfaelou, D. Raptis, V. Dracopoulos, P. Lianos, BiOI solar cells, RSC Adv. 5 (2015)
95813–95816.
[109] N. Suriyawong, B. Aragaw, J.B. Shi, M.W. Lee, Ternary CuBiS2 nanoparticles as a
sensitizer for quantum dot solar cells, J. Colloid Interface Sci. 473 (2016) 60–65.
[110] B.W. Park, B. Philippe, X. Zhang, H. Rensmo, G. Boschloo, E.M. Johansson,
Bismuth based hybrid perovskites A3Bi2I9 (A: methylammonium or cesium) for
solar cell application, Adv. Mater. 27 (2015) 6806–6813.
[111] M. Hong, Z.-G. Chen, L. Yang, G. Han, J. Zou, Enhanced thermoelectric
performance of ultrathin Bi2Se3 nanosheets through thickness control, Adv.
Electron. Mater. 1 (2015) 1500025.
[112] M. Hong, T.C. Chasapis, Z.G. Chen, L. Yang, M.G. Kanatzidis, G.J. Snyder, J. Zou,
n-Type Bi2Te3-xSex nanoplates with enhanced thermoelectric efficiency driven by
wide-frequency phonon scatterings and synergistic carrier scatterings, ACS Nano
10 (2016) 4719–4727.
[113] Y. Liu, Y. Zhang, K.H. Lim, M. Ibanez, S. Ortega, M. Li, J. David, S. Marti-Sanchez,
K.M. Ng, J. Arbiol, M.V. Kovalenko, D. Cadavid, A. Cabot, High thermoelectric
performance in crystallographically textured n-Type Bi2Te3-xSex produced from
asymmetric colloidal nanocrystals, ACS Nano 12 (2018) 7174–7184.
[114] X. Liu, D. Wang, H. Wu, J. Wang, Y. Zhang, G. Wang, S.J. Pennycook, L.-D. Zhao,
Intrinsically low thermal conductivity in BiSbSe3: a promising thermoelectric
material with multiple conduction bands, Adv. Funct. Mater. 29 (2019) 1806558.
[115] S. Li, T. Fan, X. Liu, F. Liu, H. Meng, Y. Liu, F. Pan, Graphene quantum dots
embedded in Bi2Te3 nanosheets to enhance thermoelectric performance, ACS
Appl. Mater. Interfaces 9 (2017) 3677–3685.
[116] X. Tan, J.L. Lan, K. Hu, B. Xu, Y. Liu, P. Zhang, X.Z. Cao, Y. Zhu, W. Xu, Y.H. Lin,
C.W. Nan, Boosting the thermoelectric performance of Bi2O2Se by isovalent
doping, J. Am. Chem. Soc. 101 (2018) 4634–4644.
[117] T. Van Quang, M. Kim, Role of O and Se defects in the thermoelectric properties of
bismuth oxide selenide, J. Appl. Phys. 120 (2016) 195105.
[118] J. Yin, Z. Tan, H. Hong, J. Wu, H. Yuan, Y. Liu, C. Chen, C. Tan, F. Yao, T. Li,
Y. Chen, Z. Liu, K. Liu, H. Peng, Ultrafast and highly sensitive infrared
photodetectors based on two-dimensional oxyselenide crystals, Nat. Commun. 9
(2018) 3311.
[119] G. Chen, Y. Yu, K. Zheng, T. Ding, W. Wang, Y. Jiang, Q. Yang, Fabrication of
ultrathin Bi2S3 nanosheets for high-performance, flexible, visible-NIR
photodetectors, Small 11 (2015) 2848–2855.
[120] W. Huang, C. Xing, Y. Wang, Z. Li, L. Wu, D. Ma, X. Dai, Y. Xiang, J. Li, D. Fan,
H. Zhang, Facile fabrication and characterization of two-dimensional bismuth(iii)
sulfide nanosheets for high-performance photodetector applications under
ambient conditions, Nanoscale 10 (2018) 2404–2412.
[121] L. Han, A. Islam, H. Chen, C. Malapaka, B. Chiranjeevi, S. Zhang, X. Yang,
M. Yanagida, High-efficiency dye-sensitized solar cell with a novel co-adsorbent,
Energy Environ. Sci. 5 (2012) 6057–6060.
[122] L. Wang, J. Shang, W. Hao, S. Jiang, S. Huang, T. Wang, Z. Sun, Y. Du, S. Dou,
T. Xie, A dye-sensitized visible light photocatalyst-Bi24O31Cl10, Sci. Rep. 4 (2014)
7384.
[123] R.E. Brandt, R.C. Kurchin, R.L. Hoye, J.R. Poindexter, M.W. Wilson, S. Sulekar,
F. Lenahan, P.X. Yen, V. Stevanovic, J.C. Nino, M.G. Bawendi, T. Buonassisi,
Investigation of bismuth triiodide (BiI3) for photovoltaic applications, J. Phys.
Chem. Lett. 6 (2015) 4297–4302.
[124] A.J. Lehner, H. Wang, D.H. Fabini, C.D. Liman, C.-A. Hebert, E.E. Perry, M. Wang,
G.C. Bazan, M.L. Chabinyc, R. Seshadri, Electronic structure and photovoltaic
application of BiI3, Appl. Phys. Lett. 107 (2015) 131109.
[125] K. Zhao, X. Zhang, L. Zhang, The first BiOI-based solar cells, Electrochem.
Commun. 11 (2009) 612–615.
[126] A.J. Lehner, D.H. Fabini, H.A. Evans, C.-A. Hebert, S.R. Smock, J. Hu, H. Wang,
J.W. Zwanziger, M.L. Chabinyc, R. Seshadri, Crystal and electronic structures of
complex bismuth iodides A3Bi2I9 (A ¼ K, Rb, Cs) related to perovskite: aiding the
rational design of photovoltaics, Chem. Mater. 27 (2015) 7137–7148.
[127] L.E. Bell, Cooling, heating, generating power, and recovering waste heat with
thermoelectric systems, Science 321 (2008) 1457–1461.
[128] N.A. Heinz, T. Ikeda, Y. Pei, G.J. Snyder, Applying quantitative microstructure
control in advanced functional composites, Adv. Funct. Mater. 24 (2014)
2135–2153.
[129] M.D. Nielsen, V. Ozolins, J.P. Heremans, Lone pair electrons minimize lattice
thermal conductivity, Energy Environ. Sci. 6 (2013) 570–578.
[130] Y.-L. Pei, J. He, J.-F. Li, F. Li, Q. Liu, W. Pan, C. Barreteau, D. Berardan, N. Dragoe,
L.-D. Zhao, High thermoelectric performance of oxyselenides: intrinsically low
thermal conductivity of Ca-doped BiCuSeO, NPG Asia Mater. 5 (2013) e47-e47.
[131] D. Kong, W. Dang, J.J. Cha, H. Li, S. Meister, H. Peng, Z. Liu, Y. Cui, Few-layer
nanoplates of Bi2Se3 and Bi2Te3 with highly tunable chemical potential, Nano Lett.
10 (2010) 2245–2250.
[132] O.V. Yazyev, J.E. Moore, S.G. Louie, Spin polarization and transport of surface
states in the topological insulators Bi2Se3 and Bi2Te3 from first principles, Phys.
Rev. Lett. 105 (2010) 266806.
[133] X. Luo, M.B. Sullivan, S.Y. Quek, First-principles investigations of the atomic,
electronic, and thermoelectric properties of equilibrium and strained Bi2Se3 and
Bi2Te3 including van der Waals interactions, Phys. Rev. B 86 (2012) 184111.
[134] Y. Min, G.D. Moon, B.S. Kim, B. Lim, J.S. Kim, C.Y. Kang, U. Jeong, Quick,
controlled synthesis of ultrathin Bi2Se3 nanodiscs and nanosheets, J. Am. Chem.
Soc. 134 (2012) 2872–2875.
[135] D. Xia, C. Liu, S. Fan, A solar thermoelectric conversion material based on Bi2Te3
and carbon nanotube composites, J. Phys. Chem. C 118 (2014) 20826–20831.
[136] H. Xu, G. Chen, R. Jin, D. Chen, Y. Wang, J. Pei, Y. Zhang, C. Yan, Z. Qiu,
Microwave-assisted synthesis of Bi2Se3 ultrathin nanosheets and its electrical
conductivities, Cryst. Eng. Comm. 16 (2014) 3965–3970.
K. Xu et al.
[137] M.T. Pettes, J. Maassen, I. Jo, M.S. Lundstrom, L. Shi, Effects of surface band
bending and scattering on thermoelectric transport in suspended bismuth telluride
nanoplates, Nano Lett. 13 (2013) 5316–5322.
[138] S.D.N. Luu, P. Vaqueiro, Synthesis, characterisation and thermoelectric properties
of the oxytelluride Bi2O2Te, J. Solid State Chem. 226 (2015) 219–223.
[139] H. Feng, J. Zhuang, A.D. Slattery, L. Wang, Z. Xu, X. Xu, D. Mitchell, T. Zheng,
S. Li, M. Higgins, Construction of 2D lateral pseudoheterostructures by strain
engineering, 2D Mater. 4 (2017), 025102.
[140] F. Xia, T. Mueller, Y.-m. Lin, A. Valdes-Garcia, P. Avouris, Ultrafast graphene
photodetector, Nat. Nanotechnol. 4 (2009) 839.
[141] G. Konstantatos, L. Levina, J. Tang, E.H. Sargent, Sensitive solution-processed
Bi2S3 nanocrystalline photodetectors, Nano Lett. 8 (2008) 4002–4006.
[142] C. Chen, M. Wang, J. Wu, H. Fu, H. Yang, Z. Tian, T. Tu, H. Peng, Y. Sun, X. Xu,
Electronic structures and unusually robust bandgap in an ultrahigh-mobility
layered oxide semiconductor, Bi2O2Se, Sci. Adv. 4 (2018) eaat8355.
[143] J. Wu, H. Yuan, M. Meng, C. Chen, Y. Sun, Z. Chen, W. Dang, C. Tan, Y. Liu, J. Yin,
High electron mobility and quantum oscillations in non-encapsulated ultrathin
semiconducting Bi2O2Se, Nat. Nanotechnol. 12 (2017) 530.
[144] J. Li, Z. Wang, Y. Wen, J. Chu, L. Yin, R. Cheng, L. Lei, P. He, C. Jiang, L. Feng,
J. He, High-performance near-infrared photodetector based on ultrathin Bi2O2Se
nanosheets, Adv. Funct. Mater. 28 (2018) 1706437.
[145] N. Wang, C. Chu, X. Xu, Y. Du, J. Yang, Z. Bai, S. Dou, Comprehensive new insights
and perspectives into Ti-based anodes for next-generation alkaline metal (Naþ, K
þ
) ion batteries, Adv. Energy Mater. 8 (2018) 1801888.
[146] L. Li, Y. Zheng, S. Zhang, J. Yang, Z. Shao, Z. Guo, Recent progress on sodium ion
batteries: potential high-performance anodes, Energy Environ. Sci. 11 (2018)
2310–2340.
[147] Y. Zeng, Z. Lin, Y. Meng, Y. Wang, M. Yu, X. Lu, Y. Tong, Flexible ultrafast aqueous
rechargeable Ni//Bi battery based on highly durable single-crystalline bismuth
nanostructured anode, Adv. Mater. 28 (2016) 9188–9195.
[148] C.-M. Park, S. Yoon, S.-I. Lee, H.-J. Sohn, Enhanced electrochemical properties of
nanostructured bismuth-based composites for rechargeable lithium batteries,
J. Power Sources 186 (2009) 206–210.
[149] J. Ni, Y. Zhao, T. Liu, H. Zheng, L. Gao, C. Yan, L. Li, Strongly coupled Bi2S3@ CNT
hybrids for robust lithium storage, Adv. Energy Mater. 4 (2014) 1400798.
[150] L. Ye, L. Wang, H. Xie, Y. Su, X. Jin, C. Zhang, Two-dimensional layered BiOX (X¼
Cl, Br) compounds as anode materials for lithium-ion batteries, Energy Technol. 3
(2015) 1115–1120.
[151] C. Chen, P. Hu, X. Hu, Y. Mei, Y. Huang, Bismuth oxyiodide nanosheets: a novel
high-energy anode material for lithium-ion batteries, Chem. Commun. 51 (2015)
2798–2801.
[152] Y. Zheng, T. Zhou, X. Zhao, W.K. Pang, H. Gao, S. Li, Z. Zhou, H. Liu, Z. Guo,
Atomic interface engineering and electric-field effect in ultrathin Bi2MoO6
nanosheets for superior lithium ion storage, Adv. Mater. 29 (2017) 1700396.
463
Energy Storage Materials 19 (2019) 446–463
[153] C. Wang, L. Wang, F. Li, F. Cheng, J. Chen, Bulk bismuth as a high-capacity and
ultralong cycle-life anode for sodium-ion batteries by coupling with glyme-based
electrolytes, Adv. Mater. 29 (2017) 1702212.
[154] D. Su, S. Dou, G. Wang, Bismuth: a new anode for the Na-ion battery, Nano Energy
12 (2015) 88–95.
[155] J. Chen, X. Fan, X. Ji, T. Gao, S. Hou, X. Zhou, L. Wang, F. Wang, C. Yang, L. Chen,
C. Wang, Intercalation of Bi nanoparticles into graphite results in an ultra-fast and
ultra-stable anode material for sodium-ion batteries, Energy Environ. Sci. 11
(2018) 1218–1225.
[156] W. Sun, X. Rui, D. Zhang, Y. Jiang, Z. Sun, H. Liu, S. Dou, Bismuth sulfide: a high-
capacity anode for sodium-ion batteries, J. Power Sources 309 (2016) 135–140.
[157] J. Huang, X. Lin, H. Tan, B. Zhang, Bismuth microparticles as advanced anodes for
potassium-ion battery, Adv. Energy Mater. 8 (2018) 1703496.
[158] K. Lei, C. Wang, L. Liu, Y. Luo, C. Mu, F. Li, J. Chen, A porous network of bismuth
used as the anode material for high-energy-density potassium-ion batteries,
Angew. Chem. Int. Ed. 57 (2018) 4687–4691.
[159] Q. Zhang, J. Mao, W.K. Pang, T. Zheng, V. Sencadas, Y. Chen, Y. Liu, Z. Guo,
Boosting the potassium storage performance of alloy-based anode materials via
electrolyte salt chemistry, Adv. Energy Mater. 8 (2018) 1703288.
[160] K.V. Kravchyk, L. Piveteau, R. Caputo, M. He, N.P. Stadie, M.I. Bodnarchuk,
R.T. Lechner, M.V. Kovalenko, Colloidal bismuth nanocrystals as a model anode
material for rechargeable Mg-ion batteries: atomistic and mesoscale insights, ACS
Nano 12 (2018) 8297–8307.
[161] Y.-H. Tan, W.-T. Yao, T. Zhang, T. Ma, L.-L. Lu, F. Zhou, H.-B. Yao, S.-H. Yu, High
voltage Magnesium-ion battery enabled by nanocluster Mg3Bi2 alloy anode in
noncorrosive electrolyte, ACS Nano 12 (2018) 5856–5865.
[162] X. Zhao, Z. Zhao-Karger, D. Wang, M. Fichtner, Metal oxychlorides as cathode
materials for chloride ion batteries, Angew. Chem. Int. Ed. 52 (2013)
13621–13624.
[163] Y. Li, M.A. Trujillo, E. Fu, B. Patterson, L. Fei, Y. Xu, S. Deng, S. Smirnov, H. Luo,
Bismuth oxide: a new lithium-ion battery anode, J. Mater. Chem. A 1 (2013)
12123–12127.
[164] Y. Zhong, B. Li, S. Li, S. Xu, Z. Pan, Q. Huang, L. Xing, C. Wang, W. Li, Bi
Nanoparticles Anchored in N-doped porous carbon as anode of high energy
density lithium ion battery, Nano-Micro Lett. 10 (2018) 56.
[165] Y. Zheng, T. Zhou, X. Zhao, W.K. Pang, H. Gao, S. Li, Z. Zhou, H. Liu, Z. Guo,
Atomic interface engineering and electric-field effect in ultrathin Bi2MoO6
nanosheets for superior lithium ion storage, Adv. Mater. 29 (2017) 1700396.
[166] Z. Ding, S.K. Bux, D.J. King, F.L. Chang, T.-H. Chen, S.-C. Huang, R.B. Kaner,
Lithium intercalation and exfoliation of layered bismuth selenide and bismuth
telluride, J. Mater. Chem. 19 (2009) 2588–2592.
[167] J. Sottmann, M. Herrmann, P. Vajeeston, Y. Hu, A. Ruud, C. Drathen, H. Emerich,
H. Fjellvåg, D.S. Wragg, How crystallite size controls the reaction path in
nonaqueous metal ion batteries: the example of sodium bismuth alloying, Chem.
Mater. 28 (2016) 2750–2756.