Small - 2022 - Adhikari

Review
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Recent Development Strategies for Bismuth-Driven

Materials in Sustainable Energy Systems
and Environmental Restoration
Sangeeta Adhikari, Sandip Mandal, and Do-Heyoung Kim*
in the energy sector and the environment

Bismuth(Bi)-based materials have gained considerable attention in recent have a direct impact on human health and
decades for use in a diverse range of sustainable energy and environmental daily life,[3] thus the growing demand for
applications due to their low toxicity and eco-friendliness. Bi materials are energy while simultaneously remediating
widely employed in electrochemical energy storage and conversion devices, the environment has led to the urgent
need for the development of sustainable
exhibiting excellent catalytic and non-catalytic performance, as well as
modular systems for both domains.[4] Cur-
CO2/N2 reduction and water treatment systems. A variety of Bi materials, rently, a major shift to renewable energy
including its oxides, chalcogenides, oxyhalides, bismuthates, and other is underway, with the use of solar and
composites, have been developed for understanding their physicochemical hydropower to generate other chemical
properties. In this review, a comprehensive overview of the properties of fuels.[5] Other clean-energy-producing
sources, including electrochemical energy
individual Bi material systems and their use in a range of applications is
devices such as batteries, capacitors (e.g.,
provided. This review highlights the implementation of novel strategies to supercapacitors and ultracapacitors), and
modify Bi materials based on morphological and facet control, doping/defect electrocatalysts, have significantly con-
inclusion, and composite/heterojunction formation. The factors affecting tributed to addressing energy supply
the development of different classes of Bi materials and how their control and environmental pollution issues. In
differs between individual Bi compounds are also described. In particular, the addition, advanced oxidation processes
(AOPs), which include photocatalysis and
development process for these material systems, their mass production, and
photoelectrocatalysis, have facilitated the
related challenges are considered. Thus, the key components in Bi com- sustainable generation of energy via water-
pounds are compared in terms of their properties, design, and applications. splitting and the reduction of CO2 and N2
Finally, the future potential and challenges associated with Bi complexes are using semiconductors that absorb natural
presented as a pathway for new innovations. solar energy. AOPs have also been used
in environmental remediation, mostly for
the treatment of wastewater contaminated
1. Introduction with heavy metals, pharmaceuticals, textile pollutants, and
other emerging volatile organic compounds.
Rapid industrialization has led to a significant rise in energy One of the most critical challenges currently is the develop-
consumption and the serious depletion of fossil fuels, leading ment of systems that efficiently utilize solar energy because
to a range of environmental problems worldwide.[1,2] Changes global energy consumption is lower than incident solar energy.
In addition, because the majority of technological advance-
ments are aimed toward ensuring human survival, monitoring
S. Adhikari, D.-H. Kim
School of Chemical Engineering and governing human health conditions using ultra-modern
Chonnam National University computerized equipment have become essential.[6] The key
77 Yongbong-ro, Gwangju 61186, Republic of Korea to achieving these requirements is the development of mate-
E-mail: kdhh@chonnam.ac.kr rials that have unique and diverse optoelectronic properties,
S. Adhikari, D.-H. Kim with their structures able to be precisely tailored for targeted
Catalyst Research Institute
Chonnam National University
applications.[7] As such, numerous researchers have focused on
77, Yongbong-ro, Buk-gu, Gwangju 61186, Republic of Korea nanomaterials in the search for appropriate metal–inorganic
S. Mandal and metal–organic materials.[8,9]
School of Earth Science and Environmental Engineering Bismuth (Bi)-based micro- and nanostructured materials
Gwangju Institute of Science and Technology have been widely investigated in both energy and environ-
123 Cheomdangwagi-ro, Oryong-dong, Buk-gu, Gwangju 61005, mental research, while also receiving greater attention in bio-
Republic of Korea
inspired fields over the past 20 years (Figure 1a).[10–12] Bi-based
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/smll.202206003.
micro- and nanostructured materials have been most actively
employed in environmental systems, followed by energy conver-
DOI: 10.1002/smll.202206003 sion and energy storage models (Figure 1b). Bi-based materials
Small 2023, 19, 2206003 2206003 (1 of 38) © 2022 Wiley-VCH GmbH

16136829, 2023, 10, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202206003 by IFW Dresden LBZ Inst for Solid State, Wiley Online Library on [29/09/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.small-journal.com
Figure 1. a) Number of published reports over the past 20 years with the keyword bismuth, and b) pie-chart showing the proportion of papers with
bismuth as a keyword that also have energy storage, energy conversion, or environment as a keyword over the past 20 years. (Source: Web of Science,
Sep. 22, 2022)
have been shown to exhibit properties that are beneficial for and further research directions that need to be pursued. To the
use in electronics, optoelectronics, biosciences, environmental, best of our knowledge, there have been few reviews of versatile
and other energy storage and conversion applications.[13–17] Bi-based micro- and nanostructured materials and their poten-
Because the fabrication of Bi materials and their ability to con- tial for addressing energy and environmental concerns. A sche-
form to a target design can be understood by analyzing their matic summary of the content of this review is presented in
properties, thus, evaluating the effect of individual material Figure 2.
characteristics on the performance of the target application is
necessary. The various uses of Bi-based materials, such as in
energy and environmental applications, have been covered in 2. Bismuth: Classification and Properties
a number of previously published reviews.[18–20] However, these
have primarily focused on materials for a single application, Bismuth, which is a member of group V on the periodic table, is
such as bismuth oxyhalides for photocatalytic (PC) environ- a semi-metal with overlapping valence and conduction bands.[27]
mental applications,[21] Bi photocatalysts for CO2 conversion,[10] In nature, elemental Bi is scarce, but it can be found in ores
antibiotic/environmental remediation,[22,23] Bi composites for as oxides and sulfides, and thus has considerable commercial
PC hydrogen generation,[24] and Bi-based materials in aqueous value. In particular, Bi-based compounds have received signifi-
alkaline batteries.[25,26] Thus, they do not address more versatile cant attention in recent decades because Bi is the heaviest ele-
Bi-based materials and their prospects for use in energy storage ment among its periodic table neighbors that is non-toxic.[28]
and conversion and photo- and photoelectrocatalytic applica- Bi-based micro- and nanostructured materials have been of spe-
tions that rely on a tailored material structure and the resulting cial interest due to unique features not observed in their bulk
changes to the intrinsic properties. counterparts, particularly improvements in their intrinsic mate-
In this review, we summarize recent trends in bismuth- rial properties, such as their electrical, optical, photon absorp-
based micro- and nanostructured materials for energy storage tion, and catalytic characteristics. For example, high-density
and conversion systems, including batteries, supercapacitors, Bi-metal nanoparticles (NPs) have been extensively investigated
hydrogen production, and water splitting, and for environ- due to their unique pseudo-layered structure, compositional
mental restoration, including organic pollutant removal, metal modifications, and tunable bandgaps, which have led to their
ion removal, and CO2 and N2 reduction. Bi-based material clas- excellent performance in energy storage and conversion sys-
sification, design analysis, and the strategies implemented to tems,[29,30] antimicrobial drugs,[31] catalysis,[32] optoelectronics,[33]
modify inherent Bi properties are discussed in an attempt to and photonics.[34] The free carrier density of Bi is 1018–1019 cm−3,
provide guidance on the choice of suitable materials to maxi- which is very low compared to its neighboring heavy metals
mize the target performance. A critical assessment of the rela- in the periodic table.[35,36] Bi NPs can also exhibit plasmonic
tionship between the electronic structure, properties, and appli- activity (≈5–10 nm) that is beneficial for absorbing solar pho-
cation performance of the materials developed in each study is tons, reducing the charge recombination via localized surface
presented. The most recent developments in the rational design plasmon resonance.[37] Bi-based micro- and nanostructures
of Bi-based micro- and nanostructured materials, including have been employed for a wide range of different applications,
morphological design, the control of compounds, facet engi- and this review focuses on metallic Bi, binary/ternary oxides
neering, the introduction of dopants and defects, composites, (molybdates, vanadates, perovskites, and tungstates), chalco-
heterojunctions, and polarization, are outlined. Various design genides, oxyhalides, chalcohalides, bismuthates, and bismuth
and development strategies, together with the diverse range of subcarbonates. (Other Bi nanomaterials such as organometallic
charge storage and separation mechanisms, are described in clusters, organobismuth compounds, pyrochlores, and ternary
detail to overcome efficiency bottlenecks. We conclude by sum- tetradymites are not covered here.) The classification of these Bi-
marizing the current challenges in Bi-based material systems based micro- and nanostructures is presented in Figure 3.

Figure 2. Schematic outline of the present review.
Bismuth trioxide (Bi2O3) exhibits polymorphism in four synthesis of the materials, precursors used in the synthesis,
major phases: monoclinic (α-phase, ≈730 °C), tetragonal the morphology of the material, and nano- and microstructural
(β-phase), body-centered cubic (γ-phase), and face-centered forms that alter the intrinsic behavior of the materials.[40] The
cubic (δ-phase, 730–825 °C).[38,39] In addition to phase trans- electronic band structure in these systems is influenced by both
formation during cooling, phase transitions are affected by the the crystal structure and crystal dimensions, allowing more
room for band tuning.[41] The electronic transition in γ-Bi2O3 is
much faster under light irradiation when compared to the other
polymorphs due to the two-step electron transition between
valence band maxima and conduction band minima.[42]
Perovskite-type crystal systems with a BiMO3 configura-
tion (M = metal) are well-known.[43,44] Bi-based perovskites,
including BiFeO3, BiCrO3, and BiMnO3, are important as ferro-
electrics.[45,46] The electronic structure of BiMO3 varies signifi-
cantly depending on the substituting element and the hybridi-
zation that occurs during the substitution reaction.[47] Transi-
tion metal substitution using Sc, Cr, Mn, Fe, Co, and Ni leads to
significant variation in the electronic bandgap calculated using
local-density approximation (0.33–3.3 eV), whereas the use of
X-ray emission and absorption spectra returns a range of 0.9
to 2.6 eV.[48] In a recent study on BiFeO3, the variation in the
bandgap was observed using different sintering temperatures
to change the crystallite size due to the quantum confinement
effect.[49]
BiMO4 (M = V, P, Ta, or Nb) is another group of semicon-
ducting materials, with BiVO4 and BiPO4 known to exhibit
optoelectronic properties.[50,51] These two compounds have two
polymorphic phases: orthorhombic (α) and triclinic (β). The
BiVO4 conduction band width has been observed to be higher
than that for BiNbO4 and BiTaO4 because of the significant
Figure 3. Classification of Bi-based compounds. crystal field effect from the VO4 tetrahedron.[52] In addition, the

Figure 4. a) Model structure of Bi2MO6, which is composed of [Bi2O2]2+ and [MO4]2− layers. b) Comparative illustration of the density of states and
c) UV-visible diffuse reflectance spectra of Bi2WO6, Bi2MoO6, and Bi2CrO6. Reproduced with permission.[56] Copyright 2020, Elsevier.
indirect bandgap for a hexagonal BiPO4 polymorph was calcu- cut-off for Bi2CrO6 is higher than that for Bi2WO6 and Bi2MoO6
lated to be 5.4 eV, compared to 4.6 eV for the monoclinic phase, (Figure 4c)[56] as also reflected in the bandgap (Figure 6a).
which differed from the experimentally observed values (1.6 Bismuth-based chalcogenides[60] such as Bi2S3, Bi2Se3, and
and 3.8 eV, respectively).[53] An interesting study by Natarajan Bi2Te3 are n-type semiconductors with a narrow bandgap
et al. claimed that material processing had a significant impact and high photonic and ionic conductivity.[61] In general,
on material photoexcitation, especially under light-emitting Bi2S3 exists as an anisotropic-layered orthorhombic crystal
diode (LED) irradiation. BiVO4 particles processed using solu- structure with weak van der Waals interactions holding the
tion combustion exhibited the highest catalytic activity against interlayers together and a direct bandgap of 1.3–1.7 eV due
rhodamine B dye (compared to hydrothermally and co-precipi- to the various nano- and microstructures.[62] In contrast,
tated particles) under a green LED rather than UV, blue, or red Bi2Se3 and Bi2Te3 are direct and indirect bandgap materials
LEDs.[54] with bandgaps of 0.5 and 0.165 eV, respectively.[63,64] Both
Bi2MO6 (M = Cr, Mo, and W) represents a group of impor- have a rhombohedral structure (R-3m, Z = 3) and are periodi-
tant semiconductor materials that have been comprehensively cally arranged into layers of -Se(Te)-Bi- Se(Te)-Bi- Se(Te)-Bi-,
studied in terms of their visible-light-responsive catalytic activity aligned perpendicular to the trigonal c-axis. This structure
arising from their layered structure, which facilitates charge has unoccupied octahedral and tetrahedral sites, which allow
transfer within the system.[55] All three semiconductor materials for the incorporation of guest species to tune the electrical
have similar orthorhombic crystal systems with the Pca21 space properties.[65] Chalcohalides are active as solar absorbers and
group. The layered structure in Bi2MO6 is composed of ionic have the general formula BiMX (where M = S, Se, and Te;
layers of [Bi2O2]2+ and [MO4]2−, as shown in Figure 4a.[56–58] The X = Cl, Br, and I).[66,67] For example, BiTeCl compounds con-
comparable bandgap obtained for the three materials from an sist of layered [BiTe]+ with a hexagonal structure and a P63mc
analysis of their density of states (DOS, Figure 4b) were 1.83, space group, whereas BiTeBr and BiTeI are arranged into the
1.73, and 1.53 eV, whereas the bandgaps calculated using diffuse P3m1 and P3m1 space groups, respectively.[68,69] The struc-
reflectance spectroscopy were 2.91, 2.64, and 2.00 eV for Bi2WO6, tural differences between Bi2S3 and BiSI are summarized in
Bi2MoO6, and Bi2CrO6, respectively. Similar observations have Figure 5,[70] where BiSI is prepared through the self-sacrifice
been reported by Kangrong et al.[59] The average wavelength of the Bi2S3 nanostructure.
Figure 5. Parallel view to the c-axis of a) Bi2S3 and c) Bi2S2I2 in a 1 × 1 × 5 expanded cell (violet, yellow, and green represent Bi, S, and I, respectively),
and b) partial Bi2S3 dissolution mechanism for the entry of iodine atoms. Reproduced with permission.[70] Copyright 2022, American Chemical Society.

Figure 6. Electronic band diagram of Bi-based compounds: a) oxides, bismuthates, subcarbonates, and chalcogenides and b) oxyhalides and non-stoi-
chiometric oxyhalides. Reproduced with permission.[74,84,85] Copyright 2012, Royal society of chemistry. Copyright 2017, Elsevier. Copyright 2019, Elsevier.
Bismuth oxyhalides belong to the V-VI-VII class of ternary distance of 0.684 nm, which makes them favorable for use in
semiconducting compounds BiOX (where X = Cl, Br, or I).[71] photocatalysis.
These layered structures crystallize into tetragonal matlockite Additionally, bismuth oxyhalides and chalcohalides have
with [Bi2O2]2+ slabs connected via van der Waals interactions been regarded as potential optoelectronic materials.[80,81] The
with double slabs of halogen atoms interleaved between these chemistry of the ns2 lone pair in Bi exhibits excellent carrier
slabs.[72] The position of the conduction band in BiOX hinders transport properties. Cross-band hybridization between the
the activation of molecular oxygen, which is crucial for their conduction band enriched with spatial cationic p-states in the
catalytic applications.[73] Theoretical calculations have been antibonding orbital with anion-p states and a valence band
used to propose that the position of the conduction band in composed of combined antibonding cation-s and anion-p states
Bi-based oxyhalides can be tuned by altering the amount of Bi leads to Born effective charges. The electrical conductivity and
in the systems because the conduction band is composed of Bi ion mobility of a compound is governed by the ionic charge,
6p orbitals.[74] The energy bandgap of various bismuth oxyhal- mass, polarizability, coordination number, and generated
ides is presented in Figure 6b. Interestingly, one of the studies defects. The concentration of free electrons in the electronic
reported the PC activity of oxyhalides under different types of structure present in the form of oxygen vacancies due to stoi-
LED and claimed that BiOI exhibited effective performance chiometric defects is also responsible for material conductivity
under red LED irradiation, thus demonstrating band activation in Bi systems.[82,83]
under LEDs.[75] In addition to the Bi materials mentioned above, bismuthene
Bismuthates have also become widely investigated for use in (2D bismuth, 2D-Bi) is a promising material for use in energy
a variety of applications.[76] These exist in a +5 oxidation state storage and catalysis due to its tunable bandgap and high con-
as [Xn+(BiO3)n], in which X can be Li+, Ag+, Na+, K+, Mg2+, Sr2+, ductivity.[86,87] 2D-Bi is known to exhibit a high charge carrier
Ba2+, Zn2+, or Pb2+.[77] In addition to their superconductivity, mobility due to its 0.99 eV bandgap which, combined with its
[BiO3]− ions are strong oxidizers, which is useful for nuclear high air stability, means that it has a wide range of electronic
fuel cells in terms of oxidization and separation.[78] Bismuth and energy applications.[88,89] 2D-Bi is known to have three
subcarbonate (Bi2O2CO3) or bismutite in the Sillen group phases (α-, β-, and ξ-), but only the first two have been experi-
have interlayered structures composed of polymeric [BiO]nn+ mentally obtained and reported to have theoretical stability.[88,90]
cations and [CO32−] anions with a [BiO]n layer grown perpen- A significant volume of theoretical analysis has been conducted
dicular to the y-axis.[79] The layered materials have an interlayer to understand their feasibility for use in different electronic and

catalytic applications, but experimental investigations remain a diverse range of compositions also allows for tuning through
limited, and a deeper understanding of their underlying mech- electronic band hybridization and atomic coordination, thus
anisms is required. leading to excellent energy storage and conversion efficiency
through morphological control, crystal structure design, band
regulation, defect creation, and a range of other changes. The
3. Advantages of Bi Micro- and Nanostructured advantages of Bi materials are summarized in Figure 7.
Materials
Micro- and nanostructured Bi materials have a number of 4. Tuning of Micro- and Nanostructured Bi-based
important advantages compared to other material systems.
Materials
For example, 209Bi is radioactive, with a half-life of 2.01 × 1019
years, which practically renders it non-radioactive.[28] In addi- 4.1. Structural Approaches
tion, Bi compounds have various oxidation and reduction states
between 5+ and 3−, including interactions such as BiBi, Bi- A number of physical and chemical methods have been used
metal, and Bi-non-metal.[91,92] In the 209Bi electronic configura- to construct 1D and 2D Bi-based nanostructures. Wet chem-
tion ([Xe]4f145d106s26p3), most of the electrons in the 6p orbitals ical processing using Bi salts as a precursor dissolved in
are responsible for bonding in the Bi3+ oxidation state, leading highly concentrated acid or non-aqueous media is the most
to inert 6s2 electron pairs and resulting in a stereochemical common and dependable method reported to date.[96] How-
effect. Theoretically, Bi has also been shown to have lower-lying ever, numerous research efforts have been dedicated to inves-
energy bands, which are responsible for the semi-metallic char- tigating the unusual physicochemical properties of colloidal
acteristics observed in the ultraviolet (UV)–visible and visible– NPs. In addition, laser-ablating metal Bi, which is produced in
infrared (IR) regions, whereas semiconductive properties can deionized water without the use of a surfactant, is an ablated
only be identified in the IR and tetrahertz (THz) regions.[93] colloidal Bi species that exhibits distinct advantages in terms
Another advantage is that, in addition to being a non-toxic of its high reactivity and reducibility. It can also react with
and low-cost material, micro- and nanostructured Bi materials water to form Bi(OH)3 nanowires (NWs) under atmospheric
exhibit low thermal conductivity, a low melting point, minimal conditions, exhibiting self-assembly behavior. Furthermore,
volume expansion upon freezing, and a high volumetric energy with aging at 60 °C or under light irradiation, Bi-based col-
density. These features favor the use of Bi as an electrode mate- loids assemble into nanocrystals composed of Bi2O3 and Bi2O4
rial with potential window expansion in the negative working phases.[97]
zone with three-electron redox electrochemical reactions.[26,94,95] Current barriers facing nanomaterial research are controlled
Furthermore, the majority of Bi materials are semiconductors, synthesis and surface modification. In this vein, Qiu et al.
as illustrated by the bandgap representation in Figure 6. Their described the development of α- and β-Bi2O3 using the phase-
optical and electrical properties can thus be tuned via energy selective synthesis of NWs via oxidative metal vapor transport
band engineering, and they outperform other materials in their deposition, which is similar to the vapor-liquid-solid mecha-
catalytic performance.[74,84,85] The layered crystal structure with nism (VLS).[98] Apart from inorganic salts such as Na2SO4,[99]
organic compounds such as L-lysine have been used as struc-
ture-directing agents to create various Bi2WO6 structures,
including compressed nanoplates, hierarchical flowers, and
clew-like microspheres, by altering the pH of the precursor
solution.[100] Irregular-polyhedral crystals (3.4–9.6 µm) with
dense microspherical BiVO4-C (synthesized via calcination)
have been reported to exhibit exposed redox facets.[101] A trun-
cated-bipyramidal structure with a particle size of 1.5–4 µm has
also been reported for BiVO4-H (synthesized via a hydrothermal
route). The structure observed using microscopic imaging had
a smooth surface and two (040), four (110), and four (011) well-
exposed facets. A truncated-bipyramidal shape was observed for
BiVO4-R (synthesized via a reflux process) with particle sizes in
the range of 1.5–5 µm and similarly exposed facets to BiVO4-H.
The enhanced anti-recombination observed after photoexcita-
tion was attributed to the well-exposed decreasing (040) facet
and the (110) oxidation side, which favors the development of
a facet isotype heterojunction and a high percentage of (040)
BiVO4-R reduction facets. These results demonstrate the
potential for the advancement of the morphology and selective
fabrication of facet isotype heterojunctions using relative reduc-
tion–oxidation facet exposure.
Overall, basic control over 1D and 2D structures can be
Figure 7. Properties and advantages of Bi micro- and nanostructures. achieved via complex formation between structure-directing

Figure 8. a,b) TEM images of nanostar-like 3D BiPO4 and c) from a front and diagonal perspective. Reproduced with permission.[105] Copyright
2014, American Chemical Society. SEM and TEM images of d,f) BiVO single-shell hollow spheres and e,g) BiVO double-shell hollow spheres.
Reproduced with permission.[110] Copyright 2017, Elsevier.
agents and Bi ions under wet chemical processing conditions, properties of the inner core and external shell allow for the use
which can be further governed by the reaction time, pH, and of various chemical compositions and nanostructural combi-
temperature, whereas dry-chemical processing is dependent on nations, thus improving their physicochemical properties in
the VLS mechanism and temperature. comparison with single-component systems. Theoretical and
One of the most important areas of research is dimen- experimental studies have shown that Bi–Bi2O3 core–shell NW
sionally oriented 3D nanostructures. These structures can be arrays form by transforming Bi NWs to Bi2O3 nanotube arrays
developed using both template and non-template strategies under slow oxidation conditions using an anodic alumina mem-
depending on the growth orientation and control during the brane. Oxidation preferably occurs at the border and at defects,
fabrication process; the former has generally been avoided thus slow thermal heat treatment creates core–shell NWs via
by researchers due to the inclusion of unwanted impurities. kinetic mediation, and these NWs are then transformed into
Most 3D structures are formed via self-assembly, Ostwald rip- nanotubes during the rapid heating process.[109] Zong et al. also
ening, or self-assembly following the ripening process. Hier- demonstrated the development of heterostructured multi-shell
archical flower-like Bi2O3 has been widely reported because it hollow BiVO4 spheres using sucrose as a growth-regulating pre-
can be easily fabricated under wet-chemical conditions using cursor.[110] The single-shell precursors were calcined at 550 °C
organic structure-directing reagents/capping agents, such as at a ramping rate of 10 °C min−1 to obtain BiVO single-shell
citric acid, acetic acid, and L-asparagine.[102–104] Interestingly, hollow spheres (Figure 8d–g). Double- and triple-shell hollow
highly monodisperse BiPO4 nanostars have been synthesized spheres can be obtained after further calcination by controlling
via homogeneous precipitation with the controlled release of the heating rate. Restricting the content of Bi3+ and VO3− leads
Bi from bismuth citrate complexes at 120 °C. Aging the solu- to the formation of a single shell, whereas increasing their
tion leads to an arrangement of nanorod bunches crossing concentration leads to concentric double-shell spheres, which
over at 60 °C to resemble a star-like morphology. Different become hollow after calcination, with an average shell thick-
glycerol/ethylene glycol ratios alter the viscosity, which con- ness of ≈50 nm for randomly shaped NPs. Similarly, Dmitriev
trols the ionic diffusion rate and thus governs the aggrega- et al. reported for the first time spherical single-phase BiFeO3
tion of the NPs, leading to the formation of nanostars from powder synthesized using ultrasonic spray pyrolysis. The tar-
nanorod bunches (Figure 8a–c).[105] Citrate-based structural taric acid concentration affects the hollow sphere agglomeration
growth has also been observed in BiOCl using sodium cit- with open and closed pores, and the final powder has a mean
rate,[106] and hierarchical BiFeO3 with a 3D floral pattern has particle diameter of ≈1 mm. The domain structure is destroyed
been grown in ethylene glycol,[107] while molecular organic when the concentration of tartaric acid increases from 0 to 2 m,
framework (MOF)-modified BiFeO3 microcages[108] have also possibly due to the reduced thickness of the shell layer.[111] In
been observed. addition, Marchand et al. studied the electrical and magnetic
Other interesting structures have also been developed, properties of BiFeO3 films grown via an atomic layer deposition
including core–shell and hollow morphologies. Core–shell het- (ALD) process.[112] It is worth highlighting that the ALD process
erostructures are generally designed to protect the semicon- offers an alternate method for highly regulated deposition over
ductor surface, thus stabilizing the NPs. The unusual structural different geometrical structures.

4.2. Modification Approaches: Dopants and Defects 4.3. Composite and Heterojunction Formation
Order–disorder phenomena in various Bi compositions with Composites and heterojunctions have been developed to miti-
the introduction of random point defects (vacancies, intersti- gate the problems associated with single systems. A summary
tials, substitutions, etc.) can alter their structural interactions. of the types of electron transfer in composites and heterojunc-
Defects in the system can also be introduced via doping and tion is presented in Figure 9 (A and B are the semiconductor
impregnation. Surface defects in bismuth oxides can be intro- materials and orange lines present electron/hole transfer
duced to enhance their versatility for use in a range of applica- between the semiconductors). Some of these electron transfer
tions. For example, the introduction of oxidized defect sites in mechanisms are discussed with respect to bismuth materials
bulk Bi2O3 enhances the PC efficiency through changes in the in this section, and also comprehended in energy and environ-
crystallite size, surface area, energy bandgap, and charge carrier mental applications. For instance, the synthesis of hierarchical
recombination.[113] In bismuth oxyhalides, non-stoichiometry heterostructures using MOFs has recently gained significant
and defects can be easily induced through Bi and O vacancies interest. Two BiOBr/Bi24O31Br10 heterojunctions (Figure 10a–d)
and content concentration.[114,115] In molybdates and tungstates, have been formed from a Bi MOF using a facile bromina-
ion conductivity has been reported to increase with deficient tion-annealing route with cetyltrimethylammonium bromide
Bi and oxygen vacancies.[116–118] In a similar fashion, elemental (CTAB) as the Br source.[123] Both structures maintain the rod
doping (e.g., Mo and W) in Bi phosphates and vanadates have morphology of the MOF, which grows nanosheets on the rod-
been reported to induce structural disorder that is favorable for like surface after annealing at 500 °C. Composite structures
the water oxidation reaction.[119,120] In accordance with density composed of both plates and rods arranged in a unique way
functional theory calculations, Mo and W have been doped at have also been reported for Bi2Te3 and Te/Bi2Te3 materials. For
V sites to form continuum band states above the conduction example, solvothermally processed Te/Bi2Te3 NWs and nano-
band of BiVO4 that hinder the irreversible surface reaction of plates have been produced, with the NW growth mostly due to
VO2+ into VO2+ via an electron trapping process, which restricts the presence of polyvinylpyrrolidone because Te can be restored
surface recombination and continues via a reversible redox between 90 and 150 °C.[124] Interestingly, at temperatures above
process for V5+/V4+ in the bulk material.[120] The doping of 160 °C, the epitaxial growth of Bi2Te3 occurs at the tip of the Te
BiVO4 with both Mo and W under oxygen-rich conditions has NWs when the Bi atoms react with the free Te atoms forming a
been reported to result in a smaller bandgap and formation plate over the NW heterostructure.
energy based on computational calculations, and this system The monoclinic scheelite phase (clinobisvanite) is the most
is predicted to be superior to individually doped systems due photoactive form of BiVO4, exhibiting n-type conductivity with
to the enhanced light absorption.[121] In addition, the Mo-doped a ≈2.4 eV bandgap. The attractive feature of BiVO4 is its activity
structure is significantly more stable than the W-doped system. in solar water-splitting applications due to its favorable band
Enhanced light absorption and charge separation efficiency at a edge position compared to other metal oxides (e.g., Fe2O3 and
low applied voltage have also been reported after doping BiVO4 WO3). In addition, the development of (Zr)BiVO4/nickel hexa-
core–shell nanorod array photoanodes with Sb.[122] In particular, cyanoferrate (NiFe) core–shell photoanodes for solar water-
thin layers of BiVO4 are coated onto Sb-doped SnO2 (Sb:SnO2) splitting has been reported by Shaddad et al.[125] Their method
nanorod array. The efficient charge separation is a result of the uses an FTO glass substrate for the electrodeposition of Bi with
size of the BiVO4 crystallites and the deposition technique for 2.5 mol% Zr added to the plating bath containing Bi3+, followed
the core–shell nanorod arrays. The controlled deposition of the by a reaction with vanadyl acetylacetonate (VO(acac)2). No trace
materials using electrodeposition and ALD may also enhance of lattice fringes is observed in the NiFePB shell, suggesting
the performance to a greater extent. an amorphous crystal structure (Figure 10e,f). A thick NiFePB
Figure 9. Schematic representation of the general mechanisms underlying composites and heterojunctions.

Figure 10. SEM images of a) Bi-BTC, b) Bi2O3, and c,d) BiOBr/Bi24O31Br10 (450 °C). Reproduced with permission.[123] Copyright 2020, Royal Society
of Chemistry. e) TEM image of the resulting (Zr)BiVO4 core/NiFePB shell-structured nanoparticles (NPs). f) High-resolution TEM image of one (Zr)
BiVO4 core/NiFePB shell NP. Reproduced with permission.[125] Copyright 2019, Elsevier. g) FE-SEM images of hollow SnS2-incorporated BiOCl HMSs
microspheres with citric acid. h) FE-TEM images of SnS2-incorporated BiOCl HMSs microspheres. Reproduced with permission.[126] Copyright 2015,
Royal Society of Chemistry.
layer (≈10–15 nm) exhibits the highest PC activity. The NiFePB broken structures resulting in a hollow structure. The hydrogen
layer on (Zr)BiVO4 yields a charge transfer of ≈90% at 1.23 V bond formed between the carboxyl group in citric acid and the
versus a reverse hydrogen electrode (RHE) when compared to hydroxyl ions in the complex along with the intra-hydroxyl ion
(Zr)BiVO4, which yields a charge transfer of <20%. The amor- bonding in the complex control the self-assembled growth of
phous NiFePB coating enhances the efficiency due to the inter- the heterostructured SnS2-BiOCl nanoplate.
face having a greater number of active sites and provides spatial In addition, a thin-film-based core–shell NW photoanode has
protection from the electrolyte, which is crucial in BiVO4-based been fabricated in which monoclinic BiVO4 (BVO) is deposited
photoelectrochemical systems. via alternate ALD layers of Bi2O3 and V2O5 as a nanolaminate
In several emerging PC applications, hollow Bi spheres using a super-cycle approach, followed by an annealing pro-
(BiOCl/SnS2) have been designed using one-step hydrothermal cess[127] (Figure 11a,b). The core–shell NW structure is com-
routes with polyvinyl pyrrolidone (PVP) and citric acid as tem- posed of three layers: ZnO NWs, SnO2 as a buffer layer, and
plates. These spheres exhibit an increased capacity to harness BVO as the top layer (Figure 11c–e). A 30% increase in the
light with high efficiency under visible light and sunlight irra- photocurrent is observed, claimed to be the highest reported to
diation for the oxidation of organic contaminants. In ref. [126], date for an ALD-fabricated photoanode system, thus providing
a layer of flakes self-assemble to form a hollow flower-like a pathway for the rational design of 3D nanostructured pho-
architecture. TEM and SEM images (Figure 10g,h) show that toelectrodes. The ALD SnO2 interlayer plays a significant role
the nanosheets form a porous and loosely packed surface with in restricting the photocorrosion of the initial ZnO NW layer,

Figure 11. a) Schematic representation of ALD BVO prepared using super-cycle deposition followed by annealing. b) Digital photographs of the as-
deposited ALD film (left) and annealed (right) BVO film. c) Schematic representation of ALD-coated BVO on nanostructured ZnO photoelectrodes
with an ALD SnO2 interlayer. d) SEM image of ALD-coated BVO on ZnO. e) Bright-field TEM and EDS mapping of a BVO/ZnO photoelectrode (scale
bar, 50 nm). Reproduced with permission.[127] Copyright 2019, American Chemical Society.
highlighting the importance of interface engineering using For example, layered Bi2Se3 allows for easy cation movement
ALD. Thus, ALD has been shown to be a promising alternative within the system through its large interlayer spacing. Despite
to PVD processes for the uniform deposition of various mate- a high theoretical capacity of 1064 mA h g−1, Se dissolution
rials, such as oxides, nitrides, and metals, over 3D structures at occurring during volume expansion and shrinkage limits device
a high aspect ratio and low temperatures. performance. In this context, Bi2Se3 nanocrystalline array elec-
trodes wrapped in an amorphous carbon layer have been tested
in terms of their Na-ion battery performance, with Bi2Se3 hydro-
5. Sustainable Energy and Environmental thermally grown on carbon cloth.[132] A discharge capacity of
652.1 mA h g−1 is achieved after 100 cycles at 100 mA g−1 for the
Restoration Applications
Na-ion battery. These results indicate rapid electrolyte perme-
5.1. Energy Storage and Conversion Systems ability due to array spacing and lower volume expansion due to
the ultrathin amorphous carbon cloth. Similarly, rod-like Bi2Se3
5.1.1. Batteries in carbon has been fabricated via an in situ selenization pro-
cess, in which the carbon structure increases the stability of the
Bismuth-based materials have been widely investigated matrix through a porous MOF, thus avoiding Bi2Se3 agglom-
for use in lithium-, sodium-, and potassium-ion batteries eration. According to these studies, rhombohedral Bi2Se3 is
(Table 1).[128,129] Capacity degradation is associated with the partially transformed into an orthorhombic structure after the
stress induced during the interaction at the solid–liquid inter- cycling process. The electrochemical discharging and charging
face causing volume expansion and degrading device perfor- reactions in Bi2Se3 can be expressed by Equations (1)–(3). A
mance. Therefore, stable interfaces have been developed by high reversible capacity of 637 mA h g−1 with long cycling sta-
building 2D Bi nanosheets that provide more active sites with bility and superior rate retention has been achieved.[133]
shorter diffusion lengths, thus forming a stable interface upon
contact with the electrolyte.[130] When the performance of Bi- Bi 2Se3 ( rhombohedral ) + Li + + e − → Bi + Li 2Se ( discharging ) (1)
based nanosheets is compared with bulk Bi, the internal strain
is lower due to the shortened c-axis in the nanosheets, facili-
Bi + Li + + e − → Li 3 Bi ( Discharging ) (2)
tating faster electrochemical reactions. In solid-state Li-ion bat-
teries, Bi nanosheets maintain their integrity due to the ability
to accommodate the strain caused by volume expansion during Li 3 Bi + Li 2Se → Bi + Bi 2Se3 ( orthorhombic ) + Li + + e − ( Charging ) (3)
the interfacial reactions. This leads to a capacity of 287 mAh g−1
at a rate of 250 mA g−1 after 100 cycles. However, pulverization A similar system involving graphene/Bi2Te3 has also been
is more dominant in bulk Bi than in dimensional Bi, resulting reported, with the material properties explained by the quin-
in poor cyclic performance. To address this issue, Bi nanorod tuple-layered sandwich-like structure and high structural den-
networks embedded in an N, S-co-doped carbon matrix have sity.[134] The interlayer spacing in Bi2Te3 facilitates Na ion dif-
been used to support the conductive framework by accommo- fusion and promotes the volumetric capacity due to its high
dating the large volume variation that causes strain during the density compared to S and Se. In addition, thin film electrodes
alloying–dealloying process in K-ion batteries.[131] have also been developed as integrated microelectronics for
In bismuth chalcogenide systems, the relatively weak metal– use in Li-ion micro-batteries.[135] Previous reports have shown
chalcogenide bonds favor reversibility, providing kinetic gains. that the stability of Bi2Te3-based thin film electrodes depends
Table 1. Summary of bismuth-based micro- and nanostructured materials, their processing strategy, and their electrochemical properties in battery
applications.
Material Application Processing Morphology Electrolyte Specific Capacity Stability or % Ref.

Retention
Bi nanosheets Solid-state Li-ion Planetary ball Dimensional solid LiBH4 ≈287 mA h g−1 at a 100 cycles [130]
batteries milling (coarse, aggregated, electrolyte current density of
spherical) 250 mA g−1
Bi nanorod net- K-ion batteries Solvothermal and Dimensional 1 m KPF6 in 338 mA h g−1 and 91% capacity [131]
works embedded in pyrolysis (nanorods) 1,2- DMEa) 289 mA h g−1 at 0.5 retention at 5 A g−1
an N, S co-doped and 6 A g−1 (1000 cycles)
carbon matrix
Bi2O3 Aqueous battery Soft templating Hollow hexagonal 6 m KOH aqueous 327 mA h g−1 at 64% retention rate [139]
prism electrolyte 1 A g−1 at 20 A g−1, ≈80%
(3000 cycles)
Bi@N-C Anode material Facile solvo- Multi core-shell 1 m NaPF6 in 1, SIBsb): 76% (1000 cycles) [140]
for Na- and K-ion thermal method carbon nanospheres 2-dimethoxyethane 235 mA h g−1 at
batteries (DME) 10 A g−1) and KIBs
(203 mA h g−1 at
10 A g−1)
Bi2Se3@C rod-like Li-storage K-ion Hydrothermal Dimensional 1 m LiPF6 in EC/ LIBse): 637 mA h g−1 LIBs: cycling [133]
architecture batteries and selenization (microrods) DMCc) for LIBs, and KIBsf): 305 mA h g−1 stability
3 m KFSI in DMEd) (543 mA h g−1)
for KIBs KIBs: 400 cycles
In-doped Bi2Se3 Li-ion batteries Solvothermal Hierarchical flower- 1 mol L−1 LiPF6 1st discharge 50 cycles [141]
hierarchical like morphology solution in EC- capacity = 997.9
nanostructures DMC with a volume 50th discharge
ratio of 1: 1 capacity = 160.3
Bi@C Li-ion batteries Hydrothermal Core–shell nanowires 1 m LiPF6 in 233 mA h g−1 at 350 cycles [142]
and carbonization DMC/EC/DECg) 100 mA g−1
reduction (1:1:1 v/v/v)
Bi2S3@N-doped Li-ion batteries Hydrothermal Yolk@shell 1 m LiPF6 (EC: 501 mA h g−1 at 85% (700 cycles) [143]
carbon nanowire DMC: EMC = 1:1:1, 1.0 Ag−1
in volume with 5%
FEC)
Bi2S3-CNT hybrids Sonochemical Nanorods 1 m LiPF6 solution 671 mA h g−1 at 534 mA h g−1 [144]
hydrolysis in ethylene 120 mA g−1 (90 cycles)
carbonate and
dimethyl carbonate
(1:1 by volume)
Bi2S3@Co9S8 Li- and Na-ion Modified Hetero-structured 1 m LiPF6 in a 798 and 93% (100 cycles) [129]
storage hydrothermal complex hollow par- mixture of EC/ 461 mA h g−1 at
process ticles (Bi2S3 spheres), DMC/DEC (1:1:1 in 0.1 g−1 for LIBs and
Co9S8 multi-cavity volume) SIBs
hollow shells
Bi2S3-PPy Li- and Na-ion Hydrothermal Flower-like 1 m LiPF6 solution Li storage: 450 mAh g−1 [145]
storage architecture in ethylene 621 mA h g−1 (500 cycles)
carbonate and Na storage:
dimethyl carbonate 591 mA h g−1
(1:1 by volume)
Polypyrrole-encap- Sodium-ion Hydrothermal Hollow spheres DME solution with Reversible capacity SIBs: 90% capacity [146]
sulated amorphous batteries and sulfurization 1 mol L−1 NaPF6. of 278 mA h g−1 at retention of the
Bi2S3 3000 mA g−1 second cycle
(5000 cycles at
1000 mA g−1)
Bi2S3@SC Li-ion batteries Glucose-assisted Hollow nanotubes 1 m LiPF6 in ≈950 mA h g−1 at ≈550 mA h g−1 [147]
hydrothermal ethylene carbonate/ 100 mA g−1 (1000 cycles at
strategy and a dimethyl carbonate 1000 mA g−1)
post-treatment (EC: DEC = 1:1, v/v)
process
Table 1. Continued.
Material Application Processing Morphology Electrolyte Specific Capacity Stability or % Ref.

Retention
Chrysanthemum- Li-ion and Na-ion Precipitation Chrysanthemum 1 m NaPF6 in Li-ion: 83% (250 cycles) [148]
like Bi2S3 batteries EC, DMC, and 480 mA h g−1 could for Na-Ion batteries
EMC (EC/DMC/ be maintained
EMC + 5% FEC, after 300 cycles at
volume ratio of 0.5 A g−1
EC:DMC:EMC of Na-ion: 437 mA h
1:1:1) g−1 after 250 cycles
Bi2S3/RGO Li-ion batteries Hydrothermal Grain-liked 1 m LiPF6 in 850 mA h g−1 47% (50 cycles at [149]
morphology EC:EMC:DMC = 400.5 mAh g−1)
1:1:1 in volume
Bi2S3/C Li-storage Hydrothermal Nanomeshes 1 m LiPF6 solution 750 mA h g−1 63% (40 cycles at [150]
nanomeshes in ethylene 472 mAh g−1)
carbonate and
dimethyl carbonate
(1:1 by volume)
Bi2S3@C/Ni foam Li-ion storage Ultrasonication/ Flower-like Bi2S3 1 m LiPF6 dissolved 795 mA h g−1 88% (50 cycles at [151]
hydrothermal in a mixture of EC, 700 mAh g−1)
DEC, and EMC
with a volume ratio
of 1:1:1
Bismuth ferrite Na-ion batteries Electrospinning Hollow 1 mol l−1 NaPF6 600 mA h g−1 89% (200 cycles) [152]
combined with solution, in mixed
graphene solvent of EC and
DMC (EC: DMC =
1:1) with 5% FECa)
additive
Bi2Se3/C Na-ion batteries Ball milling Nanocrystals 1 mol L−1 NaClO4 527 mA h g−1 at 89% (100 cycles) [153]
nanocomposite dissolved in 0.1 A g−1
propylene
carbonate/ethylene
carbonate (1:1 in
volume) with 5
wt.% fluoroethylene
carbonate (FEC) as
an additive
Graphene-loaded Na-ion storage Facile Curled and wrinkled 1 m NaSO3CF3 346 mA h g−1 1000 cycles [154]
Bi2Se3 selenization structure solution in Diglyme (0.1 A g−1)
Bi2Te3/G Na-ion storage Hydrothermal Nanoplates 1.0 m NaCF3SO3 in 498 mA h g−1 500 cycles [134]
DEGDME
2D layered BiOX Li-Ion batteries Hydrothermal Sheet-shaped 1 m LiPF6 dissolved 633 and 68.4 and 67.8% [155]
(X = Cl, Br) structure in a mixture of EC 605 mA h g−1 were achieved after
and DMC with the (100 mA g−1) for 15 cycles for BiOCl
volumetric ratio BiOCl and BiOBr and BiOBr
of 1:1
a)FEC: fluoroethylene carbonate
on the alloying, growth time, pure phases, and film thickness, the diffusion distance and allows for the faster diffusion of Na
while remediation of the post-cycling cracks should also be ions, with an areal capacity as high as 12.1 mAh cm−2.[137] The
considered.[136] adsorption behavior of Na ions on monolayered bismuthene
Bismuthene-based electrodes composited with graphene has also been theoretically studied by Marjaoui et al.,[138]
have also been developed to address the problem of aniso- where a similar alloy formation process is confirmed, with
tropic volume expansion that is known to take place during this transformation possibly due to the transition of the
sodiation, with the alloy reaction adversely affecting device material from a semiconductor to a conductor. In addition,
performance. In this regard, the stress along the critical z-axis the diffusion barrier for Na ions on bismuthene has been
can be alleviated by the successful design of ultrathin few-lay- found to be lower (0.18 eV). The studies described above are
ered bismuthene composited with graphene, which reduces thus useful in determining the choice of materials and their
rational design for the technical improvement of rechargeable batteries.[129] Based on density functional theory findings, the
battery systems. heteroxide structure is achieved by off-setting the bandgap,
Composition-controlled heterostructured Bi2S3/MoS2 with which can significantly improve the electrical conductivity
abundant phase boundaries[156] and Bi2S3/MoS2 shelled with (Figure 12). Moreover, with a heterojunction structure, an inte-
nitrogen-doped carbon[128] have been reported as novel anode grated electric field makes it easier for the Coulombic forces
systems for use in Na- and K-ion batteries. In terms of their to transport Li+/Na+ and one hetero-hollow structure not only
performance, the Bi2S3/MoS2 composite is preferable because effectively prevents large changes in volume but also facilitates
the obtained capacity is measured at a high current density and charge transportation.
maintained over 1200 cycles. This confirmed both theoretically To monitor the shuttle effect in polysulfides, ferroelectric
and experimentally that the self-built inner electrical field in Bi materials with a built-in electric field formed via sponta-
the Bi2S3/MoS2 composite caused by phase borders improves neous polarization can anchor polysulfides in a separator.
the kinetics of the reaction and enhances the transmission of Recently, BiFeO3 in combination with carbonaceous mate-
charge. A complex hollow core–shell heterostructure com- rials (graphene oxide and acetylene black) has been drop-cast
posed of Bi2S3@Co9S8 has also been developed with the aid onto a commercial polypropylene separator.[157] The separator
of an MOF to boost the storage performance of Li- and Na-ion exhibits a high capacity of 1226.8 mA h g−1 and, when using
Figure 12. Total density-of-states for A) bare Bi2S3, B) Bi2S3@Co9S8 heterojunctions, and C) bare Co9S8. D) Schematic illustration of the morphological
evolution during the charge/discharge process. Reproduced with permission.[129] Copyright 2020, Elsevier.
a high sulfur loading in the cathode (5.6 mg cm−2), a capacity more accessible surface area.[167] This material demonstrates a
of 1015.9 mA h g−1 is achieved, which is sufficient for practical durability of 5000 cycles with a capacity retention of 94%. In
applications. The fabricated cell exhibits a high capacity den- another study by this group, partially oxidized Bi nanoflakes are
sity of 5.1 mA h g−1 at elevated sulfur loadings, which can be prepared, with the participatory effect of OH− ion adsorption
attributed to polysulfide shuttling and its improved properties, on the Bi surface believed to play a crucial role in the redox
such as the reaction kinetics and performance rate. In addition reaction.[168] The partial surface oxidation strategy is useful,
to these materials, BiVO4,[158] Bi2MoO6/MXene,[159] BiOCl,[160] with the presence of oxygen atoms lowering the absorption
Bi2Ru2O7,[161] and others[162,163] have been developed to inves- energy of OH− on the oxidized surface (−3.71 eV) compared
tigate high-energy-producing materials that can be explicitly with the pristine metallic Bi (−3.42 eV), which results in faster
used for ionic battery systems. redox reactions and greater electrochemical performance. There
Interestingly, most contemporary carbon-based materials is no loss of capacity even after 20 000 cycles for the partially
used for anodes are either graphene, graphene oxide, or, for oxidized Bi nanoflake anode, and the constructed Ni//Bi battery
Na-ion batteries, activated carbon. As an alternative, the use system exhibits a durability of 5000 cycles with a capacity reten-
of organic pectin, a water-soluble polysaccharide, in conjunc- tion of 96%. In a recent study, an rGO/Bi hybrid scaffold is pre-
tion with BiFeO3 nanoflakes, has been reported by Sun et al. pared in which the bismuth crystals are intercalated in situ in
for rechargeable Na-ion batteries.[164] Pectin acts as a buffer the aligned rGO sheets, which are the active anode material.[169]
for BiFeO3 crystal lattice expansion, significantly improving The high mass loading results in a higher areal capacity and
the Na-ion charge–discharge process, and positively affecting an extraordinary 50 000 charge–discharge cycles with a capacity
the stability and cycle life. Given the multiferroic nature of retention of 83%. In most aqueous rechargeable batteries, the
BiFeO3, Na-ion intercalation changes the lattice of the BiFeO3 focus is on the development of stable and flexible Ni//Bi battery
crystals after 100 charge–discharge cycles due to the struc- systems with faster redox reactions and minimal decay in the
tural distortion caused by polarization, which is hindered by Bi anode, with load optimization employed to ensure a higher
1% pectin doping. For Li–metal batteries, the formation of capacity.
lithium dendrite is unavoidable prior to electrolyte decomposi-
tion, and capacity decay restricts commercialization. One effec-
tive strategy to overcome this involves distributing Li ions in 5.1.2. Supercapacitors
the bulk electrolyte so that the concentration of Li ions near the
anode is minimal and the diffusion of Li ions through the bulk Chalcohalides and oxyhalides of Bi and chalcogenides in super-
electrolyte occurs easily. Because ferroelectric materials are capacitors have been widely studied. For supercapacitors, the
reported to suppress shuttle effects in battery systems, spon- materials employed for ionic batteries can be studied in detail,
taneous polarization in BiFeO3, when attached to a commer- improving the chance of tuning the materials used in anode sys-
cial separator, can accelerate Li-ion transport through polarized tems. Substantial interest in renewable and cost-effective energy
NPs, eliminating Li-ion deficiencies at the anode surface.[165] collection and storage applications has been directed toward
The strong interfacial polarization between the BiFeO3 and Li electrical double-layer capacitors (EDLCs), which include cost-
ions results in the dense and smooth nucleation of the depos- effective and solution-processible electrode materials. Bi13S18I2
ited Li, leading to the long-term stability of lithium plating at is an underexplored material that has been investigated for its
temperatures as low as −10 °C, in which the cells with the BFO potential use as an active material in the electrodes for EDLC-
separator can deliver a high Coulombic efficiency of 95% at type supercapacitors. Bi13S18I2 has been incorporated into a
a current density of 0.5 mA cm−2 for 180 cycles. These mul- symmetric EDLC with a NaClO4 aqueous electrolyte, which
tifunctional separators are promising for use in Li-metal bat- exhibits an outstanding capacitance of 210.68 mF cm−2, with a
teries and can be applied to other battery systems to resolve retention capability of 99.7% after 5000 cycles.[67] Chalcohalide
these bottlenecks. stability has also been found to be the highest in supercapac-
Aqueous rechargeable batteries based on Ni//Bi systems itor applications. For example, 3D hexagonal Bi13S18I2 and BiSI
have proven to be excellent energy storage devices,[166–168] with 3D orthorhombic bismuth chalcogenide materials have been
Bi a state-of-the-art option for the anode material. In search of explored as active electrode materials in supercapacitors. These
a flexible battery system with excellent electrochemical perfor- materials exhibit both Faradaic pseudocapacitance and non-Far-
mance, a Ni//Bi battery system has been developed in which adaic EDLC behavior in a KOH electrolyte with a mass loading
hierarchical 3D Bi nanostructures and NiCo2O4 NWs are used of 4–5 mg cm−2. In a two-electrode device, Bi13S18I2 outperforms
as the anode and cathode, respectively.[166] The single crystalline BiSI in terms of its capacitive retention with a capacitance of
and highly conductive nature of Bi means that there is no decay 247 mF cm−2 observed at a current density of 5 mA cm−2, while
after 10 000 cycles, and it delivers a significant power density 98.4% of the initial capacitance is retained over 5000 cycles. A
of 21.2 kW kg−1 and a high energy density of 85.8 W h kg−1. high surface area is achieved in both systems by controlling the
In situ Raman spectroscopy reveals a partial transformation reaction parameters, with a relatively low temperature being a
of Bi to Bi2O3 during the discharge step, which is converted crucial parameter.[170]
back to Bi during charging, which is the likely reason for the A 2D bismuthene/antimonene composite has been
ultrafast electrochemical processing. The same research group employed as cathode material for supercapacitor applications
has developed a Bi anode by combining Bi with carbon, and with the expectation of a high energy density. The developed
an in situ activation strategy is employed to induce porosity 2D composite delivers a specific capacity of 1003.3 C g−1
for rapid charge transfer and enhanced ion diffusivity via a and 10 000 charge-discharge cycles with a cyclic stability of
87.3%, with an extraordinary capacitive distribution of 97.2% 1.5 mmol (designated as BFMO1), with small flakes forming
according to Trasatti analysis. In addition, a high energy at higher Mn concentrations. Compared to other composites,
density of 131.44 W h kg−1 has been achieved with a hybrid the micro-rectangular Mn-doped Bi2Fe4O9 (BFMO1) has the
device constructed with activated carbon as a negative elec- highest specific capacitance of 487 F g−1 at a current density of
trode.[171] Flexible supercapacitors and ionic-type capacitive 1 A g−1.[177] Despite the enhanced performance, the effect of the
sensors that use a 2D bismuthine-anchored graphene archi- Mn concentration on the electrochemical activity is not clearly
tecture have also been reported. The hierarchical porous understood. In addition to transition metal doping, rare-earth
aerogel framework with conductive 2D Bi flakes increases doping in a molybdate structure has also been carried out and
the interlayer electron conduction and encourages electrolyte used as a negative electrode material.[178] Because perovskite
infiltration for enhanced energy storage and pressure-sensing materials are attractive candidates for solving the energy crisis,
properties.[172] ferrites and manganites have been widely investigated for use
The demand for alternative materials that maintain excel- in energy storage devices. Recently, BiFeO3 nanocomposites
lent catalytic activity with improved stability and low toxicity embedded with nitrogen-doped carbon (BiFeO3-NC) have been
remains high. In this respect, BiOX (X = Cl, Br, and I) has been reported to deliver a charge storage capability of 811 F g−1 in a
conjugated with manganese due to its excellent electrical and 1 m Na2SO4 electrolyte, which is much higher than the capacity
optical properties.[173] Mn-BiOCl has an average specific capacity of similar materials in KOH electrolytes.[179] However, it should
of 220.8 mA h g−1 (2291.35 Fg−1) in an aqueous OH- electrolyte, be noted that this performance is only enhanced in an SO4−
which enables an effective oxygen change reaction to occur at a ionic electrolyte but not when OH- species are present, indi-
surplus of 160 mV because of the harmonious effects of the high cating electrolyte dependence.
surface area and excellent electrical conductivity. The capacity Despite Bi2O3 being known for its high theoretical capaci-
retention is 86% over >10 000 load-discharge cycles at a current tance of 1370 F g−1 and high energy density, this has yet to be
density of 2.4 mA cm−2, demonstrating the excellent reliability realized in practice.[180] The twofold contact of a Bi2O3 shell with
of the synthesized material. In addition to the material proper- CNTs and a metal Bi core, thus providing two electron transfer
ties, adjusting the dimensionality or structural orientation is a routes, has been shown to increase the efficiency of the elec-
promising strategy for enhancing the surface area and electroac- trochemical process. The resulting Bi-Bi2O3/CNT electrode
tive sites in the development of flexible energy storage devices. has a high gravimetric capacitance of 850 F g−1 (1 A g−1) and
In this regard, flexible thin films composed of BiOCl and mul- a specific capacitance of 714 F g−1 at 30 A g−1, representing
tiwalled carbon nanotubes (MWCNTs) on a polyethylene tere- good rate performance. The capacitive retention is higher for
phthalate (PET) substrate with excellent performance under Bi-Bi2O3/CNT than pristine Bi2O3/CNT and Bi2O3 as indicated
different bending angles have been reported by Dutta et al.[174] by Nyquist plots (Figure 13a,b). The benefit of the designed
Flexibility has become a key requirement for modern electronic structure is illustrated in Figure 13c, with contact between the
devices, thus high-performance flexible supercapacitors are in metallic core and CNTs holds facilitating electron transfer from
high demand, requiring researchers to focus on material prop- the CNTs to the metallic core and to the outer Bi2O3 shell. In
erties. In this regard, 2D BiOBr nanosheets with oxygen vacan- another study,[181] various polycrystalline and mesoporous Bi2O3
cies introduced to the system to enhance the interlayer spacing nanostructures have been grown on Ni foam, with a marigold
in layered structures have been shown to exhibit fast charge 3D Bi2O3 negative electrode displaying the highest specific
storage and transfer kinetics.[175] Interestingly, oxygen vacan- capacitance of 447 F g−1 at a current density of 2 A g−1, with
cies introduced to BiOBr nanosheets through hydrogenation an 85% retention even after 5000 redox cycles at 10 A g−1 in an
treatment lead to a considerable increase in capacitance perfor- extremely alkaline 6 m KOH electrolyte solution (Figure 13d).
mance compared with pristine electrodes. BiOBr100 electrodes The presence of interwoven nanoplatelet arrays in the marigold
(reduced at 100 °C) have a substantially greater specific capaci- structure provides channelized meso/macro-spaces that act as
tance of 689 F g−1 at a current density of 0.5 A g−1 due to a large ion-buffering reservoirs, facilitating the percolation of the elec-
number of vacant sites (≈7.8%) compared to pristine electrodes trolyte ions (Figure 13e), which is reflected in the stability of the
(≈6.3%). Another study has highlighted the combination of the asymmetric device fabricated with MnCO3 quantum dot/NiH-
battery-type materials bismuth oxyhalide and bismuth halide Mn-CO3 as the positive electrode (Figure 13f).
for the fabrication of a symmetric pouch-type supercapacitor Although other factors such as electrode–electrolyte interac-
device (with the BiOI/Bi9I2//BiOI/Bi9I2 electrodes acting as the tions have not been discussed with respect to these materials,
anode and cathode, respectively), which delivers an energy den- they have a significant impact on the charge storage properties.
sity of 38.2 Wh kg−1 at a current density of 2 A g−1 and power An appropriate combination of other materials with Bi-based
density of 2280.4 W kg−1.[176] compounds leads to a significant improvement in Li+/Na+
The addition of a transition metal to bismuth ferrite can storage performance, and the same materials can be investi-
improve the specific capacitance. The choice of dopant is gated for supercapacitor applications to understand the pos-
important because elements with multiple oxidation states sible modifications required. Hybrid negative electrodes com-
can enhance the capacitance via faster carrier mobility. For posed of sulfides with other carbon materials have been widely
example, Mn-doped Bi2Fe4O9 has been reported, where the investigated (Table 2), along with several redox-active transi-
amount of the dopant in the Bi2Fe4O9 is controlled by the pre- tion metal oxides, which are beneficial in enhancing reversible
cursor concentration during a low-temperature hydrothermal electron transfer over a wide potential range, a requirement
process. Interestingly, the formation of micro-rectangular par- for high-energy and high-power-density electrochemical
ticles is precursor-dependent, with an optimal concentration of supercapacitors.
Figure 13. a) Specific capacitance with respect to current density; b) Nyquist plots; c) schematic diagram showing the advantages of the core–shell
Bi-Bi2O3/CNT neural network nanostructure; Reproduced with permission.[180] Copyright 2020, Elsevier. e) Schematic diagram showing the hierarchical
marigold structure with presented extension as possible channels; d) Nyquist plots of A–D electrodes (A: coconut shell structure; B: marigold; C;
honey nest cross-section; D: rose morphology) in the 100 kHz to 100 MHz frequency range; f) cyclic stability of the asymmetric device (inset shows
the charge–discharge curves for the 1st and 5000th cycles and a digital image of the lit LED). Reproduced with permission.[181] Copyright 2018, American
Chemical Society.
5.1.3. Hydrogen Production semiconducting materials for the development of composites

and heterojunctions to enhance performance. A wide range of
Hydrogen production using visible-light semiconducting Bi-based compounds, such as metallic bismuth, oxides, oxyhal-
materials has long been an important research topic. There ides,[199,200] chalcogenides,[201] chalcohalides,[202] tungstates,[203]
have been many comprehensive reviews of Bi-based mate- molybdates,[204] perovskites,[205] BiMO4 (M = V and P),[206] and
rials and their prospects for hydrogen production using water other compounds,[207] have been investigated (Table 3). Because
splitting.[24,195–198] The use of Bi-based materials in hydrogen many researchers have already reviewed this topic, only the
production is due to their electronic structure, which favors important recent findings are covered in this section.
the optical absorption of solar radiation, and favorable band Crystal facet engineering via the surface atomic arrangement
position, which allows them to be compatible with other of layered materials such as BiOX (X = Cl, Br, or I) has been
Table 2. Summary of bismuth-based micro- and nanostructured materials, their processing strategy, and their electrochemical properties in superca-
pacitor applications.
Material Processing Morphology Electrolyte Specific Capacitance Stability & % Retention Ref.
BiOCl Soft-chemical route Dimensional (petals) 6 m KOH 379 F g−1 (1.25 A g−1) 80% (5000 cycles) [182]
Bi2O3-Ni-F/graphite Wet-chemical route Nanoflowers 6 m KOH 557 85% (2000 cycles) [183]
Bi2O3/MnCO3QDs/ Soft-chemical route Coconut-shell, marigold, 6 m KOH −1 g−1) 81% (5000 cycles) [181]
447 F g (2 A
NiH–Mn–CO3 honey nest cross-section, and
rose-based nanostructures
Bi2O3 Precipitation Rod-like 6 m KOH 1350 F g−1 2.4% capacitance [184]
declines after
1000 cycles
Bi2O3 Sol-gel Rod-like 6 m KOH 528 F g−1 62.33% (1000 cycles) [185]
Hierarchical rippled Bi2O3 Electrodeposition Nanobelts 1.0 m Na2SO4 250 F g−1 1000 cycles [186]
Bi2O3/AC Precipitation Flowers Li2SO4 and −1 72% [187]
Li2SO4: 29 F g
KI-added Li2SO4 KI-added Li2SO4:
99.5 F g−1
Activated carbon – Bi2O3 Vacuum impregnation Irregular and granular 6 m KOH 332.6 F g−1 59% (1000 cycles) [188]
composite and roasting
Carbon/Bi2O3 composite Microwave Worm-like 6 m KOH 386 F g−1 2% loss after [189]
1000 cycles
BiOI/Bi9I2//BiOI/Bi9I2 Chemical bath Ball-shaped 6 m KOH 122.43 F g−1 90.1% (5000 cycles) [176]
deposition
Bi(OH)3 Solvothermal Nanoflakes 6 m KOH 888 F g−1 90% (1000 cycles) [190]
Bi2S3 Hydrothermal (topo- Hierarchical (nanoflowers) 6 m KOH 233 F g−1 (1 A g−1) 2000 cycles [191]
tactic transformation
process)
Bi-Bi2O3-CNTs Solvothermal and Core–shell (3D neural 6 m KOH 104 F g−1 (1 A g−1) 72.9% (1000 cycles) [180]
annealing auto- network structure)
reduction treatment
Bi2S3 Self-sacrificing template Nanorod-stacked hollow 1 m KOH 532 F g−1 (1 A g−1) 91.0% (3000 cycles) [192]
using solvothermal microtubes
conditions
Bi2S3-rGO Hydrothermal Nanorods 2 m KOH 238 F g−1 (1 A g−1) 100 cycles [193]
Bismuth oxide–nitrogen- Solvothermal and Hollow and porous hierarchal 3 m KOH 1046 F g−1 (1 A g−1) 83.5% (1500 cycles) [194]
doped carbon dots calcination architecture
a)
dimethoxyethane; b)SIB: sodium-ion battery; c)EC: ethylene carbonate; DMC: dimethyl carbonate; d)
Potassium bis(fluorosulfonyl)imide (KFSI) in monoglyme (DME);
e)
LIB: lithium-ion battery; f)KIB: K-ion battery; g)DEC: diethyl carbonate.
proven to be an effective strategy to improve heterogeneous to improve the carrier dynamics by allowing the carrier to remain
photocatalysis despite a lack of consensus over its intrinsic pho- for longer in the system with interfacial separation.[208] Similar
toreactivity. Both the hydrogen and oxygen evolution reactions defect tailoring has also been reported for a Bi3O4Br system.[209]
are observed to be superior with (001) exposed BiOBr when In addition, in a bismuth chalcohalide system, the effect of the
compared with the (010) plane. In situ photoreduction (with halogen on the H2 evolution properties of Bi19X3S27 (X = Cl and
Pt and Au) and oxidation (MnOx from Mn2+) reactions on the Br) has been reported by Chen et al.[202] For the hydrogen evo-
(001) surface of BiOBr have been conducted, showing that lution reaction, Bi19Br3S27 (466.7 µmol g−1h−1) exhibits a higher
photogenerated holes are available for oxidation on the (001) evolution rate than Bi19Cl3S27 (195.1 µmol g−1h−1). This is attrib-
facet, whereas the photogenerated electrons undergo selective uted to the influence of the halogen atom, with an increase in
accumulation on the lateral (110) and (200) facets. Similar phe- the halogen content increasing the PC activity. However, the
nomena have been observed for (010) BiOBr, in which the rep- optimized Bi19Br3S27 sample prepared at 200 °C contains traces
resentative lateral (102) facet is involved in the photoreduction of metallic Bi, which introduces sulfur vacancies to the system
process. These studies also reveal that spatial separation occurs but does not consume the photogenerated electrons. Thus,
between the lateral and dominant facets in the system, hin- there is no shielding effect in the optimized Bi19Br3S27 sample
dering the recombination process, as supported by theoretical favoring the production of photogenerated electrons and holes
studies.[200] Introducing oxygen vacancies via the amorphization to participate in the reaction.[202] It is worth mentioning that the
of the BiOCl surface to enhance the charge carrier dynamics for effect of halogens on changes in the electronic band structure
efficient PC water oxidation has also been introduced (Figure 14) has not yet been fully discussed.
Table 3. Summary of Bi-based micro- and nanostructured materials, their processing strategy, and their catalytic properties in hydrogen production.
Catalyst Material Processing Morphology Light Source Activity Test Conditions Ref.
2D/3D g-C3N4/BiO1.2I0.6 Dispersion/heating Flowers 500 W Xe lamp 1402.7 µmol g−1 h−1 50 mg photocatalyst, [211]
λ > 420 nm
ZnmIn2S3+m + BiVO4 Hydrothermal Nanosheets 300 W xenon lamp 842 µmol g−1 h−1 0.1 g photocatalyst, [212]
λ > 420 nm
TiO2/C//Bi2WO6/C Electrospinning/ Nanofibers Labsolar-IIIAG 11 580 µmol g−1 h−1 0.1 g photocatalyst, [213]
calcination λ > 420 nm
Hierarchical Bi2WO6 Hydrothermal Peony flower-like Xe arc lamp (Osram 7400 µmol g−1 h−1 0.1 g photocatalyst, [214]
morphology XBO 300 W) λ > 420 nm
Bi2WO6/BP Hydrothermal - - 21 042 µmol g−1 h−1 λ > 420 nm [215]
Bi2MoO6/RGO a)
In situ solvothermal Nanofibers - 794.72 µmol g−1 h−1 λ > 420 nm [216]
−1 −1
Ag/Bi2WO6 microspheres Solvothermal and Microspheres 300 W Xenon lamp < 40 µmol g h 50 mg catalyst, [217]
photoreduction with λ < 420 nm
[C4-mim] BF4 ionic liquid
Ag-doped Bi2WO6-GO Solvothermal Agglomerated 300 W high-pressure 78 µmol g−1 h−1 0.05 g photocatalyst, [218]
nanoparticles mercury lamp λ > 420 nm
Hierarchical BiVO4/RGO Hydrothermal and Graphene sheets deco- 200 W Hg-Xe arc 11.5 µmol g−1 h−1 50 mg photocatalyst, [219]
precipitation rated by BiVO4 plates lamp λ > 420 nm
SrTiO3: La, Rh/Au/BiVO4: Mo Deposition - - 4750 µmol h−1 g−1 λ > 420 nm [220]
−1 −1
TiO2/BiVO4 Screen printing Nanospheres 500 W halogen lamp 173 µmol h g TiO2 loadings of 0.1, [221]
100 mW cm−2 0.8 and 1.2 wt.%
on BiVO4 thin film,
λ > 420 nm
RGO/Bi2WO6 Electrospinning, Nanofibers Xenon lamp (300 W, 935 µmol h−1 g−1 0.1 g photocatalyst, [222]
calcination PLS-SXE300/300UV λ > 380 nm
CdS/Bi2WO6 Hydrothermal Square-shaped 300 W Xenon arc 1223 µmol h−1 g−1 20 mg photocatalyst, [223]
nanosheets lamp λ > 420 nm
Fe3O4@SiO2@Bi2WO6@g-C3N4 Hydrothermal Spheres Labsolar-III (AG) 1276 µmol h−1 g−1 100 mg photocatalyst, [224]
λ > 420 nm
Bi2Ti2O7/g-C3N4/Bi4Ti3O12 Electrospinning Nanorods 300 W Xeon lamp 638 µmol h−1 g−1 100 mg photocatalyst, [225]
λ > 420 nm
a)
RGO: reduced graphene oxide.
Figure 14. Schematic representation of the photoinduced kinetics of surface-amorphized p-BiOCl and surface-crystallized c-BiOCl catalysts. Repro-
duced with permission.[208] Copyright 2021, American Chemical Society.
Although noble-metal-mediated charge transfer systems sulfite treatment of BiVO4 has been conducted to induce sur-
exhibit higher performance, despite the expected separa- face oxygen vacancies and disorder to enhance the interfacial
tion and transport, significant recombination occurs at the charge transfer efficiency.[230] The calculated ABPE is 0.27%,
interface, restricting their efficiency.[201] A binary composite which is lower than previous reports. In addition, the photo-
with Bi2O2CO3 and g-C3N4 has been constructed, exhib- current density is enhanced to 2.8 mA cm−2 (from 2.2 mA cm−2
iting a Z-scheme mechanism related to charge transport and for S-BiVO4) following coating with amorphous FeOOH. This
separation for efficient H2 production (965 µmol g−1h−1).[207] study also points out that, if the surface oxygen vacancies
Z-scheme-based Bi2O3/Bi2MoO6 produces the lowest perfor- are in excess, they can serve as recombination centers. Fol-
mance of 52 µmol g−1 under visible-light irradiation, which is lowing the addition of oxygen evolution co-catalysts FeOOH/
ascribed to the optical absorption properties of the semicon- NiOOH[231] and FeCoOx,[227] the maximum photocurrent density
ducting materials and the charge separation efficiency and has been reported to be 5.13 and 4.82 mA cm−2, respectively.
availability of photogenerated electrons for the hydrogen evolu- In the former system, the photocurrent density increases to
tion reaction.[204] 5.87 mA cm−2 at 1.23 V versus RHE using dual photoanodes,
A layered perovskite oxyhalide system (Bi4MO8X, M = Nb while unbiased photoelectrochemical water-splitting using a
and Ta; X = Cl and Br) has been formed using the oxyhalides tandem cell leads to a solar-to-hydrogen (STH) efficiency of
of bismuth, which are compared in terms of their PC H2 pro- 6.5%. Oxygen vacancies play a crucial role in both of these sys-
duction ability. Comparing Nb and Ta, Bi4NbO8Br exhibits tems. When the FeOOH/NiOOH cocatalyst is used, the oxygen
the highest performance for H2 production in the presence vacancies act as shallow donors, whereas, with the FeCoOx co-
of glycerol as a sacrificial agent. This enhanced activity in catalyst, p-n heterojunction formation with BiVO4 occurs due
the system is ascribed to the low standard oxidation poten- to the Fe in the CoOx generating oxygen vacancies, promoting
tial due to the lower twisting degree of the [Bi2O2]2+ structure hole trapping and transport.
along with the α-OH groups responsible for the photocarrier Tuning the work function with doping is another strategy
mobility of Bi4NbO8Br.[210] Recently, atomic rearrangements used to reduce the interfacial energy loss and increase the open
on the surface of 2D Bi2WO6 have been carried out to enhance circuit photovoltage for BiVO4. Moderately Mo-doped BiVO4
H2 production on the catalyst surface.[203] Bilayered Bi2O2 with a cliff-like junction has been achieved using B-doped
is sandwiched between alternating layers of WO4, with the C3N4 to enhance the interfacial charge transfer.[232] The work
bilayer terminated and easily functionalized by switching the function (0.1% Mo in BiVO4) is adjusted in such a way that
surface oxygen atoms via the in situ grafting of halogen atoms the Fermi level is far from the conduction band minimum
(Cl and Br). The change from BiO to BiCl/Br shifts the (CBM) under light-off conditions, producing low open circuit
valence band maxima, narrows the bandgap, and reduces the voltage (OCV) in the dark. However, the quasi-Fermi level posi-
recombination rate. The hydrogen generation efficiency is tion shifts near to the CBM to produce a high OCV, which is
≈56.9 µmol g−1h−1 under simulated solar light, but this is still favorable for the oxidation of water, a process that is governed
not comparable to individual chalcohalides or heterojunction by the quasi-Fermi level of the junction and the redox potential
systems. of the electrolyte (Figure 15). The light-harvesting ability of the
system is further enhanced when NiFeOx is introduced as an
OEC, producing 5.93 mA cm−2 at 1.23 V versus RHE with an
5.1.4. Water Splitting ABPE of up to 2.67% at 0.54 V versus RHE, claimed to be the
highest reported to date.
The modification of the electrode–electrolyte interface to Tailoring the conductivity through domain boundary trans-
enhance their interaction while overcoming the rate-limiting port has also been reported in BiVO4 photoanodes, with a com-
step (the four-electron process) has become a bottleneck for parison between the carrier transportation of an epitaxially
water-splitting research. BiVO4 has been reported to be an grown single domain and oriented multi-domain BiVO4.[233]
ideal photoanode, and it has been subject to multiple modifi- The vertical domain boundaries in multidomain BiVO4 films
cations.[226,227] In addition to BiVO4, comprehensive reviews of exhibit high electrical conductivity, resembling free-carrier
various Bi-based compounds, such as oxyhalides, tungstate, transport behavior. The vertical domains are responsible for
molybdates, ferrites, and CuBi2O4, have been reported in the channeling electron transport via diffusion to the domain
literature.[228,229] Surface modification of BiVO4 via doping boundary region, reducing the difference in the photocurrent
and oxygen evolution co-catalyst decoration are the most wide- under front and back illumination. Oxygen vacancy modula-
spread strategies used to enhance water oxidation reaction tion in BiVO4 has also been carried out through bismuthene
performance. For example, α-FeOOH has been recently immo- loading onto BiVO4 photoanodes, boosting oxygen evolution via
bilized on a BiVO4 photoanode to deliver a Faradaic efficiency oxy-/hydroxyl intermediate formation via NiFeOOH.[234] Interfa-
(FE) of 92% with an applied bias photon-to-current efficiency cial band bending is promoted due to bismuthene, which fills
(ABPE) of 0.59%, which is 21 times higher than that observed the vacant electron-trapping sites. The composite photoanode
for a bare BiVO4 photoanode, and a photocurrent density of delivers a 5.8-fold increase in the photocurrent compared with
2.64 mA cm−2 at 1.23 V versus RHE is achieved.[226] The crys- a bare BiVO4 photoanode. Single and double heterojunctions
talline α-FeOOH promotes hole trapping and migration at the with BiVO4 have also been constructed with other favorable
material interface after being reduced to Fe2+ via electrons from semiconducting materials and band positions, such as WO3,[235]
H2O, producing O2. In addition, photo-holes can easily regen- MoS2,[236] g-C3N4,[237] Cu3Mo2O9,[238] BiFeO3,[239] Cu2ZnSnS4
erate Fe3+ from Fe2+ to initiate the reduction process. Similarly, (CZTS),[240] and others.[241,242]
Figure 15. a) Band structures and band-bending diagrams for BiVO4, 0.05% Mo-BiVO4, 0.1% Mo-BiVO4, and 0.5% Mo-BiVO4. b) Probable band struc-
tures for 1) C3N4/Mo-BiVO4 and 2) B-C3N4/Mo-BiVO4. Reproduced with permission.[232] Copyright 2019, Nature Portfolio.
Table 4 highlights the Bi materials and their photoelectro- the DNA-modified system. However, evidence for this surface
chemical properties for use in water-splitting applications. In state generation is qualitative only (via diffusion spectroscopy),
all of these studies, the main aim was to achieve charge injec- without any quantitative support. Although the current density
tion and separation through heterojunctions to efficiently use increases fivefold with an ABPE of 25.22 × 10−4% for Bi2WO6-
photogenerated holes and electrons in the water-splitting pro- DNA-2, this is significantly lower than previously reported
cess. In a recent report, CZTS is combined with BiVO4 as a BiVO4 photoanodes.
photocathode in a tandem cell to achieve an STH conversion Poor charge separation and transport have been a bottle-
efficiency of 3.17% with extremely high stability of over 60 h.[240] neck for many semiconducting Bi-based compounds, which
In addition to factors such as photocurrent density, ABPE, can be overcome by coupling the material with carbon mate-
and STH conversion efficiency in photoelectrochemical sys- rials, such as graphene or CNTs. In this context, a Bi2S3@rGO
tems, the stability of the photoanode is crucial for long-term composite photoanode system was reported by Subramanyam
sustainability. et al., in which a high photocurrent density of 6.06 mA cm−2 at
With BiVO4 being explicitly used for photoelectrochemical 1.23 V versus RHE is achieved, exhibiting an ABPE of 4.2% at
water splitting, Bi2WO6 using deoxyribonucleic acid (DNA) 0.32 V.[244] A type-II heterojunction with BiOI and g-C3N4 has
modification has been reported as an advanced approach.[243] also been reported for this purpose, in which the photocurrent
In doing so, it is claimed that new surface states with a mid- density observed is 25 µA cm−2 with an ABPE of 4.9 × 10−3,
gap energy band are formed, facilitating electron transport in lower than those obtained for pristine BiVO4 samples reported
Table 4. Summary of Bi-based micro- and nanostructured materials, their processing strategy, and their catalytic properties in water splitting.
Catalysts Morphology Processing Light Source Current Density Stability Ref.

α-FeOOH/BiVO4 Ultrathin Chemical bath deposition 300 W Xe lamp 2.64 mA cm−2 at 1.23 V 20 h at 0.9 V [226]
nanolayers versus RHE versus RHE
FeCoOx/BiVO4 Ultrasmall Electrodeposition and 150 W Xe lamp 4.82 mA cm−2 at 1.23 V 10 h [227]
nanoparticles calcination versus RHE
Oxygen-vacant BiVO4 Nanoplates Electrodeposition and sulfite 300 W Xe lamp 2.2 mA cm−2 at 1.23 V 5h [230]
treatment versus RHE
NiFeOx/B-C3N4/Mo-BiVO4 Nanoporous Electrodeposition 1000 W Xe lamp 3.85 mA cm−2 at 0.54 V 10 h at 0.54 V [232]
particles versus RHE versus RHE
BiVO4 films Films Pulsed laser deposition 300 W Xe lamp Jback = 0.72 mA cm−2 at - [233]
1.23 VRHE
DNA-mediated Bi2WO6 Interconnected Solution precipitation 1000 W m−2 0.013 mA cm−2 2h [243]
chains
Bi2S3@rGO Nanoparticles Sonication 150 W Xe lamp 6.06 mA cm−2 at 0.32 V 90 min [244]
in rGO sheets
g-C3N4/BiOI Microspheres Pyrolysis and hydrothermal 100 mW cm−2 2.3 ± 0.1 mA cm−2 at 100 min at 1.23 V [245]
1.23 V versus RHE versus RHE
BiFeO3/SrRuO3 Films Pulsed laser deposition 100 mW cm−2 −0.47 × 10−5 A cm−2 at 1 h at −0.4 V [246]
−0.4 V
Charged domain walled Bi2WO6 Films Pulsed laser deposition 500 W Xe lamp 0.175 mA cm−2 at 500 s [247]
1.23 V versus RHE
TiO2/Bi2Se3 Nanoparticles Hydrothermal, doctor blading, 150 W Xe lamp 1.76 mA cm−2 at 1.23 V 6h [248]
Nanoflowers drop casting versus RHE
β-Bi2O3/PbS Nanoparticles Electrodeposition and - 0.65 mA cm−2 at 1.35 V 2h [249]
Nanoflakes successive ionic layer
adsorption and reaction (SILAR)
Bi2MoO6@Bi2Mo2O9 Agglomerated SILAR 100 mW cm−2 0.160 mA cm−2 at 1 h at 1.23 V [250]
particles 1.23 V versus RHE versus RHE
in the literature.[245] Energy band-gap modulation has also been Mixing it with other small-bandgap semiconductors to form
reported using an Nd-doped BiFeO3/SrRuO3 heteroepitaxial heterojunctions, such as Ag2O/Bi2O2CO3, BiVO4/Bi2O2CO3,
system, with the charge transfer controlled via the multifer- and N-BOC/GQDs, is a technique, along with doping and
roic–metal and multiferroic–electrolyte interfaces.[246] In a sim- exposing facets,[253–257] that can improve photo-induced carrier
ilar way, single-crystalline epitaxial ferroelectric Bi2WO6 thin separation to some extent (Table 5A). However, this approach
films have also been tuned for in-plane charge polarization and has no effect on the intrinsic properties of Bi2O2CO3, thus there
charge transport and separation.[247] is a need to upgrade the intrinsic PC efficiency of Bi2O2CO3
in a clear and environmentally friendly manner. Its efficacy
has been enhanced via electron–hole separation in Bi2O2CO3
5.2. Environment Restoration microspheres via acid treatment for the PC degradation of
HCHO gas and methyl orange (MO) under irradiation with vis-
5.2.1. Organic Pollutant Removal ible light (λ ≥420 nm).[258] BOC-200 microspheres (19.9 cm2 g−1)
have a size of ≈1.5 µm with a lattice spacing of 0.685 nm, corre-
As reported in ref. [251], the inclusion of a calcium dopant in sponding to the (002) facet of tetragonal Bi2O2CO3, with diffrac-
Bi2O3 and the formation of functional NPs with a nominal tion rings centered at (123), (110), (002), and (011) (Figure 16a,b).
size of 15 nm, prepared via single-step flame spray synthesis Compared with pristine BOC (35% MO degradation), acid-
(FSS), improve the specific surface area (SSA) of the material treated BOC-200 under solar irradiation leads to the rapid deg-
(≈41 m2 g−1), which enhances the degradation of methylene radation of MO, reaching 98% after 180 min. This is ascribed
blue (MB, 0.15 g catalyst; MBconc = 5 × 10−5 m, Vtot = 100 mL), a to the generation of ·OH radicals during PC degradation that
potential aqueous pollutant. The oxidized surface of CaBi2O4–x oxidizes the organic pollutant into CO2 and H2O (Figure 16d,e).
is mainly responsible for the direct PC effect due to sub-stoichi- The enhanced PC performance can also be attributed to surface
ometric oxygen. The combination of both a high surface area defects and caverns, which narrow the bandgap, thus expanding
and excellent crystallinity is needed for enhanced PC activity. the absorption in the visible-light region and increasing the
In addition, a bismuth subcarbonate (Bi2O2CO3) layered struc- radiative lifetime of BOC (Figure 16c).[258]
ture has gained interest for environmental remediation, with a Similarly, Bi impregnation in biochar aids controls the
wide bandgap of 3.1–3.5 eV that can only harvest UV light.[252] accumulation of permanent free radicals (PFRs) and the
Table 5. Summary of Bi-based micro- and nanostructured materials, their processing, and their catalytic/non-catalytic properties in A) organic pol-
lutant and B) metal-ion removal.
(A) BISMUTH MATERIALS FOR ORGANIC POLLUTANT REMOVAL

Catalyst Morphology Processing Light Source Pollutant Concentration % Removal Ref.
Bi2O2CO3/graphene Nanosheets Precipitation, UV light NO gas dry air 50% in 30 min [255]
hydrothermal (2.0 L min−1) mixed with
NO (12.0 mL min−1)
Cl-doped Bi2O2CO3 Nanosheets Ionic liquid-assisted 300 W Xe lamp Rhodamine B 100% in 20 min [256]
solvothermal 10 mg L−1
Br-doped Bi2O2CO3 Microplates Hydrothermal 500 W Xe lamp Methyl orange 100% in 12 min [257]
Rhodamine B 100% in 15 min
10 mg L−1
Biochar-Bi/Bi2O3 Hierarchical porous Impregnation, 500 W Xe lamp Estrone 94.9% in 60 min [259]
composite structure pyrolysis 10.4 µmol L−1
0D Bi nanodots on 1D Sub-microwires Molten salt-assisted 5 W white LED Tetracycline 98% in 6 h [260]
Bi6Mo2O15 synthesis 10 mg L−1
Ag2O/Bi5O7I Microspheres Solvothermal, 5 W white LED Bisphenol A 80.5% within 60 min at [264]
precipitation 20 mg L−1 940 nm
Bi5O7I-MoO3 Irregular nanosheets Precursor calcination 12 W LED Ibuprofen 89.2% in 120 min [265]
15 mg L−1
BiOCl/Cu-doped Bi2S3 Plate morphology Hydrothermal 300 W Xe lamp Norfloxacin 88.3% [266]
composites Ofloxacin 100%
Ciprofloxacin 95.2% in 30 min
20 mg L−1
Bi2S3/Bi4O5Br2 3D flower spheres Solvothermal 350 W Xe lamp Ciprofloxacin 86.5% [267]
10 mg L−1 92.7%
Tectracycline in 60 min
20 mg L−1
Bi2S3/BiFeO3 Nanofibers Electrospinning and in 300 W Xe lamp Tetracycline 74% in 120 min [268]
situ anion exchange hydrochloride
20 mg L−1
Cu2O/Bi2S3 Nanoparticles on Solution precipitation 200 W Hg lamp Tetracycline 95% in 60 min [269]
nanorods and hydrothermal 20 mg L−1
Bi2Se3/g-C3N4 Particles on In situ photo-reduction 60 W LED Phenol ≈70% in 180 min [270]
nanosheets and Se thermal vapor 100 mg L−1
treatment
Bi2S3/Bi2O2CO3 Fibers in a disc In situ sulfurized 150 W Xe lamp Tetracycline 98% in 120 min [271]
structure hydrothermal hydrochloride
20 mg L−1
Bi2MoO6/GQDs/MoS2 Hierarchical flowers Hydrothermal, 150 W Xe lamp Ofloxacin 99.5% in 100 min [272]
with quantum dots suspension 10 mg L−1
(B) BISMUTH MATERIALS FOR METAL-ION REMOVAL
Catalyst Morphology Processing Metal Ion Concentration Removal Ref.
Bi2O2.33 Flowers from nanosheets Solvothermal Iodine 285 mg g−1 and 229 mg g−1 for [273]
20 mg L−1 I− and I(V)
Hydrous bismuth - Precipitation Nitrate 1.4 mg N g−1 [274]
oxides 1 meq l−1 ( = 14 mg N l−1)
Bi-activated carbon Small white globular particles Carbonization Phosphate, chromium, 125.40 mg g−1 [275]
biochar and arsenic at 300, 10, and 12.23 mg g−1
20 mg L−1, respectively 16.21 mg g−1
Hollow Bi Nanospheres Solvothermal Cr(VI) 17.5 mg g−1 at pH 2 [276]
nanospheres 40 mg L−1
Cellulose-coated tita- Membrane Alkaline hydrothermal Cs+, I−, Cu2+, SeO42−, Pb2+, 125.4, 225.9, 136.1, 85.1, 421.1, [277]
nate bismuth oxide treatment SeO32−, Sr2+, and Br− 204.5, 81.4, and 89.6 g g−1
Bi2MoO6/GQDs/MoS2 Hierarchical flowers with Hydrothermal, suspension Cr(VI) 99.9% in 60 min in visible [272]
quantum dots light
Table 5. Continued
(B) BISMUTH MATERIALS FOR METAL-ION REMOVAL

Catalyst Morphology Processing Metal Ion Concentration Removal Ref.
Bi2S3/Bi2O2CO3 Fibers in a disc structure In situ sulfurized Cr(VI) 99% in 90 min in visible light [13]
hydrothermal
BiOI/Bi5O7I Flower morphology Solution, precipitation Hg0 gas 60% in 120 min visible light [278]
(9 W LED)
BiOI/MoS2 Flaky nanoparticles Hydrothermal Hg0 gas 58% in 120 min visible light [279]
(9 W LED)
Magnetic Quasi-spherical particles Hydrothermal Cu(II) 181.8 mg g−1 [280]
chitosan@Ag/Bi2WO6 500 W Xe lamp
development of a hierarchical porous structure in the biochar edge, the spontaneous flow of electrons to the metal Bi sites
(micropores, <2 nm).[259] Under neutral conditions, the pres- occurs. The photo-excited electrons react with O2, producing
ence of biochar aids in the pre-concentration of estrone on O2 radicals. At the same time, the h+ begins to react with H2O,
BiPB and increases the separation and transport of the charge forming OH radicals.[260]
carriers. The collaborative influence of biochar and Bi/Bi2O3 Bi2O3/Bi4Ti3O12/TiO2 double-heterostructured TiO2 nano-
leads to the production of ·OH radicals for the degradation of belts exhibit superior UV light PC efficiency than commercial
estrone. In this process, holes (h+), electrons (e−), and ROS (·O2 P25.[262] The double Bi2O3/Bi4Ti3O12/TiO2 -heterostructure
and ·OH) can be produced in the biochar-supported Bi/Bi2O3 forms on the TiO2 nanobelt surface, extending the optical
system under UV–vis light irradiation (Equations (4)–(11)). absorption of the nanobelts in the visible light region. These
Bi2O3/Bi4Ti3O12/TiO2 nanobelts significantly increase PC
biochar + hv → biochar + + biochar ( e − ) (4) activity. After 5 min, ≈95% of MO is decomposed and, after
30 min of UV light illumination, 100% of the MO is decom-
posed. The irradiation time, Bi2O3/TiO2 weight ratio, and
biochar ( e − ) + O2 → ⋅O2− (5) annealing temperature also influence PC performance. The
excellent MO PC efficiency observed under both UV and vis-
(Bi 2O3 /Bi ) + hv → Bi ( h + + e − ) (6) ible light irradiation is the result of the large number of active
sites arising from the larger surface area of the nanobelts
(47.02 m2 g−1). The photoinduced holes flow into the valence
Bi ( e − ) + O2 → ⋅O2− (7)
band of the Bi4Ti3O12 layer, while the electrons flow into the
TiO2 and Bi2O3 conduction bands. The photogenerated elec-
⋅O2− + H+ → HO2 ⋅ (8) trons also aggregate in the conduction band of Bi2O3 and com-
bine with the adsorbed oxygen molecules to create superoxide
2HO2 ⋅ → H2 O2 + O2 (9) radicals. The hydroperoxy (HO2·) radical is formed via proto-
nation, which then produces ·OH. It is claimed that the sym-
metric orthorhombic layer of (Bi2O2)2+ and (Bi2Ti3O10)2− forms
H2 O2 + ⋅O2− → OH− + O2 + ⋅OH (10)
two layers that distinguish the electron–hole pairs (Figure 16h).
As a result, the effective electron–hole separation increases
Bi ( h ) + H2 O → ⋅OH + OH−
+
(11) the charge carrier lifespan and improves the PC activity of the
Bi2O3/Bi4Ti3O12/TiO2 double-heterostructured nanobelts.[262]
The rich oxygen vacancies in 1D bismuth molybdate However, these nanobelts are unstable when repeatedly exposed
(Bi6Mo2O15) sub-microwires (B-BMO) that support 0D Bi nano- to UV and visible light, which limits their application.
dots[260] and bismuth molybdate nanosheets[261] boost PC per- In a recent study, 2D bismuthene nanosheets are fabricated
formance under visible light illumination due to the high ionic via the cathodic exfoliation of bulk Bi, which is then trans-
conductivity of the developed systems. The surface plasmon formed into 2D Bi2O2CO3 nanosheets under room conditions
resonance from the Bi quantum dots and the oxygen vacan- for a week in the presence of tetraethylammonium hexafluo-
cies in the B-BMO deliver high ionic conductivity (Figure 16f), rophosphate (TEA+).[263] The electrolyte used for exfoliation has
resulting in excellent PC performance for the degradation of a significant effect on the time required for atmosphere oxida-
tetracycline (TC). Approximately 3% B-BMO produces a max- tion; with tetramethylammonium hexafluorophosphate (TMA+)
imum PC efficiency of 98%, which is significantly higher than and tetraheptylammonium bromide (TBA), the oxidation time
that of pristine Bi6Mo2O15, which only exhibits a degradation of is 20 d and a month, respectively. The 2D Bi2O2CO3 exhibited
13.4%. TC degradation can be attributed to the electrons in the high degradation activity against the antibiotic ciprofloxacin.
valence band of Bi6Mo2O15 being excited to the defect level, fol- The wide bandgap of BiOCl exhibits strong PC activity when
lowed by some of the electrons in the defect level being directly exposed to UV light (3.2 eV). BiOI also exhibits considerable
excited to the conduction band of Bi6Mo2O15. Because Bi has a visible light absorption due to its low bandgap energy. BiOBr
higher positive Fermi level than the Bi6Mo2O15 conduction band also exhibits PC reduction and oxidation activity when exposed
Figure 16. a) SEM images of BOC-200. b) SAED image of BOC-200. c) Scheme for the formation of oxygen vacancies. PC degradation of methyl orange
d) at different times at pH 7 and e) in the presence of different scavengers. Reproduced with permisison.[258] Copyright 2018, Wiley-VCH. f) Schematic
representation of the B-BMO structure. Reproduced with permission.[260] Copyright 2021, Elsevier. g) PC performance of the different samples for the
degradation of TC. Reproduced with permission.[260] Copyright 2021, Elsevier. h) Schematic representation of charge carrier separation under UV (h-a)
and visible light (h-b) irradiation in the band structure of double-heterojunctioned Bi2O3/Bi4Ti3O12/TiO2. Reproduced with permission.[262] Copyright
2012, Royal Society of Chemistry.
to visible light. The redox ability for converting oxygen into IO3−) of 285 and 229 mg g−1, respectively over wide pH range.
superoxide radicals (·O2−) and hydrogen into h+ is critical for The iodine selectivity was attributed to the adsorption-induced
excellent photocatalysts. At pH 7, O2/·O2− has a redox poten- chemical reaction and flower-like Bi2O2.33 micro- and nano-
tial of −0.33 V/SHE, while OH−/OH has a redox potential of structure.[273] Hydrous Bi2O3 can also be used to remove nitrate,
2.3 V/SHE. It is extremely difficult for BiOI to reach these with a maximum adsorption capacity of 1.4 mg N g−1, with ion
redox potentials with its small bandgap (≈1.77 eV), but BiOCl exchange between chloride and the nitrate ions responsible
(≈3.22 eV) and BiOBr (≈2.64 eV) can meet these require- for the removal of nitrate.[274] Arsenic, phosphorus, and chro-
ments.[281] Enriching semiconductor photocatalysts with Bi mium adsorption has also been studied using Bi-impregnated
and O increases the valence band edge and decreases the con- biochar.[275] Bi particles were found to improve the microporous
duction band edge. This significant improvement in the band structure (2.00 nm) and boost the SSA of biochar by producing
edges of BiOX improves PC activity. Superoxide anions have very small white globular particles. The loaded Bi acts as an
been identified as the primary active species in the degradation adsorption site rather than the real surface area, which is cru-
process. Interestingly, Xiao and Zang[282] use a basic displace- cial for arsenic and phosphorus adsorption. This study suggests
ment method to produce various Bi-rich BiOX visible-light pho- that, based on X-ray photoelectron spectroscopy, the arsenic
tocatalysts (Bi3O4Cl, Bi12O15Cl6, Bi24O31Cl10, Bi4O5Br2, Bi12O17Cl2, adsorption process may be due to the Lewis acid–base reaction
Bi3O4Br, Bi24O31Br10, Bi5O7I Bi7O9I3, and Bi4O5I2). After 4 h of between the Bi atoms and arsenate. Phosphorus sorption can
visible-light irradiation, the obtained Bi-rich Bi7O9I3 photocata- be attributed to the Bi atoms on the activated carbon surface
lyst degraded 94% of bisphenol. The stronger oxidation power acting as sorption sites, which are hydroxylated under acidic
of Bi7O9I3 is attributed to its more positive upper valence band, conditions, resulting in the formation of BiPO4. However, no
which resulted in greater PC efficiency. Ye et al.[283] also use evidence is presented verifying the influence of Bi during the
MnOx as a co-catalyst to develop MnOx/BiOI composites for chromium reduction and adsorption processes. Thus, con-
the PC degradation of rhodamine B, with the best performance vincing evidence that Bi plays a major role in the adsorption of
observed for 1.0% MnOx. arsenic and phosphorous remains to be shown.
Bismuth oxyhalides, especially Bi5O7I, have attracted more Furthermore, hollow Bi nanospheres have also been devel-
interest than other family members due to their excellent vis- oped for the efficient removal of Cr(VI).[276] Large-scale hollow
ible light response. Existing (Bi6p + I5p + O2p) orbitals lack I Bi nanospheres (average diameter, ≈240 nm) are synthesized
atoms, and their high thermodynamic stability leads to higher via a facile template-free solvothermal method, but the use of
PC activity. Furthermore, with an optical bandgap energy of ethylene glycol and polyvinylpyrrolidone can influence their
≈2.70–2.97 eV,[284–286] this n-type semiconductor has a larger size and SSA. The study suggests that the template-free syn-
positive valence band than BiOI, which is due to the incorpo- thesis information is deceptive. Overall, chromium removal is
ration of an extra I5p orbital in the valence band. The positive found to be mildly effective (17.5 mg g−1 Cr(VI)) in a pH range
valence band edge is vital for the oxidation of organic com- of 2–11, but the Cr(VI) adsorption process is not significant and
pounds via photogenerated holes.[264] A Z-scheme constructed the interpretation of the results remains unclear. In addition,
from the synchronized calcination of both BiOI and MoS2 pre- the reported chromium removal method ignores Bi chemistry
cursors generates Bi5O7I-MoO3, which increases the degrada- and aqueous stability. Furthermore, the efficacy of titanate-
tion of ibuprofen under visible-light irradiation.[265] The degra- Bi2O3 has been studied using oily water. A flexible membrane
dation efficiency for 15 mg L−1 ibuprofen is ≈89.2% due to the composed of layered nano-cellulose hydrogel coated on titanate-
separation of the charge carriers for the generation of hydroxyl Bi2O3 (CH-TBM) is developed for sewage treatment. It is
and superoxide radicals. Even though significant advances in claimed that the organization of carboxyl/hydroxyl groups on
the PC performance of bismuth oxyhalides have been reported, the cellulose, the layered titanate nanofibers, and the occupancy
further improvement is still needed. Most importantly, bismuth of oxygen vacancies in the Bi2O3 create a synergistic effect for
oxyhalide fabrication should focus on direct Z-schemes with sewage treatment.[277] In addition to its controllable structure,
the enhanced separation of photogenerated electron and hole CH-TBM has a strong acid and alkali adaptation range, is recy-
pairs compared with type-II photocatalysts, while large-scale clable, and has a simple post-processing system. On the other
practical applications and their recovery from the reaction mix- hand, anion occupancy occurs in the oxygen holes of δ-Bi2O3,
ture also need to be addressed. leading to the formation of irreversible compounds (Figure 17).
In addition, membrane selectivity and re-usability are still chal-
lenging for the simultaneous treatment of multivariate ions.
5.2.2. Metal Ion Removal Addressing these difficulties and ensuring the commercial
viability of real-time operation will lead to a breakthrough for
The removal of metal ions using bismuth can occur through large-scale water treatment processes.
either sorptive treatment or catalytic reduction with photo- The photoreduction of metal ions such as chromium[271,272]
catalysts (Table 5B). However, only a few Bi-based compounds and mercury[278,279] using Bi-based materials has been widely
have been identified to have adsorptive/ion exchange proper- reported, with few reports for other metal ions.[280] For example,
ties for metal ion removal from aqueous solutions, whereas PC oxidative reduction of hexavalent chromium has been
PC reduction processes are commonly used. The sorption of reported with single (BiOl) and composite systems.[272,287,288]
iodine has been reported for Bi2O3 synthesized using a solvo- BiOI has been modified via variation in the calcination tem-
thermal route, with a maximum adsorption capacity for uni- perature, resulting in the formation of Bi4O5I2 and Bi5O7I at
valent iodine ions (I−) and quinquevalent iodine ions (I(V) or 450 and 490 °C, respectively. The Cr(VI) uptake is highest with
Figure 17. Representative mechanisms for cation and anion co-capture using CH-TBM. Reproduced with permission.[277] Copyright 2018, Elsevier.
Bi4O5I2, and 88.9% of Cr(VI) is photoreduced in 40 min under oxygen generated in the system is responsible for the higher
visible light.[288] Z-scheme binary and ternary composite hetero- oxidative PC activity.[279] The same research group has prepared
junctions with Bi-based photocatalysts have also met with suc- other PC heterojunctions for BiOI/Bi5O7I in the gas phase oxi-
cess. For instance, a topotactically transformed Bi2S3/Bi2O2CO3 dation of zerovalent mercury. In this study, pH adjustment is
photocatalyst system has been developed for Cr(VI) reduction, used to form the catalyst system, with BiOI/Bi5O7I produced at
producing a highest rate constant of 3.7 × 10−2 min−1, 9.3 and pH 10, delivering the highest PC oxidation of gaseous mercury.
2.3 times greater than that of Bi2O2CO3 (0.4 × 10−2 min−1) and The stronger performance is attributed to the heterojunctions,
Bi2S3 (1.6 × 10−2 min−1), respectively.[271] In another study, a ter- which only form at pH 10 (at pH > 10, Bi5O7I forms and, at
nary system composed of Bi2MoO6/graphene quantum dots/ pH < 10, BiOI is prevalent). The gaseous zerovalent mercury
MoS2 catalyst with Z-scheme heterojunctions is able to pho- undergoes photooxidation through the following steps:[278]
toreduce Cr(VI) in an aqueous solution at levels 5.95 and 6.96
times higher than that of Bi2MoO6 and MoS2, respectively. The BiOI/Bi 5O7 I + hv → BiOI/Bi 5O7 I + h + + e − (12)
high reduction efficiency of hexavalent chromium is attributed
to superoxide radicals and photogenerated holes generated
OH− + h + → ⋅OH (13)
through the inhibition of charge-carrier pair recombination.[272]
Similarly, the complete photoreduction of 100 ppm Hg2+ ions
using optimized 3 wt.% BiVO4-ZnO composites under visible O2 + 2H+ + 2e − → H2 O2 (14)
light after 45 min of illumination is due to the Z-scheme that
forms between the semiconducting materials.[289] Ag metal- H2 O2 + hv → 2 ⋅ OH (15)
doped BiVO4 has also been developed to photoreduce hexava-
lent chromium to trivalent chromium; after doping, a sixfold O2 + e − → O2− (16)
increase in reduction activity is observed (9.3%). The ratio
of Ag:Bi plays a crucial role in this performance enhance- Hg 0 ( g ) → Hg 0 ( ad ) (17)
ment, with the optimal reduction activity observed with a
1:20 ratio.[290] In a similar fashion, palladium (Pd) decoration
on Bi2S3 nanorods has been reported for the photoreduction 3Hg 0 ( ad ) + 2 ⋅ O2− + 2H+ → 3HgO + H2 O (18)
of Hg(II) ions, with 2% Pd producing a much higher rate
constant (1.18 min−1) than 0.5% Pd (0.93 min−1) and Bi2S3 Hg 0 ( ad ) + 2 ⋅ OH ( ad ) → 2HgO + H2 O (19)
(0.35×10−2 min−1). The key factors highlighted for this high
performance are Hg2+ adsorption on the catalyst surface, high Other groups have also reported light-responsive rGO-mod-
photoactive site availability, and visible light harvesting.[291] ified BiOX composites (X: Cl, I, or Br)[292] and carbon-modified
An interesting study with a BiOI/MoS2 photocatalyst with BiOI/BiOIO3 for the removal of gaseous mercury.[293] Easily
interfacial Z-scheme heterojunctions inhibiting charge-pair separable magnetic composites are extremely useful given the
recombination has been reported for the oxidation of Hg0 to difficulty associated with catalyst separation in PC research.
HgO. Mercury removal reaches 58% with BiOI/MoS2 pre- In this regard, the straightforward hydrothermally prepared
pared via calcination compared to other materials produced by magnetic chitosan@bismuth tungstate composite covered with
physical mixed and hydrothermal methods. The surface active silver (MCTS-Ag/Bi2WO6) exhibits efficient PC and adsorption
removal of Cu(II) in aqueous solutions. The study observes that versus RHE, with an impressive durability of 72 h without
the greater copper adsorption has a synergistic interaction with decay. In addition, a FE of 97.4% is obtained for formate produc-
the catalyst surface, significantly strengthening PC reduction. tion. Theoretical studies and spectroscopic data indicate that
Under the influence of simulated solar light, the theoretical the (012) facet of the Bi NPs sustains the OCHO* intermediate,
maximum adsorption capacity of Cu(II) from an aqueous solu- and strong interfacial contact contributes to the high activity,
tion at pH 6 is calculated to be 181.8 mg g−1, which is much selectivity, and durability of the Bi NP/carbon cloth electrode.
higher than reports for other metal ions.[280] Surface electron-rich Bi NPs may be the consequence of the
unique atom arrangement of the exposed (012) facet, creating
an antioxidation electric environment. The electron-rich (012)
5.2.3. CO2 Reduction facet would contribute to CO2 adsorption and the activation of
CO2 reduction.
The CO2 reduction reaction (CO2RR) powered by sustainable Mesoporous Bi nanosheets have also been proven to be
energy sources has significant potential for the mitigation of effective for formate production with high sensitivity.[295] A
the negative impacts of CO2 buildup through the conversion facile solvothermal process prepares 2D bismuth oxycarbonate
of CO2 to value-added compounds in the CO2-fuel-CO2 carbon nanosheets, which are then cathodically transformed into
cycle. The conversion of CO2 to high-value fuel through elec- mesoporous Bi nanosheets. A large cathodic current density of
trocatalytic processes is a promising technology. To maximize 18 mA cm−2 at −1.1 V (Figure 18a) is observed with excellent
formate production from electroreduced CO2, Bi-based mate- selectivity using these mesoporous Bi nanosheets. Over a broad
rials are considered promising due to their non-toxicity, low potential window, an FE of 100% (Figure 18b) with satisfactory
cost, and high selectivity in comparison to environmentally stability as a CO2RR electrocatalyst is reported. Mesoporous Bi
hazardous Pb, In, and Sn-based material systems. For example, nanosheets allow for efficient and robust CO2 reduction to for-
3D electrodes with high activity, selectivity, and endurance were mate with no activity or selectivity loss for over 12 h. Compared
reported by Wei et al.,[294] with uniformly dispersed Bi dendrites with Bi NPs, mesoporous Bi nanosheets exhibit much higher
grown on carbon cloth through the coordination between Bi3+ performance and longer stability (12 h at −0.8 V; Figure 18e).
ions and ligands during electrodeposition. The topological From the theoretical calculations, the CO2RR is found to
conversion of Bi dendrites to Bi NP electrodes with exposed occur over the (012), (111), and (101) planes, and OCHO* for-
(012) facets occurs via successive oxidation, and the reduction mation is favored by all of the surface planes. The (101) and
process in O2-saturated KHCO3 forms Bi2O2CO3, which is (111) planes can greatly stabilize OCHO*, and are responsible
subsequently electroreduced at −1.55 V versus Ag/AgCl in an for most of the activity for formate synthesis (Figure 18f). The
N2-saturated KHCO3 solution. The Bi NP/carbon cloth elec- use of nanocomposites generated using black phosphorous
trode demonstrates a current density of 6.8 mA cm−2 at −0.78 V nanosheets as support for Bi dendrites has been reported by
Figure 18. a) Polarization curves for commercial Bi nanopowder and mesoporous Bi nanosheets (mpBi) in 0.5 m NaHCO3 saturated with N2 or CO2.
b) Faradaic efficiency (FE) for HCOO, H2, and CO on mpBi nanosheets compared with the FE for HCOO on commercial Bi nanopowder. c) Analysis
of the FE for HCOO on mpBi, Sn, In, and N-doped carbon. d) Partial current density of mpBi and commercial Bi nanopowder; the inset shows the
corresponding Tafel slopes. e) Stability of mpBi over a 12 h period at −0.8 V. f) HCOOH free-energy diagram for the Bi planes (101), (111), and (012).
Reproduced with permission.[295] Copyright 2018, Wiley-VCH.
Huang et al.,[296] with the former material acting as a substrate at an optimal thickness and size can produce a stronger CO2
for the growth of Bi dendrites. The yield rate for formic acid is adsorption affinity, lower contact resistance, and a higher elec-
440 mmol dm−3 h−1 over the electrodeposited Bi dendrite/black trochemical active surface area during electrochemical CO2
phosphorous nanosheets, at a potential of −1.0 V. The FE for reduction, thus increasing the reaction kinetics and activity.[303]
formic acid production is approximately 92%, which is much Surface area-enhanced Bi derived from the reduction of BiOCl
higher than that for black phosphorous nanosheets (25.8% at has also been reported to exhibit a similar FE of 92%.[304] Previ-
−1.3 V). The authors claim black phosphorous is a potential ously, oxides of Bi nanosheets grown on a multichannel carbon
substrate for Bi dendrite-based nanocomposites that exhibit matrix (MCCM) have been developed for the CO2RR. The elec-
enhanced CO2 reduction. trocatalyst exhibits a suitable partial current density of around
Recently, free-standing bismuthene has been synthesized on 17.7 mA cm−2 at a modest overpotential, and is extremely selec-
a broad scale, exhibiting high CO2 electrocatalytic reduction to tive for HCOOH production, with an FE approaching 90% over
formate with a high FE of 99% at −580 mV versus RHE and an a wide potential window, with a maximum of 93.8% at 1.256 V.
excellent durability of 75 h without decay. According to theoret- A maximum energy efficiency of 55.3% is delivered with long-
ical studies, the selectivity of HCOO− formation on bismuthene term stability of 12 h with no deterioration at an overpotential
nanosheets is high on the (111) facet, possibly because of the of 0.846 V. More rapid electron transfer is facilitated by the
unique compressive strain.[297] In another study, rich BiO MCCM, thus increasing CO2 adsorption, with a high ratio of
bonds in bismuthene nanosheets are constructed to enhance pyrrolic-N to pyridinic-N.
CO adsorption. The formate conversion rate exceeds 90% for Ultrathin Bi2O3 nanosheets also offer abundant active sites
currents ranging between 50 to 400 mA cm−2.[298] Atomic layers by lowering the contact resistance and work function, thus
of vertically aligned bismuthene nanosheets have also been reducing the electrolyte diffusion pathway.[305] To tune the elec-
grown on Cu substrates via a galvanic replacement reaction, tronic structure of Bi2O3, a defect and interface engineering
overcoming the challenge of array growth due to high oxide for- strategy has also been applied to boost the CO2RR.[306] A
mation and the lower melting point of Bi metal. Bismuthene hybrid catalyst Bi2S3–Bi2O3@rGO is developed using a partial
nanosheets grown on Cu foam also exhibit a high FE of >90% precipitation conversion process with a considerable number
for catalyzed formate, but the stability is merely satisfactory.[299] of defects (oxygen vacancies, etc.) and a specially designed
A recent study has demonstrated that boron doping (single and interface between Bi2S3 and Bi2O3. The resultant composite
double atoms) for bismuthene catalysts can produce very high interface considerably improves the binding energy of the
selectivity in a controlled environment with water molecules.[300] intermediate HCOO* and lowers the reaction energy barrier,
Interestingly, the promotion of the CO2RR through the regu- allowing HCOOH to form more readily. With a maximal FE
lation of the reconstruction of Bi-MOFs has been reported by in HCOOH production of 90.1% at −0.9 V, the Bi2S3–Bi2O3@
Yao et al.[301] Their study highlights that electrolyte- and poten- rGO electrode exhibits outstanding electrocatalytic activity for
tial-mediated reconstruction occurs in separate processes. In the CO2RR and the suppression of H2 evolution. During CO2
particular, reconstruction of the Bi-MOFs prior to CO2 electrore- reduction, Bi2S3 stabilizes the framework of the catalytic inter-
duction occurs via two stages: 1) HCO3-initiated ligand substi- face at a moderately negative potential and provides sufficient
tution through the electrolyte-mediated conversion of Bi-MOFs durability for over 24 h. The doping of Bi2O3 nanosheets has
to Bi2O2CO3 nanosheets, and 2) a potential-mediated reduction also been investigated, with the highest formate FE of 93.4%
of Bi2O2CO3 to Bi following the first stage. The FE of the in with a 24.3 mA cm−2 current density at −0.97 V with a Sn con-
situ rebuilt Bi nanosheets (with a thickness of 3.5 nm) yields tent of 2.5 at.%.[307] A synergistic effect between the Sn and Bi
92% formate and remains stable under working conditions. facilitates the adsorption of the OCHO* intermediate on Sn,
During the two-step process, many unsaturated Bi atoms accu- enhancing the CO2 reduction reaction. Defect-rich Bi structures
mulate near the surface vacancies, allowing for more favorable derived from Bi2S3 have also been reported to offer excellent
adsorption of *OCHO intermediates, thus enhancing the reac- formate selectivity, which is one of the reasons for the partial
tion process. Surface reconstruction is triggered by bicarbonate sulfurization of Bi2O3 to enhance the CO2 reduction reaction
anions, and the applied negative potential is essential for the in previous studies.[308] However, CO2RR systems with Bi-based
development of a stable and active Bi phase. To achieve control- structures are still in the early stages of development. Table 6A
lable reconstruction, pretreatment such as electrolyte soaking summarizes previously reported micro- and nanostructured Bi-
and surface activation by cyclic voltammetry is crucial. Similar based materials, their processing strategies, and their catalytic
reconstruction studies have recently been reported with the Bi- properties for CO2 reduction.
based perovskite BaBiO3 (BBO) for the CO2RR.[302]
Bi nanosheets derived from BiOX nanoplates as precursors
have also been reported for this purpose, with 2D Bi nanosheet 5.2.4. N2 Reduction
electrocatalysts produced from BiOCl nanoplates with a max-
imum FE of 92% at −0.9 V versus RHE with a current den- The electrical-energy-driven electrocatalytic nitrogen reduction
sity of 10.5 mA cm−2. On the other hand, BiOBr-derived Bi reaction (N2RR) is a particularly promising smart technology.
nanosheets show an FE of 80% over a wide potential range According to theoretical analysis,[309] nitrogen molecules can
of −0.8 to −1.3 V, with an optimal thickness for the nano- undergo stretching and activation through BiO compounds
plate precursor of between 20 and 25 nm. However, the size through electron donor–acceptor reactions with Bi atoms. Based
range is quite wide, varying between 40 and 497 nm. Due to on this mechanism, smart surface engineering has been carried
their 2D structure, BiOBr and BiOCl nanoplate precursors out to develop 2D Bi nanosheets via the in situ electrochemical
Table 6. Summary of Bi-based micro- and nanostructured materials, their processing, and their catalytic properties for A) CO2 and B) N2 reduction.
(A) BISMUTH MATERIALS FOR CO2 REDUCTION

Catalyst Morphology Processing Current Density Faradaic Efficiency Stability Ref.
(012) facet-exposed Bi Dendrites on Electrodeposition 6.8 mA cm−2 at −0.78 V 97.4% CO2-to-formate 72 h [294]
particles conductive carbon versus RHE
cloth
Mesoporous Bi 2D nanosheets Solvothermal 18 mA cm−2 at −1.1 V 100% 12 h [295]
nanosheets following cathodic versus RHE
transformation
Bismuth dendrites/ 2D nanosheets Electrodeposition −1.0 V with 92% CO2 to formic acid 5h [296]
black phosphorous 440 µmol dm−3 h−1
Bi MOF reconstructed Nanosheets In situ reconstruction −15 mA cm−2 at 92% towards formate 10 h [301]
nanosheets and electrochemical −1.3 V versus RHE production
reduction
BaBiO3 Nanoparticles Modified sol-gel −1.2 V 60.1% in EC cell 60 h at [302]
towards formic acid 21.0 mA cm−2
Bi nanosheets Nanosheets In situ transformation 10.5 mA cm−2 at 92% 15 h at [303]
of BiOCl nanoplates −0.9 V versus RHE 10.5 mA cm−2
High-surface-area Bi Nanosheets Electrochemical 3.7 mA mg−1 92% formate 7 h at − 1.5 V on [304]
(HAS-Bi) reduction of BiOCl HSA-Bi
nanosheets
Bi2O3 nanosheets on a Nanosheets Electrospinning, seed 17.7 mA cm−2 93.8 % at −1.256 V 12 h [305]
multiple channel carbon layer formation, and
matrix (MCCM) hydrothermal
Defect-induced Nanosheets Precipitation, 6.14 mA cm−2 at −1.0 V 90% 24 h [306]
Bi2S3–Bi2O3@rGO sulfurization
Sn-doped Bi2O3 Nanosheets Solvothermal 24.3 mA cm−2 at 93.4% formate 5h [307]
−0.97 V
Defect-rich Bi Micro-urchin structure Hydrothermal and 5 mA cm−2 at −0.75 V 84% at −0.75 V 24 h [308]
electrochemical
reduction
(B) BISMUTH MATERIAL IN N2 REDUCTION
Catalyst Morphology Processing Light Source, Current Production Stability Ref.
Density, Faradaic Activity (NH3)
Efficiency
BiO quantum dots Quantum dots Oleate-modified 500 W Xe lamp 1226 µmol g−1 h−1 120 h [309]
hydrothermal synthesis
Bi nanosheets Mosaic Nanosheets In situ electrochemical 10.46 ± 1.45% at 13.23 µg mgcat.−1 h−1 25 h at −0.8 V [310]
reduction −0.8 V versus RHE versus RHE
Bi nanosheets Nanosheets In situ electrochemical 14.14% at 11.11 µg h−1 mgcat.−1 20 h at −0.5 V. [311]
reduction-assisted −0.5 V versus RHE
exfoliation
Bi@Ti3C2 MXene Nanoparticles on Liquid-phase reduction 27.2 % at 28.3 µg h−1 cm−2 24 h [312]
nanocomposite nanosheets −0.4 V versus RHE
Bi nanoparticles Nanoparticles on Calcination of bismuth 15.10 ± 0.43% at - 12 h [313]
embedded in carbon nanosheets citrate precursor −0.4 V versus RHE
nanosheets (Bi@C)
Ce-doped Bi2WO6 Nanoflowers Hydrothermal 15.9% at 22.5 µg h−1 mg−1cat. 30 h at −0.20 V [314]
−0.20 V versus RHE versus RHE
reduction of 2D BiOI. The nanosheets deliver an ammonia to accessibility restrictions for the surface electrons. In a sim-
output of 2.54 ± 0.16 µg NH3 cm−2 h−1 (≈13.23 µg mgcat.−1 h−1) ilar electrolyte, the FE improves to 14.14% with Bi nanosheets
with an FE of 10.46 ± 1.45% at −0.8 V versus RHE in a 0.1 m sul- derived from BiOCl.[311]
fate electrolyte.[310] This performance is due to efficient p-orbital Nitrogen selectivity is one of the major issues that require
electron delocalization and sufficient edge site exposure, and attention for the development of N2RR electrocatalysts.
the choice of a semiconducting material enhances the FE due Metallic Bi distributed over a Ti3C2 MXene composite has been
presented as a promising N2RR electrocatalyst with excep- transfer function of V5+, and the photogenerated electrons
tional stability and durability.[312] The activity of the composite trapped in the oxygen vacancies promote the production of
arises primarily from the Bi atoms on the MXene, which select ammonia. The inert facet (110) contains V5+, which does not
nitrogen over hydrogen while promoting electron movement initiate the chemisorption of N2. Thus, by changing the active
through the MXene. An alkaline electrolyte leads to an FE of sites on the (040) facet, PC activity increases linearly with an
27.2% at −0.4 V versus RHE, higher than that of the individual increase in the (040)/(110) facet ratio, and the maximum activity
materials. Similar to the previous study, Bi NPs on carbon approaches 103.4 µmol g−1 h−1 without the need for a sacrifi-
nanosheets have also been reported, with different BI oxida- cial reagent. It has previously been reported that the vanadium
tion states producing an FE of 15.10% at 0.4 V versus RHE.[313] dopant sites in BiVO4 exhibit the adsorption and activation of
Density functional theory calculations show that, by effectively N2 during the photoelectrocatalytic process.[316] The NH3 evo-
adjusting the oxidation state of Bi, active Bi sites may be tuned lution rate is observed to be 11.6 × 10−8 mol h−1 cm−2 with an
for p-filling and improve *NNH adsorption, representing an FE of 16.2% at −0.1 V versus RHE in a 0.1 m Li2SO4 aqueous
improvement in a potential-determining step. Doping Bi2WO6 solution, the best performance of photoelectrocatalysts reported
with cerium has also proven to be beneficial for the N2RR, deliv- to date.
ering a high FE of 15.9% at −0.2 V versus RHE with cerium A comparison of micro- and nanostructured Bi-based mate-
content of 10 wt.%. The introduction of defects through doping rials, their processing routes, and their catalytic properties for
is claimed to have increased N2 adsorption and activation.[314] N2 reduction is presented in Table 6B. N2 reduction processes
Interestingly, nitrogen adsorption has been improved by can be enhanced with the manipulation of oxygen vacancies,
anchoring Au on Bi2S3 nanorods due to the nitrogen-philicity doping, and heterojunction formation in Bi materials, while
of Bi, with the atomic coordination of Au-S-Bi increasing the the addition of an appropriate hole scavenger and sacrificial
number of nitrogen adsorption sites, thus promoting the for- reagents is also beneficial. However, no previous reports have
mation of the N2H* intermediate. The material produces a compared the effect of the electrolyte on nitrogen electro-/
relatively low FE of 3.10% at −0.8 V versus RHE, but the rate photo-reduction activity even though electrolyte variation can
of NH3 generation is 45.57 µg h−1 mgcat.−1 due to the reduction significantly affect the pH and influence the adsorption sites of
in the energy barrier in the first hydrogenation step.[315] Mor- Bi materials.
phological analysis of bismuthene nanostructures has also been
carried out recently, with sheet-like structures and NPs exhib-
iting high N2RR activity due to the increase in reactivity due to 6. Challenges in Bi-based Materials
the tips, edges, and high surface area.[317]
Photochemical and photoelectrochemical processing have 1. Despite significant work being carried out with Bi-based
also been observed for Bi materials, particularly the coupling of materials, design optimization for large-scale production is
semiconducting Bi materials, with one being oxygen-vacancy- still a bottleneck with no standards to have a real-time mate-
rich. In this regard, Bi2MoO6/OV-BiOBr p-n heterojunctions rial utilization due to non-scalability. Thus, scalability with
with an appropriate bandgap configuration show that N2 mole- low-cost production strategies should be the future step. In
cules may adhere to and be activated by the oxygen vacancies on addition, the surface tuning of these designs for active site
BiOBr nanosheets. These advantages allow the heterojunctions generation is popular, but the requirement for tuning is al-
to more effectively convert N2 into ammonia under ambient ways distinct for a specific material or application.
conditions without the need for co-catalysts made of noble 2. Although, Bi-based materials are photonically active, but the
metals or sacrificial agents.[318] Another study has reported structure-activity-performance relationship still requires a
Z-scheme ZnSe/BiVO4 composites with PC activity.[319] Optimal deeper understanding through experimental and theoreti-
performance is attained with a nitrate removal rate of 89.84% cal combinations. The solar energy utilization through high
and N2 selectivity of 91.03% in 50 min, with HCOOH identi- photon-absorbing bismuth materials is still lacking in the
fied as the best hole scavenger (compared with CH3COOH current research.
and C2H5OH). Further improvements could be achieved by 3. Active site identification and surface structural changes dur-
improving the redox properties of the photogenerated carriers ing the electro-/photochemical reactions could be solved
and increasing the light-harvesting capacity. In addition, N through in situ advanced characterization techniques. The
triple-bond activation and ammonia generation have been con- identification of active reaction sites for specific materials is
ducted with Bi4O5Br2. The ammonia yield for Bi4O5Br2 in a N2/ still challenging for applications like photocatalysis, CO2 re-
O2 environment is 122.8 µmol L−1, which is 2.55 times higher duction, and N2 reduction as these sites govern the product
than the yield in a N2 atmosphere (34.6 µmol L−1) with meth- selectivity and reaction stability. Thus, active site selectivity
anol as a hole scavenger.[320] Theoretical calculations support for stable reaction is an important direction of research in
the observation that oxygen clearly improves the activation of N Bi-based materials.
triple bonds. It is hypothesized that oxygen acts as an electron 4. To achieve an efficient energy conversion efficiency for bis-
transfer bridge to help activate nitrogen, thus speeding up the muth thin films in photoelectrochemical systems, advanced
nitrogen photoreduction pathway. technologies such as sputtering, chemical vapor deposition
An interesting study reported by Zhang et al. reports facet- and ALD should be implemented to have high conductivity,
dependent activity of BiVO4 crystals.[321] The study reports substrate adhesion, and for stable surface reactions. Interface
the cycle of oxygen vacancy-V4+/V5+ (OV-V4+/V5+) on the (040) engineering through the introduction of buffer layer can also
BiVO4 facet. The chemisorption of N2 by V4+, the electron promote charge transfer characteristics given the thickness
control which is not possible in dispersion-based deposition nanostructures, their modification strategies, and composites/
techniques. heterojunctions developed using state-of-the-art processes.
5. Researchers should look for new opportunities towards de- Figure 19 summarizes the most widely used Bi materials
signing energy storage bismuth materials from metal-organic based on their target applications. Advances in Bi-containing
framework-or multinary materials with surface and interface heterojunction-rich composites have already produced high-
engineering possibilities. Theoretical models would provide performance water-splitting, hydrogen generation, and organic
a base for understanding the interaction between the electro- pollutant removal systems. To date, significant developments
lyte ions and the bismuth materials that could pave the way have been reported in terms of energy storage, energy conver-
for better material design systems. Effort towards designing sion, and environmental remediation, but further development
suitable cathode materials for complementing the bismuth is required in terms of strong visible-light responses, biocom-
anode materials is also worth investigating. patibility, electrical conductivity, charge transfer promotion,
6. Stability is one of the crucial factors for practical application. flexibility, and stability, all of which will be beneficial for pho-
Since some of the bismuth material systems are prone to tochemical and electrochemical systems. Rational engineering,
photocorrosion, thus surface structure deterioration upon electronic structure modification, interface engineering, and
light irradiation should be carefully studied. The industrial material composites in Bi-based photoelectrodes and the identi-
requirement for stability in batteries and supercapacitors is fication of the specific properties of target compounds will pro-
far from realization with the current bismuth-based materi- vide a useful roadmap for new applications. Although signifi-
als. Phase transition studies during the electrochemical pro- cant efforts have been made to control the structure and prop-
cessing with respect to electrolytes can put insight into the erties of Bi-based materials for sustainable energy and environ-
electrolyte-specific material’s transformation which will help mental applications, the realization of their full potential is still
in constructing stable materials for prolonged reactivity. a distant goal.
Certain areas in particular require greater research attention
in relation to micro- and nanostructured Bi-based materials.
7. Summary and Future Prospects These are summarized below.
Bismuth-based micro- and nanostructures are a class of prom- 1. Material development, particularly the design of hierarchical,
ising materials that exhibit distinctive layered/non-layered core–shell, hollow, and mesoporous materials, has been re-
structures, narrow bandgaps, suitable band positions, tunable ported in the literature, but general challenges have not been
electronic properties, and interesting physical properties such fully discussed. Indeed, these difficulties in material design
as in multiferroics. An inexpensive semi-metallic element, Bi are one of the reasons for the poor performance of Bi-based
is also non-toxic and has a Fermi surface with high anisotropy, materials in environmental restoration.
a long carrier mean-free path, and a short bandgap. Metallic Bi 2. Bismuth chalcogenides and chalcohalides can serve as
also exhibits surface plasmon resonance properties, which are alternate electrodes for energy storage and conversion
important for energy-responsive applications. In this review, we devices due to their abundant structural gaps and Bi al-
highlighted the use of a diverse range of Bi-based micro- and loying ability. However, these layered structures exhibit
Figure 19. Summary of the most commonly reported Bi-based materials according to their application.
poor electrochemical activity due to time-dependent elec- Conflict of Interest

trochemical cycling and low conductivity, thus restricting
The authors declare no conflict of interest.
their practical utility. Significant efforts have been made to
address these issues, and impressive advances have been
made, mostly by utilizing nanotechnology and material
composition engineering, but the understanding of energy Keywords
storage mechanisms is still lacking. bismuth, environmental restoration, modification strategies, photo-
3. Molecular oxygen activation is a major bottleneck during electro-catalysts, sustainable energy
hydrogen production, organic pollutant removal, and water-
splitting processes. This activation is highly tunable through Received: September 29, 2022
morphological and facet engineering, structural design (e.g., Revised: November 20, 2022
core–shell, hollow, and thin-film structures), and structural Published online: December 16, 2022
modifications, thus leading to more efficient energy utiliza-
tion.
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Sangeeta Adhikari is a Research Professor in the School of Chemical Engineering at Chonnam

National University, South Korea, on a Brain-Pool fellowship. Prior to her current position, she
worked at the Indian Institute of Science, India, on a prestigious UGC-D.S. Kothari postdoctoral
fellowship. She received her Ph.D. degree from the National Institute of Technology, Rourkela,
India. Her research interests are the rational design of heterostructure-based nanomaterials via
surface structure control, thin-film processing via atomic layer deposition, and the fabrication of
devices for energy storage and conversion, sensing, and water purification applications.
Sandip Mandal has been a Full-Time Researcher in the School of Earth Science and Environmental
Engineering at the Gwangju Institute of Science and Technology, Gwangju, South Korea, since
2020. He holds a Master’s in Chemistry and received his Ph.D. degree in Chemistry from the
National Institute of Technology, Rourkela, India. His area of research is environmental chemistry
and engineering, with a primary focus on the design of novel multifunctional nanomaterials and
nanostructure-supported metal catalysts, adsorbents, and photocatalyst materials for energy and
environmental applications.
Do-Heyoung Kim is a Full Professor in the School of Chemical Engineering at Chonnam National
University, South Korea. He obtained his Ph.D. from the Department of Chemical Engineering
at Rensselaer Polytechnic Institute (Troy, NY, USA) in 1993. Prior to joining Chonnam National
University, he worked as a senior researcher at the central research center of LG Semicon after
completing his postdoctoral research at North Carolina State University. His primary research
interest is the application of atomic layer deposition for IC devices, supercapacitors, batteries,
solar cells, and sensors.

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Review

Recent Development Strategies for Bismuth-Driven

in the energy sector and the environment

Small 2023, 19, 2206003 2206003 (1 of 38) © 2022 Wiley-VCH GmbH

Small 2023, 19, 2206003 2206003 (2 of 38) © 2022 Wiley-VCH GmbH

Figure 2. Schematic outline of the present review.

Small 2023, 19, 2206003 2206003 (3 of 38) © 2022 Wiley-VCH GmbH

Small 2023, 19, 2206003 2206003 (4 of 38) © 2022 Wiley-VCH GmbH

Small 2023, 19, 2206003 2206003 (5 of 38) © 2022 Wiley-VCH GmbH

Small 2023, 19, 2206003 2206003 (6 of 38) © 2022 Wiley-VCH GmbH

Small 2023, 19, 2206003 2206003 (7 of 38) © 2022 Wiley-VCH GmbH

Small 2023, 19, 2206003 2206003 (8 of 38) © 2022 Wiley-VCH GmbH

Small 2023, 19, 2206003 2206003 (9 of 38) © 2022 Wiley-VCH GmbH

Material Application Processing Morphology Electrolyte Specific Capacity Stability or % Ref.

Material Application Processing Morphology Electrolyte Specific Capacity Stability or % Ref.

a)FEC: fluoroethylene carbonate

5.1.3. Hydrogen Production semiconducting materials for the development of composites

Catalysts Morphology Processing Light Source Current Density Stability Ref.

(A) BISMUTH MATERIALS FOR ORGANIC POLLUTANT REMOVAL

(B) BISMUTH MATERIALS FOR METAL-ION REMOVAL

(A) BISMUTH MATERIALS FOR CO2 REDUCTION

poor electrochemical activity due to time-dependent elec- Conflict of Interest

Sangeeta Adhikari is a Research Professor in the School of Chemical Engineering at Chonnam

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