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Ullah, H. Bismuth-Graphene Nanohybrids. Encyclopedia. Available online: https://encyclopedia.pub/entry/9397 (accessed on 26 July 2024).
Ullah H. Bismuth-Graphene Nanohybrids. Encyclopedia. Available at: https://encyclopedia.pub/entry/9397. Accessed July 26, 2024.
Ullah, Habib. "Bismuth-Graphene Nanohybrids" Encyclopedia, https://encyclopedia.pub/entry/9397 (accessed July 26, 2024).
Ullah, H. (2021, May 07). Bismuth-Graphene Nanohybrids. In Encyclopedia. https://encyclopedia.pub/entry/9397
Ullah, Habib. "Bismuth-Graphene Nanohybrids." Encyclopedia. Web. 07 May, 2021.
Bismuth-Graphene Nanohybrids
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This entry is adapted from the peer-reviewed paper 10.3390/en14082281

Photocatalysis is a classical solution to energy conversion and environmental pollution control problems. In photocatalysis, the development and exploration of new visible light catalysts and their synthesis and modification strategies are crucial. It is also essential to understand the mechanism of these reactions in the various reaction media. Recently, bismuth and graphene’s unique geometrical and electronic properties have attracted considerable attention in photocatalysis. 

bismuth/graphene nanohybrids photocatalysis reaction mechanisms energy pollution

1. Introduction

The increase in pollution due to urbanization and industrialization has become a significant challenge for the sustainability of human society. The waste generated in different industries during crude oil storage, transportation, and refinery has become a global problem [1][2]. The water and soil pollution caused by several pollutants’ discharge is a critical public health concern due to their toxicity. These pollutants can cause many health effects such as neurological toxicity, lung cancer, lethargy, fatigue, depression, headaches, nausea, dizziness, throat and eye irritation, and acute and chronic respiratory effects [3]. Toluene, benzene, xylene, ethyl benzene, and phenolic compounds some of the main compounds categorized as pollutants posing severe threats to our environment [4][5][6]. In the present situation, environmental pollution has increased several-fold due to the mismanagement of industrial waste. This can negatively affect the ecosystem and make lands unusable for agriculture and many other purposes [7]. Therefore, it is essential to remediate these toxic pollutants in our environment [8][9][10].

To eliminate organic pollutants from the environment, numerous technologies have recently been established for their degradation. Organic pollutants can be degraded by different methods, such as physical, chemical, biological treatments and advanced oxidation techniques [9][11][12][13][14][15]. Organic pollutant photodegradation is an attractive “green” chemical technology to control pollution, where photocatalysis is the most widely and potentially applied method used for demineralization and degradation of such pollutants [16][17].

Various light sources have been applied for the excitation of heterogeneous catalysts [18], but the photodegradation approach is more economical if sunlight can be used compared to ultraviolet light [16][19][20]. The evolution of the term “photocatalysis” shows the development of certain fundamental concepts of photochemistry. The point where photochemistry became a discipline was when it became differentiated from thermal chemistry. Indeed, several researchers saw irradiation as one of the many methods available to catalyze a response that makes it quicker by, for example, heating or processing it with certain chemicals until the beginning of the 20th century [21]. Ciamician, the first scientist to systematically understand the chemical effect of light, took great pains in finding out if he had “initiated heat” alone rather than “light” [22]. This was appropriately allotted the term “photochemical,” whilst the word “photocatalytic” applied to reactions caused by light, but with the same result as thermal reactions. Another step further was the identification of electronically excited states, which became a general idea in 1914 and were part of Bodenstein’s photochemical reactions along with reactivity and thermodynamics. In an early stage, more distinction was made in the thermochemistry of the process itself. This allowed for photosynthesis to occur when part of photon energy in the products rose [22][23].

Around 43% of visible-light energy is solar, so visible-light catalysts are chosen in photoelectrocatalysis and photocatalysis processes. Until now, several semiconductive products have been utilized, including metal oxides (Ag2O, TiO2, Cu2O, ZnO, Fe2O3, Ta2O5), metal selenides (CdSe and MOSe2), metal phosphides (Ni2P), metal sulfides (Bi2S3, ZnS, MoS2, and CdS), multi-structure oxides (Sr TiO3WO), metal halides and oxyhalides (AgBr, BiOBr) and metal-free materials (SiC, Si and g-C3N4), [24][25][26][27][28]. Those with a bandgap (Eg) greater than 3 eV, e.g., SrTiO3, TiO2, ZnO, KTaO3, ZnS, and SrTiO3, are called wide-bandgap photocatalysts, whereas catalysts with an Eg of less than 4 eV, e.g., Si, SiC, Ag2O, Bi2WO6, CdSe, InTaO4, Ag3VO4, CoO, Fe2O3, Cu2O, TaON, Ta3N5, CdS, Bi2S3, g-C3N4, and BiVO4, are photocatalysts that react to visible light [25][29].

Heterogeneous catalysts play a vital role in environmental pollution control [30][31][32]. Powdered semiconductor photocatalysts are commonly used in various areas, such as carbon reduction [33], selective organic transformations, environmental remediation [34], and water splitting [35]. There has been, in numerous applications, a growing interest in the use of semiconductors as photocatalysts. In 2015, around 5500 documents about photocatalytic applications were published, indicating that interest in heterogeneous photocatalysis was enormous and highly important in diverse research fields. This number has recently grown to over 13,000. A country-specific view of the increase in the number of publications on “photocatalytic degradation” is listed in Table 1. No commercially accessible material can currently meet all application requirements, such as cost-effectiveness, stability, high visible-light quantum efficiency, and security [36]. For such tasks to be completed, a highly effective architecture and system for environmental remediation and energy supply are needed to examine new visible-light semiconductor materials.

Table 1. Country-wise publications growth on the photocatalytic degradation of organic pollutants. (Data acquired from SciFinder).

S. No. Country No. of Publications
1 China 8838
2 India 1090
3 Iran 676
4 South Korea 384
5 United States of America 178
6 Japan 175
7 Malaysia 158
8 Saudi Arabia 103
9 Pakistan 84
10 Italy 77
11 Australia 73
12 Spain 72
13 Brazil 57
14 United Kingdom 48

The development of nanomaterials has progressed from the synthesis of single-particles to multicomponent assemblies or hierarchical structures, where two or more pre-synthesized nanomaterials are coupled to obtain multifunctionality. Such multicomponent assemblies are termed nanohybrids. The development and use of these nanohybrids requires interdisciplinary knowledge from the energy and environmental sectors, including the applications reported in references [37][38][39][40][41][42][43]. There are previously published review articles on some types and uses of nanohybrids, including gold-graphene oxide nanohybrids [39], organic/inorganic nanohybrids [44], polymer nanohybrids for oil recovery [45], nanohybrids of epoxy/polyamide with carbon nanotubes [46], protein-inorganic nanohybrids [47], gold-based inorganic nanohybrids [48] and polymer-inorganic supramolecular nanohybrids [49].

Graphene is the basic structure of all other carbon allotropes. It is well noted that the potential applications of graphene its derivatives are mainly driven by progressive production of different graphene materials such as graphene oxide (GO), reduced graphene oxide (rGO), functionalized graphene oxide (fGO), and functionalized reduced graphene oxide (frGO) with specific attention to precise applications and this is expected to continue for at least a couple of decades as promising applications and requirements are disclosed [50][51]. Various literature reports on the synthesis, modification and application of photocatalysts based on graphene for energy and environment solutions have already been published [52]. Graphene, graphene and its derivatives [53][54], graphene in photocatalysis [55], graphene doping [56], graphene and graphene oxide sponge [57], nitrogen-doped graphene [58], structure of graphene and its disorders [59], strain engineering of graphene [60], mechanics of graphene nanocomposites [61], chemical vapor deposition of graphene [62], functional modification of graphene/graphene oxide [63], graphene-based fibers [64], and graphene-based electrochemical micro-supercapacitors [65] are some of the subjects that have been reviewed.

Considering the stability, reactivity, reusability, and light-responsive effect of bismuth (Bi) it has been widely used as a photocatalyst. Several state-of-the-art review articles on topics including barium potassium bismuth oxide [66], bismuth-based composite oxides [67], bismuth ferrite nanoparticles [68], bismuth vanadate-based materials [69], bismuth tungstate photocatalysts [70], and bismuth oxyhalides [71] have been published. Annual numbers of publications on graphene photocatalysts in the last ten years are shown in Figure 1a. Similarly, bismuth-containing compounds are significant photocatalysts that react to visible light and fascinating research has been published in the field of bismuth photocatalysis over the last ten years (Figure 1b).

Energies 14 02281 g001 550

Figure 1. Annual numbers of published items in the last 10 years identified in SciFinder using the keywords: “Graphene-based photocatalysts” (a) and “Bismuth-based photocatalysts” (b).

This review, therefore, summarizes and discusses recent Bi-graphene photocatalysts and their energy and environmental sector applications. The choice of bismuth with graphene is due to the vast available literature, as shown in Figure 1. Furthermore, most bismuth-based photocatalysts are stable, reusable, photoactive, cheaper, and more environmentally friendly that other alternatives. Besides, due to some shortcomings of the pristine photocatalysts, such as charge carrier recombination, slow migration of charge carriers, and low visible light absorption [72][73].

2. Bismuth-Graphene Based Photocatalytic Materials

2.1. Bi2O3 and Bi2S3/Graphene Composites

A significant and the simplest bismuth compound is bismuth trioxide (Bi2O3). It can be used in various ceramics, fuel cells, and gas sensors [74][75]. It has also been used as a photocatalyst in organic pollutant decomposition and water splitting [76]. Bi2O3 is a visible-light-responding photocatalyst when acting as a semiconductor, and its bandgap ranges between 2.1 eV and 2.8 eV. Doping with noble materials and combination with other components have been used to increase graphene’s activity in photocatalytic (PC) form [77][78].

In recent times, the PC activity of some Bi-based semiconductors, e.g., BiVO4 [79], Bi2MoO6 [80][81], BiOX (X = Cl, Br, I), Bi2Sn2O7 [82], Bi2O3 [83], and BiSbO4 [84] in the degradation of pollutants has been described. Bismuth oxide was shown to be a strong candidate among the various Bi-based semiconductors because of its good PC and appropriate bandgap properties. Bi2O3’s PC activity is however restricted by quick recombination of the photogenerated carriers and by its susceptibility to photocorrosion. Because of the short distance between the conduction band (CB) of Bi2O3 and the valence band (VB), graphene can be designed for the sharing of Bi2O3 and graphene [85]. Under such conditions, electrons generated in the CB of Bi2O3 would quickly be coupled with graphene VB holes [86]. Therefore, the photogenerated electrons accumulated on the CB of graphene display strong reduction ability, and the photogenerated holes on the VB of Bi2O3, exhibit excellent oxidation ability [87][88]. The Z-Scheme PC activities are more effective than one component in terms of reduction and oxidation and advanced photocatalytic performance in the traditional photocatalysts [89][90]. Cui has reported a novel Z-scheme Bi2O3/graphene photocatalyst. Bi2S3 has a 1.7 eV bandgap and is a perfect photocatalytic material for light-harvesting due to its near-IR and visible light activation [91]. A number of Bi2S3 nanocrystal forms ranging from 1D nanorods and 2D nanosheets have been created with hot injection and standard non-oxidation techniques [92][93], while a solvothermal method produces 3D sea-urchin-like spheres [94].

Bismuth sulfide (Bi2S3) is a priviledged nontoxic inorganic semiconductor with excellent photocatalytic activity and chemical stability because of its good visible light response. It has been exploited and investigated mostly for optoelectronic applications. The photogenerated holes and hydroxyl radicals (-OH) in the VB of Bi2S3 (1.62 eV) are mostly utilized in dye pollutant decomposition [92]. In combination with many other photocatalysts such as CdS [95], TiO2 [28][96], and Bi2WO6 [97], the recombination rate of electron-hole pairs could be lowered. An increase in visible light absorption enhances the photocatalytic activity.

A graphene/Bi2S3 nanocomposite with narrow bandwidth was recently synthesized. Compared with the individual components, the PC of this nanocomposite was much higher. Zhou et al. stated that the well-matched bandgap of graphene/Bi2S3 heterojunction could be tailored to increase the transfer and separation efficiency of photoinduced carriers and the visible light response. These graphene/Bi2S3 composites are effective photocatalysts for the photocatalytic degradation of environmental pollutants [74].

2.2. Bi2MO6 (M = Cr, Mo, W)/Graphene Composites

Bi2MO6 (M = Mo, Cr, W) is considered the most common member of the Aurivillius family, Bi2An−1BnOn+3 (A = Sr, Ca, Ba, Bi, Pb, K, Na; B = Nb, Ti, Ta, Fe, W, Mo) is the general formula for Bi2MO6. The Bi2MO6 electronic structure is theoretically based on density functional theory (DFT) [98], while the Bi2MO6 crystal structure falls under orthorhombic space group Pca2(1). It was seen that both VB and CB of Bi2MO6 are composed of hybridized orbitals Bi6p, O2p, and Mnd (n = 3, 4, and 5) for Bi2CrO6, Bi2MoO6, and Bi2MO6, respectively [99]. Bi2MO6 compounds are suitable as visible-light-activated photocatalysts. Among all Bi2MO6 species Bi2CrO6 has a narrower bandgap, thus, it easily undergoes recombination of photogenerated holes and electrons and is thus not considered suitable as a photocatalyst and consequently few Bi2CrO6 studies are available in the field of photocatalysis. For the preparation of Bi2MoO6 samples with a wider special surface area, smaller particles, and higher photocatalytic function, the solvothermal and hydrothermal methods are effective. Several Bi2MoO6 morphologies have been described, including floral hollow spheres (solvothermal process) and nanoplates (hydrothermal method). Moreover, microwave heating was applied to synthesize Bi2MoO6 samples with high photocatalytic activity in short periods [100][101]. Major applications of Bi2MO6 (and Bi2MoO6 and Bi2WO6) photocatalysts involve the removal of organic pollutants from polluted air and water. The key pollutants that have been tested in different studies include phenol [102], dyes [103], CHCl3 and CH3CHO in wastewater [104], and NO in air [105]. Microorganisms, e.g., E. coli, were also destroyed by the addition of Bi2WO6 [106] and Bi2MoO6 [107] under visible light irradiation.

Current studies reveal the combined effect of plasmonic metals and graphene. The photocatalytic activity of semiconductors, e.g., TiO2 and ZnO, can be efficiently improved by increasing their photo-absorption ability and suppressing photogenerated electron-hole recombination. Compared to Bi2MoO6, Bi2MoO6-graphene binary composites have been developed and show improved photocatalytic performance. Graphene-based nanocomposites display desirable photocatalytic properties that their individual components do not have, therefore, improved Bi2MoO6 photocatalytic activity resulting from a combination of noble metals and graphene is expected. Bi et al. developed a rGO-Bi2MoO6/Au composite that displayed high catalytic activity for the photodegradation of rhodamine B [20]. Wang and Tian reported composites of GO-Bi2MoO6 and rGO-Bi2MoO6 [108][109]. These composites showed advanced phenol and rhodamine B degradation properties, respectively, compared to Bi2MoO6 alone [74].

2.3. BiVO4/Graphene Nanocomposites

Bismuth vanadate (BiVO4) presents interesting physicochemical properties, including ionic conductivity and ferroelasticity. A theoretical bandgap of 2.047 eV was calculated by DFT for visible-light-driven photocatalysis [110]. Both O2 p- and V3 d-orbitals are included in the BiVO4 valence band. There are three forms of BiVO4, namely monoclinic fergusonite, tetragonal zircon, and tetragonal scheelite. Reversible monoclinic fergusonite and tetragonal scheelite phase transitions occur at 255 °C. A wide range of methods have been reported for BiVO4 preparation. Monoclinic BiVO4 is obtained by both high temperature melting reactions and by solid-state reactions (SSR) [111]. Tetragonal BiVO4 has been synthesized at room temperature by a precipitation method [112]. The bandgap for the monoclinic form is 2.4 eV, while the bandgap for BiVO4 is 2.9 eV. This selective monoclinic BiVO4 preparation is advantageous for assembling effective photocatalysts with visible light shifts. There has been a report of an additional method for synthesizing monoclinic and tetragonal BiVO4 crystals in a simple water-based process [113]. A hydrothermal method has been used successfully in recent times for monoclinic BiVO4 preparation [114]. There are numerous advantages to this hydrothermal approach to selectively produce BiVO4 structures, i.e., mild experimental conditions, controllable conditions and simple experimental setups.

Photocatalytic degradation under visible light is commonly used to decompose organic pollutants (e.g., phenol and RhB) [115], and increased removal efficiency has been demonstrated [116]. BiVO4 was also used for the scission of water [117][118]. BiVO4 was shown to be an active photocatalyst for O2 evolution under visible light radiation since its conduction strip potential isn’t high enough to produce H2 by H2O reduction [119]. Booshehri et al., found BiVO4 to be a mild candidate for photocatalytic inactivation of bacteria in water under visible light irradiation [120]. For photocatalytic bactericidal activity, surface redox reactions are essential for reactive species generation [121]. In addition, the interface for charge separation and transfer in hybrid catalysts is to be considered for two components [122]. The BiVO4/Ag/graphene photocatalyst showed improved activity for photocatalytic degradation of organic pollutants [123][124] or oxidation of nitrogen monoxide and water [125]. The probability of photocatalytic wastewater or disinfection of water by the Z-scheme BiVO4/graphene is however still unknown to the best of our knowledge. Moreover, at the molecular level the photocatalysis consistency is clearly not yet investigated [74].

2.4. BiOX (X = F, Cl, Br, I)/Graphene Composites

Bismuth oxyhalides’ (BioXoptical)’s properties can work as a photocatalyst. The structure of BiOX crystals is comprised of layer structure slabs [Bi2O2] which are inserted in two halogen atoms [126][127]. Biox contain X np (n = 2–5 for Cl, F, I, and Br respectively), O 2p, and Bi 6 p-orbitals both in the valence band (VB) and conduction band (CB). In theoretical terms, the bandgaps of BiOI, BiOF, BiOBr, and BiOCl are calculated to be 1.38 eV, 2.79 eV, 1.99 eV, or 2.34 eV, while experimentally, their bandgaps are estimated to be 1.77 eV, 3.64 eV [128], 2.64 eV, and 3.22 eV [129]. There are restrictions within the GGA method that cause these differences between the experimental and calculated bandgap results. However, both indicate the general decreasing tendency of the bandgaps as the atomic number increases. BIOF was used as a photocatalyst only under UV light, while BiOI was photocatalytically active both under near-IR and visible light. Because of their appropriate bandgaps, both BiOCl and BiOBr are therefore commonly tested. For BiOX synthesis with different morphologies, several methods can be effectively applied. In addition to direct precipitation techniques, the primary methods used to synthesize the BiOX with controlled nanostructures such as nanosheets, microsphere, and nanofibers include hydrolysis, solvothermal and hydrothermal methods [130]. By adjusting the precursor pH, controlling hydrothermal treatment duration time and temperature, and by adding a template structure that can be selectively controlled, one can directly affect the photocatalytic performance. An extensive review of BiOX nanostructures was previously published [131].

Significant efforts have been carried out to design innovative photocatalysts [132][133]. Because of their excellent catalytic activity under visible light, the sequence of ternary bismuth oxyhalides (BiOX, X = Cl, Br, or I) has been commonly studied [134]. The charge separation and atomic polarization efficiency of the layered BiOX structures can be improved. BiOBr, with its crystalline PbFCl layer structure has been a big consideration among BiOX photocatalysts because of its excellent photocatalytic activity, appropriate bandgap, and high stability. The binary component and multi-component counterparts showed improved photocatalytic activity compared to single-component semiconductors. Multi-component synergies may overcome the single-component shortcomings, e.g., insufficient charge separation ability and wide-bandgap. Consequently, the BiOBr photocatalytic activity [135][136] with an indirect-transition bandgap (2.75 eV) may be efficiently enhanced by incorporating other materials.

Graphenes are currently used as a promising support platform for anchoring host NPs as well as acceptors for charge separation and superb electron transfer mediation with peculiar characteristics such as low density, high conductivity, and large surface areas [137][138][139]. The hydrothermal method has been used for the synthesis of Au/BiOBr/graphene composites [140][141].

A practical approach to shrink the bandgap, increase the catalytic activity and visible-light absorption was taken using black BiOCl material with the formation of oxygen vacancies. Although the black BiOCl is still subject to recombination of fast photocatalytic charge carriers, its photocatalytic activity is still not satisfactory. A simple and effective approach to resolve the above-related problems has been taken as the construction hetero-structures of BiOCls with the other appropriate photocatalysts. Thanks to their high electron mobility and a large surface area, the above issues could be well addressed by functional graphene-based semiconductor photocatalysts. A new BiOCl-Bi-Bi2O3/rGO heterojunction with oxygen vacancies has been developed, which provided a solid-solid, close-fit interface and strong interaction between BiOCl, Bi, rGO, and Bi2O3. BiOCl-BI2O3/rGO heterojunctions showed high photocatalytic performance due to the synergistic effect caused by effective charge separation among Bi2O3, BiOCl, rGO, and Bi-bridges. The BiOCl-Bi-Bi2O3/rGO heterojunction displayed high efficiency for photocatalytic degradation of 2-nitrophenol in industrial wastewater treatment. The significant task is to demonstrate the superior long-term photostability of the BiOCl-Bi-Bi2O3/rGO heterojunctions. In addition, a promising BiOCl-Bi-Bi-Bi2O3/rGO photocatalytic mechanism was proposed to describe primary phenomena taking place during the process, depending on multiple charge transfer channels [141].

2.5. BiPO4/Graphene Composites

BiPO4 with high photocatalytic activity for organic pollutant degradation was fabricated for the first time by a hydrothermal approach [142]. A faster hydrothermal way of synthesizing BiPO4 has also been reported [143]. The bandgap in BiPO4 prepared by hydrothermal methods is about 3.85 eV, higher than that of TiO2 (3.2 eV). BiPO4 nanocrystals synthesized with standard oxygen-free procedures have a bandwidth of around 4.6 eV. Only UV light can be used as a light source for large bandgap semiconductors. Although its bandgap is broader than that of TiO2, BiPO4 still has high photocatalytic degradation kinetics. This is because the VB of BiPO4 is 3 eV, higher than that of TiO2, and it generates more oxidative holes in its VB compared to TiO2. Photocatalytic conversion of the gas-phase benzene into CO2 by BiPO4 has also been reported in addition to the degradation of the organic pollutant in an aqueous phase. A photocatalytic gas-phase transformation of benzene to CO2 was also reported during an aqueous phase organic pollutant degradation study [144][145]. BiPO4 photocatalysts still have several drawbacks as photocatalysts however, such as low photocatalytic activity, and comparatively rapid recombination of charge carriers, wide bandgaps, low adsorption ability, and large size, which would decrease the photocatalytic activity of BiPO4 and subsequently limit its industrial-scale applications [146][147]. Consequently, it is urgent to create and design photocatalytic materials based on BiPO4, with required and useful photocatalytic performance properties. To date, numerous efforts have been made to improve the photocatalytic activity of the BiPO4 photocatalyst by doping with non-metals or metals, surface hybridization, reducing the crystal size, forming heterostructures, or combinations of μ-structure materials [148][149]. BiPO4/rGO nanocomposites exposed the importance of graphene as the support of separating electron-hole pairs, which leads to a high photocurrent. Thus, the development of BiPO4/rGO hybrids is an efficient way to improve the visible light catalytic performance of BiPO4. Extensive research has established a trend towards research in carbon-nanomaterials by doping with heteroatoms as they can adapt their fundamental properties successfully [150][151].

2.6. (BiO)2CO3/Graphene C omposites

Bismuth subcarbonate is a known solid carbonate in the BI2O3-CO2-H2O system ((BiO)2CO3 or Bi2CO5) [152]. The bandgap of (BiO)2CO3 is 3.4 eV, so wavelengths under 365 nm can therefore stimulate the bandgap [153][154]. The CB of (BiO)2CO3 generally includes hybridized p-orbitals (O2 p and Bi 6p), while its VB consists of p-orbitals (O 2p, Bi 6p, and C 2p). A hydrothermal, template-free method has been used to efficiently synthesize (BiO)2CO3 with hollow microsphere orders whose structure is dependent on Ostwald’s growing properties. The compound showed photocatalytic activity for pollutant oxidation or disinfection of air and wastewater contamination [155][156]. Several articles have described p-n heterojunctions that exhibited enhanced photocatalytic activity [74][157].

An innovative multi-component TiO2-Bi2O3/(BiO)2CO3-rGO nanocomposite has been synthesized and experimentally used for bisphenol A (BPA) photodegradation. The Bi2O3 was intended to be a visible light photosensitizer. The appropriate VB and CB’s positions TiO2 and (BiO)2CO3 were used as selective sinks for photogenerated holes and electrons, and rGO acted as a channel for charge carrier transport that extended the lifetime of the catalysts. BPA is an endocrine disruptive compound commonly used for the production of many common packaging materials [158]. These materials typically end up in waste dumps, leading to the slow leaching of BPA into water bodies. Accordingly, BPA has been chosen as the model for the photocatalytic activity of the designed photocatalysts based on environmental issues [158][159].

2.7. M(BiO3)n/Graphene Composites

Pentavalent bismuthates (M(BiO3)n (where n = 1, M = Li, Na, K, Ag; n = 2, M = Mg, Zn, Sr, Ba, and Pb) can be bought directly from commercial companies to synthesize additional Bi-based compounds, such as BiOX, as a Bi source [160]. The bandgaps of these compounds are MgBi2O6 1.61 eV, ZnBi2O6 1.53 eV, SrBi2O6 1.93 eV, SrBi2O6 1.93 eV, BaBi2O6 1.93 eV, PbBi2O6 1.92 eV [161], LiBiO3 1.8 eV, KBiO3 2.1 eV [162], NaBiO3 2.6 eV [163], and AgBiO3 2.5 eV, respectively [164]. The valency of Bi-based composites is +3 while the value of (BiO3)n is +5. The Bi3+ cation consists of two orbitals (10 d and 6 s). This indicates that the electronic structure of pentavalent bismuthates is different. Takei et al. tested nine bismuthates for degrading phenol and methylene blue [161]. High photo-catalytical activity under visible light irradiation was shown by NaBiO3, LiBiO3, BaBi2O6, and SrBi2O6. The d-electrons from Zn, Pb and Ag produce a large conduction range as well as consequently poor photocatalytic performance. Electronic systems greatly affect catalytic performance. Excellent visible-light photocatalytic activity recommends pentavalent bismuthates for different photocatalytic applications. M(BiO3)n could be used for efficient visible light photocatalytic degradation of organic pollutants [161][165].

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Habib ULLAH
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