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Synthesis, Modification of Bismuth Oxyiodide Photocatalyst for Purification of Nitric Oxide

Hanqiang Zhou , Mingfei Yu , Qiaoshan Chen , Jianchun Wang , Jinhong Bi

Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (12) : 2404 -2412.

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Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (12) : 2404-2412 DOI: 10.7536/PC210103
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Synthesis, Modification of Bismuth Oxyiodide Photocatalyst for Purification of Nitric Oxide
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Abstract

Photocatalytic technology has shown great potential for purification of low-concentration nitric oxide (NO) pollution due to its energy-saving property, high efficiency, and limited secondary pollution. Among various semiconductors, bismuth oxyiodide (BiOI) photocatalyst has drawn considerable attention in recent years due to the superior photocatalytic activity and stability, since its narrow band gap and specific layered structure is in favor of visible light absorption and electron-hole pairs separation. Hence, we overview the latest research progress in the photocatalytic purification of NO by BiOI and introduce the influence of crystalline morphology and facets on its photocatalytic performance. The modification and activity enhancement mechanism of BiOI is emphatically expounded, for example, surface modification, ion doping and heterostructure construction. The future prospects and challenges in this research spot are put forward for the sake of providing theoretical reference and technical support for the design of highly active BiOI and the efficient purification of low concentration NO.

Contents

1 Introduction

2 Reaction mechanism and pathway of photocatalytic purification of NO

3 Controlled synthesis of bismuth oxyiodide

3.1 Morphological control

3.2 Crystal plane control

4 Surface modification and ion doping of bismuth oxyiodide

5 Construction of bismuth oxyiodide heterojunction

5.1 Bismuth oxyiodide/semiconductor heterojunction

5.2 Bismuth oxyiodide/insulator heterojunction

5.3 Ternary heterojunction

6 Conclusion and outlook

Graphical abstract

Keywords

bismuth oxyiodide / nitric oxide / photocatalysis / atmospheric contamination

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Hanqiang Zhou, Mingfei Yu, Qiaoshan Chen, Jianchun Wang, Jinhong Bi. Synthesis, Modification of Bismuth Oxyiodide Photocatalyst for Purification of Nitric Oxide. Progress in Chemistry, 2021, 33(12): 2404-2412 DOI:10.7536/PC210103

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1 Introduction

With the rapid growth of population and the development of modern industrial civilization, the problem of global air pollution is becoming more and more serious. Air pollution mainly comes from nitrogen oxides (NOx), sulfur dioxide (SO2), carbon monoxide (CO), suspended particles (PM), volatile organic pollutants (VOCs) and ozone (O3). As one of the main air pollutants, NOx is composed of nitric oxide (NO) and nitrogen dioxide (NO2), and is produced through the combustion of fossil fuels, which can cause environmental problems such as acid rain and photochemical smog, and seriously endanger human health[1,2]. In 1990, the Clean Air Act was amended by the Environmental Protection Agency (EPA) to include NOx emission control in large power plants[3]. In 1999, the Protocol to Abate Acidification, Eutrophication and Ground-level Ozone, signed by the United Nations, set targets for limiting NOx emissions[4]. In 2016, China's national "13th Five-Year" ecological environment protection plan also implemented the total amount control of NOx[5]. It can be seen that the pollution of NOx has attracted great attention from the international community. In addition, with the improvement of environmental protection policies, the requirements for air quality are becoming more and more stringent. In the environmental air quality standards formulated by countries all over the world, the annual average concentration limit of NOx is mostly at ppb level, so the treatment of low concentration NOx has become a hot issue[6].
As a low valence state of NOx, nitric oxide is chemically unstable and easily oxidized into highly toxic by-products (such as NO2 and N2O4) in the air, resulting in secondary pollution, so it is difficult to purify. Traditional NO removal technologies include chemical absorption and selective catalytic reduction, which have high purification efficiency, wide application and mature technology, but most of them have high energy consumption and complex process, and are mostly used for the removal of high concentration NO, while for the treatment of low concentration NO, the economy is poor[7⇓~9]. As a new alternative technology, photocatalytic technology based on semiconductor materials has shown great prospects in the removal of low concentration of NO because of its many advantages, such as low energy consumption, mild reaction and environmental friendliness[10,11]. In the past ten years, researchers have invested a lot of energy in the field of photocatalytic purification of NO, and the number of relevant publications has increased year by year (Fig. 1). In the aspect of catalyst development, the traditional semiconductor material titanium dioxide (TiO2),TiO2 has the advantages of low cost, good stability and so on[12,13]. However, its wide band gap (3. 2 eV) limits its application under visible light conditions. With the development of photocatalytic technology, many photocatalytic materials responding to visible light have emerged, including graphitic carbon nitride (g-C3N4), zinc stannate (Zn2SnO4), bismuth-based semiconductors (bismuth tungstate (Bi2WO6), bismuth molybdate (Bi2MoO6), bismuth oxyhalide (BiOX) and so on[14][15][16][17][18,19]. Among them, BiOI materials have received extensive attention due to their good visible light absorption properties and unique crystal structure[20]. The band gap of BiOI is 1.7 ~ 1.9 eV, and its optical absorption range almost covers the whole visible light band (390 ~ 760 nm)[21]. In addition, BiOI has a tetragonal fluoro-chloro-lead structure, with I- layers and [Bi2O2]2+ layers alternating with each other, showing a unique layered structure (Figure 2a). The internal electric field formed between the layers can effectively accelerate the separation of photogenerated electrons (e-) and holes (h+), thus enhancing the photocatalytic activity of the material[22,23]. In this paper, the effects of crystal morphology and crystal face on the catalytic performance of BiOI were described, and the improvement mechanisms of various modification methods on the catalytic performance of BiOI were introduced, in order to better solve the problem of low concentration of NO pollution, and provide theoretical guidance and reference for the modification and optimization of bismuth semiconductor materials.

2 Reaction Mechanism and Pathway of Photocatalytic Purification of Nitric Oxide

Photocatalytic purification of NO is a process that uses solar energy as the energy source to oxidize NO into harmless substances under the action of h+ and e- and the strong oxidizing substances produced by them. The main purification process is shown in Figure 2b[24⇓⇓~27]. Under the irradiation of sunlight, BiOI can absorb light energy greater than or equal to its forbidden band width, and generate h+ and e- in the valence band (VB) and conduction band (CB), respectively, to form hole-electron pairs (Formula 1). Part of the photogenerated h+ and e- will participate in the oxidation and reduction reactions, respectively, to produce active species that are beneficial to the photocatalytic reaction. h+ can oxidize hydroxyl radicals (OH-) adsorbed on the surface of BiOI to generate hydroxyl radicals (· OH) (Formula 2), which play a key role in purifying NO, while e- can be captured by oxygen (O2) to form superoxide radicals (· O 2 -) (Formula 3). The generated O 2 - further reacts with substances such as h+, e- and H+ to generate more oxidation active substances.Uch as hydrogen peroxide radical (·O2H), singlet oxygen (1O2), and hydrogen peroxide (H2O2) (formulae 4 to 8).
BiOI + hv → h + + e-
h+ + OH- → ·OH
e- + O2 → · O 2 -
· O 2 - + e- → ·O 2H
· O 2 - + ·O 2H + H+ → 1O2 + H2O2
· O 2 - + h+ → 1O2
· O 2 - + e- + 2H+ → H 2O2
H2O2 + e- → ·OH + OH -
After adsorbed on the surface of the catalyst, it will be converted into NO2 and nitrogen dioxide (N2O2) under the action of O2 (Formula 9, 10), which are unstable.It is further converted into other NOx (including dinitrogen trioxide (N2O3), N2O4, nitrous acid (HNO2), etc.) (Formulae 11 to 13). Under the synergistic effect of h+ and a variety of strong oxidation active substances (mainly including · OH and · O 2 -, etc.), the NOx generated during the adsorption process will be further oxidized until the stable final product nitrate (N O 3 -) is generated (formulas 14 to 21)[27].
2NO+O2→2NO2(9 )
2NO↔N2O2(10 )
NO+NO2→N2O3(11 )
2NO2↔N2O4(12 )
N2O4+H2O→N O 2 + +OH-+HNO2(13)
2NO+2·OH→N2O3+H2O(14 )
N2O3+2·OH→2NO2+H2O(15 )
NO2+·OH→N O 2 + +OH-(16)
N O 2 + +2OH-→N O 3 - +H2O(17)
6NO+2· O 2 - +H2O→3N2O3+2OH-(18)
3N2O3+2· O 2 - +H2O→6NO2+2OH-(19)
NO2+· O 2 - +2e-+2H2O→N O 2 + +4OH-(20)
N O 2 + +H2O→N O 3 - +2H+(21)
In addition, it is worth noting that the purification process of NO will be affected by the final product N O 3 -. With the increase of the concentration of N O 3 -, the N O 3 - adsorbed on the surface of BiOI will inhibit the production of active species (· OH and · O 2 -, etc.), which will lead to the conversion of the photocatalytic oxidation process from a non-selective process to a selective process, resulting in a final product NO2 which is more toxic than NO (Formula 22 ~ 23)[19,28]. Therefore, the concentration of N O 3 - adsorbed on the surface of BiOI should be controlled in practical applications.
N O 3 - -BiOI+hv→h++e-(22)
h++NO→NO2(23 )

3 Controlled Synthesis of Bismuth Iodide Oxide

3.1 Morphology control

BiOI materials can be synthesized by room temperature hydrolysis, hydrothermal and solvothermal methods. Because of its layered crystal structure, it is easy to grow into flaky materials according to its growth habit. However, various morphologies such as plate, sphere, hollow sphere and bowl can be obtained by adjusting the reaction conditions such as the type and proportion of the reaction solvent and the reaction time[29⇓⇓~32]. Changing the crystal morphology of BiOI can effectively regulate its specific surface area and porosity, affect the adsorption and activation of the catalyst to reactants, and thus regulate its catalytic activity[33⇓~35]. In addition, the catalytic activity of BiOI is closely related to its size, sheet thickness and other microstructures[21,36].
Yosoff et al. prepared flaky and spherical BiOI nanoparticles (Fig. 3) at room temperature by using the grinding method and adjusting the type of reaction solvent and reaction time. Their specific surface areas were 4.99 and 16.06 m2·g-1, and their porosities were 0.0143 and 0.1057 cm3·g-1, respectively. Compared with flaky BiOI, spherical BiOI had larger specific surface area and porosity, so it had higher degradation efficiency for ciprofloxacin[37]. Xia et al. used a solvothermal method to prepare BiOI flower-like hollow microspheres by adding ionic liquid 1-butyl-3-methylimidazolium iodide as a solvent and a template. The specific surface area of BiOI flower-like hollow microspheres can reach 61.63 m2·g-1, which is higher than that of BiOI(5.2~22.7 m2·g-1) with other morphologies. Under visible light conditions, they exhibited methyl orange degradation efficiency superior to that of sheet BiOI and TiO2[38]. Generally speaking, the catalytic activity of BiOI follows the rule of hollow sphere > flower sphere > sheet, so researchers are more inclined to develop three-dimensional BiOI materials with hollow structure[39]. In addition to the hollow structure, the ordering degree of the microstructure of the material also plays an important role in the improvement of its specific surface area and performance. Mera et al. prepared nanoscale microspherical BiOI with a regular structure by controlling the reaction time with ethylene glycol (EG) as the reaction medium under microwave conditions. The specific surface area of BiOI can reach 76 m2·g-1, and the efficiency of visible light purification of NO (61.1%) is much higher than that of the traditional P-25 material[24].
In addition, the thickness of BiOI sheet is also a key factor affecting the photocatalytic performance. Ren et al. Prepared hollow and flower-like BiOI microspheres with specific surface areas of 45.2 and 38.8 m2·g-1, respectively, at low temperature (70 ℃)[35]; Theoretically, BiOI hollow spheres should have better photocatalytic performance, but their degradation efficiency of rhodamine B (RhB) under visible light is lower than that of flower-like BiOI microspheres, due to the thinner thickness of BiOI sheets in flower-like microspheres. The smaller the sheet thickness is, the smaller the diffusion distance of photogenerated carriers is, which is more conducive to the separation of photogenerated carriers. Jiang et al. Prepared hollow flower-like BiOI by solvothermal method, and the catalyst with a sheet thickness of 2 nm also showed higher visible-light photocatalytic performance than the catalyst with a sheet thickness of 15 nm[40]. Nava N Núñez et al. synthesized BiOI microspheres composed of ultrathin sheet structures with a thickness of 5 nm under microwave irradiation by controlling the ratio of 2-propanol to EG in the reaction medium, and the purification efficiency of NO under visible light irradiation can reach 83%[36].

3.2 Crystal plane control

Photocatalytic reactions mostly occur on the crystal surface, so it is of great significance to control the exposed crystal surface of the crystal to improve the activity of the catalyst. According to the DFT theoretical calculation, the (001) crystal face of BiOI has the lowest surface energy, so most of the BiOI nanosheets prepared by conventional methods such as solvothermal method are exposed on the (001) crystal face[41]. Suppressing the growth of BiOI crystal along the c-axis direction can effectively increase the exposure of (001) crystal plane, reduce the thickness of nanosheets and promote the separation of photogenerated electron-hole pairs. Rao et al. Synthesized BiOI microspheres composed of ultrathin nanosheets by solvothermal method. By doping Zn2+ instead of Bi3+, the exposure of (001) crystal face was increased, and the purification efficiency of NO was improved[42].
Compared with the (001) plane, the exposed (110) plane is more conducive to the generation of active oxygen species (· O 2 - and · OH, etc.), thereby improving the photocatalytic performance of BiOI[43]. Sun et al. Synthesized BiOI materials with exposed different crystal faces by pH-induced conversion method, and found that the BiOI with exposed (110) crystal face had higher catalytic activity than that with exposed (001) crystal face by using vapor phase mercury photocatalytic oxidation as a probe reaction, because the exposed (110) crystal face could produce more · O 2 -[44]. Reyna-Cavazos et al. Synthesized BiOI with highly exposed (110) crystal face by controlling the reaction temperature and time using glycerol as the reaction medium[25]. The photocatalytic activity of the BiOI samples for the purification of NO and SO2 under visible light was studied, and it was also confirmed that the exposure of the (110) crystal face could increase the concentration of · O 2 -, thus enhancing the ability of BiOI to purify gaseous pollutants.

4 Surface Modification and Ion Doping of Bismuth Iodide Oxide

Modification or doping of BiOI with specific elements can optimize the band gap structure and visible light absorption performance of BiOI, and inhibit the recombination of photogenerated carriers, which is an effective means to improve the photocatalytic activity of BiOI. Table 1 lists the purification efficiency of NO by surface modification and ion doping modified BiOI[45,46].
Surface modification of BiOI with metal Bi is one of the most commonly used methods, which can be achieved by adding reducing agents (such as NaBH4) to reduce part of the Bi3+ to elemental Bi in situ. Bi has the same surface plasmon resonance (SPR) effect as noble metals, and the generated local electromagnetic field can promote the separation of photogenerated carriers. At the same time, the introduction of Bi is beneficial to the formation of surface oxygen vacancies (OVs). These OVs can improve the adsorption capacity of the material to NO to a certain extent, and cooperate with elemental Bi to promote light harvesting and inhibit the recombination of photogenerated carriers, thus improving the photocatalytic performance of the material. For example, Sun et al. Prepared Bi/BiOI rich in OVs by precipitation and in situ reduction. Compared with BiOI, the NO purification efficiency of Bi/BiOI increased from 3.0% to 40.8%[47]. The Bi/BiOI catalyst prepared by Xing et al. By uniformly and stably modifying metal Bi on the surface of BiOI nanospheres has faster electron transfer rate and more efficient electron separation rate than pure BiOI, and the purification efficiency of NO is increased from 1.38% to 51.42%[48]. In addition, Bi modification also plays an important role in inhibiting the formation of intermediate toxic by-products. In the process of photocatalytic purification of NO, e- is more inclined to accumulate in OVs, and the increase of charge density is beneficial to the production of active oxygen species (· O 2 - and · OH, etc.), thus promoting the deep conversion of NO2 to N O 2 - and N O 3 -. Li et al. Prepared Bi/BiOI rich in OVs by solvothermal and in-situ reduction methods. Compared with pure BiOI, the purification efficiency of NO was improved to 46.5%, and the selectivity of the reaction path was also improved from 36% to 86.6%, which was due to the generation of more active oxygen species effectively inhibiting the generation of NO2 in the purification process[49].
By doping different metal or nonmetal ions in the crystal structure of the BiOI, an impurity energy level can be formed in the forbidden band of the BiOI so as to regulate and control the energy band structure and the optical absorption performance of BiOI; Ion doping can also control the crystallinity and lattice defects of the material[45]. For example, Hojamberdiev et al., under hydrothermal conditions, the purification efficiency was significantly improved by doping a proper amount of Er3+,NO, reaching 54.0%[50]; This is because the doping of Er3+ makes the crystal structure of the material change from orthorhombic to monoclinic, which leads to the red shift of the absorption edge and greatly improves the visible light absorption performance of the catalyst. Rao et al. synthesized BiOI microspheres doped with Zn2+ by solvothermal method. The Zn2+ replaced the Bi3+ in BiOI to increase the exposure of (001) crystal face and the number of OVs, so the NO purification efficiency of the material was significantly improved to 53.6% (Fig. 4)[42].
Doping and modification with a variety of different elements can make up for the deficiency of single element modification and synergistically improve the NO purification capacity. For example, Zhang et al. prepared La-doped spherical Bi5O7I samples (L-BOI) by the solvothermal method, and loaded Au nanoparticles on the L-BOI doped with 6% La by the room-temperature chemical reduction method to obtain new materials (A-L-BOI) simultaneously doped with La and deposited with Au[51]. Compared with pure BiOI, the Bi5O7I(A-BOI) of L-BOI and modified Au nanoparticles improved the photocatalytic activity to some extent, and the removal efficiency of nitric oxide reached 34. 2% and 42. 7%, respectively. The performance improvement of the L-BOI sample is mainly due to the reduction of the band gap and the increase of the number of OVs; The modification of Au nanoparticles can produce SPR effect and inhibit carrier recombination, and also can reduce the amount of intermediate NO2. The NO removal efficiency of A-L-BOI was further enhanced to 52.5% by the synergistic effect of the two.

5 Construction of Bismuth Iodide Oxide Based Heterojunction

BiOI catalyst is combined with other materials to form a heterojunction, which can promote the separation of photogenerated electron-hole pairs and improve the utilization of photogenerated charges. In addition, the combination of narrow band gap semiconductors and wide band gap semiconductors can provide sensitization for wide band gap semiconductors and increase the photoresponse range. Therefore, the construction of heterojunction is a common means to improve the photocatalytic performance of BiOI[52]. The research progress of NO purification by heterojunction BiOI is listed in Table 2.

5.1 Bismuth iodoxide/semiconductor heterojunction

Other bismuth oxyhalides, such as BiOBr and bismuth oxychloride (BiOCl), which also have unique layered structures, are the most commonly used materials to construct heterojunctions with BiOI. For example, Dong et al. Synthesized porous BiOI/BiOCl solid solution composites with flower-like structure by template-free method at room temperature. The coupling of BiOCl and BiOI reduces the band gap width of the material and improves the visible light absorption performance[53]. The hierarchical porous structure also increases the specific surface area of the material, so that the solid solution material obtains the NO purification efficiency superior to that of BiOI, P25, Bi2WO6 and C-doped TiO2. Shi et al. Synthesized ultra-thin BiOI/BiOBr heterojunction rich in OVs by hydrothermal method. Compared with conventional BiOI/BiOBr, its photocatalytic activity for NO purification increased from 10% to 57% due to the effect of OVs and ultra-thin structure[28]. However, the OVs also enhanced the adsorption of N O 3 -, resulting in the conversion of the photocatalytic process from a non-selective one to a selective one, thus producing more NO2, which can be easily removed by alkali solution.
BiOI can also be combined with other bismuth-based semiconductors by a simple preparation method, for example, Wang et al. Synthesized Bi2WO6/BiOI vertical heterostructures by heteroepitaxial anion exchange method, and most of the traditional heterostructures are Van der Waals heterostructures.There is no electron shuttle channel between adjacent materials, while the vertical heterostructure can use the connected [Bi2O2]2+ layer as an electron transfer channel to directly transfer e- to Bi atoms on the surface, promote the adsorption and activation of reactant molecules, and then enhance the photocatalytic activity (Fig. 5)[54]. Ou et al. Synthesized Bi2O2CO3/BiOI solid solution by template-free method at room temperature. Compared with Bi2O2CO3, the VB of the structure increased while the CB decreased, which was more conducive to the generation of electrons by photoexcitation. In addition, the aggregation of nanosheets made it have a three-dimensional layered porous structure with larger mesopores, so it had higher purification efficiency than pure BiOI and Bi2O2CO3 in the process of photocatalytic purification of NO[55]. Dong et al. synthesized a novel 2D BiOIO3/BiOI heterostructure using a simple comprehensive method. Since the (010) face atom arrangement of BiOIO3 is the same as the (001) face of BiOI, the exposed (010) crystal face of BiOIO3 nanosheets induces BiOI to preferentially grow along the (001) crystal face (Fig. 6). In addition, the intimate contact of the shared interfacial oxygen atoms increases the contact area between them, thus enhancing the photocatalytic activity for NO purification[56].
In addition, BiOI can also be coupled with other types of semiconductors. For example, Sun et al. Prepared BiOI/La(OH)3 nanorod heterojunction photocatalysts by a simple chemical impregnation method. The existence of BiOI extends the photoresponse range of La(OH)3 from ultraviolet region to visible region.The heterostructure further improves the separation of photogenerated carriers, and the photocatalytic activity of BiOI/La(OH)3 for NO purification is much higher than that of pure BiOI and pure La(OH)3 nanorods[57]. Chen et al. Synthesized SrTiO3/BiOI heterostructure photocatalyst by a simple chemical bath method. The construction of the heterostructure enables the material to have good visible light absorption performance. In addition, the photogenerated electrons can be directly transferred from the BiOI semiconductor to the surface of the SrTiO3 through a pre-formed electron transfer channel.Therefore, the SrTiO3/BiOI heterojunction has enhanced photocatalytic performance, and the efficiency of purifying NO reaches 59%, which is much higher than that of SrTiO3(33%) and BiOI (9%)[58]. Gong et al. synthesized a new 1D/2D BiOI/ZnWO4p-n heterojunction by a two-step method, and the formed p-n junction further improved the separation efficiency of photogenerated charges and extended the photoresponse range from ultraviolet light to visible light. Therefore, compared with pure ZnWO4 and BiOI, the photocatalytic activity of BiOI/ZnWO4 composite for NO purification was significantly improved, reaching 48.2%[59].

5.2 Bismuth oxyiodide/insulator heterostructures

Compared with the more expensive semiconductor, insulator materials have the advantages of abundant reserves and low cost. In recent years, insulator photocatalysis has attracted the attention of researchers. The key to construct semiconductor-insulator heterostructure is how to realize the effective transfer of e- from semiconductor to insulator. Wang et al. Constructed a core-shell SrCO3/BiOI heterostructure using insulator SrCO3 and semiconductor BiOI, which showed enhanced visible light absorption between 400 and 600 nm[27]. The covalent interaction between the O 2p orbit of the SrCO3 and the 6p orbit of Bi can transfer the e- from BiOI to CB of the SrCO3, thus achieving efficient charge separation and improving the catalytic activity of BiOI. Similarly, they coupled the insulator BaCO3 and BiOI to form a BaCO3/BiOI heterostructure. Under visible light irradiation, the potential difference between the Bi layer of BiOI (5.03 eV) and the carbonate layer of BaCO3 (12.37 eV) can drive the e- from Bi atoms to the adjacent carbonate layer across the energy barrier[60]. e- can oxidize small molecules on BaCO3 to produce oxidative free radicals (.OH. O 2 -, and 1O2),Promotes the conversion of NO to high-valent intermediates (NO+ and N O 2 +) so that the final product nitrate is generated (fig. 7). In addition, they have successfully constructed CaSO4-BiOI heterostructures, and the electron transfer between O2 molecules and BiOI surface and CaSO4-BiOI interface is -0.04 eV and -0.61 eV, respectively, according to density functional theory calculations.The calculated results indicate that the electron-rich environment at the interface of the CaSO4-BiOI heterostructure is beneficial to the activation of small molecules such as O2 and the generation of more active oxidation groups (· OH and · O 2 -), thus promoting the conversion of inert pollutants NO2 and reducing the generation of poisoning by-products in the NO purification process[61].

5.3 Ternary heterojunction

The BiOI can also be compounded with two or more other materials to form a multi-element heterojunction so as to achieve the effect of synergistically promoting the improvement of the photocatalytic performance. For example, Shi et al. synthesized the BiOBr0.5I0.5/BiOBr/BiOI composite photocatalyst by simple precipitation method, hydrothermal method and other methods. Compared with BiOBr0.5I0.5 and BiOBr/BiOI composite, the BiOBr0.5I0.5/BiOBr/BiOI composite photocatalyst has the highest efficiency of photocatalytic purification of NO, reaching 47.9%, and the other two are 29.7% and 7.0%, respectively, due to the enhanced photocatalytic synergistic effect of carriers and photogenerated electrons generated by the solid solution and heterojunction of BiOBr0.5I0.5/BiOBr/BiOI composite photocatalysts[62]. Sun et al. Synthesized a ternary compound Bi/BiOI/Bi2O2CO3 with double heterojunction (Bi/BiOI and BiOI/Bi2O2CO3 by in-situ assembly at room temperature using NaBH4 as a reducing agent.The enhanced photocatalytic activity is attributed to the double heterostructure of Bi/BiOI/Bi2O2CO3, oxygen vacancies and the SPR effect of Bi particles, which contribute to the separation of electrons and holes and increase the carrier concentration. The photocatalytic purification efficiency of NO under visible light reaches 50.7%, which is much higher than that of pure BiOI (1.2%)[63]. Zhu et al. Synthesized a ternary Bi/BiOI/graphene photocatalyst under solvothermal conditions, and the efficiency of photocatalytic oxidation and purification of NO under visible light irradiation reached 51.8% in 30 min, which was higher than that of pure BiOI, binary Bi-BiOI and binary BiOI/graphene composites.The enhanced NO purification efficiency of the ternary Bi-BiOI/graphene photocatalyst is mainly due to the efficient transfer of photogenerated electrons from BiOI and Bi into graphene, resulting in the effective separation of photogenerated electron-hole pairs and the synergistic SPR effect of Bi nanoparticles in the composite photocatalyst[64].

6 Conclusion and prospect

In recent years, the situation of atmospheric environmental pollution is still grim, as one of the main pollutants in the atmosphere, the problem of NO pollution needs to be solved urgently. As an effective way for the treatment of low concentration of nitric oxide, semiconductor photocatalysis technology has been widely concerned by researchers. Among them, BiOI with narrow band gap and special layered structure shows a good application prospect. However, BiOI materials also have some inherent defects, such as easy recombination of photogenerated carriers and weak redox ability, so researchers at home and abroad have modified them by a series of methods, such as controlling the morphology and crystal plane type, surface modification, ion doping and heterojunction construction, in order to improve the photocatalytic performance of BiOI for NO purification. Although these modified methods have made important progress in photocatalytic purification of NO, there is still much room for improvement. Some challenges in photocatalytic purification of NO by BiOI are listed below, and the direction is prospected:
(1) In the aspect of morphology control of BiOI, the morphology of BiOI used for photocatalytic purification of NO is mostly microspheres or hollow flower-like spheres, and 1D and 2D BiOI materials are rare, so the synthesis strategy can be changed to obtain more abundant BiOI materials;
(2) Many by-products will be produced in the process of photocatalytic purification of NO by using BiOI materials, including NO2 with stronger toxicity, etc., which can further explore the purification mechanism of NO, improve the controllability of the purification path of NO, and effectively inhibit the formation of intermediate toxic by-products;
(3) Insulator materials are abundant in nature and are often used as coatings, building materials, etc. The successful construction of BiOI/insulator heterojunction makes BiOI show great application prospects in self-cleaning coatings and other fields.

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Funding

the National Natural Science Foundation of China(5167204)

the Natural Science Foundation of Fujian Province(2019J01648)

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