Next Article in Journal
Molecular Characterization, Expression, Evolutionary Selection, and Biological Activity Analysis of CD68 Gene from Megalobrama amblycephala
Next Article in Special Issue
Recent Advances in the Synthesis, Characterization, and Application of Carbon Nanomaterials for the Removal of Endocrine-Disrupting Chemicals: A Review
Previous Article in Journal
Determination of Melting Parameters of Cyclodextrins Using Fast Scanning Calorimetry
Previous Article in Special Issue
Spark Plasma Sintering-Assisted Synthesis of Bi2Fe4O9/Bi25FeO40 Heterostructures with Enhanced Photocatalytic Activity for Removal of Antibiotics
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
IJMS
Volume 23
Issue 21
10.3390/ijms232113131
ijms-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Preparation of a Z-Type g-C3N4/(A-R)TiO2 Composite Catalyst and Its Mechanism for Degradation of Gaseous and Liquid Ammonia

by
Jiaming Zhu
1,2,
Zuohua Liu
1,
Hao Wang
1,2,
Yue Jian
1,2,
Dingbiao Long
1,2,* and
Shihua Pu
1,2,*
1
Chongqing Academy of Animal Sciences, Chongqing 402460, China
2
Scientific Observation and Experiment Station of Livestock Equipment Engineering in Southwest, Ministry of Agriculture, Chongqing 402460, China
*
Authors to whom correspondence should be addressed.
Int. J. Mol. Sci. 2022, 23(21), 13131; https://doi.org/10.3390/ijms232113131
Submission received: 28 September 2022 / Revised: 24 October 2022 / Accepted: 26 October 2022 / Published: 28 October 2022
(This article belongs to the Special Issue Recent Advances in Synthesis, Characterization and Applications of Innovative Materials in Removal of Water Contaminants)
Browse Figures
Versions Notes

Abstract

:
In this study, an (A-R)TiO2 catalyst (ART) was prepared via the sol–gel method, and g-C3N4 (CN) was used as an amendment to prepare the g-C3N4/(A-R)TiO2 composite catalyst (ARTCN). X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, N2 adsorption–desorption curves (BET), UV–Vis diffuse absorption spectroscopy (UV–Vis DRS), and fluorescence spectroscopy (PL) were used to evaluate the structure, morphology, specific surface area, optical properties, and photocarrier separation ability of the catalysts. The results showed that when the modifier CN content was 0.5 g, the dispersion of the ARTCN composite catalyst was better, with stronger light absorption performance, and the forbidden band width was smaller. Moreover, the photogenerated electrons in the conduction band of ART transferred to the valence band of CN and combined with the holes in the valence band of CN, forming Z-type heterostructures that significantly improved the efficiency of the photogenerated electron-hole migration and separation, thus increasing the reaction rate. Gaseous and liquid ammonia were used as the target pollutants to investigate the activity of the prepared catalysts, and the results showed that the air wetness and initial concentration of ammonia had a great influence on the degradation of gaseous ammonia. When the initial concentration of ammonia was 50 mg/m3 and the flow rate of the moist air was 0.9 mL/min, the degradation rate of gaseous ammonia by ARTCN-0.5 reached 88.86%, and it had good repeatability. When the catalytic dose was 50 mg and the initial concentration of NH4+ was 100 mg/L, the degradation rate of liquid ammonia by ARTCN-0.5 was 71.60% after 3 h of reaction, and small amounts of NO3− and NO2− were generated. The superoxide anion radical (·O2−) and hydroxyl radical (·OH) were the main active components in the photocatalytic reaction process.

1. Introduction

Ammonia is a colorless alkaline gas that causes strong irritation, mainly from agricultural fertilization, animal husbandry, and the use of antifreeze [1]. Estimates have shown that China emits 10 to 15 million tons of ammonia into the air every year, almost double the total of the United States and the European Union [2]. Large-scale ammonia emissions will not only cause diseases in animals and humans, such as central muscle paralysis and bronchitis, but also cause global climate change [3]. Ammonia reacts with oxides in the air, producing particulate matter such as ammonium sulfate and ammonium nitrate, which are the main factors that form haze [4]; thus, controlling ammonia emissions is beneficial to controlling haze [5]. In addition, ammonia gas will return to the surface through atmospheric dry and wet deposition, leading to the eutrophication of water and affecting the stability of the ecosystem [6]. Traditional ammonia treatment processes have high costs and poor stability, which may aggravate the secondary pollution of the environment [7].
In 1972, Fujishima discovered that TiO2 could photolyze water under ultraviolet light, and this photocatalytic reaction has been widely used in environmental governance, energy development, biological applications, self-cleaning materials, antibacterial applications, sensors, and other fields due to its thorough reaction and lack of secondary pollution [8]. For example, A. Enesca et al. [9] prepared doped tin oxide films with different dopant concentrations through spray pyrolysis deposition and found that the photodegradation efficiency of the SnO2 film could reach about 30% under the condition of zinc doping. X. Hu et al. [10] introduced and discussed the current challenges and future development prospects of CO2 photoreduction for hydrocarbon fuels. X. Liu et al. [11] prepared CdS@ZIS-SV, and its hydrogen production rate reached 18.06 mmol/g/h, which was 16.9 and 19.6 times that of original CdS (1.16 mmol/g/h) and ZIS (0.92 mmol/g/h) materials, respectively. In ammonia gas degradation, P.A. Kolinko et al. [12] and H.M. Wu et al. [13] pointed out that the N element had various valence states. Herein, its main product was N2, and its by-products were N2O, NO2−, and NO3−. Among the many photocatalytic materials, TiO2 has become photocatalyst with the most potential due to its advantages such as good chemical stability, safety, non-toxicity, low cost, and strong REDOX ability [14]. Most studies have indicated that the degradation performance of anatase (A-TiO2) is better than rutile (R-TiO2), and reports on TiO2 have mainly used the anatase phase [15]. Shen et al. [16] stated that when the A-TiO2 and R-TiO2 phases formed a heterogeneous structure, an internal electric field could form, thus promoting the transfer of charges on the interface and improving photocatalytic activity. Das et al. [17] prepared a mixed anatase/rutile crystal structure that had a higher photocatalytic performance than commercial P25 under visible light. Xiong et al. [18] showed that mixed crystalline anatase and rutile TiO2 nanoparticles exhibited a high photocatalytic carbon dioxide reduction capacity. However, its high bandgap width (3.2 eV for anatase and 3.0 eV for rutile) resulted in a response to only high-energy UV light, and its photogenerated charge carriers were easy to recombine, thus limiting its catalytic activity [19]. For example, Guarino et al. [20] sprayed TiO2 on a wall with a total area of 150 m2 at a spray quantity of 70 g/m2 and using a 36 W UV light as the light source, and the degradation rate of ammonia was found to be about 30%.
Photocatalytic materials can be used to form heterogeneous structures. For example, Shihua Pu et al. [21] achieved the degradation of ammonia under sunlight for the first time through the Cu2O improvement of {001}TiO2, and the degradation rate of ammonia was found to be more than 80% within 2 h. However, due to the photocorrosion of Cu2O itself, the degradation rate of ammonia gas was only maintained at 40% after four repeated uses, making the choice of amendment very important. g-C3N4 has shown a narrow band gap, with a wide range of light responses and good thermal stability, chemical stability, and strong corrosion resistance [22]. Most studies have found that the formation of heterostructures through the preparation of g-C3N4/TiO2 composite catalysts could broaden the solar spectral response of the catalyst, and photogenerated charge carriers are not easy to recombine [23]. For example, Li et al. [24] constructed a g-C3N4/TiO2 heterostructure that achieved effective photoinduced electron-hole separation in the photocatalytic process and showed a good photocatalytic effect and cyclic stability. Zhao S et al. [25] used synthesized g-C3N4/TiO2 to degrade phenol with 2.41 and 3.12 times g-C3N4 and TiO2 contents, respectively. Sun et al. [26] used synthetic g-C3N4/TiO2 to degrade methylene blue with 1.85 and 4 times pure g-C3N4 and TiO2 content, respectively; this showed that it was feasible to improve TiO2 degradation capacity by using g-C3N4 as an amendment, but a study on ammonia degradation has not been previously reported.
In this study, an (A-R)TiO2 catalyst (ART) was prepared via the sol–gel method, where g-C3N4 (CN) was used as an amendment to prepare g-C3N4/(A-R)TiO2 (ARTCN) with a Z-type heterostructure, which improved the efficiency of photogenerated electron-hole migration and separation. In this study, using gaseous ammonia and ammonia as the target pollutants, we explored the ARTCN degradation of ammonia, the mechanism of performance improvement, the intermediate, and the reaction process. We also studied the repeated use of ARTCN, as evidence on the properties and mechanism noted in this research regarding the effective governance of ammonia pollution has been relatively scarce, and this research could provide a certain theoretical basis for the management of ammonia.

2. Results

2.1. Analysis of the Characterization Results

2.1.1. XRD Analysis

When 2θ = 25.28°, 36.95°, 37.80°, 38.55°, 48.04°, 53.89°, 55.06°, 62.68°, 70.31°, 75.03°, and 76.02°, the characteristic peaks corresponding to the (101), (103), (004), (112), (200), (105), (211), (204), (220), (215), and (301) crystal planes, respectively, were almost consistent with the anatase TiO2 (JCPDS No. 21-1272) standard cards [27]. Furthermore, 2θ = 27.45°, 36.09°, 39.19°, 41.26°, 44.05°, 54.32°, 56.64°, 64.04°, and 69.01° corresponded to the (110), (101), (200), (111), (210), (211), (220), (310), and (301) crystal planes, respectively, which was almost consistent with the rutile TiO2 (JCPDS No. 21-1276) standard card [28]. The characteristic peaks at 2θ = 13.1°and 27.5° belonged to the (100) and (002) planes, respectively which was largely in line with g-C3N4 (JCPDS87-1526) [29].
Figure 1 shows the XRD patterns of the prepared samples. We found that ART contained not only the characteristic peaks of the anatase phase but also the characteristic peaks of the rutile phase, indicating that it was a mixed crystal type, which was the prepared (A-R)TiO2 catalyst. CN had a weak diffraction peak near 13.1°, corresponding to the (100) crystal plane of CN, which was formed by the 3-S monotriazine structural unit of the plane [30]. There was a strong diffraction peak at 27.50°, which was caused by the layered accumulation of graphite in the conjugate plane. The diffraction peak of the ARTCN-X composite corresponded to pure ART, which indicated that CN did not enter the ART lattice and was only attached to its surface. There was no diffraction peak in the composite samples of ART and CN at 13.1°, because the amount of CN was small and had a weak peak. Although the peaks of CN at 27.50° and R-TiO2 at 27.45° coincided, we observed that as the composite ratio increased from 0.1 to 1, the composite gradually widened around 27°, indicating that the composite material was successfully prepared.
The accuracy was further verified by calculating the rutile content of several materials [31], and the calculation results are shown in Table 1. We found that the rutile contents of ART, ARTCN-0.1, ARTCN-0.5, and ARTCN-1 were 23.49%, 25.06%, 29.43%, and 34.61%, respectively. High temperatures were conducive to the conversion of A-TiO2 into R-TiO2, while ART, ARTCN-0.1, ARTCN-0.5, and ARTCN-1 were prepared at the same temperature; thus, the increased rutile content was not rutile in the real sense but rather the added amendment of CN.
Table 1 shows the rutile content of each catalyst. The formula (Equation (1)) is given as follows:
X R = 1 1 + 0.8 × I A I R
where XR is the rutile content, IA is the peak intensity of anatase at 2θ = 25.28°, and IR is the peak intensity of rutile at 2θ = 27.24°.

2.1.2. Raman Analysis

The crystal form and structure of the catalyst were further determined by Raman spectroscopy, and Figure 2 shows the Raman spectra of the prepared catalyst. The anatase phase of TiO2 corresponded to ν = 144 cm−1, ν = 197 cm−1, ν = 392 cm−1, ν = 514 cm−1, and ν = 635 cm−1 [32], while ν = 437 cm−1 corresponded to rutile TiO2. The reason why other characteristic peaks did not appear was that the content of rutile in ART was low (as indicated by the peak intensity of XRD). ART and composite ARTCN-X both had anatase and rutile peaks, especially the CN peak of ARTCN-1, which further validated the XRD results.

2.1.3. Morphology and Lattice Spacing Analysis

According to Figure 3a,h, CN was a curved and folded film with certain holes. As shown in Figure 3b,i, ART consisted of a particle with a uniform size but serious agglomeration, and Figure 3c shows that CN in ARTCN-0.5 was no longer a whole film but fragmented into many small pieces; thus, its position relative to ART could not be clearly observed. Combined with Figure 3d–g, we clearly observed that elements O, Ti, and N were evenly distributed in ARTCN-0.5. This showed that a composite material with a heterogeneous structure was synthesized. In addition, as clearly shown in Figure 3j, the ART agglomeration phenomenon was significantly improved after the improvement of CN, which indicated that the utilization of light by ART in the composite ARTCN-0.5 was further enhanced.

2.1.4. Analysis of Adsorption–Desorption of N2

The Brunauer–Emmett–Teller (BET) method was used to calculate the surface area of the catalyst, and the Barrett–Joyner–Halenda (BJH) method was used to analyze the pore size and pore volume. The catalysts shown in Figure 4a all exhibited typical nitrogen adsorption–desorption isotherms of type IV, and the hysteresis loops of the catalysts all showed obvious openings, indicating the formation of mesoporous catalysts [33]. Figure 4b shows the pore size distribution of the catalyst, which showed that the pore size of the prepared catalyst was mainly concentrated at 0–20 nm, indicating that the particle size distribution of the catalyst was narrow. Combined with the data in Table 2, we found that the pores of the catalysts showed little difference, while the specific surface area and pore diameter of the catalysts increased with increasing CN content.

2.1.5. Optical Performance Analysis

The optical absorption properties of the prepared samples were investigated via the UV–Vis absorption spectra, and the results are shown in Figure 5a. The optical absorption intensity of the ARTCN-X composite material improved by CN widened in the visible light range because the specific ART surface area improved as CN increased, and the agglomeration phenomenon also significantly improved. These results indicated that CN could effectively expand the optical absorption range of ART, thus improving the response and utilization efficiency of visible light. In addition, the band gap width of the prepared material was calculated with the Kubelka-Munk method [34], as shown in Figure 5b. The bandgap widths of ART, ARTCN-0.1, ARTCN-0.5, ARTCN-1, and CN were 3.01, 2.92, 2.86, 2.85, and 2.84 eV, respectively. First, we clearly observed that the band gap width of ART was smaller than the 3.12 eV value reported in the literature, because heterostructures would form between the anatase phase TiO2 and rutile phase TiO2, enhancing the ability of photogenerated carrier separation [35]. Secondly, we found that with the increase in the CN content of the amendment, the band gap width of the composite ARTCN-X became significantly smaller than that of ART and approached that of CN, which was consistent with other studies [36].

2.1.6. PL and EPR Analysis

A PL spectrum can be used to study the separation of the photogenerated carriers in semiconductors, where the lower the peak intensity, the lower the recombination rate of the photogenerated carriers and the higher the photocatalytic activity [37]. As shown in Figure 6a, ARTCN-0.5 had the lowest peak intensity, indicating that its photocatalytic activity was the highest, which further indicated that as an amendment, the amount of CN addition did not follow the logic of “the more content the better” but had an appropriate ratio with ART. In addition, we observed that the wide wavelength range of ARTCN-X after CN modification in the interval of 451.8–468.8 nm was attributed to the oxygen vacancy that contained two captured electrons, which both promoted the formation of superoxide radicals (·O2−) and hydroxyl radicals (·OH) and was favorable for photocatalytic degradation.
Additional EPR spectra that were collected at room temperature provided information regarding the oxygen vacancies (Ov). As shown in Figure 6b, the signal at g = 2.002 corresponded to Ov [38]. We found that all samples had oxygen vacancy signals, and the intensity of ARTCN-0.5 was stronger than that of single ART and CN, which indicated that there was a large amount of Ov that could effectively inhibit the recombination of electrons and holes and improve the photocatalytic activity, thus confirming the results shown in Figure 6a.

2.2. Photocatalytic Performance Test Results

2.2.1. Study on the Photocatalytic Degradation of Gaseous Ammonia

The initial concentration of ammonia was 50 mg/m3, and the flow rate of the moist air was 0.9 mL/min. Different catalysts were used to study their influence on the degradation of gaseous ammonia, and the results are shown in Figure 7a. This indicated that PET itself was not good at removing gaseous ammonia, and the average degradation rates of gaseous ammonia by ART, ARTCN-0.1, ARTCN-0.5, ARTCN-1, and CN were 52.35%, 61.43%, 88.86%, 63.90%, and 33.51%, respectively. These results indicated that the degradation performance of gaseous ammonia by the ARTCN-X composite catalyst modified by CN was improved, and the effect was most obvious when the amount of CN was 0.5 g because ARTCN-0.5 had the strongest photogenerated carrier separation ability.
The initial concentration of ammonia was 50 mg/m3, and the flow rate of moist air was adjusted. ARTCN-0.5 was selected to study its influence on the degradation of gaseous ammonia, and the results are shown in Figure 7b. At 1.2 mL/min, the degradation rates of gaseous ammonia by ARTCN-0.5 were 57.93%, 63.98%, 78.26%, 83.38%, 88.86%, 87.10%, and 67.04%. The degradation rates of gaseous ammonia by ARTCN-0.5 first increased and then decreased with the flow rate of moist air. This was because moist air was conducive to the deposition of gaseous ammonia. However, ARTCN-0.5 could oxidize water molecules into hydroxyl radicals (·OH) with strong oxidation in the photocatalytic reaction process, thus improving the efficiency of the photocatalytic reaction. However, ammonia molecules could not tightly bind to the catalyst and flow out of the system before being reacted, resulting in a decrease in its degradation rate.
When the flow rate of moist air was 0.9 mL/min, ARTCN-0.5 was selected to study its influence on the degradation of gaseous ammonia, and the results are shown in Figure 7c. When the concentrations of gaseous ammonia were 30 mg/m3, 50 mg/m3, and 70 mg/m3, the average degradation rates of gaseous ammonia by ARTCN-0.5 were 80.38%, 88.86%, and 73.15%, respectively. The degradation rate decreased if the concentration of gaseous ammonia was too low or too high. This was because ARTCN-0.5 released a limited number of active free radicals after it degraded ammonia when the concentration of gaseous ammonia was too large. Many gaseous ammonia molecules went along with the airflow, and when the concentration of gaseous ammonia was too small, the active radicals could not completely combine with the gaseous ammonia.
The initial concentration of ammonia was 50 mg/m3, and the flow rate of moist air was 0.9 mL/min. After the degradation performance of ARTCN-0.5 was tested, PET loaded with ARTCN-0.5 was removed and kept in an oven at 70 °C for 2 h. Then, the test was repeated to explore the reuse performance of ARTCN-0.5; the results are shown in Figure 7d. The average degradation rates for the five reuse cycles were 88.86%, 85.00%, 80.40%, 76.48%, and 70.05%. Given the inevitable catalyst loss in the process of repeated testing, ARTCN-0.5 demonstrated a good overall repeatable degradation performance.
Figure 7e shows the XRD patterns of ARTCN-0.5 before and after repeated use (five times). We found that the crystal shape and structure of ARTCN-0.5 did not significantly change after five repeated uses, indicating that its properties were stable.

2.2.2. Study on the Photocatalytic Degradation of Liquid Ammonia

When pH > 10, NH4+ hydrolyzes in an alkaline solution and then exists in the form of NH3·H2O [39]. Therefore, we chose to adjust the pH of ammonia nitrogen to 10.1, and then we tested the concentration of ammonia nitrogen in the solution. We found that it decreased by 3.82% because a small amount of NH3·H2O escaped in the gaseous form. The degradation results of ammonia nitrogen by different catalysts are shown in Figure 8a, where the catalytic dose was 50 mg and the initial concentration of NH4+ was 100 mg/L. The degradation rates of liquid ammonia by ART, ARTCN-0.1, ARTCN-0.5, ARTCN-1, and CN after 3 h of reaction were 50.54%, 63.18%, 71.60%, 53.55%, and 37.91%, respectively, indicating that the degradation performance of the gaseous ammonia by the ARTCN-X composite catalyst after CN improvement was improved.
When the initial concentration of ammonia nitrogen was 100 mg/L, 50 mg of ARTCN-0.5 catalyst was added, the pH was 10.1, and the reaction was performed after 3 h. The results are shown in Figure 8b, which shows that the NO3− and NO2− concentrations were not greater than 1.4 and 0.012 mg/L, respectively. According to the literature reports, there are three main reaction products of ammonia nitrogen, nitrate, nitrite, and nitrogen, and ammonia nitrogen is mainly oxidized to N2 [40].

3. Discussion

3.1. Charge Transfer Mechanism Discussion

To understand the reason for the observed improved photocatalytic performance, we proposed a charge separation and transfer mechanism. The conduction band position of a semiconductor could be calculated by the empirical formulas shown in Equations (2) and (3) [41]:
Ec = χ − Ee − Eg/2
Ev = Ec + Eg
where χ is the geometric mean of the absolute electronegativity of each atom in the semiconductor, with TiO2 [42] and g-C3N4 [43] χ values of 5.81 eV and 4.82 eV, respectively; Ee is a constant relative to the standard hydrogen electrode of about 4.5 eV [44]; Eg is the semiconductor band gap width; Ev is the semiconductor valence band energy; and Ec is the semiconductor conduction band energy.
According to the analysis presented in Figure 5b, the Eg values of TiO2 and g-C3N4 were 3.01 and 2.84 eV, respectively. We calculated that the Ev and Ec values of ART were 2.815 and −0.195 eV, respectively, the Ev and Ec of g-C3N4 had a value of 1.59, and Ec was −1.25 V(vs NHE). CN was more negative than ART, and the Ev of ART was higher than that of CN. The high photocatalytic activity of the heterojunctions between ARTCN could be explained by the following mechanism.
Two possibilities existed for the photocatalytic mechanism of the composite catalyst: (1) conventional type II heterojunctions and (2) Z-type heterojunctions [45]. Under simulated solar irradiation, ART and CN were excited and generated electron-hole pairs. If the type II heterojunction mechanism was followed, the photogenerated electrons in the conduction band of CN would be transferred to the conduction band of ART and the photogenerated holes in the valence band of ART would be transferred to the valence band of CN [46], as shown in Figure 9a. However, the hole in the valence band of CN could not generate ·OH by reacting with H2O. This was because the valence band potential of CN (1.59 eV) was lower than the standard oxidation potential E (H2O/·OH) (2.38 eV) [47], resulting in a decrease in ·OH content, which was inconsistent with the results shown in Figure 9b. If the charge transfer mechanism of the Z-type heterostructure was followed, the photogenerated electrons in the ART conduction band would transfer to the valence band of CN and combine with the photogenerated holes in the CN valence band. This would result in a reduction in electrons in ARTCN and the accumulation of electrons in the CN conduction band and holes in the ART valence band, which was why the content of ·O2− produced by CN shown in Figure 10a was higher than that of ARTCN. The holes that accumulated in the valence band of ART had strong oxidability and could directly degrade ammonia molecules. However, the Ec (−1.10 V) of CN was more negative than EO (O2/·O2−), and the electrons that accumulated in the conduction band of CN could react with O2 to generate ·O2−. This z-type heterostructure was more consistent with the characterization results of ESR (Figure 10).
To further verify the accuracy of the above results, the test results of EIS are presented in Figure 11, which shows the impedance diagrams of ART, CN, and ARTCN. The electron transfer resistance in the sample was equivalent to the semicircle diameter on the EIS diagram, where the smaller the arc radius, the lower the charge transfer resistance of the composite sample [48]. Hence, due to the formation of the Z-type heterostructure, the charge-transfer resistance of ARTCN-0.5 was lower than ART and CN, which significantly improved the efficiency of photogenerated electron-hole migration and separation, which was consistent with the work of Y.Y. Wang [49].

3.2. Photocatalytic Degradation Mechanism Discussion

ESR was used to detect the types of free radicals in the catalysts under light, and then we explored their degradation mechanism of ammonia. As shown in Figure 10a,b, ART, CN, and ARTCN-0.5 did not produce free radicals in the absence of light, and superoxide free radicals (·O2−) and hydroxyl free radicals (·OH) were detected after light exposure. ·O2− and ·OH played decisive roles in the entire reaction [50]. The degradation mechanism was as follows. After gaseous ammonia combined with moist air, NH4+ was present as NH3·H2O under alkaline conditions. First, when the catalyst was illuminated, electrons and holes were generated [51]. The holes oxidized the water molecules on the surface of the catalyst, forming ·OH, while the electrons and dissolved oxygen underwent a series of reactions to form ·O2−, following Equations (4)–(6) [52]. ·OH and·O2− were the main active components in the photocatalytic reaction process, and they could rapidly oxidize the NH4+/NH3/NH3·H2O adsorbed on the surface of the catalyst [53]. Equations (9)–(13) show that ammonia was directly and completely oxidized to N2 [54], and the NO3− and NO2− contents were very low after the reaction. Equations (12)–(16) show that ammonia was not completely oxidized to NO3− and NO2−, which was consistent with the research of Sun et al. [55].
g-C3N4/(A-R)TiO2+hv → g-C3N4/(A-R)TiO2 (h+ + e−)
h+ + H2O → H+ + ·OH
e− + O2 →·O2−
NH3 + ·OH → NH2 + 2H2O
NH2 + ·OH → NH + H2O
NH + ·OH → N + H2O
NHx + NHy → N2Hx+y (x, y = 0, 1, 2)
N2Hx+y + (x+y)OH → N2 + (x+y) H2O
NH3 + ·OH (h+) → NH2OH + H+
NH2OH + ·O2− →·O2NHOH
O2NHOH + OH → NO2− + H2O + ·OH
NO2− + OH → HONO2
HONO2 → NO3− + H+

4. Materials and Methods

4.1. Materials

Ammonium chloride (AR, Chengdu Colon Chemicals Co., Ltd. Chengdu, Sichuan province, China), butyl titanate (AR, Chengdu Colon Chemicals Co., Ltd. Chengdu, Sichuan province, China), absolute ethanol (AR, Chongqing Chuandong Chemical Co., Ltd. Nanan district, Chongqing, China), urea (AR, Sinopharm Chemical Reagent Co., Ltd. Huangpu district, Shanghai, China), and NaOH (AR, Chongqing Chuandong Chemical Co., Ltd. Nanan district, Chongqing, China) were used in this study.

4.2. Preparation of Catalysts

We added 30 mL of absolute ethanol to 35 mL of butyl titanate, which was denoted as solution A. Then, we added 30 mL of absolute ethanol to 100 mL of distilled water, which was denoted as solution B. Solution A was dropwise added to solution B at 4 drops per second, and then it was mixed and stirred at a low speed for 2 h to obtain the TiO2 gel, which was aged at room temperature. The aged TiO2 gel was transferred to a stainless steel reaction kettle with a polytetrafluoron liner and maintained at 100 °C for 2 h. After cooling, it was centrifuged and settled, washed with deionized water and ethanol 3 times, and dried in a 100 °C air-drying oven. Then, the TiO2 catalyst powder was obtained after grinding. The TiO2 powder was maintained at 600 °C for 2 h at a heating rate of 10 °C/min, and then it was cooled to room temperature and ground to obtain ART.
Subsequently, 10 g of urea and 50 mL of water were added to the crucible and evenly stirred. The crucible was placed in a muffle furnace and maintained at 500 °C for 2 h at a heating rate of 10 °C/min. After the heating program was finished and the muffle furnace naturally cooled, the obtained bulk particles were ground to obtain CN.
We mixed 0.1 g of CN, 0.5 g of CN, 1 g of CN, and 1 g of ART; added 5 mL of absolute ethanol; stirred evenly; and then separated and dispersed the mixture using a cell fragmentation apparatus (Ningbo, Zhejiang Province, China. Xinzhi Biotechnology Co., Ltd., SCIENTZ-IID, 65 Hibiscus Road, Ningbo National High-tech Zone). Maintaining the temperature at 300 °C for 2 h at a heating rate of 10 °C/min, ARTCN-X was obtained and is denoted as ARTCN-0.1, ARTCN-0.5, and ARTCN-1.

4.3. Fixation of Photocatalytic Materials

We washed the polyester fiber cotton (PET) with 1 mol/L of NaOH to remove the surface impurities, and then we dried and set it aside. Subsequently, 100 mg of catalyst was dissolved in water, the treated PET was added and shaken in a shaker for 30 min, and the water on the surface and the excess catalyst were drained before the catalyst was dried at 70 °C for later use. The PET scanning electron microscope results before and after catalyst loading are shown in Figure 12. We clearly observed that the photocatalytic materials werare evenly loaded on PET.

4.4. Catalyst Characterization

A D8 Advance model X-ray diffractometer (XRD, Bruker, Germany) was used to analyze the crystal characteristics of the catalyst. The operating parameters were a Cu X-ray tube target and a scanning range of 10–80°. An HR800 laser confocal Raman spectrometer (Raman, Horiba Jobin Yvon, France) was used to detect the sample structures, where the excitation wavelength was 633 nm. A TriStar II 3020 series automatic specific surface analyzer (BET, GA, USA) was used to determine the specific surface area and porosity of the catalyst. The catalyst was pretreated under vacuum degassing at 200 °C for 5 h, and high-purity nitrogen was used as the adsorbent at 77 K. Then, a UV–Vis diffuse reflectance (UV–Vis DRS, Hitachi, Japan) instrument (model U-3010) was used to test the optical properties of the catalyst in the range of 200–800 nm. An F-2700 fluorescence spectrophotometer (PL, Japan, Hitachi) was used to measure the electron hole recombination, with an operating voltage of 250 V, a wavelength of 5 nm, and an excitation wavelength of 300 nm. The surface morphology and elemental distribution of the samples were analyzed by scanning electron microscopy (SEM, Sigma500, Germany) and an energy dispersive spectrometer (EDS, Bruker, Germany). Transmission electron microscopy (TEM, FEI TalOS F200S, USA) was used to analyze the lattice spacings of the samples. Fluorescence spectrophotometry (PL, HORIBA, Osaka, Japan) was used to test the photogenerated carrier separation of the catalyst with a hydrogen light source with a pulse width of 1.0 to 1.6 ns, which was used to test the fluorescence lifetime of the sample. Electron paramagnetic resonance (EPR, Bruke, Germany) was performed at room temperature using an A300 spectrometer, and 5,5-dimethyl-1-pyrrolidine N-oxide (DMPO) was used as the spin capture agent for ESR analysis. A CHI-660C electrochemical workstation was used for transient photocurrent measurements. A Na2SO4 aqueous solution (1 M) was used as the electrolyte solution, and electrochemical impedance spectroscopy (EIS, Chenhua, China) measurements were performed under visible light irradiation with frequencies ranging from 4 × 106 to 1 × 10−2 Hz.

4.5. Photocatalytic Activity Tests

4.5.1. Degradation of Gaseous Ammonia

Figure 13 shows the device diagram for the photocatalytic degradation of gaseous ammonia. The light source consisted of a 300 W xenon lamp (30.2 mW/cm2), which was installed in a quartz water pipe with a condensation cycle to absorb the heat generated by illumination. Just below the xenon lamp was a photocatalytic quartz reaction tube, and PET loaded with the photocatalytic materials was placed in the tube. After exiting the cylinder, ammonia entered the reaction tube through a flowmeter. The different concentrations of standard ammonia (mixed with nitrogen) were 30 mg/m3, 50 mg/m3, and 70 mg/m3, with a flow rate of 100 mL/min, and the stability test results of the different concentrations of ammonia are shown in Figure 14. Air entered the photocatalytic reaction tube through the water, needle valve, and flowmeter in turn (moist air was the only source of oxygen). Ammonia was mixed with air at a certain humidity to simulate gaseous ammonia. After connecting each pipeline, the standard gas was ventilated to determine whether there was air leakage. The system was run for 10 min until it was stable, and the degradation efficiency of the gaseous ammonia in the entire process was η1 (Equation (17)):
η1 = (C01 − C1) × 100%/C01
where C01 is the standard concentration of gaseous ammonia (mg/m3) and C1 is the concentration of gaseous ammonia in the reaction process (mg/m3).

4.5.2. Degradation of Liquid Ammonia

The photoreactor consisted of a 200 mL double-layer quartz beaker, for which the outer layer was permeated with cooling water to ensure a constant reaction temperature and the inner layer consisted of 100 mg/L of an ammonia nitrogen solution. The pH was adjusted to 10.1 by sodium hydroxide. The 300 W xenon lamp (30.2 mW/m2) was used as the light source to simulate sunlight while ensuring that the distance between the xenon lamp and the liquid level was 15 cm. Then, 50 mg (0.5 g/L) of catalyst was added to the solution and stirred at medium speed at room temperature; 2 mL of the sample from the reaction solution was extracted every 60 min and centrifuged for 10 min with a 10,000 r/min high-speed centrifuge, and the supernatant was obtained to determine the concentration of ammonia nitrogen and calculate its degradation rate η2 (Equation (18)). The nitrate and nitrite concentrations were determined after the reaction:
η2 = (C02 − C2) × 100%/C02
where C02 is the initial concentration of ammonia nitrogen and C2 is the concentration of ammonia nitrogen in the reaction process (mg/L).

5. Conclusions

A g-C3N4/(A-R)TiO2 composite catalyst (ARTCN) was prepared by using g-C3N4 (CN) as the amendment, and the amount of CN had a great influence on the performance of ARTCN. When the amount of CN was 0.5 g, ARTCN-0.5 had a better dispersion, a smaller band gap width, a larger specific surface area, a stronger light absorption capacity, and a stronger photogenerated carrier separation ability than ART.
The air wetness and initial concentration of the ammonia had a great influence on the degradation of the gaseous ammonia. When the initial concentration of ammonia was 50 mg/m3 and the flow rate of the moist air was 0.9 mL/min, the degradation rate of gaseous ammonia by ARTCN-0.5 reached 88.86%, and it had good repeatability. When the catalytic dose was 50 mg and the initial concentration of NH4+ was 100 mg/L, the degradation rate of the liquid ammonia by ARTCN-0.5 was 71.60% at 3 h, and small amounts of NO3− and NO2− were generated. Subsequently, ·OH and ·O2− were the main active components in the photocatalytic reaction process.
The photogenerated electrons in the conduction band of ART transferred to the valence band of CN and combined with the photogenerated holes in the valence band of CN, forming a Z-type heterostructure that significantly improved the efficiency of the photogenerated electron-hole migration and separation, thus increasing the reaction rate.

Author Contributions

Conceptualization: J.Z. and S.P.; data curation: Y.J.; investigation and methodology: H.W.; project administration: Z.L.; resources, J.Z. and Z.L.; supervision, J.Z. and D.L.; writing—original draft: J.Z. and S.P.; writing—review and editing: D.L. and J.Z. All authors have read and agreed to the published version of the manuscript.

Funding

Financial support was provided by the Chongqing scientific research institution performance Incentive and guidance special project (cstc2020jxjl20006), National Center of Technology Innovation for Pigs, Chongqing 402460, China. The Modern agroindustry technology research system (CARS-35, 21203).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Acknowledgments

We thank the editors of MDPI for their patience during the processing of this manuscript.

Conflicts of Interest

There are no conflict of interest in the manuscript submission, and it has been approved by all authors for publication. All authors listed have approved the enclosed manuscript.

References

  1. Clarisse, L.; Clerbaux, C.; Dentener, F.J.; Hurtmans, D.; Coheur, P.F. Global ammonia distribution derived from infrared satellite observations. Nat. Geosci. 2009, 2, 479. [Google Scholar] [CrossRef]
  2. Van Damme, M.; Clarisse, L.; Whitburn, S.; Hadji-Lazaro, J.; Hurtmans, D.; Clerbaux, C.; Coheur, P.F. Industrial and agricultural ammonia point sources exposed. Nature 2018, 564, 99. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  3. Schauberger, G.; Piringer, M.; Mikovits, C.; Zollitsch, W.; Hörtenhuber, S.; Baumgartner, J.; Niebuhr, K.; Anders, I.; Andre, K.; Hennig, P.I.; et al. Impact of global warming on the odour and ammonia emissions of livestock buildings used for fattening pigs. Biosyst. Eng. 2018, 175, 106. [Google Scholar] [CrossRef]
  4. Derwent, R.; Witham, C.; Redington, A.; Jenkin, M.; Stedman, J.; Yardley, R.; Hayman, G. Particulate matter at a rural location in southern England during 2006: Model sensitivities to precursor emissions. Atmos. Environ. 2013, 69, 211. [Google Scholar] [CrossRef]
  5. Bessagnet, B.; Beauchamp, M.; Guerreiro, C.D.B.B.; de Leeuw, F.; Tsyro, S.; Colette, A.; Meleux, F.; Rouïl, L.; Ruyssenaars, P.; Sauter, F.; et al. Can further mitigation of ammonia emissions reduce exceedances of particulate matter air quality standards? Environ. Sci. Policy 2014, 44, 149. [Google Scholar] [CrossRef]
  6. Pearson, J.; Stewart, G.R. The deposition of atmospheric ammonia and its effects on plants. New Phytol. 1993, 125, 283. [Google Scholar] [CrossRef]
  7. Pu, S.; Long, D.; Liu, Z.; Yang, F.; Zhu, J. Preparation of RGO-P25 Nanocomposites for the Photocatalytic Degradation of Ammonia in Livestock Farms. Catalysts 2018, 8, 189. [Google Scholar] [CrossRef] [Green Version]
  8. Zhu, J.; Jian, Y.; Long, D.; Wang, H.; Zeng, Y.; Li, J.; Xiao, R.; Pu, S. Degradation of ammonia gas by Cu2O/{001}TiO2 and its mechanistic analysis. RSC Adv. 2021, 11, 3695. [Google Scholar] [CrossRef]
  9. Enesca, A.; Andronic, L.; Duta, A. Optimization of Opto-Electrical and Photocatalytic Properties of SnO2 Thin Films Using Zn2+ and W6+ Dopant Ions. Catal. Lett. 2012, 142, 224. [Google Scholar] [CrossRef]
  10. Hu, X.; Guo, R.T.; Chen, X.; Bi, Z.X.; Wang, J.; Pan, W.-G. Bismuth-based Z-scheme structure for photocatalytic CO2 reduction: A review. J. Environ. Chem. Eng. 2022, 10, 108582. [Google Scholar] [CrossRef]
  11. Liu, X.; Xu, J.; Jiang, Y.; Du, Y.; Zhang, J.; Lin, K. In-situ construction of CdS@ZIS Z-scheme heterojunction with core-shell structure: Defect engineering, enhance photocatalytic hydrogen evolution and inhibit photo-corrosion. Int. J. Hydrog. Energy 2022, 47, 35241. [Google Scholar] [CrossRef]
  12. Kolinko, P.A.; Kozlov, D.V. Products distribution during the gas phase photocatalytic oxidation of ammonia over the various titania based photocatalysts. Appl. Catal. B Environ. 2009, 90, 126. [Google Scholar] [CrossRef]
  13. Wu, H.; Ma, J.; Li, Y.; Zhang, C.; He, H. Photocatalytic oxidation of gaseous ammonia over fluorinated TiO2 with exposed (001) facets. Appl. Catal. B Environ. 2014, 152, 82. [Google Scholar] [CrossRef]
  14. Wang, J.Y.; Liu, B.S.; Nakata, K. Effects of crystallinity, {001}/{101} ratio, and Au decoration on the photocatalytic activity of anatase TiO2 crystals. Chin. J. Catal. 2019, 40, 403. [Google Scholar] [CrossRef]
  15. Hosono, E.; Fujihara, S.; Kakiuchi, A.K.; Imai, H. Growth of submicrometer-scale rectangular parallelepiped rutile TiO2 films in aqueous TiCl3 solutions under hydrothermal conditions. J. Am. Chem. Soc. 2004, 126, 7790. [Google Scholar] [CrossRef] [PubMed]
  16. Shen, S.; Wang, X.; Chen, T.; Feng, Z.; Li, C. Transfer of photoinduced electrons in anatase-rutile TiO2 determined by time-resolved midinfrared spectroscopy. J. Phys. Chem. C 2014, 118, 12661. [Google Scholar] [CrossRef]
  17. Das, B.; Nair, R.G.; Rajbongshi, B.; Samdarshi, S. Investigation of the Photoactivity of Pristine and Mixed Phase N-doped Titania under Visible and Solar Irradiation. Mater. Charact. 2013, 83, 145–151. [Google Scholar] [CrossRef]
  18. Xiong, J.Y.; Zhang, M.M.; Cheng, G. Facile polyol triggered anatase-rutile heterophase TiO2-x nanoparticles for enhancing photocatalytic CO2 reduction. J. Colloid Interface Sci. 2020, 579, 872. [Google Scholar] [CrossRef]
  19. Rani, S.; Garg, A.; Singh, N. Highly efficient photo-degradation of cetirizine antihistamine with TiO2-SiO2 photocatalyst under ultraviolet irradiation. Int. J. Chem. React. Eng. 2022, 20, 183. [Google Scholar] [CrossRef]
  20. Guarino, M.; Costa, A.; Porro, M. Photocatalytic TiO2 coating to reduce ammonia and greenhouse gases concentration and emission from animal husbandries. Bioresour. Technol. 2008, 99, 2650. [Google Scholar] [CrossRef]
  21. Pu, S.; Wang, H.; Zhu, J.; Li, L.; Long, D.; Jian, Y.; Zeng, Y. Heterostructure Cu2O/(001)TiO2 Effected on Photocatalytic Degradation of Ammonia of Livestock Houses. Catalysts 2019, 9, 267. [Google Scholar] [CrossRef] [Green Version]
  22. Liu, C.H.; Dai, H.L.; Tan, C.Q.; Pan, Q.Y.; Hu, F.P.; Peng, X.M. Photo-Fenton degradation of tetracycline over Z-scheme Fe-g-C3N4/Bi2WO6 heterojunctions: Mechanism insight, degradation pathways and DFT calculation. Appl. Catal. B Environ. 2022, 310, 121326. [Google Scholar] [CrossRef]
  23. Luan, S.; Qu, D.; An, L.; Jiang, W.; Gao, X.; Hua, S.; Miao, X.; Wen, Y.; Sun, Z. Enhancing photocatalytic performance by constructing ultrafine TiO2 nanorods/g-C3N4 nanosheets heterojunction for water treatment. Sci. Bull. 2018, 63, 683. [Google Scholar] [CrossRef]
  24. Al-Hajji, L.; Ismail, A.A.; Atitar, M.F.; Abdelfattah, I.; El-Toni, A.M. Construction of mesoporous g-C3N4/TiO2 nanocrystals with enhanced photonic efficiency. Ceram. Int. 2019, 45, 1265. [Google Scholar] [CrossRef]
  25. Zhao, S.; Chen, S.; Yu, H.; Quan, X. g-C3N4/TiO2 hybrid photocatalyst with wide absorption wavelength range and effective photogenerated charge separation. Sep. Purif. Technol. 2012, 99, 50. [Google Scholar] [CrossRef]
  26. Sun, M.; Shen, S.; Wu, Z.; Tang, Z.; Shen, J.; Yang, J. Rice spike-like g-C3N4/TiO2 heterojunctions with tight-binding interface by using sodium titanate ultralong nanotube as precursor and template. Ceram. Int. 2018, 44, 8125. [Google Scholar] [CrossRef]
  27. Li, Y.; Zhang, M.Q.; Liu, Y.F.; Sun, Y.X.; Zhao, Q.H.; Chen, T.L.; Chen, Y.F.; Wang, S.F. In Situ Construction of Bronze/Anatase TiO2 Homogeneous Heterojunctions and Their Photocatalytic Performances. Nanomaterials 2022, 12, 1122. [Google Scholar] [CrossRef]
  28. Chouhan, L.; Srivastava, S.K. Observation of room temperature d0 ferromagnetism, band-gap widening, zero dielectric loss and conductivity enhancement in Mg doped TiO2 (rutile + anatase) compounds for spintronics applications. J. Solid State Chem. 2022, 307, 122828. [Google Scholar] [CrossRef]
  29. Mirhosseini, H.; Mostafavi, A.; Shamspur, T.; Sargazi, G. Fabrication of an efficient ternary TiO2/Bi2WO6 nanocomposite supported on g-C3N4 with enhanced visible light photocatalytic activity: Modeling and systematic optimization procedure. Arab. J. Chem. 2022, 15, 103729. [Google Scholar] [CrossRef]
  30. Guan, Y.; Wu, J.; Wang, L.; Shi, C.; Lv, K.; Lv, Y. Application of g-C3N4/CNTs nanocomposites in energy and environment. Energy Rep. 2022, 8, 1190. [Google Scholar] [CrossRef]
  31. Hou, C.T.; Hu, B.; Zhu, J.M. Photocatalytic Degradation of Methylene Blue over TiO2 Pretreated with Varying Concentrations of NaOH. Catalysts 2018, 8, 575. [Google Scholar] [CrossRef] [Green Version]
  32. Chen, Y.; Mao, G.; Tang, Y.; Wu, H.; Wang, G.; Zhang, L.; Liu, Q. Synthesis of core-shell nanostructured Cr2O3/C@TiO2 for photocatalytic hydrogen production. Chin. J. Catal. 2021, 42, 225. [Google Scholar] [CrossRef]
  33. Wang, J.; Wang, G.; Jiang, J.; Wan, Z.; Su, Y.; Tang, H. Insight into charge carrier separation and solar light utilization: rGO decorated 3D ZnO hollow microspheres for enhanced photocatalytic hydrogen evolution. J. Colloid Interface Sci. 2020, 564, 322. [Google Scholar] [CrossRef] [PubMed]
  34. Li, L.; Ouyang, W.; Zheng, Z.; Ye, K.; Guo, Y.; Qin, Y.; Wu, Z.; Lin, Z.; Wang, T.; Zhang, S. Synergetic photocatalytic and thermocatalytic reforming of methanol for hydrogen production based on Pt@TiO2 catalyst. Chin. J. Catal. 2022, 43, 1258. [Google Scholar] [CrossRef]
  35. Chen, M.; Chen, J.; Chen, C.; Zhang, C.; He, H. Distinct photocatalytic charges separation pathway on CuOx modified rutile and anatase TiO2 under visible light. Appl. Catal. B Environ. 2022, 300, 120735. [Google Scholar] [CrossRef]
  36. Wei, T.; Xu, J.; Kan, C.; Zhang, L.; Zhu, X. Au tailored on g-C3N4/TiO2 heterostructure for enhanced photocatalytic performance. J. Alloy. Compd. 2022, 894, 162338. [Google Scholar] [CrossRef]
  37. Kubiak, A.; Grzegórska, A.; Zembrzuska, J.; Zielińska, J.A.; Siwińska, C.K.; Janczarek, M.; Krawczyk, P.; Jesionowski, T. Design and Microwave-Assisted Synthesis of TiO2 Lanthanides Systems and Evaluation of Photocatalytic Activity under UV-LED Light Irradiation. Catalysts 2021, 12, 8. [Google Scholar] [CrossRef]
  38. Jian, Y.; Liu, H.; Zhu, J.; Zeng, Y.; Liu, Z.; Hou, C.; Pu, S. Transformation of novel TiOF2 nanoparticles to cluster TiO2-{001/101} and its degradation of tetracycline hydrochloride under simulated sunlight. RSC Adv. 2020, 10, 42860. [Google Scholar] [CrossRef]
  39. Zhu, J.; Liu, Z.; Yang, F.; Long, D.; Jian, Y.; Pu, S. The Preparation of {001}TiO2/TiOF2 via a One-Step Hydrothermal Method and its Degradation Mechanism of Ammonia Nitrogen. Materials 2022, 15, 6465. [Google Scholar] [CrossRef]
  40. Yao, F.; Fu, W.; Ge, X.; Wang, L.; Wang, J.; Zhong, W. Preparation and characterization of a copper phosphotungstate/titanium dioxide (Cu-H3PW12O40/TiO2) composite and the photocatalytic oxidation of high concentration ammonia nitrogen. Sci. Total Environ. 2020, 727, 138425. [Google Scholar] [CrossRef]
  41. Zhang, H.; Zhang, G.; Zhang, H.; Tang, Q.; Xiao, Y.; Wang, Y.; Cao, J. Facile synthesis hierarchical porous structure anatase–rutile TiO2/g-C3N4 composite for efficient photodegradation tetracycline hydrochloride. Appl. Surf. Sci. 2021, 567, 150833. [Google Scholar] [CrossRef]
  42. Hao, R.; Wang, G.; Tang, H.; Sun, L.; Xu, C.; Han, D. Template-free preparation of macro/mesoporous g-C3N4/TiO2 heterojunction photocatalysts with enhanced visible light photocatalytic activity. Appl. Catal. B Environ. 2016, 187, 47. [Google Scholar] [CrossRef]
  43. Zhang, B.; Hu, X.; Liu, E.; Fan, J. Novel S-scheme 2D/2D BiOBr/g-C3N4 heterojunctions with enhanced photocatalytic activity. Chin. J. Catal. 2021, 42, 1519. [Google Scholar] [CrossRef]
  44. Hong, Y.; Jiang, Y.; Li, C.; Fan, W.; Yan, X.; Yan, M.; Shi, W. In-situ synthesis of direct solid-state Z-scheme V2O5/g-C3N4 heterojunctions with enhanced visible light efficiency in photocatalytic degradation of pollutants. Appl. Catal. B Environ. 2016, 180, 663. [Google Scholar] [CrossRef]
  45. Wang, S.; Zhao, T.; Tian, Y.; Yan, L.; Su, Z. Mechanistic insight into photocatalytic CO2 reduction by a Z-scheme g-C3N4/TiO2 heterostructure. New J. Chem. 2021, 45, 11474. [Google Scholar] [CrossRef]
  46. Yang, D.; Zhao, X.; Chen, Y.; Wang, W.; Zhou, Z.; Zhao, Z.; Jiang, Z. Synthesis of g-C3N4 Nanosheet/TiO2 Heterojunctions Inspired by Bioadhesion and Biomineralization Mechanism. Ind. Eng. Chem. Res. 2019, 58, 5516–5525. [Google Scholar] [CrossRef]
  47. Xia, J.; Di, J.; Li, H.; Xu, H.; Li, H.; Guo, S. Ionic liquid-induced strategy for carbon quantum dotsbiox (x = Br, Cl) hybrid nanosheets with superior visible light driven photocatalysis. Appl. Catal. B Environ. 2016, 181, 260. [Google Scholar] [CrossRef]
  48. Abdel, K.A.M.; Fadlallah, S.A. Fabrication of titanium nanotubes array: Phase structure, hydrophilic properties, and electrochemical behavior approach. J. Appl. Electrochem. 2022, 52, 17. [Google Scholar] [CrossRef]
  49. Wang, Y.; Yang, W.; Chen, X.; Wang, J.; Zhu, Y. Photocatalytic activity enhancement of core-shell structure g-C3N4@TiO2 via controlled ultrathin g-C3N4 layer. Appl. Catal. B Environ. 2018, 220, 337. [Google Scholar] [CrossRef]
  50. Sun, X.Y.; Zhang, X.; Qian, N.X.; Wang, M.; Ma, Y.-Q. Improved adsorption and degradation performance by S-doping of (001)-TiO2. Beilstein J. Nanotechnol. 2019, 10, 2116. [Google Scholar] [CrossRef]
  51. Rej, S.; Bisetto, M.; Naldoni, A.; Fornasiero, P. Well-defined Cu2O photocatalysts for solar fuels and chemicals. J. Mater. Chem. A 2021, 9, 5915. [Google Scholar] [CrossRef]
  52. Rafiee, E.; Noori, E.; Zinatizadeh, A.A.; Zanganeh, H. A new visible driven nanocomposite including Ti-substituted polyoxometalate/TiO2: Synthesis, characterization, photodegradation of azo dye process optimization by RSM and specific removalrate calculations. J. Mater. Sci.-Mater. Electron. 2018, 29, 20668. [Google Scholar] [CrossRef]
  53. Peng, X.; Wang, M.; Hu, F.; Qiu, F.; Zhang, T.; Dai, H.; Cao, Z. Multipath fabrication of hierarchical CuAl layered double hydroxide/carbon fiber composites for the degradation of ammonia nitrogen. J. Environ. Manag. 2018, 220, 173. [Google Scholar] [CrossRef] [PubMed]
  54. Li, H.; Cao, Y.; Liu, P.; Li, Y.; Zhou, A.; Ye, F.; Xue, S.; Yue, X. Ammonia-nitrogen removal from water with g-C3N4-rGO-TiO2 Z-scheme system via photocatalytic nitrification denitrification process. Environ. Res. 2022, 205, 112434. [Google Scholar] [CrossRef]
  55. Sun, D.; Sun, W.; Yang, W.; Li, Q.; Shang, J.K. Efficient photocatalytic removal of aqueous NH4+-NH3 by palladium-modified nitrogen-doped titanium oxide nanoparticles under visible light illumination, even in weak alkaline solutions. Chem. Eng. J. 2015, 264, 728. [Google Scholar] [CrossRef]
Ijms 23 13131 g001 550
Figure 1. XRD patterns of the samples.
Figure 1. XRD patterns of the samples.
Ijms 23 13131 g001
Ijms 23 13131 g002 550
Figure 2. Raman spectra of the samples.
Figure 2. Raman spectra of the samples.
Ijms 23 13131 g002
Ijms 23 13131 g003a 550Ijms 23 13131 g003b 550
Figure 3. SEM images of CN (a), ART (b), and ARTCN-0.5 (c); images and corresponding EDS elemental mapping images (d–g) of the ARTCN-0.5, TEM of CN (h), ART (i), and ARTCN-0.5 (j).
Figure 3. SEM images of CN (a), ART (b), and ARTCN-0.5 (c); images and corresponding EDS elemental mapping images (d–g) of the ARTCN-0.5, TEM of CN (h), ART (i), and ARTCN-0.5 (j).
Ijms 23 13131 g003aIjms 23 13131 g003b
Ijms 23 13131 g004 550
Figure 4. N2 adsorption–desorption curve (a) and pore size distribution (b) of the samples.
Figure 4. N2 adsorption–desorption curve (a) and pore size distribution (b) of the samples.
Ijms 23 13131 g004
Ijms 23 13131 g005 550
Figure 5. Optical properties (a) and the band gap width (b) of the samples.
Figure 5. Optical properties (a) and the band gap width (b) of the samples.
Ijms 23 13131 g005
Ijms 23 13131 g006 550
Figure 6. PL (a) and (b) EPR of the samples.
Figure 6. PL (a) and (b) EPR of the samples.
Ijms 23 13131 g006
Ijms 23 13131 g007a 550Ijms 23 13131 g007b 550
Figure 7. Influence of different catalysts on the degradation of gaseous ammonia (a), the effect of different humid air flow rates on the degradation of gaseous ammonia (b), the effects of different ammonia concentrations on the degradation of gaseous ammonia (c), the repeated degradation performance of ARTCN-0.5 (d), and XRD patterns before and after the repeated use (5 times) of ARTCN-0.5 (e).
Figure 7. Influence of different catalysts on the degradation of gaseous ammonia (a), the effect of different humid air flow rates on the degradation of gaseous ammonia (b), the effects of different ammonia concentrations on the degradation of gaseous ammonia (c), the repeated degradation performance of ARTCN-0.5 (d), and XRD patterns before and after the repeated use (5 times) of ARTCN-0.5 (e).
Ijms 23 13131 g007aIjms 23 13131 g007b
Ijms 23 13131 g008 550
Figure 8. Degradation of the liquid ammonia by samples (a); NO3− and NO2− production after the reaction (b).
Figure 8. Degradation of the liquid ammonia by samples (a); NO3− and NO2− production after the reaction (b).
Ijms 23 13131 g008
Ijms 23 13131 g009 550
Figure 9. Charge transfer mechanism of the photocatalytic degradation conventional type II heterojunction (a) and Z-type heterostructure (b).
Figure 9. Charge transfer mechanism of the photocatalytic degradation conventional type II heterojunction (a) and Z-type heterostructure (b).
Ijms 23 13131 g009
Ijms 23 13131 g010 550
Figure 10. ESR profiles of DMPO ·O2− (a) and DMPO ·OH (b) of the samples.
Figure 10. ESR profiles of DMPO ·O2− (a) and DMPO ·OH (b) of the samples.
Ijms 23 13131 g010
Ijms 23 13131 g011 550
Figure 11. EIS spectra of the samples.
Figure 11. EIS spectra of the samples.
Ijms 23 13131 g011
Ijms 23 13131 g012 550
Figure 12. SEM of the PET scan before and after catalyst support.
Figure 12. SEM of the PET scan before and after catalyst support.
Ijms 23 13131 g012
Ijms 23 13131 g013 550
Figure 13. Device diagram of the photocatalytic degradation of gaseous ammonia.
Figure 13. Device diagram of the photocatalytic degradation of gaseous ammonia.
Ijms 23 13131 g013
Ijms 23 13131 g014 550
Figure 14. System stability test.
Figure 14. System stability test.
Ijms 23 13131 g014
Table
Table 1. Rutile content of the catalysts.
Table 1. Rutile content of the catalysts.
SamplesIR (2θ = 27.24°)IA (2θ = 25.28°)XR
ART523.482131.9323.49%
ARTCN-0.1605.192260.3325.06%
ARTCN-0.5704.022110.1429.43%
ARTCN-1953.812251.7734.61%
Table
Table 2. Structural parameters of the samples.
Table 2. Structural parameters of the samples.
SamplesSpecific Surface Area (m2/g)Pore Volume (cm3/g)Pore Diameter (nm)
ART27.280.0811.28
ARTCN-0.133.920.0910.13
ARTCN-0.536.160.089.65
ARTCN-138.080.129.29
CN42.090.118.67
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Zhu, J.; Liu, Z.; Wang, H.; Jian, Y.; Long, D.; Pu, S. Preparation of a Z-Type g-C3N4/(A-R)TiO2 Composite Catalyst and Its Mechanism for Degradation of Gaseous and Liquid Ammonia. Int. J. Mol. Sci. 2022, 23, 13131. https://doi.org/10.3390/ijms232113131

AMA Style

Zhu J, Liu Z, Wang H, Jian Y, Long D, Pu S. Preparation of a Z-Type g-C3N4/(A-R)TiO2 Composite Catalyst and Its Mechanism for Degradation of Gaseous and Liquid Ammonia. International Journal of Molecular Sciences. 2022; 23(21):13131. https://doi.org/10.3390/ijms232113131

Chicago/Turabian Style

Zhu, Jiaming, Zuohua Liu, Hao Wang, Yue Jian, Dingbiao Long, and Shihua Pu. 2022. "Preparation of a Z-Type g-C3N4/(A-R)TiO2 Composite Catalyst and Its Mechanism for Degradation of Gaseous and Liquid Ammonia" International Journal of Molecular Sciences 23, no. 21: 13131. https://doi.org/10.3390/ijms232113131

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop