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<front>
<journal-meta>
<journal-id journal-id-type="publisher-id">Front. Chem.</journal-id>
<journal-title>Frontiers in Chemistry</journal-title>
<abbrev-journal-title abbrev-type="pubmed">Front. Chem.</abbrev-journal-title>
<issn pub-type="epub">2296-2646</issn>
<publisher>
<publisher-name>Frontiers Media S.A.</publisher-name>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="publisher-id">865847</article-id>
<article-id pub-id-type="doi">10.3389/fchem.2022.865847</article-id>
<article-categories>
<subj-group subj-group-type="heading">
<subject>Chemistry</subject>
<subj-group>
<subject>Original Research</subject>
</subj-group>
</subj-group>
</article-categories>
<title-group>
<article-title>Efficient Interfacial Charge Transfer Based on 2D/2D Heterojunctions of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> for Improving the Photocatalytic Degradation of Antibiotics</article-title>
<alt-title alt-title-type="left-running-head">Huo et al.</alt-title>
<alt-title alt-title-type="right-running-head">2D/2D Heterojunctions of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>
</alt-title>
</title-group>
<contrib-group>
<contrib contrib-type="author" corresp="yes">
<name>
<surname>Huo</surname>
<given-names>Zhaohui</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<xref ref-type="corresp" rid="c001">&#x2a;</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1541441/overview"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Liao</surname>
<given-names>Yanmin</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1782788/overview"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>He</surname>
<given-names>Yongyi</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1782779/overview"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Zhang</surname>
<given-names>Yifan</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1782614/overview"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Liao</surname>
<given-names>Xiaolin</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1782791/overview"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Zhang</surname>
<given-names>Qitong</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1782625/overview"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Wu</surname>
<given-names>Haojie</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1782588/overview"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Shi</surname>
<given-names>Junjie</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1782595/overview"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Wen</surname>
<given-names>Genglong</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1782589/overview"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Su</surname>
<given-names>Haixia</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1782678/overview"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Yao</surname>
<given-names>Suyang</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1782770/overview"/>
</contrib>
</contrib-group>
<aff id="aff1">
<sup>1</sup>
<institution>School of Chemistry and Materials Science</institution>, <institution>Guangdong University of Education</institution>, <addr-line>Guangzhou</addr-line>, <country>China</country>
</aff>
<aff id="aff2">
<sup>2</sup>
<institution>Engineering Technology Development Center of Advanced Materials &#x26; Energy Saving and Emission Reduction in Guangdong Colleges and Universities</institution>, <addr-line>Guangzhou</addr-line>, <country>China</country>
</aff>
<author-notes>
<fn fn-type="edited-by">
<p>
<bold>Edited by:</bold> <ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/1368057/overview">Dejin Zang</ext-link>, Tsinghua University, China</p>
</fn>
<fn fn-type="edited-by">
<p>
<bold>Reviewed by:</bold> <ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/591324/overview">Zhao-Qing Liu</ext-link>, Guangzhou University, China</p>
<p>
<ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/1576768/overview">Qitao Zhang</ext-link>, Shenzhen University, China</p>
</fn>
<corresp id="c001">&#x2a;Correspondence: Zhaohui Huo, <email>huozhaohui@gdei.edu.cn</email>
</corresp>
<fn fn-type="other">
<p>This article was submitted to Analytical Chemistry, a section of the journal Frontiers in Chemistry</p>
</fn>
</author-notes>
<pub-date pub-type="epub">
<day>23</day>
<month>05</month>
<year>2022</year>
</pub-date>
<pub-date pub-type="collection">
<year>2022</year>
</pub-date>
<volume>10</volume>
<elocation-id>865847</elocation-id>
<history>
<date date-type="received">
<day>30</day>
<month>01</month>
<year>2022</year>
</date>
<date date-type="accepted">
<day>05</day>
<month>04</month>
<year>2022</year>
</date>
</history>
<permissions>
<copyright-statement>Copyright &#xa9; 2022 Huo, Liao, He, Zhang, Liao, Zhang, Wu, Shi, Wen, Su and Yao.</copyright-statement>
<copyright-year>2022</copyright-year>
<copyright-holder>Huo, Liao, He, Zhang, Liao, Zhang, Wu, Shi, Wen, Su and Yao</copyright-holder>
<license xlink:href="http://creativecommons.org/licenses/by/4.0/">
<p>This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.</p>
</license>
</permissions>
<abstract>
<p>Graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>) has shown to be a promising photocatalyst that, however, suffers from strong charge recombination and poor conductivity, while MXenes have shown to be perfect cocatalysts for the photocatalytic process but show poor stability. In this study, we successfully constructed 2D/2D heterojunctions of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> for the photocatalytic degradation of antibiotics. In this study, multilayer Ti<sub>3</sub>C<sub>2</sub> was obtained by etching Ti<sub>3</sub>AlC<sub>2</sub>, and then Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> photocatalyst was prepared by the one-pot microwave method and high-temperature calcination method. The synthesized samples were characterized by XRD, SEM, TEM, XPS, TGA, BET, DRS, PL, and other means. The photocatalytic degradation of tetracycline hydrochloride by Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> was in accordance with the first-order reaction kinetics model, and the apparent rate constant k was 2.83, 2.06, and 1.77 times that of g-C<sub>3</sub>N<sub>4</sub>, Fe-C<sub>3</sub>N<sub>4</sub>, and g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>, respectively. Through the mechanism study, it was shown that the most active species in the reaction system was &#x2022; O<sub>2</sub>
<sup>&#x2212;</sup>, while h<sup>&#x2b;</sup> and &#x2022;OH had a relatively lower effect on the degradation system.</p>
</abstract>
<kwd-group>
<kwd>g-C<sub>3</sub>N<sub>4</sub>
</kwd>
<kwd>Ti<sub>3</sub>C<sub>2</sub>
</kwd>
<kwd>Fe</kwd>
<kwd>2D/2D heterojunction</kwd>
<kwd>photocatalytic degradation</kwd>
</kwd-group>
</article-meta>
</front>
<body>
<sec id="s1">
<title>Introduction</title>
<p>With the rapid development of modern industry, the problems of environmental pollution and energy shortage are increasingly prominent. Water pollution is particularly prominent among many environmental pollution problems, and antibiotic wastewater is recognized as organic wastewater, that is, difficult to treat (<xref ref-type="bibr" rid="B21">Lindberg et al., 2005</xref>). Tetracycline antibiotics are widely used in clinics and belong to broad-spectrum antibiotics. However, tetracycline drugs cannot be completely absorbed after being ingested by organisms, and most of them are discharged in their original form or metabolites (<xref ref-type="bibr" rid="B10">Gibson and Skett, 1986</xref>). Moreover, the production process of this class of antibiotics is complex, and a large number of them remain in pharmaceutical wastewater. Tetracycline antibiotics can damage the aquatic environment and cause chronic effects on the behavior, reproduction, and growth of organisms. At the same time, these antibiotics have bactericidal and bacteriostatic effects, resulting in the disappearance of some microbial populations and ecological function damage, which may lead to changes in methane generation, sulfate reduction, nitrogen transformation, and organic matter degradation, bringing great threats to the ecosystem and human health (<xref ref-type="bibr" rid="B29">Pei et al., 2020</xref>). At present, the treatment of tetracycline antibiotic wastewater mainly includes the biological method (<xref ref-type="bibr" rid="B37">Xu et al., 2017b</xref>), physical method (<xref ref-type="bibr" rid="B34">Wei et al., 2019</xref>), and chemical method (<xref ref-type="bibr" rid="B16">Lee et al., 2011</xref>), but these methods have disadvantages such as low degradation rate, complex technological process, and high cost, and may produce some new pollutants. Therefore, the development of a green, efficient, and low energy consumption antibiotic degradation technology has become an urgent need. Semiconductor photocatalytic technology can convert renewable solar energy into chemical energy under mild conditions, promote the REDOX reaction, and degrade antibiotics into nontoxic small molecules, so it has become a research hotspot. The core of photocatalytic technology lies in semiconductor materials. At present, a large number of semiconductor materials have been explored and applied in this technology, such as titanium dioxide (TiO<sub>2</sub>) (<xref ref-type="bibr" rid="B8">Gao et al., 2020</xref>; <xref ref-type="bibr" rid="B7">Galeano et al., 2019</xref>), black phosphorus (P) (<xref ref-type="bibr" rid="B2">Bian et al., 2020</xref>; <xref ref-type="bibr" rid="B23">Liu D. et al., 2020</xref>), tungsten trioxide (WO<sub>3</sub>) (<xref ref-type="bibr" rid="B5">Fu et al., 2019</xref>; <xref ref-type="bibr" rid="B31">Sun et al., 2019</xref>), and graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>) (<xref ref-type="bibr" rid="B32">Tong et al., 2017</xref>). At present, there are two main aspects that restrict the photocatalytic effect of semiconductors (<xref ref-type="bibr" rid="B25">Liu N. et al., 2018</xref>): 1) Low utilization rate of light. Most semiconductor photocatalysts can only be excited by ultraviolet light, which greatly limits the utilization rate of materials to sunlight; 2) the single-component semiconductor materials often have the defect of a high recombination rate of electron&#x2013;hole pairs, which seriously restricts the photocatalytic effect. Therefore, we need to develop efficient photocatalytic materials with high visible light response and low carrier recombination rate, so as to promote the application of photocatalytic technology. In numerous semiconductor photocatalysts, the nonmetallic photocatalyst g-C<sub>3</sub>N<sub>4</sub> stands out because of its visible light response, good chemical stability, suitable conduction band (CB) and valence band (VB) location, low cost, and nontoxic advantages; is considered as a metal-free photocatalyst with broad prospects; and has a great research value in the field of photocatalytic treatment of water pollution and hydrolysis of H<sub>2</sub>. However, because of its poor conductivity, high carrier recombination rate, and small specific surface area (<xref ref-type="bibr" rid="B36">Xu et al., 2017a</xref>), the practical application of g-C<sub>3</sub>N<sub>4</sub> is limited. Therefore, researchers modified g-C<sub>3</sub>N<sub>4</sub> by means of element doping (<xref ref-type="bibr" rid="B18">Li et al., 2018</xref>; <xref ref-type="bibr" rid="B43">Zhao et al., 2019</xref>), semiconductor recombination (<xref ref-type="bibr" rid="B39">Yang et al., 2020</xref>; <xref ref-type="bibr" rid="B42">Yi et al., 2020</xref>; <xref ref-type="bibr" rid="B27">Liu et al., 2021</xref>), morphology control (<xref ref-type="bibr" rid="B4">Cui et al., 2018</xref>), and noble metal deposition (<xref ref-type="bibr" rid="B19">Li et al., 2019</xref>), to improve the photocatalytic performance. Among these strategies, doping (metal or non-metal) has been extensively used as a valid method to modulate the energy gap of semiconductors for the treatment of conductive, optical, or other physical properties (<xref ref-type="bibr" rid="B6">Fu et al., 2017</xref>; <xref ref-type="bibr" rid="B25">Liu N. et al., 2018</xref>). Doping Fe has been recognized as a facile and efficient approach to amending g-C<sub>3</sub>N<sub>4</sub> (<xref ref-type="bibr" rid="B44">Zheng et al., 2015</xref>). g-C<sub>3</sub>N<sub>4</sub> is rich in N atoms, which are filed with six lone pair electrons (<xref ref-type="bibr" rid="B33">Wang et al., 2009</xref>). This unique unit structure is quite appropriate for Fe inclusion. For example, Xu et al., 2019, designed Fe-doped surface alkalization g-C<sub>3</sub>N<sub>4</sub> photocatalyst, showing good photocatalytic activity, and the degradation rate of tetracycline hydrochloride (TC) within 80&#xa0;min was 63.70%, which was 1.29 times of that before doping. And, <xref ref-type="bibr" rid="B24">Liu G. et al., 2020</xref>, designed CNFe<sub>x</sub> samples with different Fe doping ratios, and the results showed that when the Fe doping ratio was 0.25, the samples showed the best photocatalytic activity, and the degradation rate of RhB was 87.00% within 60&#xa0;min, 2.90 times that of pure g-C<sub>3</sub>N<sub>4</sub>. Liu et al. carried out a series of studies about Fe<sub>2</sub>O<sub>3</sub> (<xref ref-type="bibr" rid="B11">He et al., 2020</xref>; <xref ref-type="bibr" rid="B15">Huang et al., 2021a</xref>), they have demonstrated that the combination of &#x3b1;-Fe<sub>2</sub>O<sub>3</sub> can further improve the transfer of photogenerated charges and improved the photoelectric conversion efficiency. In particular, Fe<sub>2</sub>O<sub>3</sub> combined with g-C<sub>3</sub>N<sub>4</sub> could improve h<sup>&#x2b;</sup> injection efficiency (<xref ref-type="bibr" rid="B14">Huang et al., 2021b</xref>). The results show that due to the lower reduction potential of Fe<sup>2&#x2b;</sup>/Fe<sup>3&#x2b;</sup> than that of g-C<sub>3</sub>N<sub>4</sub>, the addition of Fe species can effectively capture the photogenerated carriers of g-C<sub>3</sub>N<sub>4</sub> and inhibit the recombination of electron&#x2013;hole pairs. At the same time, the modification of high conductive materials on g-C<sub>3</sub>N<sub>4</sub> nanosheets to construct heterojunctions is one of the feasible ways to promote charge separation.</p>
<p>MXene is an emerging two-dimensional layered material that shows great potential in the field of photocatalysis due to its superior ability to capture light and metal conductivity. The general formula for MXene is M<sub>n&#x2b;1</sub>X<sub>n</sub>T<sub>x</sub>, where M represents the early transition metal, X represents carbon or nitrogen, and T<sub>x</sub> represents the functional groups (such as -OH, -F, and &#x3d;O) produced in the etching process and attached to the surface of MXene material. In other words, MXene material is a new type of two-dimensional material composed of transition metal carbides, nitrides, and carbonitrides. Among them, Ti<sub>3</sub>C<sub>2</sub> is a typical MXene material composed of transition metal carbide, which was successfully synthesized for the first time by <xref ref-type="bibr" rid="B28">Naguib et al. (2011)</xref>. With the advantages of multilayer structure, good electrical conductivity, large specific surface area, and excellent chemical stability, Ti<sub>3</sub>C<sub>2</sub> has become a research hotspot in the energy field in recent years. At present, a variety of hybrid materials based on Ti<sub>3</sub>C<sub>2</sub> appear in the field of photocatalysis, such as Ti<sub>3</sub>C<sub>2</sub>/Bi<sub>2</sub>WO<sub>6</sub> (<xref ref-type="bibr" rid="B13">Huang et al., 2020</xref>), Ti<sub>3</sub>C<sub>2</sub>/CdLa<sub>2</sub>S<sub>4</sub> (<xref ref-type="bibr" rid="B3">Cheng et al., 2020</xref>), and Ti<sub>3</sub>C<sub>2</sub>/CdS (<xref ref-type="bibr" rid="B41">Yang et al., 2019</xref>, <xref ref-type="bibr" rid="B13">Huang et al., 2020</xref>) prepared Ti<sub>3</sub>C<sub>2</sub>/Bi<sub>2</sub>WO<sub>6</sub> composites by electrostatic assembly method, showing excellent performance in photodegradation of formaldehyde and acetone, and the degradation rate was 2 times and 6.6 times of pure Bi<sub>2</sub>WO<sub>6</sub>, respectively. Studies have shown that this may be attributed to the strong adsorption of formaldehyde and acetone by Ti<sub>3</sub>C<sub>2</sub> and the effective promotion of photogenerated electron&#x2013;hole recombination of Bi<sub>2</sub>WO<sub>6</sub> by Ti<sub>3</sub>C<sub>2</sub>. A large number of studies have shown that (<xref ref-type="bibr" rid="B35">Xiao et al., 2016</xref>; <xref ref-type="bibr" rid="B1">Anasori et al., 2017</xref>) Ti<sub>3</sub>C<sub>2</sub> can effectively promote the separation of photogenerated electrons and holes by forming heterojunctions between Ti<sub>3</sub>C<sub>2</sub> and other semiconductors due to its excellent metal-like conductivity. Therefore, Ti<sub>3</sub>C<sub>2</sub> is widely used as a cocatalyst to improve the photocatalytic performance of semiconductors. Currently, there was also some work on the research of Ti<sub>3</sub>C<sub>2</sub> and g-C<sub>3</sub>N<sub>4</sub> composites. For example, <xref ref-type="bibr" rid="B25">Liu S. et al. (2018)</xref> prepared Ti<sub>3</sub>C<sub>2</sub>/g-C<sub>3</sub>N<sub>4</sub> composites by means of evaporative self-assembly. The heterojunction formed between g-C<sub>3</sub>N<sub>4</sub> and Ti<sub>3</sub>C<sub>2</sub> effectively inhibited the photogenerated electric&#x2013;hole pair composite of g-C<sub>3</sub>N<sub>4</sub>, and ciprofloxacin could be completely decomposed within 150&#xa0;min, which was about 10% higher than that of pure g-C<sub>3</sub>N<sub>4</sub>. Composites show better performance. <xref ref-type="bibr" rid="B22">Liu et al., 2022</xref>, designed a 3D/2D g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> heterojunction and found that benefiting from the 3D interconnected morphology and the incorporation of Ti<sub>3</sub>C<sub>2</sub> nanosheets, it exhibited high specific surface area and efficient charge transfer. <xref ref-type="bibr" rid="B42">Yi et al., 2020</xref>, designed the compound of alkalized g-C<sub>3</sub>N<sub>4</sub> with less layer Ti<sub>3</sub>C<sub>2</sub> to prepare Ti<sub>3</sub>C<sub>2</sub>/g-C<sub>3</sub>N<sub>4</sub> complex, which could effectively remove TC under visible light irradiation, with a yield of 77.0%. The kinetic constant was 1.8 times higher than that of alkalized g-C<sub>3</sub>N<sub>4</sub>, and the photocatalytic performance was effectively enhanced. <xref ref-type="bibr" rid="B27">Liu et al., 2021</xref>, prepared Ti<sub>3</sub>C<sub>2</sub>/g-C<sub>3</sub>N<sub>4</sub> photocatalysts with different mass ratios. The results showed that when the mass ratio was 1%, Ti<sub>3</sub>C<sub>2</sub>/g-C<sub>3</sub>N<sub>4</sub> had the best degradation performance for levofloxacin. It was 72.0%, which was 2.14 times that of the g-C<sub>3</sub>N<sub>4</sub> monomer. <xref ref-type="bibr" rid="B39">Yang et al., 2020</xref>, prepared the ultrathin Ti<sub>3</sub>C<sub>2</sub>/g-C<sub>3</sub>N<sub>4</sub> complex by directly calcining the mixture of massive Ti<sub>3</sub>C<sub>2</sub> and urea, which showed good performance in the photoreduction of CO<sub>2</sub>, and the total CO<sub>2</sub> conversion rate was 8.1 times higher than that of pure g-C<sub>3</sub>N<sub>4</sub>. These results showed that the 2D/2D heterojunction formed by g-C<sub>3</sub>N<sub>4</sub> and Ti<sub>3</sub>C<sub>2</sub> could effectively promote the charge separation of g-C<sub>3</sub>N<sub>4</sub> and improve photocatalytic performance. In view of the disadvantages of g-C<sub>3</sub>N<sub>4</sub>, such as small specific surface area, easy recombination of electron&#x2013;hole pairs, and low visible light utilization, the peeling process of Ti<sub>3</sub>C<sub>2</sub> reported at present was complicated and had certain risks, and the &#x201c;accordion&#x201d; lamellar structure is unstable and easy to recombine.</p>
<p>In this study , Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> was prepared by the one-pot microwave method and high-temperature calcination method. The photocatalytic performance of g-C<sub>3</sub>N<sub>4</sub> was improved by the Fe doping and Ti<sub>3</sub>C<sub>2</sub> composite, and TC was used as the target degradation material to investigate the photocatalytic performance of the sample and explore the photodegradation mechanism. The experimental results showed that both Fe doping and Ti<sub>3</sub>C<sub>2</sub> composite could reduce the bandgap energy of g-C<sub>3</sub>N<sub>4</sub> and improve the visible light utilization of the material; at the same time, it could effectively inhibit the recombination of electron&#x2013;hole pairs of g-C<sub>3</sub>N<sub>4</sub>, improve the quantum efficiency, and enhance the photocatalytic performance. The highlights of this work were as follows: 1) simple preparation method: the synthesis of g-C<sub>3</sub>N<sub>4</sub>, the intercalation and peeling multilayer Ti<sub>3</sub>C<sub>2,</sub> and the composite of Ti<sub>3</sub>C<sub>2</sub> and g-C<sub>3</sub>N<sub>4</sub> were realized simultaneously by the combination of one-pot microwave method and high-temperature calcination method. Specificaly, urea was used as the precursor to prepare g-C<sub>3</sub>N<sub>4</sub> in this study. NH<sub>3</sub> was produced in the process of calcination. As a small molecular substance, NH<sub>3</sub> could intercalate multilayer Ti<sub>3</sub>C<sub>2</sub>, effectively prevent the stacking of Ti<sub>3</sub>C<sub>2</sub> layers and play a supporting role, promote the expansion of the spacing of multilayer Ti<sub>3</sub>C<sub>2</sub> layers, and better form a tight 2D/2D interlayer interface with g-C<sub>3</sub>N<sub>4</sub>. The conventional relatively complex synthesis path of synthesizing monomer g-C<sub>3</sub>N<sub>4</sub> and multilayer Ti<sub>3</sub>C<sub>2</sub>, and then intercalation and peeling multilayer Ti<sub>3</sub>C<sub>2</sub> with dimethyl sulfoxide, and then recombination was simplified effectively (<xref ref-type="bibr" rid="B17">Li et al., 2020</xref>). 2) For the first time, Fe and Ti<sub>3</sub>C<sub>2</sub> were introduced to modify g-C<sub>3</sub>N<sub>4</sub>, and the reduction potential of Fe<sup>2&#x2b;</sup>/Fe<sup>3&#x2b;</sup> was lower than that of g-C<sub>3</sub>N<sub>4</sub>, to effectively capture the photogenerated carriers of g-C<sub>3</sub>N<sub>4</sub>. At the same time, the 2D/2D heterojunction formed by g-C<sub>3</sub>N<sub>4</sub> and Ti<sub>3</sub>C<sub>2</sub> could effectively promote the charge separation of the g-C<sub>3</sub>N<sub>4</sub> and explored whether there was a synergistic effect between these two modification methods to further promote the photocatalytic performance of the g-C<sub>3</sub>N<sub>4</sub>.</p>
</sec>
<sec id="s2">
<title>Experimental Section</title>
<sec id="s2-1">
<title>Materials</title>
<p>Urea, p-benzoquinone (BQ), and ethylenediamine tetraacetic acid disodium (EDTA-2Na) were purchased from Tianjin Damao Chemical Reagent Factory. Lithium fluoride (LiF), tetracycline hydrochloride (TC), and isopropanol (IPA) were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. Iron nitrate [Fe(NO<sub>3</sub>)<sub>3</sub>&#xb7;9H<sub>2</sub>O] was purchased from Shanghai McLean Biochemical Technology Co., Ltd. Ti<sub>3</sub>AlC<sub>2</sub> MAX phase was purchased from Hangzhou Namao Technology Co., Ltd. Hydrochloric acid (37% wt.) was purchased from Guangzhou Chemical Reagent Factory. And, all the chemicals are analytically pure except for special marked, and they were directly used without further purification.</p>
</sec>
<sec id="s2-2">
<title>Preparation of Multilayer Ti<sub>3</sub>C<sub>2</sub>
</title>
<p>HCl solution (20&#xa0;ml of 9&#xa0;mol/L) was added to the Teflon beaker, and 1.0&#xa0;g of LiF powder was slowly added to the beaker under the action of a magnetic agitator. After it gets fully dissolved, the solution was stirred for 10&#xa0;min. To avoid overheating, 1.0&#xa0;g of Ti<sub>3</sub>AlC<sub>2</sub> powder was added slowly for about 20&#xa0;min. After continuous stirring at 35&#xb0;C for 48&#xa0;h, they were centrifuged at 4,000&#xa0;rpm for 20&#xa0;min, washed with 3&#xa0;mol/L HCl solution several times to remove the residual LiF after reaction, and then washed repeatedly with deionized water until the pH of the supernatant was close to 7. The collected Ti<sub>3</sub>C<sub>2</sub> precipitate was freeze-dried thoroughly, and the obtained powder was multilayer Ti<sub>3</sub>C<sub>2</sub> powder.</p>
</sec>
<sec id="s2-3">
<title>Preparation of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>
</title>
<p>Fe(NO<sub>3</sub>)<sub>3</sub>&#xb7;9H<sub>2</sub>O (0.06&#xa0;g) was dissolved and dispersed in 50&#xa0;ml of deionized water, 10&#xa0;g of urea was added to dissolve completely, and 0.08&#xa0;g of Ti<sub>3</sub>C<sub>2</sub> powder was added under an ultrasonic environment to form a uniform dispersion solution, dried thoroughly, and ground evenly. Calcination was carried out in a 50&#xa0;ml crucible with a lid in a muffle furnace under an air atmosphere. The temperature rose to 550&#xb0;C at a rate of 50&#xb0;C/min, and the temperature was held for 1&#xa0;h. The resulting brown-yellow solid was ground thoroughly to form Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> powder (see <xref ref-type="fig" rid="F9">Scheme 1</xref>).</p>
<fig id="F9" position="float">
<label>SCHEME 1</label>
<caption>
<p>Scheme illustration for Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2.</sub>
</p>
</caption>
<graphic xlink:href="FCHEM_fchem-2022-865847_wc_sch1.tif"/>
</fig>
</sec>
<sec id="s2-4">
<title>Testing and Characterization of Materials</title>
<p>The phase characterization of the samples was determined by an X-ray powder diffract graph (D8 Advance, Brock AXS, Germany), using Cu-K&#x251; rays with a wavelength of 154 p.m. and a scanning range of 2&#x3b8; &#x3d; 5&#xb0;&#x223c;80&#xb0;; the morphology and structure of the samples were characterized by MIRA 3 LMU scanning electron microscope SEM (TESCAN Brno, S.R.O., Czech Republic) at a voltage of 15&#xa0;kV; the morphology and microstructure were also observed by transmission electron microscopy TEM and high-resolution transmission electron microscopy HR-TEM (FEI Talos F200x G2,United States); the element was mapped by the energy-dispersive spectroscopy EDS (FEI Talos F200x G2, Super-X, United States); the element composition and existence form of the samples were determined by X-ray photoelectron spectroscopy XPS (Thermo Scientific K-Alpha Hangzhou Yanqu Information Technology Co., LTD) using the Al-K&#x3b1; rays; the thermal stability of the samples was characterized by using a thermogravimetric analyzer TGA (TGA-4000, Platinum Elmer, United States); the specific surface area of the samples was analyzed by an automatic specific surface adsorption instrument BET (BELSORP-max, DKSH Commercial Co., LTD., Japan); the optical absorption performance of the sample was reflected by using the UV-visible diffuse reflector DRS (Shimadzu UV-2600, Japan) and calculating the bandgap of the photocatalyst. BaSO<sub>4</sub> was used as the reference sample; the photocatalytic activity of the samples was analyzed by fluorescence PL (Shimadzu RF-5301PC, Japan), and the excitation wavelength was 322&#xa0;nm.</p>
</sec>
<sec id="s2-5">
<title>Adsorption Properties of the Material</title>
<p>50&#xa0;ml of 20&#xa0;mg/L TC solution was added into the beaker, then 20&#xa0;mg of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> powder was added, and shook well. The mixture was stirred away from light, the proper amount of mixture was absorbed every 10&#xa0;min, and the absorbance was measured at 356&#xa0;nm by using a visible spectrophotometer.</p>
</sec>
<sec id="s2-6">
<title>Photocatalytic Performance of the Material</title>
<p>50&#xa0;ml of 20&#xa0;mg/L TC solution was added into the beaker, 20&#xa0;mg of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> powder was added, and shook well. The mixture was stirred away from light until the adsorption&#x2013;desorption is balanced, then placed it in a xenon lamp source (<italic>&#x3bb;</italic> &#x3e; 420&#xa0;nm, 280W), the proper amount of mixture was absorbed every 20&#xa0;min, and the absorbance was measured at 356&#xa0;nm by using a visible spectrophotometer. Benzoquinone (BQ), isopropyl alcohol (IPA), and ethylenediamine tetraacetic acid disodium (EDTA-2Na) were used as the trapping agent of superoxide free radical (&#x2022;O<sub>2</sub>
<sup>&#x2212;</sup>), hydroxyl free radical (&#x2022;OH), and hole (h<sup>&#x2b;</sup>), respectively, to explore the degradation mechanism of pollutants in the photocatalytic reaction.</p>
</sec>
<sec id="s2-7">
<title>Photoelectrochemical Measurements</title>
<p>The photoelectrochemical measurements were conducted on a three-electrode electrochemical workstation (A4602, Wuhan Kesite Instrument Co., LTD.), in which the working electrode, counter electrode, and reference electrode were the obtained samples, platinum foil, and Ag/AgCl electrode, respectively. The working electrodes were prepared by the drop-coating method: typically, 2&#xa0;mg of catalyst and 15&#xa0;&#x3bc;l Nafion solution were dispersed in 1&#xa0;ml of ethanol and sonicated for 30&#xa0;min. Afterward, the resulted homogeneous suspension was dripped onto the FTO and dried at room temperature. Here, all photoelectrochemical measurements were carried out in 0.5&#xa0;m Na<sub>2</sub>SO<sub>4</sub> electrolyte, and the light source was identical to that of photocatalytic measurements. Mott&#x2013;Schottky was recorded at a frequency of 1,000&#xa0;Hz.</p>
</sec>
</sec>
<sec sec-type="results|discussion" id="s3">
<title>Results and Discussion</title>
<sec id="s3-1">
<title>XRD Characterization</title>
<p>The phase of the sample was characterized by an X-ray powder diffractometer, and the results are reflected in <xref ref-type="fig" rid="F1">Figure 1A</xref> which shows the XRD patterns of Ti<sub>3</sub>AlC<sub>2</sub> and multilayer Ti<sub>3</sub>C<sub>2</sub>. A series of diffraction peaks corresponding to (002), (004), (101), (104), (105), (107), (109), and (110) crystal planes can be observed from the XRD spectra of Ti<sub>3</sub>AlC<sub>2</sub>. After being etched by HF, the strongest peak of Ti<sub>3</sub>C<sub>2</sub> at 39.0&#xb0; disappeared, and the peaks corresponding to (002) and (004) crystal planes widened and shifted to a lower angle, indicating that the Al layer in Ti<sub>3</sub>AlC<sub>2</sub> had been removed, and Ti<sub>3</sub>AlC<sub>2</sub> was successfully converted to Ti<sub>3</sub>C<sub>2</sub>. At the same time, the Ti<sub>3</sub>C<sub>2</sub> layer structure becomes thinner. From <xref ref-type="fig" rid="F1">Figure 1B</xref>, two evident diffraction peaks located at 12.83&#xb0; and 27.05&#xb0; for g-C<sub>3</sub>N<sub>4</sub> are observed, corresponding to (100) and (002) crystal planes, respectively. Fe-C<sub>3</sub>N<sub>4</sub> mainly had a peak at 27.05&#xb0;, corresponding to the (002) crystal plane of g-C<sub>3</sub>N<sub>4</sub>. The characteristic peak of Fe was not observed, probably due to the small amount of doped Fe or the weak characteristic peak. The XRD pattern of g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> shows two distinct peaks at 6.93&#xb0; and 27.05&#xb0;, respectively, corresponding to the (002) crystal plane of Ti<sub>3</sub>C<sub>2</sub> and the (002) crystal plane of g-C<sub>3</sub>N<sub>4</sub>, indicating that g-C<sub>3</sub>N<sub>4</sub> and Ti<sub>3</sub>C<sub>2</sub> have achieved good recombination. The XRD pattern of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> is similar to that of g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>. The characteristic peaks of Ti<sub>3</sub>C<sub>2</sub> and g-C<sub>3</sub>N<sub>4</sub> are observed, and the characteristic peaks of Fe are not observed, on account of the small amount of Fe doped or the weak characteristic peaks.</p>
<fig id="F1" position="float">
<label>FIGURE 1</label>
<caption>
<p>
<bold>(A)</bold> XRD pattern of Ti<sub>3</sub>C<sub>2</sub> and Ti<sub>3</sub>AlC<sub>2</sub>. <bold>(B)</bold> XRD pattern of the Ti<sub>3</sub>C<sub>2</sub>, g-C<sub>3</sub>N<sub>4</sub>, Fe-C<sub>3</sub>N<sub>4</sub>, g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2,</sub> and Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>.</p>
</caption>
<graphic xlink:href="fchem-10-865847-g001.tif"/>
</fig>
<p>Compared with multilayer Ti<sub>3</sub>C<sub>2</sub>, the intensity of characteristic peaks on the (002) plane of g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> and Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> at 6.93&#xb0; is much weaker. It is speculated that NH<sub>3</sub> released during urea calcination can be inserted into the interlayer of multilayer Ti<sub>3</sub>C<sub>2</sub> as a small molecule in the process of compounding with Ti<sub>3</sub>C<sub>2</sub>, which effectively prevents the stacking of Ti<sub>3</sub>C<sub>2</sub> interlayers, plays a supporting role, promotes the expansion of interlayer spacing of multilayer Ti<sub>3</sub>C<sub>2</sub>, and forms a close 2D/2D interlayer contact surface with g-C<sub>3</sub>N<sub>4</sub>. At the same time, it is speculated that Fe doping causes different degrees of polycondensation of g-C<sub>3</sub>N<sub>4</sub> and delays the phase transition process, resulting in the decrease of cell parameters and crystal plane spacing of g-C<sub>3</sub>N<sub>4</sub> and the increase of specific surface area. Moreover, Ti<sub>3</sub>C<sub>2</sub> and g-C<sub>3</sub>N<sub>4</sub> form a 2D/2D contact surface, which directly affects the periodic stacking interlayer structure of g-C<sub>3</sub>N<sub>4</sub>, resulting in the decrease of the diffraction peak intensity of g-C<sub>3</sub>N<sub>4</sub> at 27.05&#xb0; and the broadening.</p>
</sec>
<sec id="s3-2">
<title>SEM Characterization</title>
<p>The microstructure of the samples was characterized by SEM, and the results are shown in <xref ref-type="fig" rid="F2">Figure 2</xref>. It can be seen from <xref ref-type="fig" rid="F2">Figure 2A</xref> that the unetched Ti<sub>3</sub>AlC<sub>2</sub> is a bulk stacking structure. The morphology of Ti<sub>3</sub>C<sub>2</sub> obtained by etching is shown in <xref ref-type="fig" rid="F2">Figure 2B</xref>. Clear interlamellar spacing can be observed visually, showing a two-dimensional layered structure of MXene. Multilayer Ti<sub>3</sub>C<sub>2</sub> stacked together changed into an accordion-like structure. It is observed from <xref ref-type="fig" rid="F2">Figure 2C</xref> that g-C<sub>3</sub>N<sub>4</sub> is mostly agglomerated and a small part is thin. It is observed from <xref ref-type="fig" rid="F2">Figure 2D</xref> that the aggregation of g-C<sub>3</sub>N<sub>4</sub> after Fe-doping is weakened, showing a thin lamellar structure. It is observed from <xref ref-type="fig" rid="F2">Figure 2E</xref> that, after the combination of g-C<sub>3</sub>N<sub>4</sub> and Ti<sub>3</sub>C<sub>2</sub>, the two form a close interlayer structure. From <xref ref-type="fig" rid="F2">Figure 2F</xref>, it can be observed that there is a close interlayer structure between g-C<sub>3</sub>N<sub>4</sub> and Ti<sub>3</sub>C<sub>2</sub> in Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>. It is assumed that urea releases NH<sub>3</sub> during the calcination, and small molecule NH<sub>3</sub> inserts into the interlayer structure of Ti<sub>3</sub>C<sub>2</sub> and acts as a gas template to strip Ti<sub>3</sub>C<sub>2</sub>, effectively preventing the accumulation of Ti<sub>3</sub>C<sub>2</sub> layers (<xref ref-type="bibr" rid="B39">Yang et al., 2020</xref>).</p>
<fig id="F2" position="float">
<label>FIGURE 2</label>
<caption>
<p>SEM images of <bold>(A)</bold> Ti<sub>3</sub>AlC<sub>2</sub>, <bold>(B)</bold> Ti<sub>3</sub>C<sub>2</sub>, <bold>(C)</bold> g-C<sub>3</sub>N<sub>4</sub>, <bold>(D)</bold> Fe-C<sub>3</sub>N<sub>4</sub>, <bold>(E)</bold> g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> and <bold>(F)</bold> Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>.</p>
</caption>
<graphic xlink:href="fchem-10-865847-g002.tif"/>
</fig>
</sec>
<sec id="s3-3">
<title>TEM Characterization</title>
<p>The morphology and microstructure of the Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> catalyst were observed by TEM (<xref ref-type="fig" rid="F3">Figure 3A</xref>). It can be seen that the sample exhibits a typical layered structure. In <xref ref-type="fig" rid="F3">Figure 3B</xref>, the shallowest area is g-C<sub>3</sub>N<sub>4</sub>, the darker overlying layer is Ti<sub>3</sub>C<sub>2</sub>, and the darkest black area is Fe species. More information about Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> can be obtained from <xref ref-type="fig" rid="F3">Figure 3C</xref>. The lattice spacing of Ti<sub>3</sub>C<sub>2</sub> is 0.22&#xa0;nm, and the lattice spacing of Fe species is 0.40&#xa0;nm. In addition, the EDS element map (<xref ref-type="fig" rid="F3">Figure 3D</xref>) of the sample further confirms that there is good interaction between Fe, Ti<sub>3</sub>C<sub>2</sub>, and g-C<sub>3</sub>N<sub>4</sub>. The elements C, N, O, Ti, and Fe are distributed uniformly in the samples. According to <xref ref-type="fig" rid="F3">Figure 3E</xref>, the contents of Fe and Ti are 13.34 and 25.16%, respectively. These results show that g-C<sub>3</sub>N<sub>4</sub> is uniformly modified by Ti<sub>3</sub>C<sub>2</sub> and Fe and has close contact.</p>
<fig id="F3" position="float">
<label>FIGURE 3</label>
<caption>
<p>
<bold>(A,B)</bold> TEM images of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>, <bold>(C)</bold> HR-TEM of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2,</sub> <bold>(D,E)</bold> EDS of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>.</p>
</caption>
<graphic xlink:href="fchem-10-865847-g003.tif"/>
</fig>
</sec>
<sec id="s3-4">
<title>XPS Characterization</title>
<p>The chemical composition and valence state of the samples were characterized by X-ray photoelectron spectroscopy, and the results are shown in <xref ref-type="fig" rid="F4">Figure 4</xref>. It is observed from <xref ref-type="fig" rid="F4">Figure 4A</xref> that the measured spectra of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> show the existence of C, N, Ti, O, and Fe elements, indicating that Fe-doping and the composite of Ti<sub>3</sub>C<sub>2</sub> were successfully realized in g-C<sub>3</sub>N<sub>4</sub>. It can be seen from the C 1s spectrum (<xref ref-type="fig" rid="F4">Figure 4B</xref>) that the C 1s peak can be fitted into three peaks, namely, graphite phase carbon (C&#x2013;C) at 284.38&#xa0;eV, sp<sup>3</sup>-hybridized carbon (C-N&#x3d;C) at 285.48&#xa0;eV, and sp<sup>2</sup>-hybridized carbon (N-C&#x3d;N) at 287.58&#xa0;eV. The N 1s spectrum (<xref ref-type="fig" rid="F4">Figure 4C</xref>) shows three distinct peaks, which are ascribed to sp<sup>2</sup>-hybridized nitrogen (C-N&#x3d;C) at 398.18&#xa0;eV, tertiary nitrogen group (N-(C)<sub>3</sub>) at 399.38&#xa0;eV, and free amino groups (C-N-H) at 400.10&#xa0;eV, respectively. According to the Ti 2p spectrum (<xref ref-type="fig" rid="F4">Figure 4D</xref>), Ti 2p XPS peaks are deconvoluted into three peaks, namely, Ti-N bond at 457.70&#xa0;eV, Ti-C 2p<sup>1/2</sup> bond at 462.20&#xa0;eV, and Ti-O 2p<sup>1/2</sup> bond at 463.84&#xa0;eV. The existence of the Ti-O 2p<sup>1/2</sup> bond may be related to the slight oxidation of Ti<sub>3</sub>C<sub>2</sub>. According to the Fe 2p spectra (<xref ref-type="fig" rid="F4">Figure 4E</xref>), there are three chemical states of Fe, namely, Fe-N bond at 710.48&#xa0;eV, trivalent iron satellite peak at 718.30&#xa0;eV, and trivalent iron in Fe<sub>2</sub>O<sub>3</sub> at 713.08 and 724.28&#xa0;eV, which indicates that there are both iron&#x2013;nitrogen chemical bonds and Fe<sub>2</sub>O<sub>3</sub> in the material. From the above analysis, Fe-doping and Ti<sub>3</sub>C<sub>2</sub> composite were successfully realized in g-C<sub>3</sub>N<sub>4</sub>. In Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>, Fe mainly exists in the form of the Fe-N bond and Fe<sub>2</sub>O<sub>3</sub>, Ti forms the key existence in the Ti-N bond and Ti-C bond, which further confirms that Fe and Ti<sub>3</sub>C<sub>2</sub> have been successfully combined with g-C<sub>3</sub>N<sub>4</sub>.</p>
<fig id="F4" position="float">
<label>FIGURE 4</label>
<caption>
<p>XPS pattern of <bold>(A)</bold> Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> composites, High-resolution XPS spectra comparison of <bold>(B,C)</bold> 1s and <bold>(C)</bold> N 1s and <bold>(D)</bold> Ti 2pand <bold>(E)</bold> Fe 2p.</p>
</caption>
<graphic xlink:href="fchem-10-865847-g004.tif"/>
</fig>
</sec>
<sec id="s3-5">
<title>TGA Characterization</title>
<p>The thermal stability of the sample was characterized by a thermogravimetric analyzer, and the results are shown in <xref ref-type="fig" rid="F5">Figure 5A</xref>. It can be observed from <xref ref-type="fig" rid="F5">Figure 5A</xref> that the mass change of Ti<sub>3</sub>C<sub>2</sub> is not obvious with the increase in temperature, showing excellent stability. The mass loss of g-C<sub>3</sub>N<sub>4</sub>, Fe-C<sub>3</sub>N<sub>4</sub>, g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>, and Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> was very rapid within a certain temperature range, which was due to the decomposition of the C-N bond of g-C<sub>3</sub>N<sub>4</sub> in the material to generate CO<sub>2</sub> and NO<sub>2</sub>. At the same time, pure g-C<sub>3</sub>N<sub>4</sub> was completely decomposed when the temperature exceeded 777&#xb0;C, while Fe-C<sub>3</sub>N<sub>4</sub>, g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>, and Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> were not completely decomposed, which was attributed to the stability of Fe and Ti<sub>3</sub>C<sub>2</sub> residues in the sample.</p>
<fig id="F5" position="float">
<label>FIGURE 5</label>
<caption>
<p>
<bold>(A)</bold> The TGA curves of Ti<sub>3</sub>C<sub>2</sub>, g-C<sub>3</sub>N<sub>4</sub>, Fe-C<sub>3</sub>N<sub>4</sub>, g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2,</sub> and Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2.</sub> <bold>(B)</bold> N<sub>2</sub> adsorption-desorption isotherms of different materials. <bold>(C)</bold> UV-Vis diffuse reflectance spectra and <bold>(D)</bold> band gap of g-C<sub>3</sub>N<sub>4</sub>, Ti<sub>3</sub>C<sub>2</sub>, Fe-C<sub>3</sub>N<sub>4</sub>, g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> and Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>.</p>
</caption>
<graphic xlink:href="fchem-10-865847-g005.tif"/>
</fig>
</sec>
<sec id="s3-6">
<title>BET Characterization</title>
<p>The specific surface area of the sample was analyzed by an automatic surface adsorption instrument. <xref ref-type="fig" rid="F5">Figure 5B</xref> shows that the specific surface areas of g-C<sub>3</sub>N<sub>4</sub>, Fe-C<sub>3</sub>N<sub>4</sub>, g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>, and Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> are 38.55&#xa0;m<sup>2</sup>/g, 54.13&#xa0;m<sup>2</sup>/g, 49.25&#xa0;m<sup>2</sup>/g, and 68.58&#xa0;m<sup>2</sup>/g, respectively. Both Fe-doping and composite Ti<sub>3</sub>C<sub>2</sub> are conducive to expanding the specific surface area of photocatalyst, providing more active sites and improving the adsorption performance of materials. At the same time, the larger the specific surface area, the e<sup>&#x2212;</sup> generated by g-C<sub>3</sub>N<sub>4</sub> can migrate to the surface of the catalyst more quickly, which effectively reduces the recombination rate of electron and hole pairs and improves the photocatalytic performance of the material.</p>
</sec>
<sec id="s3-7">
<title>UV-Vis-DRS Characterization</title>
<p>The absorption properties of the samples were recorded by UV-Vis diffuse reflectance spectroscopy. The results are shown in <xref ref-type="fig" rid="F5">Figures 5C,D</xref>. It is observed from <xref ref-type="fig" rid="F5">Figure 5C</xref> that the Ti<sub>3</sub>C<sub>2</sub> shows broad absorption in the whole region (200&#x223c;800&#xa0;nm), and there is no obvious absorption with the edge, indicating that Ti<sub>3</sub>C<sub>2</sub> has metallic properties. The pristine g-C<sub>3</sub>N<sub>4</sub> displays a typical absorption region at about 450&#xa0;nm, which is consistent with the literature (<xref ref-type="bibr" rid="B9">Gebreslassie et al., 2019</xref>). The optical cutoff wavelengths of Fe-C<sub>3</sub>N<sub>4</sub>, g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>, and Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> are 467&#xa0;nm, 458, and 470&#xa0;nm, respectively. It can be seen that after Fe-doping and Ti<sub>3</sub>C<sub>2</sub> composite, the sample shows a redshift compared with the monomer g-C<sub>3</sub>N<sub>4</sub>, and the visible light absorption capacity is enhanced, indicating that Fe-doping and composite Ti<sub>3</sub>C<sub>2</sub> can effectively improve the visible light absorption performance of g-C<sub>3</sub>N<sub>4</sub>. Due to the strong absorption of dark Ti<sub>3</sub>C<sub>2</sub> in the whole wavelength range (200&#x223c;800&#xa0;nm), the absorption edge of g-C<sub>3</sub>N<sub>4</sub> can readily shift after recombination, so Ti<sub>3</sub>C<sub>2</sub> composite can effectively enhance the light absorption of g-C<sub>3</sub>N<sub>4</sub>. According to the energy level theory, it is suggested that the bandgap of g-C<sub>3</sub>N<sub>4</sub> forms the impurity energy level after Fe-doping. The electrons only need to absorb photons with small energy to realize the indirect transition of energy level, which can absorb photons with long-wavelength, broaden the visible light absorption range of g-C<sub>3</sub>N<sub>4</sub> and improve the utilization rate of visible light. From <xref ref-type="fig" rid="F5">Figure 5D</xref> the band gaps of g-C<sub>3</sub>N<sub>4</sub>, Fe-C<sub>3</sub>N<sub>4</sub>, g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>, and Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> are 2.38, 2.26, 2.21, and 2.19&#xa0;eV, respectively. It shows that Fe-doping and composite Ti<sub>3</sub>C<sub>2</sub> can reduce the bandgap energy of g-C<sub>3</sub>N<sub>4</sub>, reduce the bandgap width, expand the visible light response range, and improve the visible light utilization.</p>
</sec>
<sec id="s3-8">
<title>PL Characterization</title>
<p>The photocatalytic activity of the samples was analyzed by fluorescence spectroscopy. The results are shown in <xref ref-type="fig" rid="F6">Figure 6A</xref>. It can be seen from <xref ref-type="fig" rid="F6">Figure 6A</xref> that g-C<sub>3</sub>N<sub>4</sub> shows a strong fluorescence emission peak at 466&#xa0;nm. After Fe-doping and composite Ti<sub>3</sub>C<sub>2</sub>, the intensity of this peak was inhibited significantly. Confirming that Fe-doping and composite Ti<sub>3</sub>C<sub>2</sub> can effectively reduce the electrons and holes recombination probability of g-C<sub>3</sub>N<sub>4</sub>, and the quantum efficiency is improved.</p>
<fig id="F6" position="float">
<label>FIGURE 6</label>
<caption>
<p>
<bold>(A)</bold> PL spectra of g-C<sub>3</sub>N<sub>4</sub>, Ti<sub>3</sub>C<sub>2</sub>, Fe-C<sub>3</sub>N<sub>4</sub>, g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2,</sub> and Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2.</sub> <bold>(B)</bold> The transient photocurrent density of nude FTO, g-C<sub>3</sub>N<sub>4</sub>, Fe-C<sub>3</sub>N<sub>4</sub> and Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2.</sub> <bold>(C)</bold> Mott-Schottky curves of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2.</sub>
</p>
</caption>
<graphic xlink:href="fchem-10-865847-g006.tif"/>
</fig>
<p>According to the relevant literature (<xref ref-type="bibr" rid="B20">Li et al., 2008</xref>), Fe<sup>2&#x2b;</sup>/Fe<sup>3&#x2b;</sup> has a reduction potential lower than the conduction band potential of g-C<sub>3</sub>N<sub>4</sub>, so Fe-doping can effectively capture the photogenerated carriers of g-C<sub>3</sub>N<sub>4</sub> and inhibit the recombination of electron and hole pairs. When the g-C<sub>3</sub>N<sub>4</sub> layer is inserted into the Ti<sub>3</sub>C<sub>2</sub> sheet, the two form many intimate interfaces, thus providing the maximum contact surface between the two phases. On such a platform, electrons can be easily transferred from g-C<sub>3</sub>N<sub>4</sub> nanosheets to metal Ti<sub>3</sub>C<sub>2</sub> sheets with high conductivity (<xref ref-type="bibr" rid="B30">Su et al., 2019</xref>), inhibiting the recombination of electron and hole pairs. At the same time, it can be observed from <xref ref-type="fig" rid="F6">Figure 6A</xref> that the fluorescence intensity of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> is the lowest, indicating that there is a synergistic effect between Fe-doping and composite Ti<sub>3</sub>C<sub>2</sub> in g-C<sub>3</sub>N<sub>4</sub>. The recombination rate of the excited electrons and holes in g-C<sub>3</sub>N<sub>4</sub> is greatly reduced, the quantum efficiency shows excellent improvement, and the sample may show better photocatalytic activity.</p>
<p>As it is known to all, a higher photocurrent means a higher separation efficiency for the photogenerated charge, which is finally reflected in the better photocatalytic performance. As displayed in <xref ref-type="fig" rid="F6">Figure 6B</xref>, compared with naked FTO, the photocurrent responses of g-C<sub>3</sub>N<sub>4</sub>, Fe-C<sub>3</sub>N<sub>4</sub>, and Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> samples gradually increase, with average photocurrent densities of 17.3, 24.6, and 41.7&#xa0;&#x3bc;A/cm<sup>2</sup>. Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> shows the highest photocurrent density, which is 2.4-fold higher than g-C<sub>3</sub>N<sub>4</sub> and 1.7-fold higher than Fe-C<sub>3</sub>N<sub>4</sub>. The enhanced photocurrent density of Fe-C<sub>3</sub>N<sub>4</sub> and Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> electrodes, respectively, shows that Fe doping and Ti<sub>3</sub>C<sub>2</sub> composite can promote g-C<sub>3</sub>N<sub>4</sub> to provide more carriers to the external circuit, resulting in the greater the photocurrent and the higher the photogenerated charge. The higher the separation efficiency, the better the photocatalytic performance. The results here are mainly due to the following reasons: the reduction potential of Fe<sup>2&#x2b;</sup>/Fe<sup>3&#x2b;</sup> is lower than the conduction band potential of g-C<sub>3</sub>N<sub>4</sub>, so Fe can effectively capture the photogenerated carriers generated by g-C<sub>3</sub>N<sub>4</sub>, and the e<sup>&#x2212;</sup>&#x2013;h<sup>&#x2b;</sup> pair recombination rate is greatly reduced (<xref ref-type="bibr" rid="B12">Hu et al., 2018</xref>), and Fe doping weakens the degree of polymerization of g-C<sub>3</sub>N<sub>4</sub>, increases its surface area, and provides more photocatalytically active sites. The Ti<sub>3</sub>C<sub>2</sub> layer is embedded in thin g-C<sub>3</sub>N<sub>4</sub> nanosheets, forming a heterojunction and interfacial effect between them. The photogenerated electrons tend to transfer from g-C<sub>3</sub>N<sub>4</sub> to Ti<sub>3</sub>C<sub>2</sub>, which improves the interfacial charge transfer ability of g-C<sub>3</sub>N<sub>4</sub>, which can effectively inhibit the recombination of e<sup>&#x2212;</sup>&#x2013;h<sup>&#x2b;</sup> pairs. (<xref ref-type="bibr" rid="B17">Li et al., 2020</xref>). Metal Fe-doped and g-C<sub>3</sub>N<sub>4</sub> composite Ti<sub>3</sub>C<sub>2</sub> act simultaneously, and the photocatalytic performance is better than Fe-C<sub>3</sub>N<sub>4</sub>.</p>
</sec>
<sec id="s3-9">
<title>Adsorption Performance</title>
<p>When the catalyst dosage was 20&#xa0;mg and the initial concentration of TC is 20&#xa0;mg/L, the adsorption curve of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> on TC is shown in <xref ref-type="fig" rid="F7">Figure 7A</xref>. In the first 5&#xa0;min of the dark reaction, the adsorption amount of TC on Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> increased rapidly and reached the adsorption-desorption equilibrium after 45&#xa0;min. The equilibrium adsorption amount was 10.78&#xa0;mg/g, and the adsorption rate was 21.03%. The adsorption kinetics of TC on Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> was investigated by pseudo-first-order and pseudo-second-order adsorption kinetics models. The results are shown in <xref ref-type="fig" rid="F7">Figure 7A</xref>. The graph shows that the correlation coefficient of the pseudo-first-order kinetic equation <italic>R</italic>
<sup>2</sup> &#x3d; 0.9784, and the correlation coefficient of the pseudo-second-order kinetic equation <italic>R</italic>
<sup>2</sup> &#x3d; 0.9987, indicating that the adsorption of TC by Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> is a second-order kinetic model, that is, chemical adsorption. The equilibrium adsorption amount <italic>q</italic>
<sub>
<italic>e</italic>
</sub> &#x3d; 10.78&#xa0;mg/g, and the adsorption rate constant <italic>k</italic> &#x3d; 0.01852&#xa0;g/(mgmin) can be obtained from the slope and intercept of the straight line, respectively.</p>
<fig id="F7" position="float">
<label>FIGURE 7</label>
<caption>
<p>
<bold>(A)</bold> Absorption curve of TC on Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2&#x3002;</sub>Dynamic model: quasi-first order,quasi-second order. <bold>(B)</bold> Photocatalytic degradation curves of TC by different photocatalysts. <bold>(C)</bold> Kinetic fitting curve. <bold>(D)</bold> Photocatalytic activity changes of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> for TC degradation with different sacrificial agents.</p>
</caption>
<graphic xlink:href="fchem-10-865847-g007.tif"/>
</fig>
</sec>
<sec id="s3-10">
<title>Photocatalytic Activity</title>
<p>When the catalyst dosage was 20&#xa0;mg and the initial concentration of TC was 20&#xa0;mg/L, the photocatalytic degradation curves of different samples are shown in <xref ref-type="fig" rid="F7">Figure 7B</xref>. When no photocatalyst was added, TC was almost not degraded under xenon lamp irradiation, and the degradation rate was only about 1.41%, indicating that TC was relatively stable and difficult to be photodegraded. When only Ti<sub>3</sub>C<sub>2</sub> was added, the photocatalytic degradation rate of TC under xenon lamp irradiation was only 4.30%, indicating that Ti<sub>3</sub>C<sub>2</sub> cannot be used as a catalyst for photocatalytic degradation of TC alone. After 180&#xa0;min of illumination, the photocatalytic degradation rates of TC by g-C<sub>3</sub>N<sub>4</sub>, g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>, Fe-C<sub>3</sub>N<sub>4</sub>, and Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> were 44.37, 61.53, 68.01, and 86.80%, respectively. It can be seen that compared with g-C<sub>3</sub>N<sub>4</sub>, the degradation rate of TC by g-C<sub>3</sub>N<sub>4</sub> is improved after Fe-doping and composite Ti<sub>3</sub>C<sub>2</sub>. The degradation rate of TC by Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> within 180&#xa0;min is 86.80%, 1.96 times that of g-C<sub>3</sub>N<sub>4</sub>, which greatly improves the photocatalytic degradation efficiency of TC by photocatalyst. It can be speculated that there is a synergistic effect between Fe-doping and composite Ti<sub>3</sub>C<sub>2</sub> in g-C<sub>3</sub>N<sub>4</sub>, and the photocatalytic ability of the sample is better.</p>
<p>Linear fitting with <inline-formula id="inf2">
<mml:math id="m2">
<mml:mrow>
<mml:mi>ln</mml:mi>
<mml:mrow>
<mml:mo>(</mml:mo>
<mml:mrow>
<mml:mrow>
<mml:mrow>
<mml:msub>
<mml:mi>C</mml:mi>
<mml:mn>0</mml:mn>
</mml:msub>
</mml:mrow>
<mml:mo>/</mml:mo>
<mml:mrow>
<mml:msub>
<mml:mi>C</mml:mi>
<mml:mi>t</mml:mi>
</mml:msub>
</mml:mrow>
</mml:mrow>
</mml:mrow>
<mml:mo>)</mml:mo>
</mml:mrow>
</mml:mrow>
</mml:math>
</inline-formula> to <italic>t</italic>, and the results are shown in <xref ref-type="fig" rid="F7">Figure 7C</xref>. The photocatalytic degradation of TC by Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> conforms to the first-order reaction kinetics model, and the relevant parameters are shown in <xref ref-type="table" rid="T1">Table 1</xref>. The apparent rate constants k of Fe-C<sub>3</sub>N<sub>4</sub>, g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>, and Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> are 1.38, 1.60, and 2.83 times of g-C<sub>3</sub>N<sub>4</sub>, respectively. It shows that Fe-doping and composite Ti<sub>3</sub>C<sub>2</sub> are beneficial to improve the photocatalytic degradation activity of g-C<sub>3</sub>N<sub>4</sub>.</p>
<table-wrap id="T1" position="float">
<label>TABLE 1</label>
<caption>
<p>First-order reaction kinetic parameters.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th align="left">Photocatalyst</th>
<th align="center">First order kinetic equation</th>
<th align="center">Correlation R<sup>2</sup>
</th>
<th align="center">Degradation rate (%)</th>
<th align="center">Reaction Rate Constant k (min)</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td align="left">g-C<sub>3</sub>N<sub>4</sub>
</td>
<td align="char" char="(">ln (C<sub>0</sub>/C<sub>t</sub>) &#x3d; 0.00318t&#x2b;0.01508</td>
<td align="char" char=".">0.9957</td>
<td align="char" char=".">44.37</td>
<td align="char" char=".">0.00318<sup>&#x2013;1</sup>
</td>
</tr>
<tr>
<td align="left">Fe-C<sub>3</sub>N<sub>4</sub>
</td>
<td align="char" char="(">ln (C<sub>0</sub>/C<sub>t</sub>) &#x3d; 0.00438t&#x2b;0.08071</td>
<td align="char" char=".">0.9664</td>
<td align="char" char=".">68.01</td>
<td align="char" char=".">0.00438<sup>&#x2013;1</sup>
</td>
</tr>
<tr>
<td align="left">g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>
</td>
<td align="char" char="(">ln (C<sub>0</sub>/C<sub>t</sub>) &#x3d; 0.00510t&#x2b;0.02109</td>
<td align="char" char=".">0.9937</td>
<td align="char" char=".">61.53</td>
<td align="char" char=".">0.00510<sup>&#x2013;1</sup>
</td>
</tr>
<tr>
<td align="left">Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>
</td>
<td align="char" char="(">ln (C<sub>0</sub>/C<sub>t</sub>) &#x3d; 0.00901t&#x2b;0.12033</td>
<td align="char" char=".">0.9794</td>
<td align="char" char=".">86.80</td>
<td align="char" char=".">0.00901<sup>&#x2013;1</sup>
</td>
</tr>
</tbody>
</table>
</table-wrap>
</sec>
<sec id="s3-11">
<title>Degradation Mechanism</title>
<p>By adding sacrificial agents such as BQ, IPA, and EDTA-2Na to detect the common active radicals &#x2022;O<sub>2</sub>
<sup>&#x2212;</sup>, &#x2022;OH, and h<sup>&#x2b;</sup> to explore the degradation mechanism of the photocatalytic reaction system. The results are shown in <xref ref-type="fig" rid="F7">Figure 7D</xref>. When no radical scavengers were in the solution, the degradation rate of TC by Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> was 86.80%. When &#x2022;OH and h<sup>&#x2b;</sup> capture agents were added, the photocatalytic degradation of TC by Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> was inhibited to a certain extent, and the degradation rates were reduced to 66.30 and 63.81%, respectively. When &#x2022;O<sub>2</sub>
<sup>&#x2212;</sup> capture agent was added, the photocatalytic degradation of TC by Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> was greatly inhibited, and the degradation rate decreased to 30.96%. Therefore, the influence of active species on the degradation of TC in the photocatalytic degradation system was as follows: &#x2022;O<sub>2</sub>
<sup>&#x2212;</sup> &#x3e; h<sup>&#x2b;</sup> &#x3e; &#x2022;OH.</p>
<p>Based on the above results, we speculated on the photocatalytic degradation mechanism of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> to TC (<xref ref-type="fig" rid="F8">Figure 8</xref>). The electrons of g-C<sub>3</sub>N<sub>4</sub> in Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> were excited to CB under visible light irradiation. Thus, the photogenerated holes (h<sup>&#x2b;</sup>) were left in the VB. In the Mott&#x2013;Schottky test (<xref ref-type="fig" rid="F6">Figure 6C</xref>), we made a tangent along the longest straight line in the figure, and the slope was found to be positive, indicating that g-C<sub>3</sub>N<sub>4</sub> was an <italic>n</italic>-type semiconductor. According to the formula (E<sub>g</sub> &#x3d; E<sub>VB</sub> &#x2b; E<sub>CB</sub>) and the DRS results, the theoretical estimation of the E<sub>VB</sub> and E<sub>CB</sub> of g-C<sub>3</sub>N<sub>4</sub> were 1.35&#xa0;V and &#x2212;0.84&#xa0;V vs. NHE. In addition, the Fermi level (E<sub>f</sub>, vs. NHE, pH &#x3d; 0) of Ti<sub>3</sub>C<sub>2</sub> was &#x2212;0.60&#xa0;V, which was higher than the E<sub>CB</sub> of g-C<sub>3</sub>N<sub>4</sub> (<xref ref-type="bibr" rid="B30">Su et al., 2019</xref>). In Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> composites, a close 2D/2D contact interface is formed between Ti<sub>3</sub>C<sub>2</sub> and g-C<sub>3</sub>N<sub>4</sub>. Electrons could be easily transferred from g-C<sub>3</sub>N<sub>4</sub> nanosheets to Ti<sub>3</sub>C<sub>2</sub> surfaces, which inhibits recombination of photoinduced electrons and holes. Moreover, because the reduction potential of Fe<sup>2&#x2b;</sup>/Fe<sup>3&#x2b;</sup> (Fe<sup>2&#x2b;</sup>/Fe<sup>3&#x2b;</sup> &#x3d; &#x2212;0.77&#xa0;V) was lower than the E<sub>CB</sub> of g-C<sub>3</sub>N<sub>4</sub> (<xref ref-type="bibr" rid="B20">Li et al., 2008</xref>), Fe could effectively capture the photogenerated electrons of g-C<sub>3</sub>N<sub>4</sub> and inhibit recombination of electron and hole pairs. Then, the electrons reacted with oxygen adsorbed on the surface of the photocatalyst or dissolved in solution to form strongly oxidized &#x2022;O<sub>2</sub>
<sup>&#x2212;</sup> (O<sub>2</sub>/&#x2022;O<sub>2</sub>
<sup>&#x2212;</sup> &#x3d; &#x2212;0.33&#xa0;V). It oxidized TC to CO<sub>2</sub> and H<sub>2</sub>O. At the same time, the h<sup>&#x2b;</sup> of g-C<sub>3</sub>N<sub>4</sub> reacted with H<sub>2</sub>O or OH<sup>&#x2212;</sup> in the solution to form the &#x2022;OH (&#x2022;OH/OH<sup>&#x2212;</sup> &#x3d; 1.99&#xa0;V) with strong oxidizability. &#x2022;OH could degrade TC into CO<sub>2</sub> and H<sub>2</sub>O. The holes in the valence band of g-C<sub>3</sub>N<sub>4</sub> also had strong oxidation which could react with TC and degrade it. The process of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> photocatalytic degradation of TC is as follows.</p>
<fig id="F8" position="float">
<label>FIGURE 8</label>
<caption>
<p>Photocatalytic degradation mechanism diagram of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> to TC.</p>
</caption>
<graphic xlink:href="fchem-10-865847-g008.tif"/>
</fig>
</sec>
<sec id="s3-12">
<title>Material Performance Comparison</title>
<p>Comparing the experimental system with other related systems, the results are shown in <xref ref-type="table" rid="T2">Table 2</xref>. It can be seen from <xref ref-type="table" rid="T2">Table 2</xref> that the experimental system has a certain value in practicability and economy. A small amount of Fe-doping and a small amount of Ti<sub>3</sub>C<sub>2</sub> composite were used to modify g-C<sub>3</sub>N<sub>4</sub>, and the prepared Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> photocatalyst could be used to degrade TC efficiently with a degradation rate of 86.80%. Compared with the following table, there are certain differences in the degradation rates of different substances in different systems. The main reasons are that the types and ratios of materials, the dosage of photocatalyst, the degradation time, and the power and wavelength of the light source are different.</p>
<table-wrap id="T2" position="float">
<label>TABLE 2</label>
<caption>
<p>Comparison of photocatalytic properties of different systems.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th align="left">Years</th>
<th align="center">Photocatalyst</th>
<th align="center">Dosage (mg)</th>
<th align="center">Target degradation amount</th>
<th align="center">Degrading time (min)</th>
<th align="center">Source power (W)</th>
<th align="center">Light source wavelength</th>
<th align="center">Degradation rate (%)</th>
<th align="center">Rate constant</th>
<th align="center">References</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td align="left">2021</td>
<td align="left">Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>
</td>
<td align="center">20</td>
<td align="left">TC</td>
<td align="center">180</td>
<td align="center">280</td>
<td align="center">&#x3e;420&#xa0;nm</td>
<td align="char" char=".">86.80</td>
<td align="char" char=".">0.0090 min<sup>&#x2212;1</sup>
</td>
<td align="left">Our work</td>
</tr>
<tr>
<td align="left">2021</td>
<td align="left">Ti<sub>3</sub>C<sub>2</sub>/g-C<sub>3</sub>N<sub>4</sub>
</td>
<td align="center">20</td>
<td align="left">LEV</td>
<td align="center">30</td>
<td align="center">300</td>
<td align="center">&#x3e;420&#xa0;nm</td>
<td align="char" char=".">72.00</td>
<td align="char" char=".">0.0392 min<sup>&#x2212;1</sup>
</td>
<td align="left">
<xref ref-type="bibr" rid="B27">Liu et al. (2021)</xref>
</td>
</tr>
<tr>
<td align="left">2021</td>
<td align="left">cPTA/g-C<sub>3</sub>N<sub>4</sub>
</td>
<td align="center">30</td>
<td align="left">TC</td>
<td align="center">180</td>
<td align="center">500</td>
<td align="center">&#x3e;420&#xa0;nm</td>
<td align="char" char=".">78.00</td>
<td align="char" char=".">0.0084 min<sup>&#x2212;1</sup>
</td>
<td align="left">
<xref ref-type="bibr" rid="B40">Yang et al. (2021)</xref>
</td>
</tr>
<tr>
<td align="left">2020</td>
<td align="left">Ti<sub>3</sub>C<sub>2</sub>/alkalized g-C<sub>3</sub>N<sub>4</sub>
</td>
<td align="center">10</td>
<td align="left">TC</td>
<td align="center">60</td>
<td align="center">300</td>
<td align="center">&#x3e;420&#xa0;nm</td>
<td align="char" char=".">77.00</td>
<td align="char" char=".">0.0307 min<sup>&#x2212;1</sup>
</td>
<td align="left">
<xref ref-type="bibr" rid="B42">Yi et al. (2020)</xref>
</td>
</tr>
<tr>
<td align="left">2020</td>
<td align="left">Fe-doped g-C<sub>3</sub>N<sub>4</sub>
</td>
<td align="center">50</td>
<td align="left">RhB</td>
<td align="center">60</td>
<td align="center">300</td>
<td align="center">&#x3e;420&#xa0;nm</td>
<td align="char" char=".">87.00</td>
<td align="char" char=".">-</td>
<td align="left">
<xref ref-type="bibr" rid="B23">Liu et al. (2020a)</xref>
</td>
</tr>
<tr>
<td align="left">2018</td>
<td align="left">Fe-doped alkalinized g-C<sub>3</sub>N<sub>4</sub>
</td>
<td align="center">30</td>
<td align="left">TC</td>
<td align="center">80</td>
<td align="center">300</td>
<td align="center">&#x3e;420&#xa0;nm</td>
<td align="char" char=".">63.70</td>
<td align="char" char=".">0.0164 min<sup>&#x2212;1</sup>
</td>
<td align="left">
<xref ref-type="bibr" rid="B38">Xu et al. (2018)</xref>
</td>
</tr>
</tbody>
</table>
</table-wrap>
</sec>
</sec>
<sec sec-type="conclusion" id="s4">
<title>Conclusion</title>
<p>In this study, Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> photocatalyst was synthesized <italic>via</italic> one-pot microwave method and high-temperature calcination method. When the catalyst dosage was 20&#xa0;mg and the initial concentration of TC was 20&#xa0;mg/L, the degradation rate of TC by Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub> was 86.80%, which was 1.96, 1.28, and 1.41 times that of g-C<sub>3</sub>N<sub>4</sub>, Fe-C<sub>3</sub>N<sub>4</sub> and g-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2</sub>. The influence of active species on the degradation of TC in the photocatalytic degradation system was &#x2022;O<sub>2</sub>
<sup>&#x2212;</sup> &#x3e; h<sup>&#x2b;</sup> &#x3e; &#x2022;OH. During the synthesis of Fe-C<sub>3</sub>N<sub>4</sub>/Ti<sub>3</sub>C<sub>2,</sub> the byproduct NH<sub>3</sub> could intercalate multilayer Ti<sub>3</sub>C<sub>2</sub>, effectively preventing the stacking of Ti<sub>3</sub>C<sub>2</sub> layers. Fe-doping and the composite of Ti<sub>3</sub>C<sub>2</sub> would decrease the bandgap energy of g-C<sub>3</sub>N<sub>4</sub> and effectively inhibited the recombination of electron and hole pairs of g-C<sub>3</sub>N<sub>4</sub>. It is expected that this work provides new insight into the construction of 2D/2D heterojunction materials used in the photocatalytic application.</p>
</sec>
</body>
<back>
<sec id="s5">
<title>Data Availability Statement</title>
<p>The original contributions presented in the study are included in the article/Supplementary Material, further inquiries can be directed to the corresponding author.</p>
</sec>
<sec id="s6">
<title>Author Contributions</title>
<p>ZH contributed to the conception, design of the study, and writing the original draft. YL was responsible for the data processing and the experimental part. ZH and YL contributed equally to this work. YH, XL, and QZ were in charge of the experimental part and wrote sections of the manuscript. YZ and SY were responsible for the TEM. HW, JS, GW, and HS wrote sections of the manuscript. All authors contributed to manuscript revision and read and approved the submitted version.</p>
</sec>
<sec id="s7">
<title>Funding</title>
<p>The project was supported by the special fund for scientific and technological innovation strategy of Guangdong Province (&#x201c;Climbing&#x201d; Program, nos. pdjh 2022b0385 and pdjh 2021b0371), Guangzhou Basic and Applied Basic Project (no. 202102020424), and College Students&#x2019; Scientific and Technological Innovation Project (nos. 202114278078 and 202114278087), Key Scientific Research Projects of General Universities in Guangdong Province (no. 2021KCXTD086) and Scientific Research Project of Guangdong University of Education (Student Work Project) (no. 2021XKY009).</p>
</sec>
<sec sec-type="COI-statement" id="s8">
<title>Conflict of Interest</title>
<p>The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.</p>
</sec>
<sec sec-type="disclaimer" id="s9">
<title>Publisher&#x2019;s Note</title>
<p>All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors, and the reviewers. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.</p>
</sec>
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