Waste-to-Energy Conversion on Graphitic Carbon Nitride: Utilizing the

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Waste-to-energy conversion on graphitic carbon nitride: Utilizing the transformation of macrolide antibiotics to enhance photoinduced hydrogen production Zheng Xu, Shasha Xu, Nan Li, Fei Wu, Shichang Chen, Wangyang Lu, and Wenxing Chen ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.7b03088 • Publication Date (Web): 19 Oct 2017 Downloaded from http://pubs.acs.org on October 21, 2017

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ACS Sustainable Chemistry & Engineering

Waste-to-energy conversion on graphitic carbon nitride: Utilizing the transformation of macrolide antibiotics to enhance photoinduced hydrogen production Zheng Xu, Shasha Xu, Nan Li, Fei Wu, Shichang Chen, Wangyang Lu*, and Wenxing Chen* National Engineering Lab for Textile Fiber Material & Processing Technology (Zhejiang), Zhejiang Sci-Tech University, No.2 Street, Xiasha, Hangzhou 310018, P. R. China. E-mail: [email protected] (W. Lu); [email protected] (W. Chen). KEYWORDS: macrolide antibiotics, graphitic carbon nitride, hydrogen, photocatalysis, water splitting

ABSTRACT: Photocatalytic H2 evolution is usually from pure water or water with sacrificial agents. Surprisingly, it has been found that the presence of poisonous macrolide antibiotics in an aqueous medium for catalytic H2 evolution enhances the H2 yield while itself being degraded, using Pt/graphitic carbon nitride (Pt/g-C3N4) under visible light ( λ > 420 nm). Hence, a promising method that addresses the issues of energy shortage and environmental pollution is proposed. Among macrolide antibiotics, Roxithromycin (Rox) is so effective in facilitating the decomposition of water that it can be acted as a model in this paper to explain phenomenon as

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mentioned above. Furthermore, the mechanism of the reaction is also explored and thirteen intermediates of Rox are identified by ultra-performance liquid chromatography and highresolution mass spectrometry. The degradation pathway of Rox is proposed on basis of the identified intermediates. In the whole process, both energy generation and pollutant control can be achieved simultaneously. Thereby, this represents a surprising waste-to-energy conversion process.

INTRODUCTION Sustainable photocatalytic H2 evolution is regarded as a highly effective and promising solution to the energy shortage and environmental pollution.1-3 Since the pioneering work of Fujishima and Honda on photoelectrochemical hydrogen evolution over TiO2,4 such photocatalysis has attracted the interest of many researchers due to its potential application in direct water splitting to afford hydrogen, and for water purification by the degradation of organic contaminants.5–7 However, to the best of our knowledge, most of researchers focus on either how to split water or purify water.8-11 The combination of water purification with the direct utilization of solar energy for hydrogen fuel production by water splitting in a single process has rarely been achieved.12 Among the various polymeric photocatalysts, graphitic carbon nitride (g-C3N4) has attracted tremendous attention, as it is non-toxic, chemically stable, easily modified, and strongly visiblelight responsive.13-17 However, pure g-C3N4 shows low efficiency for hydrogen evolution in practical applications owing to a low efficiency of electron–hole separation and a high recombination rate of photogenerated charge carriers.18-20 Therefore, great efforts have been made to accelerate the hydrogen evolution rate of g-C3N4, such as by doping to optimize the capture

of

light

and

improve

the

charge-separation

kinetics;21-26

preparing


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heterojunction/composites to accelerate charge separation;27,28 forming nanostructuring to optimize distribution of light and promote charge separation;29-32 and introducing mesopores to accelerate charge separation.33 In order to improve the reaction efficiency, Pt is used as a cocatalyst to enhance the transfer of photoinduced charge. In this work, Pt/g-C3N4 has been synthesized by using a photodeposition method as the loading process. Characterization of the Pt/g-C3N4 by transmission electron microscopy (TEM) and high-resolution TEM showed that Pt had been successfully deposited and uniformly dispersed in the g-C3N4 (Figure S1). It was verified that the photoelectrochemical properties were improved by Pt (Figures S2–S4). Moreover, other properties have no obvious change (Figure S5). The hydrogen yield was clearly significantly enhanced after introducing Pt on the surface of g-C3N4, and 2 wt% Pt/g-C3N4 displayed the highest activity (Figure S6). In Figure S7 (b), we can find Pt4+ has been reduced into Pt2+ and Pt0 completely. Meanwhile, it also explains that Pt0 plays an important role in accelerating the evolution of hydrogen. 34 However, not every pollutant present in water contributes to enhancing hydrogen production during the degradation process over Pt/g-C3N4 under visible light. For example, it is not possible to accelerate photocatalytic H2 evolution by using Pt/g-C3N4 with the simultaneous removal of phenol (Figure S8). With the aim of constructing a system that combines water reduction with contaminant elimination, various contaminants have been explored in our work. Surprisingly, macrolide antibiotics, which are harmful to humans even at low concentrations in drinking water, exerting long-term biological effects,

35-37

can act as a sacrificial agent that can

enhance the decomposition of water. In this single process, the two purposes mentioned above can be achieved simultaneously. It not only provides a new solution to the energy shortage and environmental pollution, but also improves the efficiency of resource utilization.


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RESULTS AND DISCUSSION Among of macrolide antibiotics, Rox is taken as a typical model in this paper. In Figure 1, it can be seen that the hydrogen yield increased significantly with the degradation of Rox. In this case, Rox was initially degraded within 4 h, and simultaneously the evolution of hydrogen increased significantly. Thereafter, following the degradation of Rox, the hydrogen yield increased only gradually. Finally, Rox was completely removed within 7 h, and the rate of hydrogen production leveled off. Thus, the rate of hydrogen production was seen to follow the same trend as the degradation rate of Rox, indicating a relationship between these processes. Moreover, further experiments were conducted to show that the hydrogen yield was proportional to the amount of Rox in water (Figure 2). When the amount of Rox was 15 mg or more, the hydrogen yield increased significantly. Although 5 or 10 mg Rox in water led to higher hydrogen production compared to that from pure water, this enhancement effect was no longer seen after 3 h, suggesting that the Rox had been completely removed in this period. Consequently, it was clearly demonstrated Rox has a positive effect on photoinduced hydrogen production. Next, we compared the efficacy of Rox with those of the structurally similar Claricid and Kitasamycin (Figure S9). It was found that both of these compounds also facilitated the decomposition of water (Figure 3). It is of interest to note that although the hydrogen yields in these experiments were higher than that from pure water, Rox was the most effective, and there was almost no difference in the lower hydrogen yields with Claricid and Kitasamycin. To elucidate the reasons for its increased activity, a comprehensive degradation pathway of Rox was deduced. During the degradation of Rox, the first product was P1 (Figure 4), formed by


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the loss of –CH2 from an –NMe group. P1 can be further degraded into three intermediates (P2, P3, and P4). Thereafter, nine intermediates can be formed through further reaction of intermediates P2, P3, and P4. Finally, a small amount of citric acid can be detected (Table S1). According to previous studies on oximes,

38-40

the products P6 and P10 can be expected to go

through the following two processes, taking P10 as an example. In Figure 5a, it can be seen that Pt-g-C3N4, like Au-TiO2, may catalyze the chemoselective hydrogenation of oxime P10 with H2, thereby avoiding the generation of hydroxylamine, which is a noxious and unstable product. Therefore, it can be assumed that product P12 will be generated in the reaction. Simultaneously, it is also evident from Figure 3 that the partial consumption of H2 will result in an apparently lower rate of H2 evolution in 2 h under irradiation. Additionally, a new system can be envisaged when Rox is converted into oxime P10 (Figure 5b). The H+ exchange site will be closer to the Pt center, allowing intermolecular proton transfer in a cyclic intermediate, thereby enhancing the evolution of hydrogen. It is for this reason that the efficiency of hydrogen production in the presence of Rox in water is higher than with Claricid or Kitasamycin. Consequently, water is needed as an oxidizing agent in Rox degradation according to the following stoichiometry (Figure 4): C41H76N2O15 + 43H2O → 6C6H8O7 + 5CO2 + 57H2 + 2NO3-

(1)

In contrast to Figure 1, there was a slight difference between the theoretical hydrogen yield and that obtained in practice. Further observation revealed that a lot of intermediates remained in solution after irradiation for 7 h. The findings were also consistent with the mineralization of Rox being incomplete after 7 h, although it was thoroughly decomposed (Figure S10). Hence, a possible equation for the complete mineralization of Rox is proposed:


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C41H76N2O15 + 73H2O → 41CO2 + 111H2 + 2NO3-

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(2)

According to Equation (2), for every 1 mol of Rox degraded, 111 mol of hydrogen will be produced. Thus, if Rox can be completely mineralized, the hydrogen yield will be enormous. Therefore, it is further illustrated that the intermediates, mainly P6 and P10, can enhance the evolution of hydrogen. Considering practical application, the stability and cyclability of the process are also important. From Figure 6, it can be seen that the hydrogen yield increased steadily with each cycle, and the process was relatively stable. It is worth noting that the evolution of hydrogen increased a little after the first cycle. The reason for this phenomenon is that residual unpaired P6 or P10 from the previous cycle and the newly formed P6 or P10 combine with Pt to construct a system as mentioned above. Therefore, it is also proved that these intermediates can enhance water decomposition. On the basis of the above findings, a probable mechanism for photoinduced reduction of water and degradation of Rox in a single process using Pt/g-C3N4 can be proposed (Figure 7). The g-C3N4 produces hydrogen from water according to the process: 2H2O → H2O2 + H2.41

(3)

Because of the low quantum efficiency of g-C3N4, Pt is introduced on its surface to improve its photocatalytic reactivity, preventing electron–hole recombination. It is worthy of note that H2O2 is a negative factor for the decomposition of water because it can be adsorbed on the surface of g-C3N4, where it exerts a poisoning effect. Therefore, to facilitate hydrogen production, Rox as an electron donor and/or an oxygen scavenger serves to consume H2O2.42


6

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Simultaneously, a lot of intermediates will be degraded by photogenerated holes. Among the various intermediates, oximes P6 and P10 play important roles in enhancing water splitting to hydrogen. Most prominently, a new system is formed by P6 or P10 combining with Pt, which can facilitate intermolecular proton transfer. Ultimately, Rox acts as a sacrificial agent to facilitate photoinduced hydrogen production, while itself being degraded. CONCLUSION In conclusion, our work provides a solution for the photodecomposition of water and the degradation of macrolide antibiotics (e.g., Rox) in a single process by using Pt/g-C3N4. It is found that macrolide antibiotics present in water act as a sacrificial agent to consume H2O2, itself being degraded, leading to an enhancement of the hydrogen yield. Indeed, the hydrogen yield is proportional to the amount of macrolide antibiotics present in the water. The enhanced rate of photoinduced hydrogen production and efficient macrolide antibiotics degradation are the most remarkable highlights of the whole process. Excitingly, this work offers a new strategy for addressing the energy shortage and environmental pollution in a single process. Therefore, this photocatalytic technology can be regarded as a promising solution to be applied in wastewater purification with the aim of deriving hydrogen from the organic contaminants present therein. FIGURES


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Figure 1. Photocatalytic water splitting to hydrogen using 40 mg 2 wt%Pt/g-C3N4 and some substrates in the 100 ml water under the visible light irradiation (by a 300 W Xe lamp using a filter allowing λ > 420 nm) and the oxygen-free environment. Substrate is 15 mg Rox. Red column represents the removal rate of the Rox and the black line represents the evolution of hydrogen.


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Figure 2. Photocatalytic water splitting to hydrogen using 40 mg 2 wt%Pt/g-C3N4 and some substrates in the 100 ml water under the visible light irradiation

and the oxygen-free

environment. Substrates are 0 mg, 5 mg, 10 mg, 15 mg and 20 mg Rox, respectively.


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Figure 3. Photocatalytic water splitting to hydrogen using 40 mg 2 wt%Pt/g-C3N4 and some substrates in the 100 ml water under the visible light irradiation

and the oxygen-free

environment. Substrates are 20 mg Rox, 20 mg Claricid and 20 mg Kitasamycin, respectively.


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Figure 4. Pathway of Rox degradation.


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Figure 5. (a) Pathway of the degradation about P10 to P12; (b) The mechanisms of P10 enhancing the evolution of hydrogen under the visible light irradiation (by a 300 W Xe lamp using a filter allowing λ > 420 nm) and the oxygen-free environment.


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Figure 6. Photocatalytic water splitting to hydrogen using 40 mg 2 wt%Pt/g-C3N4 and 5 mg Rox in the 100 ml water under the visible light irradiation (by a 300 W Xe lamp using a filter allowing λ > 420 nm) and the oxygen-free environment. Stabilities of hydrogen evolution over the mention above system, the reaction was continued for 15 hour. After every run, 5 mg Rox added into the system.


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Figure 7. Proposed reaction mechanism for enhancing splitting water to hydrogen and degrading the Rox simultaneously by using Pt/g-C3N4 under the visible light. ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Experimental details of this study, preparation of g-C3N4 and Pt/g-C3N4, characterizations of catalysts (TEM, UV/Vis DRS spectra, Photoluminescence spectra, Transient photocurrent density responses, The thermogravimetric analysis and High resolution of XPS analysis), gas chromatography of CO2 and high-resolution parent and fragment ion data.


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AUTHOR INFORMATION Corresponding Author * E-mail: [email protected] (W. Lu), Tel/Fax: +86-571-8684-3611 * E-mail: [email protected] (W. Chen), Tel/Fax: +86-571-8684-3611 Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (No. 51133006), the Public Technology Application Research Project of Zhejiang Province (No. 2015C33018). REFERENCES 1.

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studies.

Journal

of

chromatographic

science

2013,

51

(1),

DOI:

10.1093/chromsci/bms104.


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Table of Contents Graphic and Synopsis

Synopsis Macrolide antibiotics in wastewater could be utilized to enhance photoinduced hydrogen production based on the catalytic platform with graphitic carbon nitride under visible irradiation.


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Waste-to-Energy Conversion on Graphitic Carbon Nitride: Utilizing the

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